Bio-based binder, asphalt mix composition and road surfacing based on said bio-based binder

Abstract

The present invention relates to a bio-based binder comprising, by mass relative to its total mass, at least: (a) 35% to 98% of at least one first compound based on a fat of natural origin comprising one or more unsaturated hydrocarbon fatty chains, said first compound having undergone at least one chemical reaction selected from: blowing and / or maleinization, (b) 2% to 40% of at least one structuring agent, and (c) 0% to 50% of at least one second compound based on a fat of natural origin, said second compound not having undergone any chemical reaction, such as a chemical reaction selected from: blowing and / or maleinization.

Description

Title of the invention: Bio-based binder, asphalt mix composition and road surface based on said bio-based binder Technical field of the invention

[0001] The present invention relates to the technical field of road and / or civil engineering pavements. In particular, the present invention relates to a new bio-based hydrocarbon binder, as well as its manufacturing process. The invention also relates to an asphalt mix composition incorporating said bio-based binder, such as a material for producing a construction layer or pavement. Finally, the invention also relates to a road and / or civil engineering construction layer or pavement comprising the aforementioned asphalt mix composition. State of the art

[0002] Bitumen has been an essential binder for the majority of road construction projects for several decades. Indeed, the binders used in road and highway construction are based on bitumen or acrylic or vinyl latex derived from petroleum and petrochemicals. Many, if not most, roadways are surfaced with bituminous mixes, which have proven their ability to withstand the application constraints on the one hand, and the stresses related to traffic and climatic conditions on the other. These mixes consist of aggregates bonded together by bitumen or bitumen modified by the addition of additives, in particular elastomers and / or thermoplastic polymers. Bitumen-bonded aggregates are also used in the Building and Public Works (BTP) sector to create, among other things, waterproofing membranes, sidewalk surfaces, riprap, and bridge and other structures.Bitumen is also used in so-called industrial applications such as waterproofing, thermal or acoustic insulation.

[0003] Bitumen, however, is a material derived primarily from petroleum refining. As such, it is considered a non-renewable raw material since petroleum is a fossil fuel. The processes used to obtain synthetic resins or bitumen from crude oil inevitably generate environmental impacts, particularly on the production of greenhouse gases (GHGs). Furthermore, the main purpose of oil refining is the production of fossil fuels, which constitute a very significant portion of greenhouse gas emissions. The increasing concentration of greenhouse gases (GHGs) in the atmosphere contributes to climate change.

[0004] Thus, in order to prepare for the inevitable depletion of global oil resources and with a growing concern for environmental protection, it is, by Consequently, it is desirable to seek to replace at least some, or even all, petroleum-based constituents, and in particular the binders used to manufacture asphalt compositions, with bio-based constituents.

[0005] Several technical solutions have been proposed in the prior art.

[0006] Document FR 2 853 647 describes in particular a binder for the production of layers and / or coatings for road construction and / or civil engineering comprising, in relation to the total weight of (a) and (b):

[0007] (a) from 2 to 98% by weight of at least one natural or modified natural resin, of vegetable origin, having a softening point measured according to standard EN 1427 of 30 to 200°C;

[0008] (b) from 98 to 2% by weight of at least one vegetable oil having a viscosity at 25°C, from 50 mPa.s to 1000 Pa.s,

[0009] (c) said binder having: (cl) either a penetrability at 25°C, measured according to standard NF EN 1426, from 20 to 300 l / 10th of a mm and a softening point of 30 to 75°C, measured according to standard NF EN 1427; (c2) i.e., a penetrability at 15°C, measured according to standard NF EN 1426, of 300 to 900 l / 10th of a mm and a viscosity at 60°C, measured according to standard NF EN 12596, of 2 to 20 Pa.s; and

[0010] (d) said binder being free from any natural or synthetic elastomer and from any thermoplastic polymer.

[0011] The natural resin can be a natural rosin and the vegetable oil can be a crude or refined oil. It can also be modified by chemical reactions, such as esterification.

[0012] Document FR 2 932 806 describes organic resins derived from a naturally occurring oil or fat comprising monoglycerides and / or diglycerides, esterified by a specific poly(hydroxy) acid. These resins can be used in binder compositions for manufacturing coatings.

[0013] Although these technical solutions are satisfactory, there is a need in the state of the art for new binder compositions that are more environmentally friendly compared to traditional petroleum-derived binders, while maintaining comparable technical performance, namely exhibiting, for example, good mechanical strength, such as good resistance to rutting.

[0014] There is also a need in the prior art for new bio-based binder compositions with adequate technical performance, while being easy to implement, namely, while being easily feasible in terms of its preparation process, the process being capable of and / or configured to provide stable compositions having identical or at least similar technical characteristics from one batch to another.

[0015] The aim of the present invention is therefore to propose a new binder composition which meets at least in part the aforementioned needs. Presentation of the invention

[0016] To this end, the present invention relates to a bio-based binder comprising, by mass relative to its total mass, at least:

[0017] (a) from 35% to 98% of at least a first compound based on a fat of natural origin comprising one or more unsaturated hydrocarbon fatty chains, said first compound having undergone at least one chemical reaction selected from: blowing and / or maleinization,

[0018] (b) from 2% to 40% of at least one structuring agent, and

[0019] (c) from 0% to 50% of at least a second compound based on a fat of natural origin, the said second compound not having undergone a chemical reaction chosen from: blowing and / or maleinization.

[0020] According to the invention, "bio-based" means a binder composition made entirely or at least partially from materials of biological origin (for example, plant or animal) from renewable resources, such as vegetable oil or used cooking oil.

[0021] Other non-limiting and advantageous features of the product / process according to the invention, taken individually or in all technically possible combinations, are as follows:

[0022] - said natural fat of said at least (a) first compound and / or said at least (c) second compound is selected from oils obtained in nature or their derivatives, fats obtained in nature or their derivatives, used vegetable oils, such as used oils from the food industry or their derivatives, and mixtures thereof; preferably, said fat of natural origin of (a) first compound and / or (c) second compound is selected from used oils from the food industry;

[0023] - wherein (b) said at least structuring agent is chosen from one or more of the The following compounds:

[0024] * natural polymers, including starch, plant proteins, gum welan, xanthan gum, carob gum and all other natural gums, cellulose, hemicellulose (xylane);

[0025] * semi-synthetic polymers, such as decomposed starches and their derivatives, cellulose ethers such as hydroxypropyl methyl cellulose (HPMC), hydroxide ethyl cellulose (HEC), and carboxymethyl cellulose (CMC), a chemically modified rosin;

[0026] * synthetic polymers, such as butadiene-styrene copolymer (SBS);

[0027] - said semi-synthetic polymer is a cellulose ether polymer, such as a ethylcellulose polymer;

[0028] - (a) said at least first compound presents:

[0029] * an average molecular mass by weight (Mw) ranging from 1,500 g / mol to 10,000 g / mol, preferably from 1,800 g / mol to 8,000 g / mol and typically from 1,700 g / mol to 7,300 g / mol;

[0030] * a standard of the complex modulus at 20°C, 1Hz between 10 Pa and 1,000,000 Pa, preferably from 1000 to 50000 Pa and typically from 8000 to 12000 Pa, measured according to standard NF EN 14770 (2012) with a dynamic shear rheometer (plane-plane geometry);

[0031] - said binder comprises at least one of the following characteristics, preferably all of the following characteristics:

[0032] * a PI penetration (fresh binder) at 25°C (l / 10th of a mm) measured according to the standard NF EN 1426 (2018) ranging from 10 to 260, preferably ranging from 30 to 220 and typically ranging from 70 to 160;

[0033] * a softening temperature TBA 1 (°C) (fresh binder) measured according to the standard NF EN 1427 or ASTM D36 ranging from 20°C to 90°C, preferably ranging from 35°C to 70°C and typically ranging from 43°C to 60°C;

[0034] * a P2 penetrability after the RTFOT test at 25°C (l / 10th of a mm) measured according the NF EN 1426 (2018) standard ranging from 5 to 240, preferably ranging from 10 to 200 and typically ranging from 50 to 140;

[0035] * a softening temperature TBA 2 (°C) after the RTFOT test (EN standard) 12607-1) measured according to standard NE EN 1427 or ASTM D36 ranging from 30°C to 100°C, preferably ranging from 45°C to 80°C and typically ranging from 53°C to 70°C;

[0036] * a mass loss after the RTFOT test (standard EN 12607-1) measured according to the NF EN 13303 (2017) standard less than or equal to 10%, preferably less than or equal to 5% and typically less than or equal to 1%.

