EP1986976A1 - Additive building material mixtures comprising spray-dried microparticles - Google Patents

Additive building material mixtures comprising spray-dried microparticles

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Publication number
EP1986976A1
EP1986976A1 EP07712133A EP07712133A EP1986976A1 EP 1986976 A1 EP1986976 A1 EP 1986976A1 EP 07712133 A EP07712133 A EP 07712133A EP 07712133 A EP07712133 A EP 07712133A EP 1986976 A1 EP1986976 A1 EP 1986976A1
Authority
EP
European Patent Office
Prior art keywords
microparticles
polymeric
voided
concrete
building material
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Withdrawn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
EP07712133A
Other languages
German (de)
French (fr)
Inventor
Holger Kautz
Gerd LÖHDEN
Jan Hendrik Schattka
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.)
Evonik Roehm GmbH
Original Assignee
Evonik Roehm GmbH
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Filing date
Publication date
Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP1986976A1 publication Critical patent/EP1986976A1/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Withdrawn legal-status Critical Current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
    • 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
    • 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
    • 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
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/08—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons
    • C04B16/085—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons expanded in situ, i.e. during or after mixing the mortar, concrete or artificial stone ingredients
    • 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
    • C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
    • 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
    • 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
    • C04B2103/0057—Polymers chosen for their physico-chemical characteristics added as redispersable powders
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0058—Core-shell polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y10T428/249968—Of hydraulic-setting material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254—Polymeric or resinous material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • the present invention relates to the use of polymeric microparticles in hydraulically setting building material mixtures to improve their Frostg. Freeze-thaw resistance.
  • the concrete has two time-dependent properties. First, it experiences a decrease in volume due to dehydration, which is called shrinkage. However, most of the water is bound as water of crystallization. Concrete does not dry, it binds, that is, the initially low-viscosity cement paste (cement and water) stiffens, solidifies and finally solidifies, depending on the timing and sequence of the chemical-mineralogical reaction of the cement with the water, the hydration. Due to the water-binding capacity of the cement, the concrete, in contrast to calcined lime, can also harden under water and remain firm. Secondly, concrete deforms under load, the so-called creep.
  • the frost-thaw cycle refers to the climatic change of temperatures around the freezing point of water.
  • the frost-thaw cycle is a damaging mechanism. These materials have a porous, capillary structure and are not waterproof. If such, water-soaked structure exposed to temperatures below 0 0 C, the water freezes in the Pores. Due to the density anomaly of the water, the ice now expands. This leads to damage to the building material. In the very fine pores due to surface effects, the freezing point is lowered. In micro pores, water only freezes below -M 0 C. Since the material itself also expands and contracts due to freeze-thaw cycles, there is an additional capillary pumping effect that further increases water absorption and thus indirectly the damage. The number of freeze-thaw cycles is therefore decisive for the damage.
  • the structure of a cement-bound concrete is traversed by capillary pores (radius: 2 ⁇ m - 2 mm) or gel pores (radius: 2 - 50 nm). Pore water contained therein differs in its state form depending on the pore diameter.
  • a prerequisite for an improved resistance of the concrete during frost and thaw changes is that the distance of each point in the cement stone from the next artificial air pore does not exceed a certain value. This distance is also referred to as the "distance factor” or “powers spacing factor” [TCPowers, The air requirement of frost-resistant concrete, "Proceedings of the Highway Research Board” 29 (1949) 184-202]. Laboratory tests have shown that exceeding the critical "Power spacing factor" of 500 ⁇ m leads to damage to the concrete during frost and thaw cycles. In order to achieve this with a restricted air-pore content, the diameter of the artificially introduced air pores must therefore be less than 200-300 ⁇ m [K.Snyder, K. Natesaiyer & K.Hover, The stereological and Statistical properties of entrained air voids in concrete: A mathematical basis for air void system characterization) "Materials Science of Concrete” VI (2001) 129-214].
  • an artificial air pore system depends largely on the composition and grain size of the aggregates, the type and amount of cement, the concrete consistency, the mixer used, the mixing time, the temperature, but also on the type and amount of the air entraining agent. Under consideration of the appropriate manufacturing rules, their effects can indeed be mastered, however, there may be a large number of undesired impairments, which ultimately leads to the desired air content in the concrete can be exceeded or fallen below and thus adversely affected the strength or frost resistance of the concrete ,
  • Such artificial air pores can not be metered directly, but by the addition of so-called air-entraining agents, the air introduced by mixing is stabilized [L. Du & K.J. Folliard, Mechanism of air entrainment in concrete "Cement & Concrete Research” 35 (2005) 1463-71].
  • Conventional air entraining agents are mostly of a surfactant-like structure and break the air introduced by the mixing into small air bubbles with a diameter as small as possible of 300 ⁇ m and stabilize them in the moist concrete structure. One distinguishes between two types.
  • These hydrophobic salts reduce the surface tension of the water and accumulate at the interface between cement grain, air and water. They stabilize the microbubbles and are therefore found in the hardening concrete on the surfaces of these air pores again.
  • the other type e.g. Sodium lauryl sulfate (SDS) or Natriumdodecylphenylsulfonat - on the other hand forms with calcium hydroxide soluble calcium salts, but show an abnormal solution behavior. Below a certain critical temperature these surfactants show a very low solubility, above this temperature they are very soluble. By preferentially accumulating at the air-water interface, they also reduce the surface tension, thus stabilizing the microbubbles, and are preferably found on the surfaces of these air voids in the hardened concrete.
  • SDS Sodium lauryl sulfate
  • Natriumdodecylphenylsulfonat forms with calcium hydroxide soluble calcium salts, but show an abnormal solution behavior. Below a certain critical temperature these surfactants show a very low solubility, above this temperature they are very soluble.
  • microparticles described therein have diameters of at least 10 microns (usually much larger) and have air or gas-filled cavities. This also includes porous Particles, which can be greater than 100 microns and can have a variety of smaller cavities and / or pores.
