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    • 专利摘要:
    CONSTRUCTION MATERIAL COMPOUNDS CONTAINING PLASTER The present invention relates to building material compounds containing plaster, containing plaster, if necessary one or more polymers, one or more aggregates, and if necessary one or more additives, characterized by the fact that the building material compounds containing plaster have one or more types of cement and one or more types of pozzolan.
    公开号:BR112013033754B1
    申请号:R112013033754-0
    申请日:2012-06-29
    公开日:2021-01-19
    发明作者:Wolfgang Hagen；Peter Fritze
    申请人:Wacker Chemie Ag；
    IPC主号:
    专利说明:

    [001] The present invention relates to building material compounds containing plaster and the use of them, for example, as ceramic adhesives or self-leveling compounds.
    [002] Gypsum is a mineral binder, available inexpensively in large quantities for building material compounds and is obtained, specifically, with much less energy consumption compared to cement. The reason for this is that, in addition to naturally occurring gypsum, there are considerable amounts of gypsum obtained from flue gas desulfurization plants and there is worldwide interest in the use of such gypsum. Consequently, there is a great desire to replace the material that uses a lot of energy, represented by cement, by the plaster that consumes little energy and, with that, reduce the total energy consumption in the construction sector and, in this way, contribute to the environment. . A disadvantage of plaster is its sensitivity to water, which makes buildings based on building material containing plaster lose strength in wet conditions. This deficiency is exacerbated by exposure to freezing / thawing. Currently, the range of application of plaster in the construction sector has been considerably limited and is mainly focused on the internal segment.
    [003] In order to adapt the plaster to use in the outer segment, or even in wet segments, additional measures are necessary. To that end, the proposals included the addition of hydrophobic agents to building material compounds containing gypsum. Thus, for example, DE-A 3704439 proposes the use of silicones and siloxanes, stearates and paraffin waxes. The teaching of US 2002/0040666 is to apply organopolysiloxanes to organic or inorganic substrates and incorporate them in that form to plaster-containing building material compounds. US 5437722 describes water resistant plaster products comprising paraffin, Montana wax and polyvinyl alcohol as additives. EP-A 320982 discloses the use of redispersible powders based on vinyl acetate / versatic acid-vinyl ester copolymers to render hydrophobic plaster materials. EP-A 1133455 recommends 1,3-dienovinylaromatic copolymers for this purpose.
    [004] An improvement in the adhesion of plaster compositions to the surfaces of plastics or metals is described in document DE-A 10064083 through the addition of alkali metal and alkaline earth metal salts with short chain fatty acids that are replaced by carboxyl groups. GB 1497125, lastly, refers to the improvement of the mechanical properties of plaster mortars for ceramic adhesives.
    [005] A disadvantage of hydrophobicizing agents is, in some cases, their non-negligible hydrophilicity, which imposes restrictions on the water resistance of the corresponding construction products. Construction products formed from building material compounds containing hydrophobized plaster may additionally, in many cases, be unsatisfactory in terms of their mechanical strength, specifically after storage in wet conditions or after exposure to freeze / thaw.
    [006] Against this background, the objective was to provide building material compounds containing plaster with which construction products could be obtained with high resistance to moisture or freeze / thaw storage and also high mechanical resistance.
    [007] The invention provides gypsum-containing building material compounds, optionally one or more polymers, optionally one or more additives and optionally one or more mixtures, characterized in that gypsum-containing building material compounds comprise one or more cements and a or more pozzolans.
    [008] The appropriate plaster is, for example, α- or β-hemihydrate [CaSO4. (1/2) H2O], dihydrate, anhydrite or the calcium sulfate obtained during flue gas desulfurization (FGD plaster). Plaster may be present, for example, in the form of plaster for construction, plaster for stucco or plaster for molding. However, other types of plaster can be used, such as mortar plaster or imitating marble.
    [009] Pozzolans are preferably selected from the group including kaolin, microsilica, diatomaceous earth, fly ash, finely ground braid, finely ground blast furnace slag, finely ground glass, precipitated silica and fumigated silica. Specifically preferred pozzolans are kaolin, microsilica, fly ash, finely ground blast furnace slag, more specifically metakaolin.
    [0010] Examples of suitable cements are: Portland cement (CEM I), Portland slag cement (CEM II), blast furnace cement (CEM III), pozzolanic cement (CEM IV), composite cement (CEM V), aluminate cement , more specifically calcium sulfoaluminate, aluminate cement, more specifically calcium sulfoaluminate cement, Portland powder silicate cement, Portland slate cement, Portland limestone cement, volcanic tufa cement, magnesia cement, phosphate cement, mixed cements, or loaded cements. Preferred cements are Portland cement (CEM I), Portland slag cement (CEM II) or blast furnace cement (CEM III).
