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
  • 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 belongs to the field of bitumens and relates to fluxed heat-crosslinked bitumen / polymer compositions.
• the invention also relates to a process for preparing a fluxed bitumen / heat-crosslinked polymer composition.
• a subject of the invention is also the use of these compositions as road binders, in particular for the manufacture of surface coatings or for the preparation of mixes such as hot mixes, warm mixes, cold mixes such as for example cold-cast mixes or serious emulsions.
• the invention relates to the use of these compositions for the preparation of an interior or exterior coating, a membrane or an impregnation layer.
• Bitumen is a material used in very large quantities as a building material. Combined with aggregates, fines or reinforcements, bitumen is used, for example, in the manufacture of road pavements and waterproofing screeds on roofs or in retention basins. Bitumen is generally in the form of a black material having a high viscosity, even solid at room temperature.
• bitumen Due to the high viscosity of bitumen at room temperature, its processing is problematic.
• Several techniques aimed at reducing the viscosity of bitumen have been developed, either by heating, or by putting it in the form of an emulsion, or even by mixing it with fluxing agents, also called fluxants.
• Fluxed bitumens are compositions of bitumen (s) whose viscosity has been lowered by the addition of volatile solvents, the fluxants.
• the addition of flux to a bitumen enables processing temperatures to be achieved lower than that of the same non-fluxed bitumen.
• fluidized bituminous binders and the streamed bituminous binders are grouped together in one and the same category, the terms “flowed” and “fluidized” thus being considered as synonyms.
• fluxed bitumens are obtained by mixing, hot, bituminous binder and flux.
• fluxes of petroleum origin fluxes of synthetic origin and fluxes of plant origin are known.
• Much work has focused on improving the mechanical, elastic and / or rheological properties of bituminous compositions, in particular by adding different polymers.
• the copolymers of styrene and a conjugated diene and, in particular, of styrene and butadiene or of styrene and isoprene are known to be particularly effective because they mix very easily in bitumens and their impart excellent mechanical properties and in particular very good elastic properties.
• bitumen / polymer compositions are used for the preparation of binders for coatings of various surfaces and, in particular, as road surface coatings, provided that these compositions in combination exhibit a certain number of mechanical characteristics. Optimized mechanical characteristics such as elastic properties are particularly crucial for applications in road surfaces.
• Application FR 3 050 210 describes a process for preparing a bitumen / polymer composition exhibiting improved ductility before and after aging, this process comprising contacting a bitumen base, an elastomer of SBS type and a sulfur-containing crosslinking agent.
• bitumen / polymer compositions containing a bitumen, from 0.3% to 20% by weight of at least one primary polymer chosen from certain elastomers and plastomers and from 0.01% to 12% by weight of 'at least one adjuvant of olefinic polymer type bearing epoxy or COOH groups.
• the polymers used in this document are different from those of the invention.
• the role of the adjuvant is to prevent demixing between the bituminous phase and the polymer phase, which improves the storage stability of the composition.
• bitumen / polymer compositions comprising an olefinic polymer bearing epoxy groups, an acid adjuvant and an elastomer crosslinkable with sulfur.
• the compositions illustrated using an SB copolymer are crosslinked with sulfur and do not include a fluxing agent.
• bitumen / polymer compositions comprising an olefinic polymer bearing epoxy groups, an acid adjuvant and an elastomer crosslinkable with sulfur.
• the compositions illustrated using an SB copolymer are crosslinked with sulfur and do not include a fluxing agent.
• bitumen / polymer compositions exhibiting improved cold mechanical properties and comprising: - a first bitumen base having an intrinsic stability S greater than 2.5 and / or a peptization rate Sa greater than 0.60,
• bitumen base having an intrinsic stability S less than or equal to 2.50 and / or a peptization rate Sa less than or equal to 0.60
• compositions illustrated are crosslinked with sulfur and use an SBS block terpolymer.
• bitumen / polymer compositions prepared from heat-crosslinkable polymers have been proposed, these copolymers having the advantage of not requiring the addition of sulfur-containing agents for their crosslinking.
• Application WO2008 / 137394 describes a process for preparing a bituminous binder composition modified with an elastomer in the absence of crosslinking agents by heating a bitumen to a temperature of 160 ° C to 221 ° C, adding a block copolymer composition and agitation to form a homogeneous mixture.
• the block copolymer compositions used comprise one or more block copolymers having at least one monovinylaromatic block, at least one polybutadiene block having a vinyl content of less than 15 percent by moles and at least one polybutadiene block having a content of vinyl more than 25 mole percent.
• the Applicant has unexpectedly discovered that it is possible to formulate bitumen / heat-crosslinkable polymer compositions and heat-crosslinked bitumen / polymer compositions which, when they are flowed, exhibit a satisfactory viscosity range, even after prolonged storage.
• the Applicant has sought a system which is effective in all kinds of bitumens and which is not limited to an application to very specific bitumens. It has also sought to develop compositions which have good mechanical properties, and in particular good elastic properties.
• the invention relates first of all to a bitumen / polymer composition
• a bitumen / polymer composition comprising at least:
• each S independently represents a block based on monovinyl aromatic hydrocarbon monomers and each B independently represents a block based on butadiene monomers
• heat-crosslinkable copolymer of formula S-B and the heat-crosslinkable copolymer of formula S-B-S are present in a mass ratio greater than 3: 2 and which may range up to 1: 0.
• the invention relates more particularly to a bitumen / heat-crosslinked and fluxed polymer composition obtained by a process comprising:
• each S independently represents a block based on monovinyl aromatic hydrocarbon monomers and each B independently represents a block based on butadiene monomers
• the heat-crosslinkable copolymer of formula SB and the heat-crosslinkable copolymer of formula SBS being present in a mass ratio greater than 3: 2 and possibly ranging up to 1: 0,
• bitumen / polymer composition comprising less than 6 ppm of sulfur-containing crosslinking agent, 2) mixing the bituminous composition with at least one fluxing agent.
• each S represents a polystyrene block.
• the heat-crosslinkable block copolymer of formula S-B-S has a vinyl group content greater than or equal to 25% by moles, relative to the total number of moles of the first and of the second elastomer, preferably greater than or equal to 28% by moles.
• the S blocks of the heat-crosslinkable block copolymer of formula SBS together represent from 15% to 50% by moles of the total number of moles of the first and second elastomers, preferably from 15% to 30% by moles, plus preferably from 15% to 25% by moles, and even more preferably from 15% to 20% by moles.
• the heat-crosslinkable block copolymer of formula S-B has a content of vinyl groups ranging from 9% to 35% by moles, relative to the total number of moles of copolymer S-B, preferably ranging from 10% to 30% by moles.
• the composition according to the invention comprises from 0.5% to 20% by weight of elastomer relative to the total weight of the composition, preferably from 1 to 15% by weight, more preferably from 2% to 10 % by mass, and even more preferably from 3% to 6% by mass.
• the composition according to the invention comprises from 0.05% to 2.5% by mass of olefinic polymer adjuvant functionalized with at least one epoxy group, relative to the total mass of the composition, preferably from 0.15 at 2% by mass.
• the olefinic polymer adjuvant functionalized with at least one epoxy group is chosen from the group consisting of:
• copolymers preferably random, of ethylene and of a monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 50% to 99.7% by weight of ethylene;
• terpolymers preferably random, of ethylene, of a monomer A chosen from vinyl acetate and C 1 to O Q alkyl acrylates or methacrylates and of a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 0.5% to 40% by weight of units derived from monomer A and, from 0.5% to 15% by weight of units derived from monomer B , the remainder being formed from units derived from ethylene; and
• the olefinic polymer adjuvant functionalized with at least one epoxy group is chosen from random terpolymers of ethylene, of a monomer A chosen from C 1 to C 4 alkyl acrylates or methacrylates and of a B monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 0.5% to 40% by weight of units derived from monomer A and, from 0.5% to 15% by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.
• the olefinic polymer adjuvant functionalized with at least one epoxy group is chosen from the random terpolymers of ethylene, of a monomer A chosen from among methyl acrylate, ethyl acrylate and ethyl acrylate. butyl and of a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 0.5% to 40% by mass of units derived from monomer A and from 0.5% to 15% by mass of units derived from monomer B, the remainder being formed from units derived from ethylene.
• composition according to the invention further comprises at least one fluxing agent, preferably chosen from fluxing agents of plant origin, hydrocarbon fluxing agents and mixtures thereof.
• the invention also relates to an asphalt characterized in that it comprises at least one heat-crosslinked and fluxed bitumen / polymer composition as defined above and in detail below, and mineral and / or synthetic fillers.
• the subject of the invention is also a bituminous mix characterized in that it comprises at least one heat-crosslinked and fluxed bitumen / polymer composition as defined above and in detail below, aggregates, and optionally mineral fillers and / or synthetic.
