ASSOCIATION OF ADDITIVES FOR THE RECYCLING OF BITUMINOUS PAVINGS

Abstract

ASSOCIATION OF ADDITIVES FOR RECYCLING BITUMINOUS COATINGS The present invention relates to an association of additives for recycling a bituminous coating, in particular a bituminous mix or a bituminous building coating, comprising: a) at least one thiodipropanoic acid ester compound, and b) at least one oil selected from: i) bio-based oils, possibly modified or functionalized; ii) hydrocarbon oils, of mineral origin, in particular petroleum, or synthetic origin; and iii) mixtures of i) and ii). Figure for the abstract: None

Description

Title of the invention: COMBINATION OF ADDITIVES FOR THE RECYCLING OF BITUMINOUS COATINGS

[0001] The present invention belongs to the field of bituminous coatings, in particular road coatings of the bituminous coating type or coatings for buildings such as waterproofing membranes or bituminous shingles. In particular, the invention relates to a combination of additives for the production of bituminous coatings from recycled bituminous coating aggregates, in particular from recycled bituminous coating aggregates and / or recycled waterproofing membrane aggregates and / or roofing shingles.

[0002] The invention aims to facilitate and improve the use of recycled bituminous coating aggregates during the manufacture of new bituminous coatings, in particular road coatings of the bituminous coating type or coatings intended for the construction industry such as, for example, waterproofing membranes or roofing shingles. Recycled bituminous coating aggregates are materials resulting from the operation of repairing a bituminous coating layer, such as road, sidewalk, sports field or bituminous coatings for buildings such as, for example, those used for the production of waterproofing layers and / or roofs. Bituminous coating aggregates are essentially composed of a bituminous binder and fillers, in particular aggregates and / or fillers. There are mainly two types of recycled bituminous coating aggregates depending on the nature of the initial coating.

[0003] A first type of recycled bituminous paving aggregates are recycled bituminous asphalt aggregates. They come from the operation of repairing road bituminous paving which can be either the wearing course or one of the structural layers. Recycled bituminous asphalt aggregates, also referred to by the acronym RAP (for "Reclaimed Asphalt Pavement" in English) are essentially composed of aggregates (of different granulometries depending on the applications) and bituminous binder residues adhering to these aggregates.

[0004] A second type of recycled bituminous coating aggregates are aggregates from the recycling of bituminous coatings from buildings. This second category of aggregates comes from the operation of different types of bituminous materials used in buildings, in particular waterproofing membranes and / or roofing shingles (or "shingles"). These recycled aggregates are essentially composed of fillers (of different granulometries depending on the applications) and bituminous binder residues adhering to these fillers. In the specific case of shingles, these aggregates are commonly referred to by the acronym RAS (for “Reclaimed Asphalt Shingle” in English).

[0005] In all cases, the residues of bituminous binders are called aged bituminous binders.

[0006] The formulation of new bituminous coatings from these recycled materials poses difficulties: the presence of solidified bituminous residues having a fragile and brittle behavior, of varied origins and / or compositions, provides inhomogeneous compositions, with mixtures of bituminous materials which have non-homogeneous softening temperatures and penetrabilities. The size distribution of the recycled aggregates can be wide and constitutes an obstacle to obtaining a homogeneous regenerated material which can be used as a new coating layer. The aging of the bituminous binder also leads to a modification of its properties compared to a freshly prepared bituminous binder composition, in particular a fragile and brittle behavior, a lower penetrability and a higher softening temperature than that of the original material.Therefore, bituminous pavements incorporating untreated bituminous aggregates have different properties from virgin bituminous pavements (i.e. prepared from a virgin bituminous binder and virgin aggregates / fillers). Their recycling in a new bituminous pavement is therefore difficult. Thus, untreated bituminous aggregates can only be used sparingly; generally in the form of a mixture comprising up to 20% by weight of untreated bituminous aggregates. Furthermore, in the context of road pavements, due to increasingly high technical requirements, the use of untreated recycled aggregates is generally limited to 15-20%.

[0007] It is known to mix RAPs with virgin bituminous mixes, i.e. with virgin binder and / or virgin aggregates (see, for example, US 4,549,834). Rejuvenating agents have also been developed with the aim of increasing the amount of RAP that can be incorporated into the base and surface layers. The rejuvenating agents restore some of the properties of the RAP-containing coating and the physical properties of the binder such as viscoelastic behavior, so that the properties of the RAP-containing bituminous mixes become more similar to those of virgin bituminous mixes. The improvement of the RAP properties, and in particular the properties of the aged bituminous binder present in the RAPs, allows the use of larger amounts of RAP in the bituminous mixes without compromising the properties and service life of the final pavement.

[0008] Commonly used rejuvenating agents include low viscosity products obtained by distillation of crude oil or other hydrocarbon-based materials (see, for example, US 5,766,333 or US 6,117,227).

[0009] Rejuvenating agents of plant origin have also been described. See, for example, US 7,811,372 (rejuvenating agents comprising bitumen and palm oil); US 7,008,670 (soybean oil, alkyl esters of soybean oil and terpenes used for waterproofing or rejuvenation); US 2010 / 0034586 (rejuvenating agents based on soybean, sunflower, rapeseed or other plant-derived oils); US 2008 / 0041276 (plasticizers for recycled asphalt which may be vegetable oils or alkyl esters made from vegetable oils). Rejuvenating agents derived from cashew nut oil, which mainly contain cardanol, a phenolic compound with an unsaturated C15 chain, have been introduced more recently (see, e.g., WO 2010 / 077141 and WO 2010 / 110651). Such products are commercially available from Ventraco Chemie, BV, such as RheoFalt® HP-EM.Rejuvenating agents derived from tall oil have also been proposed (see e.g. EP 2,791,248). Rejuvenating agents obtained by polymerization of oil of plant origin have also been proposed (see e.g. WO 2016 / 138390).

[0010] However, there remains a need for improved recycling additives (also called "rejuvenating agents").

[0011] In particular, the industry needs recycling agents that allow for greater incorporation of recycled bituminous paving aggregates into new pavings, particularly in new roadways and / or new pavings for the construction industry. Such recycling agents would indeed reduce dependence on virgin and non-renewable binders and aggregates / fillers. More particularly, there remains a need for recycling agents that allow for more effective restoration of the properties of recycled bituminous paving aggregates, particularly aged binder aggregates, compared to currently available recycling agents.The improvements targeted are the increase in the content of recycled aggregates in the various surfacings, particularly in roadways and / or in materials intended for buildings, but also the extension of the service life of surfacings incorporating these recycled aggregates. More specifically, there remains a need for recycling agents allowing the preparation of surfacings incorporating recycled aggregates and whose durability is significantly improved, in particular whose resistance to aging is significantly increased. Ideally, it would be desirable to have recycling agents capable of allowing the preparation of bituminous surfacings incorporating recycled aggregates and whose durability is equivalent to, or even improved, compared to surfacings prepared from virgin materials, in particular from virgin binders and aggregates (or fillers).A preferred recycling agent would reduce the viscosity of the binder to a level comparable to that of the virgin binder and also lower the temperature of . glass transition of the binder to allow for more flexible and easier to implement bituminous mixtures, while ensuring critical mechanical properties in a sustainable manner and against different modes of aggression (thermal, water, mechanical). Ideally, such agents would have good thermal stability at the high temperatures normally used to mix and apply bituminous coatings, and could restore the initial performance of the binder.

[0012] Such recycling agents would make it possible to adjust downwards the carbon footprint of bituminous surfacings by making it possible to significantly increase the content of recycled aggregates in new surfacings, i.e. by reducing the dependence on virgin and non-renewable binders and aggregates / fillers.

[0013] Finally, there remains a need for recycling agents from renewable resources to further reduce the carbon footprint of the road and construction industries. Summary of the invention

[0014] The invention firstly relates to a combination of additives for the recycling of a bituminous coating, in particular a bituminous coating or a bituminous coating of the building, comprising:

[0015] a) at least one thiodipropanoic acid ester compound, and

[0016] b) at least one oil chosen from:

[0017] i) oils of bio-sourced origin, possibly modified or functionalized;

[0018] ii) hydrocarbon oils, of mineral origin, in particular petroleum, or synthetic; and

[0019] iii) mixtures of i) and ii).

[0020] According to a preferred embodiment, the combination of additives according to the invention comprises:

[0021] - at least one oil of biosourced origin, possibly modified or functional nationalized, and

[0022] - at least one hydrocarbon oil of petroleum or synthetic origin.

[0023] Preferably, said at least one oil of biosourced origin, optionally modified or functionalized, is chosen from polymerized oils of plant origin comprising from 2% to 80% by mass of oligomers, and having a polydispersity index ranging from 1.30 to 2.20, and a sulfur content ranging from 0.001% by mass to 8% by mass.

[0024] Preferably, said at least one hydrocarbon oil, of petroleum or synthetic origin, is chosen from aromatic mineral oils.

[0025] According to a first embodiment, said at least one hydrocarbon oil is chosen from hydrocarbon oils of synthetic origin, preference among alkyl naphthalenes

[0026] According to a second embodiment, said at least one hydrocarbon oil is among the hydrocarbon oils of petroleum origin.

[0027] Advantageously, said at least one thiodipropanoic acid ester compound is chosen from diesters of thiodipropanoic acid, preferably from diesters of 3,3'-dithiopropionic acid and of a saturated linear alcohol of C1-C30, preferably of C5-C25, more preferably of C10-C20.

[0028] More advantageously, said at least one ester compound is chosen from di-dodecyl ester of 3,3'-dithiopropanoic acid, di-octadecyl ester of 3,3'-dithiopropanoic acid and any of their mixtures.

[0029] According to one embodiment, the combination of additives of the invention further comprises at least one polymer, optionally crosslinked, preferably at least one elastomer, notably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene.

[0030] The invention also relates to a binder composition for the recycling of an aged bituminous coating, in particular an aged bituminous coating or an aged bituminous building coating, comprising:

[0031] - at least one combination of additives as defined above and described in detailed below, and

[0032] - virgin bituminous binder, in particular virgin bitumen or a composition virgin bitumen / polymer, possibly crosslinked.

[0033] The invention also relates to a recycled bituminous binder composition comprising:

[0034] - aged binder, in particular aged bitumen or a bitumen / polymer composition aged, preferably recovered from aged bituminous surfacing, and

[0035] - at least one combination of additives according to the invention or at least one composition binder for recycling according to the invention as defined above and described in detail below.

