EP4284878A1 - Compositions for producing sealing membranes, and associated methods and membranes - Google Patents

Compositions for producing sealing membranes, and associated methods and membranes

Info

Publication number
EP4284878A1
EP4284878A1 EP22705442.6A EP22705442A EP4284878A1 EP 4284878 A1 EP4284878 A1 EP 4284878A1 EP 22705442 A EP22705442 A EP 22705442A EP 4284878 A1 EP4284878 A1 EP 4284878A1
Authority
EP
European Patent Office
Prior art keywords
particles
polymer
composition
bitumen
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22705442.6A
Other languages
German (de)
French (fr)
Inventor
Julie Prevost
Jean-Philippe Paillac
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Onetech SAS
Original Assignee
TotalEnergies Onetech SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TotalEnergies Onetech SAS filed Critical TotalEnergies Onetech SAS
Publication of EP4284878A1 publication Critical patent/EP4284878A1/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/30—Environmental or health characteristics, e.g. energy consumption, recycling or safety issues
    • C08L2555/34—Recycled or waste materials, e.g. reclaimed bitumen, asphalt, roads or pathways, recycled roof coverings or shingles, recycled aggregate, recycled tires, crumb rubber, glass or cullet, fly or fuel ash, or slag
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
    • C08L2555/50—Inorganic non-macromolecular ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
    • C08L2555/80—Macromolecular constituents
    • C08L2555/84—Polymers comprising styrene, e.g., polystyrene, styrene-diene copolymers or styrene-butadiene-styrene copolymers

Definitions

  • the present invention relates to the technical field of waterproofing membranes and bituminous compositions suitable for their manufacture.
  • bituminous binder for waterproofing membranes, comprising a bitumen, one or more polymers which comprise(s) at least Styrene Butadiene Styrene (SBS) and one or more fillers minerals comprising at least one phyllosilicate, the SBS/phyllosilicate mixture constituting between 3 and 20% by weight of said bituminous binder and the fraction of said phyllosilicate representing between 5 and 25% by weight of said SBS.
  • SBS Styrene Butadiene Styrene
  • fillers minerals comprising at least one phyllosilicate
  • the proposed solution is presented as a solution that makes it possible to reduce the cost price of the bituminous composition and therefore of the waterproofing membrane obtained.
  • compositions and processes for manufacturing such compositions offer new possibilities for recycling plastic waste, and are therefore particularly advantageous, from an ecological point of view and for reducing the carbon footprint.
  • compositions and membranes according to the invention offer new solutions for reducing their cost price.
  • Another object of the invention is also to provide compositions allowing a lightening of the sealing membranes obtained with such compositions, which is advantageous, in particular, to facilitate their handling and their transport. Disclosure of Invention
  • the invention relates to bituminous compositions comprising, in a bitumen-based matrix, fillers C which represent from 21 to 40% of the total mass of the composition and which consist of inorganic particles Ci and polymeric particles Cp crystal polystyrene or impact polystyrene, the mass of the polymeric particles Cp representing from 1 to 10% of the total mass of the composition and the mass of bitumen representing from 40 to 70% of the total mass of the composition.
  • fillers C which represent from 21 to 40% of the total mass of the composition and which consist of inorganic particles Ci and polymeric particles Cp crystal polystyrene or impact polystyrene, the mass of the polymeric particles Cp representing from 1 to 10% of the total mass of the composition and the mass of bitumen representing from 40 to 70% of the total mass of the composition.
  • inorganic fillers Ci by selected polymeric particles Cp which are impact or crystal polystyrene particles, in a bituminous composition intended for the manufacture of a waterproofing membrane, did not lead to any loss of properties of the waterproofing membrane obtained.
  • the compositions and membranes obtained were evaluated, in terms of penetrability at 20 and 50°C, ball-ring softening temperature (TBA), cold pliability, before and after accelerated long-term aging in a container. pressure aging (PAV), remanence Re and viscosity.
  • the substitution of part of the inorganic fillers Ci by polymeric fillers Cp selected in the context of the invention did not lead to a loss of these properties, which remained substantially identical.
  • the invention thus makes it possible to use, as fillers, polymeric particles resulting from the recycling of plastic waste, which opens up other ways of recovering waste, makes it possible to reduce the environmental footprint of the waterproofing membranes obtained with the compositions according to the invention, to promote a circular economy and to limit the use of finite resources that are inorganic fillers.
  • such a replacement of part of the inorganic fillers Ci by polymeric fillers Cp selected within the framework of the invention makes it possible to obtain a lightening of the sealing membrane obtained.
  • the impact or crystal polystyrene of the Cp polymer particles has a Mw in the range from 80 to 300 kg/mol, and preferably in the range from 100 to 250 kg/mol.
  • the Cp polymer particles comprise at least 85% by mass, preferably at least 90% by mass, and preferably at least 95% by mass of impact or crystal polystyrene; said impact or crystal polystyrene is mixed with one or more polymer(s) P1 , preferably chosen from polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene (ABS) copolymer, polycarbonates, polyethylene terephthalate (PET ).
  • PVC polyvinyl chloride
  • ABS acrylonitrile-butadiene-styrene
  • PET polyethylene terephthalate
  • such Cp polymer particles are preferably obtained from the recycling of waste.
  • compositions according to the invention further comprise, as additional component(s), one or more polymer(s) P2, preferably chosen from plastomers and thermoplastics and, in particular, thermoplastic elastomers, in particular chosen from unsaturated block copolymers.
  • the polymer(s) P2 is (are) chosen from styrene-butadiene-styrene block copolymers, preferably in branched or star-shaped form, atactic polypropylene and poly(ethylene vinyl acetate ).
  • the mass of polymer(s) P2 represents from 5 to 25%, preferably from 5 to 20% and, even more preferably, from 7 to 18% of the total mass of the composition.
  • the inorganic particles Ci are particles of calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulphate, barium sulphate, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide or glass, with calcium carbonate particles being preferred.
  • the mass of inorganic particles Ci represents 20 to 39%, preferably 25 to 37%, and even more preferably 27 to 34% of the total mass of the composition.
  • the D50 of the Cp polymer particles and/or the D50 of the Ci inorganic particles belongs(n) to the range going from 10 to 300 ⁇ m, preferably to the range going from 20 to 200 ⁇ m, and preferentially to the range going from 30 to 150 ⁇ m.
  • the preferred compositions, within the scope of the invention, comprise, or even consist of:
  • fillers C consisting of inorganic particles Ci and polymeric particles Cp of polystyrene impact or crystal, the Cp polymer particles representing from 1 to 10% m/m, preferably 1 to 5% m/m, and even more preferably from 1 to 3% m/m of the total mass of the composition and the inorganic particles Ci representing from 20 to 39% m/m, preferably from 25 to 37% m/m, and even more preferably from 27 to 34% m/m of the total mass of the composition;
  • % m/m being % by mass relative to the total mass of the composition.
  • the invention also relates to a process for the preparation of a composition according to the invention, comprising the mixing under heating of an assembly comprising:
  • the mixture under heating is carried out at a temperature belonging to the range going from 100 to 220° C., preferably for 5 minutes to 10 hours and/or with stirring from 200 to 2000 revolutions/min.
  • the mixture under heating is carried out over an assembly comprising, additionally, one or more polymer(s) P2 chosen from plastomers and thermoplastics and, in particular, thermoplastic elastomers, in particular chosen from unsaturated block copolymers, and, even more preferably, chosen from styrene-butadiene-styrene block copolymers, preferably in the form branched or star-shaped, atactic polypropylene and poly(ethylene vinyl acetate).
  • polymer(s) P2 chosen from plastomers and thermoplastics and, in particular, thermoplastic elastomers, in particular chosen from unsaturated block copolymers, and, even more preferably, chosen from styrene-butadiene-styrene block copolymers, preferably in the form branched or star-shaped, atactic polypropylene and poly(ethylene vinyl acetate).
  • the method according to the invention comprises the introduction, into the bitumen, of said polymer(s) P2, before the introduction into the bitumen of the inorganic particles Ci and Cp polymeric particles of impact or crystal polystyrene.
  • the method according to the invention comprises the introduction, into the bitumen, of inorganic particles Ci which have a D50 which belongs to the range going from 10 to 300 ⁇ m, preferably to the range going from 20 to 200 ⁇ m, and preferentially to the range going from 30 to 150 ⁇ m and/or Cp polymeric particles of impact or crystal polystyrene which have a D50 which belongs to the range going from 10 to 300 ⁇ m, preferably to the range going from 20 to 200 ⁇ m, and preferentially to the range going from 30 to 150 ⁇ m.
  • compositions according to the invention for the manufacture of a waterproofing membrane, in particular for a roof, is an integral part of the invention.
  • the invention relates to a waterproofing membrane, in particular for a roof, comprising a layer formed from a composition according to the invention.
  • the invention also relates to waterproofing membranes, in particular for roofing, comprising a composition according to the invention, impregnating, at least in part, a fibrous material.
  • the invention relates to such sealing membranes in the form of a multilayer structure.
  • the D50 is defined as being the diameter of the particles for which 50% by volume of the particles have a diameter greater than this value and 50% by volume of the particles have a diameter less than this value.
  • the D50 is determined, in the context of the invention, with a laser diffraction particle size analyzer in the liquid route (alcohol).
  • CV coefficient of variation
  • the average molecular masses can be measured by gel permeation chromatography (GPC) (or SEC for "Size Exclusion Chromatography” in English).
  • GPC gel permeation chromatography
  • SEC Size Exclusion Chromatography
  • Mw weight average molecular weight
  • the external standard used to determine the Mw of polystyrene is a polystyrene standard.
  • compositions according to the invention contain a single bitumen or a mixture of bitumens.
  • bitumens which can be used in the compositions according to the invention, mention may first be made of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or bituminous sands and bitumens originating from the refining of crude oil.
  • the bitumen(s) present in the composition are advantageously chosen from bitumens originating from the refining of crude oil, in particular bitumens containing asphaltenes or pitches.
  • the bitumens can be obtained by conventional processes for the manufacture of bitumens in refineries, in particular by direct distillation and/or vacuum distillation of petroleum.
  • bitumens can optionally be visbroken and/or deasphalted and/or air-rectified. It is common practice to carry out the vacuum distillation of the atmospheric residues resulting from the atmospheric distillation of crude oil. This manufacturing process therefore corresponds to the succession of atmospheric distillation and vacuum distillation, the charge supplying the vacuum distillation corresponding to atmospheric residues. These vacuum residues from the vacuum distillation tower can also be used as bitumen. It is also common to inject air into a charge usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from petroleum distillation. This process makes it possible to obtain a blown or semi-blown or oxidized or air-rectified or partially air-rectified bitumen.
  • bitumens obtained by refining processes can be combined in the compositions according to the invention, to obtain the best compromise, in terms of technical performance.
  • the operation is carried out at temperatures between 100° C. and 200° C., preferably between 140° C. and 200° C., and with stirring for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours.
  • the heating temperature and duration vary according to the quantity of bitumen used and are defined by standard NF EN 12594.
  • Blown bitumens can be produced in a blowing unit, by passing a flow of air and/or oxygen through a starting bitumen or mixture of bitumens.
  • This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid.
  • an oxidation catalyst for example phosphoric acid.
  • the blowing is carried out at high temperatures, of the order of 200 to 300° C., for relatively long durations typically comprised between 30 minutes and 2 hours, continuously or in batches.
  • the blowing time and temperature are adjusted according to the properties targeted for the blown bitumen and according to the quality of the starting bitumen.
  • bitumens which can be used according to the invention, mention may also be made of bitumens resulting from recycling.
  • bitumens can be hard grade bitumens (such as grades 10/20 and 20/30) or soft grade (such as grade 160/220) defined by standard EN 12591.
  • the invention is particularly suitable for cases where the composition is formed with a bitumen chosen from among bitumens of grades 160/220 and 70/100 and mixtures thereof.
  • the bitumens which can be used in the context of the invention preferably have a penetrability, measured at 25° C. according to standard EN 1426, of 5 to 330 1/10 mm, preferably between 10 to 220 1/10 mm.
  • the so-called “needle penetrability” measurement is carried out by means of a standardized test NF EN 1426 at 25° C. (Pene). This penetrability characteristic is expressed in tenths of a millimeter (dmm or 1/10 mm). Needle penetrability, measured at 25°C, according to the standardized test NF EN 1426, represents the measurement of the penetration into a sample of bitumen, after a time of 5 seconds, of a needle whose weight with its support is 100 g.
  • compositions according to the invention comprise fillers which are distributed in the bitumen or more generally in a matrix formed of one or more bitumens, or even of a mixture of bitumen(s)/polymer(s) P2 defined within the scope of the invention.
  • the fillers C in the context of the invention are of two kinds: one part consists of inorganic particles or fillers, named Ci, the other part consists of polymeric particles or fillers of impact or crystal polystyrene, named Cp. These two types of particles are defined in more detail later in the description.
  • part of the mineral fillers used in the compositions of the prior art could be replaced by Cp polymeric fillers and that this did not alter the properties evaluated in the examples, membranes obtained.
  • Cp polymer particles consisting or mainly consisting of a crystal or impact polystyrene. This therefore opens up numerous possibilities for using polymeric fillers resulting from the recycling of plastic waste, and in particular recycled polystyrene waste.
  • the fillers C present in the composition are preferably of micrometric size and in particular have a lower maximum size. or equal to 500 pm. When a particle is perfectly spherical, its maximum size is its diameter.
  • the polymer particles Cp and/or the inorganic particles Ci have a D50 which belongs to the range going from 10 to 300 ⁇ m, preferably to the range going from 20 to 200 ⁇ m, and preferentially to the range going from 30 at 150 p.m.
  • the Cp polymer particles present in the composition have a coefficient of variation CV, characterizing their dispersion in size, of 1.1 to 5, preferably from 1.1 to 4, and preferentially from 1.1 to 3 and/or the inorganic particles Ci present in the composition have a coefficient of variation CV, characterizing their dispersion in size, of 1.1 to 5, preferably from 1.1 to 4, and preferentially from 1.1 to 3 .
  • Inorganic fillers Ci having such a size are commercially available.
  • the size of the polymeric particles Cp and of the inorganic particles Ci introduced can be adjusted according to any conventional techniques well known to those skilled in the art. In particular, a grinding operation is carried out, followed by a selection of the particle size by passage through one or more sieves. In the case of Cp polymer particles, obtained from plastic waste, a rough cutting operation into chips is generally carried out, before a finer grinding operation.
  • compositions according to the invention can be obtained by introducing, into a bitumen-based matrix, Cp polymeric particles having a D50 which belongs to the range from 10 to 300 ⁇ m, preferably to the range from from 20 to 200 ⁇ m, and preferentially to the range going from 30 to 150 ⁇ m and of inorganic particles Ci having a D50 which belongs to the range going from 10 to 300 ⁇ m, preferably to the range going from 20 to 200 ⁇ m, and preferentially to the range going from 30 to 150 ⁇ m.
  • the polymeric particles Cp and the inorganic particles Ci introduced may, however, have the same or different sizes.
  • compositions according to the invention can be obtained by introducing, into a bitumen-based matrix, polymeric particles Cp having a coefficient of variation CV, characterizing their dispersion in size, of 1.1 to 5 , preferably from 1.1 to 4, and preferably from 1.1 to 3 and/or inorganic particles Ci having a coefficient of variation CV, characterizing their dispersion in size, from 1.1 to 5, preferably from 1, 1 to 4, and preferably from 1.1 to 3.
  • Cp polymeric particles having a coefficient of variation CV, characterizing their dispersion in size, of 1.1 to 5 , preferably from 1.1 to 4, and preferably from 1.1 to 3.
  • the Cp polymer particles are impact or crystal polystyrene particles.
  • High impact and crystal polystyrenes are well-known polymers, which differ from expanded polystyrene. Crystal polystyrene is transparent and is a homopolymer of styrene.
  • High impact polystyrene also called HIPS (High Impact Polystyrene) contains a part of polybutadiene and is defined, in particular, in standard EN ISO 1043-1.
  • the Cp polymer particles consist or mainly consist of crystal or impact polystyrene, which does not exclude the presence of one or more components or impurities in said particles.