• the invention further relates to the use of at least one heat-crosslinked and fluxed bitumen / polymer composition as defined above and in detail below for preparing a surface coating, a hot mix, a warm mix, a cold mix, a cold mix, a serious emulsion, said bitumen / heat-crosslinked polymer composition being combined with aggregates and / or recycling mills.
• the invention also relates to the use of at least one heat-crosslinked and fluxed bitumen / polymer composition as defined above and in a manner detailed below, to prepare a waterproofing coating, membrane or impregnation layer.
• the invention also relates to a process for manufacturing bituminous mixes comprising at least one road binder and aggregates or aggregates of recycled bituminous mixes, the road binder being in the form of a bitumen / heat-crosslinked polymer composition such as flowable. as defined above and in detail below.
• this method comprises at least the steps of:
• the invention also relates to a process for preparing a surface coating, a hot mix, a warm mix, a cold mix, a cold mix or a serious emulsion, said process comprising the use of a heat-crosslinked and fluxed bitumen / polymer composition as defined above and in detail below, in particular this process comprises the mixing of at least one heat-crosslinked and fluxed bitumen / polymer composition such as as defined above and in detail below with aggregates and / or recycling mills
• the invention finally relates to a method of manufacturing a waterproofing membrane, a vibration damping membrane, d 'a thermal and / or sound insulation membrane, a surface coating, carpet tiles, an impregnation layer, this process comprising the use of a bitumen / heat-crosslinked and fluxed polymer composition such as as defined above and in detail below.
• the invention also relates to a method of manufacturing road, pavement, sidewalk, road, urban development, soil, waterproofing or structural coverings, this method comprising the application of minus a heat-crosslinked and fluxed bitumen / polymer composition, or an asphalt composition, or a bituminous mix as defined above and in detail below.
• the Applicant has discovered that the use of a specific combination of elastomers, taken in combination with a particular polymer adjuvant, allows the preparation of heat-crosslinkable bitumen / polymer compositions and of compositions. heat-crosslinked bitumen / polymer which can be fluxed by adding a conventional fluxing agent.
• the Applicant has discovered that the combination of polymers according to the invention makes it possible to obtain bitumen / polymer compositions which, when they are fluxed, are stable in storage.
• compositions according to the invention moreover exhibit good mechanical properties and in particular good elastic properties. This observation is not limited to any particular class of bitumens.
• bitumen / polymer composition of the invention has the advantage of being economical compared to a bitumen / polymer composition based on the same SB and SBS block copolymers and without an adjuvant, in particular without an olefinic polymer adjuvant functionalized by at least one epoxy group.
• the addition of the olefinic polymer adjuvant functionalized with at least one epoxy group, in a small amount, makes it possible to significantly reduce the amount of block copolymer used, with equivalent mechanical properties.
• bitumen / polymer composition and “bitumen / polymer binder” represent the same type of composition and are used interchangeably.
• bitumen / heat-crosslinkable polymer composition denotes the composition directly obtained by mixing bitumen at room temperature with the various polymers.
• bitumen / heat-crosslinkable polymer composition has not undergone any heat treatment.
• bitumen / heat-crosslinked polymer composition denotes the composition resulting from the thermal crosslinking treatment of the mixture comprising at least the bitumen and the polymers.
• the term “flowed composition” or “fluidized composition” means a bituminous composition whose viscosity has been reduced by mixing with an oil of vegetable, synthetic or petroleum origin, optionally in the form of a mixture. .
• the oil used for the fluxing of a bituminous composition is hereinafter designated by the expression “fluxing agent” or also “fluidizing agent”.
• the expression “consists essentially of” followed by one or more characteristics, means that may be included in the process or the material of the invention, in addition to the components or steps explicitly listed, components or steps which do not significantly modify the properties and characteristics of the invention. Bitumens:
• the invention relates to bitumens. These can be formed by one or more bitumen bases.
• bitumen any bituminous compositions consisting of one or more bitumen bases and optionally comprising one or more chemical additives, said compositions being intended for road application or industrial application.
• bitumen bases that can be used according to the invention, there may be mentioned first of all bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or bituminous sands and bitumens from the refining of crude oil. .
• the bitumen bases according to the invention are advantageously chosen from bitumen bases obtained from the refining of crude oil.
• the bitumen bases can be chosen from bitumen bases or mixtures of bitumen bases originating from the refining of crude oil, in particular bitumen bases containing asphaltenes or pitches.
• Bitumen bases can be obtained by conventional processes for manufacturing bitumen bases in a refinery, in particular by direct distillation and / or vacuum distillation of petroleum.
• bitumen bases can optionally be vis-reduced and / or deasphalted and / or air-rectified. It is common practice to perform vacuum distillation of atmospheric residues from atmospheric distillation of crude oil. This manufacturing process therefore corresponds to the succession of atmospheric distillation and vacuum distillation, the feed supplying the vacuum distillation corresponding to the atmospheric residues. These vacuum residues from the vacuum distillation tower can also be used as bitumens. It is also common to inject air into a feed usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from the distillation of petroleum. This process makes it possible to obtain a blown, or semi-blown or oxidized or air-rectified or partially air-rectified base.
• bitumen bases obtained by the refining processes can be combined with each other to obtain the best technical compromise.
• the bitumen base can also be a recycling bitumen base.
• Bitumen bases can be hard grade or soft grade bitumen bases.
• the operation is carried out at manufacturing temperatures of between 100 ° C and 200 ° C, preferably between 140 ° C and 200 ° C, and with stirring for a period of d '' at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours.
• production temperature is understood to mean the heating temperature of the bitumen base (s) before mixing as well as the mixing temperature. The temperature and duration of heating vary according to the quantity of bitumen used and are defined by standard NF EN 12594.
• the blown bitumens can be manufactured in a blowing unit, by passing a flow of air and / or oxygen through a starting bituminous base.
• This operation can be carried out in the presence of 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 periods, typically between 30 minutes and 2 hours, continuously or in batches. The duration and the blowing temperature are adjusted according to the properties targeted for the blown bitumen and according to the quality of the starting bitumen.
• Bitumen can also be recycled bitumen.
• the bitumens can be hard grade or soft grade bitumens.
• the bitumens which can be used according to the invention 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, more preferably from 10 to 120 1 / 10 mm.
• the so-called “needle penetrability” measurement is carried out by means of a standardized test NF EN 1426 at 25 ° C (P 25 ).
• This penetrability characteristic is expressed in tenths of a millimeter (dmm or 1/10 mm).
• the needle penetrability, measured at 25 ° C, according to the standardized test NF EN 1426 represents the measurement of the penetration in a bitumen sample, after a time of 5 seconds, of a needle whose weight with its support is 100 g.
• the standard NF EN 1426 replaces the approved standard NF T 66-004 of December 1986 with effect from December 20, 1999 (decision of the Director General of AFNOR dated November 20, 1999).
• the composition comprises, before fluxing, from 70 to 99.5% by mass of bitumen, preferably from 75 to 99% by mass, more preferably from 80% to 98% by mass, even more preferably from 85 to 98% by mass, and advantageously from 90 to 98% by mass, relative to the total mass of the bitumen / polymer composition.
• the bitumen / fluxed polymer composition according to the invention comprises from 35 to 99% by mass of bitumen, preferably from 45% to 98% by mass, more preferably from 65% to 97% by mass, even more preferably from 75% to 90% by mass, relative to the total mass of the bitumen / polymer composition fluxed.
• the olefinic polymer builder functionalized with at least one epoxy group is preferably chosen from the group consisting of (a) ethylene / glycidyl (meth) acrylate copolymers; (b) ethylene / monomer A / monomer B terpolymers and (c) mixtures of these copolymers.
• the ethylene / glycidyl (meth) acrylate copolymers are advantageously chosen from copolymers, preferably random, of ethylene and of a monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising 50 % to 99.7% by mass, preferably from 60% to 95% by mass, more preferably 60% to 90% by mass of ethylene.
• the terpolymers are advantageously chosen from terpolymers, preferably random, of ethylene, of a monomer A and of a B monomer.
• Monomer A is chosen from vinyl acetate and C 1 to C 6 alkyl acrylates or methacrylates, preferably chosen from C 1 to C 6 alkyl acrylates or methacrylates, more preferably from acrylates or C1-C4 alkyl methacrylates, even more preferably from C1-C4 alkyl acrylates.
• the monomer A is chosen from methyl acrylate, ethyl acrylate and butyl acrylate.
• the monomer A is ethyl acrylate.
• the monomer A is chosen from methyl acrylate and butyl acrylate.
• Monomer B is chosen from glycidyl acrylate and glycidyl methacrylate.
• the monomer B is glycidyl methacrylate.
