Bitumen / polymer composition incorporating a plastic thermal conversion residue

Abstract

The present invention relates to a bitumen / polymer composition comprising: - at least one bitumen base, - at least one residue from distillation of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, - from 5% to 40% by mass of at least one elastomer, relative to the total mass of elastomer(s), of bitumen base(s) and of distillation residue(s).

Description

[0001] BITUMEN / POLYMER COMPOSITION INCLUDING A PLASTIC THERMAL CONVERSION RESIDUE

[0002] The present invention relates to a polymer-modified bituminous composition incorporating a distillation residue of a hydrocarbon product obtained by thermal conversion of plastics, in particular plastic waste. The composition of the invention is particularly suitable for the manufacture of waterproofing and / or soundproofing materials. The invention also relates to a process for preparing a bitumen / polymer composition according to the invention and its use for the manufacture of various waterproofing and / or soundproofing materials.

[0003] For many years, various waterproofing and soundproofing materials based on bitumen modified by polymers, particularly by SBS (styrene-butadiene-styrene) elastomers, have been known. Examples include waterproofing membranes, which have been widely developed since the 1970s in the flat roof waterproofing sector, or adhesives, primers and soundproofing membranes. It is also known to incorporate one or more fluxing agents into these products in order to lower their viscosity at the application temperature.

[0004] Bitumen is generally obtained from residues from the distillation of atmospheric and / or vacuum crude oil. Furthermore, in the vast majority of cases, polymers, particularly elastomers, are synthesized from petroleum. Finally, fluxing agents generally consist of fossil or synthetic oils, obtained from petroleum. The technical field of waterproofing and soundproofing products is therefore very dependent on the availability of petroleum today.

[0005] Oil resources are, however, limited. Indeed, "proven reserves" of oil reached more than 200 billion tonnes of oil equivalent (TOE) worldwide in 2018, according to experts at British Petroleum (who have been taking stock of the resource since 1980). Although significant, these reserves could only cover 50.2 years of annual consumption at the rate of 2017. These figures are confirmed by the French Alternative Energies and Atomic Energy Commission (CEA) and the International Energy Agency (IEA).

[0006] It is therefore necessary to limit our oil consumption but also the dependence of this industry on oil resources. In particular, and with a view to sustainable development, it would be useful to have bituminous compositions for waterproofing and / or soundproofing materials with a reduced content of compounds of fossil origin, in particular bitumen and / or polymer(s) and / or fluxing agent(s).

[0007] In order to reduce our oil consumption, it is envisaged here to integrate into bituminous compositions compounds / materials from recycling, in particular from the recycling of plastic waste. This approach consists of promoting the circular economy by limiting the use of fossil resources, in particular bitumen, by incorporating waste from various sources into the composition.

[0008] In this sense, it is known to valorize plastic waste by using it as an initial charge in chemical processes (gasification, pyrolysis, depolymerization, dissolution) or in mechanical processes (crushing). In the initial charge, plastic waste can also be combined with waste from biomass.

[0009] High-temperature pyrolysis processes make it possible to transform plastic waste into several products in varying proportions depending on the nature of the waste used: an oil, a gas mixture, coke.

[0010] The oil from the pyrolysis of the plastic can then be separated into several fractions by all types of separation processes known per se:

[0011] • The light naphtha type cut with a distillation range between 50 and 200°C and a density between 720 Kg / m 3 and 750 kg / m 3 ;

[0012] • The average diesel cut with a distillation interval between 200°C and 300°C and a density between 750 Kg / m 3 and and 800 Kg / m 3 ;

[0013] • The heavy cut type VGO (“Vaccum Gasoil” in English) with a distillation interval between 300°C and 450°C and a density between 800 Kg / m 3 and 840 kg / m 3 ;

[0014] • A very heavy cut type VR (Visco-Reduced) with an initial boiling point of at least 450 °C and a density between 840 Kg / m 3 and 870 kg / m 3 .

[0015] Only light naphtha cuts can be used as petrochemical feedstock for a steam cracker. Heavy VGO and very heavy VR cuts cannot be used as such as steam cracker feedstocks. There is therefore an alternative need to upgrade heavy to very heavy cuts.

[0016] EP 4 124 638 A1 describes bitumen base compositions comprising up to 5% by mass of at least one plastic pyrolysis oil having an initial boiling point of at least 300°C. The compositions obtained have improved properties in terms of softening temperature variation, compared to bitumen alone. However, this document does not specifically deal with bituminous compositions suitable for waterproofing and / or soundproofing applications. In particular, it does not specifically deal with polymer-modified bitumen compositions. In addition, the pyrolysis oil content is limited to a maximum of 5% by mass.

[0017] There therefore remains a need to provide bituminous compositions whose dependence on fossil resources is significantly reduced compared to the compositions of the prior art.

[0018] In particular, there remains a need for compositions incorporating a greater proportion of recycled components, compared to the compositions of the prior art. In other words, there remains a need for bituminous compositions whose content of material(s) of fossil origin, in particular bitumen and / or fluxing agent and / or polymer, is significantly reduced compared to the compositions of the prior art.

[0019] Thus, there remains on the one hand the need for compositions whose bitumen content is significantly reduced compared to the compositions of the prior art.

[0020] There also remains a need for compositions whose polymer content is significantly reduced compared to the compositions of the prior art.

[0021] There is also a need for compositions whose content of fluxing agents, in particular of petroleum or synthetic origin, is significantly reduced compared to the compositions of the prior art.

[0022] Furthermore, oil exploitation is currently responsible for the release of significant quantities of greenhouse gases into the atmosphere, which have a significant impact on global warming. The carbon footprint associated with bitumen / polymer compositions is even greater. Indeed, the carbon footprint of pure bitumen is estimated at 0.417 kg of CO2 equivalent per kg of bitumen (estimate made by the Ecoinvent association). The carbon footprint of a polymer, particularly a styrene and butadiene elastomer, is currently estimated at between 2.2 and 4.7 kg of CO2 equivalent per kg of polymer, depending on the process used and plant optimization.

[0023] There is therefore also a need for bituminous compositions, in particular intended for use as waterproofing and / or soundproofing materials, having a reduced carbon footprint, compared to the compositions of the prior art. It is also essential that the bituminous compositions have equivalent, or even improved, properties compared to the compositions of the prior art. Summary of the invention

[0024] The invention firstly relates to a bitumen / polymer composition comprising:

[0025] - at least one bitumen base,

[0026] - at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics,

[0027] - from 5% to 40% by mass of at least one elastomer, and relative to the total mass of elastomer(s), bitumen base(s) and distillation residue(s).

[0028] Preferably, the residue is a residue from atmospheric distillation of a hydrocarbon product, said hydrocarbon product having been obtained by pyrolysis of plastic waste.