  • the Cp polymer particles comprise at least 85% by mass, preferably at least 90% by mass, and preferentially at least 95% by mass of impact or crystal polystyrene.
  • the polymer particles Cp may comprise one or more polymer(s) P1, preferably chosen from polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonates, polyethylene terephthalate (PET).
  • PVC polyvinyl chloride
  • ABS acrylonitrile-butadiene-styrene copolymer
  • PET polyethylene terephthalate
  • the mass of polymer(s) P1 present represents at most 15%, preferably at most 10%, and preferentially at most 5%, of the mass of the polymer particles Cp.
  • the impact or crystal polystyrene of the Cp polymer particles has a Mw in the range from 80 to 300 kg/mol, and preferably in the range from 100 to 250 kg/mol.
  • the Cp polymer particles comprise an impact or crystal polystyrene, advantageously having a Mw in the range going from 80 to 300 kg/mol, and preferentially in the range going from 100 to 250 kg/mol. mol, mixed with another polymer P1, and in particular mixed with an ABS copolymer.
  • the polymeric particles Cp consist of a crystal or impact polystyrene (and in particular an impact polystyrene having, preferably, a Mw defined previously) or of a crystal or impact polystyrene/polymer P1 mixture (and in particular in which the polystyrene is an impact polystyrene, preferably having a Mw defined above), and in particular a crystal or impact polystyrene/ABS mixture.
  • the quantity of polymer P1, and in particular of ABS represents from 5 to 15%, and preferably from 8 to 12% of the mass of the polymer particles Cp.
  • Such particles are in particular obtained from recycled polymer(s), in particular from waste packaging or household appliances such as refrigerators.
  • the Cp polymer particles can consist of particles of the same nature or of particles of different natures. It is, in particular, possible to use a mixture of high impact polystyrene particles and crystal polystyrene particles. It is also possible that the composition comprises, as polymeric particles Cp, particles consisting of an impact or crystal polystyrene and particles consisting of a mixture of an impact or crystal polystyrene and a polymer P1, as previously described.
  • compositions according to the invention comprise inorganic particles Ci, which partly constitute the fillers C.
  • these inorganic particles are introduced into the compositions for waterproofing membranes to confer good walking resistance. and creep resistance of the membranes obtained.
  • any inorganic particles used by those skilled in the art in compositions suitable for producing sealing membranes can be used.
  • the inorganic particles Ci are advantageously particles of calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulphate, barium sulphate, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide or glass.
  • the compositions according to the invention comprise particles of calcium carbonate, as inorganic particles Ci.
  • compositions according to the invention further comprise at least one additional component, in addition to bitumen, inorganic particles Ci and polymeric particles Cp.
  • additional component the compositions according to the invention comprise, so as advantageously, one or more polymer(s) P2, qualified as additional polymer(s). Indeed, this or these polymers P2 are said to be additional, because they do not correspond to the polymer(s) present in the polymer particles Cp.
  • a P2 polymer is not an impact polystyrene or a crystal polystyrene.
  • polymer P2 which is particularly preferred in the context of the invention, mention may be made of polymers chosen from plastomers, in particular polyolefins and olefin copolymers, such as poly(ethylene vinyl acetate) (EVA) and atactic polypropylene (aPP), thermoplastics and, in particular, thermoplastic elastomers, in particular chosen from unsaturated block copolymers.
  • EVA poly(ethylene vinyl acetate)
  • aPP atactic polypropylene
  • thermoplastics and, in particular, thermoplastic elastomers in particular chosen from unsaturated block copolymers.
  • bituminous compositions suitable for the constitution of waterproofing membranes it is conventional for such a polymer to be used, in particular to impart satisfactory flexibility and pliability to the membrane obtained.
  • thermoplastic elastomers typical examples are styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS) or styrene-ethylene-butylene-styrene (SEBS) block copolymers, preferably in the form radial or stellate.
  • SBS styrene-butadiene-styrene
  • SIS styrene-isoprene-styrene
  • SEBS styrene-ethylene-butylene-styrene
  • Such polymers are widely available commercially, in particular from the companies Kraton or Evonik.
  • SBS block copolymer marketed under the reference D1184 from Kraton or an aPP marketed under the reference Vestoplast® 888 from Evonik.
  • compositions according to the invention are provided.
  • % m/m % by mass, relative to the total mass of the composition
  • compositions according to the invention are given below. These quantities may be used independently of each other. Of course, they can be used in combination and all the possible combinations of the ranges specified below are envisaged within the scope of the invention.
  • the widest mass % ranges given for each of the components may be used in combination, or even the intermediate mass % ranges given for each of the components may be used in combination, or even the most restricted mass % ranges given for each of the components may be used in combination.
  • compositions according to the invention comprise from 21 to 40% m/m of fillers C, preferably from 26 to 38% m/m, and even more preferably from 28 to 35% m/m.
  • These fillers C consist of polymeric particles Cp, and of inorganic particles Ci, as previously defined.
  • the Cp polymer particles represent 1 to 10% m/m, preferably 1 to 5% m/m, and even more preferably 1 to 3% m/m of the total mass of the composition.
  • the inorganic particles Ci represent 20 to 39% m/m, preferably 25 to 37% m/m, and even more preferably 27 to 34% m/m of the total mass of the composition.
  • compositions according to the invention comprise:
  • Cp polymeric particles of an impact or crystal polystyrene which, in a advantageously, has a Mw in the range from 80 to 300 kg/mol, and preferably in the range from 100 to 250 kg/mol, as Cp polymer particles; and or
  • the mass quantities of the polymeric particles Cp and of the inorganic particles Ci are selected from the above ranges, in order to have overall, in the compositions according to the invention, from 21 to 40% m/m, preferably from 26 to 38% m/m, and even more preferably from 28 to 35% m/m of C fillers.
  • such polymeric particles Cp comprise, or even consist of, a mixture of an impact or crystal polystyrene and a polymer P1 chosen from polyvinyl chloride (PVC), acrylonitrile-butadiene copolymer -styrene (ABS), polycarbonates, polyethylene terephthalate (PET), with impact or crystal polystyrene which is at least 85%, preferably at least 90%, and preferably at least 95% of the mass of the Cp polymer particles which are, preferably, derived from the recycling of waste.
  • PVC polyvinyl chloride
  • ABS acrylonitrile-butadiene copolymer -styrene
  • PET polyethylene terephthalate
  • impact or crystal polystyrene which is at least 85%, preferably at least 90%, and preferably at least 95% of the mass of the Cp polymer particles which are, preferably, derived from the recycling of waste.
  • compositions according to the invention comprise from 40 to 70% m/m of bitumen, preferably from 50 to 65% m/m, and even more preferably from 55 to 65% m/m of bitumen.
  • compositions according to the invention comprise from 5 to 25% m/m, preferably from 5 to 20% m/m and preferably from 7 to 18% m/m of one or more additional polymer(s) P2, in particular, as defined previously.
  • compositions according to the invention comprise from 5 to 25% m/m, preferably from 5 to 20% m/m, and preferentially from 7 to 18% m/m of a styrene-butadiene block copolymer -styrene, preferably in branched or star-shaped form, of atactic polypropylene, of poly(ethylene-vinyl acetate) or of a mixture of such polymers, as polymer P2.
  • a styrene-butadiene block copolymer -styrene preferably in branched or star-shaped form, of atactic polypropylene, of poly(ethylene-vinyl acetate) or of a mixture of such polymers, as polymer P2.
  • compositions according to the invention comprise, or even consist of:
  • fillers C consisting of inorganic particles Ci and polymeric particles Cp of an impact or crystal polystyrene, the Cp polymer particles representing from 1 to 10% m/m, preferably 1 to 5% m/m, and even more preferably from 1 to 3% m/m of the total mass of the composition and the inorganic particles Ci representing from 20 to 39% m/m, preferably from 25 to 37% m/m, and even more preferably from 27 to 34% m/m of the total mass of the composition;
  • the fillers C, the polymeric particles Cp, the inorganic particles Ci, the polymer(s) additional P2(s) and bitumen presented as preferred will, of course, advantageously be used.
  • compositions according to the invention comprise, or even consist of:
  • fillers C consisting of inorganic particles Ci of CaCO3 and polymeric particles Cp crystal or impact polystyrene, preferably from waste recycling; the polymeric particles Cp representing from 1 to 10% m/m, preferably 1 to 5% m/m, and even more preferably from 1 to 3% m/m of the total mass of the composition and the inorganic particles Ci representing from 20 to 39% m/m, preferably from 25 to 37% m/m, and even more preferably from 27 to 34% m/m of the total mass of the composition; preferably, said polymeric particles Cp comprise, or even consist of a mixture of polymers which is a mixture of an impact or crystal polystyrene and a polymer P1 chosen from polyvinyl chloride (PVC), the copolymer acrylonitrile-butadiene-styrene (AB
  • bitumen preferably chosen from bitumens of grades 160/220 and 70/100 and mixtures thereof;
  • styrene-butadiene-styrene block copolymer preferably under branched or star-shaped form, of an atactic polypropylene, of a poly(ethylene-vinyl acetate) or of a mixture of such polymers.
  • compositions according to the invention are suitable for the constitution of waterproofing membranes, and in particular of waterproofing membranes for roofing. Description of the process for manufacturing the compositions
  • the mixture of the bitumen and the fillers C, or even the additional polymer(s) P2 is carried out at a temperature ranging from 100 to 220° C., preferably ranging from 120 to 200° C., and preferentially ranging from from 140 to 190°C.
  • the mixing is carried out at a temperature greater than or equal to 150°C, preferably greater than or equal to 160°C.
  • Such a mixture is produced with stirring, in particular, for a period of 5 minutes to 10 hours, preferably 10 minutes to 3 hours, preferably 10 to 90 minutes, and even more preferably 20 to 90 minutes.
  • Mixing can be carried out using high shear agitation or low shear agitation.
  • the mixing is carried out with stirring at 200 to 2000 rpm, preferably at 300 to 1500 rpm.
  • the agitation is carried out so as to facilitate the dispersion and the good distribution of the fillers in the bitumen which will constitute the matrix of the composition, optionally in combination with the additional polymer(s) P2.
  • the conditions are adapted to lead to obtaining a homogeneous mixture.
  • the mixing is carried out in such a way as to promote a good distribution of the fillers C, or even of the additional polymer(s) P2, in the final bituminous composition obtained.
  • an additional polymer P2 when an additional polymer P2 is desired in the bituminous composition to be prepared, it is added to the bitumen, before the fillers C. Indeed, the presence of the fillers C makes it more difficult to distribute the polymer correctly. additional P2, within the bituminous matrix, if this is added afterwards.
  • the polymeric particles Cp and the inorganic particles Ci constituting the fillers C, these may be introduced together or separately. separate way. According to a preferred embodiment, the polymeric particles Cp are introduced, before the inorganic particles Ci.
  • the polymeric particles Cp and the inorganic particles Ci introduced may, however, have the same or different sizes.
  • polymeric particles Cp having a coefficient of variation CV characterizing their dispersion in size, from 1.1 to 5, of preferably from 1.1 to 4, and preferably from 1.1 to 3
  • inorganic particles Ci having a coefficient of variation CV characterizing their dispersion in size, from 1.1 to 5, preferably from 1.1 to 4, and preferably from 1.1 to 3.
  • bitumen or mixture of bitumens used for the manufacture of the composition is heated and stirred beforehand, before incorporating the other constituents of the composition.
  • the constituents are generally introduced in sequence. Heating is maintained throughout the process, and the heating temperature can be modulated during the process.
  • the agitation can be maintained or interrupted intermittently if necessary, in particular during the introduction of the inorganic particles Ci and/or can be modulated in intensity. In particular, the agitation may be greater during the introduction of some of the constituents and, in particular, during the introduction of the inorganic particles Ci.
  • bitumen(s), fillers C, polymeric particles Cp, and inorganic particles Ci, or even one or more polymer(s) P2 are preferably used, corresponding to the descriptions given previously in the corresponding parts.
  • bitumen, fillers C, and therefore of polymeric particles Cp, and of inorganic particles Ci, or even of polymer(s) P2 possibly present will be adjusted by the skilled in the art to ultimately obtain the desired amounts in the final composition, and in particular those mentioned in the previous part relating to the compositions according to the invention.
  • bituminous compositions capable of being obtained by such a process also form an integral part of the invention.
  • the invention also relates to a waterproofing membrane, in particular for a roof, comprising a layer formed from a composition according to the invention.
  • a layer obtained by depositing a composition according to the invention typically has a thickness of 2 to 10 mm, in particular 3 to 5 mm.
  • Obtaining a layer from a composition according to the invention, for the manufacture of a waterproofing membrane is carried out using any suitable deposition technique.
  • the composition Before its application, it is preferable for the composition to be in the form of a malleable and/or fluid paste or a viscous paste, which will require heating.
  • the application can be carried out, manually, for example with a trowel, by coating, or by projection, directly on the support whose sealing is to be ensured or on a fibrous material.
  • a fibrous material can, for example, be made of glass fibers, polyamide fibers, polyester fibers and/or be in the form of a nonwoven. Said fibrous material can be an integral part of the waterproofing membrane and play the role of reinforcement.
  • the membrane can be produced directly on site or be manufactured beforehand. In the latter case, the membrane often has a rollable nature and can be in the form of a roll, facilitating its storage before its implementation.
  • the invention also relates to a waterproofing membrane, in particular for a roof, comprising a composition according to the invention, impregnating, at least in part, a fibrous material.
  • a fibrous material may, for example, be made of glass fibers, polyamide fibers, polyester fibers and/or be in the form of a nonwoven.
  • the invention also relates to a waterproofing membrane, in particular for a roof, in the form of a multilayer structure and comprising a layer formed from a composition according to the invention.
  • a waterproofing membrane for a roof in the form of a multilayer structure, typically comprises an upper layer of polymeric material which is arranged to reflect UV rays, a lower waterproofing layer which is arranged to cover a roof , and an armature disposed between said upper layer and said lower layer.
  • the lower sealing layer then consists of a composition according to the invention.
  • the reinforcement is, in particular, a fibrous material previously described.
  • compositions according to the invention apply to the waterproofing membranes according to the invention, and, in particular, to the waterproofing membranes for roofs according to the invention.
  • PS1 and PS2 two types of polymer particles from the same impact polystyrene-based plastic waste (named PS1 and PS2), from refrigerator waste.
  • PS1 and PS2 particles The difference between PS1 and PS2 particles is in the particle size. Their characteristics are given in Table 1 below.
  • N.D. not determined, but in view of the sieving technique used for size selection, their size is between 125 and 250 ⁇ m, which means that their maximum size is less than or equal to 250 ⁇ m.
  • the D50 was determined in accordance with the method previously described in the description.
  • the mass Mw was evaluated by GPC, using tetrahydrofuran (THF), as THF solvent, on a column at 25° C., with a refractometer detector.
  • THF tetrahydrofuran
  • the calibration was carried out with 12 PS standards with masses from 1.01 to 44800 kg/mol, purchased from Tosoh.
  • Example 1 Two compositions (Examples 1 and 2) according to the invention were prepared as follows, one with the polymeric particles of polystyrene PS1, at a rate of 1% m/m (Example 1) and the other with the polymeric particles of polystyrene PS2, at a rate of 3% m/m (example 2).
  • compositions were prepared as follows:
  • the bitumen was heated for 10 minutes at a temperature of 180° C. while stirring at 200 rpm, then the stirring was increased to 400 rpm and the SBS polymer was added (to have 7 % mass of SBS polymer in the end in the composition) slowly in order to promote good dispersion of the latter. Once the SBS was introduced, the stirring was lowered to 200 rpm and maintained for about 20 minutes at 180°C. The desired quantity of PS1 or PS2 was then introduced.
  • the stirring was then increased to 800 revolutions/min. Then, the necessary quantity of CaCO3 was introduced, to have in the end in the composition 35% by mass of (CaCO3 + PS1) or (CaCO3 + PS2). The addition of CaCO3 causing air bubbles, the agitation was stopped intermittently so as not to have splashes of hot bitumen. Once the addition of CaCO3 finished, stirring was reduced to 200 rpm and the mixture was stirred for 40 minutes at 190°C.
  • a membrane was then obtained, by pouring the mixture onto a mold and pulling it out using a preheated blade, in order to ultimately obtain a membrane of the same thickness of 2 mm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

