BITUMINOUS COMPOSITION COMPRISING BIOCHAR AND A PLASTICIZING AGENT

Abstract

BITUMINOUS COMPOSITION COMPRISING BIOCHAR AND A PLASTIFYING AGENT The present invention relates to a bituminous composition comprising: a) at least one bitumen base, b) biochar, and c) at least one plasticizing agent. Figure for the abstract: None

Description

Title of the invention: BITUMINOUS COMPOSITION COMPRISING BIOCHAR AND A PLASTIFYING AGENT

[0001] The present invention relates to a bituminous composition comprising bitumen, biochar, and at least one plasticizing agent. The invention also relates to a method for preparing, or using, a bituminous composition according to the invention, particularly for road and / or industrial applications.

[0002] Bitumen is the main hydrocarbon constituent used in road construction and civil engineering. For example, it is used for road surfacing and waterproofing membranes. Bitumen is generally obtained from residues from the distillation of atmospheric and / or vacuum crude oil.

[0003] Oil resources are, however, limited. Indeed, "proven oil reserves" reached over 200 billion tonnes of oil equivalent (TOE) worldwide in 2018, according to experts at British Petroleum (who have been tracking the resource since 1980). Although substantial, these reserves could only cover 50.2 years of annual consumption at the 2017 rate. These figures are confirmed by the French Alternative Energies and Atomic Energy Commission (CEA) and the International Energy Agency (IEA). It is therefore necessary to limit our oil consumption as much as possible.

[0004] Furthermore, oil extraction is responsible for the release of significant quantities of greenhouse gases into the atmosphere, which have a significant impact on global warming. It is therefore necessary to limit our consumption of oil, particularly bitumen, in order to minimize the overall rise in Earth's temperatures.

[0005] In order to maintain and / or improve the characteristics, particularly the mechanical properties, of conventional bitumen, it is also known to use crosslinked bitumen / polymer compositions in which the bitumen (composed of one or more types of bitumen) is mixed with one or more functional polymers, in particular styrene and butadiene elastomers, these elastomers being chemically crosslinked in situ, possibly with the aid of a coupling or crosslinking agent, for example sulfur or at least one of its precursors. Optimized mechanical characteristics are indeed crucial for road surfacing applications. However, the carbon footprint associated with these bitumen / polymer compositions is much higher than that of pure bitumen. Indeed, the carbon footprint of pure bitumen is estimated at 0.2 kg of CO2 equivalent per kg of bitumen. (Estimate by the Eurobitume association). The carbon footprint of a polymer, particularly a styrene-butadiene elastomer, is currently estimated at between 2.2 and 3.3 kg of CO2 equivalent per kg of polymer, depending on the process used and plant optimization. Therefore, there remains a need for bituminous compositions, especially bitumen / polymer compositions, with a significantly reduced carbon footprint.

[0006] WO 2022 / 032152 describes the preparation of bituminous compositions incorporating biochar. However, this document does not describe compositions also incorporating a plasticizing agent. Furthermore, it does not address bitumen / polymer compositions, possibly crosslinked.

[0007] There therefore remains a need for bituminous compositions whose content of material(s) of fossil origin, in particular derived from petroleum, is reduced compared to the compositions of the prior art.

[0008] In particular, there remains a need for bituminous compositions with improved mechanical properties, especially elastic ones, compared to polymer-free compositions of the prior art, and whose content of material(s) of fossil origin, especially from petroleum, is reduced compared to compositions of the prior art.

[0009] Even more specifically, there remains a need for bitumen / polymer compositions (possibly crosslinked) whose content of material(s) of fossil origin, in particular derived from petroleum, is reduced compared to prior art compositions.

[0010] There also remains a need to provide bituminous compositions with a reduced carbon footprint, compared to prior art compositions.

[0011] In particular, there remains a need for bituminous compositions with improved mechanical properties, especially elastic ones, compared to polymer-free compositions of the prior art, and with a reduced carbon footprint compared to compositions of the prior art.

[0012] Even more specifically, there remains a need for bitumen / polymer compositions (possibly crosslinked) with a reduced carbon footprint, compared to prior art compositions.

[0013] In its previous work, the Applicant discovered that it was possible to reduce the content of fossil-based material(s) by incorporating one or more biochar(s) into a bituminous composition, particularly a bitumen / polymer composition. In particular, the Applicant discovered that it was possible to reduce the carbon footprint of prior art bituminous compositions, especially bitumen / polymer compositions, by incorporating biochar.

[0014] The compositions obtained exhibit entirely satisfactory properties both for their application as a road binder and for the preparation of membranes. The compositions do indeed comply with all the required specifications.

[0015] The Applicant has nevertheless observed that the incorporation of biochar results in the degradation of certain properties of the bituminous composition. In particular, the Applicant has noticed that the incorporation of biochar leads to a slight degradation of the composition's cold strength, as well as a decrease in the composition's mechanical properties, notably its elongation at break, compared to a bituminous composition free of biochar.

[0016] There therefore remains a need to provide bituminous compositions with a reduced carbon footprint, thanks to the incorporation of biochar, and with improved properties, particularly in terms of cold resistance and / or elastic properties. In particular, there remains a need to provide biochar-based bituminous compositions with equivalent, or even improved, properties compared to bituminous compositions without biochar, especially in terms of cold resistance and elastic properties.

[0017] In continuation of its work, the Applicant discovered that it was possible to compensate for the deterioration of the mechanical properties of the bituminous composition caused by the incorporation of biochar by adding one or more plasticizing agents. In particular, the Applicant discovered that the incorporation of one or more plasticizing agents into a bituminous composition containing biochar made it possible to improve certain of the mechanical properties of the composition, notably its cold strength and / or elongation at break. Summary of the invention

[0018] The invention relates firstly to a bituminous composition comprising:

[0019] - at least one bitumen base,

[0020] - biochar, and

[0021] - at least one plasticizing agent.

[0022] Preferably, the plasticizing agent is chosen from:

[0023] a) tall oil derivatives,

[0024] b) plastic pyrolysis oils,

[0025] c) triglycerides

[0026] d) mixtures of a) and / or b) and / or c).

[0027] Advantageously, biochar is produced by thermochemical conversion of biomass selected from forest products; crop residues; animal waste; municipal waste and any of their mixtures.

[0028] More advantageously, biochar is derived from the thermochemical conversion of biomass selected from hardwoods, particularly ash wood; the bales of cereals; nut shells, especially cashew nut shells; food waste; coffee grounds and any mixtures thereof.

[0029] Preferably, the composition of the invention has a biochar content ranging from 0.1% to 50% by mass, preferably from 0.5% to 30% by mass, preferably from 1% to 15% by mass, relative to the total mass of the bituminous composition.

[0030] According to one embodiment, the composition of the invention further comprises at least one elastomer, preferably chosen from copolymers of an aromatic monovinyl hydrocarbon and a conjugated diene.

[0031] Preferably, according to this embodiment, the composition of the invention is a crosslinked bitumen / polymer composition, obtained by crosslinking, in particular chemical or thermal, of a bituminous composition as defined above.

[0032] The invention also relates to a method for preparing a bituminous composition according to the invention, this method comprising:

[0033] 1) bringing the following components into contact:

[0034] - at least one bitumen base,

[0035] - biochar, and

[0036] - at least one plasticizing agent

[0037] 2) the mixing of the components.

[0038] Preferably, the mixing of the components 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 180°C.

[0039] The invention also relates to the use of a bituminous composition according to the invention, to prepare a surface coating, a hot mix asphalt, a cold mix asphalt, a cold poured asphalt, an emulsion gravel or a wearing course, said binder being associated with aggregates and / or recycled millings.

[0040] The invention further relates to a bituminous coating comprising a bituminous composition according to the invention, mixed with aggregates and / or recycled millings, and optionally mineral and / or synthetic fillers.

[0041] The invention also relates to an asphalt comprising a bituminous composition according to the invention, mixed with mineral and / or synthetic fillers.

[0042] The invention also relates to a waterproofing coating, preferably a membrane or an impregnation layer, comprising a bituminous composition according to the invention.