• the ethylene / monomer A / monomer B terpolymers comprise from 0.5% to 40% by weight, preferably from 5 to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and, from 0 5% to 15% by mass, preferably from 2.5% to 15% by mass of units derived from monomer B, the remainder being formed from units derived from ethylene;
• the olefinic polymer builder functionalized with at least one epoxy group may consist of a mixture of two or more copolymers chosen from categories (a) and (b).
• the olefinic polymer adjuvant functionalized with at least one epoxy group is preferably chosen from the terpolymers (b) ethylene / monomer A / monomer B described above and from mixtures (c) comprising them.
• the olefinic polymer additive functionalized by at least one epoxy group is advantageously chosen from the terpolymers (b) ethylene / monomer A / monomer B described above and from the mixtures (c) in which the terpolymers (b) represent at least 50% by mass relative to the total mass of the mixture, preferably at least 75% by mass, even better at least 90% by mass.
• the olefinic polymer adjuvant functionalized with at least one epoxy group is chosen from random terpolymers of ethylene, of a monomer A chosen from C 1 to C 6 alkyl acrylates or methacrylates and of a B monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 0.5% to 40% by weight, preferably from 5 to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and , from 0.5% to 15% by weight, preferably from 2.5% to 15% by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.
• the terms “molecular weight” or “molecular mass” or “average molar mass” are expressed in g. mol 1 .
• the molecular masses mentioned in the description and the claims can be measured by gel permeation chromatography (GPC) (or SEC for "S / ' ze Exclusion Chromatography” in English).
• GPC is a liquid chromatography method in which polymers are separated according to their hydrodynamic volume, which is then converted to weight average molecular weight (Mw) and / or number average molecular weight (Mn).
• Mw weight average molecular weight
• Mn number average molecular weight
• the CPG with universal calibration uses 2 detectors: a detector of the dRI type (Differential refractive index) and a detector of the dP type (Differential viscometer, sensitive to the molar mass).
• the molar mass obtained is also a relative molar mass, and
• the triple detection CPG has 3 detectors: an RI detector (refractive index), a light scattering detector and a viscosity detector (dP).
• the molecular weight values are obtained directly (without requiring a curve calibration) by processing the results obtained from each of the detectors.
• the molar masses obtained by triple detection GPC are absolute molar masses.
• the molecular masses, determined by GPC with conventional detection are measured according to a polystyrene calibration.
• the molecular mass of the polymers measured by GPC with conventional detection is thus a molecular mass in styrene equivalents.
• the detector used is a dRI (difference in refractive index) detector.
• the number-average molecular mass (Mn) of the olefinic polymer adjuvant functionalized with at least one epoxy group ranges from 5,000 to 50,000 g. . mol 1 , more preferably from 10,000 to 40,000 g. mol 1 , and even more preferably from 25,000 to 40,000 g. mol 1 .
• the weight average molecular mass (Mw) of the olefinic polymeric adjuvant functionalized with at least one epoxy group ranges from 10,000 to 250,000 g. . mol 1 , more preferably from 50,000 to 200,000 g. mol 1 , and even more preferably from 10,000 to 150,000 g. mol 1 .
• the number-average molecular mass (Mn) of the olefinic polymer adjuvant functionalized with at least one epoxy group, determined by triple detection gel permeation chromatography is greater than or equal to 20,000 g. mol 1 , preferably greater than or equal to 30,000 g. mol 1 , even more preferably greater than or equal to 40,000 g. mol 1 , and advantageously greater than or equal to 45,000 g. mol 1 .
• the number-average molecular mass (Mn) of the olefinic polymer adjuvant functionalized with at least one epoxy group ranges from 20,000 to 200,000 g. mol 1 , preferably from 30,000 to 180,000 g. mol 1 , even more preferably from 40,000 to 150,000 g. mol 1 , and advantageously from 45,000 to 120,000 g. mol 1 .
• the weight-average molecular mass (Mw) of the olefinic polymer adjuvant functionalized with at least one epoxy group, determined by triple detection gel permeation chromatography is greater than or equal to 60,000 g. mol 1 , preferably greater than or equal to 65,000 g. mol 1 , even more preferably greater than or equal to 70,000 g. mol 1 , and advantageously greater than or equal to 75,000 g. mol 1 .
• the weight average molecular weight (Mw) of the olefinic polymer adjuvant functionalized with at least one epoxy group, determined by triple detection gel permeation chromatography ranges from 60,000 to 200,000 g. mol 1 , preferably 65,000 to 190,000 g. mol 1 , even more preferably from 70,000 to 180,000 g. mol 1 , and advantageously from 75,000 to 170,000 g. mol 1 .
• the polydispersity index of the olefinic polymer adjuvant functionalized with at least one glycidyl group, determined by triple detection gel permeation chromatography is less than or equal to 3, preferably less than or equal to 2.5, more preferably less than or equal to 2.0, and advantageously less than or equal to 1.8.
• the polydispersity index of the olefinic polymer adjuvant functionalized with at least one glycidyl group ranges from 0.5 to 3.0, preferably from 0.8 to 2.5, more preferably from 1.0 to 2.0, and advantageously from 1.2 to 1.8.
• the olefinic polymer adjuvant functionalized with at least one glycidyl group comprises, on average, at least 500 ethylene units per macromolecule, preferably at least 800 ethylene units, more preferably at least 1000 ethylene units, even more preferably at least 1200 ethylene units, and advantageously at least 1250 ethylene units.
• the olefinic polymer adjuvant functionalized with at least one glycidyl group comprises, on average, from 500 to 10,000 ethylene units per macromolecule, preferably from 800 to 5,000 ethylene units, more preferably from 1,000 to 4,000 ethylene units , even more preferably from 1200 to 3500 ethylene units, and advantageously from 1250 to 3400 ethylene units.
• the olefinic polymer adjuvant functionalized with at least one glycidyl group comprises, on average, at least 30 alkyl (meth) acrylate units per macromolecule, preferably at least 50 alkyl (meth) acrylate units, more preferably at least at least 70 alkyl (meth) acrylate units, even more preferably at least 90 alkyl (meth) acrylate units, and advantageously at least 95 alkyl (meth) acrylate units.
• the olefinic polymer adjuvant functionalized with at least one glycidyl group comprises, on average, from 30 to 500 alkyl (meth) acrylate units per macromolecule, preferably from 50 to 400 alkyl (meth) acrylate units, more preferably from 70 to 300 alkyl (meth) acrylate units, even more preferably from 90 to 250 alkyl (meth) acrylate units, and advantageously from 95 to 200 alkyl (meth) acrylate units.
• the olefinic polymer adjuvant functionalized with at least one glycidyl group comprises, on average, at least 15 glycidyl (meth) acrylate units per macromolecule, preferably at least 20 glycidyl (meth) acrylate units.
• the olefinic polymer adjuvant functionalized with at least one glycidyl group comprises, on average, from 15 to 200 glycidyl (meth) acrylate units per macromolecule, preferably from 15 to 150 glycidyl (meth) acrylate units, more preferably from 20 to 125 glycidyl (meth) acrylate units, even more preferably from 20 to 100 glycidyl (meth) acrylate units, and advantageously from 20 to 90 glycidyl (meth) acrylate units.
• the average mass of the ethylene units present in one mole of olefinic polymer adjuvant functionalized with at least one glycidyl group is greater than or equal to 15,000 g, more preferably greater than or equal to 20,000 g, even more preferably greater than or equal to to 25,000g, advantageously greater than or equal to 30,000g, and more advantageously greater than or equal to 35,000 g.
• the average mass of ethylene units present in one mole of olefinic polymer adjuvant functionalized with at least one glycidyl group ranges from 15,000 to 200,000 g, more preferably from 20,000 to 150,000 g, even more preferably from 25,000 to 100 000 g, preferably 30,000 to 90,000 g, and more preferably 35,000 to 88,000 g.
• the average mass of the alkyl (meth) acrylate units present in one mole of olefinic polymer adjuvant functionalized with at least one glycidyl group is greater than or equal to 3,500 g, more preferably greater than or equal to 5,000 g, still more preferably greater than or equal to 7,500 g, and advantageously greater than or equal to 9500 g.
• the average mass of the alkyl (meth) acrylate units present in one mole of olefinic polymer adjuvant functionalized with at least one glycidyl group ranges from 3,500 to 50,000 g, more preferably from 5,000 to 25,000 g, even more preferably from 7,500 to 20,000 g, and advantageously from 9,500 to 19,000 g.
• the average mass of the glycidyl (meth) acrylate units present in one mole of olefinic polymer adjuvant functionalized with at least one glycidyl group is greater than or equal to 1,500 g, more preferably greater than or equal to 2,000 g, even more preferably greater than or equal to 2,500 g, advantageously greater than or equal to 2,750 g, and more advantageously greater than or equal to 2,900 g.