The present invention relates to a bituminous composition suitable for forming sealing membranes comprising, in a matrix made from bitumen, fillers C that represent between 21 and 40% of the total mass of the composition and that are constituted by inorganic particles Ci and polymeric particles Cp of crystal polystyrene or high-impact polystyrene, the mass of polymeric particles Cp representing between 1 and 10% of the total mass of the composition and the mass of bitumen representing between 40 and 70% of the total mass of the composition. The invention also relates to the method for obtaining such compositions and to the sealing membranes obtained with them.

Description

Description Description
Titre de l'invention : Compositions pour la réalisation de membranes d’étanchéité, procédés et membranes associés Title of the invention: Compositions for the production of waterproofing membranes, processes and associated membranes
Domaine Technique Technical area
[0001] La présente invention concerne le domaine technique des membranes d’étanchéité et des compositions bitumineuses adaptées à leur fabrication. The present invention relates to the technical field of waterproofing membranes and bituminous compositions suitable for their manufacture.
Technique antérieure Prior technique
[0002] De nombreux éléments de construction doivent être protégés contre l’humidité et/ou l'eau provenant notamment des intempéries. Pour cela, des membranes d'étanchéité, pour des utilisations intérieures et extérieures, et en particulier, pour le revêtement de toitures de maisons ou d’immeubles ont été proposées. De telles membranes d'étanchéité se présentant sous la forme de films, souvent multi-couches, réalisées sur place ou au préalable sous la forme de rouleaux, sont décrites dans l’art antérieur. Un certain nombre de solutions à base de bitume ont vu le jour. Au cours des dernières décennies, différentes compositions pour la constitution de membranes d’étanchéité, à base de bitume modifié par un ou plusieurs polymères, du type poly(éthylène acétate de vinyle) (EVA), polypropylène atactique (aPP), copolymère à blocs styrène-butadiène- styrène (SBS), ont été développées (Diani E, et al., “Styrenic block copolymers as bitumen modifiers for improved roofing sheets”, Rubber World, 206, 1992, pages 44-48 ; Rodriguez I, et al., “Effect of heat-aging on the thermal and mechanical properties of APP- and SBS-modified bituminous roofing membranes”, Mater. Struct., 26, 1993, pages 355-361 ; Wloczysiak P, et al, “Relationships between Rheological Properties, Morphological Characteristics, and Composition of Bitumen-Styrene Butadiene Styrene Copolymers Mixes. I. A Three-Phase System”, J. Appl. Polym. Sci.65, 1997, page 1595 ; Fawcett AH, et al., “Blends of bitumen with various polyolefins”, Polymer, 41 , 2000, pages 5315- 5326 ; Fawcett AH, et al., “Studies on Blends of Acetate and Acrylic Functional Polymers with Bitumen”, Macromol. Mater. Eng., 286, 2001 , pages 126-137 ; Airey GD “Rheological evaluation of ethylene vinylacetate polymer modified bitumens”, Construction and Building Materials, 16, 2002, pages 473-487). En effet, la viscoélasticité du bitume le rend tout à fait adapté à ce type d'applications et l’ajout de tels polymères permet d’améliorer les propriétés rhéologiques et mécaniques de la membrane obtenue, et notamment sa souplesse et sa pliabilité à basse température. Plus récemment, des charges inorganiques telles que du carbonate de calcium ont également été ajoutées aux compositions pour la constitution de membranes d’étanchéité (Techniques de l’ingénieur, Ref C5438 V1 , Comparaison des géomembranes, 10 août 2015, par Jean-Pierre Giroud). De telles membranes sont notamment proposées par la société Soprema sous les références Elastophène Flam® et Sopralène Flam® (https://www.sic-34.fr/wp- content/uploads/sites/5350/2018/01/5-09-2068-DTA-Elastophene-Flam- Sopralene-Flam.pdf). [0002] Many construction elements must be protected against humidity and/or water, particularly from bad weather. For this, sealing membranes, for interior and exterior uses, and in particular, for coating the roofs of houses or buildings have been proposed. Such waterproofing membranes in the form of films, often multi-layered, made on site or beforehand in the form of rolls, are described in the prior art. A number of bitumen-based solutions have emerged. In recent decades, various compositions for the constitution of waterproofing membranes, based on bitumen modified by one or more polymers, of the poly(ethylene vinyl acetate) (EVA) type, atactic polypropylene (aPP), block copolymer styrene-butadiene-styrene (SBS), have been developed (Diani E, et al., “Styrenic block copolymers as bitumen modifiers for improved roofing sheets”, Rubber World, 206, 1992, pages 44-48; Rodriguez I, et al ., “Effect of heat-aging on the thermal and mechanical properties of APP- and SBS-modified bituminous roofing membranes”, Mater. Struct., 26, 1993, pages 355-361; Wloczysiak P, et al, “Relationships between Rheological Properties, Morphological Characteristics, and Composition of Bitumen-Styrene Butadiene Styrene Copolymers Mixes. I. A Three-Phase System”, J. Appl. Polym. Sci.65, 1997, page 1595; Fawcett AH, et al., “Blends of bitumen with various polyolefins”, Polymer, 41, 2000, pages 5315-5326; Fawcett AH, et al., “Stud ies on Blends of Acetate and Acrylic Functional Polymers with Bitumen”, Macromol. Mater. Eng., 286, 2001, pages 126-137; Airey GD “Rheological evaluation of ethylene vinylacetate polymer modified bitumens”, Construction and Building Materials, 16, 2002, pages 473-487). In Indeed, the viscoelasticity of bitumen makes it quite suitable for this type of application and the addition of such polymers makes it possible to improve the rheological and mechanical properties of the membrane obtained, and in particular its flexibility and its bendability at low temperature. More recently, inorganic fillers such as calcium carbonate have also been added to compositions for the constitution of waterproofing membranes (Engineering techniques, Ref C5438 V1, Comparison of geomembranes, August 10, 2015, by Jean-Pierre Giroud ). Such membranes are notably offered by the company Soprema under the references Elastophène Flam® and Sopralène Flam® (https://www.sic-34.fr/wp-content/uploads/sites/5350/2018/01/5-09 -2068-DTA-Elastophene-Flam-Sopralene-Flam.pdf).
[0003] On peut également citer la demande EP 1698669 qui propose un liant bitumineux élastomère pour membranes d'étanchéité, comportant un bitume, un ou plusieurs polymères qui comporte(nt) au moins du Styrène Butadiène Styrène (SBS) et une ou plusieurs charges minérales comportant au moins un phyllosilicate, le mélange SBS / phyllosilicate constituant entre 3 et 20% en poids dudit liant bitumineux et la fraction dudit phyllosilicate représentant entre 5 et 25 % en poids dudit SBS. La solution proposée est présentée comme une solution permettant de réduire le prix de revient de la composition bitumineuse et donc de la membrane d’étanchéité obtenue. Mention may also be made of application EP 1698669 which proposes an elastomeric bituminous binder for waterproofing membranes, comprising a bitumen, one or more polymers which comprise(s) at least Styrene Butadiene Styrene (SBS) and one or more fillers minerals comprising at least one phyllosilicate, the SBS/phyllosilicate mixture constituting between 3 and 20% by weight of said bituminous binder and the fraction of said phyllosilicate representing between 5 and 25% by weight of said SBS. The proposed solution is presented as a solution that makes it possible to reduce the cost price of the bituminous composition and therefore of the waterproofing membrane obtained.
[0004] Dans le cadre de l’invention, il est proposé de fournir des compositions alternatives à celles proposées dans l’art antérieur, pour la constitution de membranes d’étanchéité, en particulier pour toiture. Les compositions et procédés de fabrication de telles compositions offrent de nouvelles possibilités de recyclage de déchets plastiques, et sont donc particulièrement avantageuses, d’un point de vue écologique et pour réduire l’empreinte carbone. Les compositions et membranes selon l’invention offrent de nouvelles solutions pour réduire leur prix de revient. Un autre objectif de l’invention est, également, de fournir des compositions permettant un allègement des membranes d’étanchéité obtenues avec de telles compositions, ce qui est avantageux, notamment, pour faciliter leur manipulation et leur transport. Exposé de l’invention [0004] In the context of the invention, it is proposed to provide alternative compositions to those proposed in the prior art, for the constitution of waterproofing membranes, in particular for roofing. The compositions and processes for manufacturing such compositions offer new possibilities for recycling plastic waste, and are therefore particularly advantageous, from an ecological point of view and for reducing the carbon footprint. The compositions and membranes according to the invention offer new solutions for reducing their cost price. Another object of the invention is also to provide compositions allowing a lightening of the sealing membranes obtained with such compositions, which is advantageous, in particular, to facilitate their handling and their transport. Disclosure of Invention
[0005] L’invention concerne des compositions bitumineuse comprenant, dans une matrice à base de bitume, des charges C qui représentent de 21 à 40% de la masse totale de la composition et qui sont constituées de particules inorganiques Ci et de particules polymériques Cp de polystyrène cristal ou de polystyrène choc, la masse des particules polymériques Cp représentant de 1 à 10% de la masse totale de la composition et la masse de bitume représentant de 40 à 70% de la masse totale de la composition. The invention relates to bituminous compositions comprising, in a bitumen-based matrix, fillers C which represent from 21 to 40% of the total mass of the composition and which consist of inorganic particles Ci and polymeric particles Cp crystal polystyrene or impact polystyrene, the mass of the polymeric particles Cp representing from 1 to 10% of the total mass of the composition and the mass of bitumen representing from 40 to 70% of the total mass of the composition.
[0006] Dans le cadre de l’invention, il a été mis en évidence que le remplacement de charges inorganiques Ci par les particules polymériques Cp sélectionnées qui sont des particules de polystyrène choc ou cristal, dans une composition bitumineuse destinée à la fabrication d’une membrane d’étanchéité, n’entrainait pas de pertes de propriétés de la membrane d’étanchéité obtenue. En particulier, les compositions et membranes obtenues ont été évaluées, en termes de pénétrabilité à 20 et 50 °C, de température de ramolissement bille-anneau (TBA), de pliabilité à froid, avant et après vieillissement long-terme accéléré dans un récipient de vieillissement sous pression (PAV) (de l’anglais « Pressure Ageing Vessel »), de rémanence Re et de viscosité. Il a été constaté qu’à % massique de charges C égale, la substitution d’une partie des charges inorganiques Ci par des charges polymériques Cp sélectionnées dans le cadre de l’invention n’entrainait pas de perte de ces propriétés, qui restaient sensiblement identiques. L’invention rend ainsi possible d’utiliser, en tant que charges, des particules polymériques issues du recyclage de déchets plastiques, ce qui ouvre d’autres voies de valorisation de déchets, permet de diminuer l’empreinte environnementale des membranes d’étanchéité obtenues avec les compositions selon l’invention, de favoriser une économie circulaire et de limiter l’utilisation de ressources finies que sont les charges inorganiques. De plus, un tel remplacement d’une partie des charges inorganiques Ci par des charges polymériques Cp sélectionnées dans le cadre de l’invention permet d’obtenir un allègement de la membrane d’étanchéité obtenue. In the context of the invention, it has been demonstrated that the replacement of inorganic fillers Ci by selected polymeric particles Cp which are impact or crystal polystyrene particles, in a bituminous composition intended for the manufacture of a waterproofing membrane, did not lead to any loss of properties of the waterproofing membrane obtained. In particular, the compositions and membranes obtained were evaluated, in terms of penetrability at 20 and 50°C, ball-ring softening temperature (TBA), cold pliability, before and after accelerated long-term aging in a container. pressure aging (PAV), remanence Re and viscosity. It was found that at equal mass % of fillers C, the substitution of part of the inorganic fillers Ci by polymeric fillers Cp selected in the context of the invention did not lead to a loss of these properties, which remained substantially identical. The invention thus makes it possible to use, as fillers, polymeric particles resulting from the recycling of plastic waste, which opens up other ways of recovering waste, makes it possible to reduce the environmental footprint of the waterproofing membranes obtained with the compositions according to the invention, to promote a circular economy and to limit the use of finite resources that are inorganic fillers. In addition, such a replacement of part of the inorganic fillers Ci by polymeric fillers Cp selected within the framework of the invention makes it possible to obtain a lightening of the sealing membrane obtained.
[0007] En particulier, le polystyrène choc ou cristal des particules polymériques Cp a une Mw dans la gamme allant de 80 à 300 kg/mol, et préférentiellement dans la gamme allant de 100 à 250 kg/mol. [0008] De manière préférée, les particules polymériques Cp comprennent, au moins 85% en masse, de préférence au moins 90% en masse, et préférentiellement au moins 95% en masse de polystyrène choc ou cristal ; ledit polystyrène choc ou cristal est en mélange avec un ou plusieurs polymère(s) P1 , de préférence, choisi parmi le chlorure de polyvinyle (PVC), le copolymère acrylonitrile-butadiène- styrène (ABS), les polycarbonates, le polyéthylène téréphtalate (PET). De manière avantageuse, de telles particules polymériques Cp sont, de préférence, issues du recyclage de déchets. [0007] In particular, the impact or crystal polystyrene of the Cp polymer particles has a Mw in the range from 80 to 300 kg/mol, and preferably in the range from 100 to 250 kg/mol. Preferably, the Cp polymer particles comprise at least 85% by mass, preferably at least 90% by mass, and preferably at least 95% by mass of impact or crystal polystyrene; said impact or crystal polystyrene is mixed with one or more polymer(s) P1 , preferably chosen from polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene (ABS) copolymer, polycarbonates, polyethylene terephthalate (PET ). Advantageously, such Cp polymer particles are preferably obtained from the recycling of waste.
[0009] De manière avantageuse, les compositions selon l’invention comprennent, en outre, en tant que composant(s) additionnel(s), un ou plusieurs polymère(s) P2, de préférence choisi(s) parmi les plastomères et les thermoplastiques et, notamment, les élastomères thermoplastiques, en particulier choisis parmi les copolymères à blocs insaturés. En particulier, le(s) polymère(s) P2 est(sont) choisi(s) parmi les copolymères à blocs styrène-butadiène-styrène, de préférence sous forme ramifiée ou étoilée, le polypropylène atactique et le poly(éthylène acétate de vinyle). Advantageously, the compositions according to the invention further comprise, as additional component(s), one or more polymer(s) P2, preferably chosen from plastomers and thermoplastics and, in particular, thermoplastic elastomers, in particular chosen from unsaturated block copolymers. In particular, the polymer(s) P2 is (are) chosen from styrene-butadiene-styrene block copolymers, preferably in branched or star-shaped form, atactic polypropylene and poly(ethylene vinyl acetate ).
[0010] A titre préféré, la masse de polymère(s) P2 représente de 5 à 25 %, de préférence de 5 à 20% et, de manière encore plus préférée, de 7 à 18% de la masse totale de la composition. Preferably, the mass of polymer(s) P2 represents from 5 to 25%, preferably from 5 to 20% and, even more preferably, from 7 to 18% of the total mass of the composition.
[0011] En particulier, les particules inorganiques Ci sont des particules de carbonate de calcium, de carbonate de magnésium, d’hydroxyde de magnésium, de sulfate de calcium, de sulfate de baryum, de silice, d’argile, de talc, de mica, de wollastonite, de montmorillonite, de zéolite, d’alumine, d’oxyde de titane, d’oxyde de magnésium, d’oxyde de zinc ou de verre, les particules de carbonate de calcium étant préférées. [0011] In particular, the inorganic particles Ci are particles of calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulphate, barium sulphate, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide or glass, with calcium carbonate particles being preferred.
[0012] A titre préféré, la masse de particules inorganiques Ci représente 20 à 39%, de préférence de 25 à 37%, et de manière encore plus préférée de 27 à 34 % de la masse totale de la composition. Preferably, the mass of inorganic particles Ci represents 20 to 39%, preferably 25 to 37%, and even more preferably 27 to 34% of the total mass of the composition.
[0013] De manière avantageuse, le D50 des particules polymériques Cp et/ou le D50 des particules inorganiques Ci appartien(nen)t à la gamme allant de 10 à 300 pm, de préférence à la gamme allant de 20 à 200 pm, et préférentiellement à la gamme allant de 30 à 150 pm. [0014] Les compositions préférées, dans le cadre de l’invention, comprennent, voire sont constituées de : [0013] Advantageously, the D50 of the Cp polymer particles and/or the D50 of the Ci inorganic particles belongs(n) to the range going from 10 to 300 μm, preferably to the range going from 20 to 200 μm, and preferentially to the range going from 30 to 150 μm. [0014] The preferred compositions, within the scope of the invention, comprise, or even consist of:
- de 21 à 40% m/m de préférence de 26 à 38 % m/m, et de manière encore plus préférée de 28 à 35% m/m de charges C, constituées de particules inorganiques Ci et de particules polymériques Cp de polystyrène choc ou cristal, les particules polymériques Cp représentant de 1 à 10% m/m, de préférence 1 à 5% m/m, et de manière encore plus préférée de 1 à 3% m/m de la masse totale de la composition et les particules inorganiques Ci représentant de 20 à 39% m/m, de préférence de 25 à 37% m/m, et de manière encore plus préférée de 27 à 34% m/m de la masse totale de la composition ; - from 21 to 40% m/m, preferably from 26 to 38% m/m, and even more preferably from 28 to 35% m/m of fillers C, consisting of inorganic particles Ci and polymeric particles Cp of polystyrene impact or crystal, the Cp polymer particles representing from 1 to 10% m/m, preferably 1 to 5% m/m, and even more preferably from 1 to 3% m/m of the total mass of the composition and the inorganic particles Ci representing from 20 to 39% m/m, preferably from 25 to 37% m/m, and even more preferably from 27 to 34% m/m of the total mass of the composition;