    [0011] Polymers are generally based on polymers of one or more ethylenically unsaturated monomers. The preferred ethylenically unsaturated monomers are selected from the group consisting of vinyl esters, (meth) acrylic esters, vinilaromatics, olefins, 1,3-dienes and vinyl halides and possibly other copolimerizable monomers therewith.
    [0012] Suitable vinyl esters are, for example, those of carboxylic acids having 1 to 15 carbon atoms. Preferred are: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of alpha-branched monocarboxylic acids with 9 to 11 carbon atoms, such as VeoVa9R or VeoVa10R (registered trademark of the company Resolution). Vinyl acetate is specifically preferred.
    [0013] Suitable monomers of the group of acrylic esters or methacrylic esters are, for example, esters of unbranched or branched alcohols having 1 to 15 carbon atoms. Preferred methacrylic esters or acrylic 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 and 2-ethylhexyl acrylate. Specifically preferred are: methyl acrylate, methyl methacrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate.
    [0014] Preferred vinilaromatics are: styrene, methylstyrene and vinyltoluene. A preferred vinyl halide is vinyl chloride. Preferred olefins are ethylene and propylene and preferred dienes are 1,3-butadiene and isoprene.
    [0015] Optionally it is also possible that 0 to 10% by weight of auxiliary monomers are copolymerized, based on the total weight of the monomeric mixture. Preference is given to the use of 0.1 to 5% by weight of adjuvant monomers. Examples of supporting monomers are ethylenically unsaturated monocarboxylic and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxamides and carbonitriles, preferably acrylamide and acrylonitrile; monoesters and diesters of fumaric acid and maleic acid, such as diethyl and diisopropyl esters and also maleic anhydride; ethylenically unsaturated sulfonic acids and their salts, preferably vinylsulfonic acid and 2-acrylamido-2-methyl-propanesulfonic acid. Other examples are pre-crosslinking comonomers, such as polyethylene-unsaturated comonomers, examples being diallyl phthalate, divinyl adipate, diallyl maleate, allyl methacrylate or trialyl cyanurate or post-crosslinking comonomers, examples being acrylamidoglycolic acid (examples AGA), methyl methylamidoglycolic acid methyl ester (MAGME), N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolalylcarbamate, alkyl ethers such as isobutoxy ether or N-methylolacrylamide and N-methylacrylamide esters of N-methylacrylamide and N-methylacrylamide esters -methylolalylcarbamate. Functional epoxide monomers, such as glycidyl methacrylate and glycidyl acrylate, are also suitable. Other examples are functional silicon comonomers, such as acryloyloxypropyltri- (alkoxy) - and methacryloyloxypropyltri (alkoxy) -silanes, vinyltrialoxysilanes and vinylmethyldialcoxysilanes, where the alkoxy groups present can be, for example, ethoxy radicals and ethoxyl radicals. Mention may be made of monomers with hydroxyl or CO groups, examples being methacrylic esters and hydroxyalkyl esters of acrylic acid, such as hydroxyethyl acrylate, hydroxypropyl or hydroxybutyl or hydroxybutyl methacrylate and also compounds, such as diacetonacrylamide and acetylacethoxy acrylate or acetylacethoxy. acetylacetoxyethyl methacrylate.
    [0016] One or more polymers are preferably selected from the group consisting of vinyl ester homopolymers, vinyl ester copolymers that contain one or more vinyl ester units and one or more monomer units from the group consisting of olefins, aromatic compounds vinyl, vinyl halides, acrylic esters, methacrylic esters, fumaric and / or maleic acid monoesters or diesters or functional silicon comonomers; methacrylic ester homopolymers or methacrylic ester copolymers comprising one or more methacrylic ester units and one or more monomeric units of the group consisting of olefins, vinyl aromatics, vinyl halides, fumaric acid and / or maleic acid monomers or diomers or comonomers functional silicon; homopolymers or copolymers of dienes, such as, butadiene or isoprene and also of olefins, such as, ethylene or propene, it being also possible for dienes to be copolymerized, for example, with styrene, methacrylic esters or fumaric or maleic acid esters; vinilaromatic homopolymers or copolymers, such as styrene, methylstyrene, vinyltoluene; homopolymers or copolymers of vinyl halogen compounds, such as vinyl chloride comprising one or more monomer units of the group encompassing vinyl esters, olefins and methacrylic and acrylic esters and it is possible that the polymers also contain supporting monomers in the amounts listed above.