[0036] The invention also relates to the use of a combination of additives according to the invention or of a composition for the recycling of an aged bituminous coating according to the invention or of a recycled bituminous binder composition according to the invention as defined above and described in detail below, for the manufacture of bituminous coatings comprising recycled bituminous coating aggregates and / or bituminous coating aggregates for buildings.

[0037] The invention also relates to the use of a combination of additives according to the invention or of a composition for the recycling of an aged bituminous coating according to the invention or of a recycled bituminous binder composition according to the invention as defined above and described in detail below, for the fa construction of a bituminous coating for buildings comprising recycled bituminous coating aggregates from the building.

[0038] The invention also relates to a bituminous coating comprising:

[0039] - a combination of additives according to the invention or a composition for recycling of an aged bituminous coating according to the invention or a recycled bituminous binder composition according to the invention as defined above and described in detail below, and

[0040] - recycled bituminous coating aggregates and / or bi-coating aggregates recycled building tuminous.

[0041] The invention finally relates to a waterproofing membrane comprising:

[0042] - a combination of additives according to the invention or a composition for recycling of an aged bituminous coating according to the invention or a recycled bituminous binder composition according to the invention as defined above and described in detail below, and

[0043] - recycled bituminous building coating aggregates, in particular recycled bituminous waterproofing membrane. Detailed description of the invention

[0044] The expression "consists essentially of" followed by one or more characteristics, means that components or steps which do not significantly modify the properties and characteristics of the invention may be included in the process or material of the invention, in addition to the components or steps explicitly listed.

[0045] The expression "between X and Y" includes the limits, unless explicitly stated otherwise. This expression therefore means that the interval in question includes the values ​​X, Y and all values ​​from X to Y.

[0046] For the purposes of the present invention, the term "binder" means a bituminous composition comprising at least one bitumen base, said composition being usable in a mixture with aggregates and / or fillers, for the preparation of a bituminous coating, in particular for the preparation of bituminous coatings and / or a waterproofing coating for buildings. A binder according to the invention may further comprise additives commonly used for the production of bituminous coatings, such as, for example, polymers, in particular elastomers, optionally crosslinked.

[0047] For the purposes of the invention, the term “bituminous coating” means a mixture of aggregates and binder, intended in particular for the production of road surfaces.

[0048] For the purposes of the invention, the term "aggregate" means materials of mineral or synthetic origin which are inert with respect to the binder and have dimensions greater than 2 mm, preferably between 2 mm and 20 mm.

[0049] By "recycled bituminous asphalt aggregates" or RAP, we mean in the sense of the invention of materials resulting from the operation of repairing a layer of bituminous road surfacing, in particular a wearing course or a structural layer. They are essentially composed of a bituminous binder and aggregates.

[0050] For the purposes of the invention, the term "building coating" or "bituminous building coating" means a mixture of fillers and binder, intended in particular for the building industry. Examples of (bituminous) building coatings include waterproofing membranes and roofing shingles.

[0051] For the purposes of the invention, the term "recycled building coating aggregates" or "recycled bituminous building coating aggregates" means materials resulting from the operation of repairing a bituminous coating recovered from one or more buildings, in particular a bituminous waterproofing membrane or a roof shingle. These aggregates are essentially composed of a bituminous binder and fillers. This term covers in particular the previously defined RAS obtained by recycling roof shingles.

[0052] For the purposes of the invention, the term “fillers” means materials of mineral or synthetic origin that are inert with respect to the binder and have dimensions less than or equal to 2 mm. Mineral fillers typically consist of fines (particles with dimensions less than 0.063 mm) or even sand (particles with dimensions between 0.063 mm and 2 mm).

[0053] For the purposes of the invention, the term "aged binder" means the residues of bituminous binder adhering to the surface of recycled bituminous coating aggregates, in particular to the surface of RAP aggregates or to the surface of the fillers of recycled building coating aggregates.

[0054] For the purposes of the invention, the term "combination of additives for recycling a bituminous coating" means the combination of at least two chemical additives, this combination being intended to restore all or part of the properties of a recycled bituminous coating, in particular of a recycled bituminous coating or of a recycled building coating.

[0055] The invention firstly relates to a combination of additives for the recycling of a bituminous coating, in particular a bituminous coating or a bituminous coating of the building, comprising:

[0056] a) at least one thiodipropanoic acid ester compound, and

[0057] b) at least one oil of biosourced origin, possibly modified or functional nationalized, and / or at least one hydrocarbon oil of mineral or synthetic origin.

[0058] In particular, the invention is based on the association of a thiodipropanoic acid ester compound with at least one oil chosen from: i) oils of origin bio-sourced, possibly modified or functionalized, ii) oils of mineral or synthetic origin and iii) their mixtures. The ester compound of thiodipropanoic acid

[0059] The combination of additives of the invention comprises at least one ester of thiodipropanoic acid.

[0060] For the purposes of the invention, the term "thiodipropanoic acid ester" means the product of the esterification reaction between a thiodipropanoic acid and at least one alcohol compound. Thus, at least one of the two carboxylic acid functions of thiodipropanoic acid has reacted with an alcohol to form the corresponding ester.

[0061] For the purposes of the invention, the term “thiodipropanoic acid” or “dithiopropionic acid” means a dicarboxylic acid of semi-developed formula S-(CH2CH2 COOH)2.

[0062] Preferably, the thiodipropanoic acid is 3,3'-dithiopropionic acid.

[0063] The alcohol is typically chosen from linear or branched, saturated or unsaturated alcohols, comprising from 1 to 50 carbon atoms.

[0064] Preferably, the alcohol is chosen from linear and saturated alcohols in CrC3o, preferably in C5-C25, more preferably in C10-C20.

[0065] According to a preferred embodiment, the ester compound of the invention is chosen from diesters of thiodipropanoic acid.

[0066] For the purposes of the invention, the term "thiodipropanoic acid diester" means the product of the esterification reaction between a thiodipropanoic acid and two alcohol compounds. Thus, each of the two carboxylic acid functions of thiodipropanoic acid has reacted with an alcohol compound to form the corresponding esters.

[0067] The two alcohol compounds reacting with the two acid functions may be identical or different and are chosen independently from linear or branched, saturated or unsaturated alcohols, comprising from 1 to 50 carbon atoms.

[0068] Preferably, the two alcohol compounds are chosen from linear and saturated alcohols of CrC3o, preferably C5-C25, more preferably C10-C20.

[0069] More preferably, the two alcohol compounds are identical.

[0070] According to one embodiment, the ester of the invention is chosen from diesters of 3,3'-dithiopropionic acid and a linear alcohol saturated in CrC3o, preferably in C5-C25, more preferably in C10-C20, advantageously in C12-C18.

[0071] Advantageously, the ester of the invention is chosen from di-dodecyl ester of 3,3'-dithiopropanoic acid, di-tridecyl ester of 3,3'-dithiopropanoic acid, di-tetradecyl ester of 3,3'-dithiopropanoic acid, di-octadecyl ester of 3,3'-dithiopropanoic acid and any of their mixtures.

[0072] Preferably, the combination of additives of the invention comprises at least 0.5% by mass of ester(s) of dithiopropanoic acid, relative to the total mass of compound ester a) and oil b), more preferably from 1% to 30% by mass, even more preferably from 2% to 20% by mass. Bio-sourced oils

[0073] According to one embodiment, the combination of additives of the invention comprises at least one oil of biosourced origin, optionally modified or functionalized.

[0074] For the purposes of the invention, the term “oil of bio-sourced origin” means an oil obtained from material derived from living things. Oils of bio-sourced origin may include oils of plant origin, for example isolated from plants; animals and algae, refined or unrefined.

[0075] Oils of vegetable origin include, but are not limited to, isolated plant oils, in particular those obtained by simple extraction from material of vegetable origin, such as, for example, soybean oil, linseed oil, canola oil, rapeseed oil, castor oil, cottonseed oil, sunflower oil, palm oil, peanut oil, safflower oil, corn oil, corn residue oil, lecithin (phospholipids), as well as combinations thereof and their crude streams. This first category of oils is hereinafter referred to as "extracted oil of vegetable origin".

[0076] Oils of vegetable origin also include oils obtained from products or by-products resulting from the conversion of raw materials of vegetable origin, such as, for example, tall oil compounds. This second category of oils is hereinafter referred to as “industrial oil of vegetable origin”.

[0077] Crude tall oil (or CTO) is a by-product of the wood-to-paper pulp process, also known as the Kraft process. Distillation of crude tall oil yields a volatile, highly saturated fraction of long-chain fatty acids (primarily palmitic acid), called "tall oil heads." The next cut is tall oil fatty acids (or TOFA). This TOFA cut consists primarily of C18 and C20 fatty acids with varying degrees of unsaturation (e.g., oleic acid, linoleic acid, linolenic acid, and various isomers thereof). Another cut, known as distilled tall oil (or DTO), is a mixture composed primarily of tall oil fatty acids and a smaller proportion of tall oil rosin.Tall oil rosin (TOR), as isolated next, consists largely of a C19-C20 tricyclic monocarboxylic acid. The lower cut from the distillation is known as tall oil pitch (or simply "pitch").

[0078] Examples of animal oils may include, but are not limited to, fat animal (e.g., lard, tallow) and lecithin (phospholipids), as well as combinations and crude streams thereof.

[0079] Bio-based oils may also include partially hydrogenated oils, oils with conjugated bonds, and body oils in which a heteroatom is not introduced, for example, but not limited to, di-glycerides, monoglycerides, free fatty acids, fatty acid alkyl esters (e.g., methyl, ethyl, propyl, and butyl), diol and triol esters (e.g., ethylene glycol, propylene glycol, butylene glycol, trimethylolpropane), and mixtures thereof. An example of a bio-based oil may be used cooking oil or other waste oils.

[0080] Oils of bio-sourced origin may have been previously modified or functionalized.

[0081] Examples of pre-modified oils are those that have been pre-vulcanized or polymerized, typically by sulfur polymerization or by treatment with maleic anhydride or modified acrylic acid; hydrogenated; modified with dicyclopentadiene; conjugated by reaction with iodine; esterified, including interesterified; treated to modify the acid number, the hydroxyl number, or any other property. Some examples of modified oils are polyol esters, for example, polyglycerol ester or castor oil ester, or estolides. These modified oils may be blended with unmodified vegetable or animal oils, fatty acids, glycerin, and / or lecithin.

[0082] Other examples of functionalized oils are those in which a heteroatom (oxygen, nitrogen, sulfur or phosphorus) has been introduced.

[0083] Advantageously, the oil of biosourced origin is chosen from oils of plant origin, possibly modified or functionalized.

