EP1751218A2 - Neues wasserdispersibles dichtungsmittel, dessen herstellung sowie verwendung im bauwesen, vor allem für mineralbindemittelzusammensetzungen - Google Patents

Neues wasserdispersibles dichtungsmittel, dessen herstellung sowie verwendung im bauwesen, vor allem für mineralbindemittelzusammensetzungen

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Publication number
EP1751218A2
EP1751218A2 EP05773070A EP05773070A EP1751218A2 EP 1751218 A2 EP1751218 A2 EP 1751218A2 EP 05773070 A EP05773070 A EP 05773070A EP 05773070 A EP05773070 A EP 05773070A EP 1751218 A2 EP1751218 A2 EP 1751218A2
Authority
EP
European Patent Office
Prior art keywords
water
repellent agent
acid
soluble
composition
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Withdrawn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
EP05773070A
Other languages
English (en)
French (fr)
Inventor
Jean-Michel Mercier
Daniel Joubert
Pascal Taquet
Martial Deruelle
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.)
Rhodia Chimie SAS
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 EP1751218A2 publication Critical patent/EP1751218A2/de
Withdrawn legal-status Critical Current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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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
    • C04B2103/0052—Hydrophobic 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
    • C04B2103/0055—Water-insoluble 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

Definitions

  • New water-dispersible water repellant its preparation and its use in the field of construction and more particularly in mineral binder compositions
  • the present invention relates to a new water-dispersible water-repellent agent based on at least one water-insoluble and water-immiscible water-repellent agent which has previously been emulsified in a water-soluble amphiphilic copolymer composition.
  • the invention also relates to the solid forms obtained by drying this composition.
  • the invention also has its use in a film-forming polymer composition insoluble in water or in a mineral binder composition for applications in the field of construction. Since centuries erected artificial dwellings, a problem has been the ingress of moisture into these dwellings. Exposure to weather phenomena such as rain and snow can be minimized by appropriate construction, for example, roofs with sufficient projection. However, this does not control the absorption of water by building materials due to their capillary action.
  • Silicones are well known for their water repellency. However, silicones, like the carboxylates of fatty acids having a divalent counterion or the carboxylic esters of fatty acids, are insoluble in water, which makes their use more difficult to obtain good dispersion of the water repellant in aqueous compositions of building materials.
  • the present invention which therefore relates to a new water-dispersible water-repellent agent based on at least one water-repellent water-insoluble and water-immiscible agent which has been previously emulsified in a water-soluble amphiphilic copolymer composition.
  • the subject of the invention is also a redispersible powder of the emulsion of water-repellent agent insoluble in water and / or immiscible with water dispersed in the aqueous phase of water-soluble amphiphilic copolymer, that is to say a water-dispersible water-repellent agent as defined above, dried in the form of a powder redispersible in water.
  • the invention also relates to a film-forming polymer composition insoluble in water (a latex) comprising at least one water-dispersible water-repellent agent as defined above.
  • a film-forming polymer composition insoluble in water comprising at least one water-dispersible water-repellent agent as defined above as an additive to improve the water-repellency properties of a composition mineral binder.
  • the subject of the invention is also a mineral binder composition comprising at least one water-dispersible water-repellent agent.
  • the invention also relates to the use of said mineral binder composition in formulations of mortars, concrete, or the like, based on hydraulic or aerial binders.
  • the invention therefore firstly relates to a new water-dispersible water-repellent agent based on at least one water-repellent water-insoluble and water-immiscible agent which has previously been emulsified in an amphiphilic copolymer composition water-soluble.
  • water dispersible is meant a compound which disperses easily and stably and homogeneously in an aqueous phase. The homogeneous nature of the dispersed phase thus obtained can be verified by a measurement of laser particle size.
  • water-repellent agents insoluble in water and immiscible with water is meant products capable of protecting porous materials against degradation caused by the absorption of water in liquid form.
  • silicones means the polyorganosiloxanes alone or in a mixture; optionally in the presence of functionalized silanes.
