WO2020221980A1 - Use of an aqueous polymer dispersion for the production of coated macadams - Google Patents

Use of an aqueous polymer dispersion for the production of coated macadams Download PDF

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Publication number
WO2020221980A1
WO2020221980A1 PCT/FR2020/050733 FR2020050733W WO2020221980A1 WO 2020221980 A1 WO2020221980 A1 WO 2020221980A1 FR 2020050733 W FR2020050733 W FR 2020050733W WO 2020221980 A1 WO2020221980 A1 WO 2020221980A1
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Prior art keywords
binder
particles
glass transition
polymer
mixes
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PCT/FR2020/050733
Other languages
French (fr)
Inventor
Thomas LEBARBE
Frédéric DELFOSSE
Pierre-Jean MERCIER
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Eurovia
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Publication date
Application filed by Eurovia filed Critical Eurovia
Priority to EP20731918.7A priority Critical patent/EP3963016A1/en
Publication of WO2020221980A1 publication Critical patent/WO2020221980A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C7/00—Coherent pavings made in situ
    • E01C7/08—Coherent pavings made in situ made of road-metal and binders
    • E01C7/30—Coherent pavings made in situ made of road-metal and binders of road-metal and other binders, e.g. synthetic material, i.e. resin

Definitions

  • the present invention relates to the use of an aqueous polymer dispersion for the preparation of a binder intended for the manufacture of a road or urban mix.
  • the aqueous polymer dispersion comprises particles based on at least two polymers each having distinct glass transition temperatures.
  • a subject of the invention is also said mixes based on this aqueous polymer dispersion and a road or urban coating comprising the mixes of the invention.
  • Roads, pavements and various urban developments must support heavy road and / or pedestrian traffic. It is therefore essential that these coatings have mechanical properties allowing them to withstand the stresses induced by this traffic over time, regardless of the environmental modifications undergone, such as for example the significant temperature changes that may take place during the different seasons. .
  • asphalt mixes which are used in particular for the manufacture of wearing courses or pavement layers.
  • a mix consists of a granular fraction and a binder.
  • the granular fraction is a mixture of aggregates, fines and sand. Aggregates are most often made from massive or sedimentary rocks (from sand to chippings) but they can also come from recycled or synthetic products.
  • the binder makes it possible to bond the aggregates together and to ensure good mechanical strength of the asphalt layer.
  • the binder in general, can for example be a hydrocarbon binder, a synthetic binder, or a plant binder.
  • the mixes are completely covered with binder during their manufacture then applied by spreading and compacted to obtain road surfaces.
  • the hydrocarbon mixes, coated with bitumen, are among the most used for these applications and responsible for the black color of the roads.
  • the properties of the mixes such as the mechanical, thermal and acoustic properties, the tightness of the resulting coating, are modulated by the nature of the granular fraction and of the binder. Thus, researchers are always on the lookout for new materials to improve these different properties.
  • an aqueous polymer dispersion comprising particles based on polymers exhibiting distinct glass transition temperatures for the preparation of a binder intended for the manufacture of mixes makes it possible to modulate the mechanical properties of asphalt in order in particular to obtain an optimum stiffness / flexibility ratio of the asphalt layer.
  • the particles suspended in the aqueous dispersion can be structured such that a positive gradual gradient of glass transition temperature is observed from the surface to the center of the particle.
  • the particles suspended in this aqueous polymer dispersion can also be in the form of so-called core / shell particles (more commonly described in English under the term “core shell particle”).
  • core / shell particle denotes polymer particles consisting of a polymer core surrounded by a shell (or shell) of a different polymer.
  • the nature of the polymers of the core or of the shell are chosen in a specific manner according to the intended uses and make it possible to modulate the mechanical, physical and chemical properties of the particles. For example, it is possible to obtain particles having the particularity of exhibiting several distinct glass transition temperatures. Thus, the envelope and the core of the particle will have different mechanical properties, exhibiting a more rigid or rubbery character depending on the nature of the polymer constituting them.
  • WO2009 / 09559 describes an aqueous dispersion comprising particles structured in the core / shell, based on polymers PI and P2 having glass transition temperatures Tgl and Tg2 for the preparation of decorative and industrial paints.
  • Application WO2009 / 016053 relates to a coating composition intended to cover substrates, in particular paper, to make them more resistant to oil and grease.
  • These compositions comprise polymer particles structured in the core / shell in an aqueous medium.
  • These particles comprise a core made up of a polymer whose glass transition temperature is lower than that of the polymer constituting the shell.
  • the envelope therefore has a more rigid character than the core of the particle which is more rubbery.
  • Application EP 1,434,803 describes an aqueous dispersion for surface coating or as an adhesive, based on various polymers, comprising in particular vinyl polymers having a specific composition in gradient allowing them to have modulable properties.
  • the aqueous dispersion obtained thus offers an advantageous combination of minimum film-forming temperature, hardness and elasticity.
  • the vinyl polymers can, for example, be obtained from compositions of monomers exhibiting distinct glass transition temperatures, but also chemical functionalities, molecular masses, hydrophobicity, etc. different.
  • an aqueous dispersion based on polymer particles exhibiting distinct glass transition temperatures within the particle itself has never been described for the preparation of a binder intended for the manufacture of road or urban mixes.
  • the use of an aqueous polymer dispersion according to the present invention makes it possible to obtain a binder intended for the production of mixes having a low film-forming temperature and giving the resulting coated layer an optimum compromise between rigidity and flexibility.
  • this type of binder has the advantage of being translucent and therefore makes it possible to produce coatings the color of which is that of the granular materials which constitute them.
  • Asphalt mixes made of such a binder are therefore particularly suitable for pedestrian and cycle-friendly areas with little traffic, forest lanes, riverbank lanes, sidewalks and can contribute to the safety of these spaces through greater readability and visual differentiation of the traffic. different arrangements.
  • the many artificial surfaces of urbanized environments are largely composed of mineral materials, such as asphalt, asphalt and concrete, with low solar reflectance powers.
  • the multiplication of these surfaces is one of the most important factors in the creation of urban heat islands.
  • the use of an aqueous polymer dispersion for the preparation of a clear binder intended for the production of mixes can thus contribute to the cooling of the coatings.
  • a first object of the invention therefore consists in the use of an aqueous dispersion comprising at least one anionic surfactant and p ⁇ particles based on at least two polymers exhibiting distinct glass transition temperatures, so that the polymer having the highest glass transition temperature, greater than or equal to 10 ° C, is at the center of the particle p ⁇ and the polymer with the lowest glass transition temperature, less than or equal to 0 ° C, is at the surface of the p ⁇ particle, for the preparation of a binder intended for the manufacture of a road or urban asphalt.
  • road or urban mix is meant, within the meaning of the present invention, a mixture of a granular fraction and a binder, said granular fraction comprising aggregates, fines and sand.
  • the coated materials are obtained by mixing the binder and the granular fraction until the breaking of the emulsion is observed which corresponds to the evaporation or to the elimination by drainage of the water included in the emulsion and to the formation of a binder film coating the granular fraction.
  • the urban asphalt according to the present invention is particularly suitable for surfaces with little traffic and urban developments such as pedestrian paths, cycle paths, greenways, squares, squares, playgrounds or sports grounds. Asphalt is particularly suitable for vehicular traffic lanes, such as roads, sidewalks and streets.
  • binder is understood to mean any binder of synthetic origin, preferably translucent, based on an aqueous dispersion of polymer particles as defined in the present application which can be used for the production of a coated material. , advantageously of a clear mix.
  • residual binder is understood to mean the binder included in the mixes after the coating and removal of the water (and / or solvents where appropriate) from the dispersion.
  • the residual binder is anhydrous.
  • anionic surfactant means a surfactant product, that is to say capable of modifying the surface tension between two surfaces, ionizing in aqueous solution to provide anions and responsible for the activity. of surface.
  • glass transition temperature (denoted Tg) is meant the temperature below which the physical properties of amorphous materials vary from a rubbery state to a glassy state. Thus, Tg is also the temperature below which molecules have little relative mobility. The glass transition temperature is typically measured by means of the following tests:
  • the highest Tg which can be denoted Tgi, is greater than or equal to 30 ° C, preferably greater than or equal to 50 ° C.
  • Tgi is between 10 ° C and 100 ° C, preferably between 30 ° C and 100 ° C, even more preferably, Tgi is between 50 ° C and 100 ° C.
  • the lowest Tg which can be denoted Tg2, is less than or equal to -10 ° C.
  • Tg2 is between 0 ° C and -100 ° C, preferably between 0 ° C and -50 ° C, even more preferably, Tg2 is between 0 ° C and -20 ° C, and in particular between - 10 ° C and -20 ° C.
  • the p ⁇ polymer particles included in the aqueous dispersion therefore have a rubbery character at the surface and a rigid character at their center.
  • This dual nature makes it possible to obtain a residual binder with a good stiffness / flexibility compromise.
  • the soft phase of the p ⁇ particles allows the formation of the binder film at lower temperatures and reduced demand for coalescing agents while the high Tg phase improves the hardness of the binder film.
  • Said residual binder thus exhibits modulus values high, being less susceptible to fracture, while remaining rigid and suitable for urban or road surfaces considered. These module values vary little as a function of the outside temperature, the latter typically ranging from -40 ° C to 60 ° C.
  • the mechanical properties of the mixes comprising said binder remain stable over a wide range of outside temperatures to which the mixes can be exposed during the year, in winter as in summer.
  • the film-forming temperature of the binder is less than 5 ° C. A low film-forming temperature ensures good cohesion of the resulting mix.
  • the particles of polymers p ⁇ included in the aqueous dispersion therefore comprise a polymer PI, having a Tgi, at their center and at least one other polymer P2, having a Tg2, at the surface of the particle p ⁇ , of so that the layers of polymers are in contact with one another, or even bonded to one another.
  • the particles of the invention do not include a void or any material other than polymer.
  • the particles of the invention consist of two polymers PI and P2 as defined above.
  • the aqueous dispersion of polymers according to the present invention is obtained by emulsion polymerization in aqueous phase of at least two compositions of monomers M1 and M2 resulting respectively in polymers PI and P2.
  • this aqueous phase emulsion polymerization can be carried out in a sequenced manner, or the M1 monomer is polymerized first and then the additives making it possible to initiate the M2 monomer are added to the medium. reaction, or the monomers M1 and M2 are each polymerized separately and then mixed.
  • Said polymerization is carried out in the presence of at least one anionic surfactant.
  • anionic surfactant makes it possible to improve the stability of the aqueous dispersion during polymerization and to effectively disperse the polymer particles.
  • the anionic surfactant is moreover useful in the aqueous dispersion for the formation of a binder for road or urban asphalt.
  • this anionic surfactant is chosen from fatty acid carboxylates, sulfates such as sodium dodecylsulfate, sulfonates such as sodium alkylbenzene sulfonates, alpha-olefin sulfonates, phosphates, sulfosuccinates and phospholipids .
  • the anionic surfactant is present in the aqueous dispersion in a content of at least 0.2% by weight relative to the total weight of said dispersion, preferably between 0.2% and 5%.
  • the polymerization can also take place in the presence of at least one nonionic surfactant, which does not ionize in water, in combination with at least one anionic surfactant as defined above. above.
  • This nonionic surfactant can represent from 0.2% to 5%, and preferably from 0.2% to 0.5% of the total weight of the dispersion.
  • This nonionic surfactant is for example selected from glycol esters such as ethylene glycol stearate, glycerol esters, sorbitan esters (Tween ®), esters of polyoxyethylene, fatty alcohol ethers and alkanolamides.
  • the resulting aqueous polymer dispersion used in the present invention for the preparation of a binder for road or urban asphalt comprises at least one anionic surfactant as defined above.
  • said aqueous dispersion also comprises at least one nonionic surfactant as defined above.
  • the polymers included in the particles of the aqueous dispersion used for the preparation of a binder according to the present invention are advantageously obtained from compositions of monomers chosen from the group consisting of vinyl and / or diene monomers, esters comprising at least one polymerizable olefinic introduction, ethylenically unsaturated monomers bearing at least one acid and / or carboxylic anhydride function and combinations thereof.
  • these monomers are chosen from styrene and its derivatives, comprising for example vinyltoluenes (ortho, meta, para), ⁇ -methylstyrene, isopropylstyrene, ferf-butylstyrene, para-butylstyrene, para-decylstyrene, para-chloro-styrene and also from butadiene, isoprene, (meth) acrylic esters, nitriles such as (meth) acrylonitrile, vinyl esters such as vinyl acetate, vinyl butyrate, vinyl caprolate, and vinyl pivalate, (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, isocrotonic acid, vinylbenzoic acid, and combinations thereof.
  • the formulation (meth) acryl * designates acryl * and methacryl *, * designating the suffix -ate or -ique.
  • the (meth) acrylic esters are preferably selected from linear C1-10 alkyl (meth) acrylates, such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate , branched C3-10 alkyl (meth) acrylates, 2-ethylhexyl acrylate, and combinations thereof.
  • the monomers are chosen from styrene and (meth) acrylic esters such as linear C1-10 alkyl (meth) acrylates, branched C3-10 alkyl (meth) acrylates.
  • the aqueous polymer dispersion used for the preparation of a binder as described above typically comprises a dry extract of between 30% and 70% by weight of polymers relative to the total weight of the dispersion, preferably between 40% and 60 %, more preferably between 45% and 55%.
  • the p ⁇ particles of polymers, included in the aqueous dispersion comprising at least two polymers having distinct Tg's are structured so that a positive gradient of Tg is observed from the surface of the particles to the center of the particles.
  • the p ⁇ particles of polymers structured so that a positive gradient of Tg is observed from the surface of the particles towards the center of the particles therefore comprise several layers of polymers, each layer having a distinct Tg.
  • the Tg gradient between each polymer layer from the surface to the center of the particle is between 10 ° C and 200 ° C, preferably between 50 ° C and 100 ° C.
  • the polymer particles can comprise more than two polymers, each polymer having a distinct Tg, so that the Tg of each polymer increases as one moves from the surface to the center of the particle.
  • the particles p ⁇ with a gradient of Tg can comprise a polymer PI at the center of the particle surrounded by one or more intermediate layers of polymer included between the polymer PI and a layer of polymer P2 at the surface of the particle, the intermediate layers having Tg between Tgl and Tg2, so that the value of the Tg of each polymer layer increases when one goes from the layer of P2 to the layer of PI.
