WO2010055038A1 - Matériaux à prise hydraulique à basses températures - Google Patents

Matériaux à prise hydraulique à basses températures Download PDF

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Publication number
WO2010055038A1
WO2010055038A1 PCT/EP2009/064923 EP2009064923W WO2010055038A1 WO 2010055038 A1 WO2010055038 A1 WO 2010055038A1 EP 2009064923 W EP2009064923 W EP 2009064923W WO 2010055038 A1 WO2010055038 A1 WO 2010055038A1
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WO
WIPO (PCT)
Prior art keywords
copolymers
water
low temperatures
hydraulically setting
compositions according
Prior art date
Application number
PCT/EP2009/064923
Other languages
German (de)
English (en)
Inventor
Hardy Herold
Andrey Glushkov
Dmitrij Firsaev
Jürgen BEZLER
Original Assignee
Wacker Chemie Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Chemie Ag filed Critical Wacker Chemie Ag
Publication of WO2010055038A1 publication Critical patent/WO2010055038A1/fr

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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
    • 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
    • C04B2103/0057—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
    • C04B2103/0065—Polymers characterised by their glass transition temperature (Tg)
    • 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
    • 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
    • C04B2111/00482—Coating or impregnation 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
    • 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
    • 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
    • C04B2111/60—Flooring materials
    • C04B2111/62—Self-levelling compositions
    • 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
    • C04B2111/76—Use at unusual temperatures, e.g. sub-zero
    • C04B2111/766—Low temperatures, but above zero

Definitions

  • the present invention relates to hydraulically setting compositions at low temperatures and to the use of homopolymers or copolymers of ethylenically unsaturated monomers, in the form of their aqueous dispersions or powders redispersible in water, for producing such compositions.
  • Hydraulically setting compounds are systems with a hydraulic binder such as cement, gypsum or waterglass, optionally with fillers, and optionally further additives such as thickeners, which are mixed with water.
  • cement accelerators can also be added to such systems, and homopolymers or copolymers of ethylenically unsaturated monomers, in the form of their aqueous dispersions or water-redispersible powders, are frequently used to improve the mechanical strength.
  • the constituents of these mixtures which in the case of water-redispersible powders may also be in the form of a dry mortar mixture, are then mixed with water to form the mortar.
  • the processing of the hydraulically setting mortar at low temperatures that is, with increasing proximity to the freezing point of the water or below the freezing point of water, only limited possible.
  • the hydration of the mortar is slowed down so that the mortar masses can freeze before the hydration is complete. Consequently, when the mortars are frozen at an early stage of hydration, the mechanical strength, hardness and water resistance of the solidified mortar masses are reduced in an intolerable manner.
  • the mortars hardened at such low temperatures can cause damage such as cracking and flaking.
  • U.S. Patents 4,054,462 and 4,482,379 calcium chloride is added to the cementitious mass to lower the freezing point.
  • US Pat. No. 3,937,282 recommends the use of alkali metal chlorides to lower the freezing point of a cementitious mortar composition.
  • JP 2006-306646 A2 the use of hectorite, a Li-oxide-containing S ⁇ hichtsili- cat, for accelerating the setting at low temperatures is recommended. From JP-2006-306647 A2 the use of lithium salts is known.
  • U.S. Patent 4,375,987 describes the addition of antifreeze agents such as alcohols (methanol, ethanol) or glycols.
  • Patent 4,054,461 recommends the addition of a combination of alkali metal nitrate and retarder to improve the low temperature processability of cementitious materials.
  • EP 241554 B1 describes the cement to be mixed with a small-scale ice mass instead of water.
  • DE 19528380 A1 discloses heterogeneous vinyl acetate-ethylene dispersions in which heterogeneous polymer particles having two different polymer phases, one ethylene-rich and one ethylene-poor, having two different glass transition temperatures TgI and Tg2 are present. These copolymers are described as highly flexible and low-temperature resistant binders in sealing slurries to -30 0 C. The disadvantage here is the complex production process.
  • the invention relates to hydraulically setting compositions which, in addition to additives for lowering the freezing point of water, contain homo- or copolymers of ethylenically unsaturated monomers which are used in the form of their aqueous dispersions or water-redispersible powders, characterized in that the homopolymers or copolymers have a minimum heat-sink temperature of ⁇ 5 ° C.
  • Typical formulations for hydraulically setting compositions contain as hydraulic binder one or more of the group containing cement, in particular Portland, aluminate, trass, metallurgical, magnesia, phosphate or blast-furnace cement; as well as mixed cement, hydraulic lime and gypsum.
  • Another constituent is one or more fillers from the group comprising quartz sand, gravel, carbonaceous fillers such as calcium carbonate, talc, light fillers, hollow spheres, pozzolanically reacting fillers such as fly ash, metakaolin, microsilica, cellulose fiber and gumshellis.
  • Suitable additives for lowering the freezing point of water are one or more compounds from the group of alkali metal salts and alkaline earth metal salts of inorganic or organic acids.
  • the lithium, sodium, potassium, magnesium and calcium salts are preferred.
  • Preferred inorganic counterions are carbonate, chloride, sulfate, nitrate and phosphate ion.
  • Preferred organic counterions are carboxylate groups which are derived from carboxylic acids having 1 to 4 C atoms, such as formate, acetate, propionate and butyric ion.
  • Particularly preferred are the calcium salts.
  • the calcium salts of carboxylic acids having 1 to 4 C atoms such as calcium formate, calcium acetate.
  • suitable additives for lowering the freezing point of water are, for example, aluminum salts such as aluminates, aluminum hydroxide, aluminum nitrate, aluminum sulfate. Also suitable are alkali metal silicates or alkali metal hydroxides,
  • the performance properties of the hydraulically setting compositions can be improved by adding additives.
  • additives examples of these are thickeners, pigments, foam stabilizers, setting accelerators, water repellents, plasticizers, fly ash, disperse silica, flow agents, air pore agents for controlling the concrete density or pumping aids to improve pumpability.
  • Suitable setting accelerators are known to the person skilled in the art: Examples of these are compounds from the group of alkali metal salts and alkaline earth metal salts of inorganic or organic acids, aluminum salts such as aluminum fluoride, aluminum sulfate or aluminum hydroxide. Further examples are alkanolamines such as triethanolamine or monoethanolamine, single or double NH 2 nATOR polyalkylene glycols with Ci to C 6 alkylene group, which may be present in each case in the form of their salts.
  • Suitable monomers for the preparation of the homopolymers and copolymers are vinyl esters of unbranched or branched alkylcarboxylic acids having 1 to 15 C atoms, methacrylic acid esters and acrylic esters of alcohols having 1 to 15 C atoms, vinylaromatics, olefins, dienes or vinyl halides.
  • the homopolymers and mixed polymers to be used according to the invention are in each case homogeneous polymers, that is to say polymers having a single glass transition temperature Tg.
  • vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of alpha-branched monocarboxylic acids having 9 to 13 C atoms, for example VeoVa9® or VeoValO® ( Trade name of the company Shell). Particularly preferred is vinyl acetate.
  • Preferred methacrylic esters or acrylic esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
  • olefins and dienes are ethylene ,. Propylene and 1,3-butadiene.
  • Suitable vinyl aromatics are styrene and vinyl toluene.
  • a suitable vinyl halide is vinyl chloride.
  • copolymers of vinyl acetate with ethylene Preference is given to copolymers of vinyl acetate with ethylene, copolymers of vinyl acetate with ethylene and one or more further vinyl esters, copolymers of vinyl acetate with ethylene and acrylic esters, copolymers of vinyl acetate with ethylene and vinyl chloride, styrene-acrylic acid ester copolymers, styrene-1, 3 Butadiene copolymers.