    [0017] Copolymers of one or more vinyl esters, especially vinyl acetate, with 1 to 50% by weight ethylene, vinyl acetate copolymers with 1 to 50% by weight of one or more other comonomers of the group are especially preferred of vinyl esters having 1 to 12 carbon atoms in the carboxylic acid radical, such as vinyl propionate esters, vinyl laurate, alpha-branched carboxylic vinyl esters that have 9 to 13 carbon atoms, such as, VeoVa9, VeoVa10, VeoVa11 and optionally from 1 to 50% by weight of ethylene and preferably 1 to 60% by weight of (meth) acrylic esters of unbranched or branched alcohols having in particular 1 to 15 carbon atoms n-butyl acrylate or 2-ethylhexyl acrylate, and copolymers of 30 to 75% by weight of vinyl acetate, 1 to 30% by weight of vinyl laurate or vinyl esters of alpha-branched carboxylic acid which has 9 to 11 carbon atoms, and also 1 to 30% by weight of esters methacrylics of unbranched or branched alcohols having 1 to 15 carbon atoms, in particular n-butyl acrylate or 2-ethylhexyl acrylate, from 1 to 40% by weight of ethylene, copolymers with one or more vinyl esters , 1 to 50% by weight of ethylene and 1 to 60% by weight of vinyl chloride, where the polymers may contain said supporting monomers in the amounts set out above, and the values in% by weight up to 100% by weight in each case.
    Also particularly preferred are polymers of methacrylic esters, such as copolymers of n-butyl acrylate or 2-ethylhexyl acrylate or copolymers of methyl methacrylate with n-butyl acrylate and / or 2- acrylate ethylhexyl; copolymers of styrene-acrylic ester with one or more monomers of the group methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate; vinyl acetate-acrylic ester copolymers with one or more monomers of the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and optionally ethylene; styrene-1,3-butadiene copolymers; the polymers may also contain supporting monomers in the quoted amounts and the values in% by weight added up to 100% in each case.
    [0019] Examples of comonomers especially preferred for vinyl chloride copolymers are α-olefins, such as ethylene or propylene and / or vinyl esters, such as vinyl acetate, vinyl laurate or vinyl esters of an alpha carboxylic acid - branched showing 9 to 11 carbon atoms and / or acrylic esters and / or methacrylic alcohol esters with 1 to 15 carbon atoms, such as methyl acrylate and methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethyl acrylate propyl, propyl methacrylate, n-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and / or fumaric and / or maleic acid monoesters or diesters , such as, dimethyl, methyl t-butyl, di-n-butyl, di-t-butyl and diethyl esters of maleic and / or fumaric acid.
    More preferred are copolymers with vinyl acetate and 5 to 50% by weight of ethylene; or copolymers with vinyl acetate, 1 to 50% by weight of ethylene and 1 to 50% by weight of a vinyl ester of α-branched monocarboxylic acids having 9 to 11 carbon atoms, or copolymers of 30 to 75% by weight of vinyl acetate, 1 to 30% by weight of vinyl laurate or vinyl esters of alpha-branched carboxylic acid having 9 to 11 carbon atoms, and from 1 to 30% by weight of methacrylic esters of unbranched or branched alcohols having 1 to 15 carbon atoms, having 1 to 40% by weight of ethylene, or copolymers with vinyl acetate, 5 to 50% by weight of ethylene and 1 to 60% by weight of vinyl chloride.
    [0021] Most preferred copolymers are also vinyl chloride-ethylene copolymers containing 60-98% by weight of vinyl chloride units and 1 to 40% by weight of ethylene units, the percentage values by weight being based on total weight of the copolymer and adding in each case 30 to 100% by weight. Copolymers of vinyl chloride-ethylene of these types are known from EP 0 149 098 A2.
    [0022] The selection of monomers and the selection of fractions by weight of the comonomers are carried out in this document, so as to result in a glass transition temperature, Tg, from -50 ° C to + 50 ° C, preferably from - 40 ° C to + 40 ° C, more preferably from -20 ° C to + 30 ° C. The glass transition temperature Tg of the polymers can be determined in a known manner by means of differential scanning calorimetry (DSC). Tg can be calculated, in advance, using Fox's equation. According to Fox T.G, Bull. Am. Physics Soc. 1, 3, page 123 (1956), the following is the case: 1 / Tg = x1 / Tg1 + x2 / Tg2 + ... + Xn / Tgn, where xn represents the fraction of mass (% by weight / 100) of the monomer and Tgn is the glass transition temperature in degrees Kelvin of the homopolymer of monomer n. Tg values for homopolymers are listed in the Polimer Handbook, 2nd Edition, J. Wiley & Sons, New York (1975).