  • the p ⁇ particles of polymers included in the aqueous dispersion are structured as core / shell particles.
  • the core / shell particles according to the invention comprise a PI polymer at their center, exhibiting a Tgi as defined above, surrounded by at least one envelope consisting of a P2 polymer exhibiting a Tg2 such as as defined above.
  • the aqueous polymer dispersion used for the preparation of a binder as described above may comprise p ⁇ particles of different polymers, that is to say p ⁇ particles based on different polymer compositions.
  • each p ⁇ particle will include at least two polymers having distinct Tg's.
  • the same dispersion may comprise p ⁇ particles consisting of polymers A and B, but also p ⁇ particles consisting of polymers C and D.
  • the aqueous dispersion used for the preparation of a binder intended for the manufacture of a road or urban mix also comprises particles p2 of polymer having a single Tg in addition to the particles p ⁇ having at least two separate Tg as described above.
  • these single Tg polymer particles p2 are prepared from a composition of monomers as described above.
  • these unique Tg particles can consist of a single polymer.
  • the particles p2 are obtained from (meth) acrylic esters.
  • the Tg of these single Tg polymer particles p2 is less than 0 ° C.
  • This variant of the invention makes it possible to improve the flexibility of the residual binder.
  • the Tg of these single Tg polymer particles p2 can also be greater than 10 ° C. According to this variant of the invention, the residual binder is more rigid.
  • the presence of particles of polymers p2 with a single Tg within the aqueous dispersion also comprising p ⁇ particles having at least two distinct Tg makes it possible to modulate the stiffness / flexibility ratio of the residual binder after coating of the mixes. This ratio can thus be adjusted as a function of the intended use of the mixes of the invention.
  • the solids content of particles n2de polymers with a single Tg within the aqueous dispersion of polymer particles used for the preparation of a binder is between 0% and 60% relative to the total weight of the solids content of the particles.
  • p ⁇ and p2 of polymer advantageously between 0% and 40%.
  • the aqueous dispersion used for the preparation of a binder according to the present invention may comprise particles p2 with a single Tg obtained which are different.
  • certain particles p2 could consist of a polymer A while other particles p2 also present within the aqueous dispersion could consist of a polymer B.
  • the present invention relates to the use of an aqueous dispersion comprising p ⁇ particles of polymers based on at least two polymers exhibiting distinct Tg's, said particles being structured in the core / shell, mixed with polymer particles p2 having a unique Tg.
  • the present invention relates to the use of an aqueous dispersion comprising p ⁇ particles of polymers based on at least two polymers exhibiting distinct Tg, said particles being structured with a gradient of Tg from the surface. at the center of the particle, in admixture with p2 polymer particles exhibiting a single Tg.
  • a second subject of the invention relates to mixes comprising a granular fraction coated with a binder, said binder being based on an aqueous dispersion of particles as defined in the invention.
  • the term “granular fraction” is understood to mean solid fractions, in particular solid mineral fractions, which can be used for the production of mixes in particular for road or urban construction, including in particular natural mineral aggregates (gravel, sand, fines) for example from quarries or gravel pits, recycling products such as asphalt aggregates, for example resulting from the recycling of materials recovered during repair of roads as well as surplus asphalt mixing plants, manufacturing scrap, "shingles” (from recycling roofing membranes), aggregates from recycling road materials including concrete, slags in particular slag, shale in particular bauxite or corundum, rubber powder from recycling tires in particular, artificial aggregates of any origin and from, for example, bottom ash from household waste incineration (MIOM), as well as their mixtures in all proportions.
  • MIOM household waste incineration
  • coated aggregates is understood to mean asphalt mixes (mixture of aggregates and binders) originating from the milling of asphalt layers, from the crushing of slabs extracted from asphalt pavements, pieces of asphalt slabs, waste from asphalt or asphalt production surplus (production surpluses are materials coated or partially coated in a plant resulting from transient phases of production). These and other recycling products can reach sizes up to 31.5mm.
  • the aggregates according to the present invention are obtained from massive rocks or from alluvial deposits according to the conditions of use of the mix and are chosen with reference to the standard EN 13043 (March 2003).
  • the calcareous or silico-calcareous materials are preferred for the formulation of the mixes according to the invention, without being limited thereto.
  • the water content of the materials must be rigorously controlled below 3% by weight, relative to the total weight of the materials, so as not to have leaching during contact with the binder in the aqueous phase.
  • the granular fraction advantageously comprises:
  • the granular fraction advantageously comprises:
  • - elements in particular chippings, having dimensions: . between 2 mm and 6 mm;
  • mineral fines or “filler” is meant any mineral filler passing through a sieve with a square mesh of 0.063 mm side.
  • the fines can be natural or filler fines, for example limestone fines (calcium carbonate), cement or hydrated lime, or recovered.
  • the “granular fraction” is also designated by the terms “0 / D solid fraction”. This 0 / D solid fraction can be separated into several particle sizes: the 0 / d solid fraction and the d / D solid fractions.
  • the “granular mineral fraction” is also denoted by the terms “0 / D mineral fraction”. This 0 / D mineral fraction can be separated into several particle sizes: the 0 / d mineral fraction and the d / D mineral fractions.
  • the finest elements are those included in the range between 0 and a maximum diameter which can be set between 2 and 6mm (from 0/2 to 0/6), advantageously between
  • solid fraction d / D advantageously the solid mineral fraction d / D.
  • the solid fraction, in particular the solid mineral fraction advantageously constitutes 80% to 99%, more advantageously 90% to 98.5%, even more advantageously from 96.5% to 97.5% of the weight of the mix after curing ( complete evaporation of water).
  • the mixes of the invention are light in color.
  • the aggregates used in the mixes of the invention preferably have a significant luminescence L *, typically greater than 50. This property gives the coatings improved visibility day and night as well as great clarity.
  • Luminescence is typically calculated according to standards NF EN 11664-1, NF EN 11664-2 and NF 11664-4, dated 07-01-2011.
  • the binder based on the aqueous dispersion as described above has a film-forming temperature less than or equal to 10 ° C, preferably less than or equal to 5 ° C, even more preferably less than or equal to 1 ° vs.
  • the whole of the granular fraction is coated using the binder based on the aqueous dispersion as defined above.
  • the mixes according to the present invention can be obtained from the process comprising the following successive steps: a) Preparation of a granular fraction as described above,
  • Step c) is carried out for a sufficient time to observe advanced rupture of the emulsion.
  • the emulsion binder resulting from step b) comprises between 0.2% and 5% by weight of anionic surfactant as defined above relative to the total weight of the emulsion binder.
  • the emulsion binder resulting from step b) can optionally comprise a nonionic surfactant as defined above in combination with at least one anionic surfactant.
  • the nonionic surfactant represents between 0.2% and 5% by weight relative to the total weight of the binder in emulsion.
  • the mix can also comprise a minor amount of hydraulic binder in combination with the binder based on the aqueous dispersion as described above.
  • minimum amount is understood to mean that the content of residual hydraulic binder is less than or equal to 2% relative to the total weight of the mix, preferably less than 1%.
  • said hydraulic binder is chosen from Portland cement, lime, milk of lime, magnesia, synthetic or natural calco-magnesian compounds such as dolomites, magnesian lime or dolomitic lime, silicate or carbonate cements. calcium and / or magnesium aluminates or any other hydraulic binder well known to those skilled in the art.
  • hydraulic binder makes it possible to increase the rigidity of the final residual binder, and therefore of the resulting asphalt coating, according to the intended uses.
  • the addition of hydraulic binder can also decrease the setting time of the asphalt, i.e. the time required for the water and possibly the solvents to evaporate (s) from the binder and for the asphalt is sufficiently consolidated and stable to be placed under traffic.
  • the hydraulic binder can be introduced either during step c) of the above process, that is to say during the mixing of the various components of the mix, or beforehand in the granular fraction during step a) or to the binder in emulsion during step b) before coating, subject to the compatibility and the stability of the hydraulic binder in the aqueous polymer dispersion as defined above.
  • the hydraulic binder is added during step a) to the granular fraction.
  • the emulsion binder resulting from step b) comprises a dry extract of between 30% and 70% by weight of polymers relative to the total weight of the emulsion, preferably between 40% and 60%, more preferably between 45 % and 55%.
  • the mixes according to the invention can comprise at least one additive, added either to the granular fraction during step a), or to the binder during step b), or to the mix, in other words during the mixing of the mixtures. aggregates and binder in step c).
  • additives can, for example, be used for mechanical purposes, for rheological purposes, for adhesion purposes and / or for aesthetic purposes, in particular for a change of color of the final road products.
  • this additive is selected from an inorganic or organic viscosifier, such as clays, or from fumed silicas, cellulosic or synthetic viscosifiers of the associative type such as HEUR (Urethane ethylene oxide modified hydrophobically, Hydrophobically modified Ethylene oxide URethane according to the appropriate acronym) / HMPE (High Modulus Polyethylene, High Modulus PolyEthylene) or HASE; or non-associative (ASE), an “anti-foam” additive, pigments, fibers or an emulsifier.
  • HEUR Urethane ethylene oxide modified hydrophobically, Hydrophobically modified Ethylene oxide URethane according to the appropriate acronym
  • HMPE High Modulus Polyethylene, High Modulus PolyEthylene
  • HASE non-associative
  • an “anti-foam” additive pigments, fibers or an emulsifier.
  • HASE a hydrophobically modified soluble alkali emulsion, is understood to mean a carboxylated copolymer based on:
  • ASE a soluble alkali emulsion
  • carboxylated copolymer based on:
  • the fibers are for example chosen from cellulosic fibers, polyacrylonitrile fibers, such as polyacrylonitrile fibers with a size of between 4 and 12 mm, and / or glass fibers.
  • the fiber content advantageously varies from 0.05 to 0.5 pph (part percent by weight) / dry solid fraction, advantageously 0.05 to 0.5 pph (part percent by weight) / dry aggregates, preferably between 0 , 07 and 0.2 ppc.
  • the addition of fibers makes it possible to limit sagging of the binder based on the aqueous dispersion and to improve the abrasion resistance at a young age of the resulting mix.
  • the state of dryness of the solid fraction, in particular of the solid mineral fraction, water, known as feed water, can be added to the granular fraction during step a) of above process.
  • the total water content by weight of the granular fraction resulting from step a), consisting of the input water and the water naturally present in the granular fraction, is between 1% and 6% by weight per relative to the total weight of the granular fraction, advantageously the water content is 4%.
  • Step a) process for preparing the mixes may include optional drying of the granular fraction if the latter contains a water content greater than 6% by weight relative to the total weight of the granular fraction, in order to achieve a content in water of between 1 and 6%, advantageously of 4%.
  • Coating step c) is preferably carried out cold.
  • the term “cold coating” means that the granular fraction, in particular the aggregates, is not dried, and is mixed as it is, that is to say with its natural moisture (more an adjustment of the water content if necessary) and at room temperature.
  • the binder then arrives in various forms, the most common being that of an emulsion which thus makes it possible to have a product that is not very viscous and therefore workable at room temperature.
  • ambient temperature is understood to mean a temperature ranging from 15 ° C to 40 ° C.
  • the mixes according to the present invention have a void content of less than 30%, preferably between 5% and 30%, even more preferably between 8% and 25%.
  • the content of anhydrous residual binder after coating step c) is typically between 1% and 20% by weight relative to the total weight of the mix, preferably between 1.5% and 10% by weight, more preferably between 2.5% and 3.5% by weight.
  • the amount of binder in the mix can be adjusted depending on the intended use of the mix.
  • hydrocarbon mixes according to the invention are deposited by spreading, for example with a finisher or a grader, then compacted. These mixes allow a return to traffic of less than 72 hours, more advantageously within 24 hours after spreading.
  • a final object of the present invention relates to a road or urban coating, comprising at least one coating layer according to the present invention.
  • the coating according to the present invention is a clear pavement layer particularly suitable for low traffic lanes such as, for example, pedestrian lanes, cycle paths, squares, squares, playgrounds, sports fields and lanes. green.
  • the coating of the invention also comprises a sealing layer over the coating layer (s), advantageously applied between 24 hours and 48 hours after the end of the use of the coated materials.
  • the term “sealing layer” is understood to mean a layer of binder sprayed onto a pavement layer intended to fix the surface gravel (the rolling stones) and to improve its waterproofing. Indeed, the good level of cohesion of the mixes guarantees the absence of gravel and sand tearing.
  • the sealing layer consists of an aqueous polymer dispersion comprising particles based on at least two polymers exhibiting distinct glass transition temperatures, polymer particles exhibiting a single glass transition temperature or mixtures thereof.
  • it is a dispersion comprising particles of core / shell polymers or of polymer particles structured so that a gradient of Tg is observed as described in the present description or of polymer particles having a Tg single such as acrylic or styrene-acrylic polymer particles.
  • the sealing layer is preferably applied at a dosage of 150 to 400 g / m 2 of residual binder.
  • the present invention also relates to a process for preparing the coating of the invention under cold conditions, comprising the following steps:
  • a ' cold preparation of the mixes of the invention by mixing the granular fraction, the binder and optionally at least one additive, according to steps a) -c) described above, b') spreading of the mixes in an ambient temperature, preferably between 5 ° C to 40 ° C, and at a degree of hygrometry which can range up to 100%,
  • the modulus of the mixes of the invention and of the control mix are similar, while at higher temperatures (in particular 40 and 60 ° C), the modulus of the mixes based on a control binder decreases more sharply than that of the coated materials of the invention.
  • the content of total residual anhydrous binder was set at 3.0 pph (or 2.9%) relative to the mass of the solid mineral fraction.
  • the particle size curve of the solid mineral fraction is as follows for all the examples below:
  • the binders tested are the polymer dispersions in aqueous phase having the following properties:
  • the binders used in the examples are commercial binders from the company Celanese ® sold under the trade name Mowilith ® . They all include an anionic surfactant. Asphalt production
  • the solid mineral fraction was introduced into a kneader, water was added to the mixture and then the binder in aqueous phase was introduced into the formulation. After 20 seconds of mixing, the asphalt is compacted using a Marshall® machine, then maturing for 14 days at 35 ° C. / 20% hygrometry is carried out.
  • the mixes are then characterized by sinusoidal diametral compressions in order to obtain the phase angle, as well as the complex modulus of the mix as a function of temperature and frequency.