[0084] More advantageously, the oil of biosourced origin of the invention is chosen from industrial oils of plant origin, optionally modified or functionalized.

[0085] According to a first embodiment, the oil of biosourced origin of the invention is chosen from oils of vegetable origin, preferably industrial oils of vegetable origin, polymerized comprising from 2% to 80% by weight of oligomers, a polydispersity index ranging from 1.30 to 2.20, and a sulfur content ranging from 0.001% by weight to 8% by weight.

[0086] Preferably, according to this embodiment, the starting oil of vegetable origin is chosen from recovered corn oil (typically residual liquids resulting from the manufacturing process of transforming corn into ethanol, also known as "corn residue oils").

[0087] The polymerization of the starting oil of vegetable origin, possibly prea modified or functionalized, is achieved by cross-anchoring the fatty acid chains and / or the glyceride moiety of the triglyceride molecules contained in the previously modified or functionalized oil of vegetable origin using a sulfur-containing compound, the sulfur in the sulfur-containing compound preferably being in a reduced form. The polymerization method comprises the following steps: (a) heating a previously modified or functionalized oil of vegetable origin, (b) adding a sulfur-containing compound to the heated oil, and (c) allowing the sulfur-containing compound to react with the oil to produce a polymerized oil.

[0088] In a first step, the previously modified or functionalized oil of vegetable origin is heated in a vessel equipped with a stirrer to at least 100°C, in more preferred aspects, the previously modified or functionalized oil of vegetable origin (may also be collectively referred to herein as "oil") is heated to at least 115°C. In preferred aspects, the sulfur-containing compound is gradually added to the heated previously modified or functionalized oil of vegetable origin and may be added in solid or molten form, but it is understood that the sulfur-containing compound may be added before the oil or at the same time as the oil.The reaction between sulfur and oil inherently increases the temperature of the oil-sulfur mixture and, in preferred aspects, the reaction is maintained at temperatures between about 130°C and about 250°C, more preferably between about 10°C and about 220°C, and even more preferably between about 160°C and about 200°C during the reaction.

[0089] The oil-sulfur mixture may be continuously supplied with a gas stream during the polymerization reaction between the oil and sulfur. The gas-containing stream may be selected from the group consisting of nitrogen, air, and other gases. The gas stream may facilitate the reaction and help reduce odors (H2S and other sulfides) associated with the reaction in the final product. The use of air may be beneficial because it may lead to oxi-polymerization of the oil in addition to the sulfurization process.

[0090] Accelerators may also be used to increase the rate of the reaction. Examples of accelerators include, but are not limited to, zinc oxide, magnesium oxide, dithiocarbamates.

[0091] The reaction may continue and be continuously monitored using gel permeation chromatography (GPC) and / or viscosity until the desired degree of polymerization is achieved, as indicated below.

[0092] The robustness of the sulfur crosslinking reaction and the possibility of using it for the polymerization of less expensive raw materials containing a high content of free fatty acids and residual moisture is an advantage of this method of po polymerization compared to other processes, which offers flexibility in the selection of raw materials.

[0093] The reaction between the sulfur-containing compound and the previously modified or functionalized biorenewable oil is carried out until a polymer distribution is obtained having from 2 wt% to 80 wt% oligomers (from 20 wt% to 98 wt% monomers), and more preferably from 15 wt% to 60 wt% oligomers (from 40 wt% to 85 wt% monomers), and even more preferably from 20 wt% to about 60 wt% oligomers (from 40 wt% to 80 wt% monomers). In even more preferred aspects, the polymer distribution ranges from 50 wt% to 75 wt% oligomers and from 25 wt% to 50 wt% monomers.

[0094] The polydispersity index of the polymerized oil typically ranges from 1.30 to 2.20, and more preferably from 1.50 to 2.05.

[0095] An advantage of the reaction described herein is the low sulfur content of the resulting polymerized oil. In some aspects, the sulfur content is less than 8% by weight of the polymerized oil. In other aspects, the sulfur content is less than 6% by weight of the polymerized oil, in still other aspects, the sulfur content is less than 4% by weight of the polymerized oil, and in still other aspects, the sulfur content is less than 2% by weight of the polymerized oil. However, the sulfur content is at least 0.001% by weight of the polymerized oil.

[0096] The flash point of the resulting polymerized oil, as measured using the Cleveland Open Cup method, is at least about 100°C and at most about 400°C. In some aspects, the flash point of the polymerized oil is between 200°C and 350°C. In other aspects, the flash point of the polymerized oil is between 220°C and 300°C. In still other aspects, the flash point of the polymerized oil is between 240°C and 275°C. The polymerized oils described herein may have a higher flash point than their starting material, particularly when compared to other polymerization techniques.

[0097] The viscosity of the polymerized oil varies depending on the type of starting oil, but generally ranges from about 1 cSt to about 100 cSt at 100°C.

[0098] According to a second embodiment, the oil of biosourced origin of the invention is chosen from tall oils.

[0099] According to this embodiment, the oil of biosourced origin is obtained directly from tall oil, by simple distillation.

[0100] Preferably, according to this embodiment, the oil of biosourced origin is chosen from: crude tall oil, fractions of crude tall oil and any of the mixtures of fractions of tall oil.

[0101] More preferably, according to this embodiment, the oil of biosourced origin is chosen from the fractions of tall oil, in particular from: "tall oil heads", tall oil fatty acids (or TOFA for "Tall Oil Fatty Acids" in English), distilled tall oil (or DTO for "Distilled Tall Oil" in English), tall oil rosin (or TOR for "Tall Oil Rosin") and tall oil pitch or tall oil pitch (in English "tall oil pitch" or simply "pitch").

[0102] Even more preferably, according to this embodiment, the oil of biosourced origin is chosen from tall oil pitch or tall oil pitch (in English "tall oil pitch" or simply "pitch").

[0103] Tall oil pitch, referenced under CAS No. 8016-81-7, is in the form of a complex mixture comprising mainly 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.

[0104] Preferably, the tall oil pitch comprises:

[0105] - up to 30% by mass of free fatty acids,

[0106] - from 15% to 20% by mass of diglycerides,

[0107] - from 50% to 60% by mass of triglycerides, and

[0108] - from 10% to 15% by mass of sterols,

[0109] relative to the total mass of the pitch.

[0110] Preferably, the tall oil pitch has an iodine index, 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.

[0111] Preferably, the tall oil pitch has an acid number, 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.

[0112] According to a third embodiment, the oil of biosourced origin of the invention is chosen from tall oil derivatives.

[0113] Tall oil derivatives include, but are not limited to, acid-functional derivatives such as monomeric, dimeric, and trimeric acids made from tall oil fatty acids, dimerized rosin acids, and refined fatty acids obtainable from tall oil.

[0114] Advantageously, according to this embodiment, the oil of biosourced origin of the invention is chosen from esterified tall oils, optionally polymerized.

[0115] As is known, an ester results from the reaction between a carboxylic acid and a alcohol with elimination of water. In the remainder of the application, the ester compound is described from the carboxylic acid and the alcohol whose esterification reaction would lead to the production of said ester.

[0116] Preferably, the esterified tall oil is chosen from C4-C36, typically C8-C20, fatty acid esters.

[0117] The alcohol may be primary, secondary or tertiary. In particular, it may be a monol, a diol or a polyol. The alcohol may also be derived from polyethers such as triethylene glycol or polyethylene glycols. Phenolic esters are also suitable.

[0118] Preferably, the alcohol is selected from: methanol, ethanol, 1-propanol, isobutyl alcohol, 2-ethylhexanol, octanol, isodecyl alcohol, benzyl alcohol, cyclohexanol, ethylene glycol monobutyl ether, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, sorbitol, sucrose and the like, and any mixture thereof.

[0119] More preferably, the alcohol is chosen from alcohols comprising a quaternary carbon atom located in the beta position relative to the oxygen of any of their hydroxyl groups. By way of example, mention may in particular be made of trimethylolpropane, neopentyl glycol, trimethylolethane, pentaerythritol, dipentaerythritol, benzyl alcohols and others.

[0120] Preferably, the fatty acid is selected from the group consisting of: oleic acid, linoleic acid, linolenic acid, palmitic acid and any of their mixtures.

[0121] Preferably, the fatty acid is chosen from monomeric acids (defined below), dimeric acids, tall oil heads, tall oil pitch, and mixtures thereof.

[0122] More preferably, the esterified tall oil is obtained from a tall oil fatty acid (also called TOFA for "Tall Oilfatty acid" in English) or from a derivative of a tall oil fatty acid, for example from a dimer acid of tall oil fatty acid. The tall oil fatty acid is obtained from crude tall oil (or CTO for "Crude Tall Oil" in English) by distillation. In general, any cut which contains at least one tall oil fatty acid is preferred for the preparation of an esterified tall oil suitable for the invention.

[0123] According to a first variant, the fatty acid is chosen from modified tall oil pitch.

[0124] Preferably, according to this first variant, the oil of biosourced origin is chosen from tall oil pitches, partially or fully esterified.

[0125] By "partially or fully esterified" is meant within the meaning of the invention that at least a portion of the free acids, in particular free fatty acids, initially present in the tall oil pitch have been esterified. Thus, partially or fully esterified tall oil pitch differs from tall oil pitch by a significantly reduced content of free acids, in particular free fatty acids.

[0126] Preferably, at least 90% by mass of the free acids, especially free fatty acids, present in the original tall oil pitch have been esterified.

[0127] According to a preferred variant, the carboxylic acid is in a polymerized form, in particular in the form of dimerized fatty acids.

[0128] Preferably, according to this embodiment, the esterified tall oil is prepared from polymerized fatty acids. The unsaturated fatty acids are generally polymerized using acidic clay catalysts. Fatty acids having high levels of mono- or polyunsaturation are preferred. In this high-temperature process, the unsaturated fatty acids undergo intermolecular addition reactions, for example the "Alder-ene reaction", to form polymerized fatty acids. The mechanism is complex and not well understood. However, the product comprises mainly dimerized fatty acids and a unique mixture of monomeric fatty acids. Distillation produces a fraction highly enriched in dimerized fatty acid, commonly referred to as "dimer acid". These dimer acids can be used for the manufacture of the esterified tall oil.

