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
  • C04B28/14—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 calcium sulfate cements
• • 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
  • 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
  • C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust cements
• • 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
  • C04B28/06—Aluminous cements
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/36—After-treatment
  • C08J9/365—Coating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
• • 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
  • 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
  • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
• • 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
  • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31971—Of carbohydrate
  • Y10T428/31989—Of wood

Definitions

• New adhesion promoting agent on a thermal insulating surface and in particular on a polystyrene surface and its use in the field of construction and more particularly in exterior thermal insulation systems
• the present invention relates to a new adhesion promoting agent on a thermal insulating surface and in particular on a polystyrene surface, in particular in the wet state or under the effect of a significant variation in temperature.
• the invention also relates to its use in a film-forming polymer composition insoluble in water or in a mineral binder composition for applications in the construction field and more particularly in exterior thermal insulation systems.
• insulating coating elements such as polystyrene such as extruded or expanded polystyrene or polyurethane constitute a support material for laying ceramic tiles in a thin bed process.
• building elements made of polystyrene materials are suitable for interrupting thermal bridges, as they appear, for example, where concrete or masonry meet.
• a common method consists in the case of thermal insulation to be fixed on the facade (for example in masonry, concrete, mineral plaster, etc.) the back of the insulating plates of polystyrene or another mineral wool insulator by means mortar or cement.
• a mortar is also applied as that coating says reinforcement.
• fiber reinforcements for example reinforcements based on glass fibers, polyester, polypropylene
• a reinforcing coating is usually applied to the fiberglass mesh again, for the complete inclusion of the mesh, the surface is leveled and, after drying, a finishing coating is applied, for example a mineral coating or a coating based on synthetic resin, such as plaster, or paint.
• One of the aims of the present invention is to provide mineral building materials which, after their consolidation, have increased adhesion, in the wet state or under the effect of a significant variation in temperature, to thermal insulating materials and in particular to materials based on polystyrene.
• This object and others are achieved by the present invention which relates to a new adhesion promoting agent on a surface of thermal insulator and in particular on a polystyrene surface, in particular in the wet state or under the effect a significant variation in temperature, based on a mono, di or tri phosphate ester or their mixture.
• the invention also relates to a film-forming polymer composition insoluble in water comprising a mono, di or tri phosphate ester or a mixture thereof.
• the subject of the invention is also the use of a film-forming polymer composition insoluble in water comprising a mono, di or tri phosphate ester - or their mixture as an adhesion primer on a thermal insulating support and in particular to polystyrene base.
• the invention also relates to a mineral binder composition
• a mineral binder composition comprising a mono, di or tri phosphate ester or a mixture thereof.
• Another subject of the invention is the use of the mineral binder composition to increase the adhesion of a thermal insulator and in particular of polystyrene to a support material.
• the invention also relates to a method for increasing the adhesion properties on a support by thermal insulation and in particular in polystyrene, in particular in the wet state or under the effect of a significant variation in temperature, after consolidation. , of a composition of hydraulic mineral binders characterized in that a sufficient amount of at least one mono, di or tri phosphate ester or their mixture is added to said composition.
• the invention therefore firstly relates to a new adhesion promoting agent on a thermal insulating surface and in particular polystyrene, in particular to wet or under the effect of a significant change in temperature, based on a mono, di or tri phosphate ester or their mixture.
• thermal insulating material or support is meant in particular polystyrene, polyurethane, mineral wools such as glass wool or rock wool.
• Polystyrene is preferred.
• R1, R2 and R3, which are identical or different, represent: a hydrogen atom, or - a saturated or unsaturated, linear or branched or cyclic alkyl radical, having from 1 to 22 carbon atoms, preferably from 2 to 12 atoms carbon, and even more preferably from 2 to 8 carbon atoms, optionally substituted by halogen atoms, such as fluorine or chlorine, hydroxyl groups, ether groups having between 1 and 12 carbon atoms and preferably between 1 and 6 carbon atoms, thioether groups, ester groups, amide groups, carboxy groups, sulfonic acid groups, carboxylic anhydride groups, and / or carbonyl groups, or an aryl radical, having from 6 to 22 carbon atoms, preferably from 6 to 8 carbon atoms, optionally substituted by halogen atoms, such as fluorine or chlorine, hydroxyl groups, ether groups having between 1 and 12 carbon atoms and preferably between 1 and 6 carbon atoms, thioether
• phosphate phosphate compounds of formula (I) of the following compounds: tris (2-ethylhexyl) phosphate, tris (2-butoxyethyl) phosphate, di (2-ethylhexyl) phosphate, mono (2-ethylhexyl) phosphate, - tris (2-isooctyl) phosphate, tricresylphosphate, cresyldiphenylphosphate, trixylilphosphate,. .. triphenylphosphate, - tributyl phosphate, triethyl phosphate, tri (2chloroethyl) phosphate, or a mixture thereof.