  • the object was achieved by the use of polymeric microparticles having a cavity in hydraulically setting building material mixtures, characterized in that gas-filled microparticles are used. As gas-filled microparticles become spray-dried core. Shell polymers used. The gas-filled microparticles are already effective when mixed into the building material mixture, since no water must diffuse out of the particle interior. This ensures a good frost or freeze-thaw resistance virtually immediately after hardening of the building material mixtures.
  • the notation (meth) acrylate as used herein means both methacrylate, e.g. Methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, e.g. Methyl acrylate, ethyl acrylate, etc., as well as mixtures of both.
  • microparticles according to the invention can preferably be prepared by emulsion polymerization and preferably have an average particle size of 100 to 5000 nm; particularly preferred is an average particle size of 200 to 2000 nm. Most preferred are average particle sizes of 250 to 1000 nm.
  • the mean particle size is determined, for example, by counting a statistically significant amount of particles on the basis of transmission electron micrographs.
  • the microparticles When prepared by emulsion polymerization, the microparticles are obtained in the form of an aqueous dispersion.
  • microparticles are already known according to the prior art and are described in the publications EP 22 633 B1, EP 73 529 B1 and EP 188 325 B1.
  • these microparticles are commercially sold under the brand name ROPAQUE® by Rohm & Haas. These products have heretofore been mainly used in inks and inks to improve the opacity and opacity of paints or prints on paper, board and other materials.
  • the cavities of the microparticles are water-filled.
  • the dispersion is spray-dried. Spray drying removes the liquid from the core-shell polymer particles. There are obtained gas-filled hollow microspheres, which are very stable.
  • the microparticles used consist of polymer particles which have a core (A) and at least one shell (B), the core / shell polymer particles having been swollen with the aid of a base.
  • the core (A) of the particle contains one or more ethylenically unsaturated carboxylic acid (derivative) monomers which allow swelling of the core; these monomers are preferably selected from the group of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and crotonic acid and mixtures thereof. Acrylic acid and methacrylic acid are particularly preferred.
  • the shell (B) predominantly of nonionic, ethylenically unsaturated monomers.
  • Preferred such monomers are styrene, butadiene, vinyltoluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, C1-C12-alkyl esters of (meth) acrylic acid or mixtures thereof.
  • the gas-filled microparticles are added to the building material mixture in a preferred amount of from 0.01 to 5% by volume, in particular from 0.1 to 0.5% by volume.
  • the building material mixture - for example in the form of concrete or mortar - can here the usual hydraulically setting binder such.
  • cement lime, gypsum or anhydrite.
  • the advantage according to the invention is manifested above all in the weathering factor, which represents a qualitative assessment of the optically visible frost damage on the surface of a sample.
  • the uncontrolled introduction of air into the building material mixture can be kept extremely low.

Abstract

The invention relates to the use of polymeric microparticles which are filled with gas, in hydraulically setting building material mixtures for improving their freeze resistance and freeze-thaw resistance.

Description

Additive Baustoffmischungen mit sprühgetrockneten Mikropartikeln Additive building material mixtures with spray-dried microparticles
Die vorliegende Erfindung betrifft die Verwendung von polymeren Mikropartikeln in hydraulisch abbindenden Baustoffgemischen zur Verbesserung deren Frostbzw. Frost-Tauwechsel-Beständigkeit.The present invention relates to the use of polymeric microparticles in hydraulically setting building material mixtures to improve their Frostbzw. Freeze-thaw resistance.
Beton als wichtiger Baustoff ist nach DIN 1045 (07/1988) definiert als künstlicher Stein, der aus einem Gemisch von Zement, Betonzuschlag und Wasser, gegebenenfalls auch mit Betonzusatzmitteln und Betonzusatzstoffen, durch Erhärten entsteht. Beton ist u.a. eingeteilt in Festigkeitsgruppen (BI-BII) und Festigkeitsklassen (B5-B55). Beim Zumischen von gas- oder schaumbildenden Stoffen entsteht Porenbeton bzw. Schaumbeton (Römpp Lexikon, 10.Aufl., 1996, Georg Thieme Verlag).Concrete as an important building material is according to DIN 1045 (07/1988) defined as artificial stone, which is formed by a mixture of cement, concrete aggregate and water, possibly also with concrete admixtures and concrete admixtures, by hardening. Concrete is u.a. divided into strength groups (BI-BII) and strength classes (B5-B55). When admixing gas or foam-forming substances produced aerated concrete or foam concrete (Römpp Lexikon, 10th edition, 1996, Georg Thieme Verlag).
Der Beton hat zwei zeitabhängige Eigenschaften. Erstens erfährt er durch die Austrocknung eine Volumenabnahme, die als Schwinden bezeichnet wird. Der größte Teil des Wassers wird jedoch als Kristallwasser gebunden. Beton trocknet nicht, er bindet ab, d.h., der zunächst dünnflüssige Zementleim (Zement und Wasser) steift an, erstarrt und wird schließlich fest, je nach Zeitpunkt und Ablauf der chemisch-mineralogischen Reaktion des Zements mit dem Wasser, der Hydratation. Durch das Wasserbindevermögen des Zements kann der Beton, im Gegensatz zum gebrannten Kalk, auch unter Wasser erhärten und fest bleiben. Zweitens verformt sich Beton unter Last, das sogenannte Kriechen.The concrete has two time-dependent properties. First, it experiences a decrease in volume due to dehydration, which is called shrinkage. However, most of the water is bound as water of crystallization. Concrete does not dry, it binds, that is, the initially low-viscosity cement paste (cement and water) stiffens, solidifies and finally solidifies, depending on the timing and sequence of the chemical-mineralogical reaction of the cement with the water, the hydration. Due to the water-binding capacity of the cement, the concrete, in contrast to calcined lime, can also harden under water and remain firm. Secondly, concrete deforms under load, the so-called creep.