[0043] The invention also relates to the use in a bituminous composition, in particular in a bitumen / polymer composition possibly crosslinked, of the association of at least one biochar and at least one plasticizing agent, to reduce the content of compound(s) of fossil origin in said composition.

[0044] The invention finally relates to the use in a bituminous composition, in particular in a bitumen / polymer composition possibly crosslinked, of the association of at least one biochar and at least one plasticizing agent, to reduce the carbon footprint of said composition. Detailed description of the invention

[0045] In the following description, and unless explicitly stated otherwise, the quantities of the different components present in a bituminous composition according to the invention are given as % mass, relative to the total mass of the composition (hereinafter referred to as % w / w).

[0046] Similarly, and unless explicitly stated otherwise, the standards mentioned in the rest of the description correspond to the standard in force on December 1, 2022.

[0047] The invention relates firstly to a bituminous composition comprising:

[0048] - at least one bitumen base,

[0049] - biochar, and

[0050] - at least one plasticizing agent. Bitumen base

[0051] The bitumen or bitumens used to prepare a bitumen / polymer composition according to the invention are called "bitumen base".

[0052] Among the bitumens that can be used according to the invention, we can first mention bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt, or oil sands, and bitumens obtained from crude oil refining. Within the scope of the invention, the bitumen(s) used are advantageously chosen from among bitumens obtained from crude oil refining, in particular bitumens containing asphaltenes or pitches. The bitumens can be obtained by conventional bitumen manufacturing processes in refineries, in particular by direct distillation and / or vacuum distillation of petroleum. These bitumens can optionally be viscoreduced and / or deasphalted and / or air rectified. It is common practice to perform vacuum distillation of 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 being atmospheric residues. These vacuum residues from the vacuum distillation tower can also be used as bitumen. It is also common to inject air into a feedstock typically composed of distillates and heavy products from the vacuum distillation of atmospheric residues from petroleum distillation. This process yields blown, semi-blown, oxidized, air-rectified, or partially air-rectified bitumen.

[0053] 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.

[0054] Generally, the blowing is carried out at high temperatures, on the order of

[0055] 200 to 300°C, for relatively long periods typically between 30 minutes to 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.

[0056] Among the usable bitumens according to the invention, recycled bitumens can also be mentioned.

[0057] 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 standard EN 12591.

[0058] 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 grade 35 / 50, 20 / 30 and 10 / 20 bitumens.

[0059] The bitumen bases usable within the scope 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, and more preferably between 10 and 120 1 / 10 mm. As is well known, the measurement known as "needle penetration" is carried out using 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 penetration, measured at 25°C according to the standardized test NF EN 1426, represents the measurement of the penetration into a bitumen sample, after a time of 5 seconds, of a needle whose weight, including its support, is 100 g.

[0060] Preferably, the bituminous composition according to the invention comprises at least 40% by mass of bitumen, relative to the total mass of the bituminous 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.

[0061] Advantageously, the bituminous composition according to the invention comprises from 40% to 99.9% by mass of bitumen, relative to the total bituminous composition, preferably from 50% to 99% by mass, more preferably from 60% to 95% by mass, even more preferably from 70% to 95% by mass, advantageously from 75% to 95% by mass, and more advantageously from 80% to 95% by mass of biochar.

[0062] The bituminous composition according to the invention also comprises biochar.

[0063] According to the International Biochar Initiative (IBI), biochar is defined as a solid material obtained by thermochemical conversion, particularly by heating and / or pyrolysis, of biomass in an oxygen-limited environment, or even in the total absence of oxygen. In particular, the thermochemical conversion of biomass leads to the production of a complex mixture consisting mainly of hydrocarbon compounds of varying chain lengths. The mixture is then separated into different fractions according to their evaporation temperature. This yields, in particular, a gaseous fraction, a (bio)fuel fraction, an oily fraction, and also a residue. This distillation residue then constitutes the biochar.

[0064] Biochar differs from charcoal in its use (as a material of interest rather than as fuel) and therefore in its environmental impact. Biochar thus constitutes a carbon sink, unlike charcoal, the combustion of which releases carbon dioxide into the atmosphere. Furthermore, biochar is generally in powder form, while charcoal is in lump form.

[0065] The chemical and physical properties of biochar depend on several parameters including the nature of the starting biomass (“feedstock” in English) but also on the parameters of the thermochemical conversion process, in particular the pyrolysis conditions.

[0066] The nature of the starting biomass is not particularly limited. Thus, the biochar present in the composition according to the invention can come from the thermochemical conversion of any type of biomass.

[0067] Typically, the biochar present in the composition according to the invention comes from the thermochemical conversion of biomass selected from forest products; agricultural crop residues; animal waste; municipal waste and any of their mixtures.

[0068] Among forest products, one can notably mention hardwoods (also called hardwoods) such as maple, oak, ash, cherry, walnut, apple, and pear wood; and softwoods such as coniferous woods, including pine, Spruce wood or fir wood. Forest products can also include leaves, needles or fruits (acorns, pine cones, etc.).

[0069] Preferably, forest products are chosen from hardwoods, more preferably ash wood.

[0070] Among crop residues, we can mention in particular straw, for example maize straw, wheat straw or rice straw; bagasse (fibrous residue) obtained by crushing sugar cane; cereal husks; peanut shells; nut shells, in particular almonds, Brazil nuts, cashew nuts, hazelnuts, pecans or walnuts.

[0071] For the purposes of this invention, "cereal chaff" or "grain" refers to a co-product derived from the processing of cereals and consisting of the glumes and lemmas that enclose the grain. In other words, cereal chaff constitutes the outer layer in which the cereal grain is contained.

[0072] By way of example, we can mention in particular corn husks, wheat husks, barley husks, sorghum husks, wheat husks, spelt husks as well as husks of any other cereal.

[0073] Preferably, the crop residues are chosen from cereal husks, nut shells, in particular cashew nut shells and any mixture thereof.

[0074] Among animal waste, we can mention in particular slurry, manure or bedding from livestock, especially poultry, pigs or cattle.

[0075] Among municipal waste, we can notably mention food waste, in particular organic waste such as peelings or coffee grounds, but also municipal biosolids.

[0076] For the purposes of this invention, "municipal biosolids" or sewage sludge refers to the material resulting from the treatment of municipal wastewater that is of sufficient quality to be recycled. It consists mainly of organic matter.

[0077] Preferably, municipal waste is chosen from food waste, coffee grounds and any of their mixtures.

[0078] According to a preferred embodiment, the biomass is selected from hardwoods, in particular ash wood; cereal husks; nut shells, in particular cashew nut shells; food waste; coffee grounds and any mixture thereof.

[0079] According to a still preferred embodiment, the biomass is selected from ash wood, cereal husks, cashew nut shells, coffee grounds and any of their mixtures.

[0080] The process for converting biomass into biochar is not particularly limited. In particular, any thermochemical conversion process known to those skilled in the art can be implemented for the preparation of biochar usable in the com positions. Suitable conversion processes are described for example in chapter 2 “Biochar for Maintaining Soil Health” of the book B. Giri, A. Vanna (eds.), Soil Healthl, Soil Biology 59. A. Tomczyk et al., “Biochar physichemical properties: pyrolysis temperature and feedstock kind effects”, Rev Environ Sci Biotechnol, February 5, 2020 also studies the impact of the choice of biomass and the thermochemical conversion conditions on the nature of the final biochar.

[0081] The conversion of biomass into biochar is typically carried out at a temperature greater than or equal to 350°C, preferably ranging from 350°C to 900°C.

[0082] Preferably, the biochar has a high carbon content C, typically greater than 20% by mass, relative to the total mass of biochar, more preferably greater than or equal to 50%.

[0083] Advantageously, biochar has a carbon content (also called total carbon content), determined by elemental analysis, ranging from 20% to 80% by mass, relative to the total mass of biochar, more preferably from 50% to 75% by mass.

[0084] For the purposes of this invention, "biogenic carbon" refers to the portion of carbon present in biochar that originates directly from biomass, in particular the portion of carbon fixed by the starting biomass through photosynthesis using atmospheric CO2. Biogenic carbon is thus distinguished from fossil carbon, notably by a difference in the ratio between the quantity of carbon-14 and carbon-13.