• the mono, di or tri phosphate ester of the agent according to the invention can be incorporated in liquid form or in the form of solid powder in a film-forming polymer composition insoluble in water or in a mineral binder composition. If the mono, di or tri phosphate ester of the invention is in liquid form at room temperature, as is the case of the particular compounds listed above with the exception of triphenylphosphate which is solid at room temperature, it it is possible to adsorb them on an inert mineral support to obtain a solid powder.
• the adsorption of the mono, di or tri phosphate ester can be carried out by any conventional method of adsorption of compounds on mineral supports inorganic. Mention may in particular be made of the methods described in documents FR 74 27893 or FR 74 36083.
• a preferred embodiment for preparing the solid powder of mono, di or tri phosphate esters is a process comprising a step of dry impregnation of a mineral oxide with a sufficient quantity of mono, di or tri phosphate esters.
• the mineral oxide can be chosen from silica, alumina, silica-alumina, sodium silico-alurninate, calcium silicate, magnesium silicate, zirconia, magnesium oxide, oxide of calcium, cerium oxide or titanium oxide.
• the mineral oxide can be completely or partially hydroxylated or carbonate.
• the mineral oxide must be of high porosity. This means that its total pore volume must be at least 1 ml / g and preferably at least 2 ml / g.
• the total pore volume of the mineral oxide is measured by a mercury porosimetry method using a MICROMERITICS Autopore III 9420 porosimeter. The preparation of each sample is carried out as follows: the sample is previously dried for 2 hours in an oven at 200 ° C. The measurements are then carried out according to the procedure described in the manual supplied by the manufacturer. The pore diameters are calculated by the relation of WASHBURN with a teta contact angle equal to 140 ° and a gamma surface tension equal to
• the mineral oxide has a useful pore volume greater than or equal to 0.5 ml / g.
• useful volume is meant the volume of the pores whose diameter is less than 1 micron. This volume is measured by the same method as the total pore volume.
• a silica is used as the mineral oxide. Even more preferably, an amorphous silica is used. This can be a natural silica or a synthetic silica such as silica gels, combustion silicas or, very preferably, precipitated silicas.
• the mineral oxide when the mineral oxide is precipitated silica, it may for example be a Tixosil 38A, Tixosil 38D or Tixosil 365 silica from the company Rhodia.
• the precipitated silica may be in the form of substantially spherical beads, in particular of average size of at least 80 microns, for example at least 150 microns, obtained by means of a nozzle atomizer, as described for example in document EP 0018866. It can for example be silica called Microperle. This form makes it possible to optimize the impregnation capacity and the flowability of the powder as described for example in documents EP 0966207 or EP 0984772. It can be, for example, a silica Tixosil 38X or Tixosil 68 from the Rhodia company.
• the precipitated silica can be a highly dispersible silica, such as the silicas described in documents EP 0520862, WO 95/09127 or WO 95/09128, which, in particular, facilitates its dispersion in the film-forming polymer composition insoluble in water or in the composition of mineral binder. It may for example be a Z1165 MP or Z1115 MP silica from the company Rhodia.
• Amorphous silica can be silica with low water uptake.
• the "water uptake” corresponds to the amount of water integrated into the sample relative to the mass of the sample in the dry state, after 24 hours at 20 ° C and 70% relative humidity.
• low water uptake is meant a water uptake of less than 6% and preferably less than 3%.
• It can be precipitated silicas described in patent application FR 01 16881 (in the name of the company Rhodia), silicas pyrogenated or partially dehydroxylated silicas by calcination or by surface treatment.
• the invention also relates to a film-forming polymer composition insoluble in water comprising a mono, di or tri phosphate ester or a mixture thereof.
• 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.
• the process for the preparation of this composition consists in mixing a mono, di or tri phosphate ester or their mixture with a film-forming polymer insoluble in water (latex).
• This mixture of the mono, di or tri phosphate ester and the latex can be produced in the form of a mixture of solid powder of mono, di or tri phosphate esters with a redispersible latex powder composition.