Der Frost-Tau-Wechsel bezeichnet den klimatischen Wechsel von Temperaturen um den Gefrierpunkt von Wasser. Insbesondere bei mineralisch gebundenen Baustoffen wie Beton ist der Frost-Tau-Wechsel ein Schädigungsmechanismus. Diese Werkstoffe besitzen eine poröse, kapillare Struktur und sind nicht wasserdicht. Wird eine solche, mit Wasser getränkte Struktur Temperaturen unter 00C ausgesetzt, so gefriert das Wasser in den Poren. Durch die Dichteanomalie des Wassers dehnt sich das Eis nun aus. Dadurch kommt es zu einer Schädigung des Baustoffs. In den sehr feinen Poren kommt es aufgrund von Oberflächeneffekten zu einer Erniedrigung des Gefrierpunktes. In Mikroporen gefriert Wasser erst unter -M0C. Da sich durch Frost-Tau-Wechsel auch der Werkstoff selbst ausdehnt und zusammenzieht, kommt es zusätzlich zu einem kapillaren Pumpeffekt, der die Wasseraufnahme, und damit indirekt die Schädigung weiter steigert. Für die Schädigung ist somit die Anzahl der Frost-Tau-Wechsel entscheidend.The frost-thaw cycle refers to the climatic change of temperatures around the freezing point of water. Especially with mineral-bound building materials such as concrete, the frost-thaw cycle is a damaging mechanism. These materials have a porous, capillary structure and are not waterproof. If such, water-soaked structure exposed to temperatures below 0 0 C, the water freezes in the Pores. Due to the density anomaly of the water, the ice now expands. This leads to damage to the building material. In the very fine pores due to surface effects, the freezing point is lowered. In micro pores, water only freezes below -M 0 C. Since the material itself also expands and contracts due to freeze-thaw cycles, there is an additional capillary pumping effect that further increases water absorption and thus indirectly the damage. The number of freeze-thaw cycles is therefore decisive for the damage.
Für den Widerstand des Betons gegen Frost und Frost-Tauwechsel bei gleichzeitiger Einwirkung von Taumitteln sind die Dichtigkeit seines Gefüges, eine bestimmte Festigkeit der Matrix und das Vorhandensein eines bestimmten Porengefüges maßgebend. Das Gefüge eines zementgebundenen Betons wird von Kapillarporen (Radius: 2 μm - 2mm) bzw. Gelporen (Radius: 2 - 50 nm) durchzogen. Darin enthaltenes Porenwasser unterscheidet sich in seiner Zustandsform in Abhängigkeit vom Porendurchmesser. Während Wasser in den Kapillarporen seine gewöhnlichen Eigenschaften beibehält, klassifiziert man in den Gelporen nach kondensiertem Wasser (Mesoporen: 50 nm) und adsorptiv gebundenem Oberflächenwasser (Mikroporen: 2 nm), deren Gefrierpunkte beispielsweise weit unter -500C liegen kann [M.J.Setzer, Interaction of water with hardened cement paste, "Ceramic Transactions" 16 (1991 ) 415-39]. Das hat zur Folge, dass selbst bei tiefen Abkühlungen des Betons ein Teil des Porenwassers ungefroren bleibt (metastabiles Wasser). Bei gleicher Temperatur ist aber der Dampfdruck über Eis geringer als der über Wasser. Da Eis und metastabiles Wasser gleichzeitig nebeneinander vorliegen, entsteht ein Dampfdruckgefälle, das zu einer Diffusion des noch flüssigen Wassers zum Eis und zu dessen Eisbildung führt, wodurch eine Entwässerung der kleineren bzw. eine Eisansammlung in den größeren Poren stattfindet. Diese Wasserumverteilung infolge Abkühlung findet in jedem porigen System statt und ist maßgeblich von der Art der Porenverteilung abhängig. Die künstliche Einführung von mikrofeinen Luftporen im Beton erzeugt also in erster Linie sogenannte Entspannungsräume für expandierendes Eis und Eiswasser. In diesen Poren kann gefrierendes Porenwasser expandieren bzw. internen Druck und Spannungen von Eis und Eiswasser auffangen, ohne dass es zu Mikrorissbildungen und damit zu Frostschäden am Beton kommt. Die prinzipielle Wirkungsweise solcher Luftporensysteme ist im Zusammenhang mit dem Mechanismus der Frostschädigung von Beton in einer Vielzahl von Übersichten beschrieben worden [Schulson, Erland M. (1998) Ice damage to concrete. CRREL Special Report 98-6; S.Chatterji, Freezing of air-entrained cement-based materials and specific actions of air-entraining agents, "Cement & Concrete Composites" 25 (2003) 759-65; G.W.Scherer, J.Chen & J.Valenza, Methods for protecting concrete from freeze damage, US-Patent 6,485,560 B1 (2002); M.Pigeon, B.Zuber & J. Marchand, Freeze/thaw resistance, "Advanced Concrete Technology" 2 (2003) 11/1-11/17; B. Erlin & B. Mather, A new process by which cyclic freezing can damage concrete - the Erlin/Mather effect, "Cement & Concrete Research" 35 (2005) 1407-11].For the resistance of the concrete against frost and freezing-thawing with the simultaneous action of de-icing agents, the tightness of its structure, a certain strength of the matrix and the presence of a certain pore structure are decisive. The structure of a cement-bound concrete is traversed by capillary pores (radius: 2 μm - 2 mm) or gel pores (radius: 2 - 50 nm). Pore water contained therein differs in its state form depending on the pore diameter. While water retains in the capillary its usual properties, is classified into the gel pores by condensed water (mesopores: 50 nm) and adsorptively bound surface water (micropores: 2 nm), the freezing point may be, for example, far below -50 0 C [MJSetzer, Interaction of water with hardened cement paste, "Ceramic Transactions" 16 (1991) 415-39]. As a result, even with deep cooling of the concrete, part of the pore water remains unfrozen (metastable water). At the same temperature, however, the vapor pressure over ice is lower than that above water. Since ice and metastable water are present side by side at the same time, creates a vapor pressure gradient, which leads to a diffusion of the still liquid water to the ice and its ice formation, whereby a drainage of the smaller or an ice accumulation takes place in the larger pores. This redistribution of water due to cooling takes place in every porous system and is significantly dependent on the type of pore distribution. The artificial introduction of microfine air pores in concrete thus creates primarily so-called relaxation rooms for expanding ice and ice water. In these pores, freezing pore water can expand or absorb internal pressure and tensions of ice and ice water, without causing microcracking and thus frost damage to the concrete. The principal mode of action of such air-entrainment systems has been described in a large number of reviews in connection with the mechanism of frost damage to concrete [Schulson, Erland M. (1998) Ice damage to concrete. CRREL Special Report 98-6; S.Chatterji, Freezing of air-entrained cement-based materials and specific actions of air-entraining agents, "Cement & Concrete Composites" 25 (2003) 759-65; GW Scherer, J.Chen & J. Valenza, Methods for protecting concrete from freeze damage, US Patent 6,485,560 B1 (2002); M. Pigeon, B.Zuber & J. Marchand, Freeze / Thaw Resistance, "Advanced Concrete Technology" 2 (2003) 11 / 1-11 / 17; Erlin & B. Mather, A new process by which cyclic freezing can damage concrete - the Erlin / Mather effect, "Cement & Concrete Research" 35 (2005) 1407-11].
