EP1912919A1 - Additif pour applications dans le domaine de la chimie du batiment - Google Patents

Additif pour applications dans le domaine de la chimie du batiment

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Publication number
EP1912919A1
EP1912919A1 EP06791572A EP06791572A EP1912919A1 EP 1912919 A1 EP1912919 A1 EP 1912919A1 EP 06791572 A EP06791572 A EP 06791572A EP 06791572 A EP06791572 A EP 06791572A EP 1912919 A1 EP1912919 A1 EP 1912919A1
Authority
EP
European Patent Office
Prior art keywords
component
hydrogen
mol
additive according
atoms
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Withdrawn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
EP06791572A
Other languages
German (de)
English (en)
Inventor
Peter GÄBERLEIN
Michael Schinabeck
Stefan Friedrich
Uwe Holland
Michael Eberwein
Patrick Weiss
Manfred Schubeck
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.)
Construction Research and Technology GmbH
Original Assignee
Construction Research and Technology GmbH
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 Construction Research and Technology GmbH filed Critical Construction Research and Technology GmbH
Publication of EP1912919A1 publication Critical patent/EP1912919A1/fr
Withdrawn legal-status Critical Current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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0004—Microcomposites or nanocomposites, e.g. composite particles obtained by polymerising monomers onto inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/12—Multiple coating or impregnating
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • C04B40/0633—Chemical separation of ingredients, e.g. slowly soluble activator
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0049—Water-swellable polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0051—Water-absorbing polymers, hydrophilic polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0053—Water-soluble polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0066—Film forming polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0067—Function or property of ingredients for mortars, concrete or artificial stone the ingredients being formed in situ by chemical reactions or conversion of one or more of the compounds of the composition
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/44—Thickening, gelling or viscosity increasing agents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide

Definitions

  • the present invention is a new additive for construction chemical applications, consisting of a core component A) and applied to this shell component B).
  • modified cellulose ether The almost most important role in such organic modifications plays the so-called modified cellulose ether, which can be summarized under this term a large variety of multi-component systems. Through the use of such cellulose ethers numerous building material properties can be specifically adapted to the particular application.
  • European Patent EP 053 768 B1 describes in detail the composition of the named components and their effects on the adhesion tendency of corresponding building material systems.
  • additive combinations of water-soluble cellulose ethers and their derivatives, polyacrylamide, alkali metal or ammonium salts of crosslinked polyacrylates optionally grafted with starch are used commonly referred to as superabsorbents (SAB);
  • starch ethers and additions of alkali metal, alkaline earth metal or ammonium salts of condensation products of naphthalenesulfonic acid or phenolsulfonic acid with formaldehyde or with sulfonic acid-modified polycondensation products of melamine and formaldehyde are also suitable.
  • this multicomponent additive contains the starch ethers together with polyacrylamide as a synthetic polymer compound in admixture with water-soluble mixed substituted cellulose ethers which, in addition to hydroxyethyl substituents, have 3-alkoxy-2-hydroxypropyl radicals having 2 to 6 carbon atoms in the alkoxy group.
  • water-soluble mixed substituted cellulose ethers which, in addition to hydroxyethyl substituents, have 3-alkoxy-2-hydroxypropyl radicals having 2 to 6 carbon atoms in the alkoxy group.
  • Cellulose ether derivatives which in addition to the hydroxyethyl substitution have at least one 3-alkoxy-2-hydroxypropyl radical having a straight-chain alkoxy radical having 2 to 6 C atoms may be preferred.
  • DE 39 135 18 A1 also teaches the composition of corresponding modified cellulose ether systems.
  • the particular effect of a special, mixed substituted cellulose ether variant is described, which in addition to hydroxyethyl substituents 3-alkoxy-2-hydroxypropyl having 2 to 8 carbon atoms in the alkoxy group and is used in combination with starch ethers and anionic polyacrylamides.