- de 40 à 70% m/m, de préférence de 50 à 65 % m/m, et de manière encore plus préférée de 55 à 65 % m/m de bitume ; - from 40 to 70% m/m, preferably from 50 to 65% m/m, and even more preferably from 55 to 65% m/m of bitumen;
- de 5 à 25 % m/m, de préférence de 5 à 20% m/m, et de manière encore plus préférée de 7 à 18% m/m d’un ou plusieurs polymère(s) P2 tel(s) que défini(s) dans le cadre de l’invention ; les % m/m étant des % massiques par rapport à la masse totale de la composition. - from 5 to 25% m/m, preferably from 5 to 20% m/m, and even more preferably from 7 to 18% m/m of one or more polymer(s) P2 such as defined in the context of the invention; the % m/m being % by mass relative to the total mass of the composition.
[0015] L’invention a également pour objet un procédé de préparation d’une composition selon l’invention, comprenant le mélange sous chauffage d’un ensemble comprenant : The invention also relates to a process for the preparation of a composition according to the invention, comprising the mixing under heating of an assembly comprising:
- du bitume, et - bitumen, and
- des charges C constituées de particules inorganiques Ci et de particules polymériques Cp de polystyrène choc ou cristal. - fillers C consisting of inorganic particles Ci and polymeric particles Cp of impact or crystal polystyrene.
[0016] En particulier, le mélange sous chauffage est réalisé à une température appartenant à la gamme allant de 100 à 220° C, de préférence pendant 5 minutes à 10 heures et/ou sous une agitation de 200 à 2000 tours/min. [0016] In particular, the mixture under heating is carried out at a temperature belonging to the range going from 100 to 220° C., preferably for 5 minutes to 10 hours and/or with stirring from 200 to 2000 revolutions/min.
[0017] De manière avantageuse, le mélange sous chauffage est mené sur un ensemble comprenant, de manière additionnelle, un ou plusieurs polymère(s) P2 choisi(s) parmi les plastomères et les thermoplastiques et, notamment, les élastomères thermoplastiques, en particulier choisis parmi les copolymères à blocs insaturés, et, de manière encore plus préférée, choisi(s) parmi les copolymères à blocs styrène-butadiène-styrène, de préférence sous forme ramifiée ou étoilée, le polypropylène atactique et le poly(éthylène acétate de vinyle). [0017] Advantageously, the mixture under heating is carried out over an assembly comprising, additionally, one or more polymer(s) P2 chosen from plastomers and thermoplastics and, in particular, thermoplastic elastomers, in particular chosen from unsaturated block copolymers, and, even more preferably, chosen from styrene-butadiene-styrene block copolymers, preferably in the form branched or star-shaped, atactic polypropylene and poly(ethylene vinyl acetate).
[0018] Aussi, de manière préférée, le procédé selon l’invention comprend l’introduction, dans le bitume, du(des)dit(s) polymère(s) P2, avant l’introduction dans le bitume des particules inorganiques Ci et des particules polymériques Cp de polystyrène choc ou cristal. Also, preferably, the method according to the invention comprises the introduction, into the bitumen, of said polymer(s) P2, before the introduction into the bitumen of the inorganic particles Ci and Cp polymeric particles of impact or crystal polystyrene.
[0019] De manière avantageuse, le procédé selon l’invention comprend l’introduction, dans le bitume, de particules inorganiques Ci qui présentent un D50 qui appartient à la gamme allant de 10 à 300 pm, de préférence à la gamme allant de 20 à 200 pm, et préférentiellement à la gamme allant de 30 à 150 pm et/ou de particules polymériques Cp de polystyrène choc ou cristal qui présentent un D50 qui appartient à la gamme allant de 10 à 300 pm, de préférence à la gamme allant de 20 à 200 pm, et préférentiellement à la gamme allant de 30 à 150 pm. Advantageously, the method according to the invention comprises the introduction, into the bitumen, of inorganic particles Ci which have a D50 which belongs to the range going from 10 to 300 μm, preferably to the range going from 20 to 200 μm, and preferentially to the range going from 30 to 150 μm and/or Cp polymeric particles of impact or crystal polystyrene which have a D50 which belongs to the range going from 10 to 300 μm, preferably to the range going from 20 to 200 μm, and preferentially to the range going from 30 to 150 μm.
[0020] L’utilisation des compositions selon l’invention pour la fabrication d’une membrane d’étanchéité, en particulier pour toiture, fait partie intégrante de l’invention. Aussi, selon un autre de ses aspects, l’invention concerne une membrane d’étanchéité, en particulier pour toiture, comprenant une couche formée d’une composition selon l’invention. The use of the compositions according to the invention for the manufacture of a waterproofing membrane, in particular for a roof, is an integral part of the invention. Also, according to another of its aspects, the invention relates to a waterproofing membrane, in particular for a roof, comprising a layer formed from a composition according to the invention.
[0021] L’invention a également pour objet les membranes d’étanchéité, en particulier pour toiture, comprenant une composition selon l’invention, venant imprégner, au moins pour partie, un matériau fibreux. The invention also relates to waterproofing membranes, in particular for roofing, comprising a composition according to the invention, impregnating, at least in part, a fibrous material.
[0022] En particulier, l’invention concerne de telles membranes d’étanchéité se présentant sous la forme d’une structure multicouche. [0022] In particular, the invention relates to such sealing membranes in the form of a multilayer structure.
Définitions et Méthodes Definitions and Methods
[0023] Le D50 est défini comme étant le diamètre des particules pour lequel 50% en volume des particules ont un diamètre supérieur à cette valeur et 50% en volume des particules un diamètre inférieur à cette valeur. Le D50 est déterminé, dans le cadre de l’invention, avec un granulomètre à diffraction laser en voie liquide (alcool). L’étendue de la distribution, ou polydispersité, est caractérisée par le coefficient de variation (CV) défini selon la relation : CV = (D90-D10)/D50 où le D90 est défini comme étant le diamètre des particules pour lequel 10% en volume des particules ont un diamètre supérieur à cette valeur et 90% en volume des particules un diamètre inférieur à cette valeur et le D10 est défini comme étant le diamètre des particules pour lequel 90% en volume des particules ont un diamètre supérieur à cette valeur et 10% en volume des particules un diamètre inférieur à cette valeur. Lorsqu’une particule n’est pas parfaitement sphérique, le diamètre est le diamètre moyen de la particule. The D50 is defined as being the diameter of the particles for which 50% by volume of the particles have a diameter greater than this value and 50% by volume of the particles have a diameter less than this value. The D50 is determined, in the context of the invention, with a laser diffraction particle size analyzer in the liquid route (alcohol). The extent of the distribution, or polydispersity, is characterized by the coefficient of variation (CV) defined according to the relation: CV = (D90-D10)/D50 where the D90 is defined as being the diameter of the particles for which 10% in volume of the particles have a diameter greater than this value and 90% by volume of the particles have a diameter less than this value and the D10 is defined as being the diameter of the particles for which 90% by volume of the particles have a diameter greater than this value and 10 % by volume of particles with a diameter less than this value. When a particle is not perfectly spherical, the diameter is the mean diameter of the particle.
[0024] Les masses moléculaires moyennes peuvent être mesurées par chromatographie de perméation sur gel (CPG) (ou SEC pour « Size Exclusion Chromatography » en anglais). La CPG est une méthode de chromatographie liquide dans laquelle les polymères sont séparés selon leur volume hydrodynamique, qui est ensuite converti par étalonnage externe conventionnel en masse moléculaire moyenne en poids (Mw). Le standard externe utilisé pour déterminer la Mw du polystyrène est un étalon de polystyrène. The average molecular masses can be measured by gel permeation chromatography (GPC) (or SEC for "Size Exclusion Chromatography" in English). GPC is a liquid chromatography method in which polymers are separated according to their hydrodynamic volume, which is then converted by conventional external calibration to weight average molecular weight (Mw). The external standard used to determine the Mw of polystyrene is a polystyrene standard.
[0025] Les normes mentionnées dans le cadre de l’invention correspondent à la version en vigueur à la date du premier janvier 2021 , à moins qu’il n’en soit spécifié autrement. The standards mentioned in the context of the invention correspond to the version in force on the date of January 1, 2021, unless otherwise specified.
Bitumes Bitumens
[0026] Les compositions selon l’invention contiennent un seul bitume ou un mélange de bitumes. Parmi les bitumes utilisables dans les compositions selon l'invention, on peut citer tout d'abord les bitumes d'origine naturelle, ceux contenus dans des gisements de bitume naturel, d'asphalte naturel ou les sables bitumineux et les bitumes provenant du raffinage du pétrole brut. Dans le cadre de l’invention, le ou les bitumes présents dans la composition sont avantageusement choisis parmi les bitumes provenant du raffinage du pétrole brut, en particulier les bitumes contenant des asphaltènes ou des brais. Les bitumes peuvent être obtenus par des procédés conventionnels de fabrication des bitumes en raffinerie, en particulier par distillation directe et/ou distillation sous vide du pétrole. Ces bitumes peuvent être éventuellement viscoréduits et/ou désasphaltés et/ou rectifiés à l'air. Il est courant de procéder à la distillation sous vide des résidus atmosphériques provenant de la distillation atmosphérique de pétrole brut. Ce procédé de fabrication correspond, par conséquent, à la succession d'une distillation atmosphérique et d'une distillation sous vide, la charge alimentant la distillation sous vide correspondant aux résidus atmosphériques. Ces résidus sous vide issus de la tour de distillation sous vide peuvent être également utilisés comme bitumes. Il est également courant d'injecter de l'air dans une charge composée habituellement de distillats et de produits lourds provenant de la distillation sous vide de résidus atmosphériques provenant de la distillation du pétrole. Ce procédé permet d'obtenir un bitume soufflé, ou semi-soufflé ou oxydé ou rectifié à l'air ou rectifié partiellement à l'air. Différents bitumes obtenus par les procédés de raffinage peuvent être combinés dans les compositions selon l’invention, pour obtenir le meilleur compromis, en termes de performances techniques. Dans les procédés conventionnels de mélanges de différents bitumes, on opère à des températures comprises entre 100 °C et 200 °C, de préférence entre 140 °C et 200 °C, et sous agitationpendant une durée d'au moins 10 minutes, de préférence comprise entre 30 minutes et 10 heures, plus préférentiellement entre 1 heure et 6 heures. La température et la durée du chauffage varient selon la quantité de bitume utilisée et sont définies par la norme NF EN 12594. Les bitumes soufflés peuvent être fabriqués dans une unité de soufflage, en faisant passer un flux d'air et/ou d'oxygène à travers un bitume ou mélange de bitumes de départ. Cette opération peut être menée en présence d'un catalyseur d'oxydation, par exemple de l'acide phosphorique. Généralement, le soufflage est réalisé à des températures élevées, de l'ordre de 200 à 300 °C, pendant des durées relativement longues typiquement comprises entre 30 minutes et 2 heures, en continu ou par lots. La durée et la température de soufflage sont ajustées en fonction des propriétés visées pour le bitume soufflé et en fonction de la qualité du bitume de départ. The compositions according to the invention contain a single bitumen or a mixture of bitumens. Among the bitumens which can be used in the compositions according to the invention, mention may first be made of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or bituminous sands and bitumens originating from the refining of crude oil. In the context of the invention, the bitumen(s) present in the composition are advantageously chosen from bitumens originating from the refining of crude oil, in particular bitumens containing asphaltenes or pitches. The bitumens can be obtained by conventional processes for the manufacture of bitumens in refineries, in particular by direct distillation and/or vacuum distillation of petroleum. These bitumens can optionally be visbroken and/or deasphalted and/or air-rectified. It is common practice to carry out the vacuum distillation of the atmospheric residues resulting from the atmospheric distillation of crude oil. This manufacturing process therefore corresponds to the succession of atmospheric distillation and vacuum distillation, the charge supplying the vacuum distillation corresponding to atmospheric residues. These vacuum residues from the vacuum distillation tower can also be used as bitumen. It is also common to inject air into a charge usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from petroleum distillation. This process makes it possible to obtain a blown or semi-blown or oxidized or air-rectified or partially air-rectified bitumen. Different bitumens obtained by refining processes can be combined in the compositions according to the invention, to obtain the best compromise, in terms of technical performance. In the conventional processes for mixing different bitumens, the operation is carried out at temperatures between 100° C. and 200° C., preferably between 140° C. and 200° C., and with stirring for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours. The heating temperature and duration vary according to the quantity of bitumen used and are defined by standard NF EN 12594. Blown bitumens can be produced in a blowing unit, by passing a flow of air and/or oxygen through a starting bitumen or mixture of bitumens. This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid. Generally, the blowing is carried out at high temperatures, of the order of 200 to 300° C., for relatively long durations typically comprised between 30 minutes and 2 hours, continuously or in batches. The blowing time and temperature are adjusted according to the properties targeted for the blown bitumen and according to the quality of the starting bitumen.
[0027] Parmi les bitumes utilisables selon l'invention, on peut également citer les bitumes issus du recyclage. Among the bitumens which can be used according to the invention, mention may also be made of bitumens resulting from recycling.
[0028] Les bitumes peuvent être des bitumes de grade dur (tels que les grades 10/20 et 20/30) ou de grade mou (tel que le grade 160/220) définis par la norme EN 12591. The bitumens can be hard grade bitumens (such as grades 10/20 and 20/30) or soft grade (such as grade 160/220) defined by standard EN 12591.
[0029] L’invention est particulièrement adaptée, aux cas où la composition est formée avec un bitume choisi(s) parmi les bitumes de grades 160/220 et 70/100 et leurs mélanges. Les bitumes utilisables dans le cadre de l'invention ont, de préférence, une pénétrabilité, mesurée à 25 °C selon la norme EN 1426, de 5 à 330 1/10 mm, de préférence entre 10 à 220 1/10 mm. De manière bien connue, la mesure dite de « pénétrabilité à l'aiguille » est réalisée au moyen d'un test normalisé NF EN 1426 à 25°C (Pene). Cette caractéristique de pénétrabilité est exprimée en dixièmes de millimètre (dmm ou 1/10 mm). La pénétrabilité à l'aiguille, mesurée à 25°C, selon le test normaliséNF EN 1426, représente la mesure de la pénétration dans un échantillon de bitume, au bout d'un temps de 5 secondes, d'une aiguille dont le poids avec son support est de 100 g. The invention is particularly suitable for cases where the composition is formed with a bitumen chosen from among bitumens of grades 160/220 and 70/100 and mixtures thereof. The bitumens which can be used in the context of the invention preferably have a penetrability, measured at 25° C. according to standard EN 1426, of 5 to 330 1/10 mm, preferably between 10 to 220 1/10 mm. In a well-known manner, the so-called “needle penetrability” measurement is carried out by means of a standardized test NF EN 1426 at 25° C. (Pene). This penetrability characteristic is expressed in tenths of a millimeter (dmm or 1/10 mm). Needle penetrability, measured at 25°C, according to the standardized test NF EN 1426, represents the measurement of the penetration into a sample of bitumen, after a time of 5 seconds, of a needle whose weight with its support is 100 g.
Charges C C-Loads
[0030] Les compositions selon l’invention comprennent des charges qui sont réparties dans le bitume ou plus généralement dans une matrice formée de un ou plusieurs bitumes, voire d’un mélange bitume(s)/polymère(s) P2 défini(s) dans le cadre de l’invention. Les charges C dans le cadre de l’invention sont de deux sortes : une partie est constituée de particules ou charges inorganiques, nommés Ci, l’autre partie est constituée de particules ou charges polymériques de polystyrène choc ou cristal, nommées Cp. Ces deux types de particules sont définis, de manière plus détaillée, plus loin dans la description. Dans le cadre de l’invention, il a été démontré qu’une partie des charges minérales utilisées dans les compositions de l’art antérieur pouvait être remplacée par des charges polymériques Cp et que ceci n’altérait pas les propriétés évaluées dans les exemples, des membranes obtenues. Il est ainsi possible d’utiliser en tant que charges, des particules polymériques Cp constituées ou majoritairement constituées d’un polystyrène cristal ou choc. Ceci ouvre donc de nombreuses possibilités pour utiliser des charges polymériques issues du recyclage de déchets plastiques, et notamment des déchets de polystyrène recyclés. The compositions according to the invention comprise fillers which are distributed in the bitumen or more generally in a matrix formed of one or more bitumens, or even of a mixture of bitumen(s)/polymer(s) P2 defined within the scope of the invention. The fillers C in the context of the invention are of two kinds: one part consists of inorganic particles or fillers, named Ci, the other part consists of polymeric particles or fillers of impact or crystal polystyrene, named Cp. These two types of particles are defined in more detail later in the description. In the context of the invention, it has been demonstrated that part of the mineral fillers used in the compositions of the prior art could be replaced by Cp polymeric fillers and that this did not alter the properties evaluated in the examples, membranes obtained. It is thus possible to use, as fillers, Cp polymer particles consisting or mainly consisting of a crystal or impact polystyrene. This therefore opens up numerous possibilities for using polymeric fillers resulting from the recycling of plastic waste, and in particular recycled polystyrene waste.
