EP1583724A2 - Verfahren zur förderung der hydrophobierung von hydraulischen bindemittelzusammensetzungen und ihre verwendungen - Google Patents

Verfahren zur förderung der hydrophobierung von hydraulischen bindemittelzusammensetzungen und ihre verwendungen

Info

Publication number
EP1583724A2
EP1583724A2 EP03813179A EP03813179A EP1583724A2 EP 1583724 A2 EP1583724 A2 EP 1583724A2 EP 03813179 A EP03813179 A EP 03813179A EP 03813179 A EP03813179 A EP 03813179A EP 1583724 A2 EP1583724 A2 EP 1583724A2
Authority
EP
European Patent Office
Prior art keywords
carboxylic acid
salt
monovalent cation
composition
weight
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Withdrawn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
EP03813179A
Other languages
English (en)
French (fr)
Inventor
Jean-Christophe Castaing
Gary Baker
Philippe Jost
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.)
Synthomer USA LLC
Original Assignee
Rhodia Chimie SAS
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 Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1583724A2 publication Critical patent/EP1583724A2/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Withdrawn legal-status Critical Current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
    • C04B24/08—Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C04B24/085—Higher fatty acids
    • 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
    • C04B40/0042—Powdery mixtures
    • 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
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/65—Water proofers or repellants