[0029] By "atmospheric distillation" we mean an operation consisting of separating the different components of a liquid mixture according to their evaporation temperature at atmospheric pressure.

[0030] Advantageously, the residue has a boiling point at 10% by mass, measured according to standard ASTM D7169:20, greater than or equal to 350°C, preferably ranging from 400°C to 600°C, typically ranging from 410°C to 550°C.

[0031] According to one embodiment, the residue has a ring and ball softening temperature (RBT), measured according to standard 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.

[0032] Preferably, the elastomer is chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene.

[0033] According to one embodiment, the elastomer is chosen from polyurethanes.

[0034] According to one embodiment, the bitumen / polymer composition according to the invention comprises:

[0035] - from 10% to 90% by mass of bitumen,

[0036] - from 0.1% to 30% by mass of said at least one distillation residue,

[0037] - from 5% to 40% by mass of elastomer(s),

[0038] - from 0% to 70% of fillers / or additives, and

[0039] - from 0% to 20% by mass of fluxing agent(s), relative to the total mass of the composition.

[0040] The invention also relates to the use of a bitumen / polymer composition according to the invention, for the manufacture of a waterproofing and / or soundproofing material, preferably chosen from: a waterproofing membrane, a liquid coating, an adhesive, a primer and a soundproofing membrane. The invention also relates to a prefabricated waterproofing membrane comprising:

[0041] - a support or reinforcement, in particular one or more fibrous reinforcement(s),

[0042] - a bitumen / polymer composition according to the invention, said support or reinforcement being coated on at least one face, preferably impregnated to the core, with said bituminous composition.

[0043] The invention also relates to a method for manufacturing a waterproofing membrane according to the invention, said method comprising the following successive steps:

[0044] 1) the provision of a bitumen / polymer composition according to the invention;

[0045] 2) the application of the composition obtained in step 1) on at least one face of a support or reinforcement.

[0046] The invention finally relates to the use in a bitumen / polymer composition, intended for the preparation of a sealing and / or soundproofing material, of at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, to reduce the content of compounds of fossil origin, in particular bitumen and / or polymer and / or fluxing agent(s), of said composition.

[0047] The inventors have surprisingly discovered that it is possible to reduce the content of material(s) of fossil origin, in particular bitumen and / or elastomer(s) and / or fluxing agent(s) of petroleum or synthetic origin, in a bitumen / polymer composition intended for the preparation of a waterproofing and / or soundproofing product, by integrating into said bitumen / polymer composition a particular residue, obtained by distillation of a hydrocarbon product, itself obtained by thermal conversion of plastic (waste).

[0048] In particular, the inventors have discovered that it is possible to reduce the content of material(s) of non-renewable origin, in particular bitumen and / or elastomer and / or fluxing agent of petroleum or synthetic origin, in the bitumen / polymer composition by integrating such a residue, without significantly affecting the properties of the final product. The final product has properties that are substantially equivalent, or even improved, compared to those of products free from said residue.

[0049] Furthermore, the inventors have surprisingly discovered that the incorporation of this type of residue into a bitumen / polymer composition makes it possible to improve the cold pliability or flexibility of the composition, at a constant polymer content. The compositions, as well as the materials obtained from these compositions, are thus less sensitive to cold cracking. More particularly, the inventors have discovered that the incorporation of such a residue into a bitumen / polymer composition intended for the preparation of a waterproofing and / or soundproofing product makes it possible to:

[0050] - at constant polymer content, to improve the properties of the composition, particularly in terms of cold bendability, or

[0051] - with equivalent performance, in particular with equivalent cold bendability, to reduce the polymer content in the composition.

[0052] The invention is thus advantageous in that it makes it possible to reduce the content of material(s) of fossil origin, in particular bitumen and / or fluxing agent and / or polymer, of the bitumen / polymer compositions conventionally used for the manufacture of waterproofing and soundproofing materials.

[0053] Detailed description of the invention

[0054] In the remainder of the description, and unless explicitly indicated otherwise, the quantities of the various components present in a bituminous composition according to the invention are given in % by mass, relative to the total mass of the composition (hereinafter referred to as % m / m).

[0055] Likewise, and unless explicitly stated otherwise, the standards mentioned in the remainder of the description correspond to the standard in force on the date of 1 er July 2023.

[0056] The term "boiling point" refers to the boiling point generally used in the oil and gas industry. Boiling points are measured at atmospheric pressure. The initial boiling point is defined as the temperature value when the first vapor bubble is formed. The final boiling point is the highest temperature that can be reached during a standard distillation. At this temperature, no more vapor can be entrained in the condensing units. The determination of the initial and final boiling point is known per se. Depending on the boiling range of the mixture, they can be determined using various standardized methods such as ASTM D2887:2019 for the boiling range distribution of petroleum fractions by gas chromatography.

[0057] For compositions containing heavier hydrocarbons, ASTM D7169:2020 or D2892-20:2020 may also be used. Distillate boiling ranges can also be advantageously measured using ASTM D7500:2019.

[0058] The invention firstly relates to a bitumen / polymer composition comprising: - at least one bitumen base, - at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, in particular plastic waste, and

[0059] - at least one polymer.

[0060] Bitumen base

[0061] The bitumen(s) used to prepare a bitumen / polymer composition according to the invention are called “bitumen base”.

[0062] Among the bitumens that can be used according to the invention, mention may firstly be made of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or oil sands and bitumens originating from the refining of crude oil. In the context of the invention, the bitumen(s) used are advantageously chosen from bitumens originating from the refining of crude oil, in particular bitumens containing asphaltenes or pitches. The bitumens can be obtained by conventional processes for the manufacture of bitumens in refineries, in particular by direct distillation and / or vacuum distillation of oil. These bitumens can optionally be visbroken and / or deasphalted and / or rectified in air. It is common practice to carry out vacuum distillation of atmospheric residues originating from the atmospheric distillation of crude oil.This manufacturing process therefore corresponds to the succession of atmospheric distillation and vacuum distillation, the feedstock feeding 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 feedstock usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from the distillation of oil. This process makes it possible to obtain a blown, or semi-blown, or oxidized, or air-rectified, or partially air-rectified bitumen.

[0063] 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 performances. In conventional processes for mixing different bitumens, the operation is carried out at temperatures between 100°C and 200°C, preferably between 140°C and 200°C, and with stirring for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours. The 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 bitumen mixture. This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid.Generally, blowing is carried out at high temperatures, in the order of.

[0064] 200 to 300°C, for relatively long periods of time, typically between 30 minutes and 2 hours, continuously or in batches. The blowing time and temperature are adjusted according to the desired properties of the blown bitumen and the quality of the starting bitumen.