[0085] According to one embodiment, at least 80% of the carbon present in the biochar is biogenic, preferably at least 90%, more preferably at least 95%, advantageously at least 98%, more advantageously at least 99%.

[0086] Advantageously, 100% of the carbon present in the biochar is biogenic.

[0087] The proportion of biogenic carbon in biochar is determined for example according to standard EN 16640, in particular standard EN 16640:2017.

[0088] Advantageously, biochar has a biogenic carbon content, measured according to standard EN 16640, ranging from 20% to 80% by mass, relative to the total mass of biochar, more preferably from 50% to 75% by mass.

[0089] Preferably, the biochar has an organic carbon content, measured according to ISO 9686, ranging from 1% to 60% by mass, more preferably from 2% to 50% by mass, typically from 3% to 45% by mass.

[0090] Preferably, the biochar has an inorganic carbon content, measured according to ISO 9686, ranging from 0.1% to 20% by mass, more preferably from 0.2% to 15% by mass, typically from 0.5% to 10% by mass. Preferably, the biochar has a graphitic carbon content, measured according to ISO 9686, ranging from 5% to 90% by mass, more preferably from 7% to 80% by mass, typically from 10% to 75% by mass.

[0091] Preferably, the biochar has a low nitrogen content N, more preferably less than or equal to 10% by mass, relative to the total mass of biochar, even more preferably ranging from 0.1% to 10% by mass, typically from 0.5% to 5% by mass.

[0092] Preferably, the biochar has a low phosphorus P content, more preferably less than or equal to 10% by mass, relative to the total mass of biochar, even more preferably ranging from 0.01% to 10% by mass, typically from 0.05% to 7.5% by mass.

[0093] Preferably, the biochar has a low potassium K content, more preferably less than or equal to 10% by mass, relative to the total mass of biochar, even more preferably ranging from 0.01% to 10% by mass, typically from 0.05% to 7.0% by mass.

[0094] Preferably, the biochar has a low calcium Ca content, more preferably less than or equal to 15% by mass, relative to the total mass of biochar, even more preferably ranging from 0% to 15% by mass, typically from 0.01% to 10% by mass.

[0095] Preferably, the biochar has a low magnesium Mg content, more preferably less than or equal to 10% by mass, relative to the total mass of biochar, even more preferably ranging from 0% to 10% by mass, typically from 0.1% to 3% by mass.

[0096] The content of nitrogen N, phosphorus P, potassium K, calcium Ca and / or magnesium Mg in the biochar is typically measured by elemental analysis.

[0097] Preferably, the biochar has an oxygen O content, measured by elemental analysis, ranging from 0.1% to 50% by mass, relative to the total mass of biochar, more preferably ranging from 0.5% to 40% by mass, typically from 2% to 35% by mass.

[0098] Preferably, the biochar has a hydrogen content H, measured by elemental analysis, ranging from 0.01% to 20% by mass, relative to the total mass of biochar, more preferably ranging from 0.05% to 15% by mass, typically from 0.1% to 8% by mass.

[0099] According to one embodiment, the ratio between the mass of hydrogen present in the biochar and the total mass of organic carbon present in the biochar ranges from 0.01 to 5, preferably from 0.015 to 3, more preferably from 0.02 to 2.

[0100] According to one embodiment, the ratio between the mass of oxygen present in the biochar and the total mass of carbon (total carbon) present in the biochar, ranges from 0.01 to 5, preferably from 0.02 to 3, more preferably from 0.04 to 1.

[0101] According to one embodiment, the biochar is porous, preferably with open porosity.

[0102] For the purposes of this invention, "open porosity" means that the pores of the material are interconnected to form a continuous network. Therefore, all the pores of the material are accessible to water.

[0103] Preferably, the biochar has a porosity ranging from 10% to 90% by volume, more preferably from 30% to 85%, even more preferably from 50% to 85%.

[0104] Methods for measuring the porosity of a biochar are known to those skilled in the art. In particular, the methods described in CE Brewer, BIOMASS AND BIOENERGY, 66, 2014, 176-185, may be cited.

[0105] Advantageously, the biochar has a specific surface area, measured according to the BET method defined in ISO 9277, ranging from 1.5 m² / g to 500 m² / g, more preferably from 5 m² / g to 450 m² / g, even more preferably from 10 m² / g to 400 m² / g. Preferably, the biochar has a high pH, ​​typically greater than or equal to 5, more preferably ranging from 5 to 12, advantageously ranging from 6 to 10.

[0106] According to one embodiment, the biochar has a cation exchange capacity ranging from 1 cmol.Kg 1 to 100 cmol.Kg *, preferably from 1.5 cmol.Kg 1 to 80 cmol.Kg *, more preferably from 2 cmol.Kg 1 to 70 cmol.Kg *.

[0107] Methods for measuring the cation exchange capacity of a biochar are known to those skilled in the art. Examples include the Metson method and the Bower method.

[0108] According to one embodiment, the surface of the biochar is functionalized.

[0109] Preferably, according to this embodiment, the surface of the biochar comprises at less one functional group chosen from: a phenol group, a lactone (cyclic ester) group, a carboxylic acid group, a carboxylic anhydride group, a peroxide group, an amine group, a quinone group, a chromene group, an ether group, a pyrone group and any combination thereof.

[0110] The bituminous composition according to the invention preferably comprises from 0.1% to 50% by mass of biochar, relative to the mass of the bituminous composition, more preferably from 0.5% to 30%, and even more preferably from 1% to 15%. Plasticizing agent

[0111] The bituminous composition according to the invention further comprises at least one plasticizing agent.

[0112] For the purposes of this invention, "plasticizing agent" means a compound capable of reducing the Young's modulus and the glass transition temperature of a material, in order to improve its cold properties, limit its brittleness, and increase its elongation at break.

[0113] The plasticizing agent is not specifically limited provided that it possesses the qualities required for the bituminous compositions of the invention. In particular, any agent A plasticizer known to those skilled in the art and suitable for use in bitumens, particularly bitumen / polymer compositions, may be used.

[0114] According to a preferred embodiment, the plasticizing agent is chosen from:

[0115] a) tall oil derivatives,

[0116] b) plastic pyrolysis oils,

[0117] c) triglycerides, and

[0118] d) mixtures of a) and / or b) and / or c) and / or d).

[0119] Preferably, the bituminous composition according to the invention has a plasticizing agent(s) content ranging from 0.1% to 30% by mass, preferably from 1% to 20% by mass, preferably from 2.5% to 10% by mass, relative to the total mass of the composition.

[0120] Preferably, the biochar(s) and the plasticizing agent are present in the bituminous composition of the invention in a mass ratio of 10:1 to 1:10, more preferably from 5:1 to 1:5, even more preferably from 2:1 to 1:2, typically in a ratio of 1:1. a) Tall oil derivatives

[0121] According to a first embodiment, the plasticizing agent is chosen from tall oil derivatives.

[0122] Crude tall oil (CTO) is a by-product of the wood pulping process, also known as the Kraft process. Distillation of crude tall oil yields a volatile and highly saturated fraction of long-chain fatty acids (mainly palmitic acid), called "tall oil heads." The next fraction consists of tall oil fatty acids (TOFA). This TOFA fraction consists mainly of Cl8 and C20 fatty acids exhibiting various degrees of unsaturation (e.g., oleic acid, linoleic acid, linolenic acid, and various isomers thereof). Another cut, known as distilled tall oil (or DTO for "Distilled Tall OU" in English), is a mixture consisting mainly of tall oil fatty acids and a smaller proportion of tall oil rosin.The tall oil rosin (or TOR for "Tall OR Rosin"), isolated subsequently, consists largely of a tricyclic C19-C20 monocarboxylic acid. The lower cut of the distillation is known as tall oil pitch or tall oil pitch (in English "tall oilpitch" or simply "pitch").

[0123] Preferably, according to this embodiment, the plasticizing agent is obtained directly from tall oil by simple distillation.

[0124] More preferably, the plasticizing agent is chosen from: crude tall oil, fractions of crude tall oil and mixtures of different fractions of tall oil.