[0129] Distillation of polymerized tall oil fatty acid provides a fraction enriched in monomeric fatty acids, known as "Monomer" (with a capital "M") or "Monomer Acid". The Monomer, a unique composition, is a preferred starting material for the preparation of the esterified tall oil according to the invention. While tall oil fatty acid derived from a natural source consists largely of linear unsaturated C[8] carboxylic acids, primarily oleic and linoleic acids, the Monomer contains relatively small amounts of oleic and linoleic acids, and instead contains significant amounts of branched and cyclic, saturated and unsaturated C[8] acids, as well as elaidic acid. The more diverse and significantly branched composition of the Monomer results from the catalytic treatment performed on the tall oil fatty acid during polymerization.It is believed that the reaction of Monomer with alcohols to make "Monomerate" esters will yield unique derivatives that differ from the corresponding tall oil fatty acid esters. The "Monomer" has been assigned CAS No. 68955-98-6. Examples of Monomer are Century® MO5 and MO6 fatty acids, produced by Arizona Chemical Company. Further information on the composition of Monomer and its conversion to various esters is given in US Patent 7,256,162.

[0130] For the purposes of the invention, the term “Monomerate of an alcohol” means the product of the reaction between the “Monomer” (defined above) and said alcohol. More particularly, the “Monomerate of an alcohol” is obtained by esterification of the monomeric fatty acids obtained by distillation of the polymerized tall oil fatty acid and said alcohol.

[0131] The esterified tall oil of the invention includes, for example, ethylene glycol tallate (i.e., tall oil fatty acid ethylene glycol ester), propylene glycol tallate, trimethylolpropane tallate, neopentyl glycol tallate, methyl tallate, ethyl tallate, glycerol tallate, oleyl tallate, octyl tallate, benzyl tallate, 2-ethylhexyl tallate, polyethylene glycol tallates, tall oil pitch esters, ethylene glycol monomerate, glycerol monomerate, trimethylolpropane monomerate, neopentyl glycol monomerate, 2-ethylhexyl monomerate, ethylene glycol dimerate, 2-ethylhexyl dimerate, trimerate 2-ethylhexyl, and their derivatives. Particularly preferred ester compounds are tallates and monomerates, including trimethylolpropane tallate, ethylene glycol monomerate, glycerol monomerate, and any mixtures thereof.

[0132] Esterified tall oil is typically non-crystalline, i.e., it has a solidification temperature, determined according to the ASTM D1982 method, of less than 30°C, preferably less than 20°C, more preferably less than 10°C, and most preferably less than 0°C.

[0133] Preferably, the esterified tall oil of the invention has a cloud point below 0°C, more preferably below -10°C, even more preferably below -20°C, and most preferably below -25°C. The cloud point is determined by gradually cooling a pure, molten sample and observing the temperature at which the clear sample just becomes cloudy.

[0134] Preferably, the esterified tall oil has a Gardner color index, determined according to standard ASTM D6166, of less than or equal to 10, more preferably less than or equal to 8.

[0135] Preferably, the esterified tall oil of the invention has a flash point, determined according to the ASTM D92 method, greater than or equal to 200°C, preferably greater than or equal to 250°C, even more preferably greater than or equal to 280°C.

[0136] Preferably, the esterified tall oil of the invention has an acidity index, determined according to the ASTM D465 method, less than or equal to 150 mg KOH / g, more preferably less than or equal to 100 mg KOH / g, even more preferably less than or equal to 50 mg KOH / g.

[0137] Advantageously, the esterified tall oil of the invention has an acidity index, determined according to the ASTM D465 method, less than or equal to 20 mg KOH / g, preferably less than or equal to 15 mg KOH / g, typically between 0.1 mg KOH / g and 15 mg KOH / g.

[0138] Preferably, the esterified tall oil of the invention has a Cannon-Fenske kinematic viscosity at 40°C, measured according to the ASTM D445 method, greater than or equal to 30 cSt, more preferably between 30 cSt and 100 cSt, even more preferably between 35 cSt and 50 cSt.

[0139] Preferably, the esterified tall oil of the invention has a Cannon-Fenske kinematic viscosity at -20°C, measured according to the ASTM D445 method, greater than or equal to 1000 cSt, more preferably between 1000 cSt and 2000 cSt, even more preferably between 1500 cSt and 1800 cSt, typically 1600 cSt.

[0140] Preferably, the esterified tall oil of the invention has a Cannon-Fenske kinematic viscosity at 0°C, measured according to the ASTM D445 method, greater than or equal to 200 cSt, more preferably between 200 cSt and 500 cSt, even more preferably between 300 cSt and 400 cSt, typically 350 cSt.

[0141] Preferably, the esterified tall oil of the invention has a Cannon-Fenske kinematic viscosity at 20°C, measured according to the ASTM D445 method, greater than or equal to 50 cSt, more preferably between 50 cSt and 200 cSt, even more preferably between 75 cSt and 150 cSt, typically 100 cSt.

[0142] Preferably, the esterified tall oil of the invention has a Cannon-Fenske kinematic viscosity at 40°C, measured according to the ASTM D445 method, greater than or equal to 10 cSt, more preferably between 10 cSt and 100 cSt, even more preferably between 15 cSt and 50 cSt, typically 40 cSt.

[0143] Preferably, the esterified tall oil of the invention has a Cannon-Fenske kinematic viscosity at 60°C, measured according to the ASTM D445 method, greater than or equal to 10 cSt, more preferably between 15 cSt and 50 cSt, even more preferably between 20 cSt and 30 cSt, typically 23 cSt.

[0144] Preferably, the esterified tall oil of the invention has a Cannon-Fenske kinematic viscosity at 100°C, measured according to the ASTM D445 method, greater than or equal to 5 cSt, more preferably between 5 cSt and 50 cSt, even more preferably between 5 cSt and 20 cSt, typically 10 cSt.

[0145] Preferably, the combination of additives of the invention comprises at least 30% by mass of oil of biosourced origin, optionally modified or functionalized, relative to the total mass of ester compound a) and oil b), more preferably from 30% to 90% by mass, even more preferably from 40% to 80% by mass, advantageously from 50% to 75% by mass. Hydrocarbon oil

[0146] According to one embodiment, the combination of additives of the invention comprises at least one hydrocarbon oil of mineral or synthetic origin, preferably of petroleum or synthetic origin.

[0147] For the purposes of the invention, the term “hydrocarbon oil” means an oil consisting of: predominantly hydrocarbon compounds, that is to say, made up almost exclusively of carbon and hydrogen atoms. Hydrocarbon oils may also contain heteroatoms, in particular oxygen, nitrogen or even sulfur, but in very small quantities.

[0148] For the purposes of the invention, the term "oil of petroleum origin" means an oil resulting from the refining of crude oil, in particular from the distillation of crude oil. The petroleum fraction obtained may optionally undergo additional stages of purification, extraction and / or dearomatization.

[0149] For the purposes of the invention, the term "oil of synthetic origin" means an oil resulting from complex chemical transformations carried out either directly from crude oil or from preselected molecules contained in crude oil. Oils of synthetic origin therefore differ from oils of petroleum origin by a transformation process leading to significant chemical modifications.

[0150] The hydrocarbon oil can be of the aromatic or paraffinic type.

[0151] Preferably, the hydrocarbon oil is chosen from aromatic hydrocarbon oils, of petroleum or synthetic origin.

[0152] More preferably, the aromatic hydrocarbon oil has a content of aromatic compounds of between 30% and 100% by mass, advantageously of between 50% and 99% by mass, more advantageously of between 60 and 98% by mass relative to the total mass of the aromatic oil (SARA method: Saturates / Aromatics / Resins / Asphaltenes, according to standard ASTM D2007).

[0153] More preferably, the aromatic hydrocarbon oils of the invention have a content of saturated compounds of between 0% and 30% by mass, advantageously of between 0.1 and 25% by mass, more advantageously of between 0.5 and 23% by mass (SARA method: Saturates / Aromatics / Resins / Asphaltenes, according to standard ASTM D2007).

[0154] More preferably, the aromatic oils have a resin compound content of between 0 and 10% by mass, advantageously between 0.1 and 5% by mass, (SARA method: Saturates / Aromatics / Resins / Asphaltenes, according to standard ASTM D2007).

[0155] More preferably, the aromatic oil has a kinematic viscosity at 100°C of between 0.1 mm2 / s and 150 mm2 / s, advantageously of between 5 mm2 / s and 120 mm2 / s (ASTM Method D 445).

[0156] More preferably, the aromatic oil has a kinematic viscosity at 40°C of between 10 mm2 / s and 2500 mm2 / s, advantageously of between 30 mm2 / s and 2400 mm2 / s (ASTM Method D 445).

[0157] More preferably, the aromatic oil has an aniline point between 20°C and 120°C, advantageously between 40°C and 120°C (ASTM Method D611).

[0158] According to a first embodiment, the hydrocarbon oil of the invention is chosen from oils of petroleum origin.

[0159] Preferably, according to this first embodiment, the hydrocarbon oil of petroleum origin comprises aromatic extracts of petroleum residues, obtained by extraction or dearomatization of residues from distillations of petroleum cuts.

[0160] Aromatic extracts are secondary products of the crude oil refining process, obtained in particular from the products of vacuum distillation of atmospheric residues. They result from a single or double extraction of the raffinate which can be used in lubricants, using a polar solvent.

[0161] The different extracts are classified into different categories according to their production process and are as follows:

[0162] - DAE (Distillate Aromatic Extract)

[0163] - MES (Mild Extract Solvated in English or mild extraction solvent),

[0164] - TDAE (Treated Distillate Aromatic Extract in English or distilled extract treated aromatic),

[0165] - RAE (Residual Aromatic Extract in English or residual aromatic extract),

[0166] - TRAE (Treated Residual Aromatic Extract in English or aromatic extract) treated residual)

[0167] The contents of naphthenic, paraffinic and aromatic compounds mentioned in the present application are determined according to the ASTM D2140 standard, in % by mass relative to the mass of the oil.

[0168] Preferably, the aromatic oil of petroleum origin has a total content of paraffinic compounds of between 35 and 65%, preferably between 40% and 60%, for example between 45% and 58%.

[0169] Preferably, the aromatic oil of petroleum origin has a total content of naphthenic compounds of between 10% and 40%, and in particular of between 15% and 35%, preferably between 20 and 30%.

[0170] Preferably, the aromatic oil of petroleum origin has a total content of aromatic compounds of between 10% and 40%, and in particular of between 15% and 35%, for example of between 18 and 30%.

[0171] More preferably, the aromatic oil of petroleum origin has a kinematic viscosity at 100°C of between 0.1 mm2 / s and 150 mm2 / s, advantageously of between 5 mm2 / s and 120 mm2 / s, more advantageously of between 7 mm2 / s and 90 mm2 / s (ASTM Method D 445).