• the additivated latex can thus be obtained in the form of an aqueous dispersion. It is also possible to carry out drying of the aqueous dispersion thus obtained in order to obtain a redispersible latex powder additivated as a mono, di or tri phosphate ester.
• the mono, di or tri phosphate ester in powder form in the latex atomization tower, that is to say at the time of drying of the latex.
• the case is preferred where the mono, di or tri phosphate ester is introduced to an aqueous dispersion of film-forming polymer (latex) in post-polymerization.
• the latex can then be dried.
• the amount of mono, di or tri phosphate ester added to the water-insoluble film-forming polymer must be sufficient to provide the water-insoluble film-forming polymer composition with good adhesion properties to the polystyrene, even at low temperatures. 'wet condition.
• the amount of mono, di or tri phosphate ester added to the film-forming polymer insoluble in water is thus generally between 0.02 and 25% by weight of mono, di or tri phosphate ester relative to the weight of dry latex.
• this amount is between 0.5 and 8% by weight of mono, di or tri phosphate ester relative to the weight of the dry latex.
• this amount is between 1 and 5% by weight of mono, di or tri phosphate ester relative to the weight of dry latex.
• Particularly suitable water-insoluble polymers are homo- or copolymers which are in the form of an aqueous dispersion or which can be converted into an aqueous dispersion, and then can be formed into a powder form 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: - vinyl esters and more particularly vinyl acetate; - 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
• esters of mono- or dicarboxylic unsaturated acids having 3 to 6 carbon atoms with alkanols having 1 to 10 carbon atoms, such as maleates, methyl, ethyl, butyl
• (meth) acrylic the (meth) allyl esters of mono and diesters of maleic, fumaric, crotonic and itaconic acids, as well as the alkenic derivatives of amides of acrylic and methacrylic acids, such as N-methallylmaleimide.
• the monomers copolymerizable with vinyl acetate and / or acrylic esters and / or styrene at least one other monomer chosen from the following list: - acrylamide, ethylenically unsaturated carboxylic acids or dibasic acids, preferably acrylic acid, methacrylic acid, or crotonic acid, ethylenically unsaturated sulfonic acids and salts thereof, preferably vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid (AMPS), or sodium methallylsulfonate; crosslinking monomers carrying at least two ethylenic unsaturations such as diallylphthalate, diallylmaleate, allylmethacrylate, triallylcyanurate, divinyladipate or ethylene glycol dimethacrylate; monomers with silane functions such as vinyltrimethoxy silane or vinyltriethoxy silane.
• - acrylamide ethylenically unsaturated carboxy
• These monomers are added in an amount generally between 0.05 and 10.0% by weight, relative to the total weight of the monomers. These monomers are added during the polymerization.
• the polymerization of the monomers is carried out in an emulsion polymerization process in the presence of an emulsifier and / or a protective colloid, 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.
• 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 hydro peroxide, paramenthane hydroperoxide, tert-butyl hydroperoxide, and by persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate. It is used in an amount generally between 0.05 and 3% by weight relative to the total of the monomers.
• hydroperoxides such as hydrogen peroxide, cumene hydroperoxide, diisopropylbenzene hydro peroxide, paramenthane hydroperoxide, tert-butyl hydroperoxide
• persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate. It is used in an amount generally 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 usually 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, 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 allylic 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.
• mercaptans such as N-dodecylmercaptan, tertiododecylmercaptan, 2-mercaptoethanol
• allylic derivatives such as allylic alcohol, cyclohexene
• halogenated hydrocarbons such as chloroform, bromoform, carbon tetrachloride. It adjusts the length of the molecular
• Protective colloids can also be used at the start, during or after the polymerization.
• the particularly 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 hydroxyethylcellulose, guar, tragacantic acid, dextran, alginates and their carboxymethyl, methyl, hydroxyethyl or hydroxypropyl derivatives , proteins, for example casein, soy proteins, gelatins, synthetic polymers, for example poly (meth) acrylic acid, poly (meth) acrylamide, polyvinylsulfonic acids, and copolymers
• 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 with mono, di or tri phosphate esters in the form of 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 particularly suitable protective colloids are the same as those mentioned above.
• 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 between 0.001 and 0.5 mm.
• the water-insoluble film-forming polymer composition comprising a mono, di or tri phosphate ester or their mixture can also comprise a water-repellent agent chosen from fatty acids, or their salts such as calcium, magnesium or sodium stearate, or sodium laurate, fatty acid esters such as those described in document WO 01/90023 (MBT). Mention may be made, as particular water-repellent agents, of the methyl esters of C10-C16 fatty acids (having 10 to 16 carbon atoms) such as those sold under the brand Estorob 1214 by the company Novance, the methyl ester of erucic acid, the methyl ester .