  • a surface cohesion test of the Surface Cohesion test (TCS) type from standard NF EN 12274-5 can be carried out to estimate the resistance to surface tearing of the asphalt. This test is carried out after a cure time of the mix of 72 hours at 20 ° C. before immersion in water. The mass share of the asphalt is then evaluated as a percentage relative to the abrasion surface.
  • TCS Surface Cohesion test
  • Example 3 Formulation according to the invention n ° l
  • a core-bark binder according to the invention was used for the formulation of clear cold mixes according to the following composition:
  • the surface cohesion test was carried out using this formula after curing for 72 hours at 20 ° C.
  • the abrasion losses on this formula are 52%.
  • Example 4 Formulation according to the invention No. 2
  • Another core-shell binder according to the invention was used for the formulation of clear cold mixes according to the following composition:
  • Example 5 Formulation according to the invention No. 3
  • a Tg gradient binder according to the invention was used for the formulation of clear cold mixes according to the following composition:
  • a core-bark binder according to the invention was used for the formulation of clear cold mixes according to the following composition:
  • the content of residual binder in this mix is therefore 2.4%.
  • Test specimens of this coated material were prepared for the surface cohesion test by setting a ripening of 72 hours at 20 ° C. After 48 hours of ripening, certain test specimens were treated with a curing product (sealant) composed of Ll 1 diluted to 50% with water. The curing product was applied at 100, 150 and 200 g / m 2 of residual binder on the test piece and then the curing continued for up to 72 hours. The mixes were then evaluated according to the surface cohesion test and the results are shown below:
  • Figure 1 illustrates the lower thermal susceptibility of the mixes formulated with binders of the invention (core-shell and Tg gradient) (see curves of triangles and circles) compared to mixes which are formulated from a binder homogeneous comprising only p2 particles with a single Tg (see curve of squares).

Abstract

The present invention relates to the use of an aqueous dispersion comprising at least one anionic surfactant and particles π1 of at least two polymers having separate glass transition temperatures, such that the polymer having the highest glass transition temperature, greater than or equal to 10°C, is at the centre of the particle π1, and the polymer having the lowest glass transition temperature, less than or equal to 0°C, is on the surface of the particle π1, for the preparation of a binder intended for the production of a coated macadam for roads and cities.

Description

Utilisation d'une dispersion aqueuse de polymère pour la fabrication d'enrobés Use of an aqueous polymer dispersion for the production of asphalt
La présente invention concerne l'utilisation d'une dispersion aqueuse de polymère pour la préparation d'un liant destiné à la fabrication d'un enrobé routier ou urbain. La dispersion aqueuse de polymère comprend des particules à base d'au moins deux polymères présentant chacun des températures de transition vitreuse distinctes. L'invention a également pour objet lesdits enrobés à base de cette dispersion aqueuse de polymère et un revêtement routier ou urbain comprenant les enrobés de l'invention. Les routes, les chaussées et les aménagements urbains divers doivent supportent un trafic routier et/ou piéton intense. Il est donc primordial que ces revêtements possèdent des propriétés mécaniques leur permettant de résister aux contraintes induites par ce trafic sur la durée, et ce quelques soit les modifications environnementales subies, comme par exemple les changements de températures important pouvant avoir lieu au cours des différentes saisons. The present invention relates to the use of an aqueous polymer dispersion for the preparation of a binder intended for the manufacture of a road or urban mix. The aqueous polymer dispersion comprises particles based on at least two polymers each having distinct glass transition temperatures. A subject of the invention is also said mixes based on this aqueous polymer dispersion and a road or urban coating comprising the mixes of the invention. Roads, pavements and various urban developments must support heavy road and / or pedestrian traffic. It is therefore essential that these coatings have mechanical properties allowing them to withstand the stresses induced by this traffic over time, regardless of the environmental modifications undergone, such as for example the significant temperature changes that may take place during the different seasons. .
Parmi les différents matériaux utilisés pour la construction des routes et des chaussées, on retrouve principalement les enrobés, qui servent notamment à la fabrication de couches de roulement ou de couches de chaussée. Among the various materials used for the construction of roads and pavements, one finds mainly asphalt mixes, which are used in particular for the manufacture of wearing courses or pavement layers.
Par définition, un enrobé est constitué d'une fraction granulaire et d'un liant. La fraction granulaire est un mélange de granulats, de fines et de sable. Les granulats sont le plus souvent issus de roches massives ou sédimentaires (du sable aux gravillons) mais ils peuvent également être issus de produits de recyclage ou de synthèse. Le liant permet de coller les granulats entre eux et d'assurer une bonne tenue mécanique de la couche d'enrobé. Le liant, de manière générale, peut être par exemple un liant hydrocarboné, un liant de synthèse, ou un liant végétal. Les enrobés sont totalement recouvert de liant lors de leur fabrication puis appliqués par répandage et compactés pour obtenir des revêtements routiers. Les enrobés hydrocarbonés, enrobés de bitume, sont parmi les plus utilisés pour ces applications et responsables de la couleur noire des routes. By definition, a mix consists of a granular fraction and a binder. The granular fraction is a mixture of aggregates, fines and sand. Aggregates are most often made from massive or sedimentary rocks (from sand to chippings) but they can also come from recycled or synthetic products. The binder makes it possible to bond the aggregates together and to ensure good mechanical strength of the asphalt layer. The binder, in general, can for example be a hydrocarbon binder, a synthetic binder, or a plant binder. The mixes are completely covered with binder during their manufacture then applied by spreading and compacted to obtain road surfaces. The hydrocarbon mixes, coated with bitumen, are among the most used for these applications and responsible for the black color of the roads.
Les propriétés des enrobés, tels que les propriétés mécaniques, thermiques, acoustiques, l'étanchéité du revêtement résultant, sont modulées par la nature de la fraction granulaire et du liant. Ainsi, les chercheurs sont toujours à la recherche de nouveaux matériaux permettant d'améliorer ces différentes propriétés. The properties of the mixes, such as the mechanical, thermal and acoustic properties, the tightness of the resulting coating, are modulated by the nature of the granular fraction and of the binder. Thus, researchers are always on the lookout for new materials to improve these different properties.
De manière surprenante, les inventeurs ont découvert que l'utilisation d'une dispersion aqueuse de polymère comprenant des particules à base de polymères présentant des températures de transition vitreuse distinctes pour la préparation d'un liant destiné à la fabrication d'enrobés permet de moduler les propriétés mécaniques des enrobés afin notamment d'obtenir un ratio rigidité/souplesse optimal de la couche d'enrobés. Surprisingly, the inventors have discovered that the use of an aqueous polymer dispersion comprising particles based on polymers exhibiting distinct glass transition temperatures for the preparation of a binder intended for the manufacture of mixes makes it possible to modulate the mechanical properties of asphalt in order in particular to obtain an optimum stiffness / flexibility ratio of the asphalt layer.
En particulier, les particules suspendues dans la dispersion aqueuse peuvent être structurées de sorte qu'un gradient progressif positif de température de transition vitreuse est observé de la surface vers le centre de la particule. Les particules suspendues dans cette dispersion aqueuse de polymère peuvent également se présenter sous la forme de particules dites cœur/écorce (plus communément décrites en anglais sous le terme « core shell particle »). In particular, the particles suspended in the aqueous dispersion can be structured such that a positive gradual gradient of glass transition temperature is observed from the surface to the center of the particle. The particles suspended in this aqueous polymer dispersion can also be in the form of so-called core / shell particles (more commonly described in English under the term “core shell particle”).
Par « particule cœur/écorce », on désigne des particules de polymères constituées d'un cœur en polymère entouré d'une écorce (ou enveloppe) d'un polymère différent. La nature des polymères du cœur ou de l'écorce sont choisies de manière spécifique selon les usages prévus et permettent de moduler les propriétés mécaniques, physiques et chimiques des particules. Par exemple, on peut obtenir des particules ayant la particularité de présenter plusieurs températures de transition vitreuse distinctes. Ainsi, l'enveloppe et le cœur de la particule auront des propriétés mécaniques différentes, présentant un caractère plus rigide ou caoutchouteux suivant la nature du polymère les constituant. The term “core / shell particle” denotes polymer particles consisting of a polymer core surrounded by a shell (or shell) of a different polymer. The nature of the polymers of the core or of the shell are chosen in a specific manner according to the intended uses and make it possible to modulate the mechanical, physical and chemical properties of the particles. For example, it is possible to obtain particles having the particularity of exhibiting several distinct glass transition temperatures. Thus, the envelope and the core of the particle will have different mechanical properties, exhibiting a more rigid or rubbery character depending on the nature of the polymer constituting them.
Ce type de particule a été décrites pour diverses applications. This type of particle has been described for various applications.
W02009/09559 décrit une dispersion aqueuse comprenant des particules structurées en cœur/écorce, à base de polymères PI et P2 ayant des températures de transition vitreuse Tgl et Tg2 pour la préparation de peintures décoratives et industrielles. WO2009 / 09559 describes an aqueous dispersion comprising particles structured in the core / shell, based on polymers PI and P2 having glass transition temperatures Tgl and Tg2 for the preparation of decorative and industrial paints.
La demande W02009/016053 porte sur une composition de revêtement destinée à recouvrir des substrats, notamment du papier, pour les rendre plus résistant à l'huile et à la graisse. Ces compositions comprennent des particules de polymères structurées en cœur/écorce dans un milieu aqueux. Ces particules comprennent un cœur constitué d'un polymère dont la température de transition vitreuse est plus faible que celle du polymère constituant l'enveloppe. Dans ce cas de figure, l'enveloppe a donc un caractère plus rigide que le cœur de la particule qui est plus caoutchouteux. Application WO2009 / 016053 relates to a coating composition intended to cover substrates, in particular paper, to make them more resistant to oil and grease. These compositions comprise polymer particles structured in the core / shell in an aqueous medium. These particles comprise a core made up of a polymer whose glass transition temperature is lower than that of the polymer constituting the shell. In this case, the envelope therefore has a more rigid character than the core of the particle which is more rubbery.
La demande EP 1,434,803 décrit une dispersion aqueuse pour revêtement de surface ou en tant qu'adhésif, à base de différents polymères, comprenant notamment des polymères vinyliques présentant une composition spécifique en gradient leur permettant d'avoir des propriétés modulables. La dispersion aqueuse obtenue offre ainsi une combinaison avantageuse de température minimum de filmification, de dureté et d’élasticité. Les polymères vinyliques peuvent par exemple être obtenus à partir de compositions de monomères présentant des températures de transition vitreuse distinctes, mais aussi des fonctionnalités chimiques, des masses moléculaires, une hydrophobicité, etc. différentes. Cependant, une dispersion aqueuse à base de particules polymériques présentant des températures de transition vitreuse distinctes au sein même de la particule n'a jamais été décrite pour la préparation d'un liant destiné à la fabrication d'enrobés routiers ou urbains. L'utilisation d'une dispersion aqueuse de polymère selon la présente invention permet l'obtention d'un liant destiné à la fabrication d'enrobés présentant une faible température de filmification et conférant à la couche d'enrobés résultante un compromis optimal entre rigidité et souplesse. Application EP 1,434,803 describes an aqueous dispersion for surface coating or as an adhesive, based on various polymers, comprising in particular vinyl polymers having a specific composition in gradient allowing them to have modulable properties. The aqueous dispersion obtained thus offers an advantageous combination of minimum film-forming temperature, hardness and elasticity. The vinyl polymers can, for example, be obtained from compositions of monomers exhibiting distinct glass transition temperatures, but also chemical functionalities, molecular masses, hydrophobicity, etc. different. However, an aqueous dispersion based on polymer particles exhibiting distinct glass transition temperatures within the particle itself has never been described for the preparation of a binder intended for the manufacture of road or urban mixes. The use of an aqueous polymer dispersion according to the present invention makes it possible to obtain a binder intended for the production of mixes having a low film-forming temperature and giving the resulting coated layer an optimum compromise between rigidity and flexibility.
Par ailleurs, ce type de liant a l'avantage d'être translucide et permet donc de réaliser des revêtements dont la teinte est celle des matériaux granulaires qui les constituent. Les enrobés constitués d'un tel liant sont donc particulièrement adaptés aux zones piétonnes et cyclables peu circulées, aux voies forestières, aux voies sur berges, aux trottoirs et peuvent contribuer à la sécurité de ces espaces par une plus grande lisibilité et une différenciation visuelle des différents aménagements. Furthermore, this type of binder has the advantage of being translucent and therefore makes it possible to produce coatings the color of which is that of the granular materials which constitute them. Asphalt mixes made of such a binder are therefore particularly suitable for pedestrian and cycle-friendly areas with little traffic, forest lanes, riverbank lanes, sidewalks and can contribute to the safety of these spaces through greater readability and visual differentiation of the traffic. different arrangements.
Les nombreuses surfaces artificielles des milieux urbanisés sont en grande partie composées de matières minérales, tels que l'enrobé, l'asphalte et le béton, ayant de faibles pouvoirs de réflectance solaire. La multiplication de ces surfaces est l'un des plus importants facteurs de création des îlots de chaleur urbains. L'utilisation d'une dispersion aqueuse de polymère pour la préparation d'un liant clair destiné à la fabrication d'enrobés peut ainsi contribuer au refroidissement des revêtements. The many artificial surfaces of urbanized environments are largely composed of mineral materials, such as asphalt, asphalt and concrete, with low solar reflectance powers. The multiplication of these surfaces is one of the most important factors in the creation of urban heat islands. The use of an aqueous polymer dispersion for the preparation of a clear binder intended for the production of mixes can thus contribute to the cooling of the coatings.
Un premier objet de l'invention consiste donc en l'utilisation d'une dispersion aqueuse comprenant au moins un tensioactif anionique et des particules pΐ à base d'au moins deux polymères présentant des températures de transition vitreuse distinctes, de sorte que le polymère ayant la température de transition vitreuse la plus élevée, supérieure ou égale à 10°C, se trouve au centre de la particule pΐ et le polymère ayant la température de transition vitreuse la plus faible, inférieure ou égale à 0°C, se trouve en surface de la particule pΐ, pour la préparation d'un liant destiné à la fabrication d'un enrobé routier ou urbain. A first object of the invention therefore consists in the use of an aqueous dispersion comprising at least one anionic surfactant and pΐ particles based on at least two polymers exhibiting distinct glass transition temperatures, so that the polymer having the highest glass transition temperature, greater than or equal to 10 ° C, is at the center of the particle pΐ and the polymer with the lowest glass transition temperature, less than or equal to 0 ° C, is at the surface of the pΐ particle, for the preparation of a binder intended for the manufacture of a road or urban asphalt.