[0031] Dans le cadre de l’invention, les charges C présentes dans la composition, qu’il s’agisse de particules polymériques Cp ou de particules inorganiques Ci, sont, de préférence, de taille micrométrique et notamment ont une taille maximale inférieure ou égale à 500 pm. Lorsqu’une particule est parfaitement sphérique, sa taille maximale est son diamètre. De manière préférée, les particules polymériques Cp et/ou les particules inorganiques Ci ont un D50 qui appartient à la gamme allant de 10 à 300 pm, de préférence à la gamme allant de 20 à 200 pm, et préférentiellement à la gamme allant de 30 à 150 pm. [0032] De manière avantageuse, les particules polymériques Cp présentes dans la composition ont un coefficient de variation CV, caractérisant leur dispersion en taille, de 1 ,1 à 5, de préférence de 1 ,1 à 4, et préférentiellement de 1 ,1 à 3 et/ou les particules inorganiques Ci présentes dans la composition ont un coefficient de variation CV, caractérisant leur dispersion en taille, de 1 ,1 à 5, de préférence de 1 ,1 à 4, et préférentiellement de 1 ,1 à 3. In the context of the invention, the fillers C present in the composition, whether they are polymeric particles Cp or inorganic particles Ci, are preferably of micrometric size and in particular have a lower maximum size. or equal to 500 pm. When a particle is perfectly spherical, its maximum size is its diameter. Preferably, the polymer particles Cp and/or the inorganic particles Ci have a D50 which belongs to the range going from 10 to 300 μm, preferably to the range going from 20 to 200 μm, and preferentially to the range going from 30 at 150 p.m. Advantageously, the Cp polymer particles present in the composition have a coefficient of variation CV, characterizing their dispersion in size, of 1.1 to 5, preferably from 1.1 to 4, and preferentially from 1.1 to 3 and/or the inorganic particles Ci present in the composition have a coefficient of variation CV, characterizing their dispersion in size, of 1.1 to 5, preferably from 1.1 to 4, and preferentially from 1.1 to 3 .
[0033] Des charges inorganiques Ci présentant une telle taille sont disponibles commercialement. Mais, la taille des particules polymériques Cp et des particules inorganiques Ci introduites pourra être ajustée selon toutes techniques classiques bien connues de l’homme du métier. En particulier, une opération de broyage est effectuée, suivie d’une sélection de la taille de particules par passage au travers de un ou plusieurs tamis. Dans le cas de particules polymériques Cp, obtenues à partir de déchets plastiques, une opération grossière de découpage en copeaux est généralement réalisée, avant une opération de broyage plus fin. Inorganic fillers Ci having such a size are commercially available. However, the size of the polymeric particles Cp and of the inorganic particles Ci introduced can be adjusted according to any conventional techniques well known to those skilled in the art. In particular, a grinding operation is carried out, followed by a selection of the particle size by passage through one or more sieves. In the case of Cp polymer particles, obtained from plastic waste, a rough cutting operation into chips is generally carried out, before a finer grinding operation.
[0034] Ainsi, les compostions selon l’invention peuvent être obtenues par introduction, dans une matrice à base de bitume, de particules polymériques Cp ayant un D50 qui appartient à la gamme allant de 10 à 300 pm, de préférence à la gamme allant de 20 à 200 pm, et préférentiellement à la gamme allant de 30 à 150 pm et de particules inorganiques Ci ayant un D50 qui appartient à la gamme allant de 10 à 300 pm, de préférence à la gamme allant de 20 à 200 pm, et préférentiellement à la gamme allant de 30 à 150 pm. Les particules polymériques Cp et les particules inorganiques Ci introduites, peuvent, cependant, avoir une taille identique ou différente. Thus, the compositions according to the invention can be obtained by introducing, into a bitumen-based matrix, Cp polymeric particles having a D50 which belongs to the range from 10 to 300 μm, preferably to the range from from 20 to 200 μm, and preferentially to the range going from 30 to 150 μm and of inorganic particles Ci having a D50 which belongs to the range going from 10 to 300 μm, preferably to the range going from 20 to 200 μm, and preferentially to the range going from 30 to 150 μm. The polymeric particles Cp and the inorganic particles Ci introduced may, however, have the same or different sizes.
[0035] De manière avantageuse, les compostions selon l’invention peuvent être obtenues par introduction, dans une matrice à base de bitume, de particules polymériques Cp ayant un coefficient de variation CV, caractérisant leur dispersion en taille, de 1 ,1 à 5, de préférence de 1 ,1 à 4, et préférentiellement de 1 ,1 à 3 et/ou de particules inorganiques Ci ayant un coefficient de variation CV, caractérisant leur dispersion en taille, de 1 ,1 à 5, de préférence de 1 ,1 à 4, et préférentiellement de 1 ,1 à 3. Particules polymériques Cp Advantageously, the compositions according to the invention can be obtained by introducing, into a bitumen-based matrix, polymeric particles Cp having a coefficient of variation CV, characterizing their dispersion in size, of 1.1 to 5 , preferably from 1.1 to 4, and preferably from 1.1 to 3 and/or inorganic particles Ci having a coefficient of variation CV, characterizing their dispersion in size, from 1.1 to 5, preferably from 1, 1 to 4, and preferably from 1.1 to 3. Cp polymeric particles
[0036] Les particules polymériques Cp sont des particules de polystyrène choc ou cristal. Les polystyrènes choc et cristal sont des polymères bien connus, qui diffèrent du polystyrène expansé. Le polystyrène cristal est transparent et est un homopolymère du styrène. Le polystyrène choc, également nommé HIPS (de l’anglais « High Impact Polystyrene ») contient une part de polybutadiène et est défini, notamment, dans la norme EN ISO 1043-1. The Cp polymer particles are impact or crystal polystyrene particles. High impact and crystal polystyrenes are well-known polymers, which differ from expanded polystyrene. Crystal polystyrene is transparent and is a homopolymer of styrene. High impact polystyrene, also called HIPS (High Impact Polystyrene) contains a part of polybutadiene and is defined, in particular, in standard EN ISO 1043-1.
[0037] Les particules polymériques Cp sont constituées ou majoritairement constituées de polystyrène cristal ou choc, ce qui n’exclut pas la présence de un ou plusieurs composants ou impuretés dans lesdites particules. Cependant, les particules polymériques Cp comprennent au moins 85% en masse, de préférence au moins 90% en masse, et préférentiellement au moins 95% en masse de polystyrène choc ou cristal. The Cp polymer particles consist or mainly consist of crystal or impact polystyrene, which does not exclude the presence of one or more components or impurities in said particles. However, the Cp polymer particles comprise at least 85% by mass, preferably at least 90% by mass, and preferentially at least 95% by mass of impact or crystal polystyrene.
[0038] En outre, les particules polymériques Cp peuvent comprendre un ou plusieurs polymère(s) P1 , de préférence, choisi parmi le chlorure de polyvinyle (PVC), le copolymère acrylonitrile-butadiène-styrène (ABS), les polycarbonates, le polyéthylène téréphtalate (PET). De manière préférée, la masse de polymère(s) P1 présent(s) représente au plus 15%, de préférence, au plus 10%, et préférentiellement au plus 5%, de la masse des particules polymériques Cp. In addition, the polymer particles Cp may comprise one or more polymer(s) P1, preferably chosen from polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonates, polyethylene terephthalate (PET). Preferably, the mass of polymer(s) P1 present represents at most 15%, preferably at most 10%, and preferentially at most 5%, of the mass of the polymer particles Cp.
[0039] De manière préférée, le polystyrène choc ou cristal des particules polymériques Cp a une Mw dans la gamme allant de 80 à 300 kg/mol, et préférentiellement dans la gamme allant de 100 à 250 kg/mol. Selon un mode de réalisation particulier, les particules polymériques Cp comprennent un polystyrène choc ou cristal, présentant, de manière avantageuse, une Mw dans la gamme allant de 80 à 300 kg/mol, et préférentiellement dans la gamme allant de 100 à 250 kg/mol, en mélange avec un autre polymère P1 , et en particulier en mélange avec un copolymère ABS. Notamment, les particules polymériques Cp sont constituées d’un polystyrène cristal ou choc (et en particulier un polystyrène choc ayant, de préférence, une Mw définie précédemment) ou d’un mélange polystyrène cristal ou choc/polymère P1 (et en particulier dans lequel le polystyrène est un polystyrène choc, ayant, de préférence, une Mw définie précédemment), et notamment d’un mélange polystyrène cristal ou choc/ABS. Dans ce cas, de préférence, la quantité de polymère P1 , et en particulier d’ABS, représente de 5 à 15%, et de préférence de 8 à 12% de la masse des particules polymériques Cp. De telles particules sont notamment obtenues à partir de polymère(s) recyclé(s), notamment issu(s) de déchets d’emballages ou d’appareils électroménagers tels que des réfrigérateurs. Preferably, the impact or crystal polystyrene of the Cp polymer particles has a Mw in the range from 80 to 300 kg/mol, and preferably in the range from 100 to 250 kg/mol. According to a particular embodiment, the Cp polymer particles comprise an impact or crystal polystyrene, advantageously having a Mw in the range going from 80 to 300 kg/mol, and preferentially in the range going from 100 to 250 kg/mol. mol, mixed with another polymer P1, and in particular mixed with an ABS copolymer. In particular, the polymeric particles Cp consist of a crystal or impact polystyrene (and in particular an impact polystyrene having, preferably, a Mw defined previously) or of a crystal or impact polystyrene/polymer P1 mixture (and in particular in which the polystyrene is an impact polystyrene, preferably having a Mw defined above), and in particular a crystal or impact polystyrene/ABS mixture. In this case, preferably, the quantity of polymer P1, and in particular of ABS, represents from 5 to 15%, and preferably from 8 to 12% of the mass of the polymer particles Cp. Such particles are in particular obtained from recycled polymer(s), in particular from waste packaging or household appliances such as refrigerators.
[0040] Par ailleurs, les particules polymériques Cp peuvent être constituées de particules de même nature ou de particules de natures différentes. Il est, notamment, possible d’utiliser un mélange de particules de polystyrène choc et de particules de polystyrène cristal. Il est possible, également, que la composition comprenne, en tant que particules polymériques Cp, des particules constituées d’un polystyrène choc ou cristal et des particules constituées d’un mélange d’un polystyrène choc ou cristal et d’un polymère P1 , comme précédemment décrit. [0040] Furthermore, the Cp polymer particles can consist of particles of the same nature or of particles of different natures. It is, in particular, possible to use a mixture of high impact polystyrene particles and crystal polystyrene particles. It is also possible that the composition comprises, as polymeric particles Cp, particles consisting of an impact or crystal polystyrene and particles consisting of a mixture of an impact or crystal polystyrene and a polymer P1, as previously described.
Particules inorganiques Ci Inorganic particles Ci
[0041] Les compositions selon l’invention comprennent des particules inorganiques Ci, qui constituent en partie les charges C. Dans l’art antérieur, ces particules inorganiques sont introduites dans les compositions pour membranes d’étanchéité pour conférer une bonne résistance à la marche et une résistance au fluage des membranes obtenues. The compositions according to the invention comprise inorganic particles Ci, which partly constitute the fillers C. In the prior art, these inorganic particles are introduced into the compositions for waterproofing membranes to confer good walking resistance. and creep resistance of the membranes obtained.
[0042] Toutes particules inorganiques utilisées par l’homme du métier dans des compositions adaptées à la réalisation de membranes d’étanchéité peuvent être utilisées. Les particules inorganiques Ci sont, avantageusement, des particules de carbonate de calcium, de carbonate de magnésium, d’hydroxyde de magnésium, de sulfate de calcium, de sulfate de baryum, de silice, d’argile, de talc, de mica, de wollastonite, de montmorillonite, de zéolite, d’alumine, d’oxyde de titane, d’oxyde de magnésium, d’oxyde de zinc ou de verre. De manière particulièrement préférée, les compositions selon l’invention comprennent des particules de carbonate de calcium, en tant que particules inorganiques Ci. [0042] Any inorganic particles used by those skilled in the art in compositions suitable for producing sealing membranes can be used. The inorganic particles Ci are advantageously particles of calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulphate, barium sulphate, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide or glass. Particularly preferably, the compositions according to the invention comprise particles of calcium carbonate, as inorganic particles Ci.
Polymères P2 dits additionnels P2 so-called additional polymers
[0043] De manière avantageuse, les compositions selon l’invention, comprennent en outre, au moins un composant additionnel, en plus du bitume, des particules inorganiques Ci et des particules polymériques Cp. A titre de composant additionnel, les compositions selon l’invention comprennent, de manière avantageuse, un ou plusieurs polymère(s) P2, qualifié(s) de polymère(s) additionnel(s). En effet, ce ou ces polymères P2 sont dits additionnels, car ils ne correspondent pas au(x) polymère(s) présent(s) dans les particules polymériques Cp. Ainsi, un polymère P2 n’est pas un polystyrène choc ou un polystyrène cristal. A titre de polymère P2, particulièrement préféré dans le cadre de l’invention, on peut citer les polymères choisis parmi les plastomères, notamment les polyoléfines et copolymères oléfiniques, tels que le poly(éthylène acétate de vinyle) (EVA) et le polypropylène atactique (aPP), les thermoplastiques et, notamment, les élastomères thermoplastiques, en particulier choisis parmi les copolymères à blocs insaturés. Dans les compositions bitumineuses adaptées à la constitution de membranes d’étanchéité, il est classique qu’un tel polymère soit utilisé, en particulier pour conférer une souplesse et pliabilité satisfaisantes à la membrane obtenue. En tant qu’élastomères thermoplastiques particulièrement préférés, les exemples typiques sont les copolymères à blocs styrène-butadiène- styrène (SBS), styrène-isoprène-styrène (SIS) ou styrène-éthylène-butylène- styrène (SEBS), de préférence sous forme radiale ou étoilée. De tels polymères sont largement disponibles dans le commerce, notamment auprès des sociétés Kraton ou Evonik. A titre d’exemple, on pourra utiliser un copolymère à blocs SBS commercialisé sous la référence D1184 de Kraton ou un aPP commercialisé sous la référence Vestoplast® 888 d'Evonik. Advantageously, the compositions according to the invention further comprise at least one additional component, in addition to bitumen, inorganic particles Ci and polymeric particles Cp. As an additional component, the compositions according to the invention comprise, so as advantageously, one or more polymer(s) P2, qualified as additional polymer(s). Indeed, this or these polymers P2 are said to be additional, because they do not correspond to the polymer(s) present in the polymer particles Cp. Thus, a P2 polymer is not an impact polystyrene or a crystal polystyrene. As polymer P2, which is particularly preferred in the context of the invention, mention may be made of polymers chosen from plastomers, in particular polyolefins and olefin copolymers, such as poly(ethylene vinyl acetate) (EVA) and atactic polypropylene (aPP), thermoplastics and, in particular, thermoplastic elastomers, in particular chosen from unsaturated block copolymers. In bituminous compositions suitable for the constitution of waterproofing membranes, it is conventional for such a polymer to be used, in particular to impart satisfactory flexibility and pliability to the membrane obtained. As particularly preferred thermoplastic elastomers, typical examples are styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS) or styrene-ethylene-butylene-styrene (SEBS) block copolymers, preferably in the form radial or stellate. Such polymers are widely available commercially, in particular from the companies Kraton or Evonik. By way of example, it is possible to use an SBS block copolymer marketed under the reference D1184 from Kraton or an aPP marketed under the reference Vestoplast® 888 from Evonik.
Compositions selon l’invention Compositions according to the invention
[0044] Les quantités des différents composants présents dans une composition selon l’invention sont données en % massique, par rapport à la masse totale de la composition (nommés ci-après % m/m), à moins qu’il n’en soit spécifié autrement. The amounts of the various components present in a composition according to the invention are given in % by mass, relative to the total mass of the composition (hereinafter referred to as % m/m), unless otherwise indicated. be specified otherwise.
[0045] Les quantités préférées des différents composants présents dans les compositions selon l’invention sont données ci-après. Ces quantités pourront être utilisées indépendamment les unes des autres. Bien entendu, elles pourront être utilisées en combinaison et toutes les combinaisons possibles des gammes spécifiées ci-après sont envisagées dans le cadre de l’invention. A titre d’exemple, les gammes de % massique les plus larges données pour chacun des composants pourront être utilisées en combinaison, ou encore les gammes de % massique intermédiaires données pour chacun des composants pourront être utilisées en combinaison, ou encore les gammes de % massique les plus restreintes données pour chacun des composants pourront être utilisées en combinaison. The preferred amounts of the various components present in the compositions according to the invention are given below. These quantities may be used independently of each other. Of course, they can be used in combination and all the possible combinations of the ranges specified below are envisaged within the scope of the invention. By way of example, the widest mass % ranges given for each of the components may be used in combination, or even the intermediate mass % ranges given for each of the components may be used in combination, or even the most restricted mass % ranges given for each of the components may be used in combination.