[0037] The present invention further relates to a process for preparing a bio-based binder as described above, comprising the following steps:

[0038] (i) the preparation of said at least first compound based on a fat of natural origin comprising one or more unsaturated hydrocarbon fatty chains having undergone at least one chemical reaction chosen from: blowing and / or maleinization;

[0039] (ii) mixing the first compound obtained in step (i) with said at least structuring agent and where applicable said second compound at a temperature below 180°C, preferably from 100 to 160°C and typically from 120°C to 150°C, preferably for a period of less than or equal to 1 hour, such as 15 minutes.

[0040] Preferably, step (i) comprises the following steps:

[0041] (il) - the supply of at least one fat of natural origin comprising one or more unsaturated hydrocarbon fatty chains, such as used oil from the food industry;

[0042] (i2) - a blowing step which consists of injecting air at high temperature ranging from 100 to 250°C, preferably from 120°C to 200°C and typically from 140°C to 180°C on said at least fat comprising one or more unsaturated hydrocarbon fatty chains,

[0043] or

[0044] (i3)- a maleinization step which consists of causing said at least matter to react fat comprising one or more unsaturated hydrocarbon fat chains with maleic anhydride, under agitation, at high temperature ranging from 100°C to 260°C, preferably from 200°C to 250°C and typically from 210°C to 230°C for 5 to 30 hours, preferably 10 to 20 hours;

[0045] or

[0046] (i4)- a blowing step (i2) followed by a malling step (i3), or vice versa.

[0047] According to one feature of the invention, during the maleinization step (i3), maleic anhydride is introduced in an amount ranging from 0.5 to 3 equivalents by unsaturation of said natural fat comprising one or more unsaturated hydrocarbon fatty chains, preferably from 0.5 to 2 equivalents, and typically from 0.5 to 1 equivalent.

[0048] The present invention also relates to a coating composition comprising at least, by mass, relative to its total mass:

[0049] - from 2% to 8%, preferably from 4% to 6% of a bio-based binder as described above or obtained according to the aforementioned process, and

[0050] - from 92% to 98%, preferably from 94% to 96% of at least one aggregate (gravel, sands, asphalt aggregates (AE), etc).

[0051] According to one embodiment, said coating composition does not include bitumen.

[0052] The present invention also relates to a road surface, characterized in that it comprises the aforementioned asphalt composition, and preferably has a thickness ranging from 2 to 15 cm, in particular from 4 to 12 cm.

[0053] Finally, the present invention relates to the use of a binder as described above or obtained according to the aforementioned process, in order to partially or totally replace the use of bitumen for the production of asphalt mix compositions and / or road construction coatings and / or civil engineering coatings (based on recycled materials such as AE or not, namely based on conventional or non-recycled aggregates).

[0054] Of course, the different features, variants and embodiments of the invention can be combined with each other in various ways insofar as they are not incompatible or mutually exclusive.

[0055] For the remainder of the description, unless otherwise specified, the indication of a range of values ​​"from X to Y" or "between X and Y" in the present invention is understood to include the values ​​X and Y.

[0056] According to the invention, unless otherwise stated, the various characteristics of the invention have been measured according to the standards mentioned below or according to the internal methods described below. Detailed description of the invention

[0057] In addition, various other features of the invention become apparent from the attached description made with reference to the drawings which illustrate non-limiting embodiments of the invention and where:

[0058] [Fig.1] represents the complex modulus G* (Pa) as a function of temperature -20°C to 60°C for a frequency of 1 Hz for different first compounds according to the invention (Ex. 1-6), as well as for a reference bitumen 35 / 50 (Ex.7) and for a reference maltene fraction (Ex.8);

[0059] [Fig.2] represents the complex modulus G* (Pa) as a function of temperature -20°C to 60°C for a frequency of 1 Hz for different binders according to the invention (Ex. 16 to 21), for a comparative example (Ex.Comp.2), as well as for the reference bitumen 35 / 50 (Ex.7) and for the reference maltene fraction (Ex.8);

[0060] [Fig.3a] represents the complex modulus G* (Pa) as a function of temperature -20°C to 60°C for a frequency of 1 Hz for different binders according to the invention (Ex.22 to 26), for a comparative example (Ex.Comp.3), as well as for the reference bitumen 35 / 50 (Ex.7);

[0061] [Fig.3b] represents the complex modulus G* (Pa) as a function of temperature -20°C to 60°C for a frequency of 1 Hz for different binders according to the invention (Ex.27 to 30), for a comparative example (Ex.Comp.3), as well as for the reference bitumen 35 / 50 (Ex.7);

[0062] [Fig. 4a] represents the calorimetric curves (temperatures as a function of enthalpy in mW / mg of the binders according to the invention (Ex. 23 to 26), of Ex. Comp. 3 and of Ex. Comp. 4 (chemically unmodified used cooking oil); and

[0063] [Fig.4b] represents the calorimetric curves (temperatures as a function of the enthalpy in mW / mg of the binders according to the invention (Ex.27 to 30), of Ex.Comp.3 and of Ex.Comp.4 (used cooking oil not chemically modified). A. Bio-based binder

[0064] The Applicant has focused on developing new binder compositions that are bio-based and capable of replacing, at least in part, but preferably totally, petroleum bitumen usually used in road construction.

[0065] In particular, it has developed a bio-based binder composition with technical characteristics, such as penetrability, softening point, and complex modulus (i.e., stiffness), that are substantially similar or close to those of a conventional bituminous binder. Thus, the Applicant has developed a bio-based binder composition that makes it possible to form an asphalt mix composition with suitable technical characteristics, such as good mechanical strength, meeting, in particular, the standards for road surfaces.

[0066] For this purpose, the present invention refers to a bio-based binder comprising, by mass relative to its total mass, at least:

[0067] (a) from 35% to 98% of at least a first compound based on a fat of natural origin comprising one or more unsaturated hydrocarbon fatty chains, said first compound having undergone at least one chemical reaction selected from: blowing and / or maleinization,

[0068] (b) from 2% to 45% of at least one structuring agent, and

[0069] (c) from 0% to 50%, preferably from 0% to 20% of at least a second compound based on a fat of natural origin, said second compound not having undergone a chemical reaction chosen from: blowing and / or maleinization.

[0070] According to one feature of the invention, the bio-based binder comprises, by mass relative to its total mass, at least:

[0071] (a) from 55% to 98%, preferably from 70% to 95% and typically from 85% to 92% of said first compound,

[0072] (b) from 2% to 45%, preferably from 5% to 30% and typically from 8% to 15% of said at minus one structuring agent.

[0073] By way of example, the binder according to the invention may comprise, by mass, relative to the total mass of the binder, 92% of the first compound and 8% of the structuring agent.

[0074] According to another feature of the invention, the bio-based binder comprises, by mass relative to its total mass, at least:

[0075] (a) from 38% to 95%, preferably from 40% to 92% and typically from 55% to 75% of said first compound,

[0076] (b) from 5% to 30%, preferably from 8% to 25% and typically from 8% to 15% of said at minus one structuring agent.

[0077] (c) from 1% to 50%, preferably from 5% to 45% and typically from 10% to 35% of said second compound.

[0078] By way of example, the binder according to the invention may comprise, by mass, relative to the total mass of the binder, 75% of the first compound, 8% of the structuring agent and 17% of the second compound.

[0079] As will be demonstrated in the experimental part described below, the use of a first unsaturated fat that has undergone a maleinization and / or blowing reaction (chemical transformation), combined with the use of a structuring agent (physical transformation) makes it possible to form a bio-based binder composition that is an alternative to conventional bitumen.

[0080] The Applicant has demonstrated that the bio-based binder according to the invention has rheological properties comparable to petroleum bitumen at 60°C (complex modulus G*, Pa). However, it is much less heat-sensitive, which can be an advantage for cold-weather properties. Despite this difference, the coating capacity of the bio-based binder according to the invention was demonstrated during the production of a road surfacing asphalt mix based on a conventional binder and aggregate formulation. This asphalt mix showed good performance in the rutting test (2.3% at 30,000 cycles compared to 2.7% for a conventional 35 / 50 bitumen). Furthermore, the life cycle analysis shows that the use of the bio-based binder according to the invention is beneficial for the environment, particularly when the carbon stored by the plant resource is taken into account.

[0081] Al. First compound

[0082] The first component of the bio-based binder according to the invention is a fat of natural origin comprising one or more unsaturated hydrocarbon fatty chains having undergone at least one chemical reaction chosen from: blowing and / or maleinization.

[0083] The maleinization reaction consists of reacting maleic anhydride at high temperature on natural fats comprising one or more unsaturated hydrocarbon fatty chains.