[0065] Among the bitumens that can be used according to the invention, recycling bitumens can also be mentioned.

[0066] Bitumens can be hard grade bitumens (such as grades 10 / 20 and 20 / 30) or soft grade bitumens (such as grade 160 / 220) as defined by EN 12591.

[0067] The invention is particularly suitable for cases where the bitumen base consists of a hard grade bitumen or a mixture of hard grade bitumens, in particular chosen from bitumens of grade 70 / 100, 35 / 50, 20 / 30 and 10 / 20.

[0068] The bitumen bases that can be used in the context of the invention preferably have a penetrability, measured at 25°C according to standard EN 1426, of 5 to 330 1 / 10 mm, preferably between 10 and 220 1 / 10 mm, more preferably from 10 to 120 1 / 10 mm. In a well-known manner, the so-called “needle penetrability” measurement is carried out by means of a standardized test NF EN 1426 at 25°C (P25). 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 into a sample of bitumen, after a time of 5 seconds, of a needle whose weight with its support is 100 g.

[0069] Preferably, the composition according to the invention comprises at least 50% by mass of bitumen, relative to the total mass of bitumen base(s), residue(s) and elastomer(s) present in the composition of the invention, preferably at least 60% by mass, more preferably at least 65% by mass, typically at least 70% by mass.

[0070] Advantageously, the composition according to the invention comprises from 50% to 94% by mass of bitumen, relative to the total mass of bitumen base(s), residue(s) and elastomer(s) present in the composition of the invention, preferably from 60% to 90% by mass, more preferably from 70% to 85% by mass. Any fillers, additives and fluxing agents are not taken into consideration in these ranges.

[0071] Distillation residue

[0072] The bitumen / polymer composition of 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.

[0073] Common industrial methods for recycling hydrocarbons from plastic include thermal conversion liquefaction of plastic waste that might otherwise have ended up in a landfill or incinerator, followed by a purification step that includes hydrotreatment and contaminant removal using a variety of purification processes such as distillation.

[0074] Plastic waste liquefaction can be achieved by pyrolysis or hydrothermal treatment. The thermal conversion step transforms plastics and most of their additives and contaminants into gaseous chemicals, while most non-volatile contaminants or additives are found in the solid by-product, carbon, or ash. In principle, all types of plastic waste can be converted. However, a preliminary sorting step for non-organic waste is desirable. Purification of the output material may also be useful because several heteroelements (i.e., elements other than carbon, hydrogen, or oxygen) can be volatilized.

[0075] Plastic waste is a complex and heterogeneous material due to several factors. First, plastic as a material refers to many different polymers with different chemical properties that can be separated from each other before recycling or recycled as a complex mixture. The main polymers found in plastic from municipal solid waste are polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), and polystyrene (PS). Other polymers mainly include polyurethanes, polyamides (PA), polycarbonates, polyethers, and polyesters other than PET. In addition, many additives other than 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, glidants, curing agents, foaming agents, biocides, antioxidants, etc.), dyes 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 metal compounds are intentionally added during plastic production (often in the form of oxides, carbonates, acids, etc.). Additives containing heteroelements other than metals are also used in plastic manufacturing, e.g., halogens such as bromine in flame retardants, plasticizers, stabilizers, etc.

[0076] Silicone polymers, which are organic materials containing silicon, are often used in plastic formulations. Due to their surface characteristics, silicone applications 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-enhancing additives (manufacturing aids), and for polymer modification.

[0077] In addition to these heteroelements, used plastic waste may have been contaminated during its lifetime by remnants 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.

[0078] Finally, since plastics are contaminated with oxygenated compounds, plastic oils from pyrolysis liquefaction may also contain oxygenated compounds such as aldehydes or ketones.

[0079] For the purposes of the invention, the term "hydrocarbon product obtained by thermal conversion of waste" or "hydrocarbon product" means the liquid products obtained after thermal conversion, in particular after thermal pyrolysis, of plastic waste or plastic waste. The thermal conversion process, in particular pyrolysis, must be understood as a non-selective thermal cracking process.

[0080] 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.

[0081] The residue incorporated 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.

[0082] The residue incorporated in the bituminous composition of the invention may 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 corresponds, for its part, to the succession of an atmospheric distillation and a vacuum distillation, the feedstock feeding 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.

[0083] Preferably, the residue incorporated into the composition of the invention is a residue obtained by vacuum distillation of the hydrocarbon product defined above. The residue of the invention typically has a penetrability at 25°C, measured according to standard EN 1426, of less than or equal to 200 1 / 10 mm.

[0084] 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.

[0085] 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.

[0086] Preferably, the residue of the invention has a ring and ball softening temperature (RBT), measured according to standard 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.

[0087] Preferably, the residue of the invention has a Cleveland flash point, measured according to the ASTM D 92 standard, 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.

[0088] Distillation is commonly performed 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 gradually. These boiling points increase during distillation.

[0089] Preferably, the residue of the invention has an initial boiling temperature, measured according to standard ASTM D7169:20, less than or equal to 500°C, more preferably ranging from 100°C to 500°C, more preferably from 200°C to 480°C.

[0090] Preferably, the residue of the invention has a final distillation point, measured according to standard ASTM D7169:20, less than or equal to 1000°C, more preferably less than or equal to 900°C.

[0091] More preferably, the residue of the invention has a final boiling point, measured according to standard ASTM D7169:20, ranging from 150°C to 1000°C, more preferably from 200°C to 900°C.

[0092] For the purposes of the invention, the term "boiling temperature at X% of product Y" means the boiling temperature of the remaining part of product Y once X% by mass of the starting product has been evaporated.

[0093] Preferably, the residue of the invention has a boiling point at 5% by mass, measured according to the ASTM D7169:20 standard, greater than or equal to 300°C, more preferably greater than or equal to 350°C, typically greater than or equal to 400°C. Preferably, the residue of the invention has a boiling point at 5% by mass, measured according to the ASTM D7169:20 standard, less than or equal to 550°C, more preferably less than or equal to 500°C.

[0094] Preferably, the residue of the invention has a boiling point at 10% by mass, measured according to standard 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.

[0095] Preferably, the residue of the invention has a boiling point at 10% by mass, measured according to standard ASTM D7169:20, less than or equal to 600°C, more preferably less than or equal to 550°C.

[0096] Preferably, the residue of the invention has a boiling point at 15% by mass, measured according to standard 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.

[0097] Preferably, the residue of the invention has a boiling point at 15% by mass, measured according to standard ASTM D7169:20, less than or equal to 600°C, more preferably less than or equal to 550°C.

[0098] Preferably, the residue of the invention has a boiling point at 30% by mass, measured according to standard 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.