Par « enrobé routier ou urbain », on entend, au sens de la présente invention un mélange d'une fraction granulaire et d'un liant, ladite fraction granulaire comprenant des granulats, des fines et du sable. Les enrobés sont obtenus par mélange du liant et de la fraction granulaire jusqu'à observer la rupture de l'émulsion qui correspond à l'évaporation ou à l'élimination par drainage de l'eau comprise dans l'émulsion et à la formation d'un film de liant enrobant la fraction granulaire. L'enrobé urbain selon la présente invention est particulièrement adapté aux surfaces peu circulées et aux aménagements urbains tels que les voies piétonnes, les pistes cyclables, les voies vertes, les places, les parvis, les aires de jeu ou encore les terrains de sports. L'enrobé routier est lui particulièrement adapté aux voies de circulations de véhicules, comme les routes, les trottoirs et les rues. By “road or urban mix” is meant, within the meaning of the present invention, a mixture of a granular fraction and a binder, said granular fraction comprising aggregates, fines and sand. The coated materials are obtained by mixing the binder and the granular fraction until the breaking of the emulsion is observed which corresponds to the evaporation or to the elimination by drainage of the water included in the emulsion and to the formation of a binder film coating the granular fraction. The urban asphalt according to the present invention is particularly suitable for surfaces with little traffic and urban developments such as pedestrian paths, cycle paths, greenways, squares, squares, playgrounds or sports grounds. Asphalt is particularly suitable for vehicular traffic lanes, such as roads, sidewalks and streets.
Par « liant », on entend au sens de la présente invention tout liant d'origine synthétique, de préférence translucide, à base d'une dispersion aqueuse de particules de polymères telle que définie dans la présente demande utilisable pour la réalisation d'un enrobé, avantageusement d'un enrobé clair. For the purposes of the present invention, the term “binder” is understood to mean any binder of synthetic origin, preferably translucent, based on an aqueous dispersion of polymer particles as defined in the present application which can be used for the production of a coated material. , advantageously of a clear mix.
Par « liant résiduel », on entend au sens de la présente invention le liant compris dans les enrobés après l'enrobage et retrait de l'eau (et/ou des solvants le cas échéant) de la dispersion. Autrement dit, le liant résiduel est anhydre. For the purposes of the present invention, the term “residual binder” is understood to mean the binder included in the mixes after the coating and removal of the water (and / or solvents where appropriate) from the dispersion. In other words, the residual binder is anhydrous.
Par « tensioactif anionique » on entend au sens de la présente invention un produit tensioactif, c'est-à-dire capable de modifier la tension superficielle entre deux surfaces, s'ionisant en solution aqueuse pour fournir des anions et responsables de l'activité de surface. For the purposes of the present invention, the term “anionic surfactant” means a surfactant product, that is to say capable of modifying the surface tension between two surfaces, ionizing in aqueous solution to provide anions and responsible for the activity. of surface.
Par « température de transition vitreuse » (notée Tg), on entend la température en dessous de laquelle les propriétés physiques des matériaux amorphes varient d’un état caoutchouteux à un état vitreux. Ainsi, la Tg est également la température en dessous de laquelle les molécules ont peu de mobilité relative. La température de transition vitreuse est typiquement mesurée au moyen des essais suivants : By "glass transition temperature" (denoted Tg) is meant the temperature below which the physical properties of amorphous materials vary from a rubbery state to a glassy state. Thus, Tg is also the temperature below which molecules have little relative mobility. The glass transition temperature is typically measured by means of the following tests:
- DSC (Differential Scanning Calorimetry ou Calorimétrie Différentielle à balayage) - DSC (Differential Scanning Calorimetry)
- DMA (Dynamic Mechanical Analysis ou Analyse mécanique dynamique) - DMA (Dynamic Mechanical Analysis)
- TMA (ThermoMechanical Analysis ou Analyse thermomécanique) - TMA (ThermoMechanical Analysis)
Avantageusement, la Tg la plus élevée, qui peut être notée Tgi, est supérieure ou égale à 30°C, de préférence supérieure ou égale à 50°C. Typiquement, Tgi est comprise entre 10°C et 100°C, de préférence entre 30°C et 100°C, de manière encore plus préférée, Tgi est comprise entre 50°C et 100°C. Advantageously, the highest Tg, which can be denoted Tgi, is greater than or equal to 30 ° C, preferably greater than or equal to 50 ° C. Typically, Tgi is between 10 ° C and 100 ° C, preferably between 30 ° C and 100 ° C, even more preferably, Tgi is between 50 ° C and 100 ° C.
Avantageusement, la Tg la moins élevée, qui peut être notée Tg2, est inférieure ou égale à -10 °C. Typiquement, Tg2 est comprise entre 0°C et -100°C, de préférence entre 0°C et -50°C, de manière encore plus préférée, Tg2 est comprise entre 0°C et -20°C, et notamment entre -10°C et -20°C. Advantageously, the lowest Tg, which can be denoted Tg2, is less than or equal to -10 ° C. Typically, Tg2 is between 0 ° C and -100 ° C, preferably between 0 ° C and -50 ° C, even more preferably, Tg2 is between 0 ° C and -20 ° C, and in particular between - 10 ° C and -20 ° C.
De manière générale, selon la présente invention, les particules pΐ de polymère, comprises dans la dispersion aqueuse ont donc un caractère caoutchouteux en surface et un caractère rigide en leur centre. Cette double nature permet d'obtenir un liant résiduel avec un bon compromis rigidité/souplesse. La phase molle des particules pΐ permet la formation du film de liant à des températures plus basses et une demande réduite d’agents coalescents alors que la phaseTg élevée améliore la dureté du film de liant. Ledit liant résiduel présente ainsi des valeurs de modules élevées, étant moins susceptible à la fracture, tout en restant rigide et adapté aux revêtements urbains ou routiers envisagés. Ces valeurs de modules varient peu en fonction de la température extérieure, cette dernière allant typiquement de -40°C à 60°C. Autrement dit, les propriétés mécaniques des enrobés comprenant ledit liant restent stables sur une large gamme de températures extérieures à laquelle les enrobés peuvent être exposés au cours de l'année, en hiver comme en été. En outre, la température de filmification du liant est inférieure à 5°C. Une faible température de filmification permet d'assurer une bonne cohésion de l'enrobé résultant. In general, according to the present invention, the pΐ polymer particles included in the aqueous dispersion therefore have a rubbery character at the surface and a rigid character at their center. This dual nature makes it possible to obtain a residual binder with a good stiffness / flexibility compromise. The soft phase of the pΐ particles allows the formation of the binder film at lower temperatures and reduced demand for coalescing agents while the high Tg phase improves the hardness of the binder film. Said residual binder thus exhibits modulus values high, being less susceptible to fracture, while remaining rigid and suitable for urban or road surfaces considered. These module values vary little as a function of the outside temperature, the latter typically ranging from -40 ° C to 60 ° C. In other words, the mechanical properties of the mixes comprising said binder remain stable over a wide range of outside temperatures to which the mixes can be exposed during the year, in winter as in summer. In addition, the film-forming temperature of the binder is less than 5 ° C. A low film-forming temperature ensures good cohesion of the resulting mix.
Selon un mode de réalisation préféré, les particules de polymères pΐ comprises dans la dispersion aqueuse comprennent donc un polymère PI, ayant une Tgi, en leur centre et au moins un autre polymère P2, ayant une Tg2, en surface de la particule pΐ, de sorte que les couches de polymères sont au contact l'une de l'autre, voire liées l'une à l'autre. Avantageusement, les particules de l'invention ne comprennent pas de vide ou de matériaux autre que du polymère. According to a preferred embodiment, the particles of polymers pΐ included in the aqueous dispersion therefore comprise a polymer PI, having a Tgi, at their center and at least one other polymer P2, having a Tg2, at the surface of the particle pΐ, of so that the layers of polymers are in contact with one another, or even bonded to one another. Advantageously, the particles of the invention do not include a void or any material other than polymer.
Selon un mode de réalisation particulier, les particules de l'invention sont constituées de deux polymères PI et P2 tel que définis ci-dessus. According to a particular embodiment, the particles of the invention consist of two polymers PI and P2 as defined above.
Typiquement, la dispersion aqueuse de polymères selon la présente invention est obtenue par polymérisation en émulsion en phase aqueuse d'au moins deux compositions de monomères Ml et M2 conduisant respectivement aux polymères PI et P2. Selon un procédé bien connu de l'homme du métier, cette polymérisation en émulsion en phase aqueuse peut se faire de manière séquencée, ou le monomère Ml est polymérisé dans un premier temps puis les additifs permettant d'initier le monomère M2 sont ajoutés au milieu réactionnel, ou les monomères Ml et M2 sont chacun polymérisés séparément puis mélangés. Typically, the aqueous dispersion of polymers according to the present invention is obtained by emulsion polymerization in aqueous phase of at least two compositions of monomers M1 and M2 resulting respectively in polymers PI and P2. According to a process well known to those skilled in the art, this aqueous phase emulsion polymerization can be carried out in a sequenced manner, or the M1 monomer is polymerized first and then the additives making it possible to initiate the M2 monomer are added to the medium. reaction, or the monomers M1 and M2 are each polymerized separately and then mixed.
Ladite polymérisation se fait en présence d'au moins un tensioactif anionique. Said polymerization is carried out in the presence of at least one anionic surfactant.
La présence d'un tensioactif anionique permet d'améliorer la stabilité de la dispersion aqueuse lors de la polymérisation et de disperser efficacement les particules de polymères. Le tensioactif anionique est par ailleurs utile dans la dispersion aqueuse pour la formation d'un liant pour enrobé routier ou urbain. The presence of an anionic surfactant makes it possible to improve the stability of the aqueous dispersion during polymerization and to effectively disperse the polymer particles. The anionic surfactant is moreover useful in the aqueous dispersion for the formation of a binder for road or urban asphalt.
De préférence, ce tensioactif anionique est choisi parmi les carboxylates d'acides gras, les sulfates tel que le dodécylsulfate de sodium, les sulfonates tels que les alkyl benzène sulfonates de sodium, les alpha-oléfines sulfonates, les phosphates, les sulfosuccinates et les phospholipides. Preferably, this anionic surfactant is chosen from fatty acid carboxylates, sulfates such as sodium dodecylsulfate, sulfonates such as sodium alkylbenzene sulfonates, alpha-olefin sulfonates, phosphates, sulfosuccinates and phospholipids .
Typiquement, le tensioactif anionique est présent dans la dispersion aqueuse à une teneur d'au moins 0,2% en poids par rapport au poids total de ladite dispersion, de préférence comprise entre 0,2% et 5 %. Typically, the anionic surfactant is present in the aqueous dispersion in a content of at least 0.2% by weight relative to the total weight of said dispersion, preferably between 0.2% and 5%.
La polymérisation peut également avoir lieu en présence d'au moins un tensioactif non-ionique, qui ne s'ionise pas dans l'eau, en combinaison avec au moins un tensioactif anionique tel que défini ci- dessus. Ce tensioactif non ionique peut représenter de 0,2% à 5%, et de préférence de 0,2% à 0,5 % du poids total de la dispersion. Ce tensioactif non-ionique est par exemple sélectionné parmi les esters de glycol comme le stéarate d'éthylèneglycol, les esters de glycérol, les esters de sorbitane (Tween®), les esters de polyoxyéthylèneglycol, les éthers d'alcool gras et les alcanolamides. The polymerization can also take place in the presence of at least one nonionic surfactant, which does not ionize in water, in combination with at least one anionic surfactant as defined above. above. This nonionic surfactant can represent from 0.2% to 5%, and preferably from 0.2% to 0.5% of the total weight of the dispersion. This nonionic surfactant is for example selected from glycol esters such as ethylene glycol stearate, glycerol esters, sorbitan esters (Tween ®), esters of polyoxyethylene, fatty alcohol ethers and alkanolamides.
Ainsi, la dispersion aqueuse de polymère résultante utilisée dans la présente invention pour la préparation d'un liant pour enrobé routier ou urbain comprend au moins un tensioactif anionique tel que défini ci-dessus. Selon un mode de réalisation particulier, ladite dispersion aqueuse comprend également au moins un tensioactif non-ionique tel que défini ci-dessus. Thus, the resulting aqueous polymer dispersion used in the present invention for the preparation of a binder for road or urban asphalt comprises at least one anionic surfactant as defined above. According to a particular embodiment, said aqueous dispersion also comprises at least one nonionic surfactant as defined above.
Les polymères compris dans les particules de la dispersion aqueuse utilisée pour la préparation d'un liant selon la présente invention sont avantageusement obtenus à partir de compositions de monomères choisis parmi le groupe constitué des monomères vinyliques et/ou diéniques, des esters comprenant au moins une instauration oléfinique polymérisable, des monomères éthyléniquement insaturés porteur d’au moins une fonction acide et/ ou anhydride carboxylique et de leurs combinaisons. The polymers included in the particles of the aqueous dispersion used for the preparation of a binder according to the present invention are advantageously obtained from compositions of monomers chosen from the group consisting of vinyl and / or diene monomers, esters comprising at least one polymerizable olefinic introduction, ethylenically unsaturated monomers bearing at least one acid and / or carboxylic anhydride function and combinations thereof.
En particulier, ces monomères sont choisis parmi le styrène et ses dérivés, comprenant par exemple les vinyltoluènes (ortho, meta, para), a-méthylstyrène, isopropylstyrène, ferf-butylstyrène, para- butylstyrène, para-décylstyrène, para-chloro-styrène et également parmi le butadiène, l'isoprène, les esters (méth)acryliques, les nitriles tels que le (meth)acrylonitrile, les esters vinyliques tels que l'acétate de vinyle, le butyrate de vinyle, le caprolate de vinyle, et le pivalate de vinyle, l’acide (méth)acrylique, l’acide itaconique, l’acide fumarique, l’acide maléique, l’acide crotonique, l’acide isocrotonique, l’acide vinylbenzoïque et leurs combinaisons. La formulation (méth)acryl* désigne l'acryl* et le méthacryl*, * désignant le suffixe -ate ou -ique. In particular, these monomers are chosen from styrene and its derivatives, comprising for example vinyltoluenes (ortho, meta, para), α-methylstyrene, isopropylstyrene, ferf-butylstyrene, para-butylstyrene, para-decylstyrene, para-chloro-styrene and also from butadiene, isoprene, (meth) acrylic esters, nitriles such as (meth) acrylonitrile, vinyl esters such as vinyl acetate, vinyl butyrate, vinyl caprolate, and vinyl pivalate, (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, isocrotonic acid, vinylbenzoic acid, and combinations thereof. The formulation (meth) acryl * designates acryl * and methacryl *, * designating the suffix -ate or -ique.