  • copolymers of vinyl acetate with 10 to 40% by weight of ethylene are particularly preferred.
  • acrylic acid ester polymers such as copolymers of n-butyl acrylate or 2-ethylhexyl acrylate or copolymers of methyl methacrylate with n-butyl acrylate and / or 2-ethylhexyl acrylate and optionally ethylene; Styrene- ⁇ crylklareester Copolyinerisate with one or more monomers from the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; Vinyl acetate-acrylic acid ester copolymers with one or more monomers from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and optionally ethylene; Styrene-1,3-butadiene copolymers; wherein the data in
  • the monomers or the choice of the weight fractions of the comonomers is made in such a way that a specialistfilm capableempe- temperature (MFT) of ⁇ 5 0 C, preferably from -10 0 C ⁇ MFT ⁇ 5 ° C sawn, Sonders preferably from -10 0 C ⁇ MFT ⁇ O 0 C results, wherein the MFT according to DIN 53787 with an aqueous (re) dispersion (solids content 50 wt .-%) of the polymers is determined.
  • MFT aqueous (re) dispersion
  • the preparation of Homo TM and copolymers in the form of their aqueous dispersions or water-redispersible powder is carried out in an aqueous medium and preferably by the emulsion polymerization process.
  • the polymers are obtained in the form of aqueous dispersions and, if appropriate, can be converted into corresponding water-redispersible powders by customary drying methods. This procedure is described, for example, in WO 2004/092094 A1, the details of which are part of the application (incorporated herein by reference).
  • the hydraulically setting compositions at low temperatures generally contain from 5 to 50% by weight, preferably from 20 to 30% by weight, of hydraulic binder; From 30 to 90% by weight, preferably from 70 to 80% by weight, of fillers; 0.5 to 5 wt .-%, preferably 1 to 3 wt .-%, addition to lower the freezing point; and from 1 to 10% by weight, preferably from 2 to 7% by weight, of homopolymers or copolymers in the form of water-redispersible powders or in the form of aqueous dispersions; and optionally in each case 0.1 to 8 wt .-% setting accelerator or further of said additives; wherein the data in wt .-% on the total weight of the dry mass of the hydraulically setting masses relate, and the data in wt
  • the invention also dry mortar compositions for the production of hydraulically setting at low temperatures compositions containing an additive for lowering the freezing point of water and homopolymers or copolymers of ethylenically unsaturated monomers, in the form of their water-redispersible powder, the homo- or copolymers a minimum film-forming temperature of ⁇ 5 ° C.
  • the dry mortar compositions preferably comprise from 5 to 50% by weight of hydraulic binder, from 30 to 90% by weight of fillers, from 0.5 to 5% by weight of additive for lowering the freezing point of water, and from 1 to 10% by weight of homoge- or Mischpoly- merisat in the form of water-redispersible powders, and optionally 0.1 to 8 wt .-% setting accelerator, wherein the data in% by weight based on the total weight of the dry mortar composition.
  • the preparation of the hydraulically setting materials at low temperatures is not bound to any special procedure or mixing device and can be carried out, for example, in a concrete mixer or a ready mixed concrete mixer.
  • the hydraulically setting masses can be delivered ready mixed as dry mortar composition to the construction site. From the constituents of the recipe can also be made only on site and mixtures are implemented by adding water to hydraulically setting masses.
  • the hydraulically setting compounds are suitable for the production of concrete, mortar, such as joint mortar, building adhesives such as tile adhesives or adhesives for thermal insulation systems, self-leveling compounds, screed, plastering, for example, rendering plasters for thermal insulation composite systems, or putties.
  • Particularly suitable are the hydraulically setting compositions according to the invention for application in thin layers at low temperatures, since the problem of freezing the masses before completion of the hydration of the hydraulic binder is particularly acute here.
  • Thin layers are to be understood as layer thicknesses of 0, 1 to 50 mm, preferably 1 to 20 mm. These layer thicknesses are especially used in building adhesives, in plasters such as reinforcing cleaning for thermal insulation composite systems and obtained in self-leveling compounds.
  • a mixture of 300 parts by weight of Portland cement, 670 parts by weight of sand (grain size ⁇ 0.63 mm), 25 parts by weight of a water-redispersible vinyl acetate-ethylene copolymer powder (MFT according to DIN 53787: 0 0 C) ), 15 parts by weight of calcium formate, 2 parts by weight of methylhydroxyethylcellulose (Walocel MW 40000 PFV) and 3 parts by weight of cellulose fiber (Arbocel PWC 500) with 210 parts by weight of water (T 25 0 C) to a Mörtelmasse touched.
  • MFT water-redispersible vinyl acetate-ethylene copolymer powder
  • Comparative Example 3 The procedure was analogous to Example 1, with the difference that no vinyl acetate-ethylene copolymer powder was used.
  • an aqueous vinyl acetate-ethylene-vinyl chloride dispersion solids content 50%, MFT according to DIN 53787: 15 0 C
  • T 25 0 C
  • Example 1 to Comparative Example 4 were each applied at -8 ° C in a layer thickness of 3 mm and over an area of 40 x 40 cm 2 on a polystyrene plate.
  • the tensile bond strength was (2 faces of sawn 50 x 50 mm) after 7 days storage at -8 0 C in accordance with DIN EN 13494:
  • Example 1 0.085 N / mm 2 (partial rupture / adhesion of polystyrene)
  • Comparative Example 4 shows the influence of the minimum film-forming temperature MFT on the adhesion when processing at low temperatures - too high MFT of the polymer leads to a drastic reduction in adhesion.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L’invention concerne des matériaux à prise hydraulique à basses températures qui contiennent, outre des additifs pour abaisser le point de congélation de l’eau, également des homo- ou copolymères de monomères éthyléniquement insaturés, qui sont utilisés sous la forme de leurs dispersions aqueuses ou de poudres redispersibles dans l’eau, caractérisés en ce que les homo- ou copolymères présentent une température minimale de formation d’un film ≤ 5 °C.
PCT/EP2009/064923 2008-11-14 2009-11-10 Matériaux à prise hydraulique à basses températures WO2010055038A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200810043766 DE102008043766A1 (de) 2008-11-14 2008-11-14 Bei tiefen Temperaturen hydraulisch abbindende Massen
DE102008043766.2 2008-11-14

