Bituminous binders with a reduced carbon footprint for producing warm mix asphalt

Abstract

The present invention is a bituminous composition comprising: - at least one bitumen base, - at least one copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs, and - at least one bisamide compound of general formula RA-X-RC-X'-RB, in which RA and RB represent a linear, cyclic or branched, saturated or unsaturated hydrocarbon chain comprising from 1 to 36 carbon atoms, and optionally comprising heteroatoms, RC represents a linear, cyclic or branched, saturated or unsaturated hydrocarbon chain comprising from 3 to 18 carbon atoms, optionally substituted, and optionally comprising heteroatoms, and X and X' represent an amide function, said bituminous composition comprising less than 3% by mass, relative to the total mass of the bituminous composition, of a copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs.

Description

Title of the invention: Bituminous binders with a reduced carbon footprint for producing warm mix asphalt. Technical field

[0001] The present invention relates to the field of bituminous compositions and their performance additives. The invention relates in particular to a bituminous composition, intended for the manufacture of asphalt mixes and / or waterproofing membranes, said composition comprising a copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs, a bisamide compound, and optionally a plastic pyrolysis residue. Prior art

[0002] The use of bitumen in materials for road and industrial applications is well known, bitumen being the main hydrocarbon binder in road construction and civil engineering.

[0003] To meet the requirements of these applications, the bitumen must possess certain specific physicochemical properties. One of the most important properties is the consistency of the bitumen; this must be sufficiently high at the application temperatures to prevent the formation of ruts caused by traffic. At the same time, the bitumen must be elastic to withstand the deformations imposed by traffic and / or temperature variations, which can lead to cracking of the bituminous mixtures or detachment of the surface aggregates. Finally, the bitumen must be sufficiently fluid at the application temperatures to allow for good coating of the aggregates, as well as their placement and compaction.

[0004] However, bitumen alone generally does not possess sufficient elasticity to meet these requirements. To improve its mechanical and elastic properties, polymers, crosslinked or not, are added to bitumen, thus creating compositions called polymer-modified bitumen (PMB). Among these polymers, random or sequenced copolymers of styrene and conjugated diene, such as styrene-butadiene or styrene-isoprene, prove particularly effective. They blend well with bitumen, giving it good mechanical properties and, in particular, excellent elasticity.

[0005] However, adding these polymers to bitumen presents a major drawback: it leads to a significant increase in the hot viscosity of the mixture. Consequently, to apply these modified compositions to the road surface, it is necessary to heat the binder to high temperatures, generally between 160°C and 180°C. This results in high energy consumption as well as a This increases the carbon footprint of the process. Furthermore, these high temperatures can accelerate the thermal aging of the bitumen, thus compromising the durability of the pavements. In addition, these polymers, produced from fossil fuels through a complex process, themselves have a high carbon footprint.

[0006] Another drawback associated with the high-temperature production of asphalt is the increase in fume emissions. Heating the bitumen to high temperatures (160-180°C) to compensate for the increased viscosity due to the addition of polymers leads to increased fume production. This fume contains volatile organic compounds (VOCs) and polycyclic aromatic hydrocarbons (PAHs), which are not only harmful to the environment but also to the health of workers on construction sites.

[0007] Faced with these challenges, it would be particularly advantageous to develop formulations enabling the production of warm mix asphalt. Warm mix asphalt is asphalt produced between 100 and 150 °C, approximately 30 to 50 °C lower than traditional hot mix asphalt. This temperature reduction offers several advantages. By lowering the application temperature, the energy requirements for heating the binder are reduced. For every 10 °C decrease in the application temperature, a reduction of approximately 1 kg of CO2 per tonne of asphalt produced is estimated (M. Sukhija, N. Saboo, Constr. Build. Mater 274 (2021) 121781). On average, warm mix asphalt thus allows for a reduction of 4 kg of CO2 per tonne compared to hot mix asphalt. In addition, lowering the coating temperature also helps to limit premature oxidation of the binder due to prolonged exposure to high temperatures.Some solutions already exist to lower the application temperature, such as adding additives like waxes or adhesion promoters. However, these additives can lead to additional costs and increase the overall carbon footprint.

[0008] Foaming of bitumen is another technique used to temporarily reduce viscosity during the coating process. However, this effect is limited in time and does not permanently improve the properties of the bitumen.

[0009] The Applicant's patent applications WO2008107551 and WO2009101275 describe the additive treatment of bitumen with organogel-forming additives similar to "supramolecular" polymers. These additives offer improved mechanical properties while reducing the viscosity of the bitumen at high temperatures. However, bitumens modified with these organogels do not exhibit good elastic properties under large deformations, which prevents them from competing with polymer-modified bitumens.

[0010] There is therefore a need to reduce the hot viscosity of polymer-modified bitumen compositions, thus enabling the manufacture of bituminous mixes at lower temperatures while maintaining or improving mechanical performance.

[0011] In particular, there is a need to offer compositions capable of producing warm mix asphalt, providing a more ecological alternative while retaining the necessary elastic performance under large deformations.

[0012] There is also a need to reduce the overall carbon footprint of bituminous compositions while minimizing polluting emissions during their preparation. Summary of the invention

[0013] The present invention relates to a bituminous composition comprising: - at least one bitumen base, - at least one copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs, and - at least one bisamide compound of general formula (I) Ra-X-Rc-X'-Rb (I) • Ra and Rb being a linear, cyclic or branched, saturated or unsaturated hydrocarbon chain comprising from 1 to 36 carbon atoms, and possibly including one or more heteroatoms, • Rc being a linear, cyclic or branched hydrocarbon chain, saturated or unsaturated, comprising 3 to 18 carbon atoms, possibly substituted, and possibly comprising one or more heteroatoms, • X and X' representing an amide function, said bituminous composition comprising less than 3% by mass, relative to the total mass of the bituminous composition, of copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs.

[0014] In one embodiment, the bisamide compound has the general formula (IA): Ra-CONH-Rc-NHCO-Rb (IA)

[0015] Preferably, Rc represents a linear and saturated hydrocarbon chain.

[0016] Preferably, Rc represents a saturated linear hydrocarbon chain comprising more than 4 carbon atoms, preferably between 6 and 12 carbon atoms.

[0017] Preferably, RA and RB, identical or different, represent a hydrocarbon chain comprising from 4 to 22 carbon atoms.

[0018] According to one embodiment, the bisamide compound is hexamethylene bis-stearate.

[0019] Advantageously, the bituminous composition comprises from 0.5% to 20% by mass, preferably from 1% to 5% by mass of bisamide compound of general formula (I).

[0020] Advantageously, the copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs is a styrene-butadiene-styrene copolymer.

[0021] Advantageously, the bituminous composition comprises from 0.05 to 2.8% by mass, preferably from 0.5 to 2.5% by mass of copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs.

[0022] According to one embodiment, the bituminous composition further comprises at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics.

[0023] Preferably, the distillation residue is an atmospheric distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by pyrolysis of plastic waste.

[0024] Advantageously, the bituminous composition comprises from 1 to 30% by mass, preferably from 0.5 to 25% of distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, relative to the total mass of the bituminous composition.

[0025] Advantageously, the bituminous composition comprises an eco-material content of at least 5% by mass, preferably at least 10% by mass, preferably at least 15% by mass relative to the total mass of the bituminous composition.

[0026] The present invention also relates to a bituminous coating comprising a bituminous composition as defined above, mixed with aggregates and / or recycled millings, and optionally mineral and / or synthetic fillers.

[0027] The present invention also relates to a method for preparing a bituminous composition according to the invention, comprising, in order, the following steps: (A) heating of the bitumen, preferably to a temperature between 100°C and 220°C, (B) possibly, heating of the distillation residue of a hydrocarbon product obtained by thermal conversion of plastics, (C) possibly, hot mixing of bitumen and distillation residue, (D) introduction of the bisamide compound of general formula (I), (E) introduction of the copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs.