Voraussetzung für eine verbesserte Beständigkeit des Betons bei Frost- und Tauwechsel ist, dass der Abstand jedes Punktes im Zementstein von der nächsten künstlichen Luftpore einen bestimmten Wert nicht überschreitet. Dieser Abstand wird auch als Abstandsfaktor oder "Powers spacing factor" bezeichnet [T.C.Powers, The air requirement of frost-resistant concrete, "Proceedings of the Highway Research Board" 29 (1949) 184-202]. Laborprüfungen haben dabei gezeigt, dass ein Überschreiten des kritischen "Power spacing factor" von 500 μm zu einer Schädigung des Betons bei Frostund Tauwechsel führt. Um dies bei beschränktem Luftporengehalt zu erreichen, muss der Durchmesser der künstlich eingeführten Luftporen daher kleiner 200 - 300 μm sein [K.Snyder, K.Natesaiyer & K.Hover, The stereological and Statistical properties of entrained air voids in concrete: A mathematical basis for air void Systems characterization) "Materials Science of Concrete" VI (2001 ) 129-214].A prerequisite for an improved resistance of the concrete during frost and thaw changes is that the distance of each point in the cement stone from the next artificial air pore does not exceed a certain value. This distance is also referred to as the "distance factor" or "powers spacing factor" [TCPowers, The air requirement of frost-resistant concrete, "Proceedings of the Highway Research Board" 29 (1949) 184-202]. Laboratory tests have shown that exceeding the critical "Power spacing factor" of 500 μm leads to damage to the concrete during frost and thaw cycles. In order to achieve this with a restricted air-pore content, the diameter of the artificially introduced air pores must therefore be less than 200-300 μm [K.Snyder, K. Natesaiyer & K.Hover, The stereological and Statistical properties of entrained air voids in concrete: A mathematical basis for air void system characterization) "Materials Science of Concrete" VI (2001) 129-214].
Die Bildung eines künstlichen Luftporensystems hängt maßgeblich von der Zusammensetzung und der Kornformität der Zuschläge, der Art und Menge des Zements, der Betonkonsistenz, dem verwendeten Mischer, der Mischzeit, der Temperatur, aber auch von der Art und Menge des Luftporenbildners ab. Unter Berücksichtigung entsprechender Herstellungsregeln lassen sich deren Einflüsse zwar beherrschen, jedoch kann es zu einer Vielzahl von ungewünschten Beeinträchtigungen kommen, was letztendlich dazu führt, dass der gewünschte Luftgehalt im Beton über- oder unterschritten werden kann und somit die Festigkeit oder den Frostwiderstand des Betons negativ beeinflusst.The formation of an artificial air pore system depends largely on the composition and grain size of the aggregates, the type and amount of cement, the concrete consistency, the mixer used, the mixing time, the temperature, but also on the type and amount of the air entraining agent. Under consideration of the appropriate manufacturing rules, their effects can indeed be mastered, however, there may be a large number of undesired impairments, which ultimately leads to the desired air content in the concrete can be exceeded or fallen below and thus adversely affected the strength or frost resistance of the concrete ,
Solche künstlichen Luftporen lassen sich nicht direkt dosieren, sondern durch die Zugabe von sogenannten Luftporenbildnern wird die durch das Mischen eingetragene Luft stabilisiert [L. Du & K.J.Folliard, Mechanism of air entrainment in concrete "Cement & Concrete Research" 35 (2005) 1463-71]. Herkömmliche Luftporenbildner sind zumeist tensidartiger Struktur und brechen die durch das Mischen eingeführte Luft zu kleinen Luftbläschen mit einem Durchmesser möglichst kleiner 300 μm und stabilisieren diese im feuchten Betongefüge. Man unterscheidet dabei zwischen zwei Typen.Such artificial air pores can not be metered directly, but by the addition of so-called air-entraining agents, the air introduced by mixing is stabilized [L. Du & K.J. Folliard, Mechanism of air entrainment in concrete "Cement & Concrete Research" 35 (2005) 1463-71]. Conventional air entraining agents are mostly of a surfactant-like structure and break the air introduced by the mixing into small air bubbles with a diameter as small as possible of 300 μm and stabilize them in the moist concrete structure. One distinguishes between two types.
Der eine Typ - z.B. Natriumoleat, das Natriumsalz der Abietinsäure oder Vinsolharz, einem Extrakt aus Kiefernwurzeln - reagiert mit dem Calciumhydroxid der Porenlösung im Zementleim und fällt als unlösliches Calciumsalz aus. Diese hydrophoben Salze reduzieren die Oberflächenspannung des Wassers und sammeln sich an der Grenzfläche zwischen Zementkorn, Luft und Wasser. Sie stabilisieren die Mikrobläschen und finden sich daher im aushärtenden Beton an den Oberflächen dieser Luftporen wieder.One type - eg sodium oleate, the sodium salt of abietic acid or vinsol resin, an extract of pine roots - reacts with the calcium hydroxide of the pore solution in the cement paste and precipitates as insoluble calcium salt. These hydrophobic salts reduce the surface tension of the water and accumulate at the interface between cement grain, air and water. They stabilize the microbubbles and are therefore found in the hardening concrete on the surfaces of these air pores again.