[0125] Even more preferably, according to this embodiment, the plasticizing agent is chosen from "tall oil heads", tall oil fatty acids (or TOFA for "Tall OU Fatty Acids" in English), distilled tall oil (or DTO for "Distilled Tall OU" in English), tall oil rosin (or TOR for "Tall Oil Rosin") and tall oil pitch or tall oil pitch (in English "tall oilpitch" or simply "pitch").

[0126] Even more preferably, the plasticizing agent is chosen from tall oil pitch or tall oil pitch (in English “tall oil pitch” or simply “pitch”).

[0127] Tall oil pitch, referenced under CAS No. 8016-81-7, is in the form of a complex mixture comprising predominantly fatty acids such as palmitic acid, linoleic acid and oleic acid; fatty acid esters; resin acids such as abietic acid and its isomers, pimaric acid, isopimaric acid and sandaracopimaric acid; resin acid esters; diterpene alcohols; fatty alcohols and sterols.

[0128] Preferably, the tall oil pitch comprises:

[0129] - up to 30% by mass of free fatty acids,

[0130] - 15% to 20% by mass of diglycerides,

[0131] - 50% to 60% by mass of triglycerides, and

[0132] - 10% to 15% by mass of sterols,

[0133] in relation to the total mass of the pitch.

[0134] Preferably, tall oil pitch has an iodine value, measured according to standard NF EN ISO 3961, less than or equal to 100 g of I2 / 100 g of pitch, more preferably ranging from 70 to 100 g of I2 / 100 g of pitch, advantageously from 75 to 95 g of I2 / 100 g of pitch.

[0135] Preferably, tall oil pitch has an acid value, measured according to standard NF EN ISO 660, less than or equal to 45 g of KOH / g of pitch, more preferably ranging from 10 to 40 g of KOH / g of pitch, advantageously from 10 to 35 g of KOH / g of pitch.

[0136] Preferably, according to this embodiment, at least 50% by mass of the plasticizing agent consists of tall oil derivatives, more preferably at least 60% by mass, more preferably at least 75% by mass, advantageously at least 80% by mass, more advantageously at least 90% by mass, typically at least 95% by mass.

[0137] More preferably, according to this embodiment, the plasticizing agent consists of tall oil derivatives. b) plastic pyrolysis oils

[0138] According to a second embodiment, the plasticizing agent is chosen from plastic pyrolysis oils.

[0139] For the purposes of this invention, "plastic pyrolysis oil" means a hydrocarbon product obtained by thermal conversion, in particular by pyrolysis, of plastics.

[0140] 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 gaseous mixture, coke.

[0141] Common industrial methods of 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 including hydrotreatment and the removal of contaminants using a variety of purification processes such as distillation.

[0142] 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 is also necessary because several heteroatoms (i.e., elements other than carbon, hydrogen, or oxygen) can be volatilized.

[0143] 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 must be separated from one another before recycling. 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, hardening 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, etc.). of carbonates, acids, etc). Additives containing heteroelements other than metals are also used in the manufacture of plastics, for example halogens such as bromine in flame retardants, plasticizers, stabilizers, etc.

[0144] 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.

[0145] 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.

[0146] Finally, since plastics are contaminated by oxygenated compounds, plastic oils resulting from pyrolysis liquefaction may also contain oxygenated compounds such as aldehydes or ketones.

[0147] The oil resulting from the pyrolysis of the plastic can then be separated into several fractions by all types of separation processes known per se:

[0148] • The light naphtha cut with a distillation range between 50 and 200°C and a density between 720 Kg / m3 and 750 Kg / m3;

[0149] • The average diesel cut with a distillation interval between 200°C and 300°C and a density between 750 Kg / m3 and 800 Kg / m3;

[0150] • Heavy cut type VGO (“Vacuum Gasoline”) with an interval of distillation temperature between 300°C and 450°C and a density between 800 Kg / m3 and 840 Kg / m3;

[0151] • A very heavy VR (Visco-Reduced) type cup with an initial boiling point of at least 450 °C and a density between 840 Kg / m3 and 870 Kg / m3.

[0152] Preferably, the plasticizing agent is chosen from light cut naphtha type, medium cut diesel type, heavy cut VGO type, very heavy cut VR type and any of their mixtures.

[0153] Preferably, according to this second embodiment, at least 50% by mass of the plasticizing agent consists of pyrolysis oils of plastics, more preferably at least 60% by mass, even more preferably at least 75% by mass, advantageously at least 80% by mass, more advantageously at least 90% by mass, typically at least 95% by mass.

[0154] More preferably, according to this second embodiment, the plasticizing agent consists of pyrolysis oils of plastics. c) triglycerides

[0155] According to a third embodiment, the plasticizing agent is chosen from triglycerides.

[0156] By "triglycerides", we mean, in the sense of the invention, glycerides, that is to say, esters of glycerol, whose three alcohol functions have been esterified.

[0157] Preferably, the triglycerides are chosen from the compounds of the following formula (I): O (i) OO

[0158] wherein RI, R2 and R3 independently represent a linear or branched, saturated or unsaturated hydrocarbon chain comprising from 1 to 300 carbon atoms, and optionally one or more heteroatoms, preferably chosen from O and N.

[0159] Preferably, each of the groups RI, R2 and R3 comprises, independently, from 0 to 3 unsaturations.

[0160] Preferably, the RI, R2 and R3 groups independently represent a CrCioo hydrocarbon chain, more preferably in C2-C50, even more preferably in C4-C36, optionally substituted by one or more heteroatoms, preferably chosen from O and N.

[0161] More preferably, the triglycerides of the invention are chosen from fatty acid triglycerides.

[0162] Preferably, the fatty acids are selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, ricinoleic acid, behenic acid, lignoceric acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, trans-vaccenic acid, linoleic acid, linoaidic acid, α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid, clupanodonic acid, docosahexaenoic acid and mixtures thereof.

[0163] More preferably, the fatty acids are chosen from palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, α-linolenic acid and their mixtures.

[0164] Even more preferably, the fatty acids are in the form of a mixture of palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, and α-linolenic acid.

[0165] Advantageously, fatty acids consist of a mixture comprising:

[0166] - 0.7% to 1.3% by mass of palmitic acid,

[0167] - from 0.9% to 1.2% by mass of stearic acid,

[0168] - from 2.8% to 5.5% by mass of oleic acid,

[0169] - from 84.2% to 94% by mass of ricinoleic acid,

[0170] - from 4.2% to 7.3% by mass of linoleic acid, and

[0171] - 0.2% to 0.5% by mass of α-linolenic acid,

[0172] relative to the total mass of fatty acids present in the triglycerides of the invention, in esterified form.

[0173] Triglycerides suitable for the invention are notably present in animal fats, vegetable oils or dairy products.

[0174] Preferably, the triglycerides of the invention are of vegetable origin.

[0175] More preferably, the triglycerides of the invention are derived from castor oil.

[0176] Preferably, according to this fourth embodiment, at least 50% by mass of the plasticizing agent consists of triglycerides, more preferably at least 60% by mass, more preferably at least 75% by mass, advantageously at least 80% by mass, more advantageously at least 90% by mass, typically at least 95% by mass.

[0177] More preferably, according to this third embodiment, the plasticizing agent consists of triglycerides. d) mixtures

[0178] The plasticizing agent of the invention may also consist of a mixture of the different compounds defined above. In particular, the plasticizing agent may consist of a mixture of tall oil derivatives and plastic pyrolysis oils, a mixture of tall oil derivatives and triglycerides, a mixture of plastic pyrolysis oils and triglycerides, or a mixture of tall oil derivatives, plastic pyrolysis oils, and triglycerides. Elastomer(s)

[0179] According to one embodiment, the composition according to the invention further comprises at least one elastomer.

[0180] The elastomer is not particularly limited provided that it has the qualities required for the bituminous compositions of the invention.

[0181] Such elastomers are well known in the arts and are generally polymers rubbery. In a preferred embodiment, the elastomer comprises styrene butadiene styrene (SBS), hydrogenated SBS, styrene isoprene styrene (SIS), styrene ethylene butadiene styrene (SEBS) and / or polyisobutadiene (PIB).