• the average mass of the glycidyl (meth) acrylate units present in one mole of olefinic polymer adjuvant functionalized with at least one glycidyl group ranges from 1,500 to 20,000 g, more preferably from 2,000 to 17,500 g, even more preferably from 2,500 to 15,000 g, advantageously from 2,750 to 12,500 g, and more advantageously from 2,900 to 12,000 g.
• the content of olefinic polymer adjuvant functionalized by at least one epoxy group in the bitumen / polymer composition before fluxing is preferably from 0.05 to 2.5% by mass relative to the total mass of the bitumen / polymer composition. , more preferably from 0.15 to 2% by mass, even more preferentially from 0.2 to 1% by mass, even more preferentially from 0.4 to 1% by mass, even more preferably from 0.4 to 0.8 % by mass.
• the bitumen / fluxed polymer composition comprises from 0.025 to 2.5% by mass of olefinic polymer adjuvant functionalized with at least one epoxy group, more preferably from 0.1 to 2% by mass, even more preferably from 0.15 at 1% by mass, and advantageously from 0.3 to 0.8% by mass, relative to the total mass of the bitumen / polymer composition fluxed.
• the crosslinked and fluxed bituminous composition according to the invention comprises at least:
• each S independently represents a block based on monovinyl aromatic hydrocarbon monomers and each B represents a block based on butadiene monomers.
• the copolymer of formula S-B and the copolymer of formula S-B-S are present in the composition according to the invention in a mass ratio greater than 3: 2 and which may range up to 1: 0.
• block is meant within the meaning of the invention a polymer chain obtained by the polymerization of one or more monomers of the same chemical nature.
• the monovinylaromatic hydrocarbon monomers from which the S blocks of the heat-crosslinkable block copolymers defined above are derived can independently be any monovinylaromatic hydrocarbon compound known for use in the preparation of block copolymers such as: styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene or mixtures thereof.
• the blocks based on butadiene B monomers entering into the composition of the block copolymers mentioned above are based on butadiene monomers which are practically pure or comprising minor proportions, up to 10% by weight, of structurally related conjugated dienes.
• the polybutadienes consist purely of units obtained from butadiene monomers.
• the bituminous composition according to the invention comprises at least a first elastomer chosen from copolymers with heat-crosslinkable block of formula S-B. According to a particular embodiment, the composition according to the invention comprises several elastomers chosen from copolymers with heat-crosslinkable block of formula S-B.
• the monovinyl aromatic hydrocarbon compound from which the S block of the block copolymer of formula SB is derived is styrene which can be used as a substantially pure monomer or as a major component in mixtures with minor proportions of one or more several other vinyl aromatic monomers of related structure, such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene.
• the styrene is used alone or as a mixture with at most 10% by weight of one or more other vinyl aromatic monomers, relative to the total weight of the monomers of the S block.
• the use of substantially pure styrene is particularly preferred.
• the heat-crosslinkable block copolymer of formula SB used in the present invention has an average molecular mass Mw, measured by gel permeation chromatography with conventional detection with a polystyrene standard, ranging from 40,000 to 500,000 g. mol 1 .
• the heat-crosslinkable block copolymer of formula SB has an average molecular mass Mw, measured by gel permeation chromatography with conventional detection with a polystyrene standard, of less than or equal to 400,000 g. mol 1 , more preferably less than or equal to 250,000 g. soft ⁇ even more preferably less than or equal to 200,000 g. mol 1 and advantageously less than or equal to 150,000 g. mol 1 .
• the heat-crosslinkable block copolymer of formula SB has a weight-average molecular mass (Mw), measured by gel permeation chromatography with conventional detection with a polystyrene standard, of greater than or equal to 50,000 g. mol 1 , more preferably greater than or equal to 65,000 g. mol 1 , even more preferably greater than or equal to 75,000 g. mol 1 , and advantageously greater than or equal to 100,000 g. mol 1 .
• Mw weight-average molecular mass
• the heat-crosslinkable block copolymer of formula SB has a mass average molecular mass (Mw), measured by triple detection gel permeation chromatography, ranging from 40,000 to 200,000 g. mol 1 , more preferably from 50,000 to 100,000 g. mol 1 , even more preferably from 60,000 to 90,000 g. mol 1 , advantageously from 65,000 to 80,000 g. mol 1 .
• Mw mass average molecular mass
• the contents of vinyl groups described below refer to the final copolymers (copolymer of formula S-B, of formula S-B-S or their mixtures) and not to the monomers used for their synthesis.
• the contents of vinyl groups defined below do not take into account the vinyl groups which may be present in the precursor monomers but which have reacted during the polymerization reaction. In particular, they do not take into account the vinyl groups present in the monovinyl aromatic monomers which have reacted to form the various S blocks.
• the content of vinyl groups characterizes only the vinyl groups present in the B blocks due to the polymerization of 1, 3-butadiene according to a 1, 2-addition mechanism.
• the heat-crosslinkable block copolymer of formula S-B has a content of vinyl groups greater than or equal to 9% by moles, relative to the total number of moles of copolymer S-B, preferably greater than or equal to 10% by moles.
• the heat-crosslinkable block copolymer of formula SB has a content of vinyl groups of less than or equal to 35% by moles, relative to the total number of moles of SB copolymer, more preferably less than or equal to 30% by moles.
• the block B of the block copolymer of formula SB has a content of vinyl groups ranging from 5% to 50% by mass, relative to the total mass of condensed polybutadiene units present in the block B, preferably 10%. at 40% by mass, more preferably from 15% to 30% by mass.
• the units obtained by the polymerization of 1, 3 butadiene according to a mechanism of 1, 2-addition or according to a mechanism of 1, 4-addition have the same molar mass.
• the contents of vinyl groups present in block B expressed in mass or in moles are equivalent.
• the block B of the block copolymer of formula SB has a content of vinyl groups ranging from 5% to 50% by moles, relative to the total amount of condensed polybutadiene units present in the block B, preferably 10%. at 40% by moles, more preferably from 15% to 30% by moles.
• block B of the block copolymer of formula SB has a glass transition temperature T v (in English T g for “glass transition”), determined by differential scanning calorimetry (or DSC in English for “Differential Scanning Calorimetry”) , less than or equal to -70 ° C, preferably less than or equal to -75 ° C.
• the block copolymer of formula SB has a glass transition temperature T v (in English T g for “glass transition”), determined by differential scanning calorimetry (or DSC in English for “Differential Scanning Calorimetry”), ranging from -100 ° C to -70 ° C, preferably from -90 to - 75 ° C.
• the block S of the block copolymer of formula SB represents from 5% to 50% by moles, relative to the total amount of moles of copolymer of formula SB, preferably from 10% to 30% by moles, even more preferably from 12% to 25% by moles, and advantageously from 14% to 20% by moles.
• the content of monovinyl aromatic hydrocarbon (advantageously styrene) in the heat-crosslinkable block copolymer of formula SB ranges from 5% to 40% by mass, preferably from 10% to 35% by mass, more preferably from 20% to 30% by mass, relative to the total mass of the copolymer of formula SB.
• the block copolymer of formula SB is in an essentially non-hydrogenated form. Such copolymers are known to those skilled in the art. Mention may be made, by way of example, of the heat-crosslinkable block copolymers sold by the company Dynasol under the reference Solprene® 1205.
• the heat-crosslinkable block copolymer of formula SB represents at least 60% by mass of the elastomers present in the composition, more preferably at least 70% by mass, even more preferably at least 90% by mass, and advantageously at least 95% en masse.
• the bitumen / polymer composition before fluxing comprises from 0.5 to 20% by mass of heat-crosslinkable block copolymer of formula SB relative to the total mass of the bitumen / polymer composition, more preferably from 1% to 15% by weight, even more preferably from 2% to 10% by weight, even more preferably from 3% to 6% by weight.
• the bitumen / fluxed polymer composition according to the invention comprises from 0.25% to 20% by weight of heat-crosslinkable block copolymer of formula SB relative to the total weight of the bitumen / fluxed polymer composition, more preferably from 0 , 5% to 15% by weight, even more preferably from 1% to 10% by weight, even more preferably from 2% to 5.5% by weight.
• bituminous composition according to the invention can also comprise at least one second elastomer chosen from the heat-crosslinkable block copolymers of formula
• the composition according to the invention comprises several elastomers chosen from copolymers with heat-crosslinkable block of formula S-B-S.
• the monovinyl aromatic hydrocarbon compound from which the S blocks of the block copolymer of formula SBS are derived is styrene which can be used as a substantially pure monomer or as a major component in mixtures with minor proportions of another.
• structurally related vinyl aromatic monomer such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene.