  • US Pat. No. 4,487,764 B1 protects a particular combination of the common cellulose ethers with swellable and non-flocculating organic polymers which are in the form of crosslinked polyacrylates, ie as superabsorbents, and are intended to ensure particularly favorable processing properties.
  • Special viscosity-increasing effects are also known from US Pat. No. 5,432,215 B1, in which connection a combination of cellulose ethers and superabsorbents is used.
  • cellulose ether substitutes based on better suitable polysaccharides or synthetic and optionally water-swellable sulfo-containing copolymers are increasingly being used.
  • Such compounds are described for example in DE 198 06482 A1, DE 100 37 629 A1, WO 2005/035603 and DE 10 2004 032 304.6, where they are used either as a complete or as a partial replacement of the cellulose ethers used otherwise.
  • WO 92/20727 discloses coated, water-soluble or water-swellable polymer particles. Crystalline substances such as sodium sulfate or sodium carbonate are used as the coating material, with saturated salt solutions in mixers preferably being sprayed onto polymer particles.
  • the thus coated particles have an improved dispersibility in aqueous solutions; However, the dissolution behavior under difficult conditions is still unsatisfactory.
  • the high coating agent levels represent an undesirable weight ballast.
  • the object of the present invention was to develop additives for broadly mixed chemical systems, dispersions and color preparations, wherein in particular an improved applicability of these additives stood in the foreground.
  • These new additives should, above all, at least ensure the well-known good properties of the construction chemical systems, but if possible give the respective systems to which they are added, additional positive properties.
  • this additive according to the invention it not only fulfills the specific task by improving the stirrability and, in particular, positively influencing the wet mortar properties, but that the addition time can play a positive role if these additives are used in thickener systems.
  • the stirrability could be drastically improved, at the same time the amount of additive to be used could be significantly reduced without negatively affecting the wet mortar properties.
  • the additives according to the present invention can be used not only in construction chemical systems containing hydraulic binders but also in other systems such as paints and varnishes, which clearly goes beyond the field of application envisaged in the task. Overall, the positive effects found on the additive according to the invention could not be predicted in their entirety.
  • the present invention takes account of variants having properties which the person skilled in the art designates as plastic and / or dynamic viscosity, yield point, rheopexy and thixotropy.
  • Water-soluble and / or water-swellable and / or water-absorbable compounds of the non-cellulosic type have proved to be particularly suitable as component A), which should have viscosity-increasing properties in the end use.
  • Particularly suitable components A) are compounds of the series oligo- and polysaccharides, preferably starch ethers, welan gum, diutan gum, xanthan, chitosan or guar derivatives and / or sulfo-containing copolymers and / or copolymers based on acrylamide and / or others Hydrocolloid or hydrogel-forming substances proved, which can be used in any mixture.
  • their derivatives come into question, as they by physical and / or chemical processes, such.
  • B. Veretherungs- and esterification processes are accessible.
  • Typical chemical derivatives are those of the carboxyl, carboxyalkyl and hydroxyalkyl types.
  • Synthetic, water-soluble polymers according to the present invention can be constructed from water-soluble and ethylenically unsaturated monomers with which nonionic, cationic, anionic or amphoteric polymers are formed.
  • the sulfo-containing copolymers just mentioned should be representatives consisting of up to 4 assemblies according to the copolymers and terpolymers according to DE 100 37 629 A1, DE 198 06 482 A1, WO 2005/035603 and DE 10 2004 032 304.6 (still unpublished) exist.
  • the disclosure of these four documents is a substantial part of this application.
  • Particularly suitable are water-soluble sulfo-containing copolymers which consist of at least three subunits a), b), c) and / or d).
  • the first component usually represents a sulfo-containing substituted acrylic or methacrylic derivative of the formula (I):
  • R 1 hydrogen or methyl
  • R 2 , R 3 , R 4 hydrogen, aliphatic hydrocarbon radical having 1 to 6
  • the monovalent or divalent metal cation is preferably sodium, potassium, calcium or magnesium ions.