[0084] The blowing reaction consists of injecting air (air bubbling into the first compound) at high temperature, generally ranging from 120°C to 220°C, for a variable duration in order to achieve the desired viscosity.

[0085] Without being bound by any theory, the Applicant discovered that these two specific chemical reactions made it possible to change the appearance of the initial fat and increase its average molecular weight, as well as its viscosity. During the blowing reaction, the formation of peroxide bridges between the Unsaturating the fatty acid chains of the initial fat will increase its average molecular weight and thus its viscosity. Also, during the maleinization reaction, the grafted anhydride will tend to "open up" (particularly under the reaction conditions listed below and used by the Applicant), leading to the beginning of polymerization. It will be possible to vary the molecular weight of the generated polymers, and therefore their viscosity, by varying experimental parameters such as the amount of maleic anhydride, the temperature, and the reaction time.

[0086] Following the maleinization and / or blowing reaction, the first compound advantageously has a weight average molecular mass (Mw) ranging from 1,500 g / mol to 10,000 g / mol, preferably from 1,800 g / mol to 8,000 g / mol and typically from 1,700 g / mol to 7,300 g / mol.

[0087] According to the invention, "a weight average molecular mass (Mw) ranging from 1,500 g / mol to 10,000 g / mol" comprises the following values ​​in g / mol or any interval between these values: 1500; 1550; 1600; 1650; 1700; 1750; 1800; 1850; 1900; 1950; 2000; 2100; 2200; 2300; 2400; 2500; 2600; 2700; 2800; 2900; 3000; 3200; 3400; 3600; 3800; 9000; 9200; 9400; 9600; 9700; 9800; 9900; 10000.

[0088] Also, following the maleinization and / or blowing reaction, the first compound generally exhibits a complex modulus G* at 20°C, 1Hz between 10 Pa and 1,000,000 Pa, preferably from 1,000 to 50,000 Pa and typically from 8,000 Pa to 12,000 Pa, measured according to standard NF EN 14770 (2012) with a dynamic shear rheometer (plane-plane geometry).

[0089] Also, according to the invention, "a complex module G* at 20°C, 1Hz between 10 Pa and 1,000,000 Pa" comprises the following values ​​in Pa or any interval between these values: 10; 50; 100; 150; 200; 250; 300; 350; 400; 450; 500; 550; 600; 650; 700; 750; 800; 850; 900; 950; 1000; 1500; 2000; 2500; 3000; 3500; 4000; 4500; 5000; 5500; 6000; 6500; 7000; 7500; 8000; 8500; 9000; 9500; 10,000; 10,500; 11,000; 11,500; 12,000; 12,500; 13,000; 14,000; 15,000; 16,000; 17,000; 18,000; 19,000; 20,000; 30,000; 40,000; 50,000; 60,000; 70,000; 80,000; 90,000; 100,000; 200,000; 300,000; 400,000; 500,000; 600,000; 700,000; 800,000; 900,000; 1,000,000.

[0090] By "naturally sourced fat comprising hydrocarbon fatty chains", according to the present invention, means fats from nature, but also their derivatives, namely those resulting from a chemical reaction, such as fatty monoesters obtained by transesterification of triglycerides (for example, a vegetable oil) by mono-alcohols.

[0091] Preferably, said natural fat comprising one or more unsaturated hydrocarbon fatty chains of said at least (a) first compound is chosen from oils obtained in nature or their derivatives, fats obtained in nature or their derivatives (i.e. vegetable and / or animal fats), used vegetable oils, such as used oils from the food industry or their derivatives, and mixtures thereof.

[0092] In general, the vegetable oil is chosen from: rapeseed oil, soybean oil, sunflower oil, castor oil, copra (coconut) oil, olive oil, wood pulp (tail) oil, palm oil, palm kernel oil, linseed oil (such as linseed stand oil - oil cooked near its boiling point and polymerized), coconut oil, hazelnut oil, cashew balsam (cardanol), peanut oil, corn oil, pumpkin oil, grapeseed oil, jojoba oil, sesame oil, walnut oil, tung oil or a mixture thereof.

[0093] Vegetable fat can be derived from cocoa beans and animal fats can be fats obtained by melting the fatty tissues of animals: lard, goose or duck fat, fish oil (especially herring), spermaceti oil (whale oil), beef or horse tallow.

[0094] The natural fats usable in the present invention can also be derived from products to be recycled, such as used cooking oils and their derivatives or so-called third-generation oils derived from biomass such as algae or microorganisms.

[0095] Fossil oils and fats, which are not renewable and are not of interest in the context of sustainable development, are therefore preferentially excluded from the scope of the invention.

[0096] According to one embodiment, the natural fat comprising one or more unsaturated hydrocarbon fatty chains will be chosen from vegetable oils or fats directly from nature (i.e. not having undergone a chemical reaction or not having been chemically functionalized other than by a maleinization and / or blowing reaction).

[0097] According to another embodiment of the invention, the compound based on natural fats comprising one or more unsaturated hydrocarbon fatty chains is a derivative of a vegetable oil or a natural fat and has been previously chemically functionalized (and will then undergo a maleinization and / or blowing reaction).

[0098] By way of example, the compound based on fats of natural origin has previously undergone at least one chemical reaction chosen from: esterification, transesterification, hydrolysis, oxidation, Diels-Alder reaction, radical reaction, thiolation, isomerization reaction.

[0099] By way of example, the natural fats usable in the present invention may have previously undergone an isomerization reaction. The natural fats may also be obtained through a Diels-Alder / radical reaction that modifies the length of the hydrocarbon fatty acid chain. Furthermore, the compound based on natural fats may have previously undergone, or be obtained through, an esterification or transesterification reaction. For example, the compound based on natural fats (ii) is obtained by transesterification of a triglyceride comprising one or more saturated or unsaturated hydrocarbon fatty acid chains comprising 6 to 22 carbon atoms, preferably 8 to 20 carbon atoms, with a C1-C4 monohydroxy alcohol, such as methanol.Following either of these reactions, at least one of the hydrocarbon chains in the initial fat contains at least one unsaturation.

[0100] According to another embodiment of the invention, the naturally sourced fat comprising one or more unsaturated hydrocarbon fatty acid chains of (a) the first compound is selected from used cooking oils from the food industry. According to the U.S. Environmental Protection Agency, 1.3 x 10⁹ L of used cooking oil is produced annually in the United States alone, and only 10% is used to manufacture biofuels. There is therefore a need to recycle this material.

[0101] As mentioned above, the first compound represents, by mass, relative to the total mass of the bio-based binder according to the invention, from 35% to 98%, in particular from 50% to 98% and typically from 60% to 98%.

[0102] According to the invention, a range of values ​​from 35 to 98% includes the following values ​​and any interval between these values: 35; 36; 37; 38; 39; 40; 41; 42; 43; 44; 45; 46; 47; 48; 49; 50; 51; 52; 53; 54; 55; 56; 57; 58; 59; 60; 61; 62; 63; 64; 65; 66; 67; 68; 69; 70; 71; 72; 73; 74; 75; 76; 77; 78; 79; 80; 81; 82; 83; 84; 85; 86; 87; 88; 89; 90; 91; 92; 93; 94; 95; 96; 97; 98.

[0103] A2. Structuring agent

[0104] The bio-based binder according to the invention also comprises one or more structuring agents (b).

[0105] “By structuring agent” according to the invention, at least one compound is meant that is capable of and / or configure to increase the viscosity of a compound or mixture into which it is incorporated.

[0106] Preferably, the structuring agent(s) is / are chosen from one or more of the following compounds:

[0107] * natural polymers, including starch, plant proteins, gum welan, xanthan gum, carob gum and all other natural gums, cellulose, hemicellulose (xylane);

[0108] * semi-synthetic polymers, such as decomposed starches and their derivatives, cellulose ethers such as hydroxypropyl methyl cellulose (HPMC), hydroxyethyl cellulose (HEC), and carboxymethyl cellulose (CMC), a chemically modified rosin;

[0109] * synthetic polymers, mainly styrene butadiene styrene (SBS), polyethers (polyethylene glycol), polyacrylamides, and those based on vinyl (polyvinyl alcohol).

[0110] Preferably, the structuring agent will be chosen from a natural polymer or a semi-synthetic polymer.

[0111] According to one feature of the invention, the structuring agent is selected from a cellulosic derivative, which is a polymer chosen from among cellulose ethers. In particular, a suitable structuring agent for forming the bio-based binder according to the invention may be an ethylcellulose polymer. Such an ethylcellulose polymer may, for example, correspond to the Ethocel® product (such as Ethocel®45, Ethocel®100, or Ethocel®300) marketed by DuPont or to the product with CAS number 9004-57-3.