[0028] The Applicant unexpectedly discovered that by partially substituting the copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs with a specific bisamide in a polymer-modified bitumen composition, and optionally incorporating a distillation residue of a hydrocarbon product obtained by thermal conversion of plastics, it is possible not not only reduces the hot viscosity of bituminous formulations, but also generates a synergistic effect between the bisamide and the copolymer. This effect results in improved mechanical and elastic properties of the bitumen, while maintaining excellent thermal resistance.

[0029] By optimizing the selection of raw materials and reducing the amount of copolymer, particularly SBS, these formulations also make it possible to decrease the carbon footprint compared to conventional polymer-modified bitumen compositions. Furthermore, they can be applied at lower temperatures, which significantly reduces the energy consumption required for their application as well as fume emissions. This also helps to limit the thermal aging of the bituminous binder, thus improving the durability of infrastructure. Detailed description

[0030] For the purposes of this invention, the terms "bitumen", "bituminous composition" and "bituminous binder" are used interchangeably and independently of each other. By "bitumen", "bituminous composition" or "bituminous binder", we mean all bitumen-based compositions consisting of one or more bitumen bases and possibly including one or more chemical additives, said compositions being capable of being used in a road application, in particular in a mixture with aggregates, or in a building application, in particular for the waterproofing of buildings.

[0031] According to one aspect, the invention relates to a bituminous composition, comprising, preferably consisting essentially of, a bitumen base, at least one copolymer consisting of conjugated diene motifs and aromatic monovinyl hydrocarbon motifs, and at least one bisamide compound of general formula (I) as defined above and detailed below.

[0032] According to a particular embodiment, the bituminous composition further comprises at least one distillation residue of a hydrocarbon product obtained by thermal conversion of plastics. The bitumen base

[0033] The bitumen or bitumens used to prepare a bituminous composition according to the invention are called "bitumen base".

[0034] The bituminous compositions according to the invention may contain one or more bitumens from different origins: bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or oil sands, and those from the refining of crude oil, in particular by atmospheric and / or vacuum distillation of oil.

[0035] In the context of the invention, the bitumens are advantageously chosen from bitumens obtained from the refining of crude oil, in particular bitumens containing asphaltenes or pitches.

[0036] Bitumens can be obtained by conventional refining processes, in particular by direct distillation and / or vacuum distillation of petroleum. These bitumens may optionally be viscoreduced and / or deasphalted and / or air rectified. It is common practice to vacuum distill the atmospheric residues from the atmospheric distillation of crude oil. This manufacturing process therefore consists of a succession of atmospheric distillation and vacuum distillation, with the feedstock for the vacuum distillation corresponding to the residues from the atmospheric distillation. These vacuum residues from the vacuum distillation tower can also be used as bitumens.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 yields a blown, semi-blown, oxidized, air-rectified, or partially air-rectified base.

[0037] 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 conventional processes for blending different bitumens, the mixture is blended at temperatures between 100°C and 200°C, preferably between 140°C and 200°C, and with agitation for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, and more preferably between 1 and 6 hours. The temperature and duration of heating vary according to the quantity of bitumen used and are defined by standard NF EN 12594. Blown bitumens can be manufactured 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.

[0038] Generally, blowing is carried out at high temperatures, on 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 temperature of blowing are adjusted according to the desired properties of the blown bitumen and the quality of the starting bitumen.

[0039] Bitumen can also be fluxed bitumen by the addition of volatile solvents, petroleum-based fluidizing agents and / or vegetable-based fluidizing agents.

[0040] Among the usable bitumens according to the invention, recycled bitumens can also be mentioned.

[0041] Bitumen can also be hard grade bitumen, such as grades 10 / 20, 20 / 30, or soft grade bitumen such as grade 160 / 220, as defined by standard EN 12591.

[0042] The bituminous composition will preferably comprise a hard grade bitumen advantageously a grade bitumen of 35 / 50, 50 / 70 or 70 / 100.

[0043] Preferably, the bituminous composition according to the invention comprises at least 40% by mass of bitumen base, relative to the total mass of the composition, preferably at least 50% by mass, more preferably at least 60% by mass, advantageously at least 70% by mass, more advantageously at least 80% by mass, even more advantageously at least 85% by mass.

[0044] Advantageously, the bituminous composition of the invention comprises from 40% to 99.9% by mass, relative to the total composition, preferably from 65% to 99% by mass, more preferably from 70% to 95% by mass, advantageously from 80% to 90% by mass. The bisamide compound

[0045] The bisamide compound(s) used in the context of the invention are selected from compounds of formula (I): Ra-X-Rc-X'-Rb (I) in which: - the RA and RB groups, identical or different, represent a linear, cyclic or branched, saturated or unsaturated hydrocarbon chain, comprising from 1 to 36 carbon atoms, and possibly including one or more heteroatoms such as N, O, S, - the Rc group represents a linear, cyclic or branched, saturated or unsaturated hydrocarbon chain, comprising from 3 to 18 carbon atoms, and possibly including one or more heteroatoms, such as N, O, S, - X and X' independently represent an amide function -NH-CO- or -CO-NH-.

[0046] The amide function in the bisamide compound can have two orientations, corresponding to the following formulas (IA) and (IB), depending on whether the amide bond is arranged in the -CONH- or -NHCO- direction between the hydrocarbon chains RA, Rc and Rb: Ra-CONH-Rc-NHCO-Rb (IA) Ra-NHCO-Rc-CONH-Rb(IB).

[0047] In a preferred embodiment, the bisamide compounds used in the context of the invention are chosen from compounds of formula (IA).

[0048] According to one embodiment, Rc represents a hydrocarbon chain comprising from 3 to 18 carbon atoms, preferably from 3 to 14 carbon atoms, preferably from 4 to 12 carbon atoms, preferably from 4 to 10 carbon atoms.

[0049] According to another embodiment, Rc represents a hydrocarbon chain comprising more than 4 carbon atoms, preferably from 6 to 14 carbon atoms, more preferably from 6 to 12 carbon atoms.

[0050] Advantageously, Rc represents a linear and saturated hydrocarbon chain.

[0051] In a preferred embodiment of the invention, Rc is chosen from the groups -C6H12-, -C8H16-, and -Ci0H20-.

[0052] Advantageously, RA and RB, identical or different, represent a hydrocarbon chain comprising from 4 to 22 carbon atoms, preferably from 8 to 20 carbon atoms, more preferably from 10 to 20 carbon atoms.

[0053] Examples of RA and RB groups include undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, oleyl, eicosyl, etc.

[0054] According to a preferred embodiment of the invention, RA and RB, identical or different, represent a linear hydrocarbon chain.

[0055] According to a preferred embodiment of the invention, RA and RB, which may be identical or different, represent a saturated hydrocarbon chain or a hydrocarbon chain comprising one or more unsaturations. According to a further preferred embodiment, RA and RB, which may be identical or different, represent a saturated hydrocarbon chain or a hydrocarbon chain comprising one unsaturation.

[0056] Preferably, RA and RB are identical.

[0057] Preferably, in formulas (I), (IA) and (IB), the sum of carbon atoms in the RA, RB and Rc groups is between 12 and 60, even more preferably between 20 and 50.

[0058] Particularly preferred bisamide compounds are, for example, compounds of formula (I), preferably compounds of formula (IA), in which: - Rc is a -C6Hi2- group and RA and RB each represent an undecyl group, preferably n-undecyl, or, - Rc is a -C6Hi2- group and RA and RB each represent an n-heptadec- 8-enyl group.

[0059] According to a particularly preferred embodiment, the bisamide compound is hexamethylene bis-stearate.

[0060] The bisamide compound of general formula (I) can be prepared by conventional synthetic methods known to those skilled in the art, such as, for example, by reaction between a diamine and two carboxylic acids or by reaction between a dicarboxylic acid and two monoamines. Some bisamide compounds conforming to the general formula (I) are commercially available.