[0172] More preferably, the aromatic oil of petroleum origin has a kinematic viscosity at 40°C of between 100 mm2 / s and 2500 mm2 / s, advantageously between 200 mm2 / s and 2400 mm2 / s, more advantageously between 400 mm2 / s and 2250 mm2 / s (ASTM Method D 445).

[0173] More preferably, the aromatic oil of petroleum origin has a Cleveland flash point greater than or equal to 150°C, advantageously between 150°C and 600°C, more advantageously between 200°C and 400°C (Method EN ISO 2592).

[0174] More preferably, the aromatic oil has an aniline point between 20°C and 120°C, advantageously between 40°C and 120°C (ASTM Method D611).

[0175] More preferably, the aromatic oil of petroleum origin has a density at 15°C of between 400 kg / m3 and 1500 kg / m3, advantageously of between 600 kg / m3 and 1200 kg / m3, more advantageously of between 800 kg / m3 and 1100 kg / m3 (ASTM Method D4052).

[0176] According to a particular embodiment, the aromatic oil of petroleum origin has a total content of aromatic compounds of between 10% and 40%, a total content of paraffinic compounds of between 35% and 65%, a total content of naphthenic compounds of between 10% and 40%, the contents being given by mass, relative to the total mass of the oil, and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100°C, measured according to the ASTM D445 method, ranging from 40 mm2 / s to 90 mm2 / s, and an aniline point, measured by the ASTM D611 method, ranging from 45°C to 95°C.

[0177] These oils result from a (simple) extraction of the raffinate which can be recovered in lubricants, using a polar solvent, and are hereinafter referred to as “RAE oil”. However, oils obtained by a process other than the RAE process, but having the same physicochemical characteristics and the same composition, also fall within the scope of the invention.

[0178] In the present application, the term "RAE oil" means an oil defined both by its content of aromatic, paraffinic and naphthenic compounds, by its viscosity at 100°C and its aniline point as defined above in the context of this first embodiment. Other preferential characteristics of these oils are reported below.

[0179] The contents of paraffinic, naphthenic and aromatic compounds mentioned in the present application are determined according to the ASTM D2140 standard, in % by mass relative to the total mass of the oil.

[0180] The RAE oils used in the context of the invention have a total content of paraffinic compounds of between 35% and 65%, preferably between 37% and 60%, for example between 40% and 55%.

[0181] The RAE oils used in the context of the invention have a total content of naphthenic compounds of between 10% and 40%, and in particular of between 15% and 35%, preferably between 20 and 30%.

[0182] The RAE oils used in the context of the invention have a total content of aromatic compounds of between 10% and 40%, and in particular of between 15% and 35%, for example of between 25 and 30%.

[0183] In a preferred embodiment, the RAE oil is chosen from those comprising:

[0184] - a total content of paraffinic compounds of between 37% and 60%;

[0185] - a total content of naphthenic compounds of between 15% and 35%; and

[0186] - a total content of aromatic compounds between 15% and 35%.

[0187] In a more particularly preferred embodiment, the RAE oil is chosen from those including:

[0188] - a total content of paraffinic compounds of between 40% and 55%;

[0189] - a total content of naphthenic compounds of between 20% and 30%; and

[0190] - a total content of aromatic compounds between 25% and 35%.

[0191] The RAE oils used in the context of the invention have a viscosity ci nematic at 100°C between 40 and 90 mm2 / s, more advantageously between 45 and 85 mm2 / s (ASTM Method D 445).

[0192] Preferably, the RAE oils used in the context of the invention have a kinematic viscosity at 40°C of between 1000 and 2500 mm2 / s, more advantageously of between 1200 and 2500 mm2 / s (ASTM Method D 445).

[0193] The RAE oils used in the context of the invention have an aniline point between 45°C and 95°C, more advantageously between 50°C and 75°C (ASTM Method D611).

[0194] Preferably, the RAE oils used in the context of the invention have a Cleveland flash point greater than or equal to 150°C, advantageously between 150°C and 600°C, more advantageously between 200°C and 400°C, even better, between 200°C and 250°C (ASTM Method D92).

[0195] More preferably, the RAE oils used in the context of the invention have a density at 15°C of between 400 kg / m3 and 1500 kg / m3, advantageously of between 600 kg / m3 and 1200 kg / m3, more advantageously of between 800 kg / m3 and 1100 kg / m3 (ASTM Method D4052).

[0196] For example, an RAE oil usable in the context of the invention may be a product marketed by the company TotalEnergies under the name: REGENIS® 50.

[0197] The respective contents of paraffinic, naphthenic and aromatic compounds depend to a certain extent on the nature of the crude oil from which the oils originate and the refining process used.

[0198] For example, REGENIS® 50 is a RAE (Residual Aromatic Extract) which presents

[0199] - a density at 15°C between 980 kg / m3 and 1010 kg / m3 (Method ASTM D4052),

[0200] - a flash point (Cleveland) of approximately 230°C (Method EN ISO 2592),

[0201] - a kinematic viscosity at 100°C between 60 and 85 mm2 / s (ASTM Method D 445),

[0202] - an aniline point between 53 and 65°C (ASTM Method D611).

[0203] According to a second embodiment, the aromatic oil has a total content of aromatic compounds of between 10% and 40%, a total content of paraffinic compounds of between 35% and 65%, a total content of naphthenic compounds of between 10% and 40%, the contents being given by mass, relative to the total mass of the oil, and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100°C, measured according to the ASTM D445 method, ranging from 15 mm2 / s to 40 mm2 / s, and an aniline point, measured by the ASTM D611 method, ranging from 50°C to 80°C.

[0204] These oils result from a double extraction of the raffinate which can be recovered in lubricants, using a polar solvent, and are hereinafter referred to as “TDAE oil”. However, oils obtained by a process other than the TDAE process, but having the same physicochemical characteristics and the same composition, also fall within the scope of the invention.

[0205] In the present application, the term "TDAE oil" means an oil defined both by its content of aromatic, paraffinic and naphthenic compounds, by its viscosity at 100°C and its aniline point as defined above in the context of this first embodiment. Other preferential characteristics of these oils are reported below.

[0206] The contents of paraffinic, naphthenic and aromatic compounds mentioned in the present application are determined according to the ASTM D2140 standard, in % by mass relative to the total mass of the oil.

[0207] The TDAE oils used in the context of the invention have a total content of paraffinic compounds of between 35% and 65%, preferably between 40% and 60%, for example between 45% and 55%.

[0208] The TDAE oils used in the context of the invention have a total content of naphthenic compounds of between 10% and 40%, and in particular of between 15% and 35%, preferably between 20 and 30%.

[0209] The TDAE oils used in the context of the invention have a total content of aromatic compounds of between 10% and 40%, and in particular of between 15% and 35%, for example of between 20 and 25%.

[0210] In a preferred embodiment, the TDAE oil is chosen from those including:

[0211] - a total content of paraffinic compounds of between 40% and 60%;

[0212] - a total content of naphthenic compounds of between 15% and 35%; and

[0213] - a total content of aromatic compounds between 15% and 35%.

[0214] In a more particularly preferred embodiment, the TDAE oil is chosen from those including:

[0215] - a total content of paraffinic compounds of between 45% and 55%;

[0216] - a total content of naphthenic compounds of between 20% and 30%; and

[0217] - a total content of aromatic compounds of between 20% and 25%.

[0218] The TDAE oils used in the context of the invention have a viscosity ci nematic at 100°C between 15 and 40 mm2 / s, more advantageously between 16 and 30 mm2 / s (ASTM Method D 445).

[0219] Preferably, the TDAE oils used in the context of the invention have a kinematic viscosity at 40°C of between 300 and 600 mm2 / s, more advantageously of between 400 and 550 mm2 / s (ASTM Method D 445).

[0220] The TDAE oils used in the context of the invention have an aniline point between 50°C and 80°C, more advantageously between 60°C and 70°C (ASTM Method D611).

[0221] Preferably, the TDAE oils used in the context of the invention have a Cleveland flash point greater than or equal to 150°C, advantageously between 150°C and 600°C, more advantageously between 200°C and 400°C, even better, between 250°C and 300°C (ASTM Method D92).

[0222] More preferably, the TDAE oils used in the context of the invention have a density at 15°C of between 400 kg / m3 and 1500 kg / m3, advantageously of between 600 kg / m3 and 1200 kg / m3, more advantageously of between 800 kg / m3 and 1100 kg / m3 (ASTM Method D4052).

[0223] For example, a TDAE oil in the context of the invention may be a product marketed by the company TotalEnergies under the name: Plaxolene TD346 ®.

[0224] The respective contents of paraffinic, naphthenic and aromatic compounds depend to a certain extent on the nature of the crude oil from which the oils originate and the refining process used.

[0225] For example, Plaxolene TD346 ® is a TDAE (Treated Distillate Aromatic Extract) oil which has:

[0226] - a density at 15°C between 940 kg / m3 and 970 kg / m3 (Method ASTM D4052),

[0227] - a flash point (Cleveland) of approximately 260 to 280°C (ASTM Method D92),

[0228] - a kinematic viscosity at 100°C between 16 and 23 mm2 / s (ASTM Method D 445),

[0229] - an aniline point between 64 and 72°C (ASTM Method D611).

[0230] According to a second embodiment, the hydrocarbon oil of the invention is chosen from hydrocarbon oils of synthetic origin, preferably from aromatic oils of synthetic origin.

[0231] Preferably, according to this embodiment, the hydrocarbon oil of synthetic origin is chosen from (poly)condensed alkyl-aromatics.

[0232] For the purposes of the invention, the term “poly(condensed) alkyl-aromatics” means aromatic hydrocarbon compounds comprising at least two condensed aromatic rings.

[0233] Preferably, according to this embodiment, the hydrocarbon oil of synthetic origin is chosen from polycyclic alkyl-aromatics comprising from 2 to 6 condensed aromatic rings, more preferably from 2 to 4 condensed aromatic rings, typically 2 condensed aromatic rings.

[0234] More preferably, according to this embodiment, the hydrocarbon oil of synthetic origin is chosen from naphthalene, its derivatives and any of their mixtures.

[0235] For the purposes of the invention, the term "naphthalene derivatives" means any compound obtained from naphthalene by at least one chemical reaction without significantly modifying the intrinsic properties of naphthalene. Examples that may be mentioned include addition reactions, in particular alkylation, substitution, or even grafting reactions.

[0236] Advantageously, according to this embodiment, the aromatic oil of synthetic origin is chosen from naphthalene derivatives obtained by one or more addition reactions.