[0112] According to another feature of the invention, the structuring agent is selected from a modified rosin that is chemically modified by esterification, preferably with glycerol or pentaerythritol. It may correspond to the commercial products Dertoline® G2L or P2L or GRANOLITE P® marketed by DRT. Generally, the chemically modified rosin resin has an acid number between 140 and 300. It also generally has a softening point between 60°C and 150°C.

[0113] The structuring agent(s) represents from 2% to 40%, by mass, relative to the total mass of said bio-based binder.

[0114] According to the invention, a range of values ​​from 2 to 40% includes the following values ​​and any interval between these values: 2; 3; 4; 5; 6; 7; 8; 9; 10; 11; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; 30; 31; 32; 33; 34; 35; 36; 37; 38; 39 and 40.

[0115] A.3 Second compound

[0116] The bio-based binder according to the invention may also contain 0% to 50% of at least a second compound based on a fat of natural origin, the latter not having undergone a chemical reaction chosen from: blowing and / or maleinization.

[0117] In the context of the present invention, a range of values ​​from 0 to 50% includes the following values ​​(in %) and any interval between these values: 0; 5; 6; 7; 8; 9; 10; 11; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; 30; 31; 32; 33; 34; 35; 36; 37; 38; 39; 40; 41; 42; 43; 44; 45; 46; 47; 48; 49 and 50.

[0118] According to the invention, the natural fat composing the second compound can be identical to the natural fat which was used to form the first compound.

[0119] Thus, fat of natural origin can be a fat from nature, but also a derivative, namely resulting from a chemical reaction.

[0120] Fossil oils and fats, which are not renewable and are of no interest in the context of sustainable development, are therefore preferably excluded from the scope of the invention.

[0121] According to one embodiment, the fat of natural origin will be chosen from vegetable oils or fats coming directly from nature (i.e. not having undergone a chemical reaction or not having been chemically functionalized).

[0122] According to another embodiment of the invention, the compound based on natural fats is a derivative of a vegetable oil or a natural fat and has been previously chemically functionalized (but has not undergone and will not undergo a maleinization and / or blowing reaction).

[0123] In particular, the fat of natural or modified origin is derived from renewable resources of plant or animal origin, and preferably of agricultural plant origin including forest or aquaculture or may be a used vegetable oil, such as a used oil from the food industry or its derivatives, and one of their mixtures.

[0124] According to one embodiment, the fat of natural origin is a natural vegetable oil which is chosen from: soybean, flaxseed, sunflower, rapeseed, grapeseed, peanut, olive, canola, safflower, copra, wheat germ, corn, walnut, almond, palm, sesame, tung, castor, cottonseed oils and mixtures thereof.

[0125] The vegetable oil may be a vegetable oil derivative or a mixture of vegetable oil derivatives such as fatty acids, fatty alcohols, fatty acid esters, or chemically modified fatty acid esters. The fatty acid ester(s) are obtained by transesterification of vegetable oils with an alcohol. The preferred fatty acid ester(s) are fatty acid triglyceride esters (glycerin esterified by fatty acid molecules) and contain unsaturates. The triglycerides are obtained by crushing seeds and extracting the oil (their hydrolysis leads to glycerol and fatty acids). The fatty acid(s) may be aliphatic monoacids. The fatty acid(s) may be saturated or unsaturated fatty acids, monocarboxylic acids comprising 6 to 24 carbon atoms, or dicarboxylic acids. comprising 12 to 48 carbon atoms and / or tricarboxylic(s) comprising 18 to 72 carbon atoms:

[0126] - linear saturated fatty acids can be selected from caproic acid, acid caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid,

[0127] - monocarboxylic unsaturated fatty acids can be selected from the acid palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, nervonic acid, and nonanonic acid,

[0128] - the defined fatty acids may be monocarboxylic fatty acids,

[0129] - fatty acids also suitable for carrying out the invention may be polymerized fatty acids, which include more than one carboxylic function, and are present for example as fatty acids in the form of dimers or trimers.

[0130] By way of example of dicarboxylic fatty acids in the form of dimers, also suitable for the production of a bio-based binder according to the invention, one may mention fatty acids comprising 12 to 48 saturated or unsaturated carbon atoms, preferably unsaturated, and in particular the unsaturated fatty acid comprising 18 carbon atoms, the CAS reference of which is 61788-89-4. By way of example of tricarboxylic fatty acids, in the form of trimers suitable for the production of a basic binder according to the invention, one may mention fatty acids comprising 18 to 72 saturated or unsaturated carbon atoms, preferably unsaturated, and in particular the unsaturated fatty acid comprising 18 carbon atoms, the CAS reference of which is 68937-90-6.

[0131] According to another embodiment of the invention, the naturally sourced fat of (c) second compound is chosen from used oils from the food industry, such as used vegetable oils.

[0132] A.4 Additives

[0133] The bio-based binder according to the invention may also contain additives commonly used to form hydrocarbon binders, such as pigments, dispersants, polymers, thickeners and / or antifoams.

[0134] A.5 Characteristics of the bio-based binder according to the invention

[0135] The bio-based binder according to the invention has technical characteristics similar or at least close to those of a conventional bitumen.

[0136] In particular, the bio-based binder according to the invention comprises at least one of the following characteristics, preferably all of the following characteristics:

[0137] * a PI penetration capability (fresh binder) at 25°C (l / 10th mm) measured according to standard NF EN 1426 (2018) ranging from 10 to 260, preferably ranging from 30 to 220 and typically ranging from 70 to 160;

[0138] * a softening temperature TBA 1 (°C) (fresh binder) measured according to the standard NF EN 1427 or ASTM D36 ranging from 20°C to 90°C, preferably ranging from 35°C to 70°C and typically ranging from 43 to 60;

[0139] - a P2 penetrability after the RTFOT test at 25°C (l / 10th mm) measured according to the NF EN 1426 (2018) standard ranging from 5 to 240, preferably ranging from 10 to 200 and typically ranging from 50 to 140;

[0140] - a softening temperature TBA 2 (°C) after the RTFOT test measured according the NE EN 1427 or ASTM D36 standard ranging from 30°C to 100°C, preferably ranging from 45°C to 80°C and typically ranging from 53°C to 70°C;

[0141] - a mass loss after the RTFOT test measured according to standard NF EN 13303 (2017) less than or equal to 10%, preferably less than or equal to 5% and typically less than or equal to 1%.

[0142] By "fresh binder" is meant a binder that has not undergone an accelerated aging protocol, such as an RTFOT (Rolling Thin Film Oven Test) or PAV (Pressure Aging Vessel). B. Process for preparing the bio-based binder

[0143] The present invention relates to a process for preparing a bio-based binder as described above, comprising the following steps:

[0144] (i) the preparation of said at least first compound (a) based on a fat of natural origin comprising one or more unsaturated hydrocarbon fatty chains having undergone at least one chemical reaction chosen from: blowing and / or maleinization;

[0145] (ii) mixing the first compound obtained in step (i) with said at least structuring agent (b) and where applicable said second compound (c) at a temperature below 180°C, preferably from 100 to 160°C and typically from 120°C to 150°C, preferably for a period of less than or equal to 1 hour, such as 15 minutes.

[0146] Preferably, step (i) comprises the following steps:

[0147] (il) - the supply of at least one fat of natural origin comprising one or more unsaturated hydrocarbon fatty chains, such as used oil from the food industry;

[0148] (i2) - a blowing step which consists of injecting air at high temperature ranging from 100 to 250°C, preferably from 120°C to 200°C and typically from 140°C to 180°C on said at least fat comprising one or more unsaturated hydrocarbon fatty chains,

[0149] or

[0150] (i3)- a maleinization step which consists of causing said at least matter to react fat comprising one or more unsaturated hydrocarbon fat chains with maleic anhydride, under agitation, at high temperature ranging from 100°C to 260°C, preferably from 200°C to 250°C and typically from 210°C to 230°C for 1 to 30 hours, preferably 5 to 20 hours;

[0151] or

[0152] (i4)- a blowing step (i2) followed by a malling step (i3), or vice versa.

[0153] Maleinization reaction:

[0154] According to one feature of the invention, during the maleinization step (i3), maleic anhydride is introduced in an amount ranging from 0.5 to 3 equivalents by unsaturation of said natural fat comprising one or more unsaturated hydrocarbon fatty chains, preferably from 0.5 to 2 equivalents, and typically from 0.5 to 1.