Definitions

  • the present invention relates to a process for increasing the water repellency of mineral hydraulic binder compositions as well as the compositions capable of being obtained by this process and their uses in the field of construction.
  • the fatty acid carboxylic esters described in this document are insoluble in water, which makes their implementation more difficult to obtain a good dispersion of the water-repellent agent in the aqueous compositions of building materials. Indeed, these compounds can only be introduced into aqueous solutions in the form of a dispersion or emulsion, which requires the addition of an emulsifier or a protective colloid which adversely affects the water-repellency property sought.
  • the present invention therefore relates to a process for increasing the water repellency of a composition of hydraulic mineral binders, characterized in that a sufficient quantity of at least one salt of a monovalent cation of a carboxylic acid is added to said composition.
  • Hydraulic binders are generally based on cement. They can be in the form of grout, mortar or concrete. They are used, for example, in the following applications: tile mortars, joint mortars, monolayer plasters, exterior thermal insulation systems, smoothing and leveling plasters, adhesives and plasters for insulation complexes, repair mortars, waterproofing coatings and grout for oil well cementing.
  • the hydraulic mineral binders can be chosen from cements which can be of the Portland, aluminous or blast furnace type. Other compounds often added as additives to cement also have hydraulic properties such as fly ash, calcined shales. Mention may also be made of pozzolans which react with lime and form calcium silicates.
  • This monovalent cation salt of a carboxylic acid can be represented by the following formula: C n H (2 ⁇ _ 1) 00- ⁇ + (I)
  • monovalent cation (X + ) is meant in particular the ions of alkali metals such as sodium, potassium, lithium, and the ions containing an ammonium group such as ammonium as well as all the quaternary amines.
  • alkali metal ion chosen from sodium or potassium is preferred.
  • the hydrocarbon chain of the carboxylic acid salt C n H (2n _ 1) can be saturated or unsaturated, and branched or linear. It can also contain halogens, such as fluorine or chlorine, and hydroxyl groups, ether groups, thioether groups, ester groups, amide groups, carboxy groups, sulfonic acid groups, carboxylic anhydride groups, and / or carbonyl groups.
  • the length of the hydrocarbon chain of the carboxylic acid varies between 4 and 18 carbon atoms.
  • Sodium laurate and potassium laurate are particularly preferred.
  • the monovalent cation salt of a carboxylic acid can be incorporated in the form of a solid powder or dissolved in aqueous solution in a sufficient amount in the construction composition.
  • the monovalent cation salt of a carboxylic acid can also be premixed in a sufficient amount with a redispersible latex composition.
  • the monovalent cation salt of a carboxylic acid when used alone can have an irritant character. When used as a premix with latex, it no longer has this irritating character.
  • cationic carboxylic acid salts whose length of the carbon chain is less than 18 carbon atoms. Even more preferably, the length of the hydrocarbon chain is 12 carbon atoms.
  • This pre-mixing of the monovalent cation salt of a carboxylic acid and of the latex can be carried out in the form of a mixture of solid powder of water-repellent agent in a sufficient amount for a redispersible latex powder composition.
  • premix a solid powder of the monovalent cation salt of a carboxylic acid is mixed in a sufficient amount with a redispersible latex powder composition.
  • the sufficient amount is between 0.001% and 3% by dry weight of the monovalent cation salt of a carboxylic acid relative to the total weight of building composition.
  • this amount is between 0.01% and 0.5% by dry weight of the monovalent cation salt of a carboxylic acid relative to the total weight of the construction composition.
  • this amount is between 0.03% and 0.15% by dry weight of the monovalent cation salt of a carboxylic acid relative to the total weight of the construction composition.
  • the sufficient amount is between 0.1% and 20% by weight of monovalent cation salt d 'a carboxylic acid based on the weight of dry latex.
  • this amount is between 1% to 10% by weight of monovalent cation salt of a carboxylic acid relative to the weight of the dry latex. Even more preferably, this amount is between 3% to 7% by weight of monovalent cation salt of a carboxylic acid relative to the weight of the dry latex.
  • the redispersible latex powder used can be very varied in nature.
  • a latex composition in the form of a redispersible powder comprising: at least one polymer insoluble in water, from 0 to 35% by weight, relative to the total weight of the polymer, of at least one protective colloid, 0 to 30% by weight, relative to the total weight of the polymer, of anti-caking agents, and from 0.1 to 20% by weight, relative to the total weight of the polymer of the monovalent cation salt of a carboxylic acid .
  • Suitable water-insoluble polymers are homo- or copolymers which are in the form of an aqueous dispersion or which can be transformed into an aqueous dispersion, and then can be formed into a powder by spray drying.
  • the average particle size of the powder is preferably from 1 to 1000 ⁇ m, more preferably from 10 to 700 ⁇ m, and particularly from 50 to 500 ⁇ m.
  • the preferred water-insoluble polymers are obtained by polymerization of monomers chosen from: - vinyl esters and more particularly vinyl acetate; alkyl acrylates and methacrylates, the alkyl group of which contains from 1 to 10 carbon atoms, for example methyl, ethyl, n-butyl, 2-ethylhexyl acrylates and methacrylates; vinyl aromatic monomers, in particular styrene.
  • These monomers can be copolymerized with each other or with other ethylenically unsaturated monomers, to form homopolymers, copolymers or terpolymers.
  • ethylene and olefins such as isobutene
  • vinyl aromatic monomers such as methylstyrenes, vinyltoluenes
  • vinyl halides such as vinyl chloride, vinylidene chloride, diolefins especially butadiene; (meth) allyl esters of
  • a terpolymer of acetate / versatate / Dibutyl maleate type By way of example, mention may be made of a terpolymer of acetate / versatate / Dibutyl maleate type.
  • acrylamide ethylenically unsaturated carboxylic acids or dacids, preferably acrylic acid or methacrylic acid, ethylenically unsaturated sulfonic acids and salts thereof, preferably vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid (AMPS), or sodium methallylsulfonate .
  • APMS 2-acrylamido-2-methylpropanesulfonic acid
  • These monomers are added in an amount of between 0.05 and 10.0% by weight, relative to the total weight of the monomers. These monomers are added during the polymerization; they ensure the colloidal stability of the latex.
  • the polymerization of the monomers is carried out as an emulsion in the presence of an emulsifier and of a polymerization initiator.
  • the monomers used can be introduced as a mixture or separately and simultaneously into the reaction medium, either before the start of the polymerization in one go, or during the polymerization by successive fractions or continuously.
  • the emulsifiers which can be used are anionic, cationic or nonionic emulsifiers.
  • emulsifying agent use is generally made of the conventional anionic agents represented in particular by alkyl sulfates, alkylsulfonates, alkylarylsulfates, alkylarylsulfonates, arylsulfates, arylsulfonates, sulfosuccinates, alkali metal alkylphosphates, salts of 1 hydrogenated abietic acid or not.
  • the emulsion polymerization initiator is more particularly represented by hydroperoxides such as hydrogen peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, tert-butyl hydroperoxide, and persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate. It is used in an amount between 0.05 and 2% by weight relative to the total of the monomers.
  • a reducing agent such as sodium bisulfite or formaldehyde sulfoxylate, polyethyleneamines, sugars (dextrose, sucrose), metal salts.
  • the amount of reducing agent used varies from 0 to 3% by weight relative to the total weight of the monomers.
  • the reaction temperature is generally between 0 and 100 ° C, and preferably between 30 and 90 ° C.