[0237] More advantageously, according to this embodiment, the aromatic oil of synthetic origin is chosen from naphthalenes substituted by at least one hydrocarbon group, preferably chosen from alkyl groups, alkenyl groups and aryl groups.

[0238] More advantageously, according to this embodiment, the aromatic oil of synthetic origin is chosen from naphthalenes substituted by at least one alkyl group, preferably from 1 to 5 alkyl groups, more preferably from 1 to 4 alkyl groups. These compounds are generally known under the name of alkyl naphthalene compounds.

[0239] Advantageously, the aromatic oil of synthetic origin comprises, preferably consists of, a mixture of naphthalene compounds substituted by a single alkyl group (monosubstituted alkyl naphthalene compounds), naphthalene compounds substituted by two alkyl groups (di-alkyl naphthalene compounds substituted), naphthalene compounds substituted by three alkyl groups (tri-substituted alkyl naphthalene compounds), and naphthalene compounds substituted by four alkyl groups (tetra-substituted alkyl naphthalene compounds).

[0240] It is understood that the alkyl substituents present on the different alkyl naphthalene compounds may be the same or different.

[0241] Advantageously, the aromatic oil of synthetic origin is mainly composed of tri-substituted alkyl naphthalene compounds.

[0242] More advantageously, the aromatic oil of synthetic origin comprises, preferably consists of:

[0243] - from 1% to 20% by mass of mono-substituted alkyl naphthalene compounds,

[0244] - from 20% to 50% by mass of di-substituted alkyl naphthalene compounds,

[0245] - from 40% to 60% by mass of tri-substituted alkyl naphthalene compounds, and

[0246] - from 5 to 15% by mass of tetra-substituted alkyl naphthalene compounds.

[0247] The degree of substitution of alkyl naphthalene compounds, as well as the proportion of mono-, di-, tri- and tetra-substituted compounds can be measured by any known method, typically by gas chromatography.

[0248] As alkyl substituent, mention may be made of a linear or branched alkyl substituent having from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms, more particularly from 10 to 15 carbon atoms.

[0249] Preferably, the aromatic oil of synthetic origin has an average molecular mass, determined by nuclear magnetic resonance 'H' NMR, ranging from 100 g.mol 'to 1000 g.mol ', more preferably from 250 g.mol1 to 750 g.mol *, even more preferably from 500 g.mol1 to 600 g.mol *.

[0250] Preferably, the combination of additives of the invention comprises at least 10% by mass of hydrocarbon oils, preferably aromatic, relative to the total mass of ester compound a) and oil b), more preferably from 15% to 80% by mass, even more preferably from 20% to 60% by mass. The polymer

[0251] According to one embodiment, the combination of additives of the invention further comprises at least one polymer, preferably at least one elastomer, optionally crosslinked.

[0252] The elastomer is not particularly limited provided that it exhibits the qualities required for coating compositions. Such elastomers are well known in the art and are generally rubbery polymers. 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).

[0253] Preferably, the elastomer is typically chosen from copolymers of a hy- monovinyl aromatic hydrocarbon and a conjugated diene

[0254] Preferably, the elastomer is chosen from block copolymers of formula SBS, in which:

[0255] - each S, which may be the same or different, independently represents a

[0256] block based on monovinyl aromatic hydrocarbon monomers,

[0257] - B represents a block based on butadiene monomers, said block B comprising pendant vinyl groups.

[0258] For the purposes of the invention, the term "block" means a polymer chain obtained by the polymerization of one or more monomers of the same chemical nature. A block is advantageously made up of the repetition of the same monomer.

[0259] In said block copolymers of formula SBS, the S blocks together represent at least 15 mol% of the total number of moles of monomeric units of the block copolymer. Said block copolymers have a weight-average molecular weight ranging from 40,000 to 500,000 g / mol and have a content of pendant vinyl groups contained in the B block, which is greater than or equal to 20 mol%, relative to the total number of moles of monomeric units of the block copolymer. These copolymers may be called, more simply, hereinafter, SBS elastomer. In general, the two S blocks of the heat-crosslinkable SBS elastomer are identical.

[0260] In the context of the invention, butadiene means 1,3-butadiene which is a conjugated diene. When butadiene, or more generally a conjugated diene, is polymerized via a 1,2-addition mechanism, the result is a vinyl group (also called a vinyl group) pendant relative to the backbone of the polymer. The pendant vinyl groups of the SBS block copolymer therefore correspond to the 1,2-addition polymerization of the conjugated diene monomers, and in particular of the majority butadiene monomers, within the B block. The units obtained by the polymerization of butadiene according to a 1,2-addition mechanism or according to a 1,4-addition mechanism have the same molar mass.

[0261] In particular, the monovinyl aromatic hydrocarbon monomer(s) present in the S blocks of the SBS heat-crosslinkable elastomer are chosen from styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene or mixtures thereof. The preferred monovinyl aromatic hydrocarbon monomer according to the present invention is styrene, which is used, for the constitution of the S blocks as the sole monomer, or as the major monomer in mixtures with minor proportions of one or more other monomers such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene, namely, in proportions of at most 10% by mass, relative to the totality of the monovinyl aromatic hydrocarbon monomers present in said S blocks. The use of styrene as the sole monomer is particularly preferred in the present invention for the constitution of the S blocks of the SBS elastomer. Thus, the monovinylaromatic hydrocarbon monomers from which the S blocks of the SBS copolymers with thermally crosslinkable blocks are derived may be, independently, any monovinylaromatic hydrocarbon monomer as previously described and are preferably styrene.

[0262] The block B based on butadiene monomers entering into the composition of the mentioned block copolymers SBS is, preferably, solely composed of butadiene monomers, or of a mixture of butadiene comprising minor proportions of one or more other structurally related conjugated dienes, and in particular chosen from isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene, in particular representing at most 10% by mass, relative to the totality of the conjugated dienes present in the block B. Preferably, the monomers constituting the block B are exclusively butadiene monomers.

[0263] The SBS heat-crosslinkable block elastomer used in the context of the invention has a weight-average molecular mass Mw, ranging from 40,000 to 500,000 g / mol. Preferably, the SBS heat-crosslinkable block elastomer has a weight-average molecular mass Mw, 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.

[0264] Preferably, the SBS block copolymer used in the context of the invention has a weight-average molecular mass Mw greater than or equal to 50,000 g / mol, more preferably greater than or equal to 65,000 g / mol, even more preferably greater than or equal to 75,000 g / mol, and advantageously greater than or equal to 100,000 g / mol. According to particular embodiments, the SBS block copolymer has a weight-average molecular mass 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.

[0265] As indicated above, the SBS block copolymer used in the context of 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 13C NMR (carbon nuclear magnetic resonance) and 1H NMR (proton nuclear magnetic resonance) spectroscopy techniques, makes it possible to characterize the polymer.

[0266] Preferably, the SBS block copolymer preferably has a content of pendant vinyl groups greater than or equal to 5 mol%, relative to the total number of moles of monomeric units of the SBS copolymer, preferably greater than or equal to 10%.

[0267] According to one embodiment, the SBS block copolymer preferably has a content of pendant vinyl groups less than or equal to 50 mol%, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably less than or equal to 40 mol%, even more preferably less than or equal to 30 mol%, typically less than or equal to 20 mol%.

[0268] 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 mole.

[0269] 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 mol%, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably greater than or equal to 30 mol%.

[0270] Preferably, according to this second embodiment, the SBS block copolymer used according to the invention preferably has a content of pendant vinyl groups of less than or equal to 50 mol%, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably less than or equal to 45 mol%. 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 from 35% to 45 mol%.

[0271] Preferably, the pendant vinyl groups are distributed along the B block of the SBS polymer in a statistical manner. This characteristic results directly from the process used for the synthesis of the copolymer.

[0272] 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% by mole.

[0273] Preferably, the number of moles of monomeric units of the S blocks of the SBS polymer represents, together, from 15% to 50% by mole, relative to the total quantity of moles of monomeric units of the SBS block copolymer, more preferably from 16% to 30% by mole, even more preferably from 16% to 25% by mole, and advantageously from 16% to 20% by mole. The number of moles of monomeric units of the S blocks of the SBS polymer can be determined by 13C NMR spectroscopy (Resonance

[0274] Carbon Nuclear Magnetic).

[0275] Preferably, the monovinyl aromatic hydrocarbon monomer content (advantageously styrene) of the SBS block copolymer, determined by 13C NMR spectroscopy (Carbon Nuclear Magnetic Resonance), is greater than or equal to 25% by mass, more preferably greater than or equal to 28% by mass, even more preferably greater than or equal to 30% by mass, relative to the total mass of the block copolymer of formula SBS.

[0276] Preferably, the content of monovinyl aromatic hydrocarbon monomer (advantageously styrene) of the SBS block copolymer, determined by 13C NMR spectroscopy (Carbon Nuclear Magnetic Resonance), ranges from 25% to 40% by mass, even more advantageously from 28% to 35% by mass, relative to the total mass of the SBS block copolymer.

[0277] Advantageously, the SBS block elastomers are in an essentially non-hydrogenated form.

[0278] According to a particular embodiment, the block copolymer of formula SBS is obtained by coupling two block copolymers of formula S-B' in which the blocks S and B' are chosen to obtain an SBS block copolymer. The block B can therefore include a residue of a coupling agent, well known in the field under consideration. As examples of difunctional coupling agents, mention may be made of dibromoethane, diethyl adipate, divinylbenzene, dimethyldichlorosilane and methyl dichlorosilane.

[0279] 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%.

[0280] Examples of SBS block copolymers which can be used in the compositions according to the invention, as well as their preparation processes, are described in particular in patent US 5,798,401, as well as in document WO 2007 / 058994 and by the applicant in patent application WO 2011 / 013073.

[0281] It is possible that, in the bituminous compositions and the processes according to the invention, a single SBS block copolymer as described in the context of the invention is used, or that a mixture of SBS block copolymers as described in the context of the invention is used, or that one or more SBS block copolymer(s) as described in the context of the invention are used in combination with one or more other elastomers. According to a preferred variant, the matrix is ​​produced with only one or more, preferably a single, SBS elastomer. The latter preferably represent 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 that it(they) represents 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 the SBS elastomers, the SBS elastomer represents at least 50%, preferably at least 70% by mass, and preferentially at least 90% of the total quantity of elastomers used (SBS + other elastomer(s)).

[0282] Preferably, the SBS elastomer(s) represent at least 80% by mass of the total quantity of elastomers, preferably at least 90% and preferentially at least 95% of the total quantity of elastomers present, if a mixture of elastomers is used to prepare the bituminous compositions according to the invention. In particular, it is possible for the mixture to contain a portion of S-B' used during the manufacture of the SBS elastomer by coupling, as explained previously.