[0155] According to one embodiment, the maleinization step (i3) can be carried out under pressure from a gas such as nitrogen or argon ranging from 1 to 10 bar. According to this embodiment, the temperature generally ranges from 120°C to 160°C, in particular from 140°C to 150°C for, for example, from 1 to 20 hours, typically from 2 to 8 hours.

[0156] According to the invention, "by 1 to 30 hours" means a duration including the following values ​​(hours) or any interval between these values: 1; 2; 3; 4; 5; 6; 7; 8; 9; 10; 11; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; 30.

[0157] According to the invention, "a pressure of 1 to 10 bars" includes the following values ​​in bar(s) or any interval between these values: 1; 2; 3; 4; 5; 6; 7; 8; 9; 10.

[0158] Blowing reaction

[0159] Generally, the blowing reaction has a duration ranging from 8 to 50 hours, preferably from 10 to 30 hours and typically from 15 to 25 hours.

[0160] The Applicant has indeed discovered that the process parameters described above made it possible to obtain a bio-based binder with adequate technical characteristics close to those of conventional bitumens. C. Asphalt Mix Composition

[0161] The present invention also relates to a coating composition comprising at least, by mass, relative to its total mass:

[0162] - from 2% to 8%, preferably from 4% to 6% of a bio-based binder as described above or obtained according to the aforementioned process, and

[0163] - from 92% to 98%, preferably from 94% to 96% of at least one aggregate (gravel, sands, asphalt aggregates (AE), etc).

[0164] According to one embodiment, said coating composition does not include bitumen.

[0165] According to another embodiment, said coating composition may include, in addition to the bio-based binder according to the invention, bitumen, preferably 0 to 4% by mass of bitumen and typically 0 to 3% by mass of bitumen, relative to the total mass of said coating composition.

[0166] The term "bitumen" refers to a mixture of natural hydrocarbon materials derived from the heavy fraction obtained during petroleum distillation, or from natural deposits, in solid or liquid form, with a density generally between 0.8 and 1.2. It can be prepared by any conventional technique. Pure bitumens as defined in standard NF EN 12591, hard bitumens as defined in standard EN 13924-1, and multigrade bitumens as defined in standard EN 13924-2 are considered bitumen within the meaning of the invention. Bitumen can also be modified bitumen as defined in standard NF EN 14023. For example, bitumens are modified by the incorporation of additives of all kinds, such as additives to improve adhesion, resistance to extreme temperatures (high and low), or mechanical strength.Examples include bitumens improved by the incorporation of synthetic or natural elastomers or plastomers such as rubber powder (polybutadiene, styrene-butadiene rubber or SBR), SBS, EVA, or others. Generally, the bitumen itself remains unchanged. It is also possible to use mixtures of different types of bitumen, ranging from hard to softer grades.

[0167] According to this embodiment, the bitumen preferably has a penetration grade at 25°C determined according to EN 1426 of 10 / 20, 15 / 25, 20 / 30, 40 / 60, 35 / 50, 50 / 70, 70 / 100, 160 / 220 l / 10 mm or a mixture thereof. Typically, the bitumen has a penetration grade at 25°C determined according to EN 1426 of 160 / 220 l / 10 mm (soft grade).

[0168] The asphalt mix composition includes at least one aggregate. In general, this corresponds to materials commonly used in road surfacing, such as "classic" natural mineral aggregates, generally virgin (non-recycled), or asphalt aggregates (EA).

[0169] Conventional natural mineral aggregates are defined as aggregates not derived from recycled materials (i.e., reclaimed asphalt pavement (RAP) or asphalt shingles). The term "RAP aggregates" refers to aggregates derived from demolition products (such as asphalt from old road surfaces that have been crushed and / or milled).

[0170] In general, "classic" natural aggregates can be, without limitation, gravel, pebbles, sands, fillers, fine-grained sands, dust, or mixtures thereof. The aggregates used can be road aggregates meeting the following standards: NF EN 13043 in Europe and ASTM C33 in North America.

[0171] Fillers, also called fines, correspond to a mineral powder generally having a particle size of less than 63 µm, while sands generally correspond to any rock in the form of small, unbound grains with a size of up to 4 mm. The proportion of fines or sands in the granular fraction will be adjusted by a person skilled in the art. These aggregates generally have an actual density measured according to standard NF EN 1097-6 greater than 2000 kg / m³ and even greater than 2500 kg / m³ and a relative bulk density measured according to standard NF EN 1097-3 of between 1.2 and 1.7.

[0172] Advantageously, the conventional aggregate comprises, by mass, relative to its total mass, 0 to 75%, preferably 0 to 55%, in particular 5 to 45% and ideally 8 to 40% of sand (0 / 4 mm). It may also comprise, by mass, relative to its total mass, 0 to 75%, preferably 5 to 45% and ideally 8 to 30% of gravel (0 / 10 mm).

[0173] By way of example, the classic natural aggregate comprises, by weight, relative to its total weight:

[0174] - from 0 to 10%, preferably from 0 to 7% of fines of diameter less than or equal to 0.063mm;

[0175] - 25 to 40%, preferably 30 to 35% of sands with a diameter ranging from 0.063 to 4 mm;

[0176] - 50 to 75%, preferably 58 to 70%, of large gravel with a diameter ranging from 4 at 16 mm.

[0177] According to another feature of the invention, said at least aggregate further comprises asphalt concrete aggregates (ACA). When present, the asphalt concrete aggregate ACA represents, by mass, from 5 to 50%, preferably from 10 to 30%, relative to the total mass of the aggregate according to the invention. D. Road surface

[0178] The present invention also relates to a road and / or civil engineering coating, characterized in that it comprises the aforementioned asphalt composition, and preferably has a thickness ranging from 2 to 15 cm, in particular from 4 to 12 cm. E. Uses

[0179] Finally, the present invention relates to the use of a binder as described above or obtained according to the aforementioned process, in order to partially replace or completely the use of bitumen for the production of asphalt mixes and / or road construction and / or civil engineering coatings.

[0180] According to one feature of the invention, said asphalt and / or road construction and / or civil engineering coating composition may include recycled materials, such as asphalt aggregates (AE) or other non-new aggregates and, for example, from old pavements.

[0181] Of course, the different features, variants and embodiments of the invention can be combined with each other in various ways insofar as they are not incompatible or mutually exclusive.

[0182] In addition, various other features of the invention emerge from the attached description which illustrate non-limiting forms of embodiment of the invention.

[0183] According to the invention, unless otherwise stated, the various characteristics of the invention have been measured according to the standards mentioned below or according to the internal methods described below. F. Examples

[0184] Example 1: Characterization of the first compound forming the binder according to the invention ([Fig. 1])

[0185] A characterization test of the first compound forming the bio-based binder according to the invention was carried out by the Applicant. In particular, the Applicant measured the complex modulus G* of various samples: the first compounds according to the invention (Ex.1 to Ex.6) and, for comparison, that of a reference bitumen (Ex.7) and a reference maltene fraction (Ex.8).

[0186] Complex modulus G* (stiffness) (EN 14770): It is determined using a dynamic shear rheometer (plane-plane geometry). For this purpose, a sinusoidal strain of defined frequency (1 Hz) is applied to each sample (Ex. 1 to Ex. 8) at a temperature ranging from -20°C to 60°C. Each sample is placed between two parallel planes, one fixed, the other moving. The upper plane imposes the shear strain, and the resulting stress is recorded. The complex modulus G* is defined as the ratio of the stress amplitude to the strain amplitude in harmonic sinusoidal oscillation.

[0187] The raw materials used and the operating conditions are as follows for the different samples (Table 1):

[0188] [Tables 1] Ex. Initial raw material Operating conditions (Blowing and / or maleinization reaction) Ex.1 Animal fat (tallow) Blowing reaction T° of injected air = 160°C Time = 16h Ex.2 Animal fat (tallow) Maleinization reaction Eq. maleic anhydride = 1 Time = 28 h T(°C) = 200 °C Ex.3 Rapeseed oil polymer Blowing reaction T° of injected air = 160°C Time = 24h Ex.4 Used cooking oil (UCO) Blowing reaction T° of injected air = 160°C Time = 20h Ex.5 Used cooking oil (UCO) Maleinization reaction Eq. Maleic anhydrance = 1-1.1 Time = 16h T(°C) = 220°C Ex.6 Used Cooking Oil (UCO) Blowing reaction T° of injected air = 160°C Time = 20h, then Maleinization reaction Eq. maleic anhydrance = 1-1.1 Time = 6h T(°C) = 220°C Ex.7 Reference bitumen Grade 35-50 - Ex.8 Maltene fraction -

[0189] Maleinization reaction (Ex.2; Ex.5 and Ex.6)

[0190] The maleinization reaction consists of mixing the initial raw materials with maleic anhydride in a reactor under the operating conditions set out in Table 1 above. In particular, the reaction mixture is heated under reduced stirring (150 rpm) until the maleic anhydride melts, then The stirring speed is increased to 300 rpm. In the examples, the reaction temperature varies from 200 to 220°C. Once the reaction mixture has reached the set temperature, it is heated for the time indicated in Table 1. The anhydride partially sublimes and deposits on the reactor lid. At the end of the reaction, size-exclusion chromatography (SEC) analysis is performed to confirm the functionalization of the starting natural fat.