    [0023] Polymers are generally prepared in an aqueous medium, and preferably by an emulsion or suspension polymerization process - for example, as described in DE-A102008043988. The polymers in that case are obtained in the form of aqueous dispersions. In polymerization it is possible to use the usual protective colloids and / or emulsifiers, as described in DE-A 102008043988. The protective colloids can be anionic or cationic or non-ionic, preferably. Also preferred are combinations of cationic and nonionic protective colloids. Preferred nonionic protective colloids are polyvinyl alcohols. Preferred cationic protective colloids are polymers that carry one or more cationic charges, as described in EW Flick, Water Soluble Resins - at Industrial Guide, Noyes Publications, Park Ridge, NJ, 1991. Since protective colloid preference is given to partially or completely hydrolyzed polyvinyl alcohols, with a degree of hydrolysis of 80 to 100 mol%, in particular partially hydrolyzed polyvinyl alcohols with a degree of hydrolysis of 8094% mol and a Hoppler viscosity in 4% aqueous solution of 1 to 30 mPas (Hoppler method at 20 ° C, DIN 53015). The mentioned protective colloids are obtained by methods known in the art and are generally used in an amount of 1 to 20% by weight, based on the total weight of monomers added during polymerization.
    [0024] Polymers in the form of aqueous dispersions, as described, for example, in DE-A 102008043988 can be converted into corresponding water-redispersible powders. In this case, it is common to use a drying aid in a total amount of 3 to 30% by weight, preferably from 5 to 20% by weight, in relation to the polymeric components of the dispersion. The polyvinyl alcohols above may be the preferred drying aid.
    [0025] Building material compounds containing gypsum may additionally comprise the usual additives and mixtures. Conventional additives include hydrated lime, preferably 1 to 10% by weight, based on the dry weight of gypsum-containing building material compounds, and / or inert fillers. Examples of inert fillers include silica sand, fine quartz powder, fine limestone powder, calcium carbonate, dolomite, clay, chalk, lime hydrate, talc or mica, rubber granules or heavy fillers, such as aluminum silicates , corundum, basalt, carbides, such as silicon carbide or titanium carbide. Suitable inert fillers are: silica sand, fine quartz powder, fine limestone powder, calcium carbonate, calcium carbonate, calcium magnesium carbonate (dolomite), chalk or hydrated lime; silica sand, fine quartz powder or fine limestone are specifically preferred. Additives can also include gravel. Gravel generally has a diameter of 2 mm or more.
    [0026] The additives have an average particle diameter preferably from 50 μm to 2.0 mm, especially preferably from 50 μm to 1.5 mm and more preferably from 50 to 800 μm (determined by laser diffraction analysis or by sieve analysis).
    [0027] With mixtures, it is possible to improve the processing quality of building material compounds containing plaster and / or the properties of construction products manufactured using them. Conventional blends are thickeners, for example, polysaccharides such as cellulose ethers, and modified cellulose ethers, starch ethers, guar gum, xanthan gum, polycarboxylic acids such as polyacrylic acid, and their partial esters and also polyvinyl alcohols have optionally been acetalized or modified for hydrophobicity, casein and associated thickeners. Other usual mixtures are retardants, such as hydroxycarboxylic acids, dicarboxylic acids or their modified salts, amino acids and amino acids, particularly N-polyoxymethylene amino acid, saccharides, oxalic acid, succinic acid, tartaric acid, glyconic acid, citric acid, sucrose, glucose, fructose, sorbitol, pentaerythritol or phosphates. Other mixtures are adjustment accelerators, such as alkali metal salts or alkaline earth metal salts of inorganic or organic acids. Additional examples of mixtures are salts of long-chain fatty acids, such as calcium stearate, sodium oleate and architectural silicone preservatives. The following can additionally be mentioned: preservatives, film-forming agents, dispersing agents, foam stabilizers, defoamers, plasticizers, superplasticizers and flame retardants (for example, aluminum hydroxide).
    [0028] In preferred embodiments of gypsum-containing building material compounds according to the invention, the mixtures comprise one or more hydrophobic additives. Hydrophobic additives preferably contain one or more organosilic compounds.
    Suitable organosilic compounds include, for example, silanes, such as tetraorganosilanes SiR4 and organoxysilanes SiRn (OR ') 4-n with n = 1 to 3, polymethylhydrogen siloxanes, siloxane resins, polysilanes preferably of the general formula R3Si (SiR2) nSiR3 with n = 0 to 500, organosilanois, such as SiRn (OH) 4-n, disiloxanes, oligosiloxanes, polysiloxanes, for example, composed of units of the general formula RcHdSi (OR ') and (OH) fO (4-cdef) / 2 with c = 0 to 3, d = 0 to 1, e = 0 to 3, f = 0 to 3 and with the sum C + d + and + f per unit being no more than 3, 5, with R in each case being identical or different and indicating branched or unbranched alkyl radicals having 1 to 22 carbon atoms, cycloalkyl radicals having 3 to 10 carbon atoms, alkylene radicals having 2 to 4 carbon atoms and also aryl radicals , aralkyl and alkylaryl or radicals other than alkyl and alkoxyalkylene radicals having in each case 1 to 4 carbon atoms, preferably me tila and ethyl, also being possible that the radicals R and R 'are replaced by halogens, such as, chlorine, by ether, thioether, ester, starch, nitrile, hydroxyl, amine, carboxyl, sulfonic acid, carboxylic anhydride and carbonyl groups and in the case of polysilanes, it is also possible for R to have the definition OR '.