[0099] Preferably, the residue of the invention has a boiling point at 30% by mass, measured according to standard ASTM D7169:20, less than or equal to 650°C, more preferably less than or equal to 600°C.

[0100] Preferably, the residue of the invention has a boiling point at 50% by mass, measured according to standard 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.

[0101] Preferably, the residue of the invention has a boiling point at 50% by mass, measured according to standard ASTM D7169:20, less than or equal to 700°C, more preferably less than or equal to 650°C.

[0102] Preferably, the residue of the invention has a boiling point at 70% by mass, measured according to standard 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.

[0103] Preferably, the residue of the invention has a boiling point at 70% by mass, measured according to standard ASTM D7169:20, less than or equal to 750°C, more preferably less than or equal to 730°C.

[0104] Preferably, the residue of the invention has a boiling point at 80% by mass, measured according to the ASTM D7169:20 standard, greater than or equal to 475°C, more preferably greater than or equal to 500°C, typically greater than or equal to 510°C. Preferably, the residue of the invention has a boiling point at 80% by mass, measured according to the ASTM D7169:20 standard, less than or equal to 775°C, more preferably less than or equal to 750°C.

[0105] Preferably, the residue of the invention has a final boiling temperature (i.e. boiling temperature at 100% by mass), measured according to standard 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.

[0106] According to one embodiment, the residue of the invention has a calcium element 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 ash obtained and analysis of the solutions by ICP-OES.

[0107] According to one embodiment, the residue of the invention has a content of phosphorus element P 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 following conventional acid conditions.

[0108] According to one embodiment, the residue of the invention has a silicon element 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.

[0109] According to one embodiment, the residue of the invention has a chlorine element 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.

[0110] According to one embodiment, the residue 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.

[0111] According to one embodiment, the residue 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 ranging from 75 to 110°C, even more preferably ranging from 80 to 110°C. Advantageously, the composition of the invention has a content of distillation residue 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 bitumen base(s), residue(s) and elastomer(s) present in the composition of the invention, preferably ranging from 1% to 25% by mass, more preferably from 5% to 20% by mass. Any fillers, additives and fluxing agents are not taken into account in these ranges.

[0112] Elastomer

[0113] The composition according to the invention further comprises at least one elastomer. Thus, the composition of the invention is a bitumen / polymer composition. It may be crosslinked or not crosslinked.

[0114] The elastomer is not specifically limited provided that it has the qualities required for the final waterproofing membranes. Such elastomers are well known in the art and are generally rubbery polymers.

[0115] Preferably, the elastomer is chosen from thermoplastic elastomers.

[0116] As elastomer, mention may be made, for example, of polyurethane elastomers. Thus, according to one embodiment, the composition according to the invention comprises at least one polyurethane as elastomer. The polyurethanes used in the compositions of the invention are obtained according to the usual methods well known to those skilled in the art.

[0117] More preferably, the elastomer is typically chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene.

[0118] Examples of elastomeric copolymers suitable for the invention include, in particular, copolymers of styrene and butadiene, optionally hydrogenated, copolymers of styrene and isoprene, copolymers of styrene, ethylene and butadiene-styrene (SEBS), polyisobutadiene (PIB), and any of their mixtures.

[0119] Preferably, the elastomer is chosen from block copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene.

[0120] Examples of elastomeric block copolymers suitable for the invention include styrene-butadiene (SB), styrene-butadiene-styrene (SBS), hydrogenated SBS, styrene-isoprene-styrene (SIS), styrene-ethylene-butadiene-styrene (SEBS), polyisobutadiene (PIB), and any mixtures thereof.

[0121] Preferably, the elastomer is chosen from block copolymers of formula S-BS in which:

[0122] - each S, which may be identical or different, represents a block based on monovinyl aromatic hydrocarbon monomers, - B represents a block based on butadiene monomers, said block B comprising pendant vinyl groups.

[0123] For the purposes of the invention, the term "block" means a polymer chain obtained by the polymerization of several monomers of the same chemical nature. A block is advantageously made up of the repetition of the same monomer.

[0124] In said block copolymers, the S blocks together represent at least 15 mol% of the total number of moles of monomeric units of the block copolymer. Said block copolymers have a weight-average molecular mass ranging from 40,000 to 500,000 g / mol and have a content of pendant vinyl groups contained in the B block(s), which is greater than or equal to 20 mol%, relative to the total number of moles of monomeric units of the block copolymer. These copolymers may hereinafter be called, more simply, SBS elastomer. In general, the two S blocks of the SBS elastomer are identical.

[0125] In the context of the invention, butadiene means 1,3-butadiene which is a conjugated diene. When butadiene, or more generally a conjugated diene, is polymerized via a 1,2-addition mechanism, the result is a vinyl group (also called a vinyl group) pendant relative to the backbone of the polymer. The pendant vinyl groups of the SBS block copolymer therefore correspond to the 1,2-addition polymerization of the conjugated diene monomers, and in particular of the majority butadiene monomers, within the B block. The units obtained by the polymerization of butadiene according to a 1,2-addition mechanism or according to a 1,4-addition mechanism have the same molar mass.

[0126] In particular, the monovinyl aromatic hydrocarbon monomer(s) present in the S blocks of the SBS elastomer are chosen from styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene or mixtures thereof. The preferred monovinyl aromatic hydrocarbon monomer according to the present invention is styrene, which is used, for the constitution of the S blocks as the sole monomer, or as the major monomer in mixtures with minor proportions of one or more other monomers such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene, namely, in proportions of at most 10% by mass, relative to the totality of the monovinyl aromatic hydrocarbon monomers present in said S blocks.The use of styrene as the sole monomer is particularly preferred in the present invention for the constitution of the S blocks of the SBS elastomer. Thus, the monovinylaromatic hydrocarbon monomers from which the S blocks of the SBS block copolymers are derived may be, independently, any monovinylaromatic hydrocarbon monomer as previously described and are preferably styrene.

[0127] The block B based on butadiene monomers entering into the composition of the mentioned block copolymers SBS is, preferably, solely composed of butadiene monomers, or of a mixture of butadiene comprising minor proportions of one or more other structurally related conjugated dienes, and in particular chosen from isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene, in particular representing at most 10% by mass, relative to the totality of the conjugated dienes present in the block B. Preferably, the monomers constituting the block B are exclusively butadiene monomers.

[0128] The SBS block elastomer used in the context of the invention has a weight-average molecular mass Mw ranging from 40,000 to 500,000 g / mol. Preferably, the SBS block elastomer has a weight-average molecular mass Mw of less than or equal to 400,000 g / mol.