Les esters (méth)acryliques sont préférentiellement sélectionnés parmi les (méth)acrylates d'alkyle en Cl-10 linéaires, tel que le (méth)acrylate de méthyle, le (meth)acrylate d'éthyle ou le (méth)acrylate de butyle, les (méth)acrylates d'alkyle en C3-10 ramifiés, l’acrylate de 2-éthylhexyle et leurs combinaisons. The (meth) acrylic esters are preferably selected from linear C1-10 alkyl (meth) acrylates, such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate , branched C3-10 alkyl (meth) acrylates, 2-ethylhexyl acrylate, and combinations thereof.
De préférence, les monomères sont choisis parmi le styrène et les esters (méth)acryliques tels que les (méth)acrylates d'alkyle en Cl-10 linéaires, les (méth)acrylates d'alkyle en C3-10 ramifiés. Preferably, the monomers are chosen from styrene and (meth) acrylic esters such as linear C1-10 alkyl (meth) acrylates, branched C3-10 alkyl (meth) acrylates.
La dispersion aqueuse de polymère utilisée pour la préparation d'un liant telle que décrite ci-dessus comprend typiquement un extrait sec compris entre 30% et 70% en poids de polymères par rapport au poids total de la dispersion, préférentiellement entre 40% et 60 %, plus préférentiellement entre 45% et 55 %. The aqueous polymer dispersion used for the preparation of a binder as described above typically comprises a dry extract of between 30% and 70% by weight of polymers relative to the total weight of the dispersion, preferably between 40% and 60 %, more preferably between 45% and 55%.
Typiquement, selon la présente invention, les particules pΐ de polymères, comprises dans la dispersion aqueuse comprenant au moins deux polymères ayant des Tg distinctes sont structurées de sorte qu'un gradient positif de Tg est observé de la surface des particules vers le centre des particules. Typically, according to the present invention, the pΐ particles of polymers, included in the aqueous dispersion comprising at least two polymers having distinct Tg's are structured so that a positive gradient of Tg is observed from the surface of the particles to the center of the particles.
Avantageusement, les particules pΐ de polymères structurées de sorte qu'un gradient positif de Tg est observé de la surface des particules vers le centre des particules comprennent donc plusieurs couches de polymères, chaque couche ayant une Tg distincte. Le gradient de Tg entre chaque couche de polymère de la surface vers le centre de la particule est compris entre 10°C et 200 °C, préférablement entre 50°C et 100 °C. Advantageously, the pΐ particles of polymers structured so that a positive gradient of Tg is observed from the surface of the particles towards the center of the particles therefore comprise several layers of polymers, each layer having a distinct Tg. The Tg gradient between each polymer layer from the surface to the center of the particle is between 10 ° C and 200 ° C, preferably between 50 ° C and 100 ° C.
Selon ce mode de réalisation, les particules de polymères peuvent comprendre plus de deux polymères, chaque polymère ayant une Tg distincte, de sorte que la Tg de chaque polymère augmente lorsqu'on va de la surface au centre de la particule. According to this embodiment, the polymer particles can comprise more than two polymers, each polymer having a distinct Tg, so that the Tg of each polymer increases as one moves from the surface to the center of the particle.
En particulier, les particules pΐ à gradient de Tg peuvent comprendre un polymère PI au centre de la particule entouré d'une ou plusieurs couches intermédiaire(s) de polymère comprise(s) entre le polymère PI et une couche de polymère P2 en surface de la particule, les couches intermédiaires ayant des Tg comprises entre Tgl et Tg2, de sorte que la valeur de la Tg de chaque couche de polymère augmente lorsque l'on va de la couche de P2 vers la couche de PI. In particular, the particles pΐ with a gradient of Tg can comprise a polymer PI at the center of the particle surrounded by one or more intermediate layers of polymer included between the polymer PI and a layer of polymer P2 at the surface of the particle, the intermediate layers having Tg between Tgl and Tg2, so that the value of the Tg of each polymer layer increases when one goes from the layer of P2 to the layer of PI.
Selon un mode particulier de réalisation de la présente invention, les particules pΐ de polymères comprises dans la dispersion aqueuse sont structurées en particules cœur/écorce. According to a particular embodiment of the present invention, the pΐ particles of polymers included in the aqueous dispersion are structured as core / shell particles.
Ainsi, de manière avantageuse, les particules cœur/écorce selon l'invention comprennent un polymère PI en leur centre, présentant une Tgi telle que définie ci-dessus, entouré d'au moins une enveloppe constituée d'un polymère P2 présentant une Tg2 telle que définie ci-dessus. Thus, advantageously, the core / shell particles according to the invention comprise a PI polymer at their center, exhibiting a Tgi as defined above, surrounded by at least one envelope consisting of a P2 polymer exhibiting a Tg2 such as as defined above.
La dispersion aqueuse de polymère utilisée pour la préparation d'un liant telle que décrite ci-dessus pourra comprendre des particules pΐ de polymères différentes, c'est-à-dire des particules pΐ à base de différentes compositions de polymères. Toutefois, chaque particule pΐ comprendra au moins deux polymères ayant des Tg distinctes. Par exemple, une même dispersion pourra comprendre des particules pΐ constituées de polymères A et B, mais également des particules pΐ constituées de polymères C et D. The aqueous polymer dispersion used for the preparation of a binder as described above may comprise pΐ particles of different polymers, that is to say pΐ particles based on different polymer compositions. However, each pΐ particle will include at least two polymers having distinct Tg's. For example, the same dispersion may comprise pΐ particles consisting of polymers A and B, but also pΐ particles consisting of polymers C and D.
Selon un mode particulier de l'invention, la dispersion aqueuse utilisée pour la préparation d'un liant destiné à la fabrication d'un enrobé routier ou urbain comprend également des particules p2 de polymère ayant une Tg unique en plus des particules pΐ ayant au moins deux Tg distinctes telles que décrites ci-dessus. Typiquement, ces particules p2 de polymère à Tg unique sont préparées à partir d'une composition de monomères tels que décrits ci-dessus. Ainsi, ces particules à Tg uniques peuvent être constituées d'un seul polymère. De préférence, les particules p2 sont obtenues à partir d'esters (méth)acryliques. According to a particular embodiment of the invention, the aqueous dispersion used for the preparation of a binder intended for the manufacture of a road or urban mix also comprises particles p2 of polymer having a single Tg in addition to the particles pΐ having at least two separate Tg as described above. Typically, these single Tg polymer particles p2 are prepared from a composition of monomers as described above. Thus, these unique Tg particles can consist of a single polymer. Preferably, the particles p2 are obtained from (meth) acrylic esters.
Avantageusement, la Tg de ces particules p2 de polymère à Tg unique est inférieure à 0°C. Cette variante de l'invention permet d'améliorer la souplesse du liant résiduel. Advantageously, the Tg of these single Tg polymer particles p2 is less than 0 ° C. This variant of the invention makes it possible to improve the flexibility of the residual binder.
La Tg de ces particules p2 de polymère à Tg unique peut également être supérieure à 10 °C. Selon cette variante de l'invention, le liant résiduel est plus rigide. The Tg of these single Tg polymer particles p2 can also be greater than 10 ° C. According to this variant of the invention, the residual binder is more rigid.
Ainsi, la présence de particules de polymères p2 à Tg unique au sein de la dispersion aqueuse comprenant également des particules pΐ présentant au moins deux Tg distinctes permet de moduler le ratio rigidité/souplesse du liant résiduel après enrobage des enrobés. Ce ratio pourra ainsi être ajusté en fonction de l'utilisation prévue des enrobés de l'invention. Thus, the presence of particles of polymers p2 with a single Tg within the aqueous dispersion also comprising pΐ particles having at least two distinct Tg makes it possible to modulate the stiffness / flexibility ratio of the residual binder after coating of the mixes. This ratio can thus be adjusted as a function of the intended use of the mixes of the invention.
Typiquement, la teneur en extrait sec de particules n2de polymères à Tg unique au sein de la dispersion aqueuse de particules de polymères utilisée pour la préparation d'un liant est comprise entre 0% et 60% par rapport au poids total en extrait sec des particules pΐ et p2 de polymère, avantageusement entre 0% et 40%. Typically, the solids content of particles n2de polymers with a single Tg within the aqueous dispersion of polymer particles used for the preparation of a binder is between 0% and 60% relative to the total weight of the solids content of the particles. pΐ and p2 of polymer, advantageously between 0% and 40%.
La dispersion aqueuse utilisée pour la préparation d'un liant selon la présente invention pourra comprendre des particules p2 à Tg unique obtenues différentes. Autrement dit, certaines particules p2 pourront être constituées d'un polymère A alors que d'autres particules p2 également présentes au sein de la dispersion aqueuse pourront être constituées d'un polymère B. The aqueous dispersion used for the preparation of a binder according to the present invention may comprise particles p2 with a single Tg obtained which are different. In other words, certain particles p2 could consist of a polymer A while other particles p2 also present within the aqueous dispersion could consist of a polymer B.
Selon un mode de réalisation préféré, la présente invention concerne l'utilisation d'une dispersion aqueuse comprenant des particules pΐ de polymères à base d'au moins deux polymères présentant des Tg distinctes, lesdites particules étant structurées en cœur/écorce, en mélange avec des particules p2 de polymère présentant une Tg unique. According to a preferred embodiment, the present invention relates to the use of an aqueous dispersion comprising pΐ particles of polymers based on at least two polymers exhibiting distinct Tg's, said particles being structured in the core / shell, mixed with polymer particles p2 having a unique Tg.
Selon un autre mode de réalisation, la présente invention concerne l'utilisation d'une dispersion aqueuse comprenant des particules pΐ de polymères à base d'au moins deux polymères présentant des Tg distinctes, lesdites particules étant structurées avec un gradient de Tg de la surface au centre de la particule, en mélange avec des particules p2 de polymère présentant une Tg unique. According to another embodiment, the present invention relates to the use of an aqueous dispersion comprising pΐ particles of polymers based on at least two polymers exhibiting distinct Tg, said particles being structured with a gradient of Tg from the surface. at the center of the particle, in admixture with p2 polymer particles exhibiting a single Tg.
Un second objet de l'invention concerne les enrobés comprenant une fraction granulaire enrobée d'un liant, ledit liant étant à base d'une dispersion aqueuse de particules telles que définie dans l'invention. A second subject of the invention relates to mixes comprising a granular fraction coated with a binder, said binder being based on an aqueous dispersion of particles as defined in the invention.
Par « fraction granulaire », on entend au sens de la présente invention des fractions solides, en particulier des fractions solides minérales, utilisables pour la réalisation d’enrobés notamment pour la construction routière ou urbaine, comprenant notamment les granulats minéraux naturels (gravillons, sable, fines) par exemple issus de carrière ou de gravière, les produits de recyclage tel que les agrégats d'enrobés, par exemple résultant du recyclage des matériaux récupérés lors de la réfection des routes ainsi que des surplus de centrales d'enrobage, les rebuts de fabrication, les « shingles » (provenant du recyclage des membranes de toitures), les granulats provenant du recyclage de matériaux routiers y compris les bétons, les laitiers en particulier les scories, les schistes en particulier la bauxite ou le corindon, les poudrettes de caoutchouc provenant du recyclage des pneus notamment, les granulats artificiels de toute origine et provenant par exemple de mâchefers d'incinération des ordures ménagères (MIOM), ainsi que leurs mélanges en toutes proportions. For the purposes of the present invention, the term “granular fraction” is understood to mean solid fractions, in particular solid mineral fractions, which can be used for the production of mixes in particular for road or urban construction, including in particular natural mineral aggregates (gravel, sand, fines) for example from quarries or gravel pits, recycling products such as asphalt aggregates, for example resulting from the recycling of materials recovered during repair of roads as well as surplus asphalt mixing plants, manufacturing scrap, "shingles" (from recycling roofing membranes), aggregates from recycling road materials including concrete, slags in particular slag, shale in particular bauxite or corundum, rubber powder from recycling tires in particular, artificial aggregates of any origin and from, for example, bottom ash from household waste incineration (MIOM), as well as their mixtures in all proportions.
On entend par « agrégats d'enrobés » des enrobés (mélange de granulats et de liants) provenant de fraisage de couches d'enrobé, de concassage de plaques extraites de chaussées en enrobés, de morceaux de plaques d'enrobés, de déchets d'enrobé ou de surplus de productions d'enrobés (les surplus de productions sont des matériaux enrobés ou partiellement enrobés en centrale résultant des phases transitoires de fabrication). Ces éléments et les autres produits de recyclage peuvent atteindre des dimensions jusqu'à 31,5 mm. The term “coated aggregates” is understood to mean asphalt mixes (mixture of aggregates and binders) originating from the milling of asphalt layers, from the crushing of slabs extracted from asphalt pavements, pieces of asphalt slabs, waste from asphalt or asphalt production surplus (production surpluses are materials coated or partially coated in a plant resulting from transient phases of production). These and other recycling products can reach sizes up to 31.5mm.
Avantageusement, les granulats selon la présente invention sont issus de roches massives ou de gisements alluvionnaires suivant les conditions d'emploi de l'enrobé et sont choisis par référence à la norme EN 13043 (août 2003). Les matériaux calcaires ou silico-calcaires sont préférés pour la formulation des enrobés selon l'invention, sans y être limité. Advantageously, the aggregates according to the present invention are obtained from massive rocks or from alluvial deposits according to the conditions of use of the mix and are chosen with reference to the standard EN 13043 (August 2003). The calcareous or silico-calcareous materials are preferred for the formulation of the mixes according to the invention, without being limited thereto.
Avantageusement, la teneur en eau des matériaux doit être rigoureusement contrôlée inférieure à 3% en poids, par rapport au poids total des matériaux, pour ne pas avoir de lixiviation lors de la mise en contact avec le liant en phase aqueuse. Advantageously, the water content of the materials must be rigorously controlled below 3% by weight, relative to the total weight of the materials, so as not to have leaching during contact with the binder in the aqueous phase.