[0061] Advantageously, the bisamide compound(s) of general formula (I), preferably of formula (IA), are used in the bituminous composition at a content ranging from 0.5 to 20%, preferably from 0.5 to 10%, more preferably from 1 to 5% by mass relative to the total mass of the bituminous composition.

[0062] The incorporation of a bisamide compound, as defined above, into a polymer-modified bitumen composition makes it possible, while maintaining or even improving the mechanical properties, to reduce the required polymer content thanks to the synergistic effect provided by the bisamide. This polymer reduction is advantageous both economically and environmentally, by decreasing the carbon footprint associated with polymer production.

[0063] Furthermore, the addition of such a bisamide compound also lowers the hot viscosity of the bituminous composition. This facilitates its application at lower temperatures, thus reducing energy consumption during the production of asphalt mixes. The copolymer

[0064] The bituminous composition according to the invention comprises at least one copolymer. The bituminous composition of the invention is a bitumen / polymer composition. It may be crosslinked or non-crosslinked.

[0065] The copolymer is advantageously a block copolymer or a mixture of block copolymers.

[0066] Preferably, the block copolymer comprises at least 2 consecutive blocks.

[0067] It is preferably chosen from block copolymers of formula SBS, in which each S independently represents a block based on aromatic monovinyl hydrocarbon monomers, B represents a block based on butadiene monomers.

[0068] By "block", for the purposes of the invention, we mean a polymeric chain obtained by the polymerization of one or more monomers of the same chemical nature.

[0069] The monovinylaromatic hydrocarbon monomers from which the S blocks of block copolymers 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.

[0070] The preferred aromatic monovinyl hydrocarbon compound according to the present invention is styrene, which is used as a substantially pure monomer or as a major component in mixtures with minor proportions of a other aromatic vinyl monomers such as for example o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene, preferably in proportions of no more than 10% by weight.

[0071] According to a particularly preferred embodiment, the aromatic monovinyl hydrocarbon compound consists essentially of styrene.

[0072] The butadiene B monomer-based block used in the composition of the block copolymers mentioned above is based on practically pure butadiene monomers or comprising minor proportions, up to 10% by weight, of structurally related conjugated dienes. Preferably, the polybutadiene is essentially composed of butadiene monomers.

[0073] When 1,3-butadiene is polymerized via a 1,2-addition mechanism, the result is a vinyl group hanging relative to the polymer backbone.

[0074] The SBS block copolymer used in the present invention preferably has a vinyl group content greater than or equal to 5% by moles, preferably greater than or equal to 10% by moles, more preferably greater than or equal to 20% by moles, relative to the total number of moles of copolymer, more preferably greater than or equal to 25% by moles.

[0075] The vinyl content can be determined by coupling 13C NMR (carbon nuclear magnetic resonance) and 'H NMR (proton nuclear magnetic resonance) spectroscopy techniques.

[0076] The SBS block copolymer used in the present invention preferably has a vinyl group content of 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 even more preferably less than or equal to 35% by moles.

[0077] The SBS block copolymer used in the present invention preferably has a vinyl group content greater than or equal to 5% by mass relative to the total mass of the copolymer, more preferably greater than or equal to 10% by mass, and even more preferably greater than or equal to 20% by mass.

[0078] The SBS block copolymer used in the present invention preferably has a vinyl group content of less than or equal to 50% by mass relative to the total mass of the copolymer, more preferably less than or equal to 40% by mass, and even more preferably less than or equal to 30% by mass.

[0079] The vinyl content in block B is preferably greater than or equal to 5% by mass relative to the total mass of the condensed polybutadiene motifs present in block B, more preferably greater than or equal to 10% by mass, even more preferably greater than or equal to 20% by mass.

[0080] The vinyl content in block B is preferably less than or equal to 50% by mass relative to the total mass of the condensed polybutadiene motifs present in block B, more preferably less than or equal to 45% by mass, even more preferably less than or equal to 40% by mass.

[0081] The motifs obtained by the polymerization of 1,3-butadiene via a 1,2-addition mechanism or via a 1,4-addition mechanism have the same molar mass. Thus, the contents of vinyl groups present in block B, expressed by mass or by moles, are equivalent.

[0082] Preferably, the vinyl groups are distributed along block B in a statistical manner.

[0083] Advantageously, the S blocks present in the block copolymer of formula SBS represent, together, at least 15% by moles, relative to the total number of moles of block copolymer of formula SBS, preferably at least 16% by moles.

[0084] Preferably, the S blocks together represent 15% to 50% by moles, relative to the total quantity of moles of block copolymer of formula SBS, more preferably 16% to 30% by moles, even more preferably 16% to 25% by moles, and advantageously 16% to 20% by moles.

[0085] Preferably, the content of monovinyl aromatic hydrocarbon (advantageously styrene) of the block copolymer of formula SBS, determined by 13C NMR spectroscopy, 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 block copolymer of formula SBS.

[0086] Preferably, the content of monovinyl aromatic hydrocarbon (advantageously styrene) of the block copolymer of formula SBS, determined by 13C NMR spectroscopy, ranges from 25% to 40% by mass, even more advantageously from 28% to 35% by mass, relative to the total mass of the block copolymer of formula SBS.

[0087] Preferably, the block copolymer of formula SBS used in the present invention has a weight average molecular mass Mw, measured by gel permeation chromatography with a polystyrene standard, less than or equal to 500,000 g.mol', more preferably less than or equal to 250,000 g.mol1, even more preferably less than or equal to 200,000 g.mol1 and advantageously less than or equal to 150,000 g.mol1.

[0088] Preferably, the block copolymer of formula SBS used in the present invention has a weight-average molecular mass Mw, measured by gel permeation chromatography with a polystyrene standard, greater than or equal to at 40,000 g.mol1, more preferably greater than or equal to 65,000 g.mol1, even more preferably greater than or equal to 75,000 g.mol1, and advantageously greater than or equal to 100,000 g.mol1.

[0089] The molecular masses of these elastomers can be measured by gel permeation chromatography (GC) (or SEC for "Size Exclusion Chromatography"). GC is a liquid chromatography method in which polymers are separated according to their hydrodynamic volume, which is then converted into weight-average molecular mass (Mw) and / or number-average molecular mass (Mn). GC can be conventional or triple-detection, depending on the conversion method used.

[0090] According to one embodiment, the block copolymer of formula SBS used in the present invention has a weight average molecular mass Mw, measured by gel permeation chromatography with polystyrene standard, ranging from 40,000 to 500,000 g.mol1.

[0091] According to a first variant, the elastomer is essentially made up of one or more block copolymer(s) of formula SBS.

[0092] According to a preferred embodiment, the block copolymer(s) of formula SBS are used in combination with one or more block copolymer(s) of formula SB in which S is a block based on aromatic monovinyl hydrocarbon monomers, preferably based on styrene, and B is a block based on butadiene monomers.

[0093] Preferably, according to this preferred variant, the mixture of copolymers consists mainly of the block copolymer(s) of formula SBS.

[0094] Even more preferably, still according to this preferred variant, the SBS / SB mass ratio goes from 99.5:0.5 to 80:20 by mass, more preferably from 99.5:0.5 to 90:10 by mass.

[0095] Advantageously, the block copolymers of the invention are in an essentially non-hydrogenated form.

[0096] According to one embodiment, the block copolymer of formula SBS is obtained by coupling two block copolymers of formula SB in which the S and B blocks are as described above in the definition of the block copolymer of formula SBS.

[0097] Preferably, according to this particular embodiment, the efficiency of the coupling of the elastomer, measured by gel permeation chromatography, is greater than or equal to 50%, more preferably greater than or equal to 75%, even more preferably greater than or equal to 90% and advantageously greater than or equal to 95%.

[0098] Examples of block copolymers of formula S-BS usable in compositions according to the invention and their preparation processes are described in particular in US 5,798,401.