[0129] Preferably, the SBS block copolymer used in the context of the invention has a weight-average molecular mass Mw greater than or equal to 50,000 g / mol, more preferably greater than or equal to 65,000 g / mol, even more preferably greater than or equal to 75,000 g / mol, and advantageously greater than or equal to 100,000 g / mol.

[0130] Preferably, the content of monovinyl aromatic hydrocarbon monomer (advantageously styrene) of the SBS block copolymer, determined by 13C NMR spectroscopy (Carbon Nuclear Magnetic Resonance), is greater than or equal to 15% by mass, more preferably greater than or equal to 20% 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.

[0131] Preferably, the content of monovinyl aromatic hydrocarbon monomer (advantageously styrene) of the SBS block copolymer, determined by 13C NMR spectroscopy (Carbon Nuclear Magnetic Resonance), ranges from 25% to 40% by mass, even more advantageously from 28% to 35% by mass, relative to the total mass of the SBS block copolymer.

[0132] Advantageously, SBS block elastomers are in an essentially non-hydrogenated form.

[0133] According to a particular embodiment, the block copolymer of formula SBS is obtained by coupling two block copolymers of formula S-B' in which the blocks S and B' are chosen to obtain an SBS block copolymer. The block B may therefore include a residue of a coupling agent, well known in the field in question. As examples of difunctional coupling agents, mention may be made of dibromoethane, diethyl adipate, divinylbenzene, dimethyldichlorosilane and methyl dichlorosilane.

[0134] Preferably, according to this particular embodiment, the efficiency of the coupling of the two block copolymers of formula S-B', 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%.

[0135] Examples of SBS block copolymers which can be used in the compositions according to the invention, as well as their preparation processes, are described in particular in patent US 5,798,401, as well as in document WO 2007 / 058994 and by the applicant in patent application WO 2011 / 013073.

[0136] The SBS block copolymer usable in the compositions according to the invention is typically chosen from linear or branched block copolymers, preferably from linear or star block polymers.

[0137] For the purposes of the invention, the term "star polymer" means a globular branched polymer having a single branching point (core) from which several linear chains (or branches) emanate.

[0138] According to a preferred embodiment, the waterproofing membrane compositions of the invention comprise at least one linear SBS block copolymer and at least one star SBS block copolymer.

[0139] Preferably, according to this embodiment, the linear copolymer and the star copolymer are present in a molar ratio ranging from 5:1 to 5:1, more preferably ranging from 2:1 to 1:2, even more preferably equal to 1:1.

[0140] It is possible that, in the waterproofing membrane compositions and methods according to the invention, a single SBS block copolymer as described in the context of the invention is used, or that a mixture of SBS block copolymers as described in the context of the invention is used, or that one or more SBS block copolymer(s) as described in the context of the invention are used in combination with one or more other elastomers. According to a preferred variant, the matrix is ​​produced with only one or more, preferably a single, SBS elastomer.

[0141] In the waterproofing membrane compositions according to the invention, said elastomer(s) is / are in a crosslinked form, but this does not affect the percentage that it / they represent within the composition. In other words, the percentages, before and after crosslinking, of the different components used for the preparation of the bituminous composition, are identical. In this case of use of a mixture of elastomers, containing at least one elastomer other than the SBS elastomers, the SBS elastomer represents at least 50%, preferably at least 70% by mass, and preferentially at least 90% of the total quantity of elastomers used (SBS + other elastomer(s)).

[0142] Preferably, the SBS elastomer(s) represent at least 80% by mass of the total quantity of elastomers, preferably at least 90% and preferentially at least 95% of the total quantity of elastomers present, if a mixture of elastomers is used to prepare the bituminous compositions according to the invention. In particular, it is possible for the mixture to contain a portion of S-B' used during the manufacture of the SBS elastomer by coupling, as explained previously.

[0143] The waterproofing membrane composition (optionally crosslinked) according to the invention preferably comprises from 5% to 40% by mass of elastomer(s), in particular of a copolymer of monovinyl aromatic hydrocarbon and conjugated diene, in particular of copolymer of styrene and butadiene, relative to the total mass of bitumen base(s), residue(s) and elastomer(s) present in the composition of the invention. Any fillers, additives and fluxing agents are not taken into consideration in these ranges.

[0144] More preferably, the composition (optionally crosslinked) according to the invention comprises from 6% to 35% by mass of elastomer(s), relative to the total mass of bitumen base(s), residue(s) and elastomer(s) present in the composition of the invention, more preferably from 7% to 20% by mass, advantageously from 10% to 15% by mass. Any fillers, additives and fluxing agents are not considered in these ranges.

[0145] Charges (optional)

[0146] According to one embodiment, the composition of the invention may further comprise fillers.

[0147] The fillers entering into the composition of the present invention are typically mineral and / or organic fillers.

[0148] Preferably, the fillers are chosen from calcium carbonate, volcanic rocks, silica, talc, dolomite, kaolin, carbon black, titanium dioxide, and mixtures thereof.

[0149] Recycled fillers can also be used (lignin, recycled fibers, polymer shreds, coke, cement shreds).

[0150] Preferably, when present, the waterproofing membrane composition (optionally crosslinked) according to the invention comprises from 20% to 70% by mass of fillers, relative to the mass of the composition, more preferably from 40% to 55% by mass, even more preferably from 45% to 55% by mass. Additives (optional)

[0151] The composition of the present invention may optionally comprise one or more additive(s).

[0152] Examples of additives that can be added to said composition according to the invention are flame retardant agents such as borates or halogens, anti-root agents such as Preventol® B5, antioxidant agents, rheological agents.

[0153] Preferably, the composition (optionally crosslinked) according to the invention comprises from 0% to 40% by mass of additives, relative to the mass of the composition (crosslinked), more preferably from 1% to 30% by mass, even more preferably from 2.5% to 20% by mass.

[0154] Fluxing agent (optional)

[0155] According to one embodiment, the composition of the invention may further comprise at least one fluxing agent.

[0156] For the purposes of the invention, the term "fluxing agent" means a product introduced into the composition of the invention with the aim of reducing its viscosity at the processing temperature.

[0157] A fluxing agent suitable for the invention is typically chosen from oils of natural, petroleum or synthetic origin, possibly recycled.

[0158] By "recycled fluxing agent" is meant, in the invention, a fluxing agent obtained by recycling used mineral oils, typically recycled engine oils.

[0159] Preferably, the fluxing agent is chosen from oils of petroleum or synthetic origin, more preferably from aromatic oils.

[0160] Preferably, the composition of the invention (optionally crosslinked) comprises from 0% to 20% by mass of fluxing agent(s), relative to the mass of the composition (crosslinked), more preferably from 1% to 15% by mass, even more preferably from 2% to 8% by mass. Any fillers, additives and fluxing agents are not considered in these ranges.