    [0030] Other examples of organosilicon compounds are organosiliconates, more specifically alkyl siliconates, such as monomeric or oligomeric alkylsilanotriois. Organosiliconates are obtained, for example, by reacting one or more organoalkoxysilanes with one or more polyhydroxy compounds, or preferably, with one or more alkali metal bleaches. Preferred organoalkoxysilanes for the preparation of organosiliconates are methyl-trimethoxysilane, methyl-triethoxysilane, ethyl-trialkoxysilane, propyl-trimethoxysilanes, butyl-trimethoxysilanes, pentyl-trialkoxysilanes, hexyl-trimethoxysilanes, hexyl-trimethoxysilanes, octyl-trimethoxysilanes, octyl-trimethoxysilanes. Examples of an alkali metal bleach are: sodium hydroxide or potassium hydroxide, more specifically in the form of its aqueous solutions. Examples of suitable polyhydroxy compounds are alkanedioles, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol or 1,3-propanediol, alkanthriols, such as, glycerol, alkanethetrols, such as, pentaerythritol, acids hydroxycarboxylics, such as, lactic acid, citric acid or tartaric acid, saccharides, such as, sugars, more specifically glucose, sucrose or fructose or starch. The reaction products can comprise basic or acidic constituents, examples being catalysts that can be added in order to promote the elimination of alkoxy groups. Methods for producing organosiliconates are described in WO 2012/022544, DE-A 102011076344.9 or DE-A 10107614, for example.
    [0031] Specifically preferred organosilicon compounds are methyl trimethoxysilane, methyl trimethoxysilane, ethyl trimethoxysilane, ethyl trimethoxysilanes, propyl trimethoxysilanes, propyl-trimethoxysilanes, isobutyl-trimethoxylsilanes, trimethylsetanes, propyl-trimethoxysilanes, pentyl-trimethoxysilanes , cyclohexyl-trimethoxysilane, methyl-tripropoxysilane, methyl-tri- (ethoxyethoxy) silane, vinyl-tri (methoxyethoxy) silane, methacryloyloxypropyl-trimethoxysilane, methacryloyloxypropyl-triethoxy-ethoxy-ethoxy-ethoxy-ethoxy-ethoxy-ethoxy, ethoxyl-ethoxy-ethoxy trimethoxysilane, Y-mercaptopropyl-triethoxysilane, phenyl-triethoxysilane, heptyl-trimethoxysilane, heptyl-triethoxysilanes, isooctyl-triethoxysilane, n-octyl-triethoxysilane, hexadecyl-triethoxysilanes, dipropyl-detoxoxyethylsilanes, methyl-diphenylsilyl ethoxyethoxy) silane, tetramethyl-diethoxy-disilane, trimethyl-trimethoxy-disilane, trimethyl-triethoxy-disilan o, dimethyl-tetramethoxy-disilane, dimethyl-tetraethoxy-disilane, methyl-hydrogen polysiloxanes finished in block with trimethylsilyloxy groups, copolymers finished in block with trimethylsilyloxy groups and compounds of dimethyl-siloxane and methyl-hydrogensyloxy and dimethyl-polyethylene units, dimethyl and dimetyl -polysiloxanes with Si-OH groups in the terminal units. Specifically preferred organosilicon compounds are also the organosiliconates mentioned above.
    [0032] Preferred hydrophobizing additives comprise one or more organosilicon compounds applied to one or more supports. Suitable supports are, for example, based on inorganic particles, water-soluble organic polymers, or water-insoluble organic polymers. Examples of inorganic particles are aluminosilicates, such as zeolite or metakaolin, fly ash, clay, lime, carbonates. Examples of water-soluble organic polymers are: starch, cellulose and polyvinyl alcohols. The water-insoluble inorganic polymers are preferably the polymers described above based on one or more ethylenically unsaturated monomers. Preferably, the water-insoluble organic polymers are in the form of water redispersible powders described above.