  • organic amine radicals are preferably substituted ammonium groups which derive from primary, secondary or tertiary Ci- to C 20 - alkyl amines, Ci- to C2o-alkanolamines, C 5 - to C 8 -Cycloalkylaminen and C 6 - to Cu aryl amines.
  • corresponding amines are methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, cyclohexylamine, dicyclohexylamine, phenylamine and diphenylamine in the protonated ammonium form.
  • the assembly a) of A) is derived from monomers such as 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid, 2-acrylamido-2,4,4 -trimethylpentansulfonklare. Particularly preferred is 2-acrylamido-2-methylpropanesulfonic acid.
  • the second module b) corresponds to the formula (II):
  • R 1 has the abovementioned meaning.
  • R 5 and R 6 independently of one another represent hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms or an aryl radical having 6 to 14 C atoms.
  • Preferred monomers which form the structure (II) are the following compounds: acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylolacrylamide, N- tertiary butylacrylamide, etc.
  • the third component c) corresponds to the formula (III)
  • R 1 has the abovementioned meaning.
  • Preferred monomers which form the structure (III) are tristyrylphenol polyethylene glycol 110 O methacrylate, behenyl polyethylene glycol 1,100 methacrylate, stearyl polyethylene glycol 1100 methacrylate, tristyrylphenol polyethylene glycol 1100 acrylate, tristyrylphenol polyethene glycol 1100- monovinyl ether, behenyl polyethylene glycol 1100-monovinyl ether, stearyl polyethene glycol 1100-monovinyl ether, tristyrylphenol polyethylene glycol 1100-vinyloxy-butyl ether, behenyl polyethylene glycol-1100- vinyloxy-butyl ether, tristyrylphenol polyethylene glycol block propylene glycol allyl ether, behenyl polyethylene glycol block propylene glycol allyl ether, stearyl polyethylene glycol block propylene glycol allyl ether, etc.
  • the fourth component d) corresponds to the formula (IV)
  • R 9 H, represent Cr to C-4-alkyl
  • R 1 , n, p and q have the abovementioned meaning.
  • Preferred monomers which form the structure (IV) are allyl polyethylene glycol (350 to 2000), methyl polyethylene glycol (350 to 2000) monovinyl ether, polyethylene glycol (500 to 5000) vinyloxy butyl ether, polyethylene glycol block propylene glycol (500 to 5000) -vinyloxy-butyl ether, methylpolyethylene glycol-block-propylene glycol allyl ether, etc.
  • the component A) in the form of a copolymer from 3 to 96 mol% of the assembly a), 3 to 96 mol% of the assembly b), 0.01 to 10 mol% of the assembly c) and / or 0.1 to 30 mol% of the assembly d).
  • Preferably used copolymers contain 30 to 80 mol% a), 5 to 50 mol% b) 0.1 to 5 mol% c) and / or 0.2 to 15 mol% d).
  • copolymers from the components a), b) and c) are referred to as type A, copolymers of the components a), b), c) and d) as type B and copolymers of the components a), b) and d) as type C.
  • copolymers of the invention of type B and C still up to 50 mol%, in particular up to 20 mol%, based on the sums of the components a), b), c) and d), still another assembly e) of the formula (V) included.
  • R 1 , R 2 , R 5 and R 6 have the abovementioned meaning.
  • monomers which form the structure (V) preferably the following compounds are suitable: [3- (methacryloylamino) -propyl] -dimethylamine, [3- (acryloylamino) -propyl] -dimethylamine, [2- (methacryloyl-oxy) ethyl] -dimethylamine, [2- (acryloyl-oxy) -ethyl] -dimethylamine, [2- (methacryloyl-oxy) -ethyl] -diethylamine, [2- (acryloyl-oxy) -ethyl] -diethylamine, etc.
  • R 1 , R 2 and m have the abovementioned meaning.