[0161] Compositions

[0162] According to one embodiment, the composition according to the invention comprises, preferably consists essentially of, even more preferably consists exclusively of:

[0163] - from 50% to 94% by mass of bitumen, preferably from 60% to 90% by mass, more preferably from 70% to 85% by mass;

[0164] - from 0.1% to 30% by mass of residue(s) from the distillation of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, preferably from 1% to 25% by mass, more preferably from 5% to 20% by mass; and - from 5% to 40% by mass of elastomer(s), preferably from 6% to 35% by mass, more preferably from 7% to 20% by mass; relative to the total mass of bitumen base(s), residue(s) and elastomer(s) present in the composition of the invention.

[0165] According to one embodiment, the composition according to the invention comprises, preferably consists essentially of, even more preferably consists exclusively of:

[0166] - from 10% to 60% by mass of bitumen,

[0167] - from 0.1% to 30% by mass of distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics,

[0168] - from 0.1% to 30% by mass of polymer,

[0169] - from 0% to 70% of fillers and / or additives, and - from 0% to 20% by mass of a fluxing agent, relative to the total mass of the composition.

[0170] Advantageously, the composition according to the invention comprises, preferably consists essentially of, even more preferably consists exclusively of:

[0171] - from 20% to 50% by mass of bitumen,

[0172] - from 1% to 25% by mass of distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics,

[0173] - from 0.5% to 20% by mass of polymer,

[0174] - from 10% to 55% of fillers and / or additives, and additives

[0175] - from 1% to 15% by mass of a fluxing agent, relative to the total mass of the composition.

[0176] More advantageously, the composition according to the invention comprises, preferably consists essentially of, even more preferably consists exclusively of:

[0177] - from 30% to 40% by mass of bitumen,

[0178] - from 5% to 20% by mass of distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics,

[0179] - from 1% to 10% by mass of polymer,

[0180] - from 2% to 55% of fillers and / or additives, and

[0181] - from 2% to 8% by mass of a fluxing agent, relative to the total mass of the composition.

[0182] Even more advantageously, the composition according to the invention comprises, preferably consists essentially of, even more preferably consists exclusively of:

[0183] - from 30% to 40% by mass of bitumen, - from 5% to 20% by mass of distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics,

[0184] - from 3% to 10% by mass of polymer,

[0185] - from 45% to 55% of fillers and / or additives, and

[0186] - from 2.5% to 7.5% by mass of a fluxing agent, relative to the total mass of the composition.

[0187] The waterproofing membrane composition according to the invention is homogeneous. For the purposes of the invention, the term "homogeneous" means that the various components of the composition, namely the plastic pyrolysis distillation residue and any polymers and / or additives, are distributed uniformly in the bituminous matrix.

[0188] According to one embodiment, the waterproofing membrane composition according to the invention has a penetrability at 50°C, measured according to standard EN 1426, ranging from 50 to 200 1 / 10 mm, more preferably from 75 to 150 1 / 10 mm, typically 80 to 120 1 / 10 mm.

[0189] According to one embodiment, the waterproofing membrane composition according to the invention has a ring and ball softening temperature, measured according to standard EN 1427, greater than 80°C, more preferably greater than or equal to 100°C, advantageously ranging from 90°C to 150°C, typically ranging from 100°C to 130°C.

[0190] According to one embodiment, the composition according to the invention has a dynamic viscosity at 170°C and at 10 s -1, measured on an Anton Paar type rheometer (MCR102) equipped with a Peltier furnace and a plane / plane geometry, less than or equal to 25 Pa.s, more preferably less than or equal to 20 Pa.s, advantageously ranging from 1 Pa.s to 15 Pa.s, typically ranging from 4 Pa.s to 17 Pa.s.

[0191] According to one embodiment, the composition according to the invention has improved cold pliability or flexibility, measured according to the UEAtc guide, in particular a lower cracking temperature, compared to the same composition free from distillation residue.

[0192] Preferably, the composition according to the invention has cold pliability or flexibility, measured according to the UEAtc guide, less than or equal to 0°C, more preferably less than or equal to -10°C, even more preferably less than or equal to -20°C, typically ranging from -30°C to -10°C, advantageously from -25°C to -20°C.

[0193] According to one embodiment, the composition of the invention comprises a significant proportion of recycled or waste materials. It can therefore have a high eco-material index. The eco-material index is defined by the following equation:

[0194] Eco-material index = 100% - [% of non-biosourced, non-biodegradable, non-recycled or non-waste materials]. According to one embodiment, the composition has an eco-material content of at least 1% by mass, preferably at least 5% by mass, preferentially at least 10% by mass, and more preferentially at least 15% by mass, relative to the total mass of the composition of the invention.

[0195] Applications

[0196] The invention also relates to a process for preparing a bitumen / polymer composition as defined above, said process comprising mixing at least:

[0197] - a bitumen base,

[0198] - a distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics,

[0199] - an elastomer,

[0200] - possibly, fillers and / or additives, and

[0201] - possibly, a fluxing agent.

[0202] Preferably, the mixing step is carried out at a temperature ranging from 90°C to 230°C, more preferably from 120°C to 200°C, even more preferably from 150°C to 190°C.

[0203] The invention also relates to the use of a bitumen / polymer composition according to the invention for the preparation of a waterproofing and / or soundproofing material.

[0204] Preferably, the sealing and / or soundproofing material is chosen from: a sealing membrane, a liquid coating, an adhesive, a primer and a soundproofing membrane.

[0205] In particular, the subject of the invention is the use of a composition according to the invention for the manufacture of a waterproofing membrane. The subject of the invention is also a waterproofing membrane prepared from a composition according to the invention.

[0206] More particularly, the invention relates to a prefabricated waterproofing membrane comprising a support (or reinforcement) coated on at least one face with a composition according to the invention.

[0207] According to one embodiment, the support or reinforcement consists of one or more fibrous or non-fibrous reinforcements.

[0208] Preferably, according to this embodiment, the fibrous or non-fibrous reinforcement(s) are impregnated to the core with said composition.

[0209] The invention also relates to a method for manufacturing a waterproofing membrane, said method comprising the following successive steps:

[0210] 1) the preparation of a composition according to the invention, preferably according to the preparation process defined above; 2) the application of said composition on at least one face of a support or reinforcement, in particular on one or more fibrous reinforcement(s).

[0211] Preferably, step 2) of applying the composition to the support or reinforcement is carried out under heating and stirring, preferably at a temperature ranging from 90°C to 230°C, more preferably from 120°C to 200°C, even more preferably from 150°C to 190°C.

[0212] According to one embodiment, the support or reinforcement is made up of fibrous or non-fibrous reinforcement(s).