[0046] Les compositions selon l’invention comprennent de 21 à 40% m/m de charges C, de préférence de 26 à 38 % m/m, et de manière encore plus préférée de 28 à 35% m/m. Ces charges C sont constituées de particules polymériques Cp, et de particules inorganiques Ci, telles que précédemment définies. Les particules polymériques Cp représentent 1 à 10% m/m, de préférence 1 à 5% m/m, et de manière encore plus préférée de 1 à 3% m/m de la masse totale de la composition. De manière avantageuse, les particules inorganiques Ci représentent 20 à 39% m/m, de préférence de 25 à 37% m/m, et de manière encore plus préférée de 27 à 34% m/m de la masse totale de la composition. The compositions according to the invention comprise from 21 to 40% m/m of fillers C, preferably from 26 to 38% m/m, and even more preferably from 28 to 35% m/m. These fillers C consist of polymeric particles Cp, and of inorganic particles Ci, as previously defined. The Cp polymer particles represent 1 to 10% m/m, preferably 1 to 5% m/m, and even more preferably 1 to 3% m/m of the total mass of the composition. Advantageously, the inorganic particles Ci represent 20 to 39% m/m, preferably 25 to 37% m/m, and even more preferably 27 to 34% m/m of the total mass of the composition.
[0047] De manière particulièrement préférée, les compositions selon l’invention comprennent : Particularly preferably, the compositions according to the invention comprise:
- de 1 à 10% m/m, de préférence 1 à 5% m/m, et de manière encore plus préférée de 1 à 3% m/m de particules polymériques Cp d’un polystyrène choc ou cristal, qui, de manière avantageuse, a une Mw dans la gamme allant de 80 à 300 kg/mol, et préférentiellement dans la gamme allant de 100 à 250 kg/mol, en tant que particules polymériques Cp; et/ou - from 1 to 10% m/m, preferably 1 to 5% m/m, and even more preferably from 1 to 3% m/m of Cp polymeric particles of an impact or crystal polystyrene, which, in a advantageously, has a Mw in the range from 80 to 300 kg/mol, and preferably in the range from 100 to 250 kg/mol, as Cp polymer particles; and or
- 20 à 39% m/m, de préférence de 25 à 37% m/m, et de manière encore plus préférée de 27 à 34% m/m de carbonate de calcium, en tant que particules inorganiques Ci. - 20 to 39% m/m, preferably from 25 to 37% m/m, and even more preferably from 27 to 34% m/m of calcium carbonate, as inorganic particles Ci.
Bien entendu, les quantités massiques des particules polymériques Cp et des particules inorganiques Ci sont sélectionnées dans les gammes ci-dessus, pour avoir au global, dans les compositions selon l’invention de 21 à 40% m/m, de préférence de 26 à 38 % m/m, et de manière encore plus préférée de 28 à 35% m/m de charges C. Of course, the mass quantities of the polymeric particles Cp and of the inorganic particles Ci are selected from the above ranges, in order to have overall, in the compositions according to the invention, from 21 to 40% m/m, preferably from 26 to 38% m/m, and even more preferably from 28 to 35% m/m of C fillers.
[0048] En particulier, de telles particules polymériques Cp comprennent, voire sont constituées, d’un mélange d’un polystyrène choc ou cristal et d’un polymère P1 choisi parmi, le chlorure de polyvinyle (PVC), le copolymère acrylonitrile- butadiène-styrène (ABS), les polycarbonates, le polyéthylène téréphtalate (PET), avec le polystyrène choc ou cristal qui présente au moins 85%, de préférence au moins 90%, et préférentiellement au moins 95% de la masse des particules polymériques Cp qui sont, de préférence, issues du recyclage de déchets. In particular, such polymeric particles Cp comprise, or even consist of, a mixture of an impact or crystal polystyrene and a polymer P1 chosen from polyvinyl chloride (PVC), acrylonitrile-butadiene copolymer -styrene (ABS), polycarbonates, polyethylene terephthalate (PET), with impact or crystal polystyrene which is at least 85%, preferably at least 90%, and preferably at least 95% of the mass of the Cp polymer particles which are, preferably, derived from the recycling of waste.
[0049] Les compositions selon l’invention comprennent de 40 à 70% m/m de bitume, de préférence de 50 à 65 % m/m, et de manière encore plus préférée de 55 à 65 % m/m de bitume. The compositions according to the invention comprise from 40 to 70% m/m of bitumen, preferably from 50 to 65% m/m, and even more preferably from 55 to 65% m/m of bitumen.
[0050] A titre optionnel, mais préféré pour la constitution de membranes d’étanchéité, en particulier pour toiture, les compositions selon l’invention comprennent de 5 à 25 % m/m, de préférence de 5 à 20% m/m et préférentiellement de 7 à 18% m/m d’un ou plusieurs polymère(s) additionnel(s) P2, en particulier, tels que précédemment définis. De manière préférée, les compositions selon l’invention comprennent de 5 à 25 % m/m, de préférence de 5 à 20% m/m, et préférentiellement de 7 à 18% m/m d’un copolymère à blocs styrène-butadiène-styrène, de préférence sous forme ramifiée ou étoilée, de polypropylène atactique, de poly(éthylène-acétate de vinyle) ou d’un mélange de tels polymères, en tant que polymère P2. [0050] As an option, but preferred for the constitution of waterproofing membranes, in particular for roofing, the compositions according to the invention comprise from 5 to 25% m/m, preferably from 5 to 20% m/m and preferably from 7 to 18% m/m of one or more additional polymer(s) P2, in particular, as defined previously. Preferably, the compositions according to the invention comprise from 5 to 25% m/m, preferably from 5 to 20% m/m, and preferentially from 7 to 18% m/m of a styrene-butadiene block copolymer -styrene, preferably in branched or star-shaped form, of atactic polypropylene, of poly(ethylene-vinyl acetate) or of a mixture of such polymers, as polymer P2.
[0051] Ainsi, les compositions préférées selon l’invention comprennent, voire sont constituées de : Thus, the preferred compositions according to the invention comprise, or even consist of:
- de 21 à 40% m/m de préférence de 26 à 38 % m/m, et de manière encore plus préférée de 28 à 35% m/m de charges C, constituées de particules inorganiques Ci et de particules polymériques Cp d’un polystyrène choc ou cristal, les particules polymériques Cp représentant de 1 à 10% m/m, de préférence 1 à 5% m/m, et de manière encore plus préférée de 1 à 3% m/m de la masse totale de la composition et les particules inorganiques Ci représentant de 20 à 39% m/m, de préférence de 25 à 37% m/m, et de manière encore plus préférée de 27 à 34% m/m de la masse totale de la composition ; - from 21 to 40% m/m, preferably from 26 to 38% m/m, and even more preferably from 28 to 35% m/m of fillers C, consisting of inorganic particles Ci and polymeric particles Cp of an impact or crystal polystyrene, the Cp polymer particles representing from 1 to 10% m/m, preferably 1 to 5% m/m, and even more preferably from 1 to 3% m/m of the total mass of the composition and the inorganic particles Ci representing from 20 to 39% m/m, preferably from 25 to 37% m/m, and even more preferably from 27 to 34% m/m of the total mass of the composition;
- de 40 à 70% m/m, de préférence de 50 à 65 % m/m, et de manière encore plus préférée de 55 à 65 % m/m de bitume ; - from 40 to 70% m/m, preferably from 50 to 65% m/m, and even more preferably from 55 to 65% m/m of bitumen;
- de 5 à 25 % m/m, de préférence de 5 à 20% m/m, et de manière encore plus préférée de 7 à 18% m/m d’un ou plusieurs polymère(s) additionnel(s) P2. - from 5 to 25% m/m, preferably from 5 to 20% m/m, and even more preferably from 7 to 18% m/m of one or more additional polymer(s) P2.
[0052] Dans les compositions préférées selon l’invention, les charges C, les particules polymériques Cp, les particules inorganiques Ci, le(s) polymère(s) additionnel(s) P2 et le bitume, présentés comme préférés seront, bien entendu, avantageusement, utilisés. In the preferred compositions according to the invention, the fillers C, the polymeric particles Cp, the inorganic particles Ci, the polymer(s) additional P2(s) and bitumen, presented as preferred will, of course, advantageously be used.
[0053] Aussi, les compositions particulièrement préférées selon l’invention comprennent, voire sont constituées de : Also, the particularly preferred compositions according to the invention comprise, or even consist of:
- de 21 à 40% m/m de préférence de 26 à 38 % m/m, et de manière encore plus préférée de 28 à 35% m/m de charges C, constituées de particules inorganiques Ci de CaCO3 et de particules polymériques Cp de polystyrène cristal ou choc, de préférence issues du recyclage de déchets ; les particules polymériques Cp représentant de 1 à 10% m/m, de préférence 1 à 5% m/m, et de manière encore plus préférée de 1 à 3% m/m de la masse totale de la composition et les particules inorganiques Ci représentant de 20 à 39% m/m, de préférence de 25 à 37% m/m, et de manière encore plus préférée de 27 à 34% m/m de la masse totale de la composition ; de manière préférée, lesdites particules polymériques Cp comprennent, voire sont constituées, d’un mélange de polymères qui est un mélange d’un polystyrène choc ou cristal et d’un polymère P1 choisi parmi, le chlorure de polyvinyle (PVC), le copolymère acrylonitrile-butadiène-styrène (ABS), les polycarbonates, le polyéthylène téréphtalate (PET), avec le polystyrène choc ou cristal qui présente au moins 85%, de préférence au moins 90%, et préférentiellement au moins 95% de la masse des particules polymériques Cp ; les particules polymériques Cp étant, de préférence issues du recyclage de déchets ; - from 21 to 40% m/m, preferably from 26 to 38% m/m, and even more preferably from 28 to 35% m/m of fillers C, consisting of inorganic particles Ci of CaCO3 and polymeric particles Cp crystal or impact polystyrene, preferably from waste recycling; the polymeric particles Cp representing from 1 to 10% m/m, preferably 1 to 5% m/m, and even more preferably from 1 to 3% m/m of the total mass of the composition and the inorganic particles Ci representing from 20 to 39% m/m, preferably from 25 to 37% m/m, and even more preferably from 27 to 34% m/m of the total mass of the composition; preferably, said polymeric particles Cp comprise, or even consist of a mixture of polymers which is a mixture of an impact or crystal polystyrene and a polymer P1 chosen from polyvinyl chloride (PVC), the copolymer acrylonitrile-butadiene-styrene (ABS), polycarbonates, polyethylene terephthalate (PET), with impact or crystal polystyrene which has at least 85%, preferably at least 90%, and preferably at least 95% of the mass of the particles Cp polymers; the polymeric particles Cp being, preferably resulting from the recycling of waste;
- de 40 à 70% m/m, de préférence de 50 à 65 % m/m, et de manière encore plus préférée de 55 à 65 % m/m de bitume, de préférence choisi parmi les bitumes de grades 160/220 et 70/100 et leurs mélanges ; - from 40 to 70% m/m, preferably from 50 to 65% m/m, and even more preferably from 55 to 65% m/m of bitumen, preferably chosen from bitumens of grades 160/220 and 70/100 and mixtures thereof;
- de 5 à 25 % m/m, de préférence de 5 à 20% m/m, et de manière encore plus préférée de 7 à 18% m/m d’un copolymère à blocs styrène-butadiène-styrène, de préférence sous forme ramifiée ou étoilée, d’un polypropylène atactique, d’un poly(éthylène-acétate de vinyle) ou d’un mélange de tels polymères. - from 5 to 25% m/m, preferably from 5 to 20% m/m, and even more preferably from 7 to 18% m/m of a styrene-butadiene-styrene block copolymer, preferably under branched or star-shaped form, of an atactic polypropylene, of a poly(ethylene-vinyl acetate) or of a mixture of such polymers.
[0054] De manière avantageuse, les compositions selon l’invention, sont adaptées à la constitution de membranes d’étanchéité, et en particulier de membranes d’étanchéité pour toiture. Description du procédé de fabrication des compositions Advantageously, the compositions according to the invention are suitable for the constitution of waterproofing membranes, and in particular of waterproofing membranes for roofing. Description of the process for manufacturing the compositions
[0055] De manière classique, le mélange du bitume et des charges C, voire du ou des polymères additionnels P2, est réalisé à une température allant de 100 à 220 °C, de préférence allant de 120 à 200 °C, et préérentiellement allant de 140 à 190 °C. De manière avantageuse, le mélange est réalisé à une température supérieure ou égale à 150 °C, de préférence supérieure ou égale à 160 °C. Conventionally, the mixture of the bitumen and the fillers C, or even the additional polymer(s) P2, is carried out at a temperature ranging from 100 to 220° C., preferably ranging from 120 to 200° C., and preferentially ranging from from 140 to 190°C. Advantageously, the mixing is carried out at a temperature greater than or equal to 150°C, preferably greater than or equal to 160°C.
[0056] Un tel mélange est réalisé sous agitation, notamment, pendant une durée de 5 minutes à 10 heures, de préférence de 10 minutes à 3 heures, préférentiellement de 10 à 90 minutes, et de manière encore plus préférée de 20 à 90 minutes. Le mélange peut être mis en oeuvre au moyen d'une agitation produisant un fort cisaillement ou d'une agitation produisant un faible cisaillement. En particulier, le mélange est réalisé sous une agitation de 200 à 2000 tr/min, de préférence de 300 à 1500 tr/min. L'agitation est réalisée de manière à faciliter la dispersion et la bonne distribution des charges dans le bitume qui va constituer la matrice de la composition, éventuellement en association avec le(s) polymère(s) additionnel(s) P2. Les conditions sont adaptées pour conduire à l’obtention d’un mélange homogène. De manière classique, l’homme du métier ajustera le temps et la puissance de l’agitation, ainsi que la température de mélange, en particulier en fonction du bitume, voire du ou des polymère(s) additionnel(s) P2, pour avoir un mélange en fusion, et de la taille et de la quantité des charges C. De manière classique, le mélange est effectué de manière à favoriser une bonne répartition des charges C, voire du ou des polymère(s) additionnel(s) P2, dans la composition bitumineuse finale obtenue. Such a mixture is produced with stirring, in particular, for a period of 5 minutes to 10 hours, preferably 10 minutes to 3 hours, preferably 10 to 90 minutes, and even more preferably 20 to 90 minutes. . Mixing can be carried out using high shear agitation or low shear agitation. In particular, the mixing is carried out with stirring at 200 to 2000 rpm, preferably at 300 to 1500 rpm. The agitation is carried out so as to facilitate the dispersion and the good distribution of the fillers in the bitumen which will constitute the matrix of the composition, optionally in combination with the additional polymer(s) P2. The conditions are adapted to lead to obtaining a homogeneous mixture. Conventionally, those skilled in the art will adjust the stirring time and power, as well as the mixing temperature, in particular according to the bitumen, or even the additional polymer(s) P2, to have a molten mixture, and the size and quantity of the fillers C. Conventionally, the mixing is carried out in such a way as to promote a good distribution of the fillers C, or even of the additional polymer(s) P2, in the final bituminous composition obtained.
[0057] De manière avantageuse, lorsqu’un polymère additionnel P2, est souhaité dans la composition bitumineuse à préparer, celui est ajouté au bitume, avant les charges C. En effet, la présence des charges C rend plus difficile une bonne répartition du polymère additionnel P2, au sein de la matrice bitumineuse, si celui-ci est ajouté après. Advantageously, when an additional polymer P2 is desired in the bituminous composition to be prepared, it is added to the bitumen, before the fillers C. Indeed, the presence of the fillers C makes it more difficult to distribute the polymer correctly. additional P2, within the bituminous matrix, if this is added afterwards.
[0058] Concernant les particules polymériques Cp et les particules inorganiques Ci, constituant les charges C, celles-ci pourront être introduites ensemble ou de manière séparée. Selon un mode de réalisation préféré, les particules polymériques Cp sont introduites, avant les particules inorganiques Ci. Concerning the polymeric particles Cp and the inorganic particles Ci, constituting the fillers C, these may be introduced together or separately. separate way. According to a preferred embodiment, the polymeric particles Cp are introduced, before the inorganic particles Ci.
[0059] En particulier, sont introduites, ensemble ou séparément, dans une matrice à base de bitume ou constituée de bitume, des particules polymériques Cp ayant un D50 qui appartient à la gamme allant de 10 à 300 pm, de préférence à la gamme allant de 20 à 200 pm, et préférentiellement à la gamme allant de 30 à 150 pm et des particules inorganiques Ci ayant un D50 qui appartient à la gamme allant de 10 à 300 pm, de préférence à la gamme allant de 20 à 200 pm, et préférentiellement à la gamme allant de 30 à 150 pm. Les particules polymériques Cp et les particules inorganiques Ci introduites, peuvent, cependant, avoir une taille identique ou différente. In particular, Cp polymer particles having a D50 which belongs to the range from 10 to 300 μm, preferably to the range from from 20 to 200 μm, and preferably to the range going from 30 to 150 μm and inorganic particles Ci having a D50 which belongs to the range going from 10 to 300 μm, preferably to the range going from 20 to 200 μm, and preferentially to the range going from 30 to 150 μm. The polymeric particles Cp and the inorganic particles Ci introduced may, however, have the same or different sizes.
[0060] En particulier, sont introduites, ensemble ou séparément, dans une matrice à base de bitume ou constituée de bitume, des particules polymériques Cp ayant un coefficient de variation CV, caractérisant leur dispersion en taille, de 1 ,1 à 5, de préférence de 1 ,1 à 4, et préférentiellement de 1 ,1 à 3 et/ou des particules inorganiques Ci ayant un coefficient de variation CV, caractérisant leur dispersion en taille, de 1 ,1 à 5, de préférence de 1 ,1 à 4, et préférentiellement de 1 ,1 à 3. In particular, are introduced, together or separately, into a matrix based on bitumen or consisting of bitumen, polymeric particles Cp having a coefficient of variation CV, characterizing their dispersion in size, from 1.1 to 5, of preferably from 1.1 to 4, and preferably from 1.1 to 3 and/or inorganic particles Ci having a coefficient of variation CV, characterizing their dispersion in size, from 1.1 to 5, preferably from 1.1 to 4, and preferably from 1.1 to 3.