• the styrene is used alone or as a mixture with at most 10% by weight of one or more other vinyl monomers. aromatic, relative to the total weight of the monomers of the S block.
• the use of substantially pure styrene is particularly preferred.
• the heat-crosslinkable copolymer of formula SBS is chosen from copolymers in which the S blocks together represent at least 15% by moles of the total number of moles of the heat-crosslinkable block copolymer of formula SBS, said heat-crosslinkable block copolymers of formula SBS have a weight average molecular weight ranging from 40,000 to 500,000 g. mol 1 and have a vinyl group content greater than or equal to 20% by moles, relative to the total number of moles of the heat-crosslinkable block copolymer.
• the heat-crosslinkable block copolymer of formula SBS exhibits a weight average molecular mass (Mw), measured by gel permeation chromatography with conventional detection with a polystyrene standard, of less than or equal to 400,000 g. mol 1 , more preferably less than or equal to 300,000 g.mol 1 , even more preferably less than or equal to 250,000 g.mol 1 .
• Mw weight average molecular mass
• the heat-crosslinkable block copolymer of formula SBS has a weight-average molecular mass (Mw), measured by gel permeation chromatography with conventional detection with a polystyrene standard, greater than or equal to 50,000 g.mol 1 , more preferably greater than or equal to 65,000 g.mol 1 , even more preferably greater than or equal to 75,000 g.mol 1 , and advantageously greater than or equal to 100,000 g.mol 1 .
• Mw weight-average molecular mass
• the heat-crosslinkable block copolymer of formula SBS has a weight-average molecular mass (Mw), measured by triple-detection gel permeation chromatography, ranging from 40,000 to 200,000 g.mol 1 , more preferably from 50,000 to 175,000 g.mol 1 , even more preferably from 60,000 to 150,000 g.mol 1 , advantageously from 80,000 to 130,000 g.mol 1 .
• Mw weight-average molecular mass
• the heat-crosslinkable block copolymer of formula SBS has a content of vinyl groups greater than or equal to 20% by moles, relative to the total number of moles of the SBS copolymer, preferably greater than or equal to 25% by moles, even more preferably greater than or equal to 28% by moles.
• the heat-crosslinkable block copolymer of formula SBS has a content of vinyl groups less than or equal to 50% by moles, relative to the total number of moles of SBS copolymer, more preferably less than or equal to 40% by moles, and again more preferably less than or equal to 35% by moles.
• the block B of the block copolymer of formula SBS has a content of vinyl groups greater than or equal to 25% by mass, relative to the total mass of condensed polybutadiene units present in the block B, preferably greater than or equal to 30. % by mass, even more preferably greater than or equal to 35% by mass.
• the block B of the block copolymer of formula SBS has a content of vinyl groups less than or equal to 50% by mass, relative to the total mass of condensed polybutadiene units present in the block B, preferably less than or equal to 45 % by mass, even more preferably less than or equal to 40% by mass.
• the block B of the block copolymer of formula SBS has a content of vinyl groups greater than or equal to 25% by moles, relative to the total amount of condensed polybutadiene units present in the block B, preferably greater than or equal to 30 % by moles, even more preferably greater than or equal to 35% by moles.
• the block B block copolymer of formula SBS has a glass transition temperature T v (in English T g for "glass transition”), determined by differential scanning calorimetry (or DSC in English for “Differential Scanning Calorimetry”), ranging from -100 ° C to -50 ° C, preferably from -90 to -60 ° C, more preferably from -80 ° C to -70 ° C.
• the S blocks present in the heat-crosslinkable block copolymer of formula S-B-S together represent at least 15% by moles, relative to the total number of moles of heat-crosslinkable block copolymer of formula S-B-S, preferably at least 16% by moles.
• the blocks S of the heat-crosslinkable block copolymer of formula SBS represent, together, from 15% to 50% by moles, relative to the total amount of moles of heat-crosslinkable block copolymer of formula SBS, more preferably from 15% to 30% by moles, even more preferably from 15% to 25% by moles, and advantageously from 15% to 20% by moles.
• the content of monovinyl aromatic hydrocarbon (advantageously styrene) in the heat-crosslinkable block copolymer of formula SBS, determined by 13 C NMR spectroscopy (Carbon Nuclear Magnetic Resonance), is greater than or equal to 25% by mass, more preferably greater than or equal to 28% by mass, even more preferably greater than or equal to 30% by mass, relative to the total mass of the heat-crosslinkable block copolymer of formula S-BS.
• the content of monovinyl aromatic hydrocarbon (advantageously styrene) of the heat-crosslinkable block copolymer of formula SBS ranges from 25% to 40% by mass, more preferably from 28% to 35% by mass, relative to the total mass of the heat-crosslinkable block copolymer of formula SBS.
• block copolymers of the invention are in an essentially non-hydrogenated form.
• the heat-crosslinkable block copolymer of formula SBS is obtained by coupling two block copolymers of formula SB in which the blocks S and B are as described above in the definition of the heat-crosslinkable block copolymer of SBS formula.
• the bitumen / polymer composition before fluxing comprises from 0 to 8% by weight of heat-crosslinkable block copolymer of formula SBS relative to the total weight of the bitumen / polymer composition, more preferably from 0% to 6% by weight , even more preferably from 0% to 4% by weight, even more preferably from 0% to 2% by weight.
• the bitumen / polymer composition according to the invention after fluxing, comprises from 0 to 8% by mass of heat-crosslinkable block copolymer of formula SBS relative to the total mass of the bitumen / polymer composition, more preferably from 0% at 6% by weight, even more preferably from 0% to 4% by weight, even more preferably from 0% to 2% by weight.
• bitumen / polymer composition according to the invention may comprise elastomers other than copolymers of formula S-B-S and block copolymers of formula S-B defined above.
• composition according to the invention may contain other known elastomers for bitumen such as the S-B1-B2 copolymers (styrene-butadiene-butadiene block copolymer in which the two butadiene blocks B1 and B2 have a different vinyl content.
• S-B1-B2 copolymers styrene-butadiene-butadiene block copolymer in which the two butadiene blocks B1 and B2 have a different vinyl content.
• SIS styrene-isoprene-styrene
• SBS * styrene-butadiene-styrene star block copolymer
• SBR styrene butadiene rubber
• EPDM modified ethylene propylene diene
• polychloroprene polynorbornene, natural rubber, recycled rubber
• polybutene polyisobutylene
• SEBS copolymer of styrene, ethylene, butylene and styrene
• the heat-crosslinkable block copolymers of formula SBS and the block copolymers of formula SB which have been defined above together represent at least 50% by weight of the elastomers present in the composition, more preferably at least 70% by weight , and even more preferably at least 90% by weight.
• the elastomers present in the composition according to the invention consist essentially of heat-crosslinkable block copolymers of formula S-B-S and of block copolymers of formula S-B defined above.
• the total elastomer content in the bitumen / polymer composition is from 0.5% to 20% by mass relative to the total mass of the bitumen / polymer composition, more preferably from 1% to 15% by weight, even more preferably from 2% to 10% by weight, even more preferably from 3% to 6% by weight.
• the elastomer content in the fluxed bitumen / polymer composition according to the invention is preferably from 0.25% to 20% by weight relative to the total weight of the fluxed bitumen / polymer composition, more preferably from 0.5% to 15% by mass, even more preferably from 1% to 10% by mass, even more preferably from 2% to 5.5% by mass.
• composition may also further comprise other plastomers distinct from the olefinic polymer builder functionalized with at least one epoxy group.
• composition according to the invention may also additionally contain one or more polymeric components chosen from the category of known thermoplastics and plastomers for bitumen.
• thermoplastics By way of example of thermoplastics, mention may in particular be made of polyethylenes such as PE (polyethylene), HDPE (high density polyethylene) and polypropylene PP.
• PE polyethylene
• HDPE high density polyethylene
• polypropylene PP polypropylene
• EVA polyethylene-vinyl acetate copolymer
• I ⁇ MA polyethylene-methyl acrylate copolymer
• I ⁇ BA polyethylene-copolymer- butyl acrylate
• copolymers of ethylene and acid esters acrylic, methacrylic or maleic anhydride acrylic, methacrylic or maleic anhydride
• ethylene-propylene copolymers and ABS (acrylonitrile-butadiene-styrene).
• the block copolymers of formula SBS and the block copolymers of formula SB defined above together represent , at least 50% by mass relative to the total mass of all the block copolymers of formula SBS, block copolymers of formula SB, thermoplastics and separate plastomers of the olefinic polymer adjuvant functionalized with at least one epoxy group present in the composition, even more preferably at least 70% by weight.
• the composition can comprise, in addition to block copolymers of formula SBS and copolymers of formula SB, at least one other elastomer as defined above and at least one plastomer as defined above .