[0099] The composition may include other elastomers than block terpolymers of formula SBS and block copolymers of formula SB as described above.

[0100] In particular, the composition according to the invention may contain other known bitumen elastomers such as 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* (star-shaped styrene-butadiene-styrene block copolymer), SBR (styrene butadiene rubber), EPDM (modified ethylene propylene diene), polychloroprene, polynorbornene, natural rubber, recycled rubber, polybutene, polyisobutylene, SEBS (styrene, ethylene, butylene and styrene copolymer).

[0101] We can also mention elastomers made from styrene monomers and butadiene monomers allowing crosslinking without crosslinking agent as described in documents WO2007 / 058994 and by the applicant in patent application WO2011 / 013073.

[0102] Advantageously, the block copolymers of formula SBS and the block copolymers of formula SB as defined above together represent at least 50% by mass of the elastomers present in the composition, more preferably at least 70% by mass, and even more preferably at least 90% by mass.

[0103] According to one embodiment of the invention, the elastomer is essentially made up of block copolymers of formula SBS and block copolymers of formula SB.

[0104] Advantageously, the bituminous composition according to the invention comprises less than 3% by mass of the conjugated monovinyl aromatic hydrocarbon and diene copolymer, in particular of styrene and butadiene SBS copolymer, relative to the total mass of the composition.

[0105] According to one embodiment, the composition of the invention comprises from 0.1 to 2.8% by mass of the conjugated monovinyl aromatic hydrocarbon and diene copolymer, in particular of styrene and butadiene SBS copolymer, relative to the total mass of the composition, more preferably from 0.5 to 2.5% by mass.

[0106] The residue from the thermal conversion distillation of plastics

[0107] According to a particular embodiment, the composition according to the invention further comprises at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, in particular plastic waste.

[0108] Common industrial methods for recycling hydrocarbons from plastic include liquefaction by thermal conversion of plastic waste which could have ended up in a landfill or incinerator, followed by a purification step including hydrotreatment and the removal of contaminants using a variety of purification processes such as distillation.

[0109] The liquefaction of plastic waste can be carried out, in particular, by pyrolysis or by hydrothermal treatment. The thermal conversion step transforms the plastics and most of their additives and contaminants into gaseous chemicals, while most of the contaminants or non-volatile additives end up in the solid by-product, charcoal, or ash. In principle, all types of plastic waste can be converted. However, a preliminary step of sorting non-organic waste is advisable. Purification of the output material can also prove useful because several heteroatoms (i.e., elements other than carbon and hydrogen, for example, oxygen) can be volatilized.

[0110] Plastic waste is a complex and heterogeneous material due to several factors. First, the term "plastic" as a material refers to many different polymers with varying chemical properties that can be separated from one another before recycling or recycled as a complex mixture. The main polymers present in plastic from municipal solid waste are polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), and polystyrene (PS). Other polymers include mainly polyurethanes, polyamides (PA), polycarbonates, polyethers, and polyesters other than PET. In addition, many different additives to the base polymers are introduced during the production phase to adjust or improve the properties of the plastic or to meet specific requirements.These include functional additives (stabilizers, antistatic agents, flame retardants, plasticizers, lubricants, sliding agents, curing agents, foaming agents, biocides, antioxidants, etc.), colorants and pigments, fillers (e.g., glass fibers, talc, carbon fibers, carbon nanotubes), commonly used in plastic packaging, as well as additives such as flame retardants, frequently used in plastics for electronics. In addition, several metallic compounds are intentionally added during plastic production (often in the form of oxides, carbonates, acids, etc.). Additives containing heteroatoms other than metals are also used in plastics manufacturing, for example, halogens such as bromine in flame retardants, plasticizers, stabilizers, etc.

[0111] Silicone polymers, which are organic materials containing silicon, are often used in plastic formulations. Thanks to their surface characteristics, the applications of silicones range from silicone rubbers, used as sealants for joints, to silicone surfactants for cosmetic products, while they are increasingly used in the plastics sector, as process-improving additives (manufacturing auxiliaries), and for polymer modification.

[0112] In addition to these heteroelements, used plastic waste may have been contaminated during its lifetime by residues of liquids with which it has been in contact (beverages, personal care products, etc.) and food, which can also contaminate the plastic. Finally, some plastic waste may be present in the form of partially decomposed waste, such as partially burned plastic.

[0113] Finally, since plastics are contaminated by oxygenated compounds, plastic oils resulting from pyrolysis liquefaction may also contain oxygenated compounds such as aldehydes or ketones.

[0114] For the purposes of this invention, the term “hydrocarbon product obtained by thermal conversion of waste” or simply “hydrocarbon product” means liquid products obtained after thermal conversion, particularly after thermal pyrolysis, of plastic waste or plastic waste. The thermal conversion process, particularly pyrolysis, should be understood as a non-selective thermal cracking process.

[0115] According to a preferred embodiment, the hydrocarbon product used for the preparation of the residue of the invention is obtained by pyrolysis of waste, in particular by pyrolysis of plastic waste.

[0116] The residue integrated into the bituminous composition of the invention corresponds to the residue obtained from the distillation of the hydrocarbon product obtained by thermal conversion of plastic waste.

[0117] The residue incorporated into the bituminous composition of the invention can be obtained by direct distillation and / or by vacuum distillation of said hydrocarbon product. When obtained by atmospheric distillation, the residue of the invention simply corresponds to the residue of the distillation carried out at atmospheric temperature and pressure. A vacuum manufacturing process, for its part, consists of a succession of atmospheric distillation and vacuum distillation, the feedstock for the vacuum distillation corresponding to the residues obtained at the end of the atmospheric distillation. Thus, when obtained by vacuum distillation, the residue of the invention corresponds to the residue obtained at the end of the vacuum distillation process.

[0118] Preferably, the residue integrated into the composition of the invention is a residue obtained by vacuum distillation of the hydrocarbon product defined above.

[0119] The residue of the invention typically exhibits a penetrability at 25°C, measured according to standard EN 1426, less than or equal to 200 1 / 10 mm.

[0120] Preferably, the residue of the invention has a penetrability at 25°C, measured according to standard EN 1426, greater than or equal to 20 1 / 10 mm, more preferably greater than or equal to 30 1 / 10 mm, even more preferably greater than or equal to 35 1 / 10 mm.

[0121] More preferably, the residue of the invention has a penetrability at 25°C, measured according to standard EN 1426, ranging from 20 to 200 1 / 10 mm, preferably from 25 to 150 1 / 10 mm, even more preferably from 30 to 120 1 / 10 mm.

[0122] Preferably, the residue of the invention has a ball and ring softening temperature (BRT), measured according to EN 1427, greater than or equal to 60°C, more preferably ranging from 60°C to 120°C, typically ranging from 65°C to 100°C.

[0123] Preferably, the residue of the invention has a Cleveland flash point, measured according to ASTM D92, greater than or equal to 150°C, more preferably greater than or equal to 200°C, typically ranging from 200°C to 350°C, for example from 230°C to 340°C.

[0124] Distillation is known to be carried out by gradually heating a product. In the case of a pure compound, the entire product is distilled at a constant temperature. Conversely, in the case of a mixture, fractions with different boiling points are evaporated progressively. These boiling points increase during the distillation process.

[0125] Preferably, the residue of the invention has an initial boiling temperature, measured according to ASTM D7169:20, less than or equal to 500°C, more preferably from 100°C to 500°C, more preferably from 200°C to 480°C.

[0126] Preferably, the residue of the invention has a distillation endpoint, measured according to ASTM D7169:20, of less than or equal to 1000°C, more preferably less than or equal to 900°C.

[0127] More preferably, the residue of the invention has a final boiling point, measured according to ASTM D7169:20, ranging from 150°C to 1000°C, more preferably from 200°C to 900°C.