  • the following compounds are preferably suitable: N- (3-sulfopropyl) -N-methacryloxyethyl-N'-N- dimethyl ammonium betaine, N- (3-sulfopropyl) -N-methacrylamidopropyl-N, N-dimethyl ammonium betaine and 1- (3-sulfopropyl) -2-vinyl-pyridinium betaine.
  • these monomers also contain a cationic assembly, this does not adversely affect the particular construction chemical application.
  • the copolymers may additionally be given a slightly branched or crosslinked structure by the incorporation of small amounts of crosslinker.
  • crosslinker components are triallylamine, triallylmethylammonium chloride, tetraallylammonium chloride, N, N'-methylenebisacrylamide, triethylene glycol bismethacrylate, triethylene glycol bisacrylate, polyethylene glycol (400) bismethacrylate, and polyethylene glycol (400) bisacrylate. These compounds may only be used in amounts such that water-soluble copolymers are still obtained.
  • the concentration will rarely exceed 0.1 mol%, based on the sums of the components a), b), c), d), e) and f) lie; However, a person skilled in the art can easily determine the maximum amount of crosslinker component that can be used.
  • copolymers described are prepared in a manner known per se by linking the monomers forming the structures a) to d) by free-radical, ionic or complex-coordinate bulk, solution, gel, emulsion, dispersion or suspension polymerization. Since the products according to the invention are water-soluble copolymers, the polymerization in the aqueous phase, the polymerization in the reverse emulsion or the polymerization in the inverse suspension are preferred. In particularly preferred embodiments, the reaction takes place as a gel polymerization in an aqueous phase.
  • polyacrylamides are contained in the additive according to the invention, these should preferably have nonionic, anionic, cationic or amphoteric properties, particularly preferably a homo- and / or copolymer of acrylamide with the monomers acrylic acid, acrylamidopropanesulfonic acid quaternized dimethylaminopropyl, acrylamide or quaternized dimethylaminoethyl acrylate.
  • a polyacrylamide is intended in particular, a water-soluble homo- or copolymer is understood to contain acrylamide as a monomer constituent.
  • Suitable anionic comonomers are, in addition to the monomer units already mentioned, but also methacrylic acid, vinylsulfonic acid, methalylsulfonic acid, maleic acid, fumaric acid and itaconic acid. All of these listed acids can be polymerized as free acids, as salts or as mixtures thereof.
  • non-ionic comonomers for the polyacrylamides completely or even limited water-soluble monomers can be used, such as, for example, (meth) acrylonitrile, N, N-dimethylacrylamide, vinylpyridine, vinylacetate, methacrylamide, hydroxy-containing esters, polymerizable acids, dihydroxyethyl- and propyl esters of acrylic acid and methacrylic acid, amino-containing esters and amides of polymerizable acids, such as.
  • dialkylamino or amides such as.
  • Dimethylaminopropylacrylamid be used.
  • cationic polyacrylamides are, for example, comonomers in the form of cationized esters of (meth) acrylic acid, cationized amides of (meth) acrylic acid and cationized N-alkyl mono- and diamides with Ci- 6 -alkyl radicals.
  • the present invention preferably proposes cationic and / or anionic charges-containing polyelectrolytes based on acrylic acid or acrylamide derivatives or other ethylenically unsaturated monomer building blocks.
  • Additives which contain component A) in crosslinked or at least partially crosslinked form have proved particularly suitable.
  • the additive according to the invention may then contain, as inorganic component A), a representative of the series borax, aluminum sulfate or zeolites.
  • component A) is only in terms of their essential feature of the invention, namely the rheology increase, limited. In general, however, all organic and / or inorganic compounds come as component A) in question, whereby the particle size is not subject to any significant restriction. Nevertheless, the present invention takes into account a preferred variant in which the
  • Component A) has an average particle size range ⁇ 500 ⁇ m and preferably ⁇ 250 ⁇ m.