Dans le cadre de l'invention, la fraction granulaire comprend avantageusement : In the context of the invention, the granular fraction advantageously comprises:
- des éléments inférieurs à 0,063 mm (filler ou fines) ; - elements less than 0.063 mm (filler or fines);
- du sable dont les éléments sont compris entre 0,063 mm et 2 mm ; et - sand whose elements are between 0.063 mm and 2 mm; and
- des éléments, en particulier des gravillons, ayant des dimensions : - elements, in particular chippings, having dimensions:
. comprises entre 2 mm et 6 mm ; . between 2 mm and 6 mm;
. éventuellement comprises entre 6 mm et 10 mm . possibly between 6 mm and 10 mm
. éventuellement comprises entre 10 mm et 14mm. . possibly between 10mm and 14mm.
Dans le cadre de l'invention, la fraction granulaire comprend avantageusement : In the context of the invention, the granular fraction advantageously comprises:
- des éléments inférieurs à 0,063 mm (filler ou fines) ; - elements less than 0.063 mm (filler or fines);
- du sable dont les éléments sont compris entre 0,063 mm et 2 mm ; et - sand whose elements are between 0.063 mm and 2 mm; and
- des éléments, en particulier des gravillons, ayant des dimensions : . comprises entre 2 mm et 6 mm ; - elements, in particular chippings, having dimensions: . between 2 mm and 6 mm;
. éventuellement comprises entre 6 mm et 10 mm. . possibly between 6 mm and 10 mm.
Par « fines minérales » ou « filler », on entend toute charge minérale passant à travers un tamis à maille carrée de 0,063 mm de côté. Les fines peuvent être des fines naturelles ou d'apport, par exemple des fines calcaires (carbonate de calcium), du ciment ou de la chaux hydratée, ou de récupération. By “mineral fines” or “filler” is meant any mineral filler passing through a sieve with a square mesh of 0.063 mm side. The fines can be natural or filler fines, for example limestone fines (calcium carbonate), cement or hydrated lime, or recovered.
On désigne également la « fraction granulaire » par les termes « fraction solide 0/D ». Cette fraction solide 0/D peut être séparée en plusieurs granulométries : la fraction solide 0/d et les fractions solides d/D. The “granular fraction” is also designated by the terms “0 / D solid fraction”. This 0 / D solid fraction can be separated into several particle sizes: the 0 / d solid fraction and the d / D solid fractions.
On désigne également la « fraction minérale granulaire » par les termes « fraction minérale 0/D ». Cette fraction minérale 0/D peut être séparée en plusieurs granulométries : la fraction minérale 0/d et les fractions minérales d/D. The “granular mineral fraction” is also denoted by the terms “0 / D mineral fraction”. This 0 / D mineral fraction can be separated into several particle sizes: the 0 / d mineral fraction and the d / D mineral fractions.
Dans le cadre de la présente invention, les éléments les plus fins (la fraction solide 0/d, avantageusement la fraction solide minérale 0/d) sont ceux compris dans la plage comprise entre 0 et un diamètre maximal que l'on peut fixer entre 2 et 6mm (de 0/2 à 0/6), avantageusement entre In the context of the present invention, the finest elements (the solid fraction 0 / d, advantageously the solid mineral fraction 0 / d) are those included in the range between 0 and a maximum diameter which can be set between 2 and 6mm (from 0/2 to 0/6), advantageously between
2 et 4 mm. Les autres éléments (diamètre minimal supérieur à 2, 3, 4, 5 ou 6 mm, notamment supérieur à 2, 3 ou 4 mm ; et environ jusqu'à 14 mm, notamment jusqu'à 10 mm, notamment jusqu'à 6 mm) constituent la fraction solide d/D, avantageusement la fraction solide minérale d/D. La fraction solide, notamment la fraction solide minérale, constitue avantageusement 80% à 99%, plus avantageusement 90% à 98,5%, encore plus avantageusement de 96,5% à 97,5% du poids de l'enrobé après mûrissement (évaporation complète de l'eau). 2 and 4 mm. Other elements (minimum diameter greater than 2, 3, 4, 5 or 6 mm, in particular greater than 2, 3 or 4 mm; and approximately up to 14 mm, in particular up to 10 mm, in particular up to 6 mm ) constitute the solid fraction d / D, advantageously the solid mineral fraction d / D. The solid fraction, in particular the solid mineral fraction, advantageously constitutes 80% to 99%, more advantageously 90% to 98.5%, even more advantageously from 96.5% to 97.5% of the weight of the mix after curing ( complete evaporation of water).
Avantageusement, les enrobés de l'invention sont de couleur claire. Ainsi, les granulats utilisés dans les enrobés de l'invention ont de préférence une luminescence L* importante, typiquement supérieure à 50. Cette propriété confère aux revêtements une visibilité améliorée de jour comme de nuit ainsi qu'une grande clarté. La luminescence est typiquement calculée selon les normes NF EN 11664-1, NF EN 11664-2 et NF 11664-4, du 07-01-2011. Advantageously, the mixes of the invention are light in color. Thus, the aggregates used in the mixes of the invention preferably have a significant luminescence L *, typically greater than 50. This property gives the coatings improved visibility day and night as well as great clarity. Luminescence is typically calculated according to standards NF EN 11664-1, NF EN 11664-2 and NF 11664-4, dated 07-01-2011.
Typiquement, le liant à base de la dispersion aqueuse telle que décrite ci-dessus possède une température de formation de film inférieure ou égale à 10 °C, de préférence inférieure ou égale à 5°C, encore plus préférentiellement inférieure ou égale à 1°C. Typically, the binder based on the aqueous dispersion as described above has a film-forming temperature less than or equal to 10 ° C, preferably less than or equal to 5 ° C, even more preferably less than or equal to 1 ° vs.
La totalité de la fraction granulaire est enrobée à l'aide du liant à base de la dispersion aqueuse telle que définie ci-dessus. The whole of the granular fraction is coated using the binder based on the aqueous dispersion as defined above.
Les enrobés selon la présente invention pourront être obtenus à partir du procédé comprenant les étapes successives suivantes : a) Préparation d'une fraction granulaire telle que décrite ci-dessus, The mixes according to the present invention can be obtained from the process comprising the following successive steps: a) Preparation of a granular fraction as described above,
b) Préparation d'un liant en émulsion à partir d'une dispersion aqueuse de particules de polymère telle que décrite ci-dessus, b) Preparation of an emulsion binder from an aqueous dispersion of polymer particles as described above,
c) Enrobage de la fraction granulaire issue de l'étape a) à l'aide du liant en émulsion issue de l'étape b). c) Coating of the granular fraction resulting from step a) using the emulsion binder resulting from step b).
L'étape c) est réalisée pendant un temps suffisant pour observer une rupture avancée de l'émulsion. Step c) is carried out for a sufficient time to observe advanced rupture of the emulsion.
Avantageusement, le liant en émulsion issu de l'étape b) comprend entre 0,2% et 5% en poids de tensioactif anionique tel que défini précédemment par rapport au poids total du liant en émulsion. Le liant en émulsion issu de l'étape b) peut éventuellement comprendre un tensioactif non ionique tel que défini précédemment en combinaison avec au moins un tensioactif anionique. Advantageously, the emulsion binder resulting from step b) comprises between 0.2% and 5% by weight of anionic surfactant as defined above relative to the total weight of the emulsion binder. The emulsion binder resulting from step b) can optionally comprise a nonionic surfactant as defined above in combination with at least one anionic surfactant.
Lorsqu'il est présent, le tensioactif non ionique représente entre 0,2% et 5% en poids par rapport au poids total du liant en émulsion. When it is present, the nonionic surfactant represents between 0.2% and 5% by weight relative to the total weight of the binder in emulsion.
Selon un mode particulier de l'invention, l'enrobé peut également comprendre une quantité minoritaire de liant hydraulique en combinaison avec le liant à base de la dispersion aqueuse telle que décrite ci-dessus. Par « quantité minoritaire », on entend que la teneur en liant hydraulique résiduel est inférieure ou égale à 2% par rapport au poids total de l'enrobé, de préférence inférieure à 1%. Avantageusement, ledit liant hydraulique est choisi parmi le ciment Portland, la chaux, le lait de chaux, la magnésie, des composés calco-magnésiens synthétiques ou naturels tels que les dolomies, les chaux magnésiennes ou les chaux dolomitiques, des ciments de silicates ou d'aluminates de calcium et/ou de magnésium ou tout autre liant hydraulique bien connu de l'homme du métier. According to a particular embodiment of the invention, the mix can also comprise a minor amount of hydraulic binder in combination with the binder based on the aqueous dispersion as described above. The term “minor amount” is understood to mean that the content of residual hydraulic binder is less than or equal to 2% relative to the total weight of the mix, preferably less than 1%. Advantageously, said hydraulic binder is chosen from Portland cement, lime, milk of lime, magnesia, synthetic or natural calco-magnesian compounds such as dolomites, magnesian lime or dolomitic lime, silicate or carbonate cements. calcium and / or magnesium aluminates or any other hydraulic binder well known to those skilled in the art.
L'ajout de liant hydraulique permet d'augmenter la rigidité du liant résiduel final, et donc du revêtement d'enrobés résultant, selon les usages prévus. L'ajout de liant hydraulique peut également diminuer le temps de prise de l'enrobé, c'est-à-dire le temps nécessaire pour que l'eau et éventuellement les solvants s'évapore(nt) du liant et que l'enrobé soit suffisamment consolidé et stable pour une mise sous trafic. The addition of hydraulic binder makes it possible to increase the rigidity of the final residual binder, and therefore of the resulting asphalt coating, according to the intended uses. The addition of hydraulic binder can also decrease the setting time of the asphalt, i.e. the time required for the water and possibly the solvents to evaporate (s) from the binder and for the asphalt is sufficiently consolidated and stable to be placed under traffic.
Le liant hydraulique peut être introduit soit lors de l'étape c) du procédé ci-dessus, c'est-à-dire lors du mélange des différents composants de l'enrobé, soit au préalable à la fraction granulaire lors de l'étape a) ou au liant en émulsion lors de l'étape b) avant enrobage, sous réserve de la compatibilité et de la stabilité du liant hydraulique dans la dispersion aqueuse de polymère telle que définie ci- dessus. Préférablement, le liant hydraulique est ajouté lors de l'étape a) à la fraction granulaire. Avantageusement, le liant en émulsion issu de l'étape b) comprend un extrait sec compris entre 30% et 70% en poids de polymères par rapport au poids total de l'émulsion, préférentiellement entre 40% et 60 %, plus préférentiellement entre 45% et 55 %. The hydraulic binder can be introduced either during step c) of the above process, that is to say during the mixing of the various components of the mix, or beforehand in the granular fraction during step a) or to the binder in emulsion during step b) before coating, subject to the compatibility and the stability of the hydraulic binder in the aqueous polymer dispersion as defined above. Preferably, the hydraulic binder is added during step a) to the granular fraction. Advantageously, the emulsion binder resulting from step b) comprises a dry extract of between 30% and 70% by weight of polymers relative to the total weight of the emulsion, preferably between 40% and 60%, more preferably between 45 % and 55%.
Les enrobés selon l'invention peuvent comprendre au moins un additif, ajouté soit à la fraction granulaire lors de l'étape a), soit au liant lors de l'étape b), soit à l'enrobé, autrement dit lors du mélange des granulats et du liant à l'étape c). Ces additifs peuvent par exemple être employés à des fins mécaniques, à des fins rhéologiques, à des fins d'adhésion et/ou à des fins esthétiques, notamment pour un changement de couleur des produits routiers finaux. De préférence, cet additif est sélectionné parmi un viscosifiant inorganique ou organique, tel que des argiles, ou parmi des silices fumées, des viscosifiants cellulosiques ou synthétiques de type associatif tels que HEUR (Uréthane oxyde d'Ethylène modifiés hydrophobiqument, Hydrophobically modified Ethylene oxyde URethane selon l’acronyme anglo-saxon approprié)/HMPE (Polyéthylène à haut module, High Modulus PolyEthylene selon l'acronyme anglo-saxon) ou HASE ; ou non associatif (ASE), un additif « anti-mousse », des pigments, des fibres ou un émulsifiant. The mixes according to the invention can comprise at least one additive, added either to the granular fraction during step a), or to the binder during step b), or to the mix, in other words during the mixing of the mixtures. aggregates and binder in step c). These additives can, for example, be used for mechanical purposes, for rheological purposes, for adhesion purposes and / or for aesthetic purposes, in particular for a change of color of the final road products. Preferably, this additive is selected from an inorganic or organic viscosifier, such as clays, or from fumed silicas, cellulosic or synthetic viscosifiers of the associative type such as HEUR (Urethane ethylene oxide modified hydrophobically, Hydrophobically modified Ethylene oxide URethane according to the appropriate acronym) / HMPE (High Modulus Polyethylene, High Modulus PolyEthylene) or HASE; or non-associative (ASE), an “anti-foam” additive, pigments, fibers or an emulsifier.
On entend par « HASE », émulsion alcali soluble modifié hydrophobiquement, un copolymère carboxylé à base : The term “HASE”, a hydrophobically modified soluble alkali emulsion, is understood to mean a carboxylated copolymer based on:
(al) d'au moins d'un monomère anionique comprenant au moins une insaturation oléfinique polymérisable, de préférence un monomère anionique comprenant au moins une insaturation oléfinique polymérisable et au moins une fonction acide carboxylique, (a1) at least one anionic monomer comprising at least one polymerizable olefinic unsaturation, preferably an anionic monomer comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function,
(a2) d'au moins un ester d'un composé dérivé d'un acide carboxylique comprenant au moins une insaturation oléfinique polymérisable, et (a2) at least one ester of a compound derived from a carboxylic acid comprising at least one polymerizable olefinic unsaturation, and
(a3) d'au moins un monomère hydrophobe associatif. (a3) of at least one associative hydrophobic monomer.
On entend par « ASE », émulsion alcali soluble, un copolymère carboxylé à base : The term “ASE”, a soluble alkali emulsion, is understood to mean a carboxylated copolymer based on:
(al) d'au moins d'un monomère anionique comprenant au moins une insaturation oléfinique polymérisable, de préférence un monomère anionique comprenant au moins une insaturation oléfinique polymérisable et au moins une fonction acide carboxylique, et (a2) d'au moins un ester d'un composé dérivé d'un acide carboxylique comprenant au moins une insaturation oléfinique polymérisable. (a1) at least one anionic monomer comprising at least one polymerizable olefinic unsaturation, preferably one anionic monomer comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function, and (a2) at least one ester of a compound derived from a carboxylic acid comprising at least one polymerizable olefinic unsaturation.