    [0033] Hydrophobizing additives optionally comprising supports are present, preferably in solid form, more preferably in particulate form. Preferably, the organosilicon compound and the supports are mixed before the hydrophobizing additives are incorporated into the plaster building material compounds. In this case, the organosilicon compounds are preferably adsorbed and / or applied to the supports. Corresponding methods for producing the supported organosilicon compounds are described, for example, in WO 2008/062018, WO 2010/012654 or WO 2010/052201. However, hydrophobizing additives that do not include supports are especially preferred.
    [0034] It is also preferred to use a combination of at least two hydrophobic additives. Preferred combinations include an organosiliconate based on at least one methyl-trialkoxysilane and an organosiliconate based on at least one silane selected from the group consisting of ethyl-trialkoxysilane, propyl-trialkoxysilane, butyl-trialkoxysilane, pentyl-trialcoxysilane, hexyl-trialoxysilane , heptyl-trialkoxysilane, octyl-trialkoxysilane. Another preferred combination comprises an organosiliconate based on at least one methyl-trialkoxysilane and one or more organoxysilanes, especially ethyl-trialkoxysilane, propyl-trialkoxysilanes, butyl-trialkoxysilane, pentyl-trialkoxysilane, hexyl-trialkoxysilane, heptyco-trialoxysilane or triallycosyl-trialoxysilane or trialyl-oxisilane-trialoxysilane.
    [0035] Typical formulations of plaster-based building material compounds that generally contain 5 to 90% by weight, more preferably from 5 to 80% by weight of plaster, 0.5 to 20% by weight, more preferably from 1 to 10% by weight of pozzolans, 0.5 to 30% by weight, particularly from 1 to 10% by weight of cement, 0.5 to 50% by weight, particularly from 1 to 10% by weight of polymer, 0 to 80% by weight, preferably 1 to 80% by weight, and especially preferably 20 to 70% by weight of additives and 0-10% by weight, in particular 0.1-4% by weight of mixtures. Hydrophobizing additives are included in gypsum-containing building material compounds, preferably 0 to 5% by weight, more preferably 0.1 to 1% by weight. The above mentioned data in% by weight are based on the dry weight of the plaster-based building material compounds and added up to a total of 100% by weight.
    [0036] The weight ratio of cement to pozzolan is preferably from 1: 4 to 4: 1, and in particular preferably 1: 3 to 3: 1, and more preferably 1: 2 to 2: 1.
    [0037] The total amount of gypsum and additives is preferably 50 to 98% by weight, particularly from 60 to 95% by weight, and more preferably from 70 to 90% by weight, based on the dry weight of the compounds of building materials. construction containing plaster.
    [0038] In preferred embodiments, building material compounds containing plaster are used as building adhesives, especially as adhesives for ceramics or as coating materials, especially as a self-leveling compound or floor load compound.
    [0039] When used as building adhesives, building material compounds generally contain 25 to 50% gypsum, 35 to 60% additives, the values in% by weight being based on the dry weight of the material compounds construction containing plaster and addition up to a total of 100% by weight. In the case of use as a building adhesive, the additional components can be used according to the above-mentioned typical recipe for building materials composed of plaster.
    [0040] When used as coating materials, building material compounds containing gypsum generally contain from 30 to 75% by weight, in particular 40 to 60% by weight of plaster, from 10 to 60% by weight, in in particular 25 to 45% by weight of additives, with the values in% by weight being based on the dry weight of the building material compounds containing plaster and addition to a total of 100% by weight. In the case of use as coating materials, the additional components can be used according to the typical formulation mentioned above for building material compounds containing gypsum.
    [0041] Water is added to the building material compounds containing gypsum, prior to application, preferably 15 to 70% by weight. In the case of construction adhesives, preferably 20 to 35% by weight, and especially preferably 15 to 30% by weight of water are added. The coating materials preferably receive an addition of 15 to 30% by weight, more preferably from 19 to 25% by weight of water. The above values, which refer to% by weight of water above, are based in each case on the dry weight of the building material compound containing the plaster in question. The declared amounts of water refer to the production of building material compounds having the desired processing properties.
    [0042] In order to produce building material compounds containing gypsum, the appropriate mixers are used to mix and homogenize plaster, cement, pozzolans, optionally additives, optionally mixtures and optionally polymers, more specifically in the form of aqueous polymeric dispersions or preferably in the form of water-redispersible polymeric powders. In an alternative procedure, the polymers in the form of aqueous dispersions or aqueous redispersions of water-redispersible polymer powders are combined with a mixture of other dry components of plaster-containing building material compounds (composed of 2-component building material). However, preferably, a dry mixture is produced and the necessary water is added immediately before work.