[0213] Preferably, according to this embodiment, step 2) consists of a step of impregnating the core of said reinforcements with said composition.

[0214] The invention also relates to the use of a composition according to the invention for the manufacture of a liquid coating. The invention also relates to a liquid coating prepared from a composition according to the invention.

[0215] The invention also relates to a process for preparing a liquid coating according to the invention, the process comprising the following successive steps: a) mixing a composition according to the invention with a solvent, so as to obtain a diluted composition; and b) adding to the diluted composition obtained in a), preferably with stirring, a polyurethane precursor.

[0216] Preferably, step b) is carried out in a vacuum disperser.

[0217] The invention also relates to the use of a composition according to the invention for the manufacture of an adhesive. The invention also relates to an adhesive prepared from a composition according to the invention.

[0218] The invention also relates to a method for preparing an adhesive according to the invention, the method comprising the following successive steps:

[0219] 1. the mixture in a tank of at least one elastomer and at least one solvent;

[0220] 2. the addition to the mixture obtained in 1) of a bituminous composition according to the invention; and

[0221] 3. the addition to the mixture obtained in 2) of at least one thixotropic filler.

[0222] Preferably, steps 1) and / or 2) and / or 3), more preferably steps 1), 2) and 3), are carried out in an arm mixer at temperatures between 50 and 110°C.

[0223] The invention also relates to the use of a composition according to the invention for the manufacture of a primer. The invention also relates to a primer prepared from a composition according to the invention. The invention also relates to a process for preparing a primer according to the invention, the process comprising the following successive steps:

[0224] 1. the mixture in a tank of at least one elastomer and at least one solvent;

[0225] 2. The addition to the mixture obtained in 1) of a bituminous composition according to the invention.

[0226] Preferably, step 1) and / or step 2, more preferably steps 1) and 2), are carried out in a disperser at temperatures between 50 and 110°C.

[0227] The invention also relates to the use of a composition according to the invention for the manufacture of a soundproofing membrane. The invention also relates to a soundproofing membrane prepared from a composition according to the invention.

[0228] More particularly, the invention relates to a prefabricated soundproofing membrane comprising a support (or reinforcement) coated on at least one face with a composition according to the invention.

[0229] According to one embodiment, the support or reinforcement consists of one or more fibrous or non-fibrous reinforcements.

[0230] The invention also relates to a method for manufacturing a soundproofing membrane, said method comprising the following successive steps:

[0231] 1) the preparation of a composition according to the invention, preferably according to the preparation method defined above,

[0232] 2) the application of said composition on at least one face of a support or reinforcement, in particular on one or more fibrous reinforcement(s).

[0233] Preferably, step 2) of applying the composition to the support or reinforcement is carried out under heating and stirring, preferably at a temperature ranging from 90°C to 230°C, more preferably from 120°C to 200°C, even more preferably from 150°C to 190°C.

[0234] According to one embodiment, the support or reinforcement is made up of fibrous or non-fibrous reinforcement(s).

[0235] The invention also relates to the use of a distillation residue of a hydrocarbon product as defined above, in a bitumen / polymer composition intended to be used for the preparation of waterproofing and / or soundproofing materials, to reduce the content of compounds of fossil origin in said bituminous composition. In particular, the invention relates to the use of a distillation residue of a hydrocarbon product as defined above, in a bitumen / polymer composition in order to reduce the content of bitumen and / or elastomer and / or fluxing agent of petroleum or synthetic origin in said composition. More particularly, the invention relates to the use of a distillation residue of a hydrocarbon product as defined above, in a bitumen / polymer composition in order to reduce the bitumen content in said composition by at least 5%, preferably from 8% to 20%, even more preferably from 9% to 15%.

[0236] More particularly, the subject of the invention is the use of a distillation residue of a hydrocarbon product as defined above, in a bitumen / polymer composition in order to reduce by at least 5% the content of elastomer(s) in said composition, preferably from 8% to 12%, even more preferably from 9% to 11%.

[0237] In the case where the composition of the invention comprises one or more fluxing agent(s) of petroleum or synthetic origin, the invention also relates to the use of a distillation residue of a hydrocarbon product as defined above, in a bitumen / polymer composition in order to reduce by at least 10% the content of fluxing agent(s) of petroleum or synthetic origin in said composition, preferably by at least 30%, more preferably by at least 50%, typically from 30% to 70%, even more preferably from 40% to 60%.

[0238] The invention also relates to the use in a bitumen / polymer composition intended to be used for the preparation of sealing and / or soundproofing materials of at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, to reduce the carbon footprint of said composition.

[0239] For the purposes of the invention, the term "carbon footprint" of a product means the quantity of carbon (generally expressed in kg of CO2 equivalent per kg of product) required for the preparation of said product, this quantity of carbon equivalent taking into account both energy consumption, particularly related to heating, and raw materials. The carbon footprint of a product is typically determined according to any of the ISO 14040 and ISO 14044 standards.

[0240] The invention is thus advantageous in that it allows the provision of waterproofing and / or soundproofing materials, in particular waterproofing membranes, having a reduced carbon footprint. The invention is also advantageous in that the binder composition, used for the preparation of the different materials, has improved resistance to aging: the variation in pliability during aging is significantly reduced, compared to a residue-free composition. In addition, this stability of pliability during aging is obtained without degrading the softening temperature of the composition. The invention is also advantageous in that it allows, at a constant elastomer content, the preparation of bituminous compositions having increased pliability. The invention is further advantageous in that it allows, at constant mechanical properties, the reduction of the elastomer content in the composition.

[0241] The invention is illustrated by the following examples given without limitation.

[0242] EXAMPLES

[0243] In the examples below, and unless explicitly instructed otherwise, the percentages are expressed by mass, relative to the total mass of the compositions.

[0244] 1. Materials and methods

[0245] 1.1. Measurement methods

[0246] In the description and examples below, the following methods have been used.

[0247] Ring Ball Temperature (RBT) or softening temperature

[0248] The TBA (or softening temperature) is measured according to the NF EN 1427 standard, June 2007. The material to be tested is placed in brass rings. The rings are placed in a TBA measuring device (ball and ring type apparatus). A metal ball is placed on the surface of the rings which are heated until the ball passes through the ring. The temperature at which the ball passes through is the TBA.

[0249] Needle penetration at 50°C (Penetrability)

[0250] Penetrability is measured according to standard NF EN 1426, December 20, 1999. The material to be tested is stored at 50°C for 2 hours and the penetration into the sample is measured with a needle penetrometer, after a time of 5 seconds, of a needle with a tip diameter of 0.14 to 0.16 mm whose weight with its support is 100 g. Penetrability is expressed in tenths of a mm.