• the block copolymers of formula SBS and the copolymers of formula SB represent at least 50% by mass relative to the total mass of all the block copolymers of formula SBS, copolymers of formula SB, other elastomers and plastomers that are distinct from the olefinic polymer adjuvant functionalized with at least one epoxy group present in the composition, even more preferably at least 70% by weight.
• composition according to the invention comprises at least one fluxing agent.
• fouling agent or "fluxing agent” or even “fluxing agent” means an oily substance which, when introduced into a bituminous composition, allows its viscosity to be significantly reduced.
• bitumen / polymer composition as defined above, and in detail below, is advantageous in that it can be fluxed by mixing with a conventional fluxing agent.
• the fluxing agent used in the context of the present invention can thus be chosen from all the fluxing agents for bitumen known from the prior art.
• the fluxing agent is chosen from fluxing agents of animal origin; fluxing agents of plant origin; hydrocarbon fluxing agents, in particular of petroleum origin; and their mixtures. More preferably, the fluxing agent is chosen from fluxing agents of plant origin, hydrocarbon-based fluxing agents and their mixtures.
• the fluxing agent can first of all be chosen from hydrocarbon fluxes.
• the hydrocarbon fluxing agent is chosen from petroleum fluxing agents or synthetic hydrocarbon fluxing agents.
• Fluxes of petroleum origin are obtained by refining petroleum and generally consist of a mixture / assembly of several fractions.
• fluxing agents of petroleum origin generally consist of a mixture of a heavy fraction and a light fraction.
• fluxing agents of petroleum origin mention may be made of the fluxing agents described in WO 2005/021655.
• fluxing agents include:
• the content of aromatic compounds is less than 5.0% by mass, relative to the total mass of the heavy petroleum cut A, and
• the initial distillation temperature is greater than or equal to 200 ° C and the final distillation temperature of which is less than or equal to 400 ° C,
• Such fluxing agents are commercially available from the company TOTAL under the name GREENFLUX® SD.
• Synthetic hydrocarbon fluxes are obtained by conversion of biomass. Synthetic fluxes are generally obtained by subjecting a crude biological load to a process comprising hydrodeoxygenation (HDO) and isomerization (ISO) steps.
• the hydrodeoxygenation (HDO) step leads to the decomposition of the structures of the biological esters or of the triglyceride constituents, to the elimination of oxygenated, phosphorus and sulfur compounds and to the hydrogenation of the olefinic bonds.
• the product resulting from the hydrodeoxygenation reaction is then isomerized.
• a fractionation step can preferably follow the hydrodeoxygenation and isomerization steps. The fractions of interest can finally be subjected to hydrotreatment and then distillation stages.
• the raw biological load also called biomass or raw material of biological origin, used to manufacture synthetic fluxes is generally chosen from vegetable oils, animal fats, fish oils and their mixtures.
• gross biological load we can cite by way of example: rapeseed oil, canola oil, tall oil, sunflower oil, soybean oil, hemp oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, walnut oil coconut, animal fats such as tallow, recycled edible fats, raw materials from genetic engineering and biological raw materials produced from microorganisms such as algae and bacteria.
• the fluxing agent can also be chosen from fluxing agents of animal or plant origin.
• Fluxes of plant or animal origin consist of oils of plant or animal origin. These oils are found in the form of free fatty acids; triglycerides; diglycerides; monoglycerides, in esterified form, for example in methyl ester form; or in the form of mixtures.
• the fluxing agent is chosen fluxing agents of plant origin.
• fluxing agents of plant origin mention may be made of those described in FR2894587 and FR2894588 in the form of a mixture of castor oil and at least one of its derivatives, in particular chosen from among ester derivatives.
• the fluxing agent can finally be chosen from mixtures of at least one oil of plant or animal origin and at least one hydrocarbon oil.
• the hydrocarbon oil can be chosen from oils of petroleum origin and synthetic oils described above.
• FR2910477 Examples of fluxing agents in the form of a mixture of an oil of plant or animal origin and of an oil of petroleum origin are described in particular in FR2910477.
• the flux described in FR2910477 comprises:
• FR3065961 Examples of fluxing agents in the form of a mixture of an oil of plant or animal origin and of a synthetic hydrocarbon oil are described in particular in FR3065961.
• the flux described in FR3065961 comprises: - from 50% to 99% of at least one hydrocarbon oil which comprises a mass content of isoparaffins ranging from 90 to 100%, a mass content of normal paraffins ranging from 0 to 10% and a carbon content of biological origin greater than or equal to 90%, relative to the total mass of the hydrocarbon oil, and
• the composition according to the invention comprises from 0.5% to 50% by mass of fluxing agent (s), relative to the total mass of the bitumen / polymer composition, more preferably from 1 to 40% by mass , even more preferably from 1 to 20% by weight.
• fluxing agent s
• bitumen / fluxed polymer composition of the invention it is also possible to add to the bitumen / fluxed polymer composition of the invention, in a known manner:
• tackifier dopes and / or surfactants are generally chosen from derivatives of alkylamines, derivatives of alkylpolyamines, derivatives of alkyl amidopolyamines and derivatives of quaternary ammonium salts, taken alone or as a mixture.
• the amount of tackifier dopes and / or surfactants in the bitumen / polymer composition is, for example, between 0.2% and 2% by mass, preferably between 0.5% and 1% by mass relative to to the total mass of the bitumen / polymer composition.
• waxes of animal, vegetable or hydrocarbon origin in particular long chain hydrocarbon waxes, for example polyethylene waxes or paraffins, optionally oxidized.
• Amide waxes such as ethylene bis-stearamide can also be added.
• paraffins having chain lengths of 30 to 120 carbon atoms (C30 to C120).
• the paraffins are chosen from polyalkylenes.
• the paraffins are polymethylene paraffins and polyethylene paraffins. These paraffins can be of petroleum origin or come from the chemical industry.
• the paraffins are synthetic paraffins resulting from the conversion of biomass and / or natural gas.
• paraffins can also contain a large proportion of so-called “normal” paraffins, that is to say straight-chain, unbranched linear paraffins (saturated hydrocarbons).
• the paraffins can comprise from 50 to 100% normal paraffins and from 0 to 50% isoparaffins and / or branched paraffins.
• the paraffins comprise from 85 to 95% of normal paraffins and from 5 to 15% isoparaffins and / or branched paraffins.
• the paraffins comprise from 50 to 100% normal paraffins and from 0 to 50% isoparaffins.
• the paraffins comprise from 85 to 95% of normal paraffins and from 5 to 15% of isoparaffins.
• the paraffins are polymethylene paraffins. More particularly, paraffins are synthetic polymethylene paraffins, in particular paraffins obtained from the conversion of synthesis gas by the Fischer-Tropsch process. In the Fischer-Tropsch process, paraffins are obtained by reacting hydrogen with carbon monoxide over a metal catalyst. Fischer-Tropsch synthesis methods are described, for example, in publications EP 1 432 778, EP 1 328 607 or EP 0 199 475.
• the paraffins are Fischer-Tropsch polymethylene paraffins marketed by Sasol, in particular under the trademark Sasobit®.
• anti-foam additives in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides obtained from vegetable or animal oils.
• detergent and / or anti-corrosion additives in particular (but not limited to) chosen from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkyl polyamines and polyetheramines; imidazolines.
• lubricity additives or anti-wear agent in particular (but not limited to) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and mono- and carboxylic acid derivatives. polycyclic.
• additives modifying crystallization, additives inhibiting paraffin deposits, additives making it possible to lower the pour point low temperature rheology modifiers such as ethylene / vinyl acetate (EVA) and / or ethylene / vinyl propionate (EVP) copolymers, ethylene / vinyl acetate / vinyl versatate (EA AA EOVA) terpolymers; ethylene / vinyl acetate / alkyl acrylate terpolymers; graft-modified EVA copolymers; polyacrylates; acrylate / vinyl acetate / maleic anhydride terpolymers; amidified maleic anhydride / alkyl (meth) acrylate copolymers capable of being obtained by reaction of a maleic anhydride / alkyl (meth) acrylate copolymer and of an alkylamines or polyalkylamine having a hydrocarbon chain of 4 and 30 carbon atoms, of preferably from 12 to 24 carbon atoms
• antioxidants for example of hindered phenolic type or amine type of alkylated paraphenylene diamine type.
• L) additives for lowering the mixing temperature of asphalts and mixes those for improving the adhesion of bituminous binders to fillers and aggregates, such as polyisobutylene succinimides.
• acids such as polyphosphoric acid or diacids, in particular fatty diacids.
• the additives are used in amounts well known to those skilled in the art, depending on the nature of the additive, depending on the bitumen base and the expected properties.