[0283] Preferably, the combination of additives of the invention comprises from 1% to 50% by mass of polymer, more preferably from 2% to 30% by mass, even more preferably from 5% to 20% by mass, relative to the total mass of the combination of the invention. The additive association

[0284] According to a first embodiment, the additive combination of the invention comprises, preferably essentially consists of:

[0285] a) at least one thiodiopropanoic acid ester compound,

[0286] b) at least one oil of biosourced origin, optionally modified or functionalized, and

[0287] c) optionally, at least one polymer, in particular at least one elastomer.

[0288] Preferably, according to this first embodiment, the additive combination of the invention comprises, preferably essentially consists of:

[0289] a) at least 0.5% by mass of thiodiopropanoic acid ester compound(s),

[0290] b) at least 30% by mass of oil(s) of biosourced origin, optionally modified or functionalized, and

[0291] c) optionally, one or more polymer(s), in particular one or more elastomer(s),

[0292] relative to the total mass of ester compound a) and oil b).

[0293] More preferably, according to this first embodiment, the additive combination of the invention comprises, preferably essentially consists of:

[0294] a) from 1% to 30% by mass of thiodiopropanoic acid ester compound(s), preferably 2% to 20% by mass,

[0295] b) from 70% to 99% by mass of oil(s) of biosourced origin, optionally modified or functionalized, preferably from 80% to 98% by mass, and

[0296] c) optionally, one or more polymer(s), in particular one or more elastomer(s),

[0297] relative to the total mass of ester compound a) and oil b).

[0298] Preferably, according to this first embodiment, the additive combination of the invention has a polymer content, in particular elastomer content, ranging from 1 to 50% by mass, relative to the total mass of the additive combination, more preferably from 2% to 30% by mass, typically from 5% to 20% by mass.

[0299] Preferably, the oil of biosourced origin is present in the combination of the invention according to a mass ratio of oil of biosourced origin / ester compound ranging from 99.5:0.5 to 60:40, preferably ranging from 99:1 to 70:30, even more preferably ranging from 98:2 to 80:20.

[0300] According to a second embodiment, the additive combination of the invention comprises, preferably essentially consists of:

[0301] a) at least one thiodiopropanoic acid ester compound,

[0302] b) at least one hydrocarbon oil, of mineral or synthetic origin, preferably of petroleum or synthetic origin, and

[0303] c) optionally, at least one polymer, in particular at least one elastomer.

[0304] Preferably, according to this second embodiment, the additive combination of the invention comprises, preferably essentially consists of:

[0305] a) at least 0.5% by mass of thiodiopropanoic acid ester compound(s),

[0306] b) at least 10% by mass of hydrocarbon oil(s), of petroleum or syn origin thetic, and

[0307] c) optionally, one or more polymer(s), in particular one or more elastomer(s),

[0308] relative to the total mass of ester compound a) and oil b).

[0309] More preferably, according to this second embodiment, the additive combination of the invention comprises, preferably essentially consists of:

[0310] a) from 1% to 30% by mass of thiodiopropanoic acid ester compound(s), preferably 2% to 20% by mass,

[0311] b) from 70% to 99% by mass of hydrocarbon oil(s), of petroleum or synthetic origin, preferably from 80% to 98% by mass, and

[0312] c) optionally, one or more polymer(s), in particular one or more elastomer(s),

[0313] relative to the total mass of ester compound a) and oil b).

[0314] Preferably, according to this second embodiment, the additive combination of the invention has a polymer content, in particular elastomer content, ranging from 1 to 50% by mass, relative to the total mass of the additive combination, more preferably from 2% to 30% by mass, typically from 5% to 20% by mass.

[0315] Preferably, the hydrocarbon oil of petroleum or synthetic origin is present in the combination of the invention according to a hydrocarbon oil / ester compound mass ratio ranging from 99.5:0.5 to 60:40, preferably ranging from 99:1 to 70:30, even more preferably ranging from 98:2 to 80:20.

[0316] According to a third embodiment, the additive combination of the invention comprises, preferably essentially consists of:

[0317] a) at least one thiodiopropanoic acid ester compound,

[0318] bl) at least one oil of biosourced origin, optionally modified or functionalized

[0319] b2) at least one hydrocarbon oil, of mineral or synthetic origin, of preferably of petroleum or synthetic origin, and

[0320] c) optionally, at least one polymer, in particular at least one elastomer.

[0321] Preferably, according to this third embodiment, the additive combination of the invention comprises, preferably essentially consists of:

[0322] a) at least 0.1% by mass of thiodiopropanoic acid ester compound(s),

[0323] bl) at least 30% by mass of oil(s) of biosourced origin, optionally modified or functionalized,

[0324] b2) at least 10% by mass of hydrocarbon oil(s), of petroleum or syn origin thetic, and

[0325] c) optionally, one or more polymer(s), in particular one or more elastomer(s),

[0326] relative to the total mass of ester compound a) and oil b).

[0327] More preferably, according to this third embodiment, the additive combination of the invention comprises, preferably essentially consists of:

[0328] a) from 1% to 30% by mass of thiodiopropanoic acid ester compound(s), preferably 2% to 20% by mass,

[0329] bl) from 40% to 80% by mass of oil(s) of biosourced origin, optionally modified or functionalized, preferably from 50% to 75% by mass

[0330] b2) from 15% to 80% by mass of hydrocarbon oil(s), of petroleum or syn origin thetic, preferably 20% to 60% by mass, and

[0331] c) optionally, one or more polymer(s), in particular one or more elastomer(s),

[0332] relative to the total mass of ester compound a) and oil b).

[0333] Preferably, according to this third embodiment, the additive combination of the invention has a polymer content, in particular elastomer content, ranging from 1 to 50% by mass, relative to the total mass of the additive combination, more preferably from 2% to 30% by mass, typically from 5% to 20% by mass.

[0334] According to a particular embodiment, the additive combination of the invention is in the form of an emulsion.

[0335] Preferably, according to this embodiment, the emulsion has an aqueous phase content, in particular water, ranging from 30% to 50% by mass, relative to the total mass of the emulsion. Binder composition for recycling

[0336] The invention also relates to a binder composition for the recycling of an aged bituminous coating, in particular an aged bituminous coating or an aged bituminous building coating, comprising:

[0337] - at least one combination of additives as defined above, and

[0338] - virgin bituminous binder.

[0339] For the purposes of the invention, the term "virgin bituminous binder" means a binder composition, composed mainly of bitumen, prepared from virgin materials, i.e. materials that have never been used in a bituminous coating. In particular, a virgin binder is distinguished from an aged binder.

[0340] The virgin bituminous binder typically comprises virgin bitumen.

[0341] Among the virgin bitumens that can be used according to the invention, mention may firstly be made of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or bituminous sands and bitumens originating from the refining of crude oil. In the context of the invention, the bitumen(s) used are advantageously chosen from bitumens originating from the refining of crude oil, in particular bitumens containing asphaltenes or pitches. The bitumens can be obtained by conventional processes for the manufacture of bitumens in refineries, in particular by direct distillation and / or vacuum distillation of oil. These bitumens can optionally be visbroken and / or deasphalted and / or rectified in air. It is common practice to carry out vacuum distillation of atmospheric residues originating from the atmospheric distillation of crude oil.This manufacturing process therefore corresponds to the succession of atmospheric distillation and vacuum distillation, the feedstock feeding the vacuum distillation corresponding to the atmospheric residues. These vacuum residues from the vacuum distillation tower can also be used as bitumens. It is also common to inject air into a feedstock usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from the distillation of oil. This . process allows to obtain a blown, or semi-blown or oxidized or rectified bitumen in air or partially rectified in air.

[0342] Different bitumens obtained by the refining processes can be combined in the compositions according to the invention, to obtain the best compromise, in terms of technical performances. In conventional processes for mixing different bitumens, the operation is carried out at temperatures between 100°C and 200°C, preferably between 140°C and 200°C, and with stirring for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours. The temperature and duration of heating vary according to the quantity of bitumen used and are defined by standard NF EN 12594. Blown bitumens can be manufactured in a blowing unit, by passing a flow of air and / or oxygen through a starting bitumen or bitumen mixture. This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid.

[0343] Generally, blowing is carried out at high temperatures, of the order of

[0344] 200 to 300°C, for relatively long periods of time typically between 30 minutes and 2 hours, continuously or in batches. The blowing time and temperature are adjusted according to the desired properties of the blown bitumen and the quality of the starting bitumen.

[0345] Among the bitumens that can be used according to the invention, mention may also be made of recycling bitumens.

[0346] Bitumens may 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.

[0347] The invention is particularly suitable for cases where the bitumen base consists of a hard grade bitumen or a mixture of hard grade bitumens, in particular chosen from bitumens of grade 35 / 50, 20 / 30 and 10 / 20.

[0348] The bitumen bases that can be used in the context of the invention preferably have a penetrability, measured at 25°C according to standard EN 1426, of 5 to 330 1 / 10 mm, preferably between 10 and 220 1 / 10 mm, more preferably from 10 to 120 1 / 10 mm. In a well-known manner, the so-called “needle penetrability” measurement is carried out 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). Needle penetrability, measured at 25°C, according to the standardized test NF EN 1426, represents the measurement of the penetration into a sample of bitumen, after a time of 5 seconds, of a needle whose weight with its support is 100 g.

[0349] The binder composition for recycling according to the invention may typically comprise at least 80% by mass of virgin bitumen, relative to the total mass of the binder composition, preferably at least 90% by mass, more preferably from 90% to 99% by mass.

[0350] According to one embodiment, the virgin bituminous binder consists of a virgin bitumen / polymer composition, optionally crosslinked.

[0351] According to this embodiment, the bitumen / polymer composition (optionally crosslinked) comprises from 1% to 15% by mass of elastomer, in particular of a copolymer of monovinyl aromatic hydrocarbon and conjugated diene, in particular of copolymer of styrene and butadiene, relative to the mass of the crosslinked bitumen / polymer composition, more preferably from 2% to 10% by mass.

[0352] According to an alternative embodiment, the bitumen / polymer composition (optionally crosslinked) comprises from 5% to 20% by mass of elastomer, in particular of a copolymer of monovinyl aromatic hydrocarbon and conjugated diene, in particular of copolymer of styrene and butadiene, relative to the mass of the crosslinked bitumen / polymer composition, more preferably from 6% to 15% by mass.