[0182] Preferably, the elastomer is typically chosen from copolymers of an aromatic monovinyl hydrocarbon and a conjugated diene

[0183] Preferably, the elastomer is chosen from block copolymers of formula SBS, in which:

[0184] - each S, which may be identical or different, independently represents a

[0185] block based on aromatic monovinyl hydrocarbon monomers,

[0186] - B represents a butadiene monomer-based block, said block B comprising pendant vinyl groups.

[0187] For the purposes of this invention, "block" means a polymer chain obtained by the polymerization of one or more monomers of the same chemical nature. A block advantageously consists of the repetition of the same monomer.

[0188] In said block copolymers of formula SBS, the S blocks together represent at least 15% by mole of the total number of moles of monomeric units of the block copolymer. These 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 block B that is greater than or equal to 20% by mole, relative to the total number of moles of monomeric units of the block copolymer. These copolymers may hereafter be referred to more simply as SBS elastomer. In general, the two S blocks of the SBS thermocurable elastomer are identical.

[0189] In the context of the invention, butadiene refers to 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 vinylic group) that hangs from the polymer backbone. The hanging vinylic groups of the SBS block copolymer therefore correspond to the 1,2-addition polymerization of the conjugated diene monomers, and in particular the major butadiene monomers, within block B. The motifs obtained by the polymerization of butadiene via a 1,2-addition mechanism or via a 1,4-addition mechanism have the same molar mass.

[0190] In particular, the aromatic monovinyl hydrocarbon monomer(s) present in the S blocks of the SBS thermocurable elastomer are selected from styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene, and vinylxylene, or mixtures thereof. The preferred aromatic monovinyl hydrocarbon monomer according to the present The 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 total of the aromatic monovinyl 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 thermocrosslinkable block SBS copolymers are derived can be, independently, any monovinylaromatic hydrocarbon monomer as previously described and are preferably styrene.

[0191] Block B based on butadiene monomers in the composition of the aforementioned SBS block copolymers is preferably made up solely of butadiene monomers, or of a butadiene mixture comprising minor proportions of one or more other structurally related conjugated dienes, and in particular selected 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 total conjugated dienes present in block B. Preferably, the monomers constituting block B are exclusively butadiene monomers.

[0192] The SBS thermocrosslinkable block elastomer used in the context of the invention has a weight-average molecular mass Mw of 40,000 to 500,000 g / mol. Preferably, the SBS thermocrosslinkable block elastomer has a weight-average molecular mass Mw of less than or equal to 400,000 g / mol, more preferably less than or equal to 250,000 g / mol, even more preferably less than or equal to 200,000 g / mol and advantageously less than or equal to 150,000 g / mol.

[0193] Preferably, the SBS block copolymer used in the context of the invention has a weight-average molecular weight 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. According to particular embodiments, the SBS block copolymer has a weight-average molecular weight Mw in any range corresponding to the maximum and minimum values ​​mentioned above, and advantageously in the range from 100,000 to 150,000 g / mol.

[0194] As previously stated, the SBS block copolymer used in the invention has a content of pendant vinyl groups greater than or equal to 5% by mole, relative to the total number of moles of monomeric units of the copolymer. This vinyl content, determined by coupling spec- 13C NMR (carbon nuclear magnetic resonance) and 1H NMR (proton nuclear magnetic resonance) troscopy allows the polymer to be characterized.

[0195] Preferably, the SBS block copolymer has a content of pendant vinyl groups greater than or equal to 5% by moles, relative to the total number of moles of monomeric units of the SBS copolymer, preferably greater than or equal to 10%.

[0196] According to one embodiment, the SBS block copolymer preferably has a content of pendant vinyl groups less than or equal to 50% by moles, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably less than or equal to 40% by moles, even more preferably less than or equal to 30% by moles, typically less than or equal to 20% by moles.

[0197] Advantageously according to this first embodiment, the SBS block copolymer has a content of pendant vinyl groups in any range corresponding to the maximum and minimum values ​​mentioned above, and advantageously in the range from 5% to 20% by moles.

[0198] According to a second embodiment, the SBS block copolymer used according to the invention preferably has a content of pendant vinyl groups greater than or equal to 25% by moles, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably greater than or equal to 30% by moles.

[0199] Preferably, according to this second embodiment, the SBS block copolymer used according to the invention has, preferably, a content of pendant vinyl groups less than or equal to 50% by mole, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably less than or equal to 45% by mole. Advantageously, according to this second embodiment, the SBS block copolymer has a content of pendant vinyl groups in any range corresponding to the maximum and minimum values ​​mentioned above, and advantageously in the range of 35% to 45% by mole.

[0200] Preferably, the pendant vinyl groups are distributed along block B of the SBS polymer in a statistical manner. This characteristic results directly from the process implemented for the synthesis of the copolymer.

[0201] The number of moles of monomeric units of the S blocks present in the SBS block copolymer represents, together, at least 15% of the total number of moles of monomeric units of the SBS copolymer, preferably at least 16% in moles.

[0202] Preferably, the number of moles of monomeric units of the S blocks of the SBS polymer represents, together, from 15% to 50% by moles, relative to the total number of moles of monomeric units of the SBS block copolymer, more preferably from 16% to 30% by moles, even more preferably from 16% to 25% by moles, and further 16% to 20% by moles. The number of moles of monomeric units of the S blocks of the SBS polymer can be determined by 13C NMR spectroscopy (Nuclear Magnetic Resonance of carbon).

[0203] Preferably, the content of aromatic monovinyl hydrocarbon monomer (advantageously styrene) of the SBS block copolymer, determined by 13C NMR (Nuclear Magnetic Resonance of carbon) 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.

[0204] Preferably, the content of aromatic monovinyl hydrocarbon monomer (advantageously styrene) of the SBS block copolymer, determined by 13C NMR (Nuclear Magnetic Resonance of carbon) spectroscopy, 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.

[0205] Advantageously, SBS block elastomers are in an essentially non-hydrogenated form.

[0206] According to a particular embodiment, the block copolymer of formula SBS is obtained by coupling two block copolymers of formula S-B' in which blocks S and B' are selected to obtain an SBS block copolymer. Block B may therefore include a residue of a coupling agent, well known in the field concerned. Examples of difunctional coupling agents include dibromoethane, diethyl adipate, divinylbenzene, dimethyldichlorosilane, and methyl dichlorosilane.

[0207] 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%.

[0208] Examples of SBS block copolymers usable in compositions according to the invention, as well as their preparation processes, are described in particular in US patent 5,798,401, as well as in document WO 2007 / 058994 and by the applicant in patent application WO 2011 / 013073.

[0209] It is possible that, in the bituminous compositions and processes according to the invention, a single SBS block copolymer as described in the scope of the invention may be used, or that a mixture of SBS block copolymers as described in the scope of the invention may be used, or that one or more SBS block copolymer(s) as described in the scope of the invention may be used in combination with one or more other elastomers. According to a preferred embodiment, the matrix is ​​not made with one or more, preferably a single, SBS elastomers. These elastomers represent, preferably, from 0.5 to 10% by mass, in particular from 1 to 6% by mass, and preferably from 1.5 to 4% by mass of the total mass of the bituminous composition. In the bituminous compositions according to the invention, said elastomer(s) is / are in a crosslinked form, but this does not affect the percentage 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.When a mixture of elastomers, containing at least one elastomer other than the SBS elastomer as described in the context of the invention, is used, the percentages of 0.5 to 10% by mass, in particular 1 to 6% by mass, and preferably 1.5 to 4% by mass, given relative to the total mass of the bituminous composition, correspond to the total quantity of elastomers used (SBS + other elastomer(s)). In this case of use of a mixture of elastomers, containing at least one elastomer other than SBS elastomers, the SBS elastomer represents at least 50%, preferably at least 70% by mass, and preferably at least 90% of the total quantity of elastomers used (SBS + other elastomer(s)).

[0210] Preferably, the SBS elastomer(s) represent at least 80% by mass of the total quantity of elastomers, preferably at least 90%, and preferably 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, the mixture may contain a portion of S-B' used in the manufacture of the SBS elastomer by coupling, as explained above.