    [0043] The plaster-containing construction materials according to the invention are particularly suitable for use as mortar, for example, as coating materials, construction adhesive or other common applications. Examples of construction adhesives are adhesive mortar, fixing mortar or adhesive for tiles of all types, such as ceramics, earthenware, fine stoneware, ceramics or natural stone, for use in the internal or external segment. Examples of coating materials are leveling compounds for walls or floors for indoor or outdoor use, self-leveling CaSO4 screeds and plaster or render for indoor or outdoor use. Other common applications include common fillers or grouts. In addition, construction materials containing plaster can also be used for the production of plasterboard or plaster molds. Other applications include, for example, plaster or working plaster including such applications in the external segment.
    [0044] Construction products obtained from the plaster-containing building material compounds of the invention are surprisingly resistant even under wet conditions and, more specifically, in the case of freezing / thawing and, after such exposures, they have resistance values or substantially better mechanical properties than construction products made of conventional plaster-containing compounds. With the building material compounds of the invention, consequently, it is possible to obtain decisive improvements in the tensile strength of the adhesive, flexural strength, compressive strength, abrasion resistance, water absorption and, therefore, the weather resistance of the products of plaster-based construction. Even after storage in water, in reality, the construction products of the invention obtain the strength levels of cementitious systems. From a performance point of view, therefore, the building material compounds of the invention are an equivalent replacement for cementitious building material compounds, but with the advantage that plaster is obtained with much less energy expenditure in contrast to cement. .
    [0045] In general, the plaster-containing building material compounds of the invention are notable for their excellent water resistance. These effects are caused, surprisingly, by the synergistic interactions between plaster, cement and pozzolans. By adding polymers and / or hydrophobizing additives, especially organosilicon compounds, the effect is further enhanced in a synergistic manner.
    [0046] The following examples serve to better illustrate the invention: Production of building material compounds containing plaster:
    [0047] First, a dry mixture was prepared from the components of the respective formulation of inventive / comparative examples 1 to 6, by homogeneous mixing of all the components of the respective formulation, apart from the water for mixing. The respective amount of water for mixing was added subsequently and the resulting mixture was combined homogeneously. Example of the Invention 1: Formulation of the ceramic adhesive:
    Example of Invention 2: Formulation of the floor leveling compound:

    Comparative Example 3: Formulation of the ceramic adhesive:
    Comparative Example 4: Formulation of the ceramic adhesive:

    Comparative Example 5: Formulation of the ceramic adhesive
    Comparative Example 6: Formulation of the floor leveling compound:

    Testing of gypsum-containing building material compounds
    [0048] The ceramic adhesives containing plaster of the inventive / comparative examples 1, 3, 4, and 5 were each tested, according to the European ceramic adhesive standard EN 1348. The tensile strength of the adhesive in this document was determined after the following storage conditions:


    [0049] The results of the examples of inventive / comparative tests 1, 3, 4 and 5 are summarized in Table 1. Table 1: Test results of the tile adhesives of the inventive / comparative examples 1, 3, 4 and 5:

    [0050] Floor leveling compounds containing


    [0051] The test results of inventive / comparative examples 2 to 4, respectively, are summarized in table 2. Table 2: Test results of the floor leveling compounds of inventive / comparative examples 2 and 6:

    [0052] The results with the ceramic adhesives in Table 1 demonstrate that, with the ceramic adhesive of the invention (Example 1), a tensile strength of the adhesive was obtained and after wet storage and freeze / thaw storage that is many times greater than that of the ceramic adhesives of Comparative Examples 3, 4 and 5. The tensile strengths of the adhesive after SC and storage under heating are at a level comparable to all the ceramic adhesive formulations of the inventive / comparative examples 1 and 3, 4 and 5 , respectively.
    [0053] The results in Table 2 show that the floor loading compound of the invention (Example 2) in both results after SC and after wet storage results in tensile flexural strengths and compressive strengths that are significantly above those for the comparative example 6. With Example 2, the tensile strength of the adhesive after wet storage is likewise significantly higher compared to Comparative Example 6.
    [0054] Thus, the results show that, with the plaster-containing building material compounds of the invention, construction products are obtained with better strength values or mechanical properties in wet conditions than construction products containing conventional plaster. Preparation of gypsum-containing building material compounds, hydrophobized: Example 7:
    [0055] As in Example 1, with the only difference that the dry mixture was additionally combined with 3 parts by weight of powdered potassium methyl siliconate (siliconate from Preparation Example 2 of WO 2012/022544: the molar potassium ratio for silicon = 0.64). Example 8:
    [0056] As in Example 1, with the only difference that the dry mixture was additionally combined with 3 parts by weight of powdered potassium isobutyl siliconate (siliconate V1a of DE-A 102011076344.9: molar ratio of potassium to silicon = 1, 00). Example 9:
    [0057] As in Example 1, with the only difference that the dry mixture was additionally combined with 5 parts by weight of silane powder (silane powder of Example 3b of EP 1394198: an alkyltrialoxysilane supported on polyvinyl alcohol). Example 10:
    [0058] As in Example 7, with the only difference that the dry mixture was additionally combined with 3 parts by weight of powdered potassium isobutylsiliconate from Example 8. Example 11:
    [0059] As in Example 7, with the only difference that the dry mixture was additionally combined with 3 parts by weight of silane powder from Example 9. Testing of building material compounds containing hydrophobized plaster:
    [0060] The ceramic adhesives containing plaster, hydrophobized from Examples 7 to 11 and ceramic adhesive containing plaster from Example 1 were each tested for their absorption in water according to the European standard EN 520.