  • the distribution of particle sizes may be homogeneous or heterogeneous; That is, according to the respective application, mainly comprises larger particles or smaller particles, which can also approach the respective extrema and / or exclusively cover them.
  • component B) of the additive which acts as a coating or shell, according to the invention, it should preferably be a film-forming polymer which initially completely surrounds component A) and liberates it with a time delay during the construction chemical application.
  • a film-forming polymer which initially completely surrounds component A) and liberates it with a time delay during the construction chemical application.
  • the shell component B) should be a compound capable of being applied to the core component A) due to physical and / or chemical interactions, forming chemical and / or physical and preferably reversible crosslinks , Dialdehydes, such as. As glyoxal, diisocyanates, diols, carboxylic acids and their derivatives and any mixtures are considered to be particularly preferred.
  • Suitable compounds are those which contain at least two functional groups and which are capable of having the functional groups, essentially the acid groups or Hydroxyl groups of component A) to react.
  • the functional groups suitable for this purpose have already been mentioned above: hydroxyl, amino, epoxy, isocyanate, ester, amido or aziridino groups.
  • Such typical representatives are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, polyglycerol, triethanolamine, propylene glycol, polypropylene glycol, block copolymers of ethylene oxide and propylene oxide, ethanolamine, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, trimethylolpropane, pentaerythritol, 1,3-butanediol, 1,4 - Butanediol, polyvinyl alcohol, sorbitol, starch, polyglycidyl ether, PolyaziridinENSen, 1, 6-Hexamethylendiethylenhamstoff, diphenylmethane bis ⁇ '- N, N'-diethylenurea, haloepoxy compounds such as epichlorohydrin and ⁇ -Methylepifluorhydrin, polyisocyan
  • polyquaternary amines such as. As condensation products of dimethylamine with epichlorohydrin, homo- and copolymers of diallyldimethylammonium chloride and homopolymers and copolymers of dimethylaminoethyl (meth) acrylate in question, which may be quaternized with methyl chloride, if necessary.
  • Suitable component B also multifunctional bases are suitable, which must also be able to form ionic crosslinks, for which polyamines or their quaternized salts are particularly suitable.
  • the present invention provides as a further variant that it contains additional process additives, which are preferably selected from the series of plasticizers, such as.
  • plasticizers such as.
  • anti-caking agents such as.
  • triethyl citrate, polysorbate 80, stearic acid, sodium lauryl sulfate, talc or defoamer come.
  • the invention takes account of the fact that it can be constructed in a multi-layered manner, wherein it preferably contains at least one reactive layer.
  • reactive layer is meant by definition that the component usually in the context of a polymerization process with component A) interacts directly. This means that in the case of a two-layered structure both the layer facing component A) and the outermost layer may have been present as reactive layers and have reacted with component A).
  • all other variants are conceivable in which, for example, only the innermost layer is a reactive layer and, for example, has interacted with component A) or only the outermost layer.
  • neither the innermost nor the outermost layer can be a reactive layer and the reactivity can be limited to layers which are arranged between the innermost and outermost layers. In this case, it is mainly layers that have delayed their respective reactivity; namely, only when the layers deposited on the outside have been separated from the additive by abrasion and / or dissolution processes.
  • component B) reacts with component A) or else further components with component B) already applied to component A).
  • the property of the present additive which is essential to the invention namely its rheology-increasing effect, can be specifically predetermined and controlled in a targeted manner for the particular use medium and the desired release profile of the core layer A) by selecting suitable shell components.
  • component B) was applied to component A) with the aid of a component C).
  • component C) in liquid form or as a physical mixture leads to a chemical crosslinking of component B) on component A).
  • Particularly suitable representatives of component C) are dialdehydes such as glyoxal, diisocyanates, diols, dicarboxylic acids and their derivatives and any mixtures.
  • all types of compounds come as suitable component C) in question, which can also be used as component B).
  • the additive according to the invention should not have too large particle sizes. For this reason, the present invention provides a mean grain spectrum for the additive consisting of the
  • Components A) and B) which is ⁇ 2,000 ⁇ m and preferably ⁇ 1 000 ⁇ m.