[0211] The bitumen / polymer composition (optionally crosslinked) according to the invention, preferably comprises from 0.1% to 20% by mass of elastomer, in particular of a copolymer of aromatic monovinyl hydrocarbon and conjugated diene, in particular of styrene and butadiene copolymer, relative to the mass of the bitumen / polymer composition (crosslinked).

[0212] According to one embodiment, the bitumen / polymer composition (optionally crosslinked) of the invention comprises from 1% to 8% by mass of elastomer, in particular of a copolymer of aromatic monovinyl hydrocarbon and conjugated diene, in particular of styrene and butadiene copolymer, relative to the mass of the crosslinked bitumen / polymer composition, more preferably from 2% to 5% by mass.

[0213] According to an alternative embodiment, the bitumen / polymer composition (optionally crosslinked) of the invention comprises from 5% to 20% by mass of elastomer, in particular a copolymer of a monovinyl aromatic hydrocarbon and a conjugated diene, in particular a copolymer of styrene and butadiene, relative to the mass of the crosslinked bitumen / polymer composition, more preferably of 10% to 15% by mass. Additives

[0214] According to one embodiment, the bituminous composition of the invention further comprises one or more additional additive(s).

[0215] These additional additives are known to those skilled in the art. By way of example, the following additives may be cited:

[0216] 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.

[0217] 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.

[0218] c) Paraffins having chain lengths of 30 to 120 carbon atoms (C30 to C120X). The paraffins are selected from polyalkylenes. Preferably, the paraffins are polymethylene paraffins and polyethylene paraffins. These paraffins may be of petroleum origin or may come from the chemical industry. Preferably, the paraffins are synthetic paraffins derived from the conversion of biomass and / or natural gas.

[0219] d) fluxes, such as oils based on animal and / or vegetable fats or hydrocarbon oils of petroleum origin. The 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 a methyl ester.

[0220] e) antifoaming additives, including (but not limited to) selected from polysiloxanes, oxyalkylated polysiloxanes and fatty acid amides derived from vegetable or animal oils.

[0221] f) 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.

[0222] g) sliding agents or anti-wear agents, in particular (but not limited to) selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glyceryl monooleate, and carboxylic acid derivatives mono- and polycyclic.

[0223] h) additives modifying crystallization, additives inhibiting paraffin deposits, additives enabling the pour point to be lowered; 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 / (meth)alkyl acrylate capable of being obtained by reaction of a maleic anhydride / (meth)alkyl acrylate copolymer and an alkylamine or polyalkylamine having a hydrocarbon chain of 4 to 30 carbon atoms, preferably of 12 to 24 carbon atoms;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.

[0224] i) antioxidants, for example of the hindered phenolic type or of the amino type, of the alkylated para-phenylenediamine type.

[0225] j) metal passivators.

[0226] k) acidity neutralizers.

[0227] 1) additives for lowering the mixing temperature of asphalts and coated, those which improve the adhesion of bituminous binders to fillers and aggregates, such as, for example, polyisobutylene succinimides.

[0228] m) acids, such as polyphosphoric acid, or diacids, in particular fatty diacids.

[0229] 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.

[0230] 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. Composition

[0231] Advantageously, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists (exclusively of): - from 40% to 99.9% bitumen by mass, - from 0.1% to 50% by mass of biochar, - from 0.1% to 30% by mass of plasticizing agent(s), - optionally, from 0.1% to 20% by mass of one or more elastomers, preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene, and - possibly, from 0.1% to 10% by mass of additional additive(s) as described above,

[0232] relative to the total mass of the bituminous composition.

[0233] According to a first embodiment, the bituminous composition of the invention comprises, preferably consists essentially, even more preferably consists (exclusively): - from 50% to 99% bitumen by mass, - from 0.5% to 30% by mass of biochar, - 1% to 20% by mass of plasticizing agent(s), - optionally, 1% to 8% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene - possibly, 0.5% to 5% by mass of additional additive(s) as described above,

[0234] relative to the total mass of the bituminous composition.

[0235] Preferably, according to this first embodiment, the bituminous composition of the invention comprises, preferably is essentially constituted, even more preferably is (exclusively) constituted: - 60% to 95% bitumen by mass, - del% to 15% by mass of biochar, - 2.5% to 10% by mass of plasticizing agent(s), and - optionally, 2% to 5% by mass of one or more elastomers, preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene - possibly, 0.5% to 2.5% by mass of additional additive(s) as described above,

[0236] relative to the total mass of the bituminous composition.

[0237] According to a second embodiment, the bituminous composition of the invention comprises, preferably consists essentially, even more preferably consists (exclusively): - from 50% to 99% bitumen by mass, - from 0.5% to 30% by mass of biochar, - from 2.5% to 20% by mass of plasticizing agent(s), and - optionally, 5% to 20% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene - possibly, 0.5% to 5% by mass of additional additive(s) as described above,

[0238] relative to the total mass of the bituminous composition.

[0239] Preferably, according to this second embodiment, the bituminous composition of the invention comprises, preferably is essentially constituted, even more preferably is (exclusively) constituted: - 60% to 95% by mass of bitumen, - 1% to 15% by mass of biochar, and - 2.5% to 10% by mass of plasticizing agent(s), - optionally, 10% to 15% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene - possibly, 0.5% to 2.5% by mass of additional additive(s) as described above,

[0240] relative to the total mass of the bituminous composition.

[0241] Preferably, the bituminous composition according to the invention is homogeneous. By "homogeneous", it is understood in the context of the invention that the different components of the composition, namely the biochar(s), the plasticizing agent(s) and any elastomers and / or additives, are distributed uniformly in the bituminous matrix.

[0242] Preferably, the composition according to the invention has a penetrability at 25°C, measured according to standard EN 1426, ranging from 25 to 60 1 / 10 mm, more preferably from 30 to 50 1 / 10 mm.

[0243] Preferably, the composition according to the invention has a ball and ring softening temperature, measured according to standard EN 1427, greater than or equal to 55°C, more preferably greater than or equal to 60°C, advantageously ranging from 60°C to 80°C, typically ranging from 60°C to 75°C.

[0244] Preferably, the composition according to the invention has a threshold stress, measured according to standard NF EN 13587, less than or equal to 5 MPa, more preferably less than or equal to 3.5 MPa, advantageously ranging from 1 MPa to 5 MPa, typically ranging from 1.5 MPa to 3 MPa.

[0245] Preferably, the composition according to the invention has a maximum elongation stress, measured according to standard NF EN 13587, greater than or equal to 0.4 MPa, more preferably greater than or equal to 1 MPa, advantageously ranging from 0.4 MPa to 3 MPa, typically ranging from 0.8 MPa to 1.5 MPa.

[0246] Preferably, the composition according to the invention has a threshold elongation, measured according to standard NF EN 13587, greater than or equal to 5%, more preferably greater than or equal to 10%, typically between 8% and 15%.

[0247] Preferably, the composition according to the invention has a maximum elongation, measured according to standard NF EN 13587, greater than or equal to 500%, more preferably greater than or equal to 550%, even more advantageously greater than or equal to 600%, typically from 550% to 650%.

[0248] Preferably, the composition according to the invention has an energy at 400%, measured according to standard NF EN 13587, greater than or equal to 20 J / cm3, more preferably greater than or equal to 21 J / cm3, advantageously ranging from 20 J / cm3 to 50 J / cm3, typically ranging from 21 J / cm3 to 30 J / cm3.

[0249] Preferably, the composition according to the invention has a total energy, measured according to standard NF EN 13587, greater than or equal to 2.5 J, more preferably greater than or equal to 2.75 J, advantageously ranging from 2.5 J to 10 J, typically ranging from 2.75 J to 5 J.

[0250] According to one embodiment, the composition of the invention comprises a significant proportion of bio-based, recycled, or waste-derived materials. It can therefore exhibit a high eco-material index. The eco-material index is defined by the following equation:

[0251] Eco-material index = 100% - [% of non-bio-based, non-biodegradable, non-recycled or non-waste-derived materials],

[0252] the percentages being expressed in mass, relative to the total mass of the composition.