• a water-repellent agent chosen from fatty acids, or their salts such as calcium, magnesium or sodium stearate, or sodium laurate, fatty acid esters such as those described in document WO 01/90023 (MBT). Mention may be made, as particular water-repellent agents, of the methyl esters of C10-C16 fatty
• e of linoleic acid 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.
• the water-insoluble film-forming polymer composition comprising a mono, di or tri phosphate ester or their mixture comprises, as a particularly advantageous water-repellent agent, a C10-C16 fatty acid methyl ester.
• This water-insoluble film-forming polymer composition comprising a mono, di or tri phosphate ester or their mixture has in particular the advantage of being able to be used as it is or in combination with other additives as an adhesion primer on a support to base of thermal insulation and in particular on a support based on polystyrene.
• the subject of the invention is also the use of the film-forming polymer composition insoluble in water comprising a mono, di or tri phosphate ester or their mixture as an adhesion primer on a support based on thermal insulator and in especially a support based on polystyrene.
• This water-insoluble film-forming polymer composition comprising a mono, di or tri phosphate ester or a mixture thereof also has the advantage of reducing the glass transition temperature (Tg) and the minimum temperature. film formation (TMFF) of the non-additive water-insoluble film-forming polymer (latex).
• the invention also relates to a mineral binder composition
• a mineral binder composition comprising a mono, di or tri phosphate ester or a mixture thereof.
• the mineral binders can be aerial binders or hydraulic binders.
• aerial binder plaster-based binders.
• the hydraulic mineral binders can be chosen from cements which can be of portian, 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.
• Mineral binders are generally made from natural materials which are treated at very high temperature to remove water and transform the materials into mineral compounds capable of reacting with water to produce a binder which after drying forms a compact mass having good mechanical properties.
• the mineral binders can be in the form of grout, mortar or concrete; thus, generally when mixing with water, fine or coarser aggregates, such as sand or pebbles, are added.
• the mono, di or tri phosphate ester can be added directly to the construction composition, in an amount which may be between 0.01 and 50% by dry weight of the mono, di or tri phosphate ester relative to the total weight of building composition.
• this amount is between 0.05 and 20% by dry weight of mono, di or tri phosphate ester relative to the total weight of the construction composition. Even more preferably, this amount is between 0.02 and 2% by dry weight of mono, di or tri phosphate ester relative to the total weight of the construction composition.
• the mono, di or tri phosphate ester 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 d be added to the mineral binder composition.
• 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 d be added to the mineral binder composition.
• the binder composition thus further comprises said mono, di or tri phosphate ester at least one film-forming polymer insoluble in water.
• compositions of film-forming polymer insoluble in water are the same as those indicated above.
• the redispersible latex powder additivated as a mono, di or tri phosphate ester 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, in particular from 3 to 15% by weight, relative to the total weight of the polymer , at least one protective colloid, from 0 to 30% by weight, in particular from 1 to 12% by weight, relative to the total weight of the polymer, of anti-caking agent, and from 0.02 to 25% by weight, in particular from 0.5 to 8% by weight, relative to the total weight of the polymer of the mono, di or tri phosphate ester.
• the redispersible latex powder with mono, di or tri phosphate esters is preferably prepared by spray drying the aqueous polymer dispersion. This drying can be carried out in conventional spray drying systems, using atomization by means of single, double or multiple liquid nozzles or a rotating disc.
• the product outlet 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 degree of drying desired.
• 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 mineral binder composition thus obtained has, after consolidation, good adhesion properties on thermal insulators and in particular on polystyrene, in particular in the wet state or under the effect of a significant variation in temperature. It also has 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.
• 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 composition can also comprise any additive usually used in mineral binder compositions.
• the composition according to the invention, in particular the mineral binder composition according to the invention can also comprise a silicone, preferably chosen from polyorganosiloxanes, in particular polyorganosiloxanes which are liquid at room temperature. This silicone can be introduced in post-polymerization, or in the form of a powder.
• the subject of the invention is also a process for increasing the adhesion properties on a thermal insulator and in particular on polystyrene, in particular in the wet state or under the effect of a significant variation in temperature, after consolidation, of a composition of mineral binders, characterized in that a sufficient amount of at least one mono, di or tri phosphate ester or their mixture is added to said composition.
