EP1554227A2 - Use of polymer powders that are redispersible in water as a binding agent for jointing sand - Google Patents

Use of polymer powders that are redispersible in water as a binding agent for jointing sand

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Publication number
EP1554227A2
EP1554227A2 EP03757997A EP03757997A EP1554227A2 EP 1554227 A2 EP1554227 A2 EP 1554227A2 EP 03757997 A EP03757997 A EP 03757997A EP 03757997 A EP03757997 A EP 03757997A EP 1554227 A2 EP1554227 A2 EP 1554227A2
Authority
EP
European Patent Office
Prior art keywords
vinyl
acrylate
acid
group
copolymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03757997A
Other languages
German (de)
French (fr)
Inventor
René GRÄWE
Gabriele Trifellner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Polymer Systems GmbH and Co KG
Original Assignee
Wacker Polymer Systems GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Polymer Systems GmbH and Co KG filed Critical Wacker Polymer Systems GmbH and Co KG
Priority to EP06014573A priority Critical patent/EP1719743B1/en
Publication of EP1554227A2 publication Critical patent/EP1554227A2/en
Withdrawn legal-status Critical Current

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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
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
    • C04B2111/00672—Pointing or jointing materials

Definitions

  • the invention relates to the use of water-redispersible polymer powders, based on polymers stabilized with protective colloid, of ethylenically unsaturated monomers, as binders for joint sand.
  • Acid-curing amino resins are known from EP-A 401674 as binders for joint fillers.
  • DE-A 3726293 discloses joint sealing compounds made from an emulsifiable epoxy resin and quartz sand.
  • DE-A 4421970 describes a joint material made of quartz sand, quartz powder and a polymer binder, liquid polybutadiene binders being used.
  • EP-A 968977 relates to jointing compounds made from a pasty component made of synthetic resin dispersion and mineral fillers and a dry component made from cement and quartz sand.
  • the invention relates to the use of water-redispersible polymer powders as binders for joint sand, characterized in that functionalized, redispersible polymer powders from the group comprising a) copolymers of one or more monomers from the group of the unbranched vinyl esters stabilized with polyvinyl alcohol or branched alkyl carboxylic acids with 1 to 18 carbon atoms, acrylic acid esters or methacrylic acid esters of branched or unbranched alcohols or diols with 1 to 18 carbon atoms
  • Atoms, dienes, olefins, vinyl aromatics and vinyl halides which contain 0.1 to 20% by weight, based on the total weight of the copolymer, of one or more post-crosslinking comonomers from the group comprising acrylamidoglycolic acid (AGA), methyl acrylamido doglycolic acid methyl ester (MAGME), N -Methylolacrylamide (NMA), N- Methylolmethacrylamide (NMMA), N-Methylolallylcarbamat, alkyl ether and esters of N-Methylolacrylamids as well as N-Methyiol-methacrylamide and N-Methylolallylcarbamats, as well as Acryloxypropyltri (alkoxy) - and Methacryloxypropyltri ( alkoxy) silanes, vinyl trialkoxysilanes and vinyl methyl dialkoxysilanes, and b) with polymers
  • Suitable vinyl esters are those of carboxylic acids with 1 to 12 carbon atoms.
  • Vinyl acetate is particularly preferred.
  • Suitable monomers from the group of acrylic acid esters or methacrylic acid esters are esters of unbranched or branched alcohols having 1 to 15 carbon atoms.
  • Preferred methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate.
  • Methyl acrylate, methyl methacrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
  • Styrene, methylstyrene and vinyltoluene are preferred as vinyl aromatics.
  • the preferred vinyl halide is vinyl chloride.
  • the preferred olefins are ethylene, propylene and the preferred dienes are 1,3-butadiene and isoprene.
  • polymers which contain one or more monomer units from the group vinyl acetate, vinyl esters of ⁇ -branched monocarboxylic acids with 9 to 13 carbon atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate , n-Butyl methacrylate, 2-ethylhexyl acrylate, styrene included.
  • Polymers of vinyl acetate with ethylene are most preferred; of vinyl acetate, ethylene and a vinyl ester of ⁇ -branched monocarboxylic acids with 9 to 13 carbon atoms; of n-butyl acrylate with 2-ethylhexyl acrylate and / or methyl methacrylate; of styrene with one or more monomers from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; vinyl acetate with one or more monomers from the group consisting of methyl acrylate, ethyl rylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and optionally ethylene; wherein in the case of the polymer powders a) the corresponding amount of post-crosslinking comonomers is still present.
  • Preferred post-crosslinking comonomers are N-methylolacrylamide (NMA), N-methylolmethacrylamide (NMMA) and their isobutoxy ether, as well as acryloxypropyltri (alkoxy) and methacryloxypropyltri (alkoxy) silanes, vinyltrialkoxysilanes and vinylmethyldi- alkoxysilanes, where methoxy groups are methoxy groups. , Ethoxy and ethoxypropylene glycol ether residues are included.
  • NMA N-Methylolacrylamide
  • NMMA N-methylolmethacrylamide
  • acryloxypropyltriethoxy- and methacryloxypropyltriethoxy-silane, vinyltriethoxysilane and vinylmethyldiethoxysilane are particularly preferred.
  • Most preferred are N-methylolacrylamide and N-methylolmethacrylamide.
  • the postcrosslinking comonomers are preferably present in an amount of 1 to 10% by weight, based on the total weight of the copolymer.
  • the selection of monomers and the selection of the proportions by weight of the comonomers is carried out in such a way that a glass transition temperature Tg of -50 ° C. to + 120 ° C., preferably 0 ° C. to + 50 ° C., generally results.
  • the glass transition temperature Tg of the polymers can be determined in a known manner by means of differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the Tg can also be roughly predicted using the Fox equation. According to Fox T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956) applies:
  • Tg x / Tg + X2 / g2 + ... + x n / Tg n , where x n stands for the mass fraction (% by weight / 100) of the monomer n, and Tg n the glass transition temperature in Kelvin of the homopolymer of the monomer n. Tg values for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).
  • Suitable polyvinyl alcohol protective colloids for the redispersible polymer powders a) are partially saponified or fully saponified polyvinyl alcohols.
  • Partially saponified, hydrophobically modified polyvinyl alcohols with a degree of hydrolysis of 80 to 95 mol% and a Höppler viscosity, in 4% aqueous solution of 1 to 30 mPas are also preferred.
  • Examples include partially saponified copolymers of vinyl acetate with hydrophobic comonomers such as isopropenyl acetate, vinyl pivalate, vinyl ethyl hexanoate, vinyl esters of saturated alpha-branched monocarboxylic acids with 5 or 9 to 11 carbon atoms, dialkyl maleate and dialkyl fumarates such as diisopropyl vinyl maleate and diisopropyl chloride and diisopropyl chloride and diisopropyl chloride and diisopropyl chloride Vinyl butyl ether, olefins such as ethene and decene.
  • the proportion of the hydrophobic units is preferably 0.1 to 10% by weight, based on the total weight of the partially hydrolyzed polyvinyl alcohol. Mixtures of the polyvinyl alcohols mentioned can also be used.
  • polyvinyl alcohols are partially hydrolyzed, hydrophobicized polyvinyl alcohols which are obtained by polymer-analogous reaction, for example acetalization of the vinyl alcohol units with C x to C 4 aldehydes such as butyraldehyde.
  • the proportion of the hydrophobic units is preferably 0.1 to 10% by weight, based on the total weight of the partially saponified polyvinyl acetate.
  • the degree of hydrolysis is from 80 to 95 mol%, preferably 85 to 94 mol%, the Höppler viscosity (DIN 53015, Höppler method, 4% aqueous solution) from 1 to 30 mPas, preferably 2 to 25 mPas.
  • polyvinyl alcohols with a degree of hydrolysis of 85 to 94 mol% and a Höppler viscosity, in 4% aqueous solution of 3 to 15 mPas (Höppler method at 20 ° C., DIN 53015.