[0128] Preferably, the residue of the invention has a boiling point at 5% by mass, measured according to ASTM D7169:20, greater than or equal to 300°C, more preferably greater than or equal to 350°C, typically greater than or equal to 400°C.

[0129] Preferably, the residue of the invention has a boiling point at 5% by mass, measured according to ASTM D7169:20, less than or equal to 550°C, more preferably less than or equal to 500°C.

[0130] Preferably, the residue of the invention has a boiling point at 10% by mass, measured according to ASTM D7169:20, greater than or equal to 350°C, more preferably greater than or equal to 400°C, typically greater than or equal to 410°C.

[0131] Preferably, the residue of the invention has a boiling point at 10% by mass, measured according to ASTM D7169:20, less than or equal to 600°C, more preferably less than or equal to 550°C.

[0132] Preferably, the residue of the invention has a boiling point at 15% by mass, measured according to ASTM D7169:20, greater than or equal to 380°C, more preferably greater than or equal to 400°C, typically greater than or equal to 430°C.

[0133] Preferably, the residue of the invention has a boiling point at 15% by mass, measured according to ASTM D7169:20, less than or equal to 600°C, more preferably less than or equal to 550°C.

[0134] Preferably, the residue of the invention has a boiling point at 30% by mass, measured according to ASTM D7169:20, greater than or equal to 400°C, more preferably greater than or equal to 430°C, typically greater than or equal to 450°C.

[0135] Preferably, the residue of the invention has a boiling point at 30% by mass, measured according to ASTM D7169:20, less than or equal to 650°C, more preferably less than or equal to 600°C.

[0136] Preferably, the residue of the invention has a boiling point at 50% by mass, measured according to ASTM D7169:20, greater than or equal to 450°C, more preferably greater than or equal to 460°C, typically greater than or equal to 470°C.

[0137] Preferably, the residue of the invention has a boiling point at 50% by mass, measured according to ASTM D7169:20, less than or equal to 700°C, more preferably less than or equal to 650°C.

[0138] Preferably, the residue of the invention has a boiling point at 70% by mass, measured according to ASTM D7169:20, greater than or equal to 450°C, more preferably greater than or equal to 500°C, typically greater than or equal to 510°C.

[0139] Preferably, the residue of the invention has a boiling point at 70% by mass, measured according to ASTM D7169:20, less than or equal to 750°C, more preferably less than or equal to 730°C.

[0140] Preferably, the residue of the invention has a boiling point at 80% by mass, measured according to ASTM D7169:20, greater than or equal to 475°C, plus preferably greater than or equal to 500°C, typically greater than or equal to 510°C.

[0141] Preferably, the residue of the invention has a boiling point at 80% by mass, measured according to ASTM D7169:20, less than or equal to 775°C, more preferably less than or equal to 750°C.

[0142] Preferably, the residue of the invention has a final boiling point (i.e. boiling point at 100% by mass), measured according to ASTM D7169:20, greater than or equal to 500°C, more preferably greater than or equal to 550°C, typically greater than or equal to 600°C.

[0143] By "boiling point at X% of product Y", for the purposes of the invention we mean the boiling point of the remaining part of product Y once X% by mass of the starting product has been evaporated.

[0144] According to one embodiment, the residue used in the composition of the invention has a calcium (Ca) content greater than or equal to 1 ppm, more preferably greater than or equal to 1.5 ppm, typically ranging from 1 to 1000 ppm. The calcium content is typically determined by calcination of the material, followed by acidification of the resulting ash and analysis of the solutions by ICP-OES.

[0145] According to one embodiment, the residue used in the composition of the invention has a phosphorus (P) content greater than or equal to 10 ppm, more preferably greater than or equal to 15 ppm, typically ranging from 10 to 200 ppm. The phosphorus content is typically determined by acid digestion in a closed microwave instrument due to its volatility. The resulting solution is then analyzed by ICP-OES under conventional acidic conditions.

[0146] According to one embodiment, the residue used in the composition of the invention has a silicon (Si) content greater than or equal to 5 ppm, more preferably greater than or equal to 10 ppm, typically ranging from 10 to 750 ppm. The silicon content is typically determined by X-ray fluorescence (XRF) after homogenization of the material and appropriate calibration.

[0147] According to one embodiment, the residue used in the composition of the invention has a chlorine (Cl) content greater than or equal to 10 ppm, more preferably greater than or equal to 20 ppm, typically ranging from 10 to 1,500 ppm. The chlorine content is typically determined by ion chromatography coupled with a combustion system (C-IC) after appropriate calibration.

[0148] According to one embodiment, the residue used in the composition of the invention has an initial melting temperature, measured by thermal analysis (DSC), during a second heating ramp between -80°C and 180°C at 10°C / min, greater than or equal to -40°C, preferably ranging from -35 to -5°C, even more preferably ranging from -25 to -10°C.

[0149] According to one embodiment, the residue used in the composition of the invention has a final melting temperature, measured by thermal analysis (DSC), during a second heating ramp between -80°C and 180°C at 10°C / min, less than or equal to 110°C, preferably from 75 to 110°C, even more preferably from 80 to 110°C.

[0150] Advantageously, the bituminous composition of the invention has a residue content of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, ranging from 0.1% by mass to 30% by mass, relative to the total mass of the bituminous composition, preferably ranging from 0.5% to 25% by mass, more preferably from 1% to 20% by mass.

[0151] According to one embodiment, the bituminous composition of the invention comprises more than 5% by mass of distillation residue of a hydrocarbon product as defined above. Preferably, according to this embodiment, the bituminous composition of the invention comprises from 5% to 30% by mass of residue, more preferably from 7.5% to 25% by mass, relative to the total mass of the bituminous composition.

[0152] The incorporation of a distillation residue, as defined above, into a bitumen / polymer / bisamide composition makes it possible to significantly improve the mechanical properties of the formulation, in particular by increasing the ball and ring softening temperature, while further reducing the high-temperature viscosity. Additives

[0153] According to one embodiment, the bituminous composition according to the invention further comprises one or more additional additive(s).

[0154] These additional additives are known to those skilled in the art. By way of example, the following additives may be cited: a) Bonding agents and / or surfactants. These are generally selected from alkylamine derivatives, alkylpolyamine derivatives, alkylamidopolyamine derivatives, and quaternary ammonium salt derivatives, used alone or in mixtures. The quantity of bonding agents and / or surfactants present in the bitumen / polymer composition is, for example, between 0.2% and 2% by weight, preferably between 0.5% and 1% by weight, relative to the total mass of the bitumen / polymer composition. b) Waxes of animal or vegetable origin or hydrocarbon waxes, in particular long-chain hydrocarbon waxes, for example polyethylene waxes or paraffins, possibly oxidized. Amide waxes, such as ethylene bis(stearamide), may also be added. c) Paraffins with chain lengths of 30 to 120 carbon atoms (C30 to C120). The paraffins are selected from polyalkylenes. Preferably, the Paraffins are polymethylene paraffins and polyethylene paraffins. These paraffins can be of petroleum origin or from the chemical industry. Preferably, paraffins are synthetic paraffins derived from the conversion of biomass and / or natural gas. d) melting agents, such as oils based on animal and / or vegetable fats or hydrocarbon oils of petroleum origin. Oils of animal and / or vegetable origin may be in the form of free fatty acids, triglycerides, diglycerides, monoglycerides or in esterified form, for example as methyl ester. e) resins of plant origin, such as rosin. f) antifoaming additives, including (but not limited to) selected from polysiloxanes, oxyalkylated polysiloxanes and fatty acid amides derived from vegetable or animal oils. (g) detergent additives and / or corrosion inhibitors, including (but not limited to) those selected from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkylpolyamines, polyetheramines and imidazolines. (h) sliding agents or anti-wear agents, including (but not limited to) those selected from the group consisting of fatty acids and their ester or amide derivatives, including glyceryl monooleate, and mono- and polycyclic carboxylic acid derivatives. (i) additives modifying crystallization, additives inhibiting paraffin deposits, additives for lowering 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; amide copolymers of maleic anhydride / alkyl (meth)acrylate capable of being obtained by reaction of a maleic anhydride / alkyl (meth)acrylate copolymer and an alkylamine or polyalkylamine having a hydrocarbon chain of 4 to 30 carbon atoms, preferably of 12 to 24 carbon atoms;Amidated α-olefin / maleic anhydride copolymers that can be obtained by reacting an α-olefin / maleic anhydride copolymer with an alkylamine or polyalkylamine, the α-olefin being selectable from C10-C50 α-olefins, preferably C16-C20 α-olefins, and the alkylamine or polyalkylamine advantageously having a hydrocarbon chain of 4 to 30 carbon atoms, preferably 12 to 24 carbon atoms. j) antioxidants, for example of the hindered phenolic type or of the amino type, of the alkylated para-phenylenediamine type. k) metal passivators. 1) Acidity neutralizers. (m) Additives that lower the mixing temperature of asphalts and asphalt mixes, and those that improve the adhesion of bituminous binders to fillers and aggregates, such as, for example, polyisobutylene succinimides. n) acids, such as polyphosphoric acid, or diacids, in particular fatty diacids.