[0191] Blowing reaction (Ex.1; Ex.5; Ex.4 and Ex.6)

[0192] The blowing reaction consists of injecting high-temperature compressed air under the operating conditions set out in Table 1 above while stirring. Result

[0193] The result of this characterization test is illustrated in [Fig. 1]. As shown in [Fig. 1], Ex. 1 to 6, representing the first compound according to the invention, exhibit a complex modulus ranging from 10 Pa (Ex. 4) to 10,000 MPa (Ex. 1) at 20°C. Ex. 5 also exhibits a complex modulus close to that of the reference bitumen (Ex. 7) and, moreover, situated between that of the maltene fraction (Ex. 8) and that of the reference bitumen (Ex. 7). Ex. 2 exhibits a complex modulus between -20°C and 60°C similar to that of the maltene fraction (Ex. 8).

[0194] Thus, the first compounds according to the invention exhibit adequate rigidity for forming asphalt mix compositions. It should be noted that the performance of the complex modulus of the first compounds according to the invention can be optimized by modifying the operating conditions and combining it with the structuring agent according to the invention.

[0195] Example 2: Bio-based binder compositions and determination of thermal stability

[0196] Different bio-based binder compositions have been prepared by the Applicant and are shown in Table 2 below (mass percentage). The structuring agent is an ethylcellulose polymer (Ethocel® STD 45, DuPont),

[0197] [Tables2] First compound Used cooking oil, maleinized or not Structuring agent, Ethocel® Operating conditions Mass (%) Mass (%) Maleic acid equivalent Time (h) T(°C) Ex. Comp.l - - - 100 0 Ex.10 1 2 180 95 5 Ex.ll 1 1 2 180 90 10 Ex.12 1 2 180 85 15 Ex.13 1 2 180 80 20 Ex.14 1 2 180 95 5 Ex.15 1 2 180 80 20

[0198] For these different binder compositions according to the invention as well as for an unmodified used cooking oil (comparative), thermal stability was evaluated by thermogravimetric analysis (TGA) (Table 3).

[0199] Thermal stability (thermogravimetric analysis, TGA) - the analysis conditions are as follows:

[0200] - heating up to 150°C with a ramp of 10°C / min, then stabilization in temperature 1 hour (for comparative used cooking oil) or 3 hours (bio-based binder according to the invention);

[0201] - under N2 gas (50 mL / min).

[0202] [Tables3] Examples of Mass Loss (%) Ex. Com.1 4.0% (after 1 hour) Ex.10 3.5% (after 3 hours) Ex.11 3.8% (after 3 hours) Ex.12 3.0% (after 3 hours) Ex.13 2.3% (after 3 hours) Ex.14 3.4% (after 3 hours) Ex.15 3.8% (after 3 hours)

[0203] Thus, the maleinization reaction of the initial fat (used cooking oil) combined with the use of a structuring agent makes it possible to greatly improve clearly the thermal stability of a used cooking oil that has not undergone chemical modification.

[0204] Moreover, the mass loss of the bio-based binders according to the invention is quite satisfactory and is between 2.3% and 3.8% after 3 hours.

[0205] Example 3: Bio-based binder compositions and influence of the structuring agent

[0206] For this test, the Applicant prepared different compositions of bio-based binder according to the invention by varying in particular the structuring agent (rosin corresponding to the commercial product Granolite marketed by the company DRT, or product Ethocel®STD 45, Dupont), as well as its mass content. Tested compositions

[0207] The compositions of bio-based binder are illustrated in Table 4 below.

[0208] [Tables4] First compound Used food oil maleinized and / or blown Structuring agent Operating conditions Mass (%) Mass (%) Anh. eq. maleic Tps (h) T(°C) Mw (g / mol) Ex.Com p.2 1 17 220 6504 100 0 Ex.16 1 31 200 6325 70% 20% Ethocel® 10% rosin Ex.17 1 16 220 6771 80% 20% Ethocel® Ex.18 1 17 220 6504 80% 20% Ethocel® Ex.19 1 16 220 6771 80% 20% Ethocel® Ex.20 1 17 220 6504 70% 20% Ethocel® 10% rosin Ex.21 1 17 220 6504 80% 20% Ethocel®

[0209] The maleinization and / or blowing reactions are carried out according to the process described in Example 1 and following the operating conditions of Table 4. In particular, Ex.21 underwent a maleinization and blowing reaction (the temperature of the injected air was 220°C, for 17 hours).

[0210] The bio-based binder according to the invention is then prepared by mixing used cooking oil that has undergone a maleinization and / or blowing reaction with the structuring agent at 130°C for 15 minutes using a cross stirrer at 1000 rpm. It has indeed appeared that it is preferable to carry out the mixing at temperatures below 180°C, in particular ranging from 100 to 160°C and typically ranging from 130°C to 150°C in order not to degrade the structuring agent and not to lose its viscosifying effect.

[0211] Result: complex modulus G* (determined according to the method described in Example 1)

[0212] As shown in [Fig. 2], structuring agents, such as rosin and cellulose ether polymer, make it possible to structure maleinized and / or blown used cooking oil in order to achieve the rigidity of a conventional 35 / 50 bitumen. Indeed, a mass content of 20% to 30% of a structuring agent such as Ethocel®100 or 300, mixed or not with rosin, makes it possible to increase the rigidity of the bio-based binder according to the invention and to obtain a complex modulus G* between -20°C and 60°C which is almost identical to that of the reference 35 / 50 bitumen.

[0213] Example 4: Binder compositions with the addition of a second compound and characterization tests

[0214] For this test, the Applicant prepared bio-based binder compositions comprising a first compound that had undergone a maleinization reaction (maleinized used cooking oil), a structuring agent (Ethocel® STD 45), and a second compound that had not been chemically modified (used cooking oil). In particular, the operating conditions for the maleinization reaction of the first compound are as follows, and the embodiment followed is identical to that mentioned in Example 1:

[0215] - 1.1 Eq. of maleic anhydride,

[0216] - time: 2 hours,

[0217] - T= 150°C. Tested binder compositions

[0218] The compositions of bio-based binder are illustrated in Table 5 below (percentages are given by mass relative to the total mass of the binder).

[0219] [Tables5] First component Structuring agent Second component Appearance of mixture Ex.Comp.3 Mixture 8 100 0 0 Liquid Ex.22 Mixture 1 43.5 13 43.5 Gel (1 hour after mixing) Ex.23 Mixture 2 47.5 5 47.5 Liquid Ex.24 Mixture 3 60 5 35 Liquid Ex.25 Mixture 4 75 5 20 Liquid Ex.26 Mixture 5 60 8 32 Liquid Ex.27 Mixture 6 75 8 17 Premix gel Ex.28 Mixture 7 95 5 0 Liquid Ex.29 Mixture 9 92 8 0 Liquid Ex.30 Mixture 10 87 13 0 Liquid and a little gel around the blade

[0220] The bio-based binder according to the invention is then prepared by mixing the used food oil which has undergone a maleinization reaction with the structuring agent and the used food oil at 150°C for 15 minutes using a cross stirrer at 1000 rpm.

[0221] Results ([Fig.3a] and 3b and [Fig.4a] and 4b)

[0222] Complex modulus G* (determined according to the method described in Example 1) - [Fig. 3a] and [Fig.3b]

[0223] As shown in [Fig. 3a] and [b], all the binders according to the present invention (Ex. 22 to 29) have a complex modulus G* and therefore a stiffness close to that of the reference bitumen. In particular, the binders of Ex. 22, 26, 27, 29, and 30 have a modulus close to that of bitumen at 60°C. Also, when the structuring agent is Ethocel®, it is preferable that its mass content be greater than 5% in order to to obtain binders whose complex modulus is as close as possible to that of bitumen, and less than or equal to 15% in order to avoid excessive gelling of the mixture with the first compound and, if applicable, the second compound.