  • the polyvinyl alcohols mentioned are suitable
  • the polyvinyl alcohols are generally present in the redispersion powder a) in a total amount of 1 to 40% by weight, based on the total weight of the base polymer.
  • Suitable protective colloids based on polymers of ethylenically unsaturated mono- or dicarboxylic acids, for the redispersible polymer powders b), are homopolymers and copolymers of one or more monomers from the group comprising acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride. Homopolymers and copolymers of acrylic acid, methacrylic acid and maleic anhydride are preferred. Polyacrylic acid and polymethacrylic acid are particularly preferred. Also preferred are copolymers with acrylic acid, methacrylic acid and maleic acid (anhydride) units and units copolymerizable therewith monomers, the acid fraction being 80 to 99 mol%.
  • copolymerizable monomers examples include alkenes such as ethylene and propylene, vinyl aromatics such as styrene, acrylic esters such as butyl acrylate, methacrylic acid esters such as methyl methacrylate, alkyl vinyl ethers such as methyl vinyl ether, methacrylamide and acrylamide.
  • Examples of preferred copolymers are maleic acid-methyl vinyl ether, methacrylic acid-methyl methacrylate, methacrylic acid-acrylamide copolymers.
  • the molecular weights of the protective colloids mentioned for the redispersible polymer powders b) are ⁇ . 250,000 g / mol, preferably ⁇ 150,000 g / mol, particularly preferably 5,000 to 50,000 g / mol, each determined as the weight average Mw, for example with gel permeation chromatography.
  • the carboxyl-functional protective colloids are generally present in the redispersion powder b) in a total amount of 1 to 40% by weight, based on the total weight of the base polymer.
  • the carboxyl-functional protective colloids mentioned are accessible by means of processes known to the person skilled in the art or are commercially available.
  • the base polymers for the water-redispersible polymer powders a) and b) are prepared by means of the customary polymerization processes, such as suspension polymerization and emulsion polymerization, at from 40 ° C. to 100 ° C., after initiation of the polymerization with the customary water-soluble or monomer-soluble initiators.
  • the customary polymerization processes such as suspension polymerization and emulsion polymerization, at from 40 ° C. to 100 ° C., after initiation of the polymerization with the customary water-soluble or monomer-soluble initiators.
  • surface-active substances such as protective colloids and / or emulsifiers polymerized.
  • post-polymerization can be carried out using known methods to remove residual monomers, or volatile residual monomers can be removed by distillation and / or by passing or passing through inert entraining gases such as air, nitrogen or water vapor.
  • the aqueous dispersions are dried, if appropriate after the addition of protective colloids as a spraying aid, for example by means of fluidized-bed drying, freeze drying or spray drying.
  • the dispersions are preferably spray dried.
  • the protective colloid portion can be added before, during or after the polymerization.
  • the functionalized, water-redispersible polymer powder is generally used in an amount of 0.5 to 10% by weight, preferably 1.0 to 5.0% by weight, based on the sand content.
  • additives can also be incorporated into the mixture of sand and redispersion powder. Examples of these are crosslinkers, such as bifunctional, masked aldehydes having at least 3 carbon atoms, from which aldehyde groups are released in the acidic medium and can form covalent bonds with the OH groups of the polyvinyl alcohol protective colloid of redispersible powder a).
  • alkali hydrogen sulfite adducts of glutaraldehyde and succinaldehyde preferably glutaraldehyde bis (sodium hydrogensu ⁇ fit) and succinaldehyde bis (sodium hydrogen sulfite).
  • these crosslinkers are used in an amount of 0.001 to 1.0% by weight, based on the redispersible polymer powder.
  • Suitable additives are also agents for adjusting the pH of the redispersion of the polymer powder.
  • powdery, acidic additives such as alkali hydrogen sulfates, in particular sodium hydrogen sulfate, are preferably added.
  • the amount added is preferably 2 to 10% by weight, based on the polymer powder, which generally leads to a pH of the redispersion of pH ⁇ . 2 leads.
  • powdery, basic additives sentences like calcium carbonate added is preferably 5 to 40% by weight, based on the polymer powder, which generally leads to a pH of the redispersion of pH > 8.
  • the mixture of joint sand, polymer powder and possibly other additives is introduced in the dry or moist state by sweeping into the joints between the paving stones.
  • the crosslinking of the polymer powder a) is promoted in the moisture with the acidic additives mentioned.
  • the basic additives mentioned the dissolution of the carboxyl-functional protective colloid of the polymer powder b) is promoted in the moisture. In both cases, especially in critical weather conditions such as rain, this increases the binding power of the powder and prevents the sand from washing out of the joint.
  • a mixture of 95 parts by weight of standard sand T, 5 parts by weight of a polymer powder from a vinyl acetate-ethylene copolymer (Tg 9 ° C.) and a polyacrylic acid (Mw approx. 20,000, 20% by weight, based on Copolymer) and 1.1 parts by weight of calcium carbonate.
  • This mixture was shaped in a mold into a cuboid test specimen measuring 1 cm ⁇ 4 cm ⁇ 16 cm, and solidified under pressure to a density of 1.56 g / cm 3 .
  • Tg 10 ° C
  • % based on copolymer was stabilized, was used, and no acidic or basic additive was used.
  • test the water resistance of the jointing compound a test tube was closed with the shaped body at the bottom, and the test body was covered with 57 ml of water. The water flow per unit of time and area was determined. The moldings were tested immediately after their production and after 24 hours of storage at room temperature.
  • the water permeability of the shaped body was 21.3 l / m 2 / min immediately after its production and improved to 3.1 1 / mVmin after 24 h.
  • the water permeability of the shaped body was 3.4 l / m 2 / min immediately after its production and improved to 1.1 l / m 2 / min after 24 h.

Abstract

The use of water dispersible polymer powders based on protective colloid stabilized polymerisates of ethylenically unsaturated monomers as binders for jointing sands is new. Use of a water dispersible polymer powder as binder for jointing sand, where the functionalized redispersed polymer powder includes: (a) a polyvinyl alcohol stabilized copolymerisate of one or more monomers selected from:vinyl esters of optionally branched 1-18C alkylcarboxylic acids, (meth)acrylic acid esters of 1-18C optionally branched alcohol, dienes, or olefins, vinyl aromatics and vinyl halides having 0.1-20 wt.% on the total weight of copolymer of one or more post-crosslinked comonomers selected from a group including:acrylamidoglycol acid (AGA), methylacrylamidoglycol acid methylester (MAGME), N-methylolacrylamide, (NMA), N-methylolmethacrylamide (NMMA), N-methylolallyl carbamate, alkyl ether and ester of N-methylolacrylamide and of N-methylolmethacrylamide, and of N-methylolallyl carbamate, acryloxypropyltri(alkoxy)- and methacryloxypropyltri(alkoxy)-silane, vinyltrialkyloxysilane, and vinylmethyldialkyloxysilane, and (b) with polymerisates of ethylenically unsaturated monomers of dicarboxylic acids or their anhydrides, of acid content of 50-99 mole%, stabilized polymerizate of one or more monomers from vinyl esters of optionally branched 1-18C alkylcarboxylic acids, (meth)acrylic acid esters of optionally branched 1-18C alcohols or diols, dienes, olefins, vinyl aromatics and vinyl halides, mixed with sand.

Description

Verwendung von in Wasser redispergierbaren Polymerpulvern als Bindemittel für FugensandUse of polymer powders redispersible in water as binders for joint sand
Die Erfindung betrifft die Verwendung von in Wasser redisper- gierbaren Polymerpulvern, auf Basis von mit Schutzkolloid stabilisierten Polymerisaten ethylenisch ungesättigter Monomere, als Bindemittel für Fugensand.The invention relates to the use of water-redispersible polymer powders, based on polymers stabilized with protective colloid, of ethylenically unsaturated monomers, as binders for joint sand.