[0061 ] En général, et ce de manière connue de l’homme du métier, le bitume ou mélange de bitumes utilisé pour la fabrication de la composition est préalablement chauffé et agité, avant incorporation des autres constituants de la composition. Les constituants sont, en général, introduits de manière séquencée. Un chauffage est maintenu tout au long du procédé, et la température de chauffage peut être modulée au cours du procédé. L’agitation peut être maintenue ou interrompue par intermittence si besoin, notamment lors de l’introduction des particules inorganiques Ci et/ou peut être modulée en intensité. En particulier, l’agitation pourra être plus importante lors de l’introduction de certains des constituants et, en particulier, lors de l’introduction des particules inorganiques Ci. [0061] In general, and in a manner known to those skilled in the art, the bitumen or mixture of bitumens used for the manufacture of the composition is heated and stirred beforehand, before incorporating the other constituents of the composition. The constituents are generally introduced in sequence. Heating is maintained throughout the process, and the heating temperature can be modulated during the process. The agitation can be maintained or interrupted intermittently if necessary, in particular during the introduction of the inorganic particles Ci and/or can be modulated in intensity. In particular, the agitation may be greater during the introduction of some of the constituents and, in particular, during the introduction of the inorganic particles Ci.
[0062] Dans le procédé selon l’invention, sont, de préférence, utilisés un ou plusieurs bitume(s), des charges C, des particules polymériques Cp, et des particules inorganiques Ci, voire un ou plusieurs polymère(s) P2, correspondant aux descriptions données précédemment dans les parties correspondantes. [0063] Bien entendu, dans le procédé, les quantités utilisées de bitume, charges C, et donc de particules polymériques Cp, et de particules inorganiques Ci, voire de polymère(s) P2 éventuellement présent(s), seront ajustées par l’homme du métier pour obtenir au final les quantités souhaitées dans la composition finale, et en particulier celles mentionnées dans la précédente partie relative aux compositions selon l’invention. In the process according to the invention, one or more bitumen(s), fillers C, polymeric particles Cp, and inorganic particles Ci, or even one or more polymer(s) P2, are preferably used, corresponding to the descriptions given previously in the corresponding parts. Of course, in the process, the quantities used of bitumen, fillers C, and therefore of polymeric particles Cp, and of inorganic particles Ci, or even of polymer(s) P2 possibly present, will be adjusted by the skilled in the art to ultimately obtain the desired amounts in the final composition, and in particular those mentioned in the previous part relating to the compositions according to the invention.
[0064] Les compositions bitumineuses susceptibles d’être obtenues par un tel procédé font également partie intégrante de l’invention. The bituminous compositions capable of being obtained by such a process also form an integral part of the invention.
Membranes d’étanchéité Waterproofing membranes
[0065] L’invention a également pour objet une membrane d’étanchéité, en particulier pour toiture, comprenant une couche formée d’une composition selon l’invention. Une telle couche obtenue par dépôt d’une composition selon l’invention, a typiquement une épaisseur de 2 à 10 mm, notamment de 3 à 5 mm. The invention also relates to a waterproofing membrane, in particular for a roof, comprising a layer formed from a composition according to the invention. Such a layer obtained by depositing a composition according to the invention typically has a thickness of 2 to 10 mm, in particular 3 to 5 mm.
[0066] L’obtention d’une couche à partir d’une composition selon l’invention, pour la fabrication d’une membrane d’étanchéité, est réalisée selon toute technique de dépôt adaptée. Avant son application, il est préférable que la composition soit à l’état de pâte malléable et/ou fluide ou de pâte visqueuse, ce qui va nécessiter un chauffage. L’application peut être réalisée, manuellement, par exemple à la taloche, par enduction, ou par projection, directement sur le support dont l’étanchéité est à assurer ou sur un matériau fibreux. Un tel matériau fibreux peut, par exemple, être en fibres de verre, en fibres de polyamide, en fibres de polyester et/ou se trouver sous la forme d’un non-tissé. Ledit matériau fibreux peut faire partie intégrante de la membrane d’étanchéité et jouer le rôle d’armature. Obtaining a layer from a composition according to the invention, for the manufacture of a waterproofing membrane, is carried out using any suitable deposition technique. Before its application, it is preferable for the composition to be in the form of a malleable and/or fluid paste or a viscous paste, which will require heating. The application can be carried out, manually, for example with a trowel, by coating, or by projection, directly on the support whose sealing is to be ensured or on a fibrous material. Such a fibrous material can, for example, be made of glass fibers, polyamide fibers, polyester fibers and/or be in the form of a nonwoven. Said fibrous material can be an integral part of the waterproofing membrane and play the role of reinforcement.
[0067] La membrane peut être réalisée directement sur site ou être fabriquée au préalable. Dans ce dernier cas, la membrane présente, bien souvent, un caractère enroulable et peut se trouver sous la forme d’un rouleau, facilitant son stockage avant sa mise en oeuvre. The membrane can be produced directly on site or be manufactured beforehand. In the latter case, the membrane often has a rollable nature and can be in the form of a roll, facilitating its storage before its implementation.
[0068] L’invention a également pour objet une membrane d’étanchéité, en particulier pour toiture, comprenant une composition selon l’invention, venant imprégner, au moins pour partie, un matériau fibreux. Un tel matériau fibreux peut, par exemple, être en fibres de verre, en fibres de polyamide, en fibres de polyester et/ou se trouver sous la forme d’un non-tissé. The invention also relates to a waterproofing membrane, in particular for a roof, comprising a composition according to the invention, impregnating, at least in part, a fibrous material. Such fibrous material may, for example, be made of glass fibers, polyamide fibers, polyester fibers and/or be in the form of a nonwoven.
[0069] L’invention a également pour objet une membrane d’étanchéité, en particulier pour toiture se présentant sous la forme d’une structure multicouche et comprenant une couche formée d’une composition selon l’invention. The invention also relates to a waterproofing membrane, in particular for a roof, in the form of a multilayer structure and comprising a layer formed from a composition according to the invention.
[0070] Une membrane d’étanchéité pour toiture, sous la forme d’une structure multicouche, comprend typiquement une couche supérieure en matière polymère qui est agencée pour réfléchir des rayons UV, une couche inférieure d’étanchéité qui est agencée pour recouvrir une toiture, et une armature disposée entre ladite couche supérieure et ladite couche inférieure. La couche inférieure d’étanchéité est alors constituée d’une composition selon l’invention. L’armature est, notamment, un matériau fibreux précédemment décrit. [0070] A waterproofing membrane for a roof, in the form of a multilayer structure, typically comprises an upper layer of polymeric material which is arranged to reflect UV rays, a lower waterproofing layer which is arranged to cover a roof , and an armature disposed between said upper layer and said lower layer. The lower sealing layer then consists of a composition according to the invention. The reinforcement is, in particular, a fibrous material previously described.
[0071] Bien entendu, toutes les préférences mentionnées pour les compositions selon l’invention s’appliquent aux membranes d’étanchéité selon l’invention, et, en particulier aux membranes d’étanchéité pour toiture selon l’invention. Of course, all the preferences mentioned for the compositions according to the invention apply to the waterproofing membranes according to the invention, and, in particular, to the waterproofing membranes for roofs according to the invention.
Exemples Examples
[0072] Les composants suivants ont été utilisés : The following components were used:
- un bitume de grade 160/220 présentant une TBA de 38,4°C et une pénétrabilité à 25°C de 197 1/10mm, - a 160/220 grade bitumen with a TBA of 38.4°C and a penetrability at 25°C of 197 1/10mm,
- des particules de CaCO3, commercialisées par MEAC. Ces particules présentaient une taille maximale inférieure à 90 pm. - CaCO3 particles, marketed by MEAC. These particles had a maximum size of less than 90 μm.
- deux types de particules polymériques issues des mêmes déchets plastiques à base de polystyrène choc (nommées PS1 et PS2), issus de déchets de réfrigérateurs. La différence entre les particules PS1 et PS2 réside dans la taille des particules. Leurs caractéristiques sont données dans le Tableau 1 ci-après.- two types of polymer particles from the same impact polystyrene-based plastic waste (named PS1 and PS2), from refrigerator waste. The difference between PS1 and PS2 particles is in the particle size. Their characteristics are given in Table 1 below.
- un copolymère à bloc SBS branché commercialisé sous la référence D1184 ASM par la société Kraton. [0073] [Tableau 1 ] - a branched SBS block copolymer marketed under the reference D1184 ASM by the company Kraton. [0073] [Table 1 ]
[0074] N.D. non déterminé, mais au vu de la technique de tamisage utilisée pour la sélection de taille, leur taille est comprise entre 125 et 250 pim, ce qui signifie que leur taille maximale est inférieure ou égale à 250 pim. Le D50 a été déterminé conformément à la méthode précédemment décrite dans la description. [0074] N.D. not determined, but in view of the sieving technique used for size selection, their size is between 125 and 250 µm, which means that their maximum size is less than or equal to 250 µm. The D50 was determined in accordance with the method previously described in the description.
[0075] *PS = polystyrène choc [0075] *PS = impact polystyrene
[0076] La masse Mw a été évaluée par CPG, en utilisant du tetrahydrofurane (THF), en tant que solvant THF, sur une colonne à 25 °C, avec un détecteur réfracto mètre. Le calibrage a été réalisé avec 12 étalons PS de masses 1 ,01 à 44800 kg/mol, achetés chez Tosoh. The mass Mw was evaluated by GPC, using tetrahydrofuran (THF), as THF solvent, on a column at 25° C., with a refractometer detector. The calibration was carried out with 12 PS standards with masses from 1.01 to 44800 kg/mol, purchased from Tosoh.
[0077] Les performances des compositions et des membranes qui ont été évaluées sont : The performances of the compositions and of the membranes which have been evaluated are:
- la température bille-anneau TBA, selon la norme EN1427 (évaluée sur les compositions), - the ball-ring temperature TBA, according to the EN1427 standard (evaluated on the compositions),
- la pénétrabilité à 25 °C et 50 °C (qui est plus petinente pour les compositions bitumineuses pour membranes), selon la norme EN 1426 (évaluée sur les compositions), - penetrability at 25°C and 50°C (which is more relevant for bituminous compositions for membranes), according to standard EN 1426 (evaluated on the compositions),
- la pliabilité à froid selon la norme EN 1 109 (évaluée sur les membranes), qui permet de connaître le comportement d’une membrane à des températures faibles et donc de connaître son point de fracture, - the cold bendability according to standard EN 1 109 (evaluated on the membranes), which makes it possible to know the behavior of a membrane at low temperatures and therefore to know its fracture point,
- la rémanence selon la norme NFT 46009 (évaluée sur les membranes), qui permet de connaître la déformation résiduelle d’une membrane après une sollicitation à de grandes déformations, - the remanence according to the NFT 46009 standard (evaluated on the membranes), which makes it possible to know the residual deformation of a membrane after a stress with large deformations,
- viscosité Brookfield CAP 2000+ à 180 °C, avec un g"adient de vitesse de 50 s-1 et utilisation d’un mobile 7 à géométrie cone-plan (évaluée sur les compositions),- Brookfield CAP viscosity 2000+ at 180°C, with a speed g"adient of 50 s-1 and use of a mobile 7 with cone-plane geometry (evaluated on the compositions),
- un vieillissement PAV a été réalisé dans les conditions suivantes : 21 bar d’air et 100 °C, pendant 44h. Les mesures de TBA, pénétrablité et pliabilité à froid ont été répétées après un tel vieillissement. - PAV aging was carried out under the following conditions: 21 bar of air and 100°C, for 44 hours. Measurements of TBA, penetrability and cold bendability were repeated after such aging.
[0078] Deux compositions (exemples 1 et 2) selon l’invention ont été préparées comme suit, l’une avec les particules polymériques du polystyrène PS1 , à raison de 1 % m/m (exemple 1 ) et l’autre avec les particules polymériques du polystyrène PS2, à raison de 3% m/m (exemple 2). Two compositions (Examples 1 and 2) according to the invention were prepared as follows, one with the polymeric particles of polystyrene PS1, at a rate of 1% m/m (Example 1) and the other with the polymeric particles of polystyrene PS2, at a rate of 3% m/m (example 2).
[0079] Compositions de l’exemple 1 : [0079] Compositions of Example 1:
- bitume : 58% m/m, - bitumen: 58% m/m,
- CaCO3 : 34% m/m, - CaCO3: 34% m/m,
- PS1 : 1 % m/m, - PS1: 1% m/m,
- S BS : 7% m/m. - S BS: 7% m/m.
[0080] Composition de l’exemple 2 : Composition of Example 2:
- bitume : 58% m/m, - bitumen: 58% m/m,
- CaCO3 : 32% m/m, - CaCO3: 32% m/m,
- PS2 : 3% m/m, - PS2: 3% m/m,
- S BS : 7% m/m. - S BS: 7% m/m.
[0081] Ces compositions ont été préparées comme suit : These compositions were prepared as follows:
[0082] Le bitume a été chauffé pendant 10 minutes à une température de 180°C tout en agitant à 200 tr/min, puis l’agitation a été augmentée à 400 tr/min et le polymère SBS a été ajouté (pour avoir 7 % massique en polymère SBS au final dans la composition) lentement afin de favoriser la bonne dispersion de celui-ci. Une fois le SBS introduit, l’agitation a été rabaissée à 200 tr/min et maintenue, pendant environ 20 minutes à 180 °C. La quantité so haitée de PS1 ou PS2 a alors été introduite. The bitumen was heated for 10 minutes at a temperature of 180° C. while stirring at 200 rpm, then the stirring was increased to 400 rpm and the SBS polymer was added (to have 7 % mass of SBS polymer in the end in the composition) slowly in order to promote good dispersion of the latter. Once the SBS was introduced, the stirring was lowered to 200 rpm and maintained for about 20 minutes at 180°C. The desired quantity of PS1 or PS2 was then introduced.
[0083] L’agitation a alors été augmentée à 800 tours/min. Ensuite, la quantité nécessaire de CaCO3 a été introduite, pour avoir au final dans la composition 35 % massique de (CaCO3 + PS1) ou (CaCO3 + PS2). L’ajout de CaCO3 provoquant des bulles d’air, l’agitation a été stoppée par intermittence pour ne pas avoir des projections de bitume chaud. Une fois l’addition de CaCO3 terminée, l’agitation a été rabaissée à 200 tr/min et le mélange a été agité pendant 40 minutes à 190 ° C. The stirring was then increased to 800 revolutions/min. Then, the necessary quantity of CaCO3 was introduced, to have in the end in the composition 35% by mass of (CaCO3 + PS1) or (CaCO3 + PS2). The addition of CaCO3 causing air bubbles, the agitation was stopped intermittently so as not to have splashes of hot bitumen. Once the addition of CaCO3 finished, stirring was reduced to 200 rpm and the mixture was stirred for 40 minutes at 190°C.
[0084] Une membrane a alors été obtenue, en coulant le mélange sur un moule et en réalisant un tirage à l’aide d’une lame préalablement chauffée, afin d’obtenir au final une membrane de même épaisseur de 2 mm. [0084] A membrane was then obtained, by pouring the mixture onto a mold and pulling it out using a preheated blade, in order to ultimately obtain a membrane of the same thickness of 2 mm.
[0085] Les résultats obtenus pour les deux compositions selon l’invention ont été comparés avec ceux obtenus avec une composition de référence qui ne comprend que des charges inorganiques, soit 35% m/m de CaCO3, et pas de particules polymériques en tant que charge. [0086] Composition de référence : The results obtained for the two compositions according to the invention were compared with those obtained with a reference composition which only comprises inorganic fillers, i.e. 35% m/m of CaCO3, and no polymeric particles as charge. [0086] Reference composition:
- bitume : 58% m/m, - bitumen: 58% m/m,
- CaCO3 : 35% m/m, - CaCO3: 35% m/m,
- S BS : 7% m/m. - S BS: 7% m/m.
[0087] Les résultats sont présentés dans le Tableau 2 ci-dessous. The results are presented in Table 2 below.
[0088] [Tableau 2] [0088] [Table 2]
[0089] Ces résultats montrent que la substitution d’une partie du CaCO3 par des particules à base de polystyrène choc, issues de déchets, n’affectent en rien les propriétés étudiées. En particulier, les résultats obtenus sont conformes au repère UEatc (Union européenne pour l’agrément technique dans la construction) qui correspond à des recommandations à atteindre pour être en adéquation avec le matériel utilisé sur des chantiers. On utilise ce repère pour les membranes d’étanchéité, afin de garantir la résistance à la pluie, au vent et au feu. [0090] Il ressort également des résultats de ce Tableau que la pénétrabilité à 50 °C, qui est associée à la résistance à la marche, est améliorée avec les compositions selon l’invention. These results show that the substitution of part of the CaCO3 by particles based on impact polystyrene, obtained from waste, in no way affects the properties studied. In particular, the results obtained comply with the UEatc benchmark (European Union for technical approval in construction) which corresponds to recommendations to be achieved in order to be in line with the equipment used on construction sites. This mark is used for waterproofing membranes, in order to guarantee resistance to rain, wind and fire. It also emerges from the results of this Table that the penetrability at 50° C., which is associated with the walking resistance, is improved with the compositions according to the invention.