• the bitumen base comprises from 0.1% to 10% by mass, preferably from 0.5% to 5% by mass, more preferably from 0.5% to 2.5% by mass. mass of chemical additive relative to the total mass of the bitumen base.
• composition The composition :
• the application describes the composition resulting from the simple mixture of the components described above but also the heat-crosslinked composition resulting from the heat treatment of this composition.
• the heat treatment is described below in the section titled "The Preparation Process”.
• the percentages described below relate to the mixture of the components of the heat-crosslinkable composition and are found in the heat-crosslinked composition.
• the bitumen / polymer composition is free from sulfur crosslinking agent.
• the bitumen / polymer composition comprises less than 6 ppm of sulfur-containing crosslinking agent.
• bitumen / fluxed polymer composition essentially consists of:
• bitumen / fluxed polymer composition preferably comprises, preferably consists essentially of:
• bitumen / fluxed polymer composition comprises, preferably essentially consists:
• bitumen / fluxed polymer composition comprises, preferably essentially consists:
• bitumen / fluxed polymer composition comprises, preferably essentially consists:
• bitumen / fluxed polymer composition comprises, preferably essentially consists:
• bitumen / fluxed polymer composition comprises, preferably essentially consists:
• the elastomer / olefinic polymer adjuvant mass ratio is advantageously from 2/1 to 15/1, preferably from 5/2 to 12/1.
• the heat-crosslinked composition is obtained directly by heat treatment of the bitumen / polymer composition defined above, the heat treatment inducing crosslinking of the bitumen / polymer composition.
• the crosslinking is essentially thermal.
• essentially thermal crosslinking is meant within the meaning of the invention a crosslinking created by heat treatment.
• a composition obtained by such a process is thus distinguished from the compositions obtained by means of a chemical crosslinking, in particular using crosslinking agents chosen from sulfur-containing crosslinking agents.
• the crosslinked and fluxed bitumen / polymer compositions of the invention can be prepared by any process known to those skilled in the art. Typically these methods include mixing the components and heating the mixture. Bitumen can be heated before mixing. Usually, the bitumen is heated before mixing, and the other components are added to the bitumen without having been previously heated.
• bitumen / polymer composition is prepared by bringing into contact:
• the mass percentages are calculated relative to the total mass of said composition.
• the operation is carried out at temperatures ranging from 100 ° C to 200 ° C, preferably from 150 ° C to 200 ° C, preferably from 160 ° C to 200 ° C, more preferably 160 ° C to 195 ° C, even more preferably 160 ° C to 190 ° C.
• This embodiment allows the preparation of a bitumen / heat-crosslinked polymer composition.
• the operation is preferably carried out with stirring, advantageously for a period of at least 10 minutes, preferably comprised from 1 hour to 24 hours, more preferably from 1 hour to 10 hours.
• the method of the invention can be carried out by means of agitation producing high shear or agitation producing low shear.
• the method of the invention may comprise successive sequences with different agitation modes, for example the method of the invention may comprise at least two successive sequences of agitation, a first sequence producing agitation at high shear followed by a second sequence producing low shear agitation, preferably ranging from 400 revolutions / min to 1000 revolutions / min.
• the process for manufacturing the bitumen / heat-crosslinked polymer composition comprises, for example, the following successive steps:
• bitumen, heat-crosslinkable elastomers and olefinic polymer additive functionalized with at least one epoxy group, optionally additives, are introduced into a reactor,
• the mixture is stirred until a homogeneous mixture is obtained and heated to a temperature ranging from 100 ° C to 200 ° C, preferably from 150 ° C to 200 ° C, preferably from 160 ° C to 200 ° C , more preferably 160 ° C to 195 ° C, even more preferably 160 ° C to 190 ° C.
• step ii) is preferably carried out for a period of at least 10 minutes, preferably from 1 hour to 24 hours, more preferably from 1 hour to 10 hours.
• the olefinic polymer adjuvant functionalized with at least one epoxy group can be incorporated into the bitumen before or after the heat-crosslinkable elastomer, simultaneous incorporation also being possible.
• the olefinic polymer additive functionalized with at least one epoxy group is incorporated into the bitumen before or after the elastomers.
• the process for manufacturing the bitumen / heat-crosslinked polymer composition comprises, for example, the following successive steps:
• bitumen previously heated to a temperature ranging from 100 ° C to 200 ° C, the heat-crosslinkable elastomers and the olefinic polymer additive functionalized with at least one epoxy group, optionally the additives, are introduced into a reactor,
• the mixture is homogenized by passing through a high shear mill, preferably between 1000 and 6000 revolutions / min, preferably for a period of at least 1 minute, more preferably ranging from 1 min to 2 hours, even more preferably from 1 min to 30 min,
• step iii) the mixture obtained in step ii) is then transferred to a maturation tank, preferably for a period of at least 30 min, more preferably from 30 min to 24 hours, even more preferably from 1 hour to 10 hours before storage or use.
• the maturation step iii) described above is preferably carried out at a temperature ranging from 100 ° C to 200 ° C, more preferably ranging from 150 ° C to 200 ° C, even more preferably ranging from 160 ° C. ° C to 200 ° C, preferably 160 ° C to 195 ° C and even more preferably 160 ° C to 190 ° C.
• the stirring at high shear and in particular the stirring carried out by passing through a high shear mill, makes it possible to facilitate good dispersion and good distribution of the polymer and of the olefinic polymer additive.
• the application describes a bitumen / heat-crosslinked polymer composition capable of being obtained by carrying out the process defined above.
• the method described above further comprises, after step ii) or iii), an additional step of introducing one or more fluxing agent (s) as defined above .
• the method according to the invention can further comprise, before the step of introducing the fluxing agent (s), a preliminary step of diluting the bitumen / polymer composition by adding a or several bitumen bases.
• This optional dilution step makes it possible to adjust the additive contents in the bitumen / polymer composition fluxed.
• the implementation of this step is up to a person skilled in the art who knows, depending on the intended application and in particular the desired properties, how to adapt the content of additives in the final composition.
• the process according to the invention allows the preparation of a bitumen / heat-crosslinked and fluxed polymer composition.
• the introduction of the fluxing agent is carried out in the bitumen / polymer composition previously heated to a temperature ranging from 100 ° C. to 200 ° C. and with stirring.
• the bituminous composition is heated to a temperature ranging from 150 ° C to 200 ° C, preferably from 160 ° C to 200 ° C, more preferably from 160 ° C to 195 ° C, even more preferably from 160 ° C to 190 ° C.
• a subject of the invention is also a heat-crosslinked and fluxed bitumen / polymer composition capable of being obtained by carrying out the above process.
• bitumen / polymer compositions according to the invention:
• the heat-crosslinked and fluxed bitumen / polymer compositions obtained according to the invention are envisaged.
• the heat-crosslinked and fluxed bitumen / polymer compositions can be used for the preparation of a bitumen / polymer binder.
• the bitumen / polymer binder according to the invention can be used in combination with aggregates, in particular road.
• the heat-crosslinked and fluxed bituminous composition according to the invention is used, optionally as a mixture with aggregates or aggregates of recycled bituminous mixes, to manufacture a surface coating, a hot mix, a cold mix, a mixed bituminous mix. cold, a severe emulsion, a base coat, a tie coat, a tack coat or a wearing course.
• bituminous mixes as materials for the construction and maintenance of pavement bodies and their coating, as well as for carrying out all road works.
• bituminous mixes as materials for the construction and maintenance of pavement bodies and their coating, as well as for carrying out all road works.
• bituminous mix is meant a mixture of a bituminous binder with aggregates and optionally mineral and / or synthetic fillers.
• the bituminous mix comprises a bitumen / heat-crosslinked and fluxed polymer binder according to the invention, and optionally mineral and / or synthetic fillers, preferably chosen from fines, sand, chippings and recycling mills.
• the aggregates are mineral and / or synthetic aggregates, in particular, recycling mills, with dimensions greater than 2 mm, preferably between 2 mm and 20 mm.
• the bitumen / polymer binder according to the invention can advantageously be used to prepare a surface coating, a hot mix, a warm mix, a cold mix, a cold mix or a serious emulsion.
• the invention also relates to asphalts as a material for making and covering sidewalks.
• asphalt is meant a mixture of bituminous binder with mineral and / or synthetic fillers.
• An asphalt comprises a bitumen / heat-crosslinked and fluxed polymer binder according to the invention and mineral fillers such as fines, sand or chippings and / or synthetic fillers.
• Mineral fillers consist of fine (particles with dimensions less than 0.063 mm), sand (particles with dimensions between 0.063 mm and 2 mm) and possibly chippings (particles with dimensions greater than 2 mm, preferably between 2 mm and 4 mm).
• Asphalts have 100% compactness and are mainly used to make and cover sidewalks, while asphalt has a compactness of less than 100% and are used to make roads. Unlike asphalt, asphalts are not compacted with a roller during their placement.