Der andere Typ - z.B. Natrium-Iaurylsulfat (SDS) oder Natriumdodecylphenylsulfonat - bildet dagegen mit Calciumhydroxid lösliche Calciumsalze, die aber ein anormales Lösungsverhalten zeigen. Unter einer gewissen kritischen Temperatur zeigen diese Tenside eine sehr geringe Löslichkeit, oberhalb dieser Temperatur sind sie sehr gut löslich. Durch eine bevorzugtes Ansammeln an der Luft-Wasser-Grenzschicht verringern sie ebenfalls die Oberflächenspannung, stabilisieren somit die Mikrobläschen und sind bevorzugt an der Oberflächen dieser Luftporen im ausgehärteten Beton wiederzufinden.The other type - e.g. Sodium lauryl sulfate (SDS) or Natriumdodecylphenylsulfonat - on the other hand forms with calcium hydroxide soluble calcium salts, but show an abnormal solution behavior. Below a certain critical temperature these surfactants show a very low solubility, above this temperature they are very soluble. By preferentially accumulating at the air-water interface, they also reduce the surface tension, thus stabilizing the microbubbles, and are preferably found on the surfaces of these air voids in the hardened concrete.
Bei der Verwendung dieser Luftporenbildner nach dem Stand der Technik treten eine Vielzahl von Probleme auf [L. Du & K.J.Folliard, Mechanism of air entrainment in concrete "Cement & Concrete Research" 35 (2005) 1463-71. Beispielsweise können längere Mischzeiten, unterschiedliche Mischerdrehzahlen, veränderte Dosierabläufe bei den Transportbetonen dazu führen, dass die stabilisierte Luft (in den Luftporen) wieder ausgetrieben wird.The use of these prior art air entraining agents presents a variety of problems [L. Du & K.J. Folliard, Mechanism of air entrainment in concrete "Cement & Concrete Research" 35 (2005) 1463-71. For example, longer mixing times, different mixer speeds, changing metering sequences in the case of ready-mixed concrete can lead to the stabilized air being expelled again (in the air pores).
Die Beförderung von Betonen mit verlängerten Transportzeiten, schlechter Temperierung und unterschiedlichen Pump- und Fördereinrichtungen, sowie das Einbringen dieser Betone einhergehend mit veränderter Nachbearbeitung, Ruckelverhalten und Temperaturbedingungen kann einen zuvor eingestellten Luftporengehalt signifikant verändern. Das kann im schlimmsten Fall bedeuten, dass ein Beton die erforderlichen Grenzwerte einer bestimmten Expositionsklasse nicht mehr erfüllt und somit unbrauchbar geworden ist [EN 206-1 (2000), Concrete - Part 1 : Secification, Performance, production and conformity]. Der Gehalt an feinen Stoffen im Beton (z.B. Zement mit unterschiedlichem Alkaligehalt, Zusatzstoffe wie Flugasche, Silikastaub, oder Farbzusätze) beeinträchtigt die Luftporenbildung ebenfalls. Auch können Wechselwirkungen mit entschäumend wirkenden Fließmitteln auftreten, die somit Luftporen austreiben, aber auch zusätzlich unkontrolliert einführen können.The transport of concretes with extended transport times, poor temperature control and different pumping and conveying devices, as well as the introduction of these concretes along with modified post-processing, jerking behavior and temperature conditions can significantly change a previously set air pore content. In the worst case, this may mean that a concrete no longer fulfills the required limit values of a specific exposure class and has therefore become unusable [EN 206-1 (2000), Concrete - Part 1: Secification, Performance, Production and Conformity]. The content of fine substances in the concrete (eg cement with different alkali content, additives such as fly ash, silica fume, or color additives) also affects the air entrainment. Also, interactions with defoaming agents can occur, which thus expel air voids, but also can introduce uncontrolled.
Als Nachteil des Einbringens von Luftporen ist außerdem zu sehen, daß die mechanische Festigkeit des Betons mit steigendem Luftgehalt abnimmt.As a disadvantage of the introduction of air pores is also seen that the mechanical strength of the concrete decreases with increasing air content.
All diese die Herstellung von frostbeständigen Beton erschwerenden Einflüsse lassen sich vermeiden, wenn das erforderliche Luftporensystem nicht durch o.g. Luftporenbildner mit tensidartiger Struktur erzeugt wird, sondern der Luftgehalt durch das Zumischen bzw. feste Dosieren von polymeren Mikropartikeln (Mikrohohlkugeln) herrührt [H.Sommer, A new method of making concrete resistant to frost and de-icing salts, "Betonwerk & Fertigteiltechnik" 9 (1978) 476-84]. Da die Mikropartikel zumeist Partikelgrößen kleiner 100 μm aufweisen, lassen sie sich im Betongefüge auch feiner und gleichmäßiger als künstlich eingeführte Luftporen verteilen. Dadurch reichen bereits geringe Mengen für einen ausreichenden Widerstand des Betons gegen Frost- und Tauwechsel aus.All of these influences, which make aggravating the production of frost-resistant concrete, can be avoided if the required air pore system is not prevented by o.g. Air entraining agent is produced with surfactant-like structure, but the air content by admixing or solid metering of polymeric microparticles (hollow microspheres) stems [H.Sommer, A new method of making concrete resistant to frost and de-icing salts, "Concrete Plant & Precast Technology" 9 (1978) 476-84]. Since the microparticles usually have particle sizes smaller than 100 μm, they can also be distributed finer and more uniformly than artificially introduced air pores in the concrete structure. As a result, even small amounts are sufficient for a sufficient resistance of the concrete against freezing and thawing.
Die Verwendung von solchen polymeren Mikropartikeln zur Verbesserung der Frost- und Frost-Tauwechsel-Beständigkeit von Beton ist entsprechend dem Stand der Technik bereits bekannt [vgl. DE 2229094 A1 , US 4,057,526 B1 , US 4,082,562 B1 , DE 3026719 A1]. Die darin beschriebenen Mikropartikel haben Durchmesser von mindestens 10 μm (üblicherweise deutlich größer) und besitzen luft- bzw. gasgefüllte Hohlräume. Das schließt ebenfalls poröse Partikel ein, die größer 100 μm sein können und eine Vielzahl an kleineren Hohlräumen und/oder Poren besitzen können.The use of such polymeric microparticles to improve the frost and freeze-thaw resistance of concrete is already known according to the prior art [cf. DE 2229094 A1, US Pat. No. 4,057,526 B1, US Pat. No. 4,082,562 B1, DE 3026719 A1]. The microparticles described therein have diameters of at least 10 microns (usually much larger) and have air or gas-filled cavities. This also includes porous Particles, which can be greater than 100 microns and can have a variety of smaller cavities and / or pores.
Bei der Verwendung von hohlen Mikropartikeln zur künstlichen Luftporenbildung im Beton erwiesen sich zwei Faktoren nachteilig für die Durchsetzung dieser Technologie auf dem Markt aus. Zum einen ist sowohl aus Umwelt- als auch Kostengesichtspunkten der Einsatz von organischen Lösungsmitteln bedenklich, und zum anderen ist nur mit relativ hohen Dosierungen eine zufrieden stellende Resistenz des Betons gegenüber Frost- und Tauwechseln zu erzielen. Der vorliegenden Erfindung lag daher die Aufgabe zu Grunde, ein Mittel zur Verbesserung der Frost- bzw. Frost-Tauwechsel-Beständigkeit für hydraulisch abbindende Baustoffmischungen bereitzustellen, welche auch bei relativ geringen Dosierungen seine volle Wirksamkeit entfaltet. Bestandteil der Aufgabe war es, die volle Wirksamkeit dieses Mittels sofort nach dem Einarbeiten in die Baumischung zu erhalten.When using hollow microparticles for artificial air entrainment in concrete, two factors proved detrimental to the enforcement of this technology in the marketplace. On the one hand, the use of organic solvents is questionable both from an environmental and a cost point of view, and secondly, only with relatively high dosages can a satisfactory resistance of the concrete to frost and thaw cycles be achieved. The present invention was therefore based on the object to provide a means for improving the frost or freeze-thaw resistance for hydraulically setting building material mixtures, which unfolds its full effectiveness even at relatively low dosages. Part of the task was to obtain the full effectiveness of this agent immediately after incorporation into the construction mixture.
Die Aufgabe wurde gelöst durch die Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikeln in hydraulisch abbindenden Baustoffmischungen, dadurch gekennzeichnet, dass gasgefüllte Mikropartikel verwendet werden. Als gasgefüllte Mikropartikel werden sprühgetrocknete Kern. Schale-Polymerisate verwendet. Die gasgefüllten Mikropartikel sind bereits beim Einmischen in die Baustoffmischung wirksam, da kein Wasser aus dem Partikelinneren herausdiffundieren muß. Damit ist eine gute Frost- bzw. Frost-Tauwechsel-Beständigkeit praktisch sofort nach dem Erhärten der Baustoffmischungen gewährleistet.The object was achieved by the use of polymeric microparticles having a cavity in hydraulically setting building material mixtures, characterized in that gas-filled microparticles are used. As gas-filled microparticles become spray-dried core. Shell polymers used. The gas-filled microparticles are already effective when mixed into the building material mixture, since no water must diffuse out of the particle interior. This ensures a good frost or freeze-thaw resistance virtually immediately after hardening of the building material mixtures.
Es wurde gefunden, dass durch Sprühtrocknung den Mikropartikel- Dispersionen das Wasser entzogen werden kann. Überraschend wurde gefunden, dass somit schnell und kostengünstig intakte gasgefüllte Mikrohohlkugeln gewonnen werden können. Hierdurch wird der logistische Aufwand für den Transport und die Verarbeitung erheblich reduziert. Die so erhaltenen Pulver lassen sich problemlos in Baustoffmischungen dosieren.It has been found that the water can be removed from the microparticle dispersions by spray-drying. It was surprising found that thus intact gas-filled hollow microspheres can be obtained quickly and inexpensively. As a result, the logistical effort for transport and processing is significantly reduced. The powders thus obtained can be readily metered into building material mixtures.
Die Schreibweise (Meth)acrylat bedeutet hier sowohl Methacrylat, wie z.B. Methylmethacrylat, Ethylmethacrylat usw., als auch Acrylat, wie z.B. Methylacrylat, Ethylacrylat usw., sowie Mischungen aus beiden.The notation (meth) acrylate as used herein means both methacrylate, e.g. Methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, e.g. Methyl acrylate, ethyl acrylate, etc., as well as mixtures of both.
Die erfindungsgemäßen Mikropartikel können vorzugsweise durch Emulsionspolymerisation hergestellt werden und weisen vorzugsweise eine mittlere Teilchengröße von 100 bis 5000 nm auf; besonders bevorzugt ist eine mittlere Teilchengröße von 200 bis 2000 nm. Am meisten bevorzugt sind mittlere Teilchengrößen von 250 bis 1000 nm.The microparticles according to the invention can preferably be prepared by emulsion polymerization and preferably have an average particle size of 100 to 5000 nm; particularly preferred is an average particle size of 200 to 2000 nm. Most preferred are average particle sizes of 250 to 1000 nm.
Die Bestimmung der mittleren Teilchengröße erfolgt zum Beispiel durch Auszählung einer statistisch signifikanten Menge an Partikeln anhand von transmissionselektronenmikroskopischen Aufnahmen.The mean particle size is determined, for example, by counting a statistically significant amount of particles on the basis of transmission electron micrographs.
Bei der Herstellung durch Emulsionspolymerisation werden die Mikropartikel in Form einer wäßrigen Dispersion erhalten.When prepared by emulsion polymerization, the microparticles are obtained in the form of an aqueous dispersion.
Derartige Mikropartikel sind entsprechend dem Stand der Technik bereits bekannt und in den Druckschriften EP 22 633 B1 , EP 73 529 B1 sowie EP 188 325 B1 beschrieben. Außerdem werden diese Mikropartikel unter dem Markennamen ROPAQUE® von der Fa. Rohm & Haas kommerziell vertrieben. Diese Produkte fanden bislang hauptsächlich ihre Verwendung in Tinten und Farben zur Verbesserung der Deckfähigkeit und Lichtundurchlässigkeit (Opazität) von Anstrichen oder Drucken auf Papier, Pappen und anderen Materialien. Bei der Herstellung und in der Dispersion sind die Hohlräume der Mikropartikel wassergefüllt. Erfindungsgemäß wird die Dispersion sprühgetrocknet. Über die Sprühtrocknung wird den Kern-Schale-Polymerteilchen die Flüssigkeit entzogen. Es werden gasgefüllte Mikrohohlkugeln erhalten, die sehr stabil sind.Such microparticles are already known according to the prior art and are described in the publications EP 22 633 B1, EP 73 529 B1 and EP 188 325 B1. In addition, these microparticles are commercially sold under the brand name ROPAQUE® by Rohm & Haas. These products have heretofore been mainly used in inks and inks to improve the opacity and opacity of paints or prints on paper, board and other materials. During production and in the dispersion, the cavities of the microparticles are water-filled. According to the invention, the dispersion is spray-dried. Spray drying removes the liquid from the core-shell polymer particles. There are obtained gas-filled hollow microspheres, which are very stable.
Gemäß einer bevorzugten Ausführungsform bestehen die eingesetzten Mikropartikel aus Polymerteilchen, die einen Kern (A) und mindestens eine Schale (B) besitzen, wobei die Kern/Schale-Polymerteilchen mit Hilfe einer Base gequollen wurden.According to a preferred embodiment, the microparticles used consist of polymer particles which have a core (A) and at least one shell (B), the core / shell polymer particles having been swollen with the aid of a base.
Der Kern (A) des Partikels enthält eine oder mehrere ethylenisch ungesättigte Carbonsäure-(Derivat-)Monomere die eine Quellung des Kerns ermöglichen; diese Monomere sind vorzugsweise ausgewählt aus der Gruppe Acrylsäure, Methacrylsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure und Crotonsäure und deren Mischungen. Acrylsäure und Methacrlysäure sind besonders bevorzugt.The core (A) of the particle contains one or more ethylenically unsaturated carboxylic acid (derivative) monomers which allow swelling of the core; these monomers are preferably selected from the group of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and crotonic acid and mixtures thereof. Acrylic acid and methacrylic acid are particularly preferred.
Die Schale (B) überwiegend aus nicht-ionischen, ethylenisch ungesättigten Monomeren. Als solche Monomere werden bevorzugt Styrol, Butadien, Vinyltoluol, Ethylen, Vinylacetat, Vinylchlorid, Vinylidenchlorid, Acrylnitril, Acrylamid, Methacrylamid, C1-C12-Alkylester der (Meth)acrylsäure oder Mischungen daraus eingesetzt.The shell (B) predominantly of nonionic, ethylenically unsaturated monomers. Preferred such monomers are styrene, butadiene, vinyltoluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, C1-C12-alkyl esters of (meth) acrylic acid or mixtures thereof.
Die Herstellung dieser polymeren Mikropartikel durch Emulsionspolymerisation sowie deren Quellung mit Hilfe von Basen wie z. B. Alkali- oder Alkalihydroxide sowie Ammoniak oder einem Amin werden ebenfalls in den europäischen Patentschriften EP 22 633 B1 , EP 735 29 B1 sowie EP 188 325 B1 beschrieben. Es können Kern-Schale Teilchen dargestellt werden, die ein- oder mehrschalig aufgebaut sind, oder deren Schalen einen Gradienten aufweisen. Der Polymergehalt der eingesetzten Mikropartikel kann - abhängig z.B. vom Durchmesser, dem Kern/Schale-Verhältnis und der Effizienz der Quellung - bei 2 bis 98 Vol. -% liegen.The preparation of these polymeric microparticles by emulsion polymerization and their swelling using bases such. As alkali or alkali metal hydroxides and ammonia or an amine are also described in European patents EP 22 633 B1, EP 735 29 B1 and EP 188 325 B1. It can be represented core-shell particles, which are mono- or multi-shelled, or whose shells have a gradient. Depending on the diameter, the core / shell ratio and the efficiency of the swelling, the polymer content of the microparticles used can be from 2 to 98% by volume.
Die gasgefüllten Mikropartikel werden der Baustoffmischung in einer bevorzugten Menge von 0,01 bis 5 Vol%, insbesondere 0,1 bis 0,5 Vol%, zugegeben. Die Baustoffmischung - zum Beispiel in Form von Beton oder Mörtel - kann hierbei die üblichen hydraulisch abbindenden Bindemittel wie z. B. Zement, Kalk, Gips oder Anhydrit enthalten.The gas-filled microparticles are added to the building material mixture in a preferred amount of from 0.01 to 5% by volume, in particular from 0.1 to 0.5% by volume. The building material mixture - for example in the form of concrete or mortar - can here the usual hydraulically setting binder such. As cement, lime, gypsum or anhydrite.
Bei Baustoffmischungen, die sehr schnell nach dem Erhärten einer Frost/Tau- Belastung ausgesetzt sind zeigt sich der erfindungsgemäße Vorteil vor allem im Abwitterungsfaktor, welcher eine qualitative Beurteilung für die optisch sichtbaren Frostschäden an der Oberfläche einer Probe darstellt.For building material mixtures which are exposed to a frost / thaw load very quickly after hardening, the advantage according to the invention is manifested above all in the weathering factor, which represents a qualitative assessment of the optically visible frost damage on the surface of a sample.
Durch die Verwendung der erfindungsgemäßen Mikropartikel kann der unkontrollierte Lufteintrag in die Baustoffmischung außerordentlich niedrig gehalten werden.By using the microparticles according to the invention, the uncontrolled introduction of air into the building material mixture can be kept extremely low.
An Beton wurden z.B. Verbesserungen der Druckfestigkeiten von über 35 % festgestellt, verglichen mit Beton, der mit herkömmlicher Luftporenbildung erhalten wurde.On concrete, e.g. Improved compressive strengths of over 35% compared to concrete obtained with conventional air entrainment.
Höhere Druckfestigkeiten sind auch und vor allem in sofern von Interesse, als der für die Festigkeitsentwicklung erforderliche Gehalt an Zement im Beton verringert werden kann, wodurch der Preis pro m3 Beton signifikant gesenkt werden kann. Higher compressive strengths are also and especially in so far of interest, as the required strength for the development of cement content in the concrete can be reduced, whereby the price per m 3 of concrete can be significantly reduced.