    [0061] After storage for 28 days under standard conditions, and subsequent drying to constant weight, storage with water for two hours followed, as described in EN 520. The test results are summarized in Table 3.
    [0062] The results in Table 3 show that the addition of organosilicon compounds of the invention to ceramic adhesives containing gypsum leads to a very effective hydrophobization of the ceramic adhesives. Water absorption is significantly reduced by up to 90%. The combined use of the two additives (examples 10 and 11) proved to be specifically advantageous. Table 3: Results of the test of hydrophobized ceramic adhesives:
    5 a) increase in the mass of the respective specimen after storage in water, based on the mass before storage in water.
    权利要求:
    Claims (4)
    [0001]
    1. Composed of construction material containing plaster characterized by comprising: 30 to 75% by weight of plaster; 1 to 10% by weight of metakaolin; 1 to 10% by weight of cement; 1 to 10% by weight of at least one polymer; 10 to 60% by weight of aggregates; 0 to 5% by weight of hydrophobizing additives; and 0 to 10% by weight of mixtures of one or more components selected from thickeners, retardants, adjustment accelerators and long-chain fatty acid salts, where weight percentages are based on the dry weight of the building material compound containing plaster and added in total to 100% by weight and at least one polymer is a member selected from the group consisting of (a) vinyl ester homopolymers, (b) vinyl ester copolymers comprising one or more vinyl ester units and one or more vinyl ester units of monomers selected from the group consisting of olefins, vinyl aromatics, vinyl halides, acrylic esters, methacrylic esters, fumaric acid monoesters, maleic acid monoesters, fumaric acid diesters and maleic acid diesters, (c) homopolymer compounds of halogen vinyl and (d) halogen vinyl copolymer compounds comprising at least one monomer unit selected from the group consisting of vinyl esters, olefins, meta esters acrylics and acrylic esters, where the weight ratio of cement to metakaolin is 1: 2 to 2: 1.
    [0002]
    2. Building material compound containing plaster, according to claim 1, characterized in that the plaster is selected from the group comprising α- or β-hemihydrate (CaSO4.1 / 2 H2O), dihydrate, anhydrite and a calcium sulfate obtained during flue gas desulfurization (FGD plaster).
    [0003]
    3. Building material compound containing plaster, according to claim 1 or 2, characterized in that the aggregates are selected from the group comprising hydrated lime, silica sand, fine quartz powder, fine limestone powder, calcium carbonate, dolomite , clay, chalk, lime hydrate, talc, mica, rubber granules, heavy fillers, or carbides.
    [0004]
    Plaster-based building material compound according to any one of claims 1 to 3, characterized in that the total amount of plaster and additives is 60 to 95% by weight, based on the dry weight of the building material compounds containing plaster.
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    同族专利:
    公开号 | 公开日
    KR20140023426A|2014-02-26|
    AU2012280400B2|2014-09-25|
    RU2608834C2|2017-01-25|
    WO2013004621A1|2013-01-10|
    IN2014CN00636A|2015-04-03|
    MX2014000096A|2014-02-17|
    EP2726436B1|2018-04-11|
    SG2013096268A|2014-12-30|
    TR201807286T4|2018-06-21|
    EP2726436A1|2014-05-07|
    CN103649006B|2017-05-10|
    CN103649006A|2014-03-19|
    KR101604075B1|2016-03-17|
    RU2014103285A|2015-08-20|
    US20140121303A1|2014-05-01|
    BR112013033754A2|2017-02-07|
    PL2726436T3|2018-09-28|
    US9216927B2|2015-12-22|
    AU2012280400A1|2014-01-30|
    MX362518B|2019-01-21|
    DE102011078531A1|2013-01-03|
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    法律状态:
    2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-03-24| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-08-04| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-12-08| B09A| Decision: intention to grant|
    2021-01-19| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102011078531,0|2011-07-01|
    DE201110078531|DE102011078531A1|2011-07-01|2011-07-01|Gypsum-containing building materials|
    PCT/EP2012/062717|WO2013004621A1|2011-07-01|2012-06-29|Gypsum-containing construction material compounds|
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