  • R are similar or different and represent a C1-C18 alkyl group, an aryl or C6-C12 aralkyl group, optionally substituted by halogen atoms (fluorine in particular);
  • halogen atoms fluorine in particular
  • the symbols X are similar or different and represent a functional radical chosen from those bearing at least one epoxy, carboxy, hydroxy, alkoxy, amino, polyether, phosphate, phosphonate, ester, carboxylate, dicarboxy and / or anhydride unit;
  • Said polyorganosiloxanes containing the units of formula (I) may be linear polymers which may optionally have up to 50% by weight of branches (units other than "D" units), cyclic polymers or three-dimensional polymers (resins). With regard to resins, it is intended to define oligomers or three-dimensional organopolysiloxane polymers which are well known and commercially available.
  • radicals R are as defined above. It should be understood that in the resins, part of the radicals R optionally represents X functions.
  • silicones As examples of resins, mention may be made of MQ resins, MDQ resins, TD resins and MDT resins, the reactive X functions being able to be carried by the patterns M, D, and / or T Silicones are known to allow protection of various surfaces or of mass materials with respect to liquid water, without preventing the passage of water vapor, which is very often an advantage, allowing in particular to access properties called "breathability". There are many types of silicones which are capable of providing hydrophobic or water-repellent effects which are known to those skilled in the art. Mention may in particular be made of the silicones described in patent application FR 03 02921 filed by the Applicant on March 10, 2003.
  • the length of the graft hydrocarbon chain varies between 6 and 18 carbon atoms.
  • the length of the hydrocarbon chain is between 8 and 12 carbon atoms. Even more preferably, the length of the hydrocarbon chain is 12 carbon atoms.
  • the graft hydrocarbon chain 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, groups carboxy, sulfonic acid groups, carboxylic anhydride groups, and / or carbonyl groups. Mention may also be made of the polyether silicones described in patent application FR 03 11759 filed on October 8, 2003. These polyether silicones verify the following formula (I):
  • the terminal groups of the ethylene or propylene oxides being OR groups in which: OE signifies -O-CH2-CH2- OP signifies -O-CH2-CH2-CH2- R represents a hydrogen atom, or a linear or branched alkyl radical having from 1 to 22 carbon atoms, and preferably having from 1 to 4 carbon atoms, x is a number between 5 and 50, y is a number between 3 and 10, e is a number between 10 and 30, p is a number between 0 and 10, it being understood that: x / y is less than 10 and preferably less than or equal to 8, e + p is less than 30 and preferably less than or equal to 20 , e / p is greater than 1 and preferably greater than or equal to 4, and x + y is less than 60 and preferably less than 40.
  • the silicone used is fluid.
  • fluid silicone is meant free flowing silicones. In general, these silicones have a viscosity of less than or equal to 500,000 mPA.
  • water-repellent agents other than silicones insoluble in water and immiscible with water there may be mentioned in particular:
  • - fatty acid esters such as the methyl esters of C10-C16 fatty acids (having from 10 to 16 carbon atoms), the methyl ester of erucic acid, the methyl ester of linoleic acid, l the ethylhexyl ester of lauric acid, the butyl ester of oleic acid, the ethylhexyl ester of oleic acid, or the methyl ester of oleic acid;
  • - waxes of variable chemical nature such as fatty acid triglycerides comprising from 8 to 22 carbon atoms. or their mixtures.
  • at least one silicone is used as water-repellent agent insoluble in water and immiscible with water.
  • at least one fluid silicone is used.
  • a water-insoluble and water-immiscible water-repellent agent a mixture of at least one silicone (preferably fluid) with at least one water-insoluble and water-immiscible water-repellent agent. water other than silicones indicated above.
  • water-soluble amphiphilic copolymer a polymer consisting of polymerizable (ethylenically unsaturated) monomers of hydrophobic nature and of polymerizable (ethylenically unsaturated) monomers of hydrophilic nature, in proportions such that the copolymer is soluble in water.
  • the hydrophilic polymerizable and co-polymerizable monomer can be anionic, cationic, amphoteric, zwitterionic or nonionic in nature. It is preferably anionic and preferably carboxylic or polycarboxylic or also in the form of carboxylic anhydride.
  • a water-soluble amphiphilic copolymer is used such that its dry extract has a solid and pulverulent form.