[0251] Cold pliability or flexibility

[0252] Pliability is measured according to the UEAtc guide. A 2 mm thick specimen is formed with a film puller. The specimen's susceptibility to cracking under the effect of bending at low temperatures is determined. The lowest temperature at which the specimen can be bent around a 30 mm diameter mandrel is thus sought.

[0253] Viscosity at 170°C

[0254] The viscosity at 170°C (V170) is measured on an Anton-Paar MCR102 rheometer equipped with a Peltier oven and a plane / plane geometry. The bituminous composition is first placed in an oven at 170°C for 30 minutes and then placed between the rheometer plate and the upper plane geometry with a diameter of 25 mm. A viscosity measurement is carried out over a shear range between 0, 1 and 100s -1 . The general shape of the curve is taken into consideration but the viscosity value at 10s -1is taken as a reference value.

[0255] 1.2. Raw materials

[0256] Bituminous compositions were prepared from the following raw materials:

[0257] - B1 bitumen base with a penetrability at 25°C, measured according to standard NF EN 1426, equal to 86 1 / 10 mm, and a ring and ball softening temperature (RBT), measured according to standard NF EN 1427, equal to 45.8°C; commercially available from TotalEnergies under the reference AZALT® 70-100;

[0258] - Distillation residue R1;

[0259] - Elastomer E1: SBS (styrene-butadiene-styrene) type block copolymer with a content of constituent units derived from 70 / 30 Butadiene / Styrene monomers, linear structure, molecular mass of approximately 170,000 daltons polystyrene equivalent (PS), commercially available under the name D1101 from the company KRATON;

[0260] - Elastomer E2: SBS (styrene-butadiene-styrene) type block copolymer with a content of constituent units derived from 70 / 30 Butadiene / Styrene monomers, star structure, molecular mass of approximately 400,000 daltons polystyrene equivalent (PS), commercially available under the name D1184 from the company KRATON;

[0261] - Elastomer E3: thermoplastic elastomer polyurethane type polymer formed by the reaction between a polyester polyol having a molar mass of 3,000 g / mol and a functionality of 2, an MDI type isocyanate with a functionality of 2 and 1,4-butanediol;

[0262] - Fluxant: oil resulting from the recycling of used oils of petroleum origin and obtained by vacuum distillation of these, commercially available under the name 700SR from the company ECO HUILE;

[0263] - Fillers: mixture consisting of at least 90% by mass of calcium carbonate and at least 90% by mass of which at least 90% by mass of the particles have a particle size of less than 100 pm, commercially available from Omya under the name Etanchcarb® P2. The physical characteristics of the distillation residue R1 are given in the following table 1:

[0264] 2. Preparation of bituminous membrane compositions Bituminous compositions CO to C5 were prepared according to the protocol defined below:

[0265] The bitumen or bitumen / residue mixture prepared upstream is placed in an oven at 185°C for approximately 1 hour and then placed on a heating plate at 180°C. The flux is then added. With regular stirring using a propeller blade, the elastomer(s) are gradually added and then stirring is maintained for approximately 40-45 minutes, gradually increasing the stirring. Once the elastomer(s) are mixed with the bitumen, the heating is then stopped and the compositions are then characterized.

[0266] For compositions C2, C3 and C4, an additional step of adding the flux and fillers under stirring was also carried out, after the introduction of the elastomer(s). The details of the compositions are given in the following table 2.

[0267] Compositions CO and C2 are comparative in that they do not include a distillation residue of a hydrocarbon product obtained by thermal conversion of plastics.

[0268] Compositions C1, C3, C4 and C5 are according to the invention.

[0269] 3. Evaluation of the properties of bituminous compositions

[0270] The physicochemical properties of the waterproofing membrane compositions CO, C1, C2, C3, C4 and C5 are evaluated according to the protocols detailed above. The results are reported in the following Table 3. It is observed that the compositions according to the invention have a softening temperature similar to that of the comparative compositions CO* and C2*. The compositions according to the invention also have a significantly increased penetrability at 50°C compared to the comparative compositions. Thus, the incorporation of the residue makes it possible to improve the penetrability of the compositions, without affecting their softening temperature.

[0271] It is also observed that compositions C3, C4 and C5 according to the invention have significantly improved pliability (or cold flexibility) compared to comparative composition C2*.

Claims

CLAIMS 1. Bitumen / polymer composition comprising: - at least one bitumen base, - at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, - from 5% to 40% by mass of at least one elastomer, and relative to the total mass of elastomer(s), bitumen base(s) and distillation residue(s).

2. Composition according to claim 1, in which said at least one residue is a residue from atmospheric distillation of a hydrocarbon product, said hydrocarbon product having been obtained by pyrolysis of plastic waste.

3. Composition according to claim 1 or claim 2, wherein said residue has a boiling point at 10% by mass, measured according to standard ASTM D7169:20, greater than or equal to 350°C, preferably ranging from 400°C to 600°C, typically ranging from 410°C to 550°C.

4. Composition according to any one of the preceding claims, in which said residue has a ring and ball softening temperature (RBT), measured according to standard 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.

5. Composition according to any one of the preceding claims, in which the elastomer is chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene.

6. Composition according to any one of the preceding claims, in which the elastomer is chosen from polyurethanes.

7. Composition according to any one of the preceding claims, comprising: - from 10% to 90% by mass of bitumen, - from 0.1% to 30% by mass of said at least one distillation residue, - from 5% to 40% by mass of elastomer(s), - from 0% to 70% of fillers / or additives, and - from 0% to 20% by mass of fluxing agent(s), relative to the total mass of the composition.

8. Use of a bitumen / polymer composition according to any one of claims 1 to 7, for the manufacture of a waterproofing and / or soundproofing material, preferably chosen from: a waterproofing membrane, a liquid coating, an adhesive, a primer and a soundproofing membrane.

9. Prefabricated waterproofing membrane comprising: - a support or reinforcement, in particular one or more fibrous reinforcement(s), - a bitumen / polymer composition according to any one of claims 1 to 7, said support or reinforcement being coated on at least one face, preferably impregnated to the core, with said bituminous composition.

10. Method for manufacturing a waterproofing membrane according to claim 9, said method comprising the following successive steps: 1) the provision of a bitumen / polymer composition according to any one of claims 1 to 7, 2) the application of the composition obtained in step 1) on at least one face of a support or reinforcement.

11. Use in a bitumen / polymer composition, intended for the preparation of a waterproofing and / or soundproofing material, of at least one distillation residue of a hydrocarbon product, said hydrocarbon product having been obtained by thermal conversion of plastics, to reduce the content of compounds of fossil origin, in particular bitumen and / or polymer and / or fluxing agent(s), of said composition.

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