[0224] Characterization by differential calorimetry - [Fig.4a] and [Fig.4b]

[0225] Ex.23 to 30, as well as Ex. Comp.3 and Ex. Comp.4 corresponding to used cooking oil (without chemical modification), were evaluated by differential calorimetry, which provides information on the glass transition temperature, melting and crystallization temperatures, and enthalpies of reaction. The x-axis represents temperature and the y-axis represents enthalpy in mW / mg ([Fig.4a] and [Fig.4b]).

[0226] Figures 4a and 4b provide insight into the phase transitions of Ex. 23 to 30 according to the invention, particularly with respect to Examples Comp. 3 and 4, during a temperature ramp increasing at 10 °C / min. The thermogram of Ex. Comp. 4 is characterized by a broad endothermic peak from -50 °C to -5 °C, which corresponds to the melting of the used cooking oil. In contrast, no endothermic peak associated with melting is observed for Ex. Comp. 3 (maleinized used cooking oil). Instead, an inflection point is observed, which certainly reflects a glass transition induced by maleinization.

[0227] For the binders according to the invention (Ex. 23 to 30), a thermal behavior intermediate between that of used cooking oil (Ex. Comp. 4) and maleinized used cooking oil (Ex. Comp. 3) is observed. The higher the quantity of used cooking oil (second component), the greater the endothermic peak. Quantifying the energy associated with this endothermic peak therefore makes it possible to dose the used cooking oil (second component) with the maleinized used cooking oil (first component). On the other hand, no particular thermal effect is attributable to the structuring agent, here Ethocel® STD 45.

[0228] Example 5: Thermal stability and aging behavior of a bio-based binder according to the invention Tested compositions

[0229] For this test, the Applicant prepared a bio-based binder composition Ex.31 with the formulation illustrated in Table 6 below. In particular, the operating conditions for the maleinization reaction of the first compound are mentioned in Table 6, and the embodiment followed is identical to that mentioned in Example 1. Furthermore, the binder was prepared by mixing used cooking oil that had undergone a maleinization reaction with the structuring agent (Ethocel®STD 45) and used cooking oil at 150°C for 15 minutes using a cross stirrer at 1000 rpm.

[0230] [Tableauxô] First compound: Maleinized and / or blown used cooking oil; Structuring agent: Ethocel®; Second compound: Used cooking oil; Operating conditions: Mass (%) Mass (%) Mass (%) Maleic acid equivalent; Time (h); T (°C); Mw (g / mol); Ex.31; 1.1; 2; 150; 85; 15%; 0%

[0231] This binder Ex.31 was subsequently compared to the specifications of a grade 70 / 100 bitumen according to standard EN 12591.

[0232] Results - Table 7

[0233] The results are shown in Table 7 below. Fresh binder means that the binder was tested without undergoing an accelerated aging protocol such as RTFOT or PAV.

[0234] [Tables7] Ex.31 (invention) Bitumen specifications 70 / 100 (EN12591) Fresh binder Penetration P1 at 25°C (l / 10th mm) measured according to standard NF EN 1426 (2018) 113 70-100 Softening temperature TBA 1 (°C) measured (standard NF EN 1427) 56.2 43-51 Mass loss at 150°C (%) (thermogravimetric analysis identical to that described in Example 2) 5.0 (after 3 hours) - After the RTFOT (Rolling Thin Film Oven Test) (EN 12607-1) Penetration P2 at 25°C (l / 10th mm) measured according to standard NF EN 1426 (2018) 69 - Softening temperature TBA 2 (°C) measured (NF EN 1427 standard) 74.2 - Remaining penetrability P2-P1 (%) 61 >46 TB2-TB1 18 <9 Mass loss at 150°C (%) (thermogravimetric analysis identical to that described in Example 2) 4.6 <0.8

[0235] Table 7 shows that the binder according to the invention Ex.31 has technical characteristics that are close to those of a 70 / 100 bitumen. However, the binder according to the invention cannot be fully compared to the conventional specifications of bitumens that require high temperatures, particularly for the standardized RTFOT test (a test that is too stringent compared to what should be applied to the bio-based binder according to the invention). Indeed, as mentioned in Example 3 above, the structuring agent used in this Example 5, Ethocel®STD 45, degrades at temperatures above 180°C. It is preferable to apply temperatures ranging from 130°C to 150°C.

[0236] Example 6: Formulation of an asphalt mix composition according to the invention and performance evaluation. Compositions tested

[0237] For this test, the composition of the bio-based binder Ex.31 was tested. The binder in Ex.31 has the same composition as that indicated in Example 5 above (see Table 6). In particular, the binder in Ex.31 (20 kg) was prepared in batch by mixing used cooking oil that had undergone a maleinization reaction with the structuring agent and used cooking oil at 150°C for 15 minutes in a reactor for 2 hours with mechanical stirring between 300 and 600 rpm. No gelling of the 20 kg mixture was observed compared to what has been observed on a smaller scale.

[0238] A mix composition according to the invention (EX.34) was then prepared and compared to a conventional mix composition based on conventional road bitumen of type 35 / 50. Results

[0239] The compositions tested and the results obtained are illustrated in Table 8.

[0240] [Tables8] Asphalt Mix Composition According to the Invention Comparative Asphalt Mix Composition Specifications Bitumen NE EN 13108-1 Binder - Binder of Ex.31 5.6% 0% - bitumen 35 / 50 0% 5.60% Aggregate - Fillers < 63 µm 1% - sands 0 / 2 mm 31% - gravel 2 / 6.3 mm 17% - gravel 6.3 / 10 45.4% TOTAL 100% RESULTS - Water sensitivity NE EN 12697-12-method B: i / C (%) 81.0% >70% - Permanent deformation resistance NE EN 12697-22+al * rut depth in % at 300,000 cycles and at 60°C * Average void percentage of specimens 2.3% 2.7 7.3 <5% 5-8%

[0241] The results of rutting resistance tests indicate that the asphalt according to the invention formulated with the bio-based binder of Ex.31 gives a rutting resistance of 2.3% at 30,000 cycles compared to 2.7% at 30,000 cycles with a conventional 35 / 50 bitumen.

[0242] The bio-based binder according to the invention thus meets the technical expectations in terms of resistance to rutting for an asphalt mix intended for the manufacture of road construction and / or civil engineering.

[0243] Example 7: Evaluation of potential environmental impacts by Life Cycle Assessment (LCA)

[0244] For this Life Cycle Assessment (LCA) study, two categories of environmental impacts were deemed relevant to illustrate the decarbonization challenge facing the bitumen sector:

[0245] - climate change (according to potential greenhouse gas emissions, hereinafter referred to as GHGs (kg CO2 eq.) and

[0246] - the depletion of fossil resources (according to the depletion of the energy resource fossil, MJ).

[0247] The calculation methods are those of the European Commission's Environmental Footprint method, v.3.0 (EF 3.0, updated 2019) (https: / / eplca.jrc.ec.europa.eu / permalink / PEF_method.pdf).

[0248] The LCA was conducted using a “C2G” or “cradle to gate” approach (the C2G or “cradle to gate” scope does not include use and end-of-life). This means that the potential environmental impacts of the bio-based binder according to the invention and the reference bitumen are calculated from the production of the raw materials to the finished product at the factory gate. The potential environmental impacts related to its use as bitumen and its end-of-life are excluded from the scope of the study.

[0249] The environmental impact results presented below depend on the quality of the experimental data, the robustness of the calculation methods used to calculate the impacts, and also on the methodological choices made for modeling. Compositions tested

[0250] For this test, the Applicant prepared a bio-based binder according to the invention (Ex.31) and its environmental impact was compared to a reference bitumen.

[0251] - The reference bitumen is a conventional petroleum-based bitumen according to the standard EN 12591, used in road construction, building and industry, and widely used in Europe. The Life Cycle Inventories used are those from the Eurobitume database (version 3) recently published in 2020 (Eurobitume, 2020). The Eurobitume Life-Cycle-Inventory for Bitumen. Version 3.1. European Bitumen Association).

[0252] - The bio-based binder Ex31 has the formulation illustrated in Table 6 above. Results

[0253] The results are shown in Table 9 above.

[0254] [Tables9] Environmental Impact Category Climate Change Fossil Resource Depletion Environmental Indicator A C2G GHG Emissions without StC* B C2G GHG Emissions with StC C Early Life Cycle GHG Emissions with StC Depletion of Energy Fossil Resources (MJ) Ex.31 1.72 -0.22 1.72 35.4 Petroleum bitumen ref., Eurobitumen, 1kg 0.15 0.15 3.20 45.0

[0255] * Stc= biogenic carbon storage

[0256] A GHG emissions correspond to emissions from binders within the C2G perimeter, without taking into account biogenic carbon storage.