  • the co-monomers, as well as their relative proportions are chosen such that the copolymers obtained have a dried solid and pulverulent form. This can be done by those skilled in the art through the use of experimental designs.
  • the copolymers having a dry extract in solid and pulverulent form mention may be made of water-soluble amphiphilic copolymers comprising one or more carboxylic functions.
  • the water-soluble amphiphilic copolymer comprising one or more carboxylic functions can be selected for example from: (i) at least one polymer obtained by polymerizing ° of at least one monomer (I) of ethylenically unsaturated monocarboxylic or polycarboxylic acid, or precursor 'carboxylic acids of anhydride, aliphatic, cyclic, linear or branched type, and ° of at least one hydrocarbon (II) monomer, linear or branched, monoethylenically unsaturated; (ii) at least one polymer resulting from the polymerization of at least one monomer (I) monocarboxylic or polycarboxylic acid, or anhydride, aliphatic, cyclic, linear or branched, ethylenically unsaturated, and comprising at least one hydrophobic, hydrocarbon graft, in C4-C30, saturated or not, possibly interrupted by one or more heteroatoms; (iii) at least one poly
  • the water-soluble amphiphilic copolymer comprising one or more carboxylic functions is chosen from: (i) at least one polymer obtained by polymerization - of at least one ethylenically unsaturated monomer (I) of monocarboxylic or polycarboxylic acid type, or else a precursor of carboxylic acids of the anhydride, aliphatic, cyclic, linear or branched type, and - of at least one hydrocarbon monomer (II), linear or branched, monoethylenically unsaturated, this hydrocarbon monomer not being aromatic;
  • the water-insoluble water-immiscible water-repellent agent in emulsion in the water-soluble amphiphilic copolymer is carried out by simple addition of the water-insoluble water-repellent agent and not miscible with water in a concentrated aqueous solution of water-soluble amphiphilic copolymer.
  • concentration solution means a solution comprising at least 10% by weight of water-soluble amphiphilic copolymer, and preferably at least 25% of this copolymer.
  • the proportions of the water-repellent agent which is not soluble in water and / or immiscible with water and of the water-soluble amphiphilic copolymer in the emulsion can be between:
  • water-soluble amphiphilic copolymers mentioned above have the advantage of having sufficient emulsifying properties to obtain, without the addition of an additional emulsifier, the emulsification of water-repellent water-insoluble and / or water-immiscible agent, especially when it is a water repellent based on fluid silicones.
  • concentrated solutions of water-soluble amphiphilic copolymer comprising carboxylic functions mentioned above have the advantage of having a viscosity which is sensitive to pH.
  • Alkaline solutions are very fluid. Their viscosities increase when the pH decreases. This property is very interesting because it thus makes it very simple to regulate the viscosity of this solution of water-soluble amphiphilic copolymer which corresponds to the aqueous phase of the emulsion.
  • this viscosity adjustment combined with well-adapted stirring conditions and temperature and dry extract dosage adjustments, allows the particle size of the emulsion to be adjusted, that is to say the size of the droplets. of water-repellent agent insoluble in water or immiscible with water in the aqueous solution of water-soluble amphiphilic copolymer.
  • the subject of the invention is also a redispersible powder of the emulsion of water-repellent agent insoluble in water and / or immiscible with water dispersed in the aqueous phase of water-soluble amphiphilic copolymer, that is to say a water-dispersible water-repellent agent as defined above, dried in the form of a powder redispersible in water.
  • a water-soluble waterproofing agent as defined above dried in the form of a powder redispersible in water has many advantages. Storage is easy. In addition, this shaping makes it possible to incorporate this powder of water-repellent agent into dry mortar formulations ready for use.
  • the invention also relates to a film-forming polymer composition insoluble in water (a latex) comprising at least one water-dispersible water-repellent agent as defined above.
  • a film-forming polymer composition insoluble in water comprising at least one water-dispersible water-repellent agent as defined above.
  • This composition can be in the form of an aqueous dispersion of film-forming polymer insoluble in water (latex) or in the form of a redispersible latex powder.
  • redispersible latex powder means latex powder redispersible in water.
  • Redispersible latex powders are known to those skilled in the art.