[0155] Additives are used in quantities well known to those skilled in the art, depending on the nature of the additive, the bituminous base and the expected properties.

[0156] Preferably, when present, the content of additional additives varies 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, relative to the total mass of the bituminous composition of the invention. Compositions according to the invention

[0157] According to one embodiment, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists of: - from 77.2% to 99.4% by mass of bitumen, - from 0.5% to 20% by mass of one or more bisamide compounds of general formula (I), - from 0.1% to 2.8% by mass of a copolymer of aromatic monovinyl hydrocarbon and conjugated diene (e.g. SBS), relative to the total mass of the bituminous composition.

[0158] According to one embodiment, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists of: - from 47.2% to 99.3% by mass of bitumen, - from 0.5% to 20% by mass of one or more bisamide compounds, - from 0.1% to 2.8% by mass of a copolymer of aromatic monovinyl hydrocarbon and conjugated diene (e.g. SBS), - 0.1 to 30% by mass of a plastic pyrolysis residue, resulting from the distillation of a hydrocarbon product obtained by thermal conversion of plastics, particularly plastic waste, relative to the total mass of the bituminous composition.

[0159] According to one embodiment, the composition according to the invention has a ball and ring softening temperature, measured according to standard EN 1427, higher than the ball and ring softening temperature of the same composition free from bisamide compound and / or distillation residue.

[0160] Preferably, the composition according to the invention has a ball and ring softening temperature, measured according to standard EN 1427, greater than 60°C, more preferably greater than or equal to 80°C, advantageously ranging from 60°C to 120°C.

[0161] The bituminous composition according to the invention has a reduced hot viscosity, and can therefore be fluidized at a lower temperature than the same composition free of bisamide compound and / or distillation residue. Thus, the bituminous composition of the invention is advantageous in that it can be applied at a lower temperature. This reduction in application temperature therefore results in a reduction of the energy required for the application of the compositions of the invention, particularly for the preparation of bituminous mixes.

[0162] For the purposes of this invention, "application temperature" means the minimum temperature to which a bituminous composition must be heated so that it is sufficiently fluid and / or ductile to be transformed into a final product, in particular to be mixed with aggregates to form a bituminous coating.

[0163] According to one embodiment, the composition according to the invention has an average dynamic viscosity of 400 mPa.s measured according to standard NF EN 13702 at a temperature lower than that required to achieve the same viscosity value in a polymer-modified bitumen composition free of the bisamide compound and / or the distillation residue.

[0164] Advantageously, at equivalent viscosity, the implementation temperature of the bituminous composition according to the invention is reduced by 5 to 40°C, preferably by 10 to 20°C compared to the application temperature of a polymer-modified bitumen composition free of the bisamide compound and / or the distillation residue.

[0165] According to one embodiment, the composition according to the invention achieves an average dynamic viscosity of 400 mPa.s measured according to standard NF EN 13702 at a temperature below 170 °C, preferably below 165 °C, preferably even below 160 °C.

[0166] According to one embodiment, the composition according to the invention has an elastic recovery at low stress, measured according to standard EN 13398, greater than or equal to that of a polymer-modified bitumen composition free of the bisamide compound and / or the distillation residue.

[0167] Advantageously, the bituminous composition according to the invention has a reduced carbon footprint of at least 5%, preferably at least 10%, preferably even more at least 15%, and advantageously between 15% and 25% compared to a polymer-modified bitumen composition free of the bisamide compound and / or the distillation residue.

[0168] Advantageously, the bituminous composition according to the invention has a carbon footprint of less than 290 g CO2eq (grams of carbon dioxide equivalent per kilogram of product), preferably less than 270 g CO2eq, preferably even less than 250 g CO2eq, as determined according to ISO 14067.

[0169] The "carbon footprint" of a product, as defined in the invention, refers to the amount of carbon required to produce said product. This amount of carbon equivalent takes into account both energy consumption, particularly related to heating, and raw material consumption. The carbon footprint of a product is typically determined according to ISO 14067, based on the life cycle assessment (LCA) method, in accordance with ISO 14040 and ISO 14044. The carbon footprint is generally expressed in kilograms of carbon dioxide equivalent (kg CO2eq) or in grams of carbon dioxide equivalent (g CO2eq), a unit that takes into account not only CO2, but also other greenhouse gases (GHGs) such as methane (CH4) and nitrous oxide (N2O), by converting them into an equivalent amount of CO2 to simplify the comparison.

[0170] In the context of the present invention, the carbon footprint is advantageously calculated using an approach that includes only emissions related to the production of the materials (raw material extraction, processing, and delivery to the factory using a "Cradle-to-Gate" approach), without taking into account the product's use or end-of-life phases. For example, if a composition has a carbon footprint of 228 g CO2eq, this corresponds to the emissions generated solely during the production of the composition according to the invention, before its use on the construction site or its disposal.

[0171] According to one embodiment, the composition according to the invention comprises a significant proportion of recycled or waste-derived materials. It can therefore exhibit a high eco-material index. The eco-material index is defined by the following equation:

[0172] Eco-material index = 100% - [% of non-bio-based, non-biodegradable, non-recycled or non-waste-derived materials].

[0173] According to one embodiment, the composition has an eco-material content of at least 5% by mass, relative to the total mass of the composition, preferably at least 10%, preferably at least 15%.

[0174] Method for preparing a bituminous composition according to the invention

[0175] The bituminous compositions of the invention can be prepared by any process known to those skilled in the art. Generally, these processes include bringing the different components into contact, followed by mixing them, preferably under heating.

[0176] Preferably, the bitumen, and optionally the distillation residue, are heated separately and then hot-mixed. The copolymer and the bisamide compound are then added without having been preheated.

[0177] The invention thus relates to a method for preparing a bituminous composition as defined above, said method comprising: 1) bringing into contact: - at least one bitumen base; - at least one copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs as defined above, - at least one bisamide compound as described above, - possibly the distillation residue as described above, - possibly one or more additives, 2) their mixture under heating.

[0178] Advantageously, the process of the invention comprises the following successive steps: - heating the bitumen - possibly, heating the distillation residue, - possibly, the hot mixing of bitumen and distillation residue, - the introduction of the bisamide compound, - the introduction of the copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs, - possibly the introduction of one or more additives.

[0179] It has been found that the prior addition of the bisamide compound of formula (I), followed by the incorporation of the copolymer into the bituminous composition, improves the mechanical properties of the composition while providing the advantages mentioned above.

[0180] According to a preferred embodiment, the bitumen, and optionally the distillation residue when present in the composition, are heated before mixing, preferably separately.

[0181] The heating temperature of the bitumen base depends on its grade. In particular, the bitumen base is heated in accordance with the requirements given in standard NF EN 12594.