Die Verlegung von KopfSteinpflaster erfolgt in der Regel auf einem Sandbett, wobei zur Befüllung der Fugen zwischen den Pflastersteinen üblicherweise loser Sand oder eine Sandauf- schlämmung eingekehrt wird. Nachteilig ist dabei, dass im Laufe der Zeit, beispielsweise bei häufigen Niederschlägen, der Sand aus der Fuge entfernt wird.As a rule, cobblestones are laid on a bed of sand, whereby loose sand or a sand slurry is usually swept in to fill the joints between the paving stones. The disadvantage here is that the sand is removed from the joint over time, for example in the event of frequent rainfall.
Aus der EP-A 401674 sind säurehärtende Aminoharze als Bindemittel für Fugenfüllmassen bekannt. Aus der DE-A 3726293 sind Fugenvergussmassen aus einem emulgierbaren Epoxidharz und Quarz- sand bekannt. Die DE-A 4421970 beschreibt ein Fugenmaterial aus Quarzsand, Quarzmehl und einem Polymerbindemittel, wobei flüssige Polybutadienbindemittel verwendet werden. Die EP-A 968977 betrifft Fugenmassen aus einer pastösen Komponente aus Kunstharzdispersion und mineralischen Füllstoffen sowie einer Tro- ckenkomponente aus Zement und Quarzsand. Aus der JP-A 05-085792 ist bekannt, als Fugenfüllmasse ein Gemisch aus Sand und Re- dispersionspulver auf Basis von Polyvinylester, konkret Vinyl- acetat-VeoVa-Copolymeren, einzusetzen. Nachteilig ist bei den reaktionsvernetzenden Systemen deren hoher Preis und deren auf- wändige Verarbeitung. Fugenfüllmassen mit flüssigen Bindemitteln haben ebenfalls Nachteile bei der Verarbeitung, da diese nicht durch einfaches Einkehren in die Fuge eingebracht werden können. Sandmischungen mit redispergierbaren Polyvinylestern lassen sich zwar leicht verarbeiten, bringen aber nur unzurei- chende Verfestigung der Fugenfüllmasse. Es bestand daher die Aufgabe, eine Fugenfüllmasse aus Sand und Bindemittel zur Verfügung zu stellen, welche einen pulverförmi- gen Binder enthält, welcher zur dauerhaften Verfestigung der Fugenfüllmasse führt.Acid-curing amino resins are known from EP-A 401674 as binders for joint fillers. DE-A 3726293 discloses joint sealing compounds made from an emulsifiable epoxy resin and quartz sand. DE-A 4421970 describes a joint material made of quartz sand, quartz powder and a polymer binder, liquid polybutadiene binders being used. EP-A 968977 relates to jointing compounds made from a pasty component made of synthetic resin dispersion and mineral fillers and a dry component made from cement and quartz sand. From JP-A 05-085792 it is known to use a mixture of sand and dispersion powder based on polyvinyl ester, specifically vinyl acetate-VeoVa copolymers, as the joint filling compound. A disadvantage of the reaction crosslinking systems is their high price and their complex processing. Joint fillers with liquid binders also have disadvantages during processing, since they cannot be introduced into the joint simply by sweeping them in. Sand mixtures with redispersible polyvinyl esters are easy to process, but only insufficiently solidify the joint filler. It was therefore an object to provide a joint filler made of sand and binder which contains a powdery binder which leads to permanent solidification of the joint filler.
Gegenstand der Erfindung ist die Verwendung von in Wasser re- dispergierbaren Polymerpulvern als Bindemittel für Fugensand, dadurch gekennzeichnet, dass funktionalisierte, redispergierba- re Polymerpulver aus der Gruppe umfassend a) mit Polyvinylalkohol stabilisierte Copolymerisate von einem oder mehreren Monomeren aus der Gruppe der Vinylester von unverzweigten oder verzweigten Alkylcarbonsäuren mit 1 bis 18 C- Atomen, Acrylsäureester oder Methacrylsäureester von verzweig- ten oder unverzweigten Alkoholen oder Diolen mit 1 bis 18 C-The invention relates to the use of water-redispersible polymer powders as binders for joint sand, characterized in that functionalized, redispersible polymer powders from the group comprising a) copolymers of one or more monomers from the group of the unbranched vinyl esters stabilized with polyvinyl alcohol or branched alkyl carboxylic acids with 1 to 18 carbon atoms, acrylic acid esters or methacrylic acid esters of branched or unbranched alcohols or diols with 1 to 18 carbon atoms
Atomen, Diene, Olefine, Vinylaromaten und Vinylhalogenide, welche 0.1 bis 20 Gew.-%, bezogen auf das Gesamtgewicht des Copo- lymers, ein oder mehrere nachvernetzende Comonomere aus der Gruppe umfassend Acrylamidoglykolsäure (AGA) , Methylacrylami- doglykolsäuremethylester (MAGME) , N-Methylolacrylamid (NMA) , N- Methylolmethacrylamid (NMMA) , N-Methylolallylcarbamat, Alkyl- ether und Ester des N-Methylolacrylamids sowie des N-Methyiol- methacrylamids und des N-Methylolallylcarbamats, sowie Acryl- oxypropyltri (alkoxy) - und Methacryloxypropyltri (alkoxy) -Silane, Vinyltrialkoxysilane und Vinylmethyldialkoxysilane, enthalten, und b) mit Polymerisaten von ethylenisch ungesättigten Mono- oder Dicarbonsäuren oder deren Anhydride, mit einem Säuregehalt von 50 bis 100 Mol-%, stabilisierte Polymerisate von einem oder mehreren Monomeren aus der Gruppe der Vinylester von unverzweigten oder verzweigten Alkylcarbonsäuren mit 1 bis 18 C- Atomen, Acrylsäureester oder Methacrylsäureester von verzweigten oder unverzweigten Alkoholen oder Diolen mit 1 bis 18 C- Atomen, Diene, Olefine, Vinylaromaten und Vinylhalogenide, im Gemisch mit Sand verwendet werden. Geeignete Vinylester sind solche von Carbonsäuren mit 1 bis 12 C-Atomen. Bevorzugt werden Vinylacetat, Vinylpropionat, Vinyl- butyrat, Vinyl-2-ethylhexanoat , Vinyllaurat, 1-Methylvinyl- acetat, Vinylpivalat und Vinylester von α-verzweigten Monocar- bonsäuren mit 9 bis 13 C-Atomen, beispielsweise VeoVa9R oder VeoVal0R (Handelsnamen der Firma Shell) . Besonders bevorzugt ist Vinylacetat.Atoms, dienes, olefins, vinyl aromatics and vinyl halides which contain 0.1 to 20% by weight, based on the total weight of the copolymer, of one or more post-crosslinking comonomers from the group comprising acrylamidoglycolic acid (AGA), methyl acrylamido doglycolic acid methyl ester (MAGME), N -Methylolacrylamide (NMA), N- Methylolmethacrylamide (NMMA), N-Methylolallylcarbamat, alkyl ether and esters of N-Methylolacrylamids as well as N-Methyiol-methacrylamide and N-Methylolallylcarbamats, as well as Acryloxypropyltri (alkoxy) - and Methacryloxypropyltri ( alkoxy) silanes, vinyl trialkoxysilanes and vinyl methyl dialkoxysilanes, and b) with polymers of ethylenically unsaturated mono- or dicarboxylic acids or their anhydrides, with an acid content of 50 to 100 mol%, stabilized polymers of one or more monomers from the group of vinyl esters of unbranched or branched alkyl carboxylic acids having 1 to 18 carbon atoms, acrylic acid ester or methacrylic acid ester of branched or unbranched alcohols or diols having 1 to 18 carbon atoms, dienes, olefins, vinyl aromatics and vinyl halides, used in a mixture with sand. Suitable vinyl esters are those of carboxylic acids with 1 to 12 carbon atoms. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of α-branched monocarboxylic acids with 9 to 13 C atoms, for example VeoVa9 R or VeoVal0 R (trade names from Shell). Vinyl acetate is particularly preferred.