• the present invention also relates to the use of this mineral binder composition to increase the adhesion of a thermal insulator and in particular of polystyrene on a support material.
• the support materials can be composed of concrete, bricks, aerated concrete, agglomerated concrete (concrete block), fiber cement, masonry or wall plaster.
• the proportions and percentages indicated in the examples are by weight unless otherwise indicated.
• the particle sizes (d50) are measured using a Coulter LS 230 laser diffraction particle size analyzer. Examples
• the mortar is spread over the insulation with a thickness of 3 mm a quarter of an hour after mixing. After drying the mortar for 28 days (at (23 ⁇ 2) ° C and (50 ⁇
• the pull-out test is carried out under the following conditions without additional conditioning (in the dry state), - after immersion of the mortar in water for 2 days and drying for 2 hours (at (23 ⁇ 2) ° C and (50 ⁇ 5)% RH).
• the average peel value is based on the results of eight trials. The individual and average values are recorded and the results expressed in
• Three sandstone tiles are prepared for each formulation.
• the coating (thickness 3 mm) is applied using a trowel on one side of the sandstone tile.
• the sandstone tile thus prepared is conditioned for 28 days (at (23 ⁇ 2) ° C and (50 ⁇ 5)% RH).
• the lateral faces of the sandstone tile are sealed against water so as to ensure that only the face coated with the coating layer is subjected to the uptake of water for the duration of the test.
• the surface covered by the coating of the sandstone tile is brought into contact with a sponge (a paper filter is previously deposited between the sandstone tile and the sponge) placed in a tank containing water.
• the sandstone tiles are weighed before immersion (reference weight) and then after 30 minutes, 1 hour, 2 hours, 4 hours, 6 hours, 24 hours. Before the second and subsequent weighings, the surface of the sandstone tiles is wiped with absorbent paper. The calculation aims to determine the average water uptake per square meter over time.
• Example 1 Production of a latex emulsion with additive from a vinyl acetate / vinyl neodecanoate copolymer (sold under the brand Veova 10 by the company Resolution) and tris (2-butoxyethyl) phosphate
• a latex composed of a vinyl acetate-vinyl versatate copolymer with a composition of 50% vinyl acetate and 50% vinyl versatate (Veova 10) by weight.
• This latex is synthesized by an emulsion polymerization process using polyvinyl alcohol with a hydrolysis rate of about 88% as a protective colloid and potassium persulfate as a radical initiator.
• the characteristics of this latex Dry extract: 50.73% pH: 4.7 TMFF: 7.6 ° C Tg: 16 ° C Brookfield viscosity at 50 rpm: 2420 mPa.s Granulometry: d50: 2 ⁇ m
• control latex 801.7 grams are introduced into a 1 liter reactor fitted with anchor type stirring. This latex is heated to a temperature between 60 and 70 ° C. and 16.3 grams of Amgard TBEP are poured in over a period of approximately 20 minutes. After the addition of the Amgard TBEP is completed, the temperature is further maintained for 20 to 30 minutes, then the mixture is cooled to room temperature.
• This latex can then be formulated as or be atomized in the presence of an anti-caking agent (for example kaolin or silica) in order to obtain a powder redispersible in water.
• an anti-caking agent for example kaolin or silica
• composition of the coating formulation used for bonding and the basic polystyrene coating • CPA CEMI 42.5 gray cement: 600g • Sand HN38 (0.4-4 mm) 1296g • Cellulosic ether Culminai 9101: 1g • Cellulosic ether Culminai 9104: 3g • Lime: 40g • Latex emulsion with additive Amgard TBEP: 115.6g
• the mortar containing the control latex additive with Amgard TBEP has an adhesion to polystyrene (0.065 N / mm2) after immersion in water for 2 days and drying for 2 hours (at 23 ° C ⁇ 2 ° C) superior to the mortar containing the non-additive control latex (0.045 N / mm 2 ).
• Amgard TOF tris (2-ethylhexyl) phosphate (CAS 1806-54-8) sold by the company Rhodia.
• Amgard TBEP tris (2-butoxyethyl) phosphate (CAS 78-51-3) sold by the company Rhodia. Physical form: liquid
• a latex composed of a copolymer of vinyl acetate-vinyl versatate with a composition of 50% vinyl acetate and 50% of versatate is used.
• This latex is synthesized by an emulsion polymerization process using polyvinyl alcohol with a hydrolysis rate of approximately 88% as a protective colloid and potassium persulfate as a radical initiator.