  • the process for the preparation of this composition consists in mixing a water-dispersible water-repellent agent as defined above with a film-forming polymer insoluble in water (latex).
  • This mixture of the water-dispersible water-repellent agent and the latex can be produced in the form of a mixture of redispersible powder of water-soluble water-repellent agent with a composition of redispersible latex powder.
  • the additivated latex can thus be obtained in the form of an aqueous dispersion.
  • the water-dispersible water-repellent agent is introduced in the form of a redispersible powder to a latex powder which is also redispersible, or when the water-soluble water-repellent agent is added in the form of powder in the latex atomization tower, ie when the latex dries.
  • a latex powder with additive water repellency is thus obtained in the form of a redispersible powder.
  • This has many advantages. Storage is easy.
  • this shaping makes it possible to use this latex powder with additive in water-repellent agent in ready-to-use dry mortar formulations.
  • this shaping makes it possible to obtain a very good dispersion of this latex powder additivated as a water-repellent agent in the mass of mineral binder during the phase of mixing with water and therefore effective water-repellency throughout the mass of the consolidated material after addition of mixing water and in particular on all surfaces of the consolidated material.
  • the amount of water-soluble water repellent added to the water-insoluble film-forming polymer must be sufficient to provide good water-repellency properties to the water-insoluble film-forming polymer composition and / or to the mineral binder composition for which it is desired to improve the water repellency properties.
  • the amount of water-dispersible water-repellent added to the film-forming polymer insoluble in water is such that: the quantity of water-dispersible water-repellent is between 10% and 90% by weight of dry water-dispersible water-repellent relative to the total weight of the dry mixture, the amount of the aqueous dispersion of film-forming polymer insoluble in water (latex) is between 90% to 10% by weight of dry latex relative to the total weight of the dry mixture.
  • the quantity of water-dispersible water-repellent agent added to the water-insoluble film-forming polymer is such that: the quantity of water-dispersible water-repellent agent is between 40%> to 60% by weight of dry water-dispersible water-repellent agent relative to the total weight of the dry mixture,
  • the amount of the aqueous dispersion of film-forming polymer insoluble in water (latex) is between 60% to 40% by weight of dry latex relative to the total weight of the dry mixture.
  • 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 10 to 1000 ⁇ m, more preferably from 20 to 700 ⁇ m, and particularly from 50 to 500 ⁇ m.
  • the preferred water-insoluble polymers are obtained by polymerization of monomers chosen from:
  • alkyl acrylates and methacrylates in which the alkyl group 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 or alpha-olefins having from 6 to 20 carbon atoms and preferably from 8 to 14 carbon atoms
  • a terpolymer of vinyl acetate / vinyl versatate / Dibutyl maleate type may be mentioned. It is also possible to add to the monomers copolymerizable with vinyl acetate and / or acrylic esters and / or styrene at least one other monomer chosen from the following list:
  • APMS 2-acrylamido-2-methylpropanesulfonic acid
  • crosslinking monomers carrying at least two ethylenic unsaturations such as diallylphthalate, diallylmaleate, allylmethacrylate, triallylcyanurate, divinyladipate or ethylene glycol dimethacrylate;
  • the polymerization of the monomers is carried out in an emulsion polymerization process in the presence of a emulsifier and / or a protective colloid, and 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 for the emulsion polymerization or co-polymerization of water-insoluble polymers (latex) are anionic, cationic or non-ionic emulsifiers. They are generally used in an amount of 0.01 to 5% by weight relative to the total weight of the monomers.
  • the conventional anionic agents generally used are represented, in particular by alkylsulfates, alkylsulfonates, alkylarylsulfates, alkylarylsulfonates, arylsulfates, arylsulfonates, sulfosuccinates, alkali metal alkylphosphates, salts of l 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 by persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate. It is used in an amount of between 0.05 and 3%> by weight relative to the total of the monomers.
  • hydroperoxides such as hydrogen peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, tert-butyl hydroperoxide
  • persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate. It is used in an amount of between 0.05 and 3%> by weight relative to the total of the monomers.