[0253] According to one embodiment, the composition has an eco-material content of at least 5%, preferably at least 10%, preferably at least 15%.

[0254] Advantageously, the bituminous composition of the invention has a bio-based compound content, measured according to ASTM D6866, greater than or equal to 5% by mass, relative to the total mass of the composition, preferably greater than or equal to 10% by mass, more preferably greater than or equal to 15% by mass.

[0255] For the purposes of this invention, "bio-based compound" means a material derived at least in part from biomass resources. Biomass resources are organic materials available on a renewable or recurring basis, such as crop residues, wood residues, grasses, and aquatic plants. Corn ethanol is a well-known example of a bio-based material derived from biomass resources.

[0256] The bio-based material content of a sample is typically determined by measuring the Carbon-14 (radioactive isotope of carbon) content present in said sample.

[0257] Indeed, the method defined in ASTM D6866 makes it possible to measure the traces of carbon-14 still present in a fossil. These traces of carbon-14 then allow us to date the last time the molecules were absorbed (by ingestion or photosynthesis). This information is obtained thanks to the knowledge of the "half-life," which is the time it takes for half the quantity of the isotope initially present to decay and disappear. This time is approximately 5,700 years, meaning that every 5,700 years, the quantity of carbon-14 decreases by half. We also conclude that if a dead plant contains half as much carbon-14 as a living plant, it must have been alive 5,700 years ago. Beyond 50,000 years, a sample contains virtually no trace of the original radioactive compound. If a measurement carried out by a laboratory finds no remains in a fossil, the latter is certainly more than 50,000 years old.This is the case, for example, with oil and dinosaur bones.

[0258] Preferably, the bituminous composition of the invention has a carbon 14 content, measured according to ASTM D6866, greater than or equal to 4% by mass, relative to the total mass of the composition, preferably greater than or equal to 9% by mass, more preferably greater than or equal to 14% by mass.

[0259] Method for preparing a bituminous composition according to the invention

[0260] The bituminous compositions of the invention can be prepared by any process known to those skilled in the art. Generally, these processes include mixing the components and heating the resulting mixture. The bitumen may be heated before mixing. Usually, the bitumen is heated before mixing, and the additive(s) are added to the bitumen without having been preheated. According to a particular embodiment of the invention, a bitumen composition is prepared by bringing into contact:

[0261] - at least one bitumen base;

[0262] - biochar, preferably as defined above;

[0263] - at least one plasticizing agent, preferably as defined above;

[0264] - possibly an elastomer as defined above;

[0265] - possibly one or more other additive(s), in particular one or more additional additive(s) as described above.

[0266] In particular, the following components are mixed under heating and stirring:

[0267] - at least one bitumen base,

[0268] - biochar, preferably as defined above,

[0269] - at least one plasticizing agent, preferably as defined above,

[0270] - possibly an elastomer as defined above, chosen from among the copolymers of an aromatic monovinyl hydrocarbon and a conjugated diene

[0271] - possibly one or more other additive(s), in particular one or more additional additive(s) as described above.

[0272] The mixture of bitumen, biochar, plasticizing agent, and even elastomer(s) and / or other additive(s) present, can be carried out at a temperature ranging from 90°C to 230°C, preferably ranging from 120°C to 200°C, and preferably ranging from 150°C to 180°C.

[0273] Such a mixture is prepared under agitation to facilitate the dispersion and even distribution of the biochar and plasticizer, and possibly the elastomer, in the bitumen that will form the matrix of the composition, possibly in combination with the additional additive(s). The conditions are adapted to ensure a homogeneous mixture and the distribution of the biochar and plasticizer (and elastomer). Typically, a person skilled in the art will adjust the agitation time and power, as well as the mixing temperature, particularly according to the type of bitumen, the precise nature of the biochar, the plasticizer, and the elastomer when present, to obtain a molten mixture. Advantageously, the mixing is carried out in such a way as to promote good distribution of the biochar (and elastomer) in the final bituminous composition obtained.

[0274] Generally, and as is known to those skilled in the art, the bitumen or mixture of bitumens used to manufacture the composition is preheated and stirred before the other constituents of the composition are incorporated. The incorporation of biochar (and elastomer) is generally carried out while the bitumen is maintained at a temperature in the range of 90 to 230°C, preferably in the range of 120 to 200°C, and preferably in the range of 150 to 180°C.

[0275] The constituents can be introduced simultaneously or sequentially. 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.

[0276] According to particular embodiments, the process according to the invention includes a homogenization step which allows, in particular, the distribution of the biochar (and the elastomer) in said composition. Such a step is in particular a mixing step of the different constituents, under agitation at a speed of 100 to 600 rpm, preferably 200 to 400 rpm and for a duration of 2 to 30 hours, preferably 6 to 24 hours, while the mixture is heated to a temperature in the range of 90 to 230°C, preferably in the range of 120 to 200°C, and preferably in the range of 150 to 180°C.

[0277] In the process according to the invention, one or more bitumen(s), one or several biochar(s), one or more plasticizing agent(s), optionally one or more elastomer(s), and even one or more additional additive(s), corresponding to the descriptions given previously in the relevant sections. The crosslinked elastomers are introduced in a crosslinkable form into the compositions according to the invention and crosslinked in situ.

[0278] Of course, in the process, the quantities used of bitumen, biochar, plasticizing agent(s), or even elastomer(s) and / or additional additive(s) possibly present, will be adjusted by a person skilled in the art to obtain in the end the desired quantities in the final composition, and in particular those mentioned in the previous part relating to the compositions according to the invention.

[0279] The characteristics described in the preceding sections also apply to the preparation processes according to the invention. Thus, the components involved in the preparation process will preferably be chosen from among those previously described and introduced in proportions that lead to the quantities given for the description of the bituminous compositions according to the invention.

[0280] Bituminous compositions that can be obtained by such processes also form an integral part of the invention. Applications

[0281] 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.

[0282] The bituminous binder or bituminous composition according to the invention can in turn be used to prepare a mixture with aggregates, particularly road 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.

[0283] 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.

[0284] Aggregates are mineral and / or synthetic aggregates, in particular recycled millings, with dimensions greater than 2 mm, preferably between 2 mm and 20 mm.

[0285] The invention also relates to a method for preparing a bituminous coating comprising the hot mixing of a bituminous composition according to the invention, with aggregates, and optionally mineral and / or synthetic fillers.

[0286] The bituminous binder according to the invention can advantageously be used to prepare a surface dressing, hot mix asphalt, cold mix asphalt, cold-applied asphalt, or emulsion aggregate. With regard to road applications, the invention also relates to asphalts as materials for manufacturing and surfacing sidewalks.

[0287] 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.

[0288] The invention also relates to a process for preparing an asphalt comprising the hot mixing of a bituminous composition according to the invention, with mineral and / or synthetic fillers.

[0289] Another aspect of the invention relates to the use of a bituminous composition in various industrial applications, particularly for preparing a waterproofing coating, a membrane, or an impregnating layer. Industrial applications of bituminous compositions include the manufacture of waterproofing membranes, soundproofing membranes, insulation membranes, surface coatings, carpet tiles, and impregnating layers.

[0290] The invention also relates to the use of the combination of at least one biochar and at least one plasticizing agent, preferably as defined above, in a bituminous composition, preferably in a bitumen / polymer composition possibly crosslinked, to reduce the carbon footprint of said composition.

[0291] For the purposes of this invention, the "carbon footprint" of a product means the amount of carbon (generally expressed in kg of CO2 equivalent per kg of product) required to produce said product. This amount of carbon equivalent takes into account both energy consumption, particularly related to heating, and the consumption of raw materials. The carbon footprint of a product is typically determined according to either ISO 14040 or ISO 14044.

[0292] Preferably, the use of a combination of at least one biochar and at least one plasticizing agent as defined above makes it possible to reduce the carbon footprint of a bituminous composition, in particular a composition, by at least 20% bitumen / polymer (crosslinked or not), compared to the same composition free of biochar and plasticizer, more preferably at least 30%, even more preferably at least 40%, advantageously at least 80%, more advantageously at least 90%, typically at least 95%, for example at least 98%. The values ​​expressed above are calculated assuming that the end-of-life bitumen is not burned and that the biogenic carbon present in the bitumen is not re-emitted.