[0257] B The scores presented below correspond to the GHG emissions of the binders within the C2G scope, from which carbon absorbed from the atmosphere during photosynthesis and stored in the plant resource (oilseed plant from which used cooking oil and cellulose are derived) has been deducted. The potential GHG emissions of the bio-based binder according to the invention are considerably reduced compared to the situation without accounting for StC. Within the C2G scope considered, the use and end-of-life stages of the bitumens were not taken into account, which explains the negative carbon balance for the binder according to the invention. Indeed, the biogenic carbon temporarily stored in the raw materials is actually re-emitted into the ecosphere in various forms during the use and end-of-life stages.

[0258] This column represents the total potential GHG emissions over the entire life cycle, assuming that all the carbon stored in the binders will eventually be re-emitted into the atmosphere. Within this scope, the carbon balance of the bio-based binder according to the invention will be the same as for the C2G scope without taking StC into account, because the carbon re-emitted at the end of its life is offset by that stored during biomass growth, and therefore does not contribute any additional GHGs to climate change. On the other hand, for the reference petroleum-based bitumen, the fossil carbon emitted at the end of its life must be added to the C2G carbon balance of the material. Petroleum is formed by the decomposition of the residues of living organisms and biomass that have been transformed into petroleum through chemical processes over millions of years. Thus, the carbon in petroleum-based bitumen is also of fossil origin. bio-based, but on a much longer timescale, not allowing to "offset" the potential impact on the greenhouse effect.

[0259] Thus, the use of raw materials of natural origin makes it possible to significantly reduce the potential environmental impact of the bio-based binder according to the invention, which therefore appears more favorable than petroleum-based bitumen in terms of depletion of fossil resources. The environmental footprint of the bio-based binder according to the invention on this indicator is mainly linked to the use of anhydride, which is of petroleum origin.

[0260] In conclusion, according to the two impact categories Climate Change (taking into account biogenic carbon) and Depletion of fossil resources, the bio-based binder according to the invention presents a significantly more favorable potential environmental footprint than the reference petroleum-based bitumen.

Claims

Demands

1. Use of a bio-based binder to partially or totally replace the use of bitumen in the production of asphalt mixes and / or road construction and / or civil engineering coatings, said bio-based binder comprising, by mass relative to its total mass, at least: (a) 35% to 98% of at least one first compound based on a fat of natural origin comprising one or more unsaturated hydrocarbon fatty acid chains, said first compound having undergone at least one chemical reaction selected from: blowing and / or maleinization, (b) 2% to 40% of at least one structuring agent, and (c) 0% to 50% of at least one second compound based on a fat of natural origin, said second compound not having undergone a chemical reaction selected from: blowing and / or maleinization,characterized in that said asphalt and / or road construction and / or civil engineering coating composition is prepared by mixing at least one aggregate with said bio-based binder, said aggregate comprising, by weight, relative to its total weight: from 0% to 10% of fines with a diameter less than or equal to 0.063 mm, from 25% to 40% of sands with a diameter ranging from 0.063 mm to 4 mm and from 50% to 75% of gravel with a diameter ranging from 4 mm to 16 mm.

2. Use according to claim 1, wherein said naturally sourced fat of said at least (a) first compound and / or of said at least (c) second compound of said bio-based binder is selected from oils obtained in nature or their derivatives, fats obtained in nature or their derivatives, used vegetable oils, such as used oils from the food industry or their derivatives, and mixtures thereof; preferably, said naturally sourced fat of (a) first compound and / or (c) second compound is selected from used oils from the food industry.

3. Use according to claim 1 or 2, wherein (b) said at least one structuring agent of said bio-based binder is selected from one or more of the following compounds: * natural polymers, including starch, plant proteins, welan gum, xanthan gum, carob gum and all other natural gums, cellulose, hemicellulose (xylan); * semi-synthetic polymers, such as decomposed starches and their derivatives, cellulose ethers such as hydroxypropyl methyl cellulose (HPMC), hydroxyethyl cellulose (HEC), and carboxymethyl cellulose (CMC), a chemically modified rosin.

4. Use according to claim 3, wherein said semi-synthetic polymer is a cellulose ether polymer, such as an ethylcellulose polymer.

5. Use according to any one of the preceding claims, wherein (a) said at least first compound of said bio-based binder has: - a weight average molecular mass of 1,500 g / mol to 10,000 g / mol, preferably of 1,800 g / mol to 8,000 g / mol and typically of 1,700 g / mol to 7,300 g / mol; - a complex modulus standard at 20°C, 1Hz of between 10 Pa and 1,000,000 Pa, preferably of 1,000 to 50,000 and typically of 8,000 to 12,000 Pa, measured according to standard NF EN 14770 (2012) with a dynamic shear rheometer (plane-plane geometry).

6. Use according to any one of the preceding claims, characterized in that said bio-based binder comprises at least one of the following characteristics, preferably all of the following characteristics: - a PI penetration (fresh binder) at 25°C (l / 10th mm) measured according to standard NF EN 1426 (2018) ranging from 10 to 260, preferably ranging from 30 to 220 and typically ranging from 70 to 160; - a TBA 1 softening temperature (°C) (fresh binder) measured according to standard NF EN 1427 or ASTM D36 ranging from 20°C to 90°C, preferably ranging from 35°C to 70°C and typically ranging from 43°C to 60°C; - a P2 penetration capability after the RTFOT test (standard EN12607-1) at 25°C (l / 10th mm) measured according to standard NF EN 1426 (2018) ranging from 5 to 240, preferably ranging from 10 to 200 and typically ranging from 50 to 140; - a softening temperature TBA 2 (°C) after the RTFOT test measured according to standard NE EN 1427 or ASTM D36 ranging from 30°C to 100°C, preferably ranging from 45°C to 80°C and typically ranging from 53°C to 70°C; - a mass loss after the RTFOT test (standard EN12607-1) measured according to standard NF EN 13303 (2017) less than or equal to 10%, preferably less than or equal to 5% and typically less than or equal to 1%.

7. Use according to any one of the preceding claims, wherein said bio-based binder is prepared according to the process comprising the following steps: (i) the preparation of said at least first compound based on a fat of natural origin comprising one or more unsaturated hydrocarbon fatty chains having undergone at least one chemical reaction selected from: blowing and / or maleinization; (ii) mixing the first compound obtained in step (i) with said at least structuring agent and, where applicable, said second compound at a temperature below 180°C, preferably from 100 to 160°C and typically from 120°C to 150°C, preferably for a period of less than or equal to 1 hour, such as 15 minutes.

8. Use according to claim 7, wherein step (i) comprises the following steps: (il) - the supply of at least one fat of natural origin comprising one or more unsaturated hydrocarbon fatty chains, such as used oil from the food industry; (i2) - a blowing step which consists of injecting air at a high temperature ranging from 100 to 250°C, preferably from 120°C to 200°C and typically from 140°C to 180°C onto said at least fat comprising one or more unsaturated hydrocarbon fatty chains, Or (i3)- a maleinization step which consists of reacting said at least fat comprising one or more unsaturated hydrocarbon fatty chains with maleic anhydride, under stirring, at high temperature ranging from 100°C to 260°C, preferably from 200°C to 250°C and typically from 210°C to 230°C for 1 to 30 hours, preferably 5 to 20 hours; or (i4)- a blowing step (i2) followed by a malling step (i3), or vice versa.

9. Use according to claim 8, wherein during the maleinization step (i3), maleic anhydride is introduced in an amount from 0.5 to 3 equivalents by unsaturation of said natural fat comprising one or more unsaturated hydrocarbon fatty chains, preferably from 0.5 to 2 equivalents, and typically from 0.5 to 1.

10. Use according to any one of the preceding claims, wherein said at least one aggregate comprises asphalt aggregates.

11. Asphalt composition comprising at least, by mass, in relation to its total mass: - from 2% to 8%, preferably from 4% to 6% of a bio-based binder as defined in any one of claims 1 to 9, and - from 92% to 98%, preferably from 94% to 96% of at least one aggregate comprising, by weight, in relation to its total weight: from 0 to 10% of fines of diameter less than or equal to 0.063 mm, from 25 to 40% of sands of diameter ranging from 0.063 to 4 mm and from 50 to 75% of gravel of diameter ranging from 4 to 16 mm.

12. Mixture composition according to claim 11, characterized in that it does not comprise bitumen.

13. Road surface, characterized in that it comprises the asphalt composition according to claim 11 or 12, and has a thickness ranging from 2 to 15 cm, in particular from 4 to 12 cm.

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