  • initiators are optionally combined with a reducing agent, such as bisulfite, hydrogen sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, polyethyleneamines, sugars (dextrose, sucrose), ascorbic or isoascorbic acid, or metal salts .
  • a reducing agent such as bisulfite, hydrogen sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, polyethyleneamines, sugars (dextrose, sucrose), ascorbic or isoascorbic acid, or 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 depending on the initiator used, 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, tertiododecylmercaptan, 2-mercaptoethanol, allylic derivatives such as allyl alcohol, cyclohexene, halogenated hydrocarbons 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. Protective colloids can also be used at the start, during or after polymerization.
  • Suitable protective colloids are polyvinyl alcohols and derivatives thereof, for example vinyl alcohol-vinyl acetate copolymers, modified polyvinyl alcohols comprising reactive functions such as silanols, mercaptans, amines, formamides, and comprising hydrophobic co-monomers such as ethylene, vinyl versatate, vinyl 2-ethylhexylhexanoate, polyvinylpyrrolidones (PVP), polysaccharides, for example starches (amylose and amylopectin), cellulose, cellulose ethers such as, for example, hydroxyethylcellulose, guar, tragacantic acid, dextran, alginates and their carboxymethyl, methyl, hydroxyethyl or hydroxypropyl derivatives, proteins, for example casein, soy proteins, gelatins, polymers synthetics, e.g.
  • Polyvinyl alcohol is particularly preferred as a protective colloid for polymerization.
  • a particular protective colloid used is a polyvinyl alcohol having a degree of polymerization from 200 to 3500 and having a degree of hydrolysis from 80 to 99 mol% and preferably from 86% to 92%.
  • the protective colloids are added in proportions of between 0.5% and 15% by weight relative to the total weight of the monomers and preferably between 2% and 10% by weight relative to the total weight of the monomers.
  • the latex composition containing a water-dispersible water-repellent agent 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 polymer insoluble in water.
  • the suitable protective colloids are the same as those mentioned above.
  • the preferred anti-caking agents are aluminum silicates, calcium or magnesium carbonates, or mixtures thereof, silicas, hydrated alumina, bentonite, talc, or mixtures of dolomite and talc, or calcite and talc, kaolin, barium sulfate, titanium oxide, or sulfoaluminate of calcium (satin white).
  • the particle size of the anti-caking agents is preferably in the range of 0.001 to 0.5 mm.
  • the water-insoluble film-forming polymer composition comprising a water-dispersible water-repellent agent may also comprise another water-repellent powdered agent, chosen in particular from fatty acids in the form of free acid or in the form of their alkaline salts, such as lauric acid, stearic acid, alkali laurates, or alkaline stearates.
  • This water-insoluble film-forming polymer composition comprising a water-dispersible water-repellent agent has the advantage of being able to be used as it is or in combination with other components as an additive to improve the water-repellency properties of a mineral binder composition.
  • the subject of the invention is also the use of the film-forming polymer composition insoluble in water comprising a water-dispersible water-repellent agent as an additive to improve the water-repellency properties of a mineral binder composition.
  • the invention also relates to a mineral binder composition comprising a water-dispersible water-repellent agent.
  • the mineral binders can be aerial binders or hydraulic binders.
  • aerial binder is meant for example binders based on lime or among plasters.
  • the hydraulic mineral binders can be chosen from cements which can be of the Portland, aluminous or blast furnace type, or mixtures of these hydraulic binders. Other compounds often added as additives to cement also have hydraulic properties such as fly ash, calcined shales.
  • Mineral binders are made from natural materials which are treated at very high temperatures to remove water and transform the materials into mineral compounds capable of reacting with water or with carbon dioxide (CO 2 ) to produce a binder which after drying forms a compact mass with good mechanical properties.
  • the mineral binders can be in the form of grout, mortars or concretes, that is to say that, generally when mixing with water, fine or coarser aggregates, such as sand or pebbles, are added.
  • the water-soluble water-repellent agent can be added directly to the mineral binder composition, in an amount of between 0.05% and 10% by weight of the dry water-soluble water-repellent agent relative to the total weight of the dry mineral binder composition.
  • this amount is between 0.1% and 5% by weight of the dry water-dispersible water-repellent agent relative to the total weight of the dry mineral binder composition.