Les fibres sont par exemples choisies parmi les fibres cellulosiques, les fibres polyacrylonitriles, telles que les fibres en polyacrylonitrile de taille comprise entre 4 et 12 mm, et/ou des fibres de verre. La teneur en fibre varie avantageusement de 0,05 à 0,5 ppc (partie pour cent en poids) / fraction solide sèche, avantageusement 0,05 à 0,5 ppc (partie pour cent en poids) / granulats secs, préférentiellement entre 0,07 et 0,2 ppc. L'ajout de fibres permet de limiter les coulures du liant à base de la dispersion aqueuse et d'améliorer la résistance à l'abrasion au jeune âge de l'enrobé résultant. The fibers are for example chosen from cellulosic fibers, polyacrylonitrile fibers, such as polyacrylonitrile fibers with a size of between 4 and 12 mm, and / or glass fibers. The fiber content advantageously varies from 0.05 to 0.5 pph (part percent by weight) / dry solid fraction, advantageously 0.05 to 0.5 pph (part percent by weight) / dry aggregates, preferably between 0 , 07 and 0.2 ppc. The addition of fibers makes it possible to limit sagging of the binder based on the aqueous dispersion and to improve the abrasion resistance at a young age of the resulting mix.
En fonction des conditions climatiques, de l'état de sécheresse de la fraction solide, notamment de la fraction solide minérale, de l'eau, dite eau d'apport, peut être ajoutée à la fraction granulaire lors de l'étape a) du procédé ci-dessus. La teneur totale en poids en eau de la fraction granulaire issue de l'étape a), constituée de l'eau d'apport et de l'eau naturellement présente dans la fraction granulaire, est comprise entre 1% et 6 % en poids par rapport au poids total de la fraction granulaire, avantageusement la teneur en eau est de 4%. Depending on the climatic conditions, the state of dryness of the solid fraction, in particular of the solid mineral fraction, water, known as feed water, can be added to the granular fraction during step a) of above process. The total water content by weight of the granular fraction resulting from step a), consisting of the input water and the water naturally present in the granular fraction, is between 1% and 6% by weight per relative to the total weight of the granular fraction, advantageously the water content is 4%.
L'étape a) procédé de préparation des enrobés peut inclure un éventuel séchage de la fraction granulaire si celle-ci contient une teneur en eau supérieure à 6% en poids par rapport au poids total de la fraction granulaire, afin d'atteindre une teneur en eau comprise entre 1 et 6%, avantageusement de 4%. Step a) process for preparing the mixes may include optional drying of the granular fraction if the latter contains a water content greater than 6% by weight relative to the total weight of the granular fraction, in order to achieve a content in water of between 1 and 6%, advantageously of 4%.
L'étape c) d'enrobage est de préférence réalisée à froid. Coating step c) is preferably carried out cold.
Par « enrobage à froid », on entend au sens de la présente invention que la fraction granulaire, en particulier les granulats, n'est pas séchée, et est mélangée telle quelle, c'est-à-dire avec son humidité naturelle (plus un ajustement de la teneur en eau si nécessaire) et à température ambiante. Le liant arrive alors sous diverses formes, la plus courante étant celle d'une émulsion qui permet ainsi d'avoir un produit peu visqueux et donc maniable à température ambiante. For the purposes of the present invention, the term “cold coating” means that the granular fraction, in particular the aggregates, is not dried, and is mixed as it is, that is to say with its natural moisture (more an adjustment of the water content if necessary) and at room temperature. The binder then arrives in various forms, the most common being that of an emulsion which thus makes it possible to have a product that is not very viscous and therefore workable at room temperature.
Par « température ambiante », on entend au sens de la présente invention une température allant de 15°C à 40°C. For the purposes of the present invention, the term “ambient temperature” is understood to mean a temperature ranging from 15 ° C to 40 ° C.
Préférablement, les enrobés selon la présente invention ont une teneur en vide inférieure à 30%, préférablement comprise entre 5% et 30%, encore plus préférablement entre 8% et 25%. Preferably, the mixes according to the present invention have a void content of less than 30%, preferably between 5% and 30%, even more preferably between 8% and 25%.
La teneur en liant résiduel anhydre après l'étape c) d'enrobage est typiquement comprise entre 1% et 20% en poids par rapport au poids total de l'enrobé, de préférence entre 1,5% et 10% en poids, plus préférentiellement entre 2,5% et 3,5% en poids. La quantité de liant au sein de l'enrobé pourra être ajusté en fonction de l'usage prévu des enrobés. The content of anhydrous residual binder after coating step c) is typically between 1% and 20% by weight relative to the total weight of the mix, preferably between 1.5% and 10% by weight, more preferably between 2.5% and 3.5% by weight. The amount of binder in the mix can be adjusted depending on the intended use of the mix.
Les enrobés hydrocarbonés selon l'invention sont déposés par répandage, par exemple avec un finisseur ou une niveleuse, puis compactés. Ces enrobés permettent une remise sous trafic inférieure à 72 heures, plus avantageusement dans les 24 heures après répandage. The hydrocarbon mixes according to the invention are deposited by spreading, for example with a finisher or a grader, then compacted. These mixes allow a return to traffic of less than 72 hours, more advantageously within 24 hours after spreading.
Ainsi, un dernier objet de la présente invention concerne un revêtement routier ou urbain, comprenant au moins une couche d'enrobés selon la présente invention. Thus, a final object of the present invention relates to a road or urban coating, comprising at least one coating layer according to the present invention.
Avantageusement, le revêtement selon la présente invention est une couche de chaussée claire particulièrement adaptée pour les voies peu circulées comme par exemple les voies piétonnes, les pistes cyclables, les places, les parvis, les aires de jeu, les terrains de sport et les voies vertes. De manière avantageuse, le revêtement de l'invention comprend également une couche de scellement par-dessus la ou les couche(s) d'enrobés, avantageusement appliquée entre 24h et 48h après la fin de la mise en oeuvre des enrobés. Advantageously, the coating according to the present invention is a clear pavement layer particularly suitable for low traffic lanes such as, for example, pedestrian lanes, cycle paths, squares, squares, playgrounds, sports fields and lanes. green. Advantageously, the coating of the invention also comprises a sealing layer over the coating layer (s), advantageously applied between 24 hours and 48 hours after the end of the use of the coated materials.
Par « couche de scellement », on entend au sens de la présente invention une couche de liant projetée sur une couche de chaussée destinée à fixer les gravillons de surface (les roulants) et à améliorer son imperméabilisation. En effet, le bon niveau de cohésion des enrobés garantit l'absence d'arrachement de gravillons et de sables. For the purposes of the present invention, the term “sealing layer” is understood to mean a layer of binder sprayed onto a pavement layer intended to fix the surface gravel (the rolling stones) and to improve its waterproofing. Indeed, the good level of cohesion of the mixes guarantees the absence of gravel and sand tearing.
De préférence, la couche de scellement est constituée d'une dispersion aqueuse de polymère comprenant des particules à base d'au moins deux polymères présentant des températures de transition vitreuse distinctes, des particules de polymère présentant une température de transition vitreuse unique ou leurs mélanges. En particulier, il s'agit d'une dispersion comprenant des particules de polymères cœur/écorce ou de particules de polymères structurées de sorte qu'un gradient de Tg est observé telles que décrites dans la présente description ou de particules de polymère ayant une Tg unique telle que des particules de polymère acrylique ou styrène-acrylique. La couche de scellement est préférablement appliquée à un dosage de 150 à 400 g/m2 de liant résiduel. Preferably, the sealing layer consists of an aqueous polymer dispersion comprising particles based on at least two polymers exhibiting distinct glass transition temperatures, polymer particles exhibiting a single glass transition temperature or mixtures thereof. In particular, it is a dispersion comprising particles of core / shell polymers or of polymer particles structured so that a gradient of Tg is observed as described in the present description or of polymer particles having a Tg single such as acrylic or styrene-acrylic polymer particles. The sealing layer is preferably applied at a dosage of 150 to 400 g / m 2 of residual binder.
La présente invention concerne également un procédé de préparation du revêtement de l'invention à froid comprenant les étapes suivantes : The present invention also relates to a process for preparing the coating of the invention under cold conditions, comprising the following steps:
a') préparation des enrobés de l'invention à froid par mélange de la fraction granulaire, du liant et éventuellement d'au moins un additif, selon les étapes a)-c) décrites ci-dessus, b') épandage des enrobés à une température ambiante, préférablement comprise entre 5°C à 40°C, et à un degré d'hygrométrie pouvant aller jusqu'à 100%, a ') cold preparation of the mixes of the invention by mixing the granular fraction, the binder and optionally at least one additive, according to steps a) -c) described above, b') spreading of the mixes in an ambient temperature, preferably between 5 ° C to 40 ° C, and at a degree of hygrometry which can range up to 100%,
c') compactage des enrobés, de sorte que la teneur en vide au sein des enrobés est comprise entre 5 et 30%, de préférence entre 8 et 25%, et obtention d'un revêtement d') éventuellement application d'une couche de scellement telle que décrite ci-dessus à la surface du revêtement, 24h à 72 h après l'étape c), c ') compacting the mixes, so that the void content within the mixes is between 5 and 30%, preferably between 8 and 25%, and obtaining a coating d') optionally applying a layer of sealing as described above on the surface of the coating, 24 hours to 72 hours after step c),
e') remise sous trafic, avantageusement dans les 72 heures, plus avantageusement dans les 24 heures après l'épandage. e ') put back under traffic, advantageously within 72 hours, more advantageously within 24 hours after spreading.
La figure 1 représente la variation du module E* (MPa) en fonction de la température (°C) de différent enrobés préparés avec des liants à base de dispersion aqueuse comprenant au moins des particules pΐ selon la présente invention (exemples 4 (triangles) et 5 (ronds)) ou à base d'une dispersion aqueuse ne comprenant que des particules p2 à Tg unique (liant témoin, exemple 2 - comparatif (carrés)). On observe que la pente de la courbe E=f(T) correspondant aux enrobés à base de liant témoin est plus importante que celle des courbes correspondant aux enrobés selon l'invention. Ainsi, à faible température (-20 et 0°C), le module des enrobés de l'invention et de l'enrobé témoin sont similaires tandis qu'à température plus élevées (notamment 40 et 60 °C), le module des enrobés à base de liant témoin diminue plus fortement que celui des enrobés de l'invention. FIG. 1 represents the variation of the modulus E * (MPa) as a function of the temperature (° C) of different mixes prepared with binders based on aqueous dispersion comprising at least p particules particles according to the present invention (examples 4 (triangles) and 5 (round)) or based on an aqueous dispersion comprising only p2 particles with a single Tg (control binder, example 2 - comparative (squares)). It is observed that the slope of the curve E = f (T) corresponding to mixes based on a control binder is greater than that of the curves corresponding to mixes according to invention. Thus, at low temperature (-20 and 0 ° C), the modulus of the mixes of the invention and of the control mix are similar, while at higher temperatures (in particular 40 and 60 ° C), the modulus of the mixes based on a control binder decreases more sharply than that of the coated materials of the invention.
EXEMPLES EXAMPLES
Pour tous les exemples ci-dessous, la teneur en liant anhydre résiduel total a été fixée à 3,0 ppc (ou 2,9%) par rapport à la masse de fraction solide minérale. For all the examples below, the content of total residual anhydrous binder was set at 3.0 pph (or 2.9%) relative to the mass of the solid mineral fraction.
La courbe granulométrique de la fraction solide minérale est la suivante pour tous les exemples ci- dessous : The particle size curve of the solid mineral fraction is as follows for all the examples below:
Table 1
Figure imgf000016_0001
Table 1
Figure imgf000016_0001
Les liants testés sont les dispersions de polymère en phase aqueuse ayant les propriétés suivantes : The binders tested are the polymer dispersions in aqueous phase having the following properties:
Table 2 Table 2
Figure imgf000016_0002
Figure imgf000016_0002
* les liants utilisés dans les exemples sont des liants commerciaux de la société Celanese® vendus sous la désignation commerciale Mowilith®. Ils comprennent tous un tensioactif anionique. Fabrication des enrobés * the binders used in the examples are commercial binders from the company Celanese ® sold under the trade name Mowilith ® . They all include an anionic surfactant. Asphalt production
Dans chaque exemple ci-dessous, la fraction minérale solide a été introduite dans un malaxeur, de l'eau a été ajoutée au mélange puis le liant en phase aqueuse a été introduit à la formulation. Après 20 secondes de malaxage, l'enrobé est compacté à la dame Marshall® puis un mûrissement de 14 jours à 35°C/20% d'hygrométrie est réalisé. In each example below, the solid mineral fraction was introduced into a kneader, water was added to the mixture and then the binder in aqueous phase was introduced into the formulation. After 20 seconds of mixing, the asphalt is compacted using a Marshall® machine, then maturing for 14 days at 35 ° C. / 20% hygrometry is carried out.
Propriétés mécaniques en compression diamétrale sinusoïdale Mechanical properties in sinusoidal diametral compression
Les enrobés sont ensuite caractérisés par compressions diamétrales sinusoïdales afin d'obtenir l'angle de phase, ainsi que le module complexe de l'enrobé en fonction de la température et de la fréquence. The mixes are then characterized by sinusoidal diametral compressions in order to obtain the phase angle, as well as the complex modulus of the mix as a function of temperature and frequency.