• control latex 11 kg are introduced into a 25 liter reactor fitted with an anchor type agitation. This latex is heated to a temperature between 60 and 70 ° C. and 220 grams of Amgard TBEP or Amgard TOF are poured over a period of approximately 20 minutes. After the addition of the Amgard is complete, the temperature is further maintained for 20 to 30 minutes and then the mixture is cooled to room temperature. The drying of the suspension was developed by a Niro type atomization process. The temperature of the attack air is between 110 and 160 ° C, preferably here between 120 and 150 ° C, the outlet temperature is between 50 and 90 ° C, preferably here between 60 and 80 ° C.
• the polymer suspension is sprayed in the presence of mineral or organic fillers which improve the flowability of the product and prevent caking.
• mineral or organic fillers can be, for example, carbonates, silicates, silica, double salts (talc, kaolin) or mixtures of these different fillers.
• the contents of these mineral fillers vary from 2 to 20% and preferably here between 5 and 15%.
• Control powder % residual moisture: 1% Average rate of mineral agent: 9.6% Average particle size d50: 74 ⁇ m
• Example latex powder additive Amgard TBEP Amgard rate / dry latex: 4% - Characteristics of the latex: Dry extract: 50.8% pH: 4.8 TMFF: 0 ° C Brookfield viscosity at 50 rpm: 3024 mPa. s Grain size: d50: 1.9 ⁇ m - Characteristics of the powder:% residual moisture: 1.2% Average mineral agent level: 12% Average grain size d50: 79 ⁇ m
• Example latex powder additive Amgard TOF Amgard rate / dry latex: 4% - Characteristics of the latex: Dry extract: 51, 1% pH: 4.8 TMFF 0 ° C Brookfield viscosity at 50 rpm: 2968 mPa.s Granulometry: d50: 1, 9 ⁇ m - Characteristics of the powder:% residual humidity: 0.83% Average rate of mineral agent: 13% Average granulometry d50: 62 ⁇ m
• the adhesion measured after 28 days and after curing in water is greater in the case of mortars containing control powders additive with Amgard TBEP and Amgard TOF compared to the mortar containing control powder not additive.
• the amounts of water absorbed are lower in the case of mortars containing the control powders additive with Amgard TBEP and Amgard TOF compared to the mortar containing the non-additive control powder.
• Example 3 (Terpo emulsion + additives)
• a latex composed of a copolymer of vinyl acetate-vinyl versatate and dibutyl maleate having a composition of 50% vinyl acetate, 50% vinyl versatate (Veova 10) and 25% dibutyl is used maleate by weight.
• This latex is synthesized by an emulsion polymerization process using polyvinyl alcohol having a hydrolysis rate of about 88% as a protective colloid and potassium persulfate as a radical initiator.
• the characteristics of this latex are: Dry extract: 50.73% pH: 4.7 TMFF: 5 ° C Tg: 16 ° C Brookfield viscosity at 50 rpm: 2420 mPa.s Granulometry: d50: 2 ⁇ m
• Example control latex added with Amgard TBEP Gray cement 42.5 R: 600g Sand HN38 (0.4-4 mm) 1295.7g Cellulosic ether Culminai 9101: 1g Cellulosic ether Culminai 9104: 3g Lime: 40g Latex emulsion additive Amgard : 116.3g Water / powder ratio 0.22
• Example control latex additive Amgard TBEP and Estorob 1214 Gray cement 42.5 R: 600g Sand HN38 (0.4-4 mm) 1295.7g Cellulosic ether Culminai 9101: 1g Cellulosic ether Culminai 9104: 3g Lime: 40g Latex emulsion with additive Amgard TBEP and Estorob 1214: 116g Water / powder ratio 0.22
• the quantities of water absorbed are lower in the case of the mortar containing the control emulsion added with the mixture Amgard TBEP and Estorob 1214.
• DEHPA (0.5% by weight / latex powder) is pre-mixed with the latex powder before introduction into the mixture containing the different fillers.
• Gray cement 42.5 R: 600g Sand HN38 (0.4-4 mm) 1295.4g Cellulosic ether Culminai 9101: 1g Cellulosic ether Culminai 9104: 3g Lime: 40g Latex powder: 60g DEHPA: 0.3g Water / powder ratio 0.22
• the amount of water absorbed is lower in the case of the mortar containing the control powder mixed with DEHPA compared to the mortar containing the non-additive control powder.

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