[0182] The distillation residue is typically heated to a temperature greater than or equal to its melting point. The heated residue is thus in a fluid form so as to facilitate its mixing with the bitumen.

[0183] Generally, and as is known to those skilled in the art, the bitumen or mixture of bitumens used for the preparation of the composition according to the invention is preheated and stirred before the other constituents of the composition are incorporated. The incorporation of the copolymer and the bisamide compound, and possibly the distillation residue and other additives, is generally carried out while the bitumen is maintained at a temperature in the range of 90°C to 230°C, preferably in the range of 120°C to 200°C, and preferably in the range of 150°C to 180°C.

[0184] Advantageously, heating is maintained throughout the process, and the heating temperature can be modulated during the process. Agitation can be maintained or interrupted intermittently as needed, or modulated during the process.

[0185] The various embodiments, variants, preferences and advantages described above for each of the objects of the invention also apply to the process according to the invention and can be taken separately or in combination.

[0186] The bituminous compositions that can be obtained by this process also form an integral part of the invention. Applications

[0187] Various uses of the bituminous compositions according to the invention are envisaged. In particular, the bituminous compositions according to the invention can be used as a bituminous binder.

[0188] The bituminous composition according to the invention can be used to prepare bituminous mixes, in combination with aggregates. With regard to road applications, the invention relates in particular to bituminous mixes as materials for the construction and maintenance of roadbeds and their surfacing, as well as for carrying out all roadworks.

[0189] Bituminous mix refers to a mixture of a bituminous binder with aggregates and optionally mineral and / or synthetic fillers. The bituminous mix comprises a bituminous binder according to the invention, and optionally mineral and / or synthetic fillers, preferably selected from fines, sand, gravel, and recycled millings.

[0190] Aggregates are mineral and / or synthetic aggregates, in particular recycled millings, with dimensions greater than 2 mm, preferably between 2 mm and 20 mm.

[0191] According to one aspect, the present invention also relates to a bituminous coating comprising a composition as described above and aggregates, and optionally mineral and / or synthetic fillers.

[0192] The invention also relates to a method for preparing a bituminous mix, in particular a warm mix, comprising the hot mixing of a bituminous composition according to the invention, with aggregates, and optionally mineral and / or synthetic fillers.

[0193] Advantageously, the process for preparing a warm mix coating according to the present invention comprises at least the steps of: - heating the aggregates to a temperature below 150°C, preferably from 100°C to 140°C, preferably from 120°C to 140°C, - mixing of aggregates with the bituminous composition according to the invention, - obtaining bituminous coatings.

[0194] With regard to road applications, the invention also relates to asphalts as materials for manufacturing and covering sidewalks.

[0195] Asphalt is defined as a mixture of bituminous binder with mineral and / or synthetic fillers. An asphalt comprises a bituminous composition as described in the context of the invention and mineral fillers such as fines, sand, or gravel, and / or synthetic fillers. The mineral fillers consist of fines (particles smaller than 0.063 mm), sand (particles between 0.063 mm and 2 mm), and optionally gravel (particles larger than 2 mm, preferably between 2 mm and 4 mm). Asphalts have 100% compaction and are primarily used for manufacturing and surfacing sidewalks, whereas asphalt mixes have less than 100% compaction and are used for constructing roads. Unlike asphalt mixes, asphalts are not roller-compacted during placement.

[0196] The invention also relates to a method for preparing an asphalt comprising the hot mixing of a bituminous composition according to the invention, with mineral and / or synthetic fillers.

[0197] Bituminous mixes and asphalts prepared from the bituminous composition according to the invention can be used for the manufacture of road surfaces, pavements, sidewalks, roads, urban developments, soils, in particular for the manufacture of foundation layers, base layers, sub-base layers, surface layers such as binder layers and / or wearing courses.

[0198] Another aspect of the invention relates to the use of a bituminous composition in various industrial applications, particularly for preparing an impregnation layer. Examples of industrial applications of bituminous compositions include the manufacture of noise-reducing membranes, insulation membranes, surface coatings, carpet tiles, and impregnation layers. Examples

[0199] The invention is illustrated by the following examples given by way of non-limiting example.

[0200] I- Materials:

[0201] - Grade 35 / 50 bitumen, rated B0, with a penetration of 39.10-1 mm and a TBA of 52°C, commercially available from TotalEnergies under the AZALT® brand, - SBS DI 192 Kraton® triblock copolymer, with a molar mass of approximately 150 kg / mol and a polystyrene content of 30% by weight, - Sulfur-based crosslinking agent PAXL B, Scavenger Baerostab L233, - Plastic pyrolysis residue noted H5: heavy fraction from the distillation of pyrolysis oil from plastic waste, characterized by the following properties: boiling point at 10% of 432 °C, flash point between 256 and 278 °C, penetrability of 61 dmm, BWT of 82.7 °C, initial melting temperature (IM) of -18 °C and final melting temperature (FM) of 94 °C, - Bisamide Al (according to the invention) synthesized from 1,6-hexanediamine and stearic acid. This bisamide compound has two outer carbon chains of 18 carbon atoms each, and a central block of 6 carbon atoms as represented by the following formula: - Bisamide A2 (according to the invention): synthesized from 1,6-hexanediamine and oleic acid. This bisamide compound has a central block of 6 carbon atoms and two outer carbon chains of 18 carbon atoms. Each outer chain includes an ethylenic unsaturation, as represented by the following formula:

[0202] The bisamide compounds Al and A2 were synthesized without solvent by heating the reactants in a flask for several hours. The amidation reaction produces the bisamide compound as well as water as a byproduct. A Dean-Stark apparatus is used to remove this water: the water formed is condensed in the condenser and then collected in the Dean-Stark apparatus, allowing it to be quantified and the progress of the reaction to be monitored. Once the desired amount of water has been obtained, the contents of the flask are transferred to a suitable container to allow the product to solidify.

[0203] The carbon footprint values ​​of the raw materials and the process used in the synthesis of bisamide compounds, estimated or found in databases, are summarized in Table 1.

[0204] [Table 1] Carbon footprints of raw materials and the synthesis process of bisamide compounds Carbon footprint (kg CO2 / kg of product) Source Stearic acid 0.5 Ecoinvent Oleic acid 2.85 ITERG 1,6-Hexanediamine 6.2 CarbonMinds Amidification 0.215 Esterification value NYCO Al-1.23 A2 0.85 SBS 2.68

[0205] II- Bituminous formulations: 11-1) Bitumen - SBS Polymer Bitumen B0 is first heated to 160 °C for 1 hour, then transferred to a glass reactor. Under stirring at 6000 rpm using a rotor-stator, half of the Scavenger is rapidly added, and the mixture is held for 15 minutes. Next, the SBS polymer and the crosslinking agent are gradually added. The mixture is again stirred under the same conditions for 15 minutes to ensure homogeneous dispersion of the components. The reactor is then placed in a heating mantle set at 180 °C and maintained under stirring at 200 rpm for 24 hours. The second half of the Scavenger is added 15 minutes before the end of the reaction.

[0206] 11-2) Bitumen - Bisamide - SBS Polymer Initially, bitumen B0 is heated to 160 °C for 1 hour and then poured into a glass reactor. The reactor is then placed in a heating mantle preheated to 160 °C, and stirring is initiated at 200 rpm. The bisamide compound is gradually added using a funnel while maintaining stirring, thus ensuring homogeneous dispersion. Once the bisamide compound is incorporated, the SBS polymer is added to the mixture under continuous stirring. The formulation is maintained under stirring at 170–180 °C for 24 hours. Unlike the formulation containing only bitumen and SBS polymer, here the SBS polymer is not cross-linked.