Claims

Revendications Claims
[Revendication 1] Composition bitumineuse comprenant, dans une matrice à base de bitume, des charges C qui représentent de 21 à 40% de la masse totale de la composition et qui sont constituées de particules inorganiques Ci et de particules polymériques Cp de polystyrène cristal ou de polystyrène choc, la masse des particules polymériques Cp représentant de 1 à 10% de la masse totale de la composition et la masse de bitume représentant de 40 à 70% de la masse totale de la composition. [Claim 1] Bituminous composition comprising, in a bitumen-based matrix, fillers C which represent from 21 to 40% of the total mass of the composition and which consist of inorganic particles Ci and polymeric particles Cp of crystal polystyrene or of impact polystyrene, the mass of the Cp polymer particles representing from 1 to 10% of the total mass of the composition and the mass of bitumen representing from 40 to 70% of the total mass of the composition.
[Revendication 2] Composition selon la revendication 1 , caractérisée en ce que le polystyrène choc ou cristal des particules polymériques Cp a une Mw dans la gamme allant de 80 à 300 kg/mol, et préférentiellement dans la gamme allant de 100 à 250 kg/mol. [Claim 2] Composition according to Claim 1, characterized in that the impact or crystal polystyrene of the Cp polymer particles has a Mw in the range going from 80 to 300 kg/mol, and preferably in the range going from 100 to 250 kg/mol. soft.
[Revendication 3] Composition selon la revendication 1 ou 2, caractérisée en ce que les particules polymériques Cp comprennent, au moins 85% en masse, de préférence au moins 90% en masse, et préférentiellement au moins 95% en masse de polystyrène choc ou cristal, en mélange avec un ou plusieurs polymère(s) P1 , de préférence, choisi parmi le chlorure de polyvinyle (PVC), le copolymère acrylonitrile-butadiène-styrène (ABS), les polycarbonates, le polyéthylène téréphtalate (PET), et les particules polymériques Cp étant, de préférence, issues du recyclage de déchets. [Claim 3] Composition according to Claim 1 or 2, characterized in that the Cp polymer particles comprise at least 85% by mass, preferably at least 90% by mass, and preferentially at least 95% by mass of high-impact polystyrene or crystal, mixed with one or more polymer(s) P1 , preferably chosen from polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene (ABS) copolymer, polycarbonates, polyethylene terephthalate (PET), and Cp polymeric particles being, preferably, derived from the recycling of waste.
[Revendication 4] Composition selon l’une des revendications 1 à 3, caractérisée en ce qu’elle comprend en outre, en tant que composant(s) additionnel(s),un ou plusieurs polymère(s) P2, de préférence choisi(s) parmi les plastomères et les thermoplastiques et, notamment, les élastomères thermoplastiques, en particulier choisis parmi les copolymères à blocs insaturés. [Claim 4] Composition according to one of Claims 1 to 3, characterized in that it further comprises, as additional component(s), one or more polymer(s) P2, preferably chosen ( s) from plastomers and thermoplastics and, in particular, thermoplastic elastomers, in particular chosen from unsaturated block copolymers.
[Revendication 5] Composition selon la revendication 4, caractérisée en ce que le(s) polymère(s) P2 est(sont) choisi(s) parmi les copolymères à blocs styrène-butadiène-styrène, de préférence sous forme ramifiée ou étoilée, le polypropylène atactique et le poly(éthylène acétate de vinyle). [Claim 5] Composition according to Claim 4, characterized in that the polymer(s) P2 is (are) chosen from styrene-butadiene-styrene block copolymers, preferably in branched or star-shaped form, atactic polypropylene and poly(ethylene vinyl acetate).
[Revendication 6] Composition selon la revendication 4 ou 5, caractérisée en ce que la masse de polymère(s) P2 représente de 5 à 25 %, de préférence de 5 à 20% et, de manière encore plus préférée, de 7 à 18% de la masse totale de la composition. [Claim 6] Composition according to Claim 4 or 5, characterized in that the mass of polymer(s) P2 represents from 5 to 25%, preferably from 5 to 20% and, even more preferably, from 7 to 18% of the total weight of the composition.
[Revendication 7] Composition selon l’une des revendications 1 à 6, caractérisée en ce que les particules inorganiques Ci sont des particules de carbonate de calcium, de carbonate de magnésium, d’hydroxyde de magnésium, de sulfate de calcium, de sulfate de baryum, de silice, d’argile, de talc, de mica, de wollastonite, de montmorillonite, de zéolite, d’alumine, d’oxyde de titane, d’oxyde de magnésium, d’oxyde de zinc ou de verre, les particules de carbonate de calcium étant préférées. [Claim 7] Composition according to one of Claims 1 to 6, characterized in that the inorganic particles Ci are particles of calcium carbonate, of magnesium carbonate, of magnesium hydroxide, of calcium sulphate, of barium, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide or glass, calcium carbonate particles being preferred.
[Revendication 8] Composition selon l’une des revendications 1 à 7 caractérisée en ce que la masse de particules inorganiques Ci représente 20 à 39%, de préférence de 25 à 37%, et de manière encore plus préférée de 27 à 34 % de la masse totale de la composition. [Claim 8] Composition according to one of Claims 1 to 7, characterized in that the mass of inorganic particles Ci represents 20 to 39%, preferably 25 to 37%, and even more preferably 27 to 34% of the total mass of the composition.
[Revendication 9] Composition selon l’une des revendications 1 à 8, caractérisée en ce que le D50 des particules polymériques Cp et/ou le D50 des particules inorganiques Ci appartien(nen)t à la gamme allant de 10 à 300 pm, de préférence à la gamme allant de 20 à 200 pm, et préférentiellement à la gamme allant de 30 à 150 pm. [Claim 9] Composition according to one of Claims 1 to 8, characterized in that the D50 of the polymeric particles Cp and/or the D50 of the inorganic particles Ci belong(n) to the range going from 10 to 300 μm, from preferably in the range going from 20 to 200 μm, and preferably in the range going from 30 to 150 μm.
[Revendication 10] Composition selon l’une des revendications 1 à 9, caractérisée en ce qu’elle comprend, voire est constituée de : [Claim 10] Composition according to one of Claims 1 to 9, characterized in that it comprises, or even consists of:
- de 21 à 40% m/m, de préférence de 26 à 38 % m/m, et de manière encore plus préférée de 28 à 35% m/m de charges C, constituées de particules inorganiques Ci et de particules polymériques Cp de polystyrène choc ou cristal, les particules polymériques Cp représentant de 1 à 10% m/m, de préférence 1 à 5% m/m, et de manière encore plus préférée de 1 à 3% m/m de la masse totale de la composition et les particules inorganiques Ci représentant de 20 à 39% m/m, de préférence de 25 à 37% m/m, et de manière encore plus préférée de 27 à 34% m/m de la masse totale de la composition ; - from 21 to 40% m/m, preferably from 26 to 38% m/m, and even more preferably from 28 to 35% m/m of fillers C, consisting of inorganic particles Ci and polymeric particles Cp of impact or crystal polystyrene, the Cp polymer particles representing from 1 to 10% m/m, preferably 1 to 5% m/m, and even more preferably from 1 to 3% m/m of the total mass of the composition and the inorganic particles Ci representing from 20 to 39% m/m, preferably from 25 to 37% m/m, and even more preferably from 27 to 34% m/m of the total mass of the composition;
- de 40 à 70% m/m, de préférence de 50 à 65% m/m, et de manière encore plus préférée de 55 à 65 % m/m de bitume ; - from 40 to 70% m/m, preferably from 50 to 65% m/m, and even more preferably from 55 to 65% m/m of bitumen;
- de 5 à 25% m/m, de préférence de 5 à 20% m/m, et de manière encore plus préférée de 7 à 18% m/m d’un ou plusieurs polymère(s) P2 tel(s) que défini(s) à la revendication 4 ou 5 ; les % m/m étant des % massiques par rapport à la masse totale de la composition. - from 5 to 25% m/m, preferably from 5 to 20% m/m, and even more preferably from 7 to 18% m/m of one or more polymer(s) P2 such as defined in claim 4 or 5; the % m/m being % by mass relative to the total mass of the composition.
[Revendication 11] Procédé de préparation d’une composition selon l’une des revendications 1 à 10, comprenant le mélange sous chauffage d’un ensemble comprenant : [Claim 11] Process for the preparation of a composition according to one of Claims 1 to 10, comprising mixing, under heating, an assembly comprising:
- du bitume, et - bitumen, and
- des charges C constituées de particules inorganiques Ci et de particules polymériques Cp de polystyrène choc ou cristal. - fillers C consisting of inorganic particles Ci and polymeric particles Cp of impact or crystal polystyrene.
[Revendication 12] Procédé selon la revendication 11 , caractérisé en ce que le mélange sous chauffage est réalisé à une température appartenant à la gamme allant de 100 à 220 °C, de préférence pendants minutes à 10 heures et/ou sous une agitation de 200 à 2000 tours/min. [Claim 12] Process according to claim 11, characterized in that the mixture under heating is carried out at a temperature belonging to the range going from 100 to 220°C, preferably during minutes to 10 hours and/or under an agitation of 200 at 2000 rpm.
[Revendication 13] Procédé selon la revendication 11 ou 12, caractérisé en ce que le mélange sous chauffage est mené sur un ensemble comprenant, de manière additionnelle, un ou plusieurs polymère(s) P2 choisi(s) parmi les plastomères et les thermoplastiques et, notamment, les élastomères thermoplastiques, en particulier choisis parmi les copolymères à blocs insaturés, et, de manière encore plus préférée, choisi(s) parmi les copolymères à blocs styrène-butadiène-styrène, de préférence sous forme ramifiée ou étoilée, le polypropylène atactique et le poly(éthylène acétate de vinyle). [Claim 13] Process according to Claim 11 or 12, characterized in that the mixing under heating is carried out on an assembly comprising, additionally, one or more polymer(s) P2 chosen from plastomers and thermoplastics and , in particular, thermoplastic elastomers, in particular chosen from unsaturated block copolymers, and, even more preferably, chosen from styrene-butadiene-styrene block copolymers, preferably in branched or star-shaped form, polypropylene atactic and poly(ethylene vinyl acetate).
[Revendication 14] Procédé selon la revendication 13, caractérisé en ce qu’il comprend l’introduction, dans le bitume, du(des)dit(s) polymère(s) P2, avant l’introduction dans le bitume des particules inorganiques Ci et des particules polymériques Cp de polystyrène choc ou cristal. [Claim 14] Process according to claim 13, characterized in that it comprises the introduction, into the bitumen, of the said polymer(s) P2, before the introduction into the bitumen of the inorganic particles Ci and Cp polymer particles of high impact or crystal polystyrene.
[Revendication 15] Procédé selon l’une des revendications 11 à 14, caractérisé en ce qu’il comprend l’introduction, dans le bitume, de particules inorganiques Ci qui présentent un D50 qui appartient à la gamme allant de 10 à 300 pm, de préférence à la gamme allant de 20 à 200 pm, et préférentiellement à la gamme allant de 30 à 150 pm et/ou de particules polymériques Cp de polystyrène choc ou cristal qui présentent un D50 qui appartient à la gamme allant de 10 à 300 pm, de préférence à la gamme allant de 20 à 200 pm, et préférentiellement à la gamme allant de 30 à 150 pm. [Claim 15] Process according to one of Claims 11 to 14, characterized in that it comprises the introduction, into the bitumen, of inorganic particles Ci which have a D50 which belongs to the range going from 10 to 300 μm, preferably in the range extending from 20 to 200 μm, and preferably in the range extending from 30 to 150 μm and/or Cp polymeric particles of impact or crystal polystyrene which have a D50 which belongs to the range extending from 10 to 300 μm , preferably in the range from 20 to 200 μm, and preferably in the range from 30 to 150 μm.
[Revendication 16] Membrane d’étanchéité, en particulier pour toiture, comprenant une couche formée d’une composition selon l’une des revendications 1 à 10. [Claim 16] Waterproofing membrane, in particular for roofing, comprising a layer formed from a composition according to one of Claims 1 to 10.
[Revendication 17] Membrane d’étanchéité, en particulier pour toiture, comprenant une composition selon l’une des revendications 1 à 10, venant imprégner, au moins pour partie, un matériau fibreux. [Claim 17] Waterproofing membrane, in particular for roofing, comprising a composition according to one of Claims 1 to 10, impregnating, at least in part, a fibrous material.
[Revendication 18] Membrane d’étanchéité selon la revendication 16 ou 17 se présentant sous la forme d’une structure multicouche. [Claim 18] Waterproofing membrane according to claim 16 or 17 in the form of a multilayer structure.
EP22705442.6A 2021-01-28 2022-01-28 Compositions for producing sealing membranes, and associated methods and membranes Pending EP4284878A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2100809A FR3119170B1 (en) 2021-01-28 2021-01-28 Compositions for producing waterproofing membranes, processes and associated membranes
PCT/FR2022/050161 WO2022162322A1 (en) 2021-01-28 2022-01-28 Compositions for producing sealing membranes, and associated methods and membranes

Publications (1)

Publication Number Publication Date
EP4284878A1 true EP4284878A1 (en) 2023-12-06

Family

ID=74871665

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22705442.6A Pending EP4284878A1 (en) 2021-01-28 2022-01-28 Compositions for producing sealing membranes, and associated methods and membranes

Country Status (5)

Country Link
US (1) US20240101827A1 (en)
EP (1) EP4284878A1 (en)
CA (1) CA3205587A1 (en)
FR (1) FR3119170B1 (en)
WO (1) WO2022162322A1 (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997030121A1 (en) * 1996-02-16 1997-08-21 Polyphalt Inc. Stabilized bituminous composition based on polymer in-situ blend
FR2882758B1 (en) 2005-03-04 2007-12-28 Axter Sa IMPROVED BITUMINOUS BINDER COMPRISING A REDUCED SBS FRACTION FOR SEALING AND SEALING MEMBRANE
CN103665899B (en) * 2013-12-06 2015-12-02 合肥工业大学 A kind of modifying asphalt base embedding agent and preparation method utilizing waste foam

Also Published As

Publication number Publication date
CA3205587A1 (en) 2022-08-04
US20240101827A1 (en) 2024-03-28
FR3119170A1 (en) 2022-07-29
FR3119170B1 (en) 2023-02-10
WO2022162322A1 (en) 2022-08-04

Similar Documents

Publication Publication Date Title
EP2459621B1 (en) Method for preparing cured asphalt/polymer compositions without a curing agent
EP1877491B1 (en) Bituminous products, the mixture thereof with aggregates and the use thereof
EP1917309A1 (en) Method for preparing bitumen base
JP2011510101A (en) Asphalt modifier composition with improved melting rate and modified asphalt produced using the same
CA2936469A1 (en) Bitumen/polymer composition having improved mechanical properties under cold conditions
EP0605377A2 (en) Composition for bituminous draining mixes
EP1184423B1 (en) Synthetic bitumen aqueous emulsions, preparation process and applications thereof
WO2022162322A1 (en) Compositions for producing sealing membranes, and associated methods and membranes
FR2774997A1 (en) BITUMINOUS COMPOSITIONS PRODUCED FROM THERMOPLASTIC POLYOLEFINS AND THEIR USES
EP3283571B1 (en) Clear binder and applications thereof
EP1794234B1 (en) Method for producing a polymer/bitumen compound, and polymer/bitumen and bitumen/polymer compounds obtained
WO2021019141A1 (en) Fluxed bitumen/polymer composition and method for preparing same
WO2020128313A1 (en) Coating comprising petroleum coke
WO2015173205A1 (en) Bituminous composition performing well at low temperature and at intermediate temperature
FR2944811A1 (en) PROCESS FOR THE PREPARATION OF A HOT SPRAY FOR OBTAINING COILS COMPRISING A REDUCED BINDER CONTENT
WO2023089281A1 (en) Bituminous composition comprising aluminium-based plastic waste, and methods and uses thereof
EP3891223B1 (en) Bituminous mastic, method for preparing same and uses thereof
EP3440130A1 (en) Method for preparing a bitumen/polymer composition with improved properties
WO2014174190A1 (en) Premix composition for bitumens
FR3131920A1 (en) Composition of clear binder and its applications for road surfaces and landscaping
CH694860A5 (en) Bituminous binder for hot mix for the implementation of pavement wearing hot and qu'enrobés made from such a bituminous binder.
CH694990A5 (en) Hot mix composition, useful for coating a road surface with reflective properties, comprises cullet and a bituminous binder comprising nitrogen compounds as agents to improve the adhesiveness; and a melting agent
WO2008142249A1 (en) Modified bitumen composition and methods for producing said composition
FR2613375A1 (en) PROCESS FOR THE PREPARATION OF A BITUMEN AND POLYMER-BASED BINDER
FR2922216A1 (en) Bitumen composition modified by adding an adipic acid, useful for the preparation of road coating and pavement sealing, comprises adipic acid

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230718

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)