Publications (1)

Publication Number Publication Date
WO2010055038A1 true WO2010055038A1 (fr) 2010-05-20

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WO (1) WO2010055038A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2431341B1 (fr) * 2010-09-21 2019-04-17 STO SE & Co. KGaA Composition destinée à la formation d'un revêtement rapidement durcissable et séchant entièrement sur un sous-sol et/ou un composant côté construction
EP3279172A1 (fr) * 2013-03-07 2018-02-07 STO SE & Co. KGaA Composition sèche contenant du ciment et procédé d'augmentation de la stabilité de stockage d'une composition sèche contenant du ciment
PL3225606T3 (pl) * 2016-04-01 2020-10-19 Wetherby Stone Products Ltd Materiały konstrukcyjne

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4340510A (en) * 1977-12-30 1982-07-20 Friedrich Howanietz Concrete mixtures or mortar mixtures or concretes or mortars and process for their production
EP1081161A1 (fr) * 1999-02-18 2001-03-07 Konishi Co., Ltd. Procede de production d'emulsion de resine d'acetate de vinyle et d'adhesif a base d'eau
DE10126560C1 (de) * 2001-05-31 2002-09-12 Wacker Polymer Systems Gmbh Verwendung von Mischpolymerisaten von Vinylester-, (Meth)acrylsäureester- und gegebenenfalls Ethylen-Comonomeren in Baustoffen
US6699339B2 (en) * 2000-12-21 2004-03-02 Wacker Polymer Systems Gmbh & Co. Kg Gypsum plaster compositions with improved adhesion to plastic surfaces and metal surfaces

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
US3937282A (en) 1973-06-28 1976-02-10 Halliburton Company Method for cementing wells in low temperature formations
US4054462A (en) 1976-03-01 1977-10-18 The Dow Chemical Company Method of cementing
US4054461A (en) 1976-03-25 1977-10-18 The Dow Chemical Company Method of cementing
US4375987A (en) 1981-11-23 1983-03-08 W. R. Grace & Co. Additive combination for hydraulic cement compositions
US4482379A (en) 1983-10-03 1984-11-13 Hughes Tool Company Cold set cement composition and method
US4830669A (en) 1985-07-03 1989-05-16 Toshiro Suzuki Method of producing and applying mortar
DE19528380A1 (de) * 1995-08-02 1997-02-06 Hoechst Ag Heterogene Vinylacetat/Ethylen-Dispersion
DE10317882A1 (de) 2003-04-17 2004-11-11 Wacker Polymer Systems Gmbh & Co. Kg Redispersionspulver-Zusammensetzung mit abbindebeschleunigender Wirkung
JP4634213B2 (ja) 2005-04-27 2011-02-16 電気化学工業株式会社 アルミナセメント組成物およびそれを用いた補修工法
JP4634212B2 (ja) 2005-04-27 2011-02-16 電気化学工業株式会社 アルミナセメント組成物およびそれを用いた補修工法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4340510A (en) * 1977-12-30 1982-07-20 Friedrich Howanietz Concrete mixtures or mortar mixtures or concretes or mortars and process for their production
EP1081161A1 (fr) * 1999-02-18 2001-03-07 Konishi Co., Ltd. Procede de production d'emulsion de resine d'acetate de vinyle et d'adhesif a base d'eau
US6699339B2 (en) * 2000-12-21 2004-03-02 Wacker Polymer Systems Gmbh & Co. Kg Gypsum plaster compositions with improved adhesion to plastic surfaces and metal surfaces
DE10126560C1 (de) * 2001-05-31 2002-09-12 Wacker Polymer Systems Gmbh Verwendung von Mischpolymerisaten von Vinylester-, (Meth)acrylsäureester- und gegebenenfalls Ethylen-Comonomeren in Baustoffen

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