[0207] 11-3) Bitumen - Bisamide - SBS Polymer - Plastic Pyrolysis Residue Bitumen B0 is heated to 150 °C for 1 hour and 30 minutes, then transferred to a glass reactor. Residue H5 is added gradually while stirring with a rod. The reactor is then placed in a heating mantle preheated to 150 °C, and stirring is initiated at 200 rpm. The formulation is maintained under stirring at this temperature for 30 minutes. The bisamide compound is added gradually using a funnel while maintaining stirring, thus ensuring homogeneous dispersion. Once the bisamide compound is incorporated, the SBS polymer is added to the mixture under continuous stirring. The formulation is maintained under stirring at 170–180 °C for 24 hours. Unlike the formulation containing only bitumen and SBS polymer, here the SBS polymer is not crosslinked.

[0208] Table 2 summarizes the formulations prepared, with parts and percentages expressed by weight.

[0209] [Table 2] Prepared bituminous formulations Fl F2 F3 F4 F5 B0 96.6 96 96.5 96 86 SBS 3.4 2 2 2 2 H5 10 Al 2 1.5 2 A2 2

[0210] III- Characterization of bituminous formulations: The characteristics of the bituminous formulations referred to in these examples are measured according to the methods indicated in Table 3.

[0211] [Table 3] Measured properties and measurement methods of bituminous formulations Property Abbreviation Unit Measurement Standard Softening Temperature (°C) NF EN 1427 Dynamic Viscosity (V) mPa·s NF EN 13702 Elastic Recovery (εr) % NF EN 13398 Maximum Elongation at Break (εmax) % EN 13587 Carbon Footprint (g CO2 eq) ISO 14067

[0212] The carbon footprints of the prepared binder formulations were calculated according to the IPCC 2013 GWP 100 methodology, using Simapro (V9.3.0.3) in a "Cradle to Gate" approach, which allows for an assessment of greenhouse gas emissions over a period of 100 years in CO2 equivalents (IPCC, 2013).

[0213] IV- Results: The results obtained with the different formulations prepared are reported in Table 4.

[0214] [Table 4] Thermal, rheological and environmental properties of the prepared bituminous formulations Fl F2 F3 F4 F5 TBA (°C) >60 100.5 69.5 80.8 113 Temperature corresponding to a screw diameter of 400 mPa.s (°C) 170 164 158 164 138 Temperature gain at 400 mPa.s (°C) 0 6 12 6 32 eR at 0.1 Pa (%) 83 93 98 92 98 eR at 3.2 Pa (%) 84 76 37 47 51.1 Maximum elongation (%) 700 506 655 nd nd Carbon footprint (g CO2 eq / kg) 291 228 235 269 nd CO2 gain (%) compared to Fl - -22% -19% -8% nd

[0215] nd= not determined

[0216] These results show that formulations comprising a combination of bisamide compounds and SBS copolymer provide a significant improvement in softening temperature compared to the reference formulation Fl (bitumen + SBS). For example, formulation F2 (bitumen + Al) achieves a softening temperature of 100.5 °C, and formulation F4 (bitumen + A2) reaches 80.8 °C. This increase indicates that bisamide compounds improve the thermal resistance of the bituminous binder, which is essential for preventing rutting under high-temperature traffic.

[0217] Formulation F5 (bitumen + SBS + bisamide + plastic pyrolysis residue H5) exhibits the highest TBA, reaching 113 °C. This suggests that the addition of residue H5 further enhances the thermal stability of the binder.

[0218] With regard to dynamic viscosity, formulation Fl requires a temperature of 170 °C to achieve a viscosity of 400 mPa·s, while formulations containing bisamide compounds (F2 to F4) show lower temperatures, ranging from 158 °C to 164 °C. Formulation F5, containing residue H5, exhibits the lowest application temperature, at 138 °C. These results indicate The addition of bisamide compounds, and more specifically plastic pyrolysis residue, significantly reduces the hot viscosity of bitumen. This facilitates its application at lower temperatures, thus paving the way for the production of warm mix asphalt, which requires less energy and reduces greenhouse gas emissions during its manufacture.

[0219] In terms of elastic recovery under low stress (0.1 Pa), all formulations show good performance with values ​​exceeding 90%. Formulations F3 (bitumen + Al) and F5 (bitumen + SBS + H5) stand out in particular, achieving a maximum elastic recovery of 98%. This demonstrates that the addition of bisamide compounds according to the invention and the plastic pyrolysis residue does not compromise the elastic properties of the binder under low stress.

[0220] The F2 formulation (bitumen + Al) has the lowest carbon footprint with 228 g CO2 eq / kg, representing a significant reduction of 22% compared to FL. This underlines the potential of bisamide compounds to reduce the environmental impact of conventional bituminous formulations containing SBS.

[0221] V- Effect of the order of introduction of additives in formulations: An experiment conducted with bisamide Al showed that adding the SBS polymer (2%) before the bisamide (2%) resulted in a significant decrease in the TB A temperature, which dropped from 106.5 °C when the bisamide was introduced first to only 68.5 °C. This result highlights the importance not only of the choice of additives, but also of optimizing the mixing process.

Claims

Demands

1. Bituminous composition comprising: - at least one bitumen base, - at least one copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs, and - at least one bisamide compound of general formula (I) Ra-X-Rc-X'-Rb(I) • Ra and Rb being a linear, cyclic or branched, saturated or unsaturated hydrocarbon chain comprising from 1 to 36 carbon atoms, and optionally comprising one or more heteroatoms, • Rc being a linear, cyclic or branched, saturated or unsaturated hydrocarbon chain comprising from 3 to 18 carbon atoms, optionally substituted, and optionally comprising one or more heteroatoms, • X and X' representing an amide function, said bituminous composition comprising less than 3% by mass, relative to the total mass of the bituminous composition, of a copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs.

2. Bituminous composition according to claim 1, wherein the bisamide compound has the general formula (IA): Ra-CONH-Rc-NHCO-Rb(IA)

3. Bituminous composition according to claim 1 or claim 2, wherein RC represents a linear and saturated hydrocarbon chain.

4. Bituminous composition according to any one of claims 1 to 3, wherein RC represents a saturated linear hydrocarbon chain comprising more than 4 carbon atoms, preferably between 6 and 12 carbon atoms.

5. Bituminous composition according to any one of claims 1 to 4, wherein RA and RB, identical or different, represent a hydrocarbon chain comprising from 4 to 22 carbon atoms.

6. Bituminous composition according to any one of the preceding claims wherein the bisamide compound is hexamethylene bis-stearate.

7. Bituminous composition according to any one of the preceding claims, comprising from 0.5% to 20% by mass preferably from 1% to 5% by mass of bisamide compound of general formula (I).

8. Bituminous composition according to any one of the preceding claims, wherein the copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs is a styrene-butadiene-styrene copolymer.

9. Bituminous composition according to any one of the preceding claims, comprising from 0.05 to 2.8% by mass, preferably from 0.5 to 2.5% by mass of copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs.

10. Bituminous composition according to any one of the preceding claims further comprising at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics.

11. The bituminous composition according to claim 10, wherein the distillation residue is an atmospheric distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by pyrolysis of plastic waste.

12. Composition according to claim 10 or 11, comprising from 1 to 30% by mass preferably of 0.5 to 25% of distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, relative to the total mass of the bituminous composition.

13. Bituminous composition according to any one of the preceding claims comprising an eco-material content of at least 5% by mass, preferably at least 10% by mass, preferably at least 15% by mass relative to the total mass of the bituminous composition.

14. Bituminous coating comprising a bituminous composition according to any one of claims 1 to 8, mixed with aggregates and / or recycled millings, and optionally mineral and / or synthetic fillers.

15. A method for preparing a bituminous composition according to any one of the preceding claims, comprising, in order, the following steps: (A) heating the bitumen, preferably to a temperature between 100°C and 220°C, (B) optionally, heating the distillation residue of a hydrocarbon product obtained by thermal conversion of plastics, (C) optionally, hot mixing of the bitumen and the distillation residue, (D) introduction of the bisamide compound of general formula (I), (E) introduction of the copolymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs.