EP1986975A2 - Additive baustoffmischungen mit nichtionischen emulgatoren - Google Patents

Additive baustoffmischungen mit nichtionischen emulgatoren

Info

Publication number
EP1986975A2
EP1986975A2 EP07704252A EP07704252A EP1986975A2 EP 1986975 A2 EP1986975 A2 EP 1986975A2 EP 07704252 A EP07704252 A EP 07704252A EP 07704252 A EP07704252 A EP 07704252A EP 1986975 A2 EP1986975 A2 EP 1986975A2
Authority
EP
European Patent Office
Prior art keywords
microparticles
polymeric
voided
building material
concrete
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Withdrawn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
EP07704252A
Other languages
German (de)
English (en)
French (fr)
Inventor
Holger Kautz
Jan Hendrik Schattka
Gerd LÖHDEN
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
Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm 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 Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP1986975A2 publication Critical patent/EP1986975A2/de
Withdrawn legal-status Critical Current

Links

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
    • 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
    • C04B16/082—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons other than polystyrene based, e.g. polyurethane foam
    • 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
    • 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
    • C04B20/0016—Granular materials, e.g. microballoons
    • C04B20/002—Hollow or porous granular materials
    • C04B20/0024—Hollow or porous granular materials expanded in situ, i.e. the material is expanded or made hollow after primary shaping of the mortar, concrete or artificial stone mixture
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • 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
    • 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
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/29—Frost-thaw resistance

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. Second, 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 limited 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 dosed directly, but by the addition of so-called air entraining agents, the air introduced by the 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 therefore find themselves in the hardening concrete on the surfaces of these air pores again.
  • the other type e.g. Sodium lauryl sulfate (SDS) or sodium dodecyl phenylsulfonate - 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
  • sodium dodecyl phenylsulfonate 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.
  • the content of fine substances in concrete also affects air entrainment. Also, interactions with defoaming agents can occur, which thus expel air voids, but also can introduce uncontrolled.
  • 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 may be greater than 100 microns and may have a plurality of smaller voids and / or pores.
  • the production costs of hollow microspheres according to the prior art are too high and, on the other hand, 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 develops its full effectiveness even at relatively low dosages.
  • An additional object was not or not significantly affect the mechanical strength of the cured construction mixture by this means.
  • the object has been achieved by the use of polymeric microparticles having a cavity in hydraulically setting building material mixtures, characterized in that the microparticles are stabilized by nonionic emulsifiers.
  • non-ionic emulsifiers significantly reduced the foaming tendency in the dispersion as well as in the building material mixture.
  • a reduced foaming tendency is advantageous because thus less air is introduced into the building material mixtures, which in turn leads to a smaller impairment of the mechanical strength of the cured building material mixture.
  • Nonionic emulsifiers are surface-active substances (surfactants) with an uncharged, in the neutral pH range no ion charge-carrying, polar, hydrophilic water-solubilizing group (s) adsorbing at interfaces and aggregating above the critical micelle concentration to neutral micelles.
  • the nonionic emulsifiers used are preferably selected from the group of emulsifiers whose hydrophilic group (s) belong to the alcohols, amine oxides, or (oligo) oxyalkylenes or mixtures thereof.
  • the alkyl polyglucosides sucrose esters, sorbitan esters, acetylenediols, alkanediols and fatty acid N-methylglucamides are preferred.
  • the alkyldimethylamine oxides are preferred from the group of amine oxides.
  • the (oligo) oxyethylene groups are particularly preferred. These include in particular fatty alcohol polyglycol ethers (fatty alcohol ethoxylates), alkylphenol polyglycol ethers and fatty acid ethoxylates, fatty amine ethoxylates, ethoxylated triglycerides and mixed ethers (polyethylene alkylated on both sides).
  • block copolymers which can be used according to the invention are for example: linear systems such as AB, ABA, BAB or AB) n , star-shaped systems such as A (B) n , B (A) n or (A) n -BA- (B) m , dendrimer systems such as ((A) n -B) 1n A, ((B) n -A) 1n B, (((A) m -B) n A) p B or (((B) m -A) n B) p A or comb-like systems such as ((A) n -A (B)) q , or ((B) n -B (A)) q , where m, n, p and q symbolize integers greater than 1.
  • hydrophobic blocks are poly (propylene oxide), poly (siloxanes) and poly (alkanes) e.
  • the nonionic emulsifiers according to the invention are used in amounts of ⁇ 5% by weight, more preferably of ⁇ 3% by weight and most preferably ⁇ 1% by weight, based on the polymer content of the microparticles.
  • 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 a 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. Accordingly, the addition of the microparticles to the building material mixture preferably also takes place in this form, with nonionic emulsifiers in particular being present in the dispersion.
  • nonionic emulsifiers are added to the dispersion during or after the preparation.
  • 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. Without limiting the invention to the effect, it is assumed that the water, the particles in setting the Building material mixture - at least partially - loses, according to which gas or air-filled hollow spheres are present.
  • This process takes place e.g. also in the use of such microparticles in paints instead.
  • the microparticles used consist of polymer particles which have a polymer core (A) which has been swollen with the aid of an aqueous base and at least one polymer shell or shell (B).
  • 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) consists predominantly of nonionic, ethylenically unsaturated monomers. As such, preference is given to using 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 polymer content of the microparticles used may vary depending on e.g. from the diameter, the core / shell ratio and the efficiency of swelling - are 2 to 98 wt .-%.
  • the water-filled, polymeric microparticles are used in the form of an aqueous dispersion. It is also possible within the scope of the present invention to add the water-filled microparticles directly as a solid to the building material mixture.
  • the microparticles are coagulated, for example, with calcium dichloride (CaCl 2) and isolated from the aqueous dispersion by methods known to those skilled in the art (eg filtration, centrifuging, sedimentation and decanting) and the particles subsequently dried, whereby the hydrous core can be retained ,
  • the water-filled microparticles are added to the building material mixture in a preferred amount of 0.01 to 5% by volume, in particular 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.
  • the air introduced into the building material mixture can be kept extremely low.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
EP07704252A 2006-02-23 2007-01-30 Additive baustoffmischungen mit nichtionischen emulgatoren Withdrawn EP1986975A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006008970A DE102006008970A1 (de) 2006-02-23 2006-02-23 Additive Baustoffmischungen mit nichtionischen Emulgatoren
PCT/EP2007/050905 WO2007096234A2 (de) 2006-02-23 2007-01-30 Additive baustoffmischungen mit nichtionischen emulgatoren

Publications (1)

Publication Number Publication Date
EP1986975A2 true EP1986975A2 (de) 2008-11-05

Family

ID=38319876

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07704252A Withdrawn EP1986975A2 (de) 2006-02-23 2007-01-30 Additive baustoffmischungen mit nichtionischen emulgatoren

Country Status (11)

Country Link
US (1) US20070197689A1 (enExample)
EP (1) EP1986975A2 (enExample)
JP (1) JP2009527447A (enExample)
KR (1) KR20080112204A (enExample)
CN (1) CN101024559A (enExample)
BR (1) BRPI0708216A2 (enExample)
CA (1) CA2642800A1 (enExample)
DE (1) DE102006008970A1 (enExample)
MX (1) MX2008010791A (enExample)
RU (1) RU2008137546A (enExample)
WO (1) WO2007096234A2 (enExample)

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AU2002247681A1 (en) * 2001-02-07 2002-09-12 Rohm Gmbh And Co. Kg Hot sealing compound for aluminum foils applied to polypropylene and polystyrene
DE10350786A1 (de) * 2003-10-29 2005-06-02 Röhm GmbH & Co. KG Mischungen zur Herstellung von Reaktivschmelzklebstoffen sowie daraus erhältliche Reaktivschmelzklebstoffe
DE102004035937A1 (de) * 2004-07-23 2006-02-16 Röhm GmbH & Co. KG Plastisole mit verringerter Wasseraufnahme
DE102005042389A1 (de) * 2005-06-17 2006-12-28 Röhm Gmbh Heißversiegelungsmasse für Aluminium- und Polyethylenterephthalatfolien gegen Polypropylen-Polyvinylchlorid- und Polystyrolbehälter
DE102005045458A1 (de) * 2005-09-22 2007-03-29 Röhm Gmbh Verfahren zur Herstellung von ABA-Triblockcopolymeren auf (Meth)acrylatbasis
DE102005052130A1 (de) * 2005-10-28 2007-05-03 Röhm Gmbh Spritzbare Akustikmassen
DE102006008969A1 (de) * 2006-02-23 2007-08-30 Röhm Gmbh Additive Baustoffmischungen mit Mikropartikeln mit sehr dünnen Schalen
DE102006008964A1 (de) * 2006-02-23 2007-08-30 Röhm Gmbh Additive Baustoffmischungen mit ionischen Emulgatoren
CN102695687A (zh) * 2010-01-08 2012-09-26 株式会社日本触媒 水硬性材料用减缩剂
JP2018162214A (ja) * 2018-07-11 2018-10-18 鹿島建設株式会社 コンクリート硬化体

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Also Published As

Publication number Publication date
WO2007096234A2 (de) 2007-08-30
DE102006008970A1 (de) 2007-08-30
RU2008137546A (ru) 2010-03-27
BRPI0708216A2 (pt) 2011-05-17
JP2009527447A (ja) 2009-07-30
WO2007096234A3 (de) 2007-12-06
KR20080112204A (ko) 2008-12-24
CA2642800A1 (en) 2007-08-30
CN101024559A (zh) 2007-08-29
MX2008010791A (es) 2008-09-01
US20070197689A1 (en) 2007-08-23

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