Geeignete Monomeren aus der Gruppe Acrylsäureester oder Methacrylsäureester sind Ester von unverzweigten oder verzweigten Alkoholen mit 1 bis 15 C-Atomen. Bevorzugte Methacrylsäureester oder Acrylsäureester sind Methylacrylat , Methylmethacrylat, Ethylacrylat, Ethylmethacrylat , Propylacrylat, Propylmethacry- lat, n-Butylacrylat, n-Butylmethacrylat , t-Butylacrylat , t-Bu- tylmethacrylat, 2-Ethylhexylacrylat . Besonders bevorzugt sind Methylacrylat, Methylmethacrylat, n-Butylacrylat, t-Butylacrylat und 2-Ethylhexylacrylat .Suitable monomers from the group of acrylic acid esters or methacrylic acid esters are esters of unbranched or branched alcohols having 1 to 15 carbon atoms. Preferred methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate. Methyl acrylate, methyl methacrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
Als Vinylaromaten bevorzugt sind Styrol, Methylstyrol und Vi- nyltoluol. Bevorzugtes Vinylhalogenid ist Vinylchlorid. Die bevorzugten Olefine sind Ethylen, Propylen und die bevorzugten Diene sind 1,3-Butadien und Isopren.Styrene, methylstyrene and vinyltoluene are preferred as vinyl aromatics. The preferred vinyl halide is vinyl chloride. The preferred olefins are ethylene, propylene and the preferred dienes are 1,3-butadiene and isoprene.
Besonders bevorzugt werden Polymerisate, welche ein oder mehrere Monomer-Einheiten aus der Gruppe Vinylacetat, Vinylester von α-verzweigten Monocarbonsäuren mit 9 bis 13 C-Atomen, Vinylchlorid, Ethylen, Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, Propylacrylat, Propylmethacrylat , n- Butylacrylat, n-Butylmethacrylat, 2-Ethylhexylacrylat, Styrol enthalten. Am meisten bevorzugt werden Polymerisate von Vinylacetat mit Ethylen; von Vinylacetat, Ethylen und einem Vinylester von α-verzweigten Monocarbonsäuren mit 9 bis 13 C-Atomen; von n-Butylacrylat mit 2-Ethylhexylacrylat und/oder Methyl- methacrylat; von Styrol mit einem oder mehreren Monomeren aus der Gruppe Methylacrylat, Ethylacrylat, Propylacrylat, n- Butylacrylat, 2-Ethylhexylacrylat ; von Vinylacetat mit einem oder mehreren Monomeren aus der Gruppe Methylacrylat, Ethylac- rylat, Propylacrylat, n-Butylacrylat, 2-Ethylhexylacrylat und gegebenenfalls Ethylen; wobei im Falle der Polymerpulver a) noch die entsprechende Menge an nachvernetzenden Comonomeren enthalten ist.Particularly preferred are polymers which contain one or more monomer units from the group vinyl acetate, vinyl esters of α-branched monocarboxylic acids with 9 to 13 carbon atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate , n-Butyl methacrylate, 2-ethylhexyl acrylate, styrene included. Polymers of vinyl acetate with ethylene are most preferred; of vinyl acetate, ethylene and a vinyl ester of α-branched monocarboxylic acids with 9 to 13 carbon atoms; of n-butyl acrylate with 2-ethylhexyl acrylate and / or methyl methacrylate; of styrene with one or more monomers from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; vinyl acetate with one or more monomers from the group consisting of methyl acrylate, ethyl rylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and optionally ethylene; wherein in the case of the polymer powders a) the corresponding amount of post-crosslinking comonomers is still present.
Bevorzugte nachvernetzende Comonomere sind N-Methylolacrylamid (NMA) , N-Methylolmethacrylamid (NMMA) sowie deren Isobutoxy- ether, sowie Acryloxypropyltri (alkoxy) - und Methacryloxypro- pyltri (alkoxy) -Silane, Vinyltrialkoxysilane und Vinylmethyldi- alkoxysilane, wobei als Alkoxygruppen Methoxy- , Ethoxy- und Ethoxypropylenglykolether-Reste enthalten sind. Besonders bevorzugt sind N-Methylolacrylamid (NMA) , N-Methylolmethacrylamid (NMMA) , Acryloxypropyltriethoxy- und Methacryloxypropyltrietho- xy-Silan, Vinyltriethoxysilan und Vinylmethyldiethoxysilan. Am meisten bevorzugt sind N-Methylolacrylamid und N-Methylolmeth- acrylamid. Vorzugsweise sind die nachvernetzenden Comonomere in einer Menge von 1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht des Copolymers, enthalten.Preferred post-crosslinking comonomers are N-methylolacrylamide (NMA), N-methylolmethacrylamide (NMMA) and their isobutoxy ether, as well as acryloxypropyltri (alkoxy) and methacryloxypropyltri (alkoxy) silanes, vinyltrialkoxysilanes and vinylmethyldi- alkoxysilanes, where methoxy groups are methoxy groups. , Ethoxy and ethoxypropylene glycol ether residues are included. N-Methylolacrylamide (NMA), N-methylolmethacrylamide (NMMA), acryloxypropyltriethoxy- and methacryloxypropyltriethoxy-silane, vinyltriethoxysilane and vinylmethyldiethoxysilane are particularly preferred. Most preferred are N-methylolacrylamide and N-methylolmethacrylamide. The postcrosslinking comonomers are preferably present in an amount of 1 to 10% by weight, based on the total weight of the copolymer.
Die Monomerauswahl bzw. die Auswahl der Gewichtsanteile der Comonomere erfolgt dabei so, dass im allgemeinen eine Glasübergangstemperatur Tg von -50°C bis +120°C, vorzugsweise 0°C bis +50°C resultiert. Die Glasübergangstemperatur Tg der Polymerisate kann in bekannter Weise mittels Differential Scan- ning Calorimetry (DSC) ermittelt werden. Die Tg kann auch mittels der Fox-Gleichung näherungsweise vorausberechnet werden. Nach Fox T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956) gilt:The selection of monomers and the selection of the proportions by weight of the comonomers is carried out in such a way that a glass transition temperature Tg of -50 ° C. to + 120 ° C., preferably 0 ° C. to + 50 ° C., generally results. The glass transition temperature Tg of the polymers can be determined in a known manner by means of differential scanning calorimetry (DSC). The Tg can also be roughly predicted using the Fox equation. According to Fox T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956) applies:
1/Tg = x /Tg + X2/ g2 + ... + xn/Tgn, wobei xn für den Masse- bruch (Gew.-%/100) des Monomeren n steht, und Tgn die Glasübergangstemperatur in Kelvin des Homopolymeren des Monomeren n ist. Tg-Werte für Homopolymerisate sind in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) aufgeführt.1 / Tg = x / Tg + X2 / g2 + ... + x n / Tg n , where x n stands for the mass fraction (% by weight / 100) of the monomer n, and Tg n the glass transition temperature in Kelvin of the homopolymer of the monomer n. Tg values for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).
Geeignete Polyvinylalkohol-Schutzkolloide für die redispergier- baren Polymerpulver a) sind teilverseifte oder vollverseifte Polyvinylalkohole . Bevorzugt sind teilverseifte Polyvinylalko- hole mit einem Hydrolysegrad von 80 bis 95 Mol-% und einer Höpplerviskosität , in 4 %-iger wässriger Lösung von 1 bis 30 mPas (Methode nach Höppler bei 20°C, DIN 53015) . Bevorzugt sind auch teilverseifte, hydrophob modifizierte Polyvinylalkohole mit einem Hydrolysegrad von 80 bis 95 Mol-% und einer Höppler- Viskosität, in 4 %-iger wässriger Lösung von 1 bis 30 mPas .Suitable polyvinyl alcohol protective colloids for the redispersible polymer powders a) are partially saponified or fully saponified polyvinyl alcohols. Partially saponified polyvinyl alcohols with a degree of hydrolysis of 80 to 95 mol% and one are preferred Höppler viscosity, in 4% aqueous solution from 1 to 30 mPas (Höppler method at 20 ° C, DIN 53015). Partially saponified, hydrophobically modified polyvinyl alcohols with a degree of hydrolysis of 80 to 95 mol% and a Höppler viscosity, in 4% aqueous solution of 1 to 30 mPas, are also preferred.
Beispiele hierfür sind teilverseifte Copolymerisate von Vinylacetat mit hydrophoben Comonomeren wie Isopropenylacetat , Vi- nylpivalat, Vinylethylhexanoat , Vinylester von gesättigten al- pha-verzweigten Monocarbonsäuren mit 5 oder 9 bis 11 C-Atomen, Dialkylmaleinate und Dialkylfumarate wie Diisopropylmaleinat und Diisopropylfumarat , Vinylchlorid, Vinylalkylether wie Vi- nylbutylether, Olefine wie Ethen und Decen. Der Anteil der hydrophoben Einheiten beträgt vorzugsweise 0.1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht des teilverseiften Polyvinylalko- hols . Es können auch Gemische der genannten Polyvinylalkohole eingesetzt werden.Examples include partially saponified copolymers of vinyl acetate with hydrophobic comonomers such as isopropenyl acetate, vinyl pivalate, vinyl ethyl hexanoate, vinyl esters of saturated alpha-branched monocarboxylic acids with 5 or 9 to 11 carbon atoms, dialkyl maleate and dialkyl fumarates such as diisopropyl vinyl maleate and diisopropyl chloride and diisopropyl chloride and diisopropyl chloride Vinyl butyl ether, olefins such as ethene and decene. The proportion of the hydrophobic units is preferably 0.1 to 10% by weight, based on the total weight of the partially hydrolyzed polyvinyl alcohol. Mixtures of the polyvinyl alcohols mentioned can also be used.
Weitere bevorzugte Polyvinylalkohole sind teilverseifte, hydro- phobierte Polyvinylalkohole, die durch polymeranaloge Umset- zung, beispielsweise Acetalisierung der Vinylalkoholeinheiten mit Cx- bis C4-Aldehyden wie Butyraldehyd erhalten werden. Der Anteil der hydrophoben Einheiten beträgt vorzugsweise 0.1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht des teilverseiften Po- lyvinylacetats . Der Hydrolysegrad beträgt von 80 bis 95 Mol-%, vorzugsweise 85 bis 94 Mol-%, die Höpplerviskosität (DIN 53015, Methode nach Höppler, 4 %-ige wässrige Lösung) von 1 bis 30 mPas, vorzugsweise 2 bis 25 mPas .Further preferred polyvinyl alcohols are partially hydrolyzed, hydrophobicized polyvinyl alcohols which are obtained by polymer-analogous reaction, for example acetalization of the vinyl alcohol units with C x to C 4 aldehydes such as butyraldehyde. The proportion of the hydrophobic units is preferably 0.1 to 10% by weight, based on the total weight of the partially saponified polyvinyl acetate. The degree of hydrolysis is from 80 to 95 mol%, preferably 85 to 94 mol%, the Höppler viscosity (DIN 53015, Höppler method, 4% aqueous solution) from 1 to 30 mPas, preferably 2 to 25 mPas.
Am meisten bevorzugt werden Polyvinylalkohole mit einem Hydro- lysegrad von 85 bis 94 Mol-% und einer Höpplerviskosität, in 4 %-iger wässriger Lösung von 3 bis 15 mPas (Methode nach Höppler bei 20°C, DIN 53015. Die genannten Polyvinylalkohole sind mittels dem Fachmann bekannter Verfahren zugänglich oder im Handel erhältlich. Die Polyvinylalkohole sind im allgemeinen in einer Menge von insgesamt 1 bis 40 Gew.-%, bezogen auf das Gesamtgewicht des Basispolymerisats, in dem Redispersionspulver a) enthalten . Geeignete Schutzkolloide auf Basis von Polymerisaten von ethy- lenisch ungesättigten Mono- oder Dicarbonsäuren, für die re- dispergierbaren Polymerpulver b) , sind Homo- und Copolymerisate von einem oder mehreren Monomeren aus der Gruppe umfassend Ac- rylsäure, Methacrylsäure, Fumarsäure, Maleinsäure, sowie Maleinsäureanhydrid. Bevorzugt werden Homo- und Copolymerisate von Acrylsäure, Methacrylsäure und Maleinsäureanhydrid. Besonders bevorzugt sind Polyacrylsäure und Polymethacrylsäure . Bevorzugt sind auch Copoly ere mit Acrylsäure-, Methacrylsäure- und Maleinsäure (anhydrid) -Einheiten und Einheiten damit copoly- merisierbarer Monomere, wobei der Säureanteil dabei 80 bis 99 Mol-% beträgt. Beispiele für copolymerisierbare Monomere sind Alkene wie Ethylen und Propylen, Vinylaromaten wie Styrol, Acrylsäureester wie Butylacrylat , Methacrylsäureester wie Methyl- methacrylat, Alkylvinylether wie Methylvinylether, Methacryl- amid und Acrylamid. Beispiele für bevorzugte Copolymere sind Maleinsäure-Methylvinylether- , Methacrylsäure-Methylmethacrylat- , Methacrylsäure-Acrylamid-Copolymere .Most preferred are polyvinyl alcohols with a degree of hydrolysis of 85 to 94 mol% and a Höppler viscosity, in 4% aqueous solution of 3 to 15 mPas (Höppler method at 20 ° C., DIN 53015. The polyvinyl alcohols mentioned are suitable The polyvinyl alcohols are generally present in the redispersion powder a) in a total amount of 1 to 40% by weight, based on the total weight of the base polymer. Suitable protective colloids based on polymers of ethylenically unsaturated mono- or dicarboxylic acids, for the redispersible polymer powders b), are homopolymers and copolymers of one or more monomers from the group comprising acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride. Homopolymers and copolymers of acrylic acid, methacrylic acid and maleic anhydride are preferred. Polyacrylic acid and polymethacrylic acid are particularly preferred. Also preferred are copolymers with acrylic acid, methacrylic acid and maleic acid (anhydride) units and units copolymerizable therewith monomers, the acid fraction being 80 to 99 mol%. Examples of copolymerizable monomers are alkenes such as ethylene and propylene, vinyl aromatics such as styrene, acrylic esters such as butyl acrylate, methacrylic acid esters such as methyl methacrylate, alkyl vinyl ethers such as methyl vinyl ether, methacrylamide and acrylamide. Examples of preferred copolymers are maleic acid-methyl vinyl ether, methacrylic acid-methyl methacrylate, methacrylic acid-acrylamide copolymers.
Die Molekulargewichte der genannten Schutzkolloide für die re- dispergierbaren Polymerpulver b) betragen <. 250000 g/mol, vorzugsweise < 150000 g/mol, besonders bevorzugt 5000 bis 50000 g/mol, jeweils bestimmt als Gewichtsmittel Mw, beispielsweise mit Gelpermeationschromatographie . Die carboxylfunktionellen Schutzkolloide sind im allgemeinen in einer Menge von insgesamt 1 bis 40 Gew.-%, bezogen auf das Gesamtgewicht des Basispolymerisats, in dem Redispersionspulver b) enthalten. Die genannten carboxylfunktionellen Schutzkolloide sind mittels dem Fachmann bekannter Verfahren zugänglich oder im Handel erhältlich.The molecular weights of the protective colloids mentioned for the redispersible polymer powders b) are < . 250,000 g / mol, preferably <150,000 g / mol, particularly preferably 5,000 to 50,000 g / mol, each determined as the weight average Mw, for example with gel permeation chromatography. The carboxyl-functional protective colloids are generally present in the redispersion powder b) in a total amount of 1 to 40% by weight, based on the total weight of the base polymer. The carboxyl-functional protective colloids mentioned are accessible by means of processes known to the person skilled in the art or are commercially available.
Die Herstellung der Basispolymerisate für die in Wasser re- dispergierbaren Polymerpulver a) und b) erfolgt mittels der gebräulichen Polymerisationsverfahren wie Suspensionspolymerisation und Emulsionspolymerisation bei 40 °C bis 100 °C, nach Initiierung der Polymerisation mit den gebräuchlichen wasserlöslichen bzw. monomerlöslichen Initiatoren. Bei den genannten Verfahren der Suspensions- und Emulsionspolymerisation wird in Gegenwart von oberflächenaktiven Substanzen wie Schutzkolloiden und/oder Emulgatoren polymerisiert . Nach Abschluß der Polymerisation kann zur Restmonomerentfernung in Anwendung bekannter Methoden nachpolymerisiert werden, oder flüchtige Restmonomere mittels Destillation, und/oder Durchleiten oder Überleiten von inerten Schleppgasen wie Luft, Stickstoff oder Wasserdampf entfernt werden. Zur Herstellung der Polymerpulver werden die wässrigen Dispersionen, gegebenenfalls nach Zusatz von Schutzkolloiden als Verdüsungshilfe, getrocknet, beispielsweise mittels Wirbelschichttrocknung, Gefriertrocknung oder Sprühtrock- nung. Vorzugsweise werden die Dispersionen sprühgetrocknet. Der Schutzkolloid-Anteil kann dabei vor, während oder nach der Polymerisation zugegeben werden.The base polymers for the water-redispersible polymer powders a) and b) are prepared by means of the customary polymerization processes, such as suspension polymerization and emulsion polymerization, at from 40 ° C. to 100 ° C., after initiation of the polymerization with the customary water-soluble or monomer-soluble initiators. In the processes of suspension and emulsion polymerization mentioned, in the presence of surface-active substances such as protective colloids and / or emulsifiers polymerized. After the end of the polymerization, post-polymerization can be carried out using known methods to remove residual monomers, or volatile residual monomers can be removed by distillation and / or by passing or passing through inert entraining gases such as air, nitrogen or water vapor. To prepare the polymer powders, the aqueous dispersions are dried, if appropriate after the addition of protective colloids as a spraying aid, for example by means of fluidized-bed drying, freeze drying or spray drying. The dispersions are preferably spray dried. The protective colloid portion can be added before, during or after the polymerization.
Das funktionalisierte, in Wasser redispergierbare Polymerpulver wird im allgemeinen in einer Menge von 0.5 bis 10 Gew.-%, vorzugsweise 1.0 bis 5.0 Gew.-%, bezogen auf den Sandanteil, eingesetzt. Gegebenenfalls können noch Zusatzstoffe in das Gemisch aus Sand und Redispersionspulver eingearbeitet werden. Beispiele hierfür sind Vernetzer wie bifunktioneile, maskierte Aldehy- de mit wenigstens 3 Kohlenstoffatomen, aus denen im sauren Medium Aldehydgruppen freigesetzt werden, welche mit den OH- Gruppen des Polyvinylalkohol-Schutzkolloid des Redispersi- onspulvers a) kovalente Bindungen eingehen können. Beispiele hierfür sind die Alkalihydrogensulfit-Addukte von Glutaraldehyd und Succinaldehyd, vorzugsweise Glutaraldehydbis (natrium- hydrogensuϊfit) und Succinaldehydbis (natriumhydrogensulfit) . Im allgemeinen werden diese Vernetzer in einer Menge von 0.001 bis 1.0 Gew.-%, bezogen auf das redispergierbare Polymerpulver, eingesetzt .The functionalized, water-redispersible polymer powder is generally used in an amount of 0.5 to 10% by weight, preferably 1.0 to 5.0% by weight, based on the sand content. If necessary, additives can also be incorporated into the mixture of sand and redispersion powder. Examples of these are crosslinkers, such as bifunctional, masked aldehydes having at least 3 carbon atoms, from which aldehyde groups are released in the acidic medium and can form covalent bonds with the OH groups of the polyvinyl alcohol protective colloid of redispersible powder a). Examples of these are the alkali hydrogen sulfite adducts of glutaraldehyde and succinaldehyde, preferably glutaraldehyde bis (sodium hydrogensuϊfit) and succinaldehyde bis (sodium hydrogen sulfite). In general, these crosslinkers are used in an amount of 0.001 to 1.0% by weight, based on the redispersible polymer powder.
Geeignete Zusatzstoffe sind auch Mittel zur Einstellung des pH- Wertes der Redispersion der Polymerpulver. Bei den vernetzbaren Polymerpulvern a) werden vorzugsweise pulverförmige, saure Zusätze wie Alkalihydrogensulfate, insbesondere Natriumhydrogensulfat, zugegeben. Die Zusatzmenge beträgt vorzugsweise 2 bis 10 Gew.-%, bezogen auf das Polymerpulver, was im allgemeinen zu einem pH-Wert der Redispersion von pH <. 2 führt . Bei den Polymerpulvern b) werden vorzugsweise pulverförmige, basische Zu- sätze wie Calciumcarbonat zugegeben. Die Zusatzmenge beträgt vorzugsweise 5 bis 40 Gew.-%, bezogen auf das Polymerpulver, was im allgemeinen zu einem pH-Wert der Redispersion von pH > 8 führt .Suitable additives are also agents for adjusting the pH of the redispersion of the polymer powder. In the case of the crosslinkable polymer powders a), powdery, acidic additives such as alkali hydrogen sulfates, in particular sodium hydrogen sulfate, are preferably added. The amount added is preferably 2 to 10% by weight, based on the polymer powder, which generally leads to a pH of the redispersion of pH < . 2 leads. In the case of the polymer powders b), preferably powdery, basic additives sentences like calcium carbonate added. The amount added is preferably 5 to 40% by weight, based on the polymer powder, which generally leads to a pH of the redispersion of pH > 8.
Das Gemisch aus Fugensand, Polymerpulver und gegebenenfalls weiteren Zusätzen wird im trockenen oder feuchten Zustand durch Einfegen in die Fugen zwischen den Pflastersteinen eingebracht .The mixture of joint sand, polymer powder and possibly other additives is introduced in the dry or moist state by sweeping into the joints between the paving stones.
Mit den genannten sauren Zusätzen wird in der Feuchte die Vernetzung des Polymerpulvers a) gefördert. Mit den genannten basischen Zusätzen wird in der Feuchte die Auflösung des carboxylfunktionellen Schutzkolloids des Polymerpulvers b) gefördert. In beiden Fällen wird damit, gerade bei kritischen Wetterbedingungen wie Regen, die Bindekraft des Pulvers verstärkt, und die Auswaschung des Sands aus der Fuge verhindert.The crosslinking of the polymer powder a) is promoted in the moisture with the acidic additives mentioned. With the basic additives mentioned, the dissolution of the carboxyl-functional protective colloid of the polymer powder b) is promoted in the moisture. In both cases, especially in critical weather conditions such as rain, this increases the binding power of the powder and prevents the sand from washing out of the joint.
Beispiele :Examples:
Beispiel 1:Example 1:
Es wurde eine Mischung aus 95 Gew. -Teilen Normsand T , 5 Gew.- Teilen eines Polymerpulvers aus einem Vinylacetat-Ethylen- Copolymer (Tg = 9°C) und einer Polyacrylsäure (Mw ca. 20000, 20 Gew.-% bezogen auf Copolymer) , sowie 1.1 Gew. -Teile Calciumcar- bonat hergestellt.A mixture of 95 parts by weight of standard sand T, 5 parts by weight of a polymer powder from a vinyl acetate-ethylene copolymer (Tg = 9 ° C.) and a polyacrylic acid (Mw approx. 20,000, 20% by weight, based on Copolymer) and 1.1 parts by weight of calcium carbonate.
Diese Mischung wurde in einer Form zu einem quaderförmigen Probekörper mit den Abmessungen 1 cm x 4 cm x 16 cm geformt, und unter Druck zu einer Dichte von 1.56 g/cm3 verfestigt.This mixture was shaped in a mold into a cuboid test specimen measuring 1 cm × 4 cm × 16 cm, and solidified under pressure to a density of 1.56 g / cm 3 .
Beispiel 2 :Example 2:
Es wurde analog Beispiel 1 vorgegangen, mit dem Unterschied, dass als Polymerpulver ein Vinylacetat-Ethylen-N-Methylol- acrylamid-Copolymer (4 Gew.-% NMA-Anteil, Tg = 21.5°C), welches mit einem teilverseiften Polyvinylalkohol (Hydrolysegrad 88 Mol-%, Höppler-Viskosität 4 mPas, 15 Gew.-% bezogen auf Copolymer) stabilisiert war, eingesetzt wurde, und 0.25 Gew. -Teile Kaliumhydrogensulfat (anstelle Calciumcarbonat) eingesetzt wurden. Vergleichsbeispiel 3 :The procedure was analogous to Example 1, with the difference that a vinyl acetate-ethylene-N-methylol-acrylamide copolymer (4% by weight of NMA, Tg = 21.5 ° C.) was used as the polymer powder, which was mixed with a partially saponified polyvinyl alcohol (degree of hydrolysis 88 mol%, Höppler viscosity 4 mPas, 15% by weight, based on the copolymer) was stabilized, was used, and 0.25 part by weight of potassium hydrogen sulfate (instead of calcium carbonate) was used. Comparative Example 3:
Es wurde analog Beispiel 1 vorgegangen, mit dem Unterschied, dass als Polymerpulver ein Vinylacetat-Ethylen-Copolymer (Tg = 10 °C) , welches mit einem teilverseiften Polyvinylalkohol (Hydrolysegrad 88 Mol-%, Höppler-Viskosität 4 mPas, 15 Gew.-% bezogen auf Copolymer) stabilisiert war, eingesetzt wurde, und kein saurer oder basischer Zusatz eingesetzt wurde.The procedure was analogous to Example 1, with the difference that the polymer powder used was a vinyl acetate-ethylene copolymer (Tg = 10 ° C) which was mixed with a partially hydrolyzed polyvinyl alcohol (degree of hydrolysis 88 mol%, Höppler viscosity 4 mPas, 15% by weight). % based on copolymer) was stabilized, was used, and no acidic or basic additive was used.
Zur Prüfung der Wasserfestigkeit der Fugenmasse wurde ein Proberohr mit dem Formkörper unten verschlossen, und der Probekörper mit 57 ml Wasser überschichtet. Es wurde der Wasserdurch- fluss pro Zeiteinheit und Fläche bestimmt. Die Formkörper wurden unmittelbar nach deren Herstellung und nach 24 Stunden La- gerzeit bei Raumtemperatur getestet .To test the water resistance of the jointing compound, a test tube was closed with the shaped body at the bottom, and the test body was covered with 57 ml of water. The water flow per unit of time and area was determined. The moldings were tested immediately after their production and after 24 hours of storage at room temperature.
Je geringer die Durchflussrate ist, umso stabiler der Probekörper und umso fester die Bindung des Formsands .The lower the flow rate, the more stable the test specimen and the stronger the binding of the molding sand.
Es wurden folgende Ergebnisse erhalten:The following results were obtained:
Beispiel 1:Example 1:
Die Wasserdurchlässigkeit des Formkörpers betrug unmittelbar nach dessen Herstellung 21.3 l/m2/min und verbesserte sich nach 24 h auf 3.1 1/mVmin.The water permeability of the shaped body was 21.3 l / m 2 / min immediately after its production and improved to 3.1 1 / mVmin after 24 h.
Beispiel 2 :Example 2:
Die Wasserdurchlässigkeit des Formkörpers betrug unmittelbar nach dessen Herstellung 3.4 l/m2/min und verbesserte sich nach 24 h auf 1.1 l/m2/min.The water permeability of the shaped body was 3.4 l / m 2 / min immediately after its production and improved to 1.1 l / m 2 / min after 24 h.
Vergleichsbeispiel 3 :Comparative Example 3:
Mit einem herkömmlichen Redispersionspulver konnte keine Bindung des Formkörpers erreicht werden. Die Wasserdurchlässigkeit konnte daher nicht bestimmt werden. With a conventional redispersion powder, it was not possible to bind the shaped body. The water permeability could therefore not be determined.

Claims

Patentansprüche : Claims:
1. Verwendung von in Wasser redispergierbaren Polymerpulvern als Bindemittel für Fugensand, dadurch gekennzeichnet, dass funktionalisierte, redispergierbare Polymerpulver aus der Gruppe umfassend a) mit Polyvinylalkohol stabilisierte Copolymerisate von einem oder mehreren Monomeren aus der Gruppe der Vinylester von unverzweigten oder verzweigten Alkylcarbonsäuren mit 1 bis 18 C-Atomen, Acrylsäureester oder Methacrylsäureester von verzweigten oder unverzweigten Alkoholen oder Diolen mit 1 bis 18 C-Atomen, Diene, Olefine, Vinylaromaten und Vinylhalogenide, welche 0.1 bis 20 Gew.-%, bezogen auf das Gesamtgewicht des Copolymers, ein oder mehrere nachvernetzende Comonomere aus der Gruppe umfassend Acryl- amidoglykolsäure (AGA) , Methylacrylamidoglykolsäuremethy- lester (MAGME) , N-Methylolacrylamid (NMA) , N-Methylolmethacrylamid (NMMA) , N-Methylolallylcarbamat, Alkylether und Ester des N-Methylolacrylamids sowie des N-Methylolmeth- acrylamids und des N-Methylolallylcarbamats, sowie Acryl- oxypropyltri (alkoxy) - und Methacryloxypropyltri (alkoxy) - Silane, Vinyltrialkoxysilane und Vinylmethyldialkoxysilane enthalten, und b) mit Polymerisaten von ethylenisch ungesättigten Mono- oder Dicarbonsäuren oder deren Anhydride, mit einem Säuregehalt von 50 bis 99 Mol-%, stabilisierte Polymerisate von einem oder mehreren Monomeren aus der Gruppe der Vinylester von unverzweigten oder verzweigten Alkylcarbonsäuren mit 1 bis 18 C-Atomen, Acrylsäureester oder Methacrylsäu- reester von verzweigten oder unverzweigten Alkoholen oder Diolen mit 1 bis 18 C-Atomen, Diene, Olefine, Vinylaromaten und Vinylhalogenide, im Gemisch mit Sand verwendet werden. 1. Use of water-redispersible polymer powders as binders for joint sand, characterized in that functionalized, redispersible polymer powders from the group comprising a) copolymers stabilized with polyvinyl alcohol of one or more monomers from the group of vinyl esters of unbranched or branched alkylcarboxylic acids with 1 to 18 C atoms, acrylic acid esters or methacrylic acid esters of branched or unbranched alcohols or diols with 1 to 18 C atoms, dienes, olefins, vinyl aromatics and vinyl halides, which 0.1 to 20 wt .-%, based on the total weight of the copolymer, one or more post-crosslinking Comonomers from the group comprising acrylic amidoglycolic acid (AGA), methyl acrylamidoglycolic acid methyl ester (MAGME), N-methylolacrylamide (NMA), N-methylol methacrylamide (NMMA), N-methylolallyl carbamate, alkyl ether and ester of N-methylolacrylamide and of N-methylolmethamide acrylamides and N-methylolallyl carbamate, and Contain Acryloxypropyltri (alkoxy) - and Methacryloxypropyltri (alkoxy) - silanes, Vinyltrialkoxysilane and Vinylmethyldialkoxysilane, and b) with polymers of ethylenically unsaturated mono- or dicarboxylic acids or their anhydrides, with an acid content of 50 to 99 mol%, stabilized polymers one or more monomers from the group of vinyl esters of unbranched or branched alkylcarboxylic acids with 1 to 18 C atoms, acrylic acid esters or methacrylic acid esters of branched or unbranched alcohols or diols with 1 to 18 C atoms, dienes, olefins, vinyl aromatics and vinyl halides, mixed with sand.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass Copolymerisate a) welche ein oder mehrere Monomer-Einheiten aus der Gruppe Vinylacetat, Vinylester von α-verzweigten Monocarbonsäuren mit 9 bis 13 C-Atomen, Vinylchlorid, Ethylen, Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, Propylacrylat, Propylmethacrylat , n- Butylacrylat , n-Butylmethacrylat, 2-Ethylhexylacrylat , Styrol enthalten, sowie 1 bis 10 Gew.-% ein oder mehrere Monomer-Einheiten aus der Gruppe N-Methylolacrylamid, N- Methylolmethacrylamid, Acryloxypropyltriethoxy- und Me- thacryloxypropyltriethoxy-Silan, Vinyltriethoxysilan und Vinylmethyldiethoxysilan enthalten, verwendet werden.2. Use according to claim 1, characterized in that copolymers a) which comprise one or more monomer units from the group vinyl acetate, vinyl esters of α-branched monocarboxylic acids having 9 to 13 carbon atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, styrene, and 1 to 10 wt .-% one or more monomer units from the group N-methylol acrylamide, N-methylol methacrylamide, acryloxypropyltriethoxy and Me - Containing thacryloxypropyltriethoxy-silane, vinyltriethoxysilane and vinylmethyldiethoxysilane.
3. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass als Copolymerisate a) Polymerisate von Vinylacetat mit3. Use according to claim 1, characterized in that as copolymers a) polymers of vinyl acetate with
Ethylen, von Vinylacetat mit Ethylen und einem Vinylester von α-verzweigten Monocarbonsäuren mit 9 bis 13 C-Atomen, von n-Butylacrylat mit 2-Ethylhexylacrylat und/oder Methylmethacrylat, von Styrol mit einem oder mehreren Monome- ren aus der Gruppe Methylacrylat, Ethylacrylat, Propylacrylat, n-Butylacrylat, 2-Ethylhexylacrylat ; von Vinylacetat mit einem oder mehreren Monomeren aus der Gruppe Methylacrylat, Ethylacrylat, Propylacrylat, n-Butylacrylat, 2-Ethylhexylacrylat und gegebenenfalls Ethylen; mit 1 bis 10 Gew.-% N-Methylolacrylamid oder N-Methylolmethacrylamid, verwendet werden.Ethylene, of vinyl acetate with ethylene and a vinyl ester of α-branched monocarboxylic acids with 9 to 13 carbon atoms, of n-butyl acrylate with 2-ethylhexyl acrylate and / or methyl methacrylate, of styrene with one or more monomers from the group of methyl acrylate, ethyl acrylate , Propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; vinyl acetate with one or more monomers from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and optionally ethylene; with 1 to 10% by weight of N-methylolacrylamide or N-methylolmethacrylamide.
4. Verwendung nach Anspruch 1 bis 3, dadurch gekennzeichnet, dass als Polyvinylalkohol teilverseifte Polyvinylalkohole oder teilverseifte, hydrophob modifizierte Polyvinylalkohole mit einem Hydrolysegrad von 80 bis 95 Mol-% und einer Höpplerviskosität, in 4 %-iger wässriger Lösung, von 1 bis 30 mPas enthalten sind.4. Use according to claims 1 to 3, characterized in that partially saponified polyvinyl alcohols or partially saponified, hydrophobically modified polyvinyl alcohols with a degree of hydrolysis of 80 to 95 mol% and a Höppler viscosity, in 4% aqueous solution, of 1 to 30 mPas as polyvinyl alcohol are included.
5. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass Copolymerisate b) welche ein oder mehrere Monomer-Einheiten aus der Gruppe Vinylacetat, Vinylester von α-verzweigten Monocarbonsäuren mit 9 bis 13 C-Atomen, Vinylchlorid, Ethylen, Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, Propylacrylat, Propylmethacrylat , n- Butylacrylat , n-Butylmethacrylat, 2-Ethylhexylacrylat , Styrol enthalten sind, welche mit 1 bis 40 Gew.-% eines Schutzkolloides aus der Gruppe der Homo- und Copolymerisate von einem oder mehreren Monomeren aus der Gruppe umfassend Acrylsäure, Methacrylsäure, Fumarsäure, Maleinsäure, sowie Maleinsäureanhydrid stabilisiert sind, verwendet werden .5. Use according to claim 1, characterized in that copolymers b) which contain one or more monomer units from the group vinyl acetate, vinyl esters of α-branched monocarboxylic acids having 9 to 13 carbon atoms, vinyl chloride, Ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, styrene, which are present with 1 to 40% by weight of a protective colloid from the group of homo- and copolymers of one or more monomers from the group comprising acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride are stabilized.
Verwendung nach Anspruch 1 oder 5, dadurch gekennzeichnet, dass als Schutzkolloide Polyacrylsäure oder Polymethacryl- säure enthalten sind.Use according to claim 1 or 5, characterized in that polyacrylic acid or polymethacrylic acid are contained as protective colloids.
7. Verwendung nach Anspruch 1 oder 5, dadurch gekennzeichnet, dass als Schutzkolloide Copolymere mit Acrylsäure-, Methacrylsäure- und Maleinsäure (anhydrid) -Einheiten und Einheiten damit copolymerisierbarer Monomere, wobei der Säureanteil dabei 80 bis 99 Mol-% beträgt, enthalten sind.7. Use according to claim 1 or 5, characterized in that copolymers with acrylic acid, methacrylic acid and maleic acid (anhydride) units and units copolymerizable therewith as protective colloids, the acid fraction being 80 to 99 mol%, are included.
8. Verwendung nach Anspruch 1 bis 4, dadurch gekennzeichnet, dass die Pulver auf Basis der Copolymerisate a) noch bi- funktionelle, maskierte Aldehyde mit wenigstens 3 Kohlenstoffatomen, aus denen im sauren Medium Aldehydgruppen freigesetzt -werden, als Vernetzer enthalten.8. Use according to claims 1 to 4, characterized in that the powders based on the copolymers a) also contain bifunctional, masked aldehydes with at least 3 carbon atoms, from which aldehyde groups are released in the acidic medium, as crosslinkers.
9. Verwendung nach Anspruch 1 bis 4 und 8, dadurch gekennzeichnet, dass die Pulver auf Basis der Copolymerisate a) noch pulverförmige, saure Zusätze enthalten.9. Use according to claims 1 to 4 and 8, characterized in that the powders based on the copolymers a) also contain powdery, acidic additives.
10. Verwendung nach Anspruch 1 und 5 bis 7, dadurch gekennzeichnet, dass die Pulver auf Basis der Copolymerisate b) noch pulverförmige, basische Zusätze enthalten. 10. Use according to claim 1 and 5 to 7, characterized in that the powders based on the copolymers b) still contain powdery, basic additives.
EP03757997A 2002-10-24 2003-10-16 Use of polymer powders that are redispersible in water as a binding agent for jointing sand Withdrawn EP1554227A2 (en)

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DE10249636A DE10249636A1 (en) 2002-10-24 2002-10-24 Use of polymer powders redispersible in water as binders for joint sand
PCT/EP2003/011489 WO2004037741A2 (en) 2002-10-24 2003-10-16 Use of polymer powders that are redispersible in water as a binding agent for jointing sand

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DE10249636A1 (en) 2004-05-13
ES2290933T3 (en) 2008-02-16
ATE369322T1 (en) 2007-08-15
WO2004037741A3 (en) 2004-06-17
US20060020058A1 (en) 2006-01-26
EP1719743B1 (en) 2007-08-08
US7582695B2 (en) 2009-09-01
DE50307917D1 (en) 2007-09-20
WO2004037741A2 (en) 2004-05-06

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