  • the present invention also claims the use of this additive, in particular as an additive with delayed onset effect.
  • the time delay is mainly caused by the component B), ie the shell component, which, as already stated, can be made up of a different number of layers and in particular reactive layers.
  • the additive according to the invention is in particular suitable for use in paints and, above all, in emulsion paints and inks, in paints, in pigment preparations and in pigment concentrates, which is likewise included in the present invention.
  • cellulose ether substitutes are representatives of the series oligo- and polysaccharides, preferably starch ethers, welan gum, diutan gum, xanthan, chitosan or guar derivatives and / or sulfo-containing copolymers and / or copolymers based on Acrylamide and / or other hydrocolloid or hydrogel-forming substances, as have already been described in detail above in respect of the component A).
  • the filled aqueous systems are preferably building material systems based on inorganic and, in particular, mineral binders and particularly preferably cement, gypsum, lime, anhydrite or other calcium sulfate-based binders.
  • Tile adhesives, plasters, setting compounds, grouts, masonry mortar, repair mortar and grout are particularly suitable representatives of such building material systems, which are preferably suitable for mechanical stirring and / or machine application according to the present invention, and in particular highly stable coated and / or thickened dry mortar, such as z.
  • plasters or tile adhesive represent.
  • the additives of the invention for construction chemical applications due to their time-controllable rheology-enhancing properties over the previously known prior art significant improvements, which is not least based on the comparison with the prior art compounds that as component A) or as component B ) are contained in the additive.
  • a fluidized bed granulator 300 g of an anionic polyacrylamide were charged with a charge of 20 to 50% and heated by a heated to 80 0 C inlet air flow (70 m 3 / h) in the fluidized bed. As a layer resulted temperature 70 0 C.
  • the metering rate of about 3.2 g / min of a 1% glyoxal aqueous solution were sprayed onto the polyacrylamide 300 g.
  • the amounts of glyoxal were varied and applied in amounts of 1, 2 and 3 wt .-%, based on the commercially available anionic polyacrylamide.
  • Example 2 An analogous to Example 1 produced and, coated with 3 wt .-% of polyvinyl alcohol polyacrylamide was in the fluidized bed at a fluidized bed temperature of 60 0 C with 300 g of a 1% Glyoxaates (metering rate of 3 g / min) sprayed and thus post-crosslinking the polyvinyl alcohol.
  • the amounts of glyoxal were varied and adjusted to 1, 2 and 3 wt .-%, based on the already coated polyacrylamide.
  • Example 1 300 g of an anionic polyacrylamide were charged with a charge of 20 to 50% in a fluidized bed granulator and heated by a heated to 65 0 C inlet air flow (70 m 3 / h) in the fluidized bed.
  • temperature 55 0 C. at a rate of about 3.2 g / min were 330 g of a mixture of 10 to 98 Mowiol and glyoxal Coated form on the granulate.
  • the mixture contained 10% by weight of Mowiol 10 to 98 and 1% by weight of glyoxal.
  • the amounts of the coating material were varied and adjusted to 1, 2, 3, 5 and 10 wt .-% coating material (stated in weight percent coating material based on the polyacrylamide).
  • Example 1 300 g of an anionic polyacrylamide were charged with a charge of 20 to 50% in a fluidized bed granulator and heated by a heated to 65 0 C inlet air flow (70 m 3 / h) in the fluidized bed. As a layer resulted temperature 55 0 C.
  • the metering rate of about 3.2 g / min, 330 g of a mixture of Pharmacoat 606 (Hypromellose of Fa. Syntapharm) and glyoxal Coated form on the granulate.
  • the mixture contained 10% by weight of Pharmacoat and 2% by weight of glyoxal.
  • the amounts of the coating material were varied and prepared with 1, 2, 5 and 10 wt .-% coating material (stated in weight percent coating material based on the polyacrylamide used.