  • a transfer agent can be used in proportions ranging from 0 to 3% by weight relative to the monomer (s), generally chosen from mercaptans such as N-dodecylmercaptan or tertiododecyl ercaptan, cyclohexene, hydrocarbons halogens such as chloroform, bromoform, carbon tetrachloride. It adjusts the length of the molecular chains. It is added to the reaction medium either before the polymerization, or during polymerization.
  • the latex composition in the form of a redispersible powder comprises 0 to 35% by weight, preferably 3 to 15% by weight, of protective colloid, relative to the total weight of the water-insoluble polymer .
  • Suitable protective colloids are polyvinyl alcohols and derivatives thereof, for example vinyl alcohol-vinyl acetate copolymers, polyvinylpyrrolidones, polysaccharides, for example starches (amylose and amylopectin), cellulose, guar, l tragacantic acid, dextran, alginates and their carboxymethyl, methyl, hydroxyethyl, or hydroxypropylic derivatives, proteins, for example casein, soy proteins, gelatins, synthetic polymers, for example poly (meth ) acrylic, poly (meth) acrylamide, polyvinylsulfonic acids, and water-soluble copolymers thereof, melamine-formaldehyde sulfonates, naphthalene-
  • the preferred anti-caking agents are aluminum silicates, calcium or magnesium carbonates, or mixtures thereof, silicas, hydrated alumina, bentonite, talc, or dolomite mixtures and talc, or calcite and talc, kaolin, barium sulfate, titanium oxide, or calcium sulfoaluminate (satin white).
  • the particle size of the anti-caking agents is preferably in the range of 0.001 to 0.5 mm.
  • the redispersible latex powder is preferably prepared by spray drying the aqueous polymer dispersion. This drying is carried out in conventional spray drying systems, using atomization by means of single, double or multiple liquid nozzles or a rotating disc.
  • the discharge temperature chosen is generally in the range of 50 to 100 ° C, preferably 60 to 90 ° C, depending on the system, the glass transition temperature of the latex, and the desired degree of drying.
  • the present invention also relates to a composition of hydraulic mineral binders with improved water-repellent properties which can be obtained by the process described above.
  • Another subject of the present invention is the use of this hydraulic binder composition to increase the water content of construction compositions.
  • the building compositions can in particular be coating compositions or mineral building mixes for producing mineral components.
  • the coating compositions are used in particular for mineral substrates.
  • the coating compositions can be aqueous, or in powder form. Preferably they are in powder form.
  • coating compositions are mineral paints, lime paints, silicate paints, lime emulsion paints, silicate emulsion paints, base coats, plasters, for example mineral plasters and silicate plasters, high-load coatings based on dispersions, fillers applied by brush, reinforcing compositions, trowel-coated compounds, and tile adhesives, monolayer coatings and also mortars, for example example of waterproofing mortars, mortars for external thermal insulation systems or joint mortars.
  • mineral construction mixtures are any of the crude mixtures which can be used to produce mineral components which are themselves used in civil engineering works, and are part of engineering works civilian, especially if they are exposed to the weather or require another type of waterproofing.
  • components are precast bricks and concrete roofing slabs, fiber-loaded concrete panels, and also other finished products or insulating components.
  • Mineral construction mixtures can be composed of concrete, lime, cement, quartz sand, clay minerals, such as calcium silicate, porous concrete, bricks, or otherwise fiber-based construction mixtures in which the fibers are natural fibers or synthetic fibers.
  • Suitable natural fibers are mineral fibers, such as rock wool, quartz fibers, or ceramic fibers, or vegetable fibers, such as cellulose.
  • cellulose fibers are jute fibers, coconut fibers, and hemp fibers, or fibers derived from paper, cardboard, or recycled paper.
  • suitable synthetic fibers are glass fibers, polymer fibers, and carbon fibers.
  • the mineral construction compositions can also comprise organic additives, for example cellulose ethers or plasticizers. Other organic additives which can be used in mineral construction compositions are known to the person skilled in the art.
  • compositions of hydraulic mineral binders with improved water-repellent properties generally used in construction compositions are between 0.01 and 80% by weight.
  • compositions of hydraulic mineral binders with improved water repellency properties preferably used in the mortar compositions are between 30 and 50% by weight.
  • Example 1 A VeoValO acetate / versatate latex (70/30) stabilized with polyvinyl alcohol is mixed with a monovalent cation salt of a carboxylic acid according to the various methods described below:
  • Method 1 The latex is used in the form of an emulsion at 50
  • a VeoValO acetate / versatate latex (70/30) stabilized by polyvinyl alcohol is mixed with a solution of sodium laurate (purity 95%) at 20% concentration.
  • the solution is brought to a temperature of 50 ° C. then introduced with stirring into the latex in the following proportions (see table 2): 100 parts of latex emulsions
  • a mortar formula (silicic fillers) having the following composition is prepared:
  • polymer means an acetate / versatate latex VeoValO (70/30) stabilized by polyvinyl alcohol.
  • the latex is used in the form of an emulsion having a dry extract of 50% and prepared according to method 1 described in Example 1. The proportions indicated above refer to the mass latex dryer contained in the emulsion. The accompanying water is taken into account in the mixing water. The mixing rate is 18%.
  • the mortars are mixed and then introduced into cylindrical molds (50 g of mortar).
  • the whole is placed in an enclosure whose relative humidity and C0 2 content are controlled by a solution of supersaturated sodium bromide containing 1M of sodium hydroxide.
  • the samples are demolded after 1 day of packaging; then, after 7 days of conditioning, the curved face of the cylinders is coated with a mixture of paraffin.
  • a mortar formula (fillers based on calcium carbonate) having the following composition is prepared:
  • polymer means an acetate / versatate latex VeoValO (70/30) stabilized by polyvinyl alcohol.
  • the latex is used in the form of an emulsion having a dry extract of 50% and prepared according to method 1 described in Example 1. The proportions indicated above refer to the mass latex dryer contained in the emulsion. The accompanying water is taken into account in the mixing water. The mixing rate is 28%.
  • Mortar formulas are prepared according to the compositions described in examples 3 and 4 (formula 1 and formula 2).
  • the polymer introduced into these formulations corresponds to the preparations described in Example 1 (method 2 and method 3).
  • the mortars are mixed and then poured into standard 4 * 4 * 16 cm molds and passed over a shock table. They are removed from the mold the next day and then placed in a room conditioned at 23 ° C and 55% relative humidity. One week after the mortar was made, they were coated with paraffin on 4 of their faces forming a crown and including the 2 square faces. The samples are then soaked by one of their free sides in deionized water. The amount of water taken up by capillarity is measured by weighing after 30 min and 240 min.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Paints Or Removers (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP03813179A 2002-12-13 2003-12-12 Verfahren zur förderung der hydrophobierung von hydraulischen bindemittelzusammensetzungen und ihre verwendungen Withdrawn EP1583724A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0215849A FR2848552B1 (fr) 2002-12-13 2002-12-13 Un procede pour augmenter l'hydrofugation de compositions de liants hydrauliques mineraux ainsi que les compositions susceptibles d'etre obtenues par ce procede et leurs utilisations
FR0215849 2002-12-13
PCT/FR2003/003699 WO2004054941A2 (fr) 2002-12-13 2003-12-12 Un procede pour augmenter l'hydrofugation de compositions de liants hydrauliques mineraux ainsi que les compositions susceptibles d'etre obtenues par ce procede et leurs utilisations