[0353] Preferably, the binder composition for recycling an aged bituminous coating comprises:

[0354] - from 1% to 40% by mass of one or more combination(s) of additives such that defined above, and

[0355] - from 60% to 99% by mass of one or more virgin bitumen bases, and

[0356] - optionally, from 2% to 30% by mass of polymer, in particular elastomer,

[0357] relative to the total mass of the recycling binder composition. Composition of recycled bituminous binder

[0358] The invention also relates to a recycled bituminous binder composition, obtained by recycling aged binder using a combination of additives or a recycling binder composition according to the invention.

[0359] In particular, the invention relates to a recycled bituminous binder composition comprising:

[0360] - aged binder, and

[0361] - at least one combination of additives as defined above or at least one recycling binder composition as defined above.

[0362] According to a first embodiment, the recycled bituminous binder composition comprising:

[0363] - from 50% to 99% by mass of aged binder, and

[0364] - from 1% to 50% by mass of one or more combination(s) of additives such as defined above,

[0365] relative to the total mass of the recycled bituminous binder composition.

[0366] According to a second embodiment, the recycled bituminous binder composition comprising:

[0367] - from 20% to 99% by mass of aged binder, and

[0368] - from 1% to 80% by mass of one or more binder composition(s) for the recycling of an aged bituminous coating as defined above, relative to the total mass of the recycled bituminous binder composition. Applications

[0369] The invention also relates to the use of a combination of additives or a binder composition for the recycling of an aged bituminous coating or a recycled bituminous binder composition, for the manufacture of bituminous coatings comprising recycled bituminous coating aggregates and / or bituminous building coating aggregates.

[0370] Bituminous mixes are used as materials for the construction and maintenance of road surfaces and their surfacing, as well as for carrying out all road works. Examples include surface dressings, hot mixes, cold mixes, cold-poured mixes, emulsion gravels, base, bonding, tack and rolling layers, and other combinations of a bituminous binder and road aggregate with specific properties, such as anti-rutting layers, draining mixes, or asphalts (a mixture of a bituminous binder and aggregates such as sand). As is known, the layers of bituminous mix that have been removed from roads or pavements, for example, are crushed before being reused. They are called recycled asphalt aggregates or RAP (for “Recycled Asphalt Pavement” in English).

[0371] The combination of additives according to the invention, the recycling binder composition of the invention and / or the recycled bituminous binder composition can be used for the manufacture of new bituminous mixes from recycled bituminous aggregates, in particular from recycled bituminous mix aggregates and / or recycled bituminous building coating aggregates. The combination of additives according to the invention has the property of fluidifying the aggregated bituminous residues around the aggregates forming the recycled bituminous aggregates, of correcting the adhesiveness of the bituminous composition composed of binder and bituminous residues and their cohesion around the aggregates. The combination of additives according to the invention makes it possible to reduce the application temperature of the bituminous mixes formed from recycling aggregates.By facilitating the mixing and homogenization of the compositions resulting from the recycled aggregates, it makes it possible to form a bituminous coating with a substantially homogeneous composition and mechanical properties substantially identical to those of bituminous coatings obtained solely with bitumen which has never been used to form bituminous coatings.

[0372] Another subject of the invention thus relates to a method for manufacturing bituminous coatings from recycled bituminous aggregates, in particular from recycled bituminous coating aggregates and / or bituminous building coating aggregates. recycled.

[0373] According to a first embodiment, the method for manufacturing bituminous coatings of the invention comprises at least the steps of:

[0374] - heating of recycled bituminous aggregates, in particular of bi-coated aggregates recycled bituminous aggregates and / or recycled bituminous building coating aggregates, preferably recycled bituminous asphalt aggregates, at a temperature ranging from 100°C to 180°C, preferably from 120°C to 160°C in a tank such as a mixer or a mixer drum,

[0375] - introduction and mixing of a combination of additives or a binder composition recycling or a recycled bituminous binder composition as defined above at a temperature ranging from 25°C to 160°C, preferably from 40°C to 120°C,

[0376] - obtaining bituminous coatings.

[0377] The method for manufacturing asphalt mixes according to the invention does not require a step of heating the combination of additives or the recycling binder composition or the recycled binder composition before mixing with the recycling aggregates. The simple contact of the rejuvenating composition of the invention with the hot aggregate mixture is sufficient to bring said composition to a temperature satisfactory for the manufacture of bituminous asphalt mixes.

[0378] According to a second embodiment, the additive combination used in the process for manufacturing bituminous coatings of the invention is in the form of an emulsion as defined above.

[0379] Preferably, according to this second embodiment, the method for manufacturing bituminous coatings of the invention comprises at least the steps of:

[0380] i) introducing recycled bituminous aggregates, in particular recycled bituminous asphalt aggregates and / or recycled bituminous building surfacing aggregates, preferably recycled bituminous asphalt aggregates, into a tank such as a mixer or a mixer drum,

[0381] ii) introducing and mixing a combination of additives or a recycling binder composition or a recycled bituminous binder composition as defined above, the combination of additives or recycling binder composition or recycled bituminous binder composition being in the form of an emulsion,

[0382] iii) obtaining bituminous coatings.

[0383] Preferably, step ii) is carried out at a temperature ranging from 0°C to 90°C, more preferably from 10°C to 60°C, even more preferably from 25°C to 40°C.

[0384] The invention also relates to a bituminous coating comprising:

[0385] - a combination of additives or a composition for the recycling of a bi-coating aged bituminous binder or a recycled bituminous binder composition as defined above, and

[0386] - recycled bituminous mix aggregates and / or bi-surfacing aggregates recycled building tuminous.

[0387] The invention also relates to the use of a combination of additives or a composition for the recycling of an aged bituminous coating or a recycled bituminous binder composition as defined above, for the manufacture of a bituminous coating for a building, in particular a waterproofing membrane, comprising aggregates of recycled bituminous coating of the building.

[0388] The invention also relates to bituminous coatings intended for the construction industry, in particular waterproofing membranes, noise-reducing membranes, insulation membranes, surface coverings, carpet tiles, impregnation layers or even roofing shingles. These coatings intended for the construction industry are typically made up of a mixture of binder and fillers whose particle size depends on the intended applications.

[0389] The invention thus relates to a bituminous coating for buildings comprising:

[0390] - a combination of additives or a composition for the recycling of a bi-coating aged bituminous binder or a recycled bituminous binder composition as defined above, and

[0391] - recycled bituminous building coating aggregates, in particular recycled bituminous waterproofing membrane.

[0392] In particular, the invention relates to a waterproofing membrane comprising:

[0393] - a combination of additives or a composition for the recycling of a bi-coating aged bituminous binder or a recycled bituminous binder composition as defined above, and

[0394] - recycled bituminous building coating aggregates, in particular recycled bituminous waterproofing membrane.

[0395] The various embodiments, variations, preferences and advantages described above for each of the objects of the invention apply to all of the objects of the invention and may be taken separately or in combination.

Claims

Claims

1. Combination of additives for the recycling of a bituminous coating, in particular a bituminous coating or a bituminous coating of the building, comprising: a) at least one thiodipropanoic acid ester compound, and b) at least one oil chosen from: i) oils of biosourced origin, optionally modified or functionalized; ii) hydrocarbon oils, of mineral origin, in particular petroleum, or synthetic; and iii) mixtures of i) and ii).

2. Association according to claim 1, comprising at least one oil of biosourced origin, optionally modified or functionalized, and at least one hydrocarbon oil of petroleum or synthetic origin.

3. Association according to claim 1 or according to claim 2, in which said at least one oil of biosourced origin, optionally modified or functionalized, is chosen from polymerized oils of plant origin comprising from 2% to 80% by mass of oligomers, and having a polydispersity index ranging from 1.30 to 2.20, and a sulfur content ranging from 0.001% by mass to 8% by mass.

4. Association according to any one of claims 1 to 3, in which said at least one hydrocarbon oil, of petroleum or synthetic origin, is chosen from aromatic mineral oils.

5. Association according to any one of claims 1 to 4, in which said at least one hydrocarbon oil is chosen from hydrocarbon oils of synthetic origin, preferably from alkyl naphthalenes

6. Association according to any one of claims 1 to 4, in which said at least one hydrocarbon oil is among hydrocarbon oils of petroleum origin.

7. Association according to any one of the preceding claims, in which said at least one thiodipropanoic acid ester compound is chosen from diesters of thiodipropanoic acid, preferably from diesters of 3,3'-dithiopropionic acid and a linear saturated alcohol of C1-C30, preferably C5-C25, more preferably C10-C20.

8. Association according to claim 7, wherein said at least one ester compound is selected from di-dodecyl ester of 3,3'-dithiopropanoic acid, di-octadecyl ester of 3,3'-dithiopropanoic acid and any of their mixtures.

9. Association according to any one of the preceding claims, further comprising at least one polymer, optionally crosslinked, preferably at least one elastomer, in particular chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene.

10. Binder composition for recycling an aged bituminous coating, in particular an aged bituminous coating or an aged bituminous building coating, comprising: - at least one combination of additives according to any one of claims 1 to 9, and - virgin bituminous binder, in particular virgin bitumen or a virgin bitumen / polymer composition, optionally crosslinked.

11. A recycled bituminous binder composition comprising: - aged binder, in particular aged bitumen or an aged bitumen / polymer composition, preferably recovered from an aged bituminous coating, and - at least one combination of additives according to any one of claims 1 to 9 or at least one binder composition for recycling according to claim 10.

12. Use of a combination of additives according to any one of claims 1 to 9 or of a composition for recycling an aged bituminous coating according to claim 10 or of a recycled bituminous binder composition according to claim 11, for the manufacture of bituminous coatings comprising recycled bituminous coating aggregates and / or bituminous building coating aggregates.

13. Use of a combination of additives according to any one of claims 1 to 9 or of a composition for recycling an aged bituminous coating according to claim 10 or of a recycled bituminous binder composition according to claim 11, for the manufacture of a bituminous coating for buildings comprising aggregates of recycled bituminous coating of the building.

14. Bituminous coating comprising: - a combination of additives according to any one of claims 1 to 9 or a composition for recycling an aged bituminous coating according to claim 10 or a recycled bituminous binder composition according to claim 11, and - recycled bituminous coating aggregates and / or recycled building bituminous coating aggregates.

15. Waterproofing membrane comprising: - combination of additives according to any one of claims 1 to 9 or a composition for recycling an aged bituminous coating according to claim 10 or a composition of recycled bituminous binder according to claim 11, and - aggregates of recycled bituminous coating of the building, in particular of recycled bituminous waterproofing membrane.