  • the water-dispersible water-repellent agent as defined above is preferably added dried in the form of a powder redispersible in water.
  • the water-dispersible water-repellent agent can also be premixed in a sufficient amount with a film-forming polymer composition insoluble in water in the form of an aqueous dispersion (latex) or in the form of a redispersible latex powder before being added to the composition. mineral binder.
  • the binder composition thus also comprises, in addition to the water-dispersible water-repellent agent of the invention, at least one film-forming polymer insoluble in water.
  • the amounts of water-dispersible water repellant introduced into the water-insoluble film-forming polymer compositions are the same as those indicated above.
  • the redispersible latex powder added with a water-dispersible water-repellent agent used can be very varied in nature.
  • a latex composition in the form of a redispersible powder comprising:
  • the redispersible latex powder added with water-dispersible water-repellent agent can be 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 outlet temperature of the product 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 redispersible latex powder In order to increase the storage stability and the flowability of the redispersible latex powder, it is preferable to introduce an anti-caking agent in the atomization tower together with the aqueous polymer dispersion, which results in a preferable deposit of the anti-caking agent on the particles of the dispersion.
  • the composition of mineral binders thus obtained has, after consolidation, good water repellency properties and a reduction in the uptake of water by capillarity.
  • the mineral binder compositions can also comprise organic additives, for example hydrocolloids such as cellulose ethers or guars, plasticizers, water-repellent agents such as those mentioned previously in the insoluble film-forming polymer compositions in water, mineral or organic fibers such as fibers of the polypropylene, polyethylene, polyamide, cellulose, crosslinked polyvinyl alcohol type or a mixture thereof.
  • the mineral binder composition can also include mineral or organic dyes. This is particularly the case when this mineral binder composition is used as a top coat.
  • the mineral binder compositions can also comprise all the additives usually used in mineral binder compositions.
  • the invention also relates to a process for increasing the water-repellency properties of a composition of mineral binders, characterized in that a sufficient quantity of at least one water-soluble water-repellant is added to said composition.
  • a sufficient quantity of at least one water-soluble water-repellant is added to said composition.
  • silicone fluids were the subject of the shaping according to the invention - Silicone (A) PDMS with end of carboxylated chain supplied by the company Rhodia.
  • silicone oil A 1680 g of silicone oil A is dispersed with stirring in 5640 g of solution of the amphiphilic and water-soluble copolymer of EGPM brand (Rhodia), at 25% dry extract, the initial pH (11.2) of which is gradually lowered by addition small quantities of dilute hydrochloric acid, until the desired emulsion size is reached (measurement by laser granulometry of Horiba type on a sample of the medium).
  • the average diameter of the emulsion obtained is approximately 0.3 microns, thanks to stirring at 600 rpm maintained for 25 minutes L '
  • the emulsion thus obtained is then slightly diluted with deionized water so that its viscosity drops to 400 mPa / s, then is sprayed in a Niro Minor type atomizer supplied with hot air.
  • the air inlet temperature is 140 to 160 ° C and the air outlet temperature between 80 and 100 ° C. A dry, manipulable powder is thus obtained, the average diameter of which is close to 80 microns.
  • Invention 1 Dry emulsion of silicone oil
  • Invention 2 Dry emulsion of silicone oil
  • Comparative 1 Silicone oil (B) absorbed on Silica Tixosil 38X®
  • sodium laurate becomes a water repellent in situ in contact with calcium in the cement phase: in the state of sodium laurate it is not water repellent.
  • the beading effect is evaluated by depositing a drop of water on the surface to be characterized, measuring the initial contact angle by an optical method and, if necessary, observing the speed of penetration of the drop of water. in the material.
  • the penetration time, if the cementitious material is strongly hydrophobic, can be several hours;
  • test pieces being placed on a film of water which only wets the foot of the '' test tube over a height of 5 mm;
  • the products according to the invention are superior to the other products on all the examination criteria, in particular on the fact that the "beading" effect is observed on all the faces of the test pieces and including, moreover, mass (tests carried out after rupture of the test pieces for the mechanical test, on the broken edge).