Test de cohésion de surface Surface cohesion test
Un essai de cohésion superficielle de type test de Cohésion de Surface (TCS) issu de la norme NF EN 12274-5 peut être réalisé pour estimer la résistance à l'arrachement de surface de l'enrobé. Cet essai est réalisé après un temps de cure de l'enrobé de 72 heures à 20°C avant immersion dans l'eau. La parte de masse de l'enrobé est ensuite évalué en pourcentage par rapport à la surface d'abrasion. Exemple 1 : Formulation témoin n°l A surface cohesion test of the Surface Cohesion test (TCS) type from standard NF EN 12274-5 can be carried out to estimate the resistance to surface tearing of the asphalt. This test is carried out after a cure time of the mix of 72 hours at 20 ° C. before immersion in water. The mass share of the asphalt is then evaluated as a percentage relative to the abrasion surface. Example 1: Control formulation n ° l
Un exemple de formulation d'enrobé à froid de référence avec une fraction granulaire 0/6 et un liant en phase aqueuse à base d'une dispersion aqueuse comprenant uniquement des particules à Tg unique est donné dans le tableau suivant : An example of a standard cold mix formulation with a 0/6 granular fraction and an aqueous phase binder based on an aqueous dispersion comprising only particles with a single Tg is given in the following table:
Table 3 Table 3
Figure imgf000017_0001
Figure imgf000017_0001
Afin de caractériser les propriétés mécaniques des enrobés obtenus, un mûrissement à 35°C/20% d'hygrométrie a été réalisé suite à la fabrication à froid des enrobés. Les propriétés mécaniques en compression diamétrale sinusoïdale des enrobés obtenus à partir de cette formulation sont données dans le tableau suivant : In order to characterize the mechanical properties of the mixes obtained, a ripening at 35 ° C / 20% hygrometry was carried out following the cold production of the mixes. The mechanical properties in sinusoidal diametral compression of the mixes obtained from this formulation are given in the following table:
Table 4 Table 4
Figure imgf000018_0001
Exemple 2 : Formulation témoin n°2
Figure imgf000018_0001
Example 2: Control formulation No. 2
Un autre liant témoin a été employé pour la formulation d'enrobés clairs à froid. Another control binder was used for the formulation of clear cold mixes.
Table 5 Table 5
Figure imgf000018_0002
Figure imgf000018_0002
Les propriétés mécaniques en compression diamétrale sinusoïdale des enrobés obtenus à partir de cette formulation sont données dans le tableau suivant : The mechanical properties in sinusoidal diametral compression of the mixes obtained from this formulation are given in the following table:
Table 6 Table 6
Figure imgf000018_0003
Exemple 3 : Formulation selon l'invention n°l
Figure imgf000018_0003
Example 3: Formulation according to the invention n ° l
Un liant cœur-écorce selon l'invention a été employé pour la formulation d'enrobés clairs à froid selon la composition suivante : A core-bark binder according to the invention was used for the formulation of clear cold mixes according to the following composition:
Table 7 Table 7
Figure imgf000019_0001
Figure imgf000019_0001
Les propriétés mécaniques en compression diamétrale sinusoïdale des enrobés obtenus à partir de cette formulation sont données dans le tableau suivant : The mechanical properties in sinusoidal diametral compression of the mixes obtained from this formulation are given in the following table:
Table 8 Table 8
Figure imgf000019_0002
Le test de cohésion de surface a été réalisé à partir de cette formule suite à un mûrissement de 72h à 20°C. Les pertes à l'abrasion sur cette formule sont de 52%.
Figure imgf000019_0002
The surface cohesion test was carried out using this formula after curing for 72 hours at 20 ° C. The abrasion losses on this formula are 52%.
Exemple 4 : Formulation selon l'invention n°2 Example 4: Formulation according to the invention No. 2
Un autre liant cœur-écorce selon l'invention a été employé pour la formulation d'enrobés clairs à froid selon la composition suivante : Another core-shell binder according to the invention was used for the formulation of clear cold mixes according to the following composition:
Table 9 Table 9
Figure imgf000019_0003
Les propriétés mécaniques en compression diamétrale sinusoïdale des enrobés obtenus à partir de cette formulation sont données dans le tableau suivant :
Figure imgf000019_0003
The mechanical properties in sinusoidal diametral compression of the mixes obtained from this formulation are given in the following table:
Table 10 Table 10
Figure imgf000020_0001
Figure imgf000020_0001
Exemple 5 : Formulation selon l'invention n°3 Example 5: Formulation according to the invention No. 3
Un liant à gradient de Tg selon l'invention a été employé pour la formulation d'enrobés clairs à froid selon la composition suivante : A Tg gradient binder according to the invention was used for the formulation of clear cold mixes according to the following composition:
Table 11 Table 11
Figure imgf000020_0002
Figure imgf000020_0002
Les propriétés mécaniques en compression diamétrale sinusoïdale des enrobés obtenus à partir de cette formulation sont données dans le tableau suivant : The mechanical properties in sinusoidal diametral compression of the mixes obtained from this formulation are given in the following table:
Table 12 Table 12
Figure imgf000020_0003
Exemple 6 : Revêtement selon l'invention
Figure imgf000020_0003
Example 6: Coating according to the invention
Un liant cœur-écorce selon l'invention a été employé pour la formulation d'enrobés clairs à froid selon la composition suivante : A core-bark binder according to the invention was used for the formulation of clear cold mixes according to the following composition:
Table 13 Table 13
Figure imgf000021_0001
Figure imgf000021_0001
La teneur en liant résiduel de cet enrobé est donc de 2,4%. The content of residual binder in this mix is therefore 2.4%.
Des éprouvettes de cet enrobé ont été préparées pour le test de cohésion de surface en fixant un mûrissement de 72h à 20°C. Après 48h de mûrissement, certaines éprouvettes ont été traitées par un produit de cure (scellement) composé de Ll 1 dilué à 50% par de l'eau. Le produit de cure a été appliqué à 100, 150 et 200g/m2 de liant résiduel sur l'éprouvette puis le mûrissement s'est poursuivi jusqu'à 72h. Les enrobés ont ensuite été évalués selon le test de cohésion de surface et les résultats figurent ci-dessous : Test specimens of this coated material were prepared for the surface cohesion test by setting a ripening of 72 hours at 20 ° C. After 48 hours of ripening, certain test specimens were treated with a curing product (sealant) composed of Ll 1 diluted to 50% with water. The curing product was applied at 100, 150 and 200 g / m 2 of residual binder on the test piece and then the curing continued for up to 72 hours. The mixes were then evaluated according to the surface cohesion test and the results are shown below:
Table 14 Table 14
Figure imgf000021_0002
Figure imgf000021_0002
La figure 1 illustre la susceptibilité thermique moindre des enrobés formulés avec des liants de l'invention (cœur-écorce et gradient de Tg) (voir courbes des triangles et des ronds) par rapport à des enrobés qui sont formulés à partir d'un liant homogène comprenant uniquement des particules p2 à Tg unique (voir courbe des carrés). Figure 1 illustrates the lower thermal susceptibility of the mixes formulated with binders of the invention (core-shell and Tg gradient) (see curves of triangles and circles) compared to mixes which are formulated from a binder homogeneous comprising only p2 particles with a single Tg (see curve of squares).

Claims

REVENDICATIONS : CLAIMS:
1. Utilisation d'une dispersion aqueuse comprenant au moins un tensioactif anionique et des particules pΐ à base d'au moins deux polymères présentant des températures de transition vitreuse distinctes, de sorte que le polymère ayant la température de transition vitreuse la plus élevée, supérieure ou égale à 10°C, se trouve au centre de la particule pΐ et le polymère ayant la température de transition vitreuse la plus faible, inférieure ou égale à 0°C, se trouve en surface de la particule pΐ, pour la préparation d'un liant destiné à la fabrication d'un enrobé routier ou urbain. 1. Use of an aqueous dispersion comprising at least one anionic surfactant and pΐ particles based on at least two polymers having distinct glass transition temperatures, so that the polymer having the highest glass transition temperature, higher or equal to 10 ° C, is at the center of the pΐ particle and the polymer with the lowest glass transition temperature, less than or equal to 0 ° C, is at the surface of the pΐ particle, for the preparation of a binder intended for the manufacture of a road or urban asphalt.
2. Utilisation selon la revendication 1, caractérisée en ce que la température de transition vitreuse la plus élevée est supérieure ou égale à 30°C, préférentiellement supérieure ou égale à 50°C et en ce que la température de transition vitreuse la plus faible est inférieure ou égale -10°C. 2. Use according to claim 1, characterized in that the highest glass transition temperature is greater than or equal to 30 ° C, preferably greater than or equal to 50 ° C and in that the lowest glass transition temperature is less than or equal to -10 ° C.
3. Utilisation selon la revendication 1 ou 2, caractérisée en ce qu'un gradient positif de température de transition vitreuse des polymères est observé de la surface vers le centre des particules pΐ. 3. Use according to claim 1 or 2, characterized in that a positive gradient of the glass transition temperature of the polymers is observed from the surface towards the center of the pΐ particles.
4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que la dispersion aqueuse comprenant les particules pΐ est préparée par polymérisation en émulsion en phase aqueuse d'au moins deux compositions de monomères choisis parmi des monomères vinyliques et/ou diéniques, des esters comprenant au moins une instauration oléfinique polymérisable et des monomères éthylèniquement insaturés porteur d’au moins une fonction acide et/ ou anhydride carboxylique. 4. Use according to any one of claims 1 to 3, characterized in that the aqueous dispersion comprising the particles pΐ is prepared by emulsion polymerization in aqueous phase of at least two compositions of monomers chosen from vinyl monomers and / or diene, esters comprising at least one polymerizable olefinic establishment and ethylenically unsaturated monomers bearing at least one acid and / or carboxylic anhydride function.
5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que la dispersion aqueuse comprend en outre des particules p2 de polymère présentant une température de transition vitreuse unique. 5. Use according to any one of claims 1 to 4, characterized in that the aqueous dispersion further comprises particles p2 of polymer having a single glass transition temperature.
6. Enrobés comprenant une fraction granulaire enrobée d'un liant, ledit liant étant à base d'une dispersion aqueuse de particules telle que définie aux revendications 1 à 5. 6. Mixtures comprising a granular fraction coated with a binder, said binder being based on an aqueous dispersion of particles as defined in claims 1 to 5.
7. Enrobés selon la revendication 6, caractérisés en ce que la fraction granulaire comprend : 7. Asphalt according to claim 6, characterized in that the granular fraction comprises:
- des éléments de taille inférieure à 0,063 mm, - elements smaller than 0.063 mm,
- du sable dont les éléments ont une taille comprise entre 0,063 mm et 2 mm, et - sand whose elements have a size between 0.063 mm and 2 mm, and
- des gravillons dont les éléments ont des dimensions - chippings whose elements have dimensions
. comprises entre 2 mm et 6 mm, . between 2 mm and 6 mm,
. éventuellement comprises entre 6 mm et 10 mm. . possibly between 6 mm and 10 mm.
8. Enrobés selon la revendication 6 ou 7, caractérisés en ce que lesdits enrobés comprennent également une quantité minoritaire de liant hydraulique choisi parmi le ciment Portland, la chaux, le lait de chaux, la magnésie, des composés calco-magnésiens, des ciments de silicates ou d'aluminates de calcium et/ou de magnésium, la teneur en liant hydraulique résiduel étant inférieure ou égale à 2% par rapport au poids total de l'enrobé. 8. Asphalt according to claim 6 or 7, characterized in that said mixes also comprise a minor amount of hydraulic binder chosen from Portland cement, lime, milk of lime, magnesia, calco-magnesian compounds, cements. calcium and / or magnesium silicates or aluminates, the residual hydraulic binder content being less than or equal to 2% relative to the total weight of the mix.
9. Enrobés selon l'une quelconque des revendications 6 à 8, caractérisés en ce que la teneur en liant résiduel après enrobage est comprise entre 1% et 20% en poids par rapport au poids total de l'enrobé, de préférence entre 1,5% et 10% en poids, plus préférentiellement entre 2,5% et 3,5% en poids. 9. Mix according to any one of claims 6 to 8, characterized in that the content of residual binder after coating is between 1% and 20% by weight relative to the total weight of the coated material, preferably between 1, 5% and 10% by weight, more preferably between 2.5% and 3.5% by weight.
10. Enrobés selon l'une quelconque des revendications 6 à 9, caractérisés en ce que lesdits enrobés comprennent également au moins un additif, de préférence sélectionné parmi un viscosifiant inorganique ou organique, tel que des argiles, des silices fumées, des viscosifiants cellulosiques ou synthétiques de type associatif ou non associatif, un additif « anti-mousse », des pigments, des fibres ou un émulsifiant. 10. Mix according to any one of claims 6 to 9, characterized in that said mixes also comprise at least one additive, preferably selected from an inorganic or organic viscosifier, such as clays, fumed silicas, cellulosic viscosifiers or synthetic associative or non-associative type, an “anti-foam” additive, pigments, fibers or an emulsifier.
11. Revêtement comprenant au moins une couche d'enrobés tels que définis aux revendications 6 à 10. 11. Coating comprising at least one coating layer as defined in claims 6 to 10.
12. Revêtement selon la revendication 11 comprenant également une couche de scellement, ladite couche de scellement étant constituée d'une dispersion aqueuse de polymère comprenant des particules à base d'au moins deux polymères présentant des températures de transition vitreuse distinctes, des particules de polymère présentant une température de transition vitreuse unique, ou leurs mélanges. 12. Coating according to claim 11 also comprising a sealing layer, said sealing layer consisting of an aqueous dispersion of polymer comprising particles based on at least two polymers having distinct glass transition temperatures, polymer particles. exhibiting a single glass transition temperature, or mixtures thereof.
PCT/FR2020/050733 2019-05-02 2020-04-30 Use of an aqueous polymer dispersion for the production of coated macadams WO2020221980A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1434803A1 (en) 2001-10-02 2004-07-07 Avecia B.V. Polymer composition comprising a polymer having a gradient polymeric morphology
JP2008019143A (en) * 2006-07-14 2008-01-31 Sumitomo Kinzoku Kozan Siporex Kk Emulsion composition for anti-corrosive treating material of autoclaved lightweight concrete reinforcing steel
WO2009009559A1 (en) 2007-07-09 2009-01-15 Nigelpower, Llc Wireless energy transfer using coupled antennas
WO2009016053A1 (en) 2007-07-30 2009-02-05 Basf Se Core shell polymer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1434803A1 (en) 2001-10-02 2004-07-07 Avecia B.V. Polymer composition comprising a polymer having a gradient polymeric morphology
JP2008019143A (en) * 2006-07-14 2008-01-31 Sumitomo Kinzoku Kozan Siporex Kk Emulsion composition for anti-corrosive treating material of autoclaved lightweight concrete reinforcing steel
WO2009009559A1 (en) 2007-07-09 2009-01-15 Nigelpower, Llc Wireless energy transfer using coupled antennas
WO2009016053A1 (en) 2007-07-30 2009-02-05 Basf Se Core shell polymer

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