Publications (1)

Publication Number Publication Date
EP1583724A2 true EP1583724A2 (de) 2005-10-12

Family

ID=32338785

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03813179A Withdrawn EP1583724A2 (de) 2002-12-13 2003-12-12 Verfahren zur förderung der hydrophobierung von hydraulischen bindemittelzusammensetzungen und ihre verwendungen

Country Status (7)

Country Link
US (1) US7671115B2 (de)
EP (1) EP1583724A2 (de)
CN (2) CN1726173A (de)
AU (1) AU2003300587A1 (de)
BR (1) BR0317069B8 (de)
FR (1) FR2848552B1 (de)
WO (1) WO2004054941A2 (de)

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GB0606468D0 (en) * 2006-03-31 2006-05-10 Ici Plc Improved paint compositions
KR20090096687A (ko) * 2006-10-02 2009-09-14 다우 글로벌 테크놀로지스 인크. 고 알코올-함량 폼
WO2009006377A1 (en) * 2007-07-03 2009-01-08 Dow Global Technologies Inc. Granular composites of inorganic particulates and redispersible latex powders and methods
EP2540687B1 (de) * 2011-06-29 2017-11-15 Dow Global Technologies LLC Hydrophobe zementartige zusammensetzung
KR101203919B1 (ko) 2012-05-31 2012-11-22 최종윤 스티렌-프로페노에이트계 터폴리머 라텍스로 개질된 초속경 콘크리트 조성물과 이를 이용한 콘크리트 포장 보수공법
CN102863593B (zh) * 2012-09-18 2014-08-13 中国地质大学（武汉） 一种泥饼固化剂及其制备与使用方法
US9278875B2 (en) 2012-11-27 2016-03-08 Veolia Water Solutions & Technologies Support Process for reducing the sulfate concentration in a wastewater stream by employing regenerated gibbsite
CN105969256A (zh) * 2016-04-28 2016-09-28 李鲁源 胶体溶液材料及其制备方法、水硬胶粘剂及其制备方法
CN107759232A (zh) * 2016-08-19 2018-03-06 张丽媛 一种回转窑炉衬修补料
CN111269025B (zh) * 2020-02-04 2021-11-16 北京建筑大学 一种锂基渗透液改性混凝土表面增强剂及制备和使用方法

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Also Published As

Publication number Publication date
US7671115B2 (en) 2010-03-02
BR0317069A (pt) 2005-10-25
WO2004054941A3 (fr) 2004-08-05
AU2003300587A8 (en) 2004-07-09
AU2003300587A1 (en) 2004-07-09
BR0317069B8 (pt) 2013-02-19
CN102351481A (zh) 2012-02-15
US20060116446A1 (en) 2006-06-01
CN1726173A (zh) 2006-01-25
FR2848552A1 (fr) 2004-06-18
BR0317069B1 (pt) 2013-01-08
WO2004054941A2 (fr) 2004-07-01
FR2848552B1 (fr) 2005-05-27

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