  • tile adhesive mortar 1 kg was mixed with a commercial drill (1000 W, 800 U / min) and a helical stirrer. There was added 340 grams of mixing water per 1000 grams of dry mortar.
  • a tile (15 x 25 cm weight 1, 9 kg) is inserted into the tile adhesive formulation and loaded with 5 kg weight for 30 seconds. At the top of the tile, a mark is placed and the sample set upright. Then it is observed whether and how far the tile slips off. A slip of 1 to 10 mm is rated as stable.
  • the mixed, fresh mortar is introduced by means of a spatula in a 250 g tin can as free of air bubbles.
  • the can is filled to the upper edge and smoothed off with the spatula.
  • the material is compacted by means of the lifting table (10 strokes, approx. 1 stroke per second) and covered with the can lid (vice versa). From this moment the time measurement is started.
  • the first viscosity measurement (Brookfield Viscosimeter, Model RV) is performed after 5 minutes, the second after 20 minutes. Measure with the TF spindle (Spindle 96 (TF) marked at 3.2 cm) at 2.5 rpm by dipping the spindle into the mortar as far as the mark.
  • the highest displayed value (mPa * s or cP) is noted. At least 3 values should be determined per measurement. (Tolerance of measured values between each other: +/- 10%) Table 1 :
  • the sulfo-containing polymer was the sales product SWR 308/4198 from Construction Research & Technology GmbH.
  • component A) polyacrylamide

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Composite Materials (AREA)
  • Nanotechnology (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Civil Engineering (AREA)

Abstract

L'invention concerne des additifs destinés à des applications dans le domaine de la chimie du bâtiment, ces additifs comprenant un composant central A) organique et/ou inorganique possédant des propriétés améliorant la rhéologie et un composant d'enveloppe B) appliqué sur le composant A) en raison d'interactions physiques et/ou chimiques et servant de revêtement. Le composant A) doit comprendre des composés solubles dans l'eau et/ou pouvant gonfler et/ou adsorbants du type non cellulosique qui développent des propriétés augmentant la viscosité dans l'application finale. Le composant d'enveloppe B) doit être de préférence un polymère filmogène pouvant libérer de façon différée le composant A) lors de l'utilisation en chimie du bâtiment, tel que l'alcool polyvinylique, l'acétate polyvinylique et le polyéthylèneglycol. Le composant B) peut présenter une structure multicouche et comprendre au moins une couche réactive. Ce nouvel additif peut être utilisé comme adjuvant à action différée dans des colorants, mais aussi pour commander dans le temps l'augmentation de viscosité ou le développement de rhéologie dans des systèmes de matériaux de construction à base de liants inorganiques.
EP06791572A 2005-08-10 2006-08-10 Additif pour applications dans le domaine de la chimie du batiment Withdrawn EP1912919A1 (fr)

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DE102005037777A DE102005037777A1 (de) 2005-08-10 2005-08-10 Additiv für bauchemische Anwendung
PCT/EP2006/007935 WO2007017286A1 (fr) 2005-08-10 2006-08-10 Additif pour applications dans le domaine de la chimie du batiment

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US (1) US8846784B2 (fr)
EP (1) EP1912919A1 (fr)
JP (1) JP5430934B2 (fr)
CN (1) CN101268028B (fr)
AU (1) AU2006278152B2 (fr)
DE (1) DE102005037777A1 (fr)
WO (1) WO2007017286A1 (fr)

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AU2006278152A1 (en) 2007-02-15
CN101268028A (zh) 2008-09-17
US20100234490A1 (en) 2010-09-16
JP2009504821A (ja) 2009-02-05
AU2006278152B2 (en) 2012-01-19
US8846784B2 (en) 2014-09-30
DE102005037777A1 (de) 2007-02-15
WO2007017286A1 (fr) 2007-02-15
CN101268028B (zh) 2012-09-05
JP5430934B2 (ja) 2014-03-05

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