  • the impact of the water-dispersible water-repellent agents according to the invention on the mechanical properties is low, or even a positive effect observed for the dry emulsion of the silicone oil (A).
  • the dry emulsion form of water-dispersible water-repellent agent is superior in performance compared to the same water-repellent agent insoluble in water and / or immiscible with the initial water which is absorbed on a mineral support, in particular support consisting of precipitated silica Tixosil 38X ®. It suffices to compare the performance of the dry silicone emulsion (B) with Comparative Example 1.
  • the photograph in Figure 1 illustrates the behavior in water of different forms of water-repellent powders. It corresponds to a contact time of 10 min after the powder has been deposited on the surface of the water, without stirring. It is noted that most of the water repellents are poorly dispersed or not dispersed at all in water (magnesium stearate, silicone deposited on a silica support, Wacker PC-A and PC-B comparative products).
  • Sodium laurate partially disperses and dissolves, but in its sodium laurate form, it is not a good water repellant. It becomes so in situ in a cement or plaster suspension by transformation into calcium salts which is insoluble in it and floats on the surface of the aqueous solution.
  • the dry emulsion form of silicone of the invention rapidly provides a calibrated dispersion of the water repellant throughout the homogeneous and stable suspension.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Sealing Material Composition (AREA)
EP05773070A 2004-05-27 2005-05-24 Neues wasserdispersibles dichtungsmittel, dessen herstellung sowie verwendung im bauwesen, vor allem für mineralbindemittelzusammensetzungen Withdrawn EP1751218A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0405725A FR2870851B1 (fr) 2004-05-27 2004-05-27 Nouvelle agent hydrofugeant hydrodispersable, sa preparation et son utilisation dans le domaine de la construction et plus particulierement dans les compositions de liants mineraux
PCT/FR2005/001281 WO2005118683A2 (fr) 2004-05-27 2005-05-24 Nouvel agent hydrofugeant hydrodispersable, sa preparation et son utilisation dans le domaine de la construction et plus particulierement dans les compositions de liants mineraux

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EP1751218A2 true EP1751218A2 (de) 2007-02-14

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US (1) US20080319106A1 (de)
EP (1) EP1751218A2 (de)
JP (1) JP2008500420A (de)
CN (1) CN1989181B (de)
FR (1) FR2870851B1 (de)
WO (1) WO2005118683A2 (de)

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EP1982964B1 (de) 2007-04-20 2019-02-27 Evonik Degussa GmbH Organosiliciumverbindung enthaltende Mischung und deren Verwendung
US7875674B2 (en) * 2008-05-01 2011-01-25 Wacker Chemical Corporation Building materials incorporated with hydrophobic silicone resin(s)
FR2942475B1 (fr) * 2009-02-26 2011-04-01 Sika Technology Ag Composition seche comprenant un liant et une huile vegetale modifiee
RU2577864C2 (ru) 2010-04-01 2016-03-20 Эвоник Дегусса Гмбх Способная к отверждению смесь
CN102561578B (zh) * 2010-12-20 2014-06-04 北京仁创科技集团有限公司 墙体砌块
CN102226072A (zh) * 2011-05-06 2011-10-26 同济大学 一种有机硅微胶囊粉末防水剂的制备方法
CN109912813B (zh) * 2019-01-31 2021-08-03 上海舜雅化工有限公司 一种阳离子石蜡乳液及其制备方法、用途
CN111875286A (zh) * 2020-05-21 2020-11-03 江苏博拓新型建筑材料股份有限公司 一种改性硅油疏水剂及制法与采用该疏水剂制备的防水砂浆及制法
CN112811935A (zh) * 2020-12-31 2021-05-18 苏州佳固士新材料科技有限公司 适用于混凝土的色差调整材及其制备方法和应用
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Publication number Publication date
FR2870851A1 (fr) 2005-12-02
CN1989181A (zh) 2007-06-27
CN1989181B (zh) 2011-08-24
JP2008500420A (ja) 2008-01-10
WO2005118683A2 (fr) 2005-12-15
WO2005118683A3 (fr) 2006-07-20
FR2870851B1 (fr) 2008-07-04
US20080319106A1 (en) 2008-12-25

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