[0293] The invention is illustrated by the following examples given by way of non-limiting example. EXAMPLES 1. Materials and methods

[0294] In the examples below, the bituminous compositions were evaluated according to the following protocols:

[0295] - the measurement of needle penetration at 25°C (abbreviation: P25), according to the standard EN 1426, the results being expressed in 1 / 10 mm,

[0296] - the measurement of the ring ball softening temperature (abbreviation: BBT), according to standard EN 1427, with results expressed in °C,

[0297] - the elastic return at 25°C (R25), expressed as a percentage according to standard EN 13398,

[0298] - the mechanical properties (stress at maximum elongation, threshold elongation, maximum elongation, energy at 400%, total energy), measured according to standard NF EN 13587,

[0299] - the evaluation of the low-temperature behavior of compositions (BBR), according to the EN 14771 standard, by measuring the flexural stiffness modulus of the composition.

[0300] - Aging acceleration protocol (PAV), according to standard NF EN 14769, Conditions: 25 hours, 21 bars and 100°C.

[0301] Raw materials

[0302] The detailed compositions below were prepared from the following raw materials:

[0303] Bitumen Base (B): grade 35 / 50 bitumen having a P25 penetration of 40 1 / 10 mm and a TBA of 52°C, commercially available from TotalEnergies under the brand AZALT®;

[0304] Thermocrosslinkable elastomer SB S (E): styrene / butadiene / styrene (SBS) sequence copolymer, comprising 30.5% by mass of styrene and 69.5% by mass of butadiene. The content of pendant vinyl groups resulting from the 1,2-addition polymerization of butadiene is 27.8% by mass relative to the total mass of the copolymer. The copolymer has a weight-average molecular weight (Mw) of 142,500 Daltons and a polydispersity index Ip of 1.09. This copolymer is commercially available from KRATON under the name DI 192;

[0305] Biochar: biochar of softwood commercially available from the company TERRA FERTILIS;

[0306] Plasticizing agent: tall oil pitch, commercially available from KRATON under the reference TALL OIL PITCH PN;

[0307] Crosslinking agent: sulfur-rich agent

[0308] Additive: additive for trapping hydrogen sulfide emissions (in English, "H2S scavenger") 2. Preparation of compositions

[0309] Compositions Cl*, C2* and C3 are prepared according to the following protocol:

[0310] The pure bitumen is preheated to 160°C in an oven, then transferred to a 3L reactor in which it is heated for 1h at 180°C.

[0311] The elastomer, and possibly the biochar and the plasticizing agent, are then added and the mixture ground for 30 min at 6000 rpm, always at 180°C, using a high shear rotorstator (Silverson).

[0312] The reactor is then placed under mechanical stirring at 400 rpm for 2 hours at 180 °C.

[0313] Thus, the thermocrosslinked matrix of the bituminous composition is obtained.

[0314] The details of the compositions are given in Table 1 below. The contents are given by mass, relative to the total mass of the bitumen / crosslinked polymer composition.

[0315] [Tables 1] Cl* (comparative) C2* (comparative) C3 (according to the invention) Bitumen 96.81% 91.81% 86.64% Elastomer 3% 3% 3% Crosslinking agent 0.07% 0.07% 0.12% Additive 0.12% 0.12% 0.24% Biochar - 5% 5% Plasticizing agent - - 3%

[0316] The compositions Cl* and C2* are comparative.

[0317] Compositions C3 are according to the invention. 3. Composition Evaluations

[0318] The properties of the Cl*, C2* and C3 compositions were evaluated according to the protocols defined above. The results are summarized in Table 2 below.

[0319] [Tables2] Cl* (comparative) C2* (comparative) C3 (according to the invention) P25 (1 / 10 mm) 37 29 34 TBA (°C) 66.4 70 69.0 Elastic return at 25°C (%) 85 77 81 Evaluation of energy at 400%, from yield stress at 5°C to maximum elongation (MPa) 1.01 1.02 0.96 Yield elongation (%) 11.68 10.16 13.38 Maximum elongation (%) 656 432 541 Energy at 400% (J / cm²) 21.09 23.71 21.29 Total energy (J) 3.86 3.49 3.29 BBR before PA VT°@S = 300MPa (°C) @60s -16 -14.8 -15.6 T° @ m = 0.300 (°C) @60s -17 -15.3 -16.7 m-value @ T @ S= 300MPa, 60s 0.319 0.306 0.314 BBR after PA VT°@S = 300MPa (°C) @60s -13.9 -12.6 -13.2 T° @ m = 0.300 (°C) @60s -11.9 -10.3 -12.1 m-value @ T @ S= 300MPa, 60s 0.280 0.279 0.288

[0320] It is observed that the Cl*, C2* and C3 compositions exhibit equivalent properties. In particular, the compositions all exhibit satisfactory properties, meeting the required technical specifications.

[0321] By comparing the results obtained for compositions Cl* and C2*, it is observed that the incorporation of biochar into the bitumen / polymer matrix leads to a decrease in penetrability at 25°C and in elastic recovery at 25°C, as well as to a dete deterioration of cold performance (BBR) of the composition, before and after aging.

[0322] However, these deteriorations are not observed in the context of composition C3 according to the invention, which further includes the plasticizing agent. The incorporation of the plasticizing agent therefore compensates for the properties degraded by the integration of biochar. The composition of the invention thus exhibits properties similar to those of the comparative composition Cl, which is free of bio-based compounds.

Claims

Claims

1. Bituminous composition comprising: - at least one bitumen base, - biochar, and - at least one plasticizing agent.

2. Bituminous composition according to claim 1, in which the plasticizing agent is chosen from: a) tall oil derivatives, b) plastic pyrolysis oils, c) triglycerides d) mixtures of a) and / or b) and / or c).

3. A bituminous composition according to claim 1 or claim 2, wherein the biochar is derived from thermochemical conversion of biomass selected from forest products; crop residues; animal waste; municipal waste and any mixture thereof.

4. Bituminous composition 'any one of claims 1 to 3, wherein the biochar is derived from the thermochemical conversion of biomass chosen from hardwoods, in particular ash wood; cereal husks; nut shells, in particular cashew nuts; food waste; coffee grounds and any of their mixtures.

5. Bituminous composition according to any one of the preceding claims, having a biochar content ranging from 0.1% to 50% by mass, preferably from 0.5% to 30% by mass, preferably from 1% to 15% by mass, relative to the total mass of the bituminous composition.

6. Bituminous composition according to any one of the preceding claims, further comprising at least one elastomer, preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene.

7. Crosslinked bitumen / polymer composition, obtained by crosslinking, in particular chemical or thermal, of a bituminous composition according to claim 6.

8. A process for preparing a bituminous composition according to any one of the preceding claims, this process comprising: 1) bringing the following components into contact: - at least one bitumen base, - biochar, and - at least one plasticizing agent 2) the mixture of components.

9. Preparation process according to claim 8, wherein the mixing of the components 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 180°C.

10. Use of a bituminous composition according to any one of claims 1 to 7, for preparing a surface coating, a hot mix, a cold mix, a cold-poured mix, a gravel emulsion or a wearing course, said binder being associated with aggregates and / or recycled millings.

11. Bituminous coating comprising a bituminous composition according to any one of claims 1 to 7, mixed with aggregates and / or recycled millings, and optionally mineral and / or synthetic fillers.

12. Asphalt comprising a bituminous composition according to any one of claims 1 to 7, in admixture with mineral and / or synthetic fillers.

13. A waterproofing coating, preferably a membrane or an impregnation layer, comprising a bituminous composition according to any one of claims 1 to 7.

14. Use in a bituminous composition, in particular in an optionally crosslinked bitumen / polymer composition, of the combination of at least one biochar and at least one plasticizing agent, to reduce the content of compound(s) of fossil origin in said composition.

15. Use in a bituminous composition, in particular in an optionally crosslinked bitumen / polymer composition, of the combination of at least one biochar and at least one plasticizing agent, to reduce the carbon footprint of said composition.