Claims

PATENTANSPRÜCHE
1. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikeln in hydraulisch abbindenden Baustoffmischungen, dadurch gekennzeichnet, dass gasgefüllte Mikropartikel verwendet werden.1. Use of polymeric, voided microparticles in hydraulically setting building material mixtures, characterized in that gas-filled microparticles are used.
2. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikeln nach Anspruch 1 , dadurch gekennzeichnet, dass sprühgetrocknete Kern-Schale-Polymerisate verwendet werden.2. Use of polymeric, voided microparticles according to claim 1, characterized in that spray-dried core-shell polymers are used.
3. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikeln nach Anspruch 1 , dadurch gekennzeichnet, dass die Mikropartikel aus Polymerteilchen bestehen, die einen mit Hilfe einer wässrigen Base gequollenen Polymerkern (A), der eine oder mehrere ungesättigte Carbonsäure-(Derivat-)Monomers enthält, sowie eine Polymerhülle (B), die überwiegend aus nicht-ionischen, ethylenisch ungesättigten Monomeren besteht, enthalten..The use of polymeric voided microparticles according to claim 1, characterized in that the microparticles consist of polymer particles containing a polymer nucleus (A) swollen by means of an aqueous base containing one or more unsaturated carboxylic acid (derivative) monomers , and a polymer shell (B), which consists predominantly of nonionic, ethylenically unsaturated monomers ..
4. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikeln nach Anspruch 3, dadurch gekennzeichnet, dass die ungesättigten Carbonsäure-(derivat-)monomere gewählt sind aus der Gruppe Acrylsäure, Methacrylsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure und Crotonsäure. 4. Use of polymeric, voided microparticles according to claim 3, characterized in that the unsaturated carboxylic acid (derivative) monomers are selected from the group of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and crotonic acid.
5. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikeln nach Anspruch 3, dadurch gekennzeichnet, dass die nichtionischen, ethylenisch ungesättigten Monomere aus Styrol, Butadien, Vinyltoluol, Ethylen, Vinylacetat, Vinylchlorid, Vinylidenchlorid, Acrylnitril, Acrylamid, Methacrylamid, C1-C12-Alkylester der Acryl- oder Methacrylsäure bestehen.5. Use of polymeric, voided microparticles according to claim 3, characterized in that the nonionic, ethylenically unsaturated monomers of styrene, butadiene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, C1-C12 alkyl esters consist of acrylic or methacrylic acid.
6. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikel nach Anspruch 1 , dadurch gekennzeichnet, dass die Mikropartikel einen Polymergehalt von 2 bis 98 Vol.-% aufweisen.6. Use of polymeric, voided microparticles according to claim 1, characterized in that the microparticles have a polymer content of 2 to 98 vol .-%.
7. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikel nach Anspruch 1 , dadurch gekennzeichnet, dass die Mikropartikel eine mittlere Teilchengröße von 100 bis 5000 nm aufweisen.7. Use of polymeric, voided microparticles according to claim 1, characterized in that the microparticles have an average particle size of 100 to 5000 nm.
8. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikel nach Anspruch 7, dadurch gekennzeichnet, dass die Mikropartikel eine mittlere Teilchengröße von 200 bis 2000 nm aufweisen.8. Use of polymeric, voided microparticles according to claim 7, characterized in that the microparticles have an average particle size of 200 to 2000 nm.
9. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikel nach Anspruch 8, dadurch gekennzeichnet, dass die Mikropartikel eine mittlere Teilchengröße von 250 bis 1000 nm aufweisen.9. Use of polymeric, voided microparticles according to claim 8, characterized in that the microparticles have an average particle size of 250 to 1000 nm.
10. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikel nach Anspruch 1 , dadurch gekennzeichnet, dass die Mikropartikel in einer Menge von 0.01 bis 5 Vol.-%, bezogen auf die Baustoffmischung eingesetzt werden. 10. Use of polymeric, voided microparticles according to claim 1, characterized in that the microparticles are used in an amount of 0.01 to 5 vol .-%, based on the building material mixture.
11. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikel nach Anspruch 10, dadurch gekennzeichnet, dass die Mikropartikel in einer Menge von 0.1 bis 0.5 Vol.-%, bezogen auf die Baustoffmischung, eingesetzt werden.11. Use of polymeric, voided microparticles according to claim 10, characterized in that the microparticles in an amount of 0.1 to 0.5 vol .-%, based on the building material mixture, are used.
12. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikel nach Anspruch 1 , dadurch gekennzeichnet, dass die Baustoffmischungen aus einem Bindemittel, ausgewählt aus der Gruppe Zement, Kalk, Gips und Anhydrit, bestehen.12. Use of polymeric, voided microparticles according to claim 1, characterized in that the building material mixtures consist of a binder selected from the group consisting of cement, lime, gypsum and anhydrite.
13. Verwendung von polymeren, einen Hohlraum aufweisenden Mikropartikel nach Anspruch 1 , dadurch gekennzeichnet, dass es sich bei den Baustoffmischungen um Beton oder Mörtel handelt. 13. Use of polymeric microparticles having a cavity according to claim 1, characterized in that the building material mixtures are concrete or mortar.
EP07712133A 2006-02-23 2007-01-30 Additive building material mixtures comprising spray-dried microparticles Withdrawn EP1986976A1 (en)

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DE200610008966 DE102006008966A1 (en) 2006-02-23 2006-02-23 Additive building material mixtures with spray-dried microparticles
PCT/EP2007/050907 WO2007096235A1 (en) 2006-02-23 2007-01-30 Additive building material mixtures comprising spray-dried microparticles

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KR20080112206A (en) 2008-12-24
JP5065302B2 (en) 2012-10-31
CA2643456A1 (en) 2007-08-30
US20070193156A1 (en) 2007-08-23
CN101024557B (en) 2012-12-05
CN101024557A (en) 2007-08-29
RU2008137544A (en) 2010-03-27
BRPI0708118A2 (en) 2011-05-17
WO2007096235A1 (en) 2007-08-30
DE102006008966A1 (en) 2007-08-30

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