• Another aspect of the invention is the use of a bitumen / polymer composition according to the invention in various industrial applications, in particular for preparing an interior or exterior coating, a membrane or an impregnation layer.
• a subject of the invention is also the use of heat-crosslinked and fluxed bitumen / polymer binders, of mixes and of mastic asphalt according to the invention for the manufacture of road, pavement, sidewalk, road, pavement and pavement coverings.
• bitumens The properties of bitumens are measured using the methods described below:
• TSA Ball and ring softening temperature
• the STV pseudo-viscosity measurement is carried out using a flow viscometer and represents the flow time (expressed in seconds) of 50 cm 3 of the bituminous composition flowed through an orifice 10 mm in diameter.
• the fluxed bituminous composition must have an STV pseudo-viscosity value less than or equal to 500 s.
• a measurement of the STV pseudo-viscosity of the bituminous composition after prolonged storage makes it possible to characterize the storage stability of the fluxed compositions.
• the STV pseudo-viscosity of the compositions is measured before storage, after 3 days of storage at 160 ° C and after 10 days of storage at 160 ° C.
• B1 bitumen base 35/50 grade bitumen base with a P 25 penetrability of 47 1/10 mm and a TBA of 51.8 ° C and available commercially from the TOTAL group under the brand AZALT ® , and
• B2 bitumen base 70/100 grade bitumen base with a P25 penetrability of 84 1/10 mm and a TBA of 47.2 ° C and available commercially from the TOTAL group under the AZALT ® brand.
• Adjuvant A1 Ethylene / butyl acrylate / glycidyl methacrylate terpolymer in mass proportions, determined by 1 H NMR spectroscopy (proton nuclear magnetic resonance), respectively of 70/21/9 and having a melt index MFR (English acronym for “Melt Flow Rate”) (190 ° C / 2.16 kg) of 8g / 10min, calculated according to standard ASTM D1238-IS01 133.
• This polymer is commercially available under the name Elvaloy® 4170P from the company Dupont and has:
• Mn number-average molecular mass (Mn), measured by triple-detection gel permeation chromatography, equal to 16,220 g. mol 1 ,
• Mw mass average molecular mass
• Adjuvant A2 ethylene / ethyl acrylate / glycidyl methacrylate terpolymer in proportions by mass of 74/16/10 respectively and having an MFR melt index (English acronym for “Melt Flow Rate”) (190 ° C / 2, 16 kg) of 8g / 10min, calculated according to standard ASTM D1238- IS01 133.
• MFR melt index English acronym for “Melt Flow Rate”
• Mn a number-average molecular mass (Mn), measured by triple-detection gel permeation chromatography, equal to 1 16 700 g. mol 1 ,
• Mw mass-average molecular mass
• Elastomer E1 blend based on block copolymer S-B1 -B2 also comprising copolymer (S-BI-B2) nX with S represents a monovinyl aromatic hydrocarbon block having a peak molecular weight of 10,000 to 25,000, Bl is a polybutadiene block having a vinyl content of less than or equal to 15 mole percent, B2 is a polybutadiene block having a vinyl content of greater than or equal to 25 mole percent, the ratio of BI / B2 is greater than or equal to 1 : 1, the S-B1 -B2 block copolymer has a peak molecular weight of 40,000-200,000, n is an integer ranging from 2 to 6, X is the residue of a coupling agent, the block copolymer (S- BI-B2) nX has a peak molecular weight which is 1.5 to 6.0 times the peak molecular weight of the S-B1 -B2 block copolymer, wherein the S-B1 -
• the content of vinyl groups in the mixture is 24.1% by moles relative to the total number of moles of polymers.
• the content of monovinyl aromatic hydrocarbon monomers is 15.8% by moles relative to the total number of moles of polymers.
• the weight average molecular weight of the mixture is 285,000 g. mol 1 .
• This elastomer is available from the company Kraton under the name MD246.
• Elastomer E2 styrene / butadiene / styrene (SBS) block copolymer, at 18.8% by moles of styrene and at 81.2% by moles of butadiene, relative to the total number of moles of copolymer.
• the content of vinyl groups is 29.4% by moles relative to the total number of moles of copolymer.
• the copolymer has a molecular mass by mass (Mw), determined by gel permeation chromatography with a polystyrene standard, equal to 144,000 g. mol 1 .
• Mw molecular mass by mass
• This copolymer is commercially available from the company KRATON under the name D1 192.
• Elastomer E3 styrene / butadiene (SB) block copolymer, 14.6% by moles of styrene and 85.4% by moles of butadiene, relative to the total number of moles of copolymer.
• the content of vinyl groups is 10.1% by moles relative to the total number of moles of copolymer.
• the copolymer has a mass molecular mass (Mw), determined by triple detection gel permeation chromatography, equal to 66,000 g. mol 1 .
• Mw mass molecular mass
• This copolymer is commercially available from the company DYNASOL under the reference Solprene 1205.
• the fluxing agent a fluxing agent of petroleum origin available commercially from the company TOTAL under the name GREENFLUX® SD was used.
• bitumen bases B1 and B2 are heated to a temperature of 160 ° C and mixed in a reactor according to a mass ratio equal to 1: 1. The mixture is then placed in an oven for 45 minutes at a temperature equal to 190 ° VS,
• the elastomer (s) and the olefinic polymer admixture are then added to the mixture of bitumen bases using a Silverson ® mixer at a shear of 6000 revolutions / min for 30 minutes at a temperature of 190 ° C to obtain a homogeneous mixture,
• compositions C3 and C4 lead to crosslinked and fluxed compositions according to the invention and compositions C1, C2 and C5 lead to comparative crosslinked and fluxed compositions. [Table 1]
• compositions C1 to C5 exhibit satisfactory penetrability and ball and ring softening temperature (TBA) values.
• compositions C1 to C5 also have a high maximum elongation suitable for the uses targeted by the present application.
• compositions C3 and C4 exhibit lower energy at 400%, total energy and maximum strain stress than those of compositions C1, C2 and C5.
• compositions C1 F to C5F are then obtained, respectively, by fluxing the compositions C1 to C5 prepared above.
• bitumen / polymer compositions C1 to C5 obtained above are diluted by mixing with the bitumen base B2 as follows:
• compositions C1 to C5 and the bitumen base B2 are heated to a temperature of 160 ° C for 2 hours, and
• compositions C1 to C5 are mixed, with stirring by means of a turbine available commercially from the company VMI under the brand RAYNERI®, with the bitumen base B2. Stirring is continued for 5 to 10 minutes until a homogeneous mixture is obtained.
• the fluxing agent is then introduced, with stirring, into the dilute compositions. Stirring is maintained for 2 min to obtain homogeneous compositions.
• the fluxed compositions C1 F to C5F are thus obtained by mixing: - 53% by mass of the starting bitumen / polymer composition (C1, C2, C3, C4 or
• the pseudo-viscosity of the compositions is measured according to the method described above.
• compositions C1 F and C5F exhibit a pseudo-viscosity value STV, before and after prolonged storage at 160 ° C., too high to be used as a road binder or for the preparation of industrial coatings (viscosity> 500 s).
• composition C2F has a pseudo-viscosity value STV before storage equal to 464 s, suitable for the applications targeted by the present application.
• STV pseudo-viscosity value
• the viscosity of the composition C2F increases significantly: after storage for 3 days, the composition C2F has an STV pseudo-viscosity value greater than 600 s; after 10 days of storage, composition C2F exhibits an STV pseudo-viscosity value greater than 1200 s.
• composition C2F has a pseudo-viscosity value STV incompatible with the applications targeted by the present application.
• the C3F and C4F compositions according to the invention exhibit a pseudo-viscosity value, before and after storage, of less than 500 s.
• the C3F and C4F compositions according to the invention can thus be used as a road binder or for the preparation of industrial coatings.
• the C3 F and C4F compositions according to the invention can be used in an equivalent manner directly after their preparation, after 3 days of storage at 160 ° C or again after 10 days of storage at 160 ° C.
• the fluxed compositions according to the invention are thus advantageous in that they can be stored for several days at a temperature of 160 ° C. without their viscosity being deteriorated.

Landscapes

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

Applications Claiming Priority (2)

Publications (1)

Family

ID=69172865

Family Applications (1)

Country Status (3)

Families Citing this family (1)

Family Cites Families (18)

• 2019
  • 2019-07-31 FR FR1908729A patent/FR3099486B1/fr active Active
• 2020
  • 2020-07-15 EP EP20753401.7A patent/EP4004119A1/de active Pending
  • 2020-07-15 WO PCT/FR2020/051273 patent/WO2021019141A1/fr unknown

Also Published As

Similar Documents

Legal Events