FR3054568A1 - FLUXANT AGENTS FOR HYDROCARBON BINDERS - Google Patents

Abstract

The invention relates to the use, as fluxing agent, of at least one compound corresponding to formula (I) R1-XRY-R2 (I) in which: R1 and R2, which are identical or different, are hydrocarbon chains, linear or branched, C2-C11; each of -X- and -Y-, identical or different, is -O- (C = O) -; - (C = O) -O-; -NR '- (C = O) - with R' representing a hydrogen atom or a C1-C4 alkyl radical, or - (C = O) -NR'- with R 'representing a hydrogen atom or a C1-C4 alkyl radical, the group -R- is a divalent C1-C10 hydrocarbon chain, linear or branched, and optionally interrupted by one or more oxygen atoms in a composition comprising a hydrocarbon binder for the preparation of a bituminous product based on mineral solid particles in contact with said hydrocarbon-based binder, wherein said compound of formula (I) is present in said composition when said composition is brought into contact with said mineral solid particles.

Description

® FRENCH REPUBLIC

NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number: 3,054,568 (to be used only for reproduction orders) (© National registration number: 16 57180

COURBEVOIE © Int Cl ⁸ : E 01 C 7/24 (2017.01), C 07 C 69/52, 237/16

A1 PATENT APPLICATION

©) Date of filing: 07.26.16. (© Applicant (s): RHODIA OPERATIONS Company by (© Priority: simplified actions— FR and EUROVIA - FR. @ Inventor (s): LEBARBE THOMAS, MARTIN HELENE, ROUSSEAU SIMON, BOURDETTE (43) Date of public availability of the ARNAUD, DELFOSSE FREDERIC and LABEAU Marie- request: 02.02.18 Bulletin 18/05. Pierre. ©) List of documents cited in the report preliminary research: Refer to end of present booklet (© References to other national documents ® Holder (s): RHODIA OPERATIONS Company by related: simplified actions, EUROVIA. ©) Extension request (s): (© Agent (s): REGIMBEAU.

FR 3 054 568 - A1 fluxing agents for hydrocarbon binders.

The invention relates to the use as fluxing agent of at least one compound corresponding to formula (I)

R ¹ -XRYR ² (I) where:

R ¹ and R ² , identical or different, are linear or branched C 1 -C 4 hydrocarbon chains;

each of -X- and -Y-, identical or different, is a group -O- (C = O) -; - (C = O) -O-; -NR '- (C = O) - with R' representing a hydrogen atom or a C _r C ₄ alkyl radical, or - (C = O) -NR'- with R 'representing a hydrogen atom or an alkyl radical in the group -R- is a divalent hydrocarbon chain, in Ci-Ci ₀ , linear or branched, and optionally interrupted by one or more oxygen atoms in a composition comprising a hydrocarbon binder for the preparation of a product bituminous based on solid mineral particles in contact with said hydrocarbon binder, wherein said compound of formula (I) is present in said composition when said composition is brought into contact with said solid mineral particles.

FLOWING AGENTS FOR HYDROCARBON BINDERS

The present invention relates to the field of fluxing agents for hydrocarbon binders, which can be used in particular in road applications. More specifically, the invention relates to the use, as fluxing agent, of a specific volatile compound of formula (I) as defined below in a composition comprising a hydrocarbon binder used for the production of a product bituminous based on mineral particles joined by said composition comprising the hydrocarbon binder.

In so-called “bituminous” products, mineral particles are linked by a hydrocarbon binder, in particular a bitumen. The hydrocarbon binders which are used in bituminous products of this type are very viscous products, typically viscoelastic, which require, to be handled, to be heated, emulsified and / or additivated by so-called "fluxing" compounds which allow , among others, to reduce their viscosity. These fluxes can be of petroleum, petrochemical, carbochemical or even vegetable origin.

Common fluxes are fluxes of petroleum origin which include:

"petroleum fluxes" which are products resulting from the distillation of crude oil (light fraction (s)), which could possibly have undergone a hydrotreatment operation. Mention may be made, for example, of the fluxing agents sold by Total (Greenflux® 2000, Greenflux® SD in particular).

“petrochemical fluxes” which are products resulting from the distillation of crude oil (light fraction (s)), having undergone at least one thermal cracking and additional distillation operation. Mention may be made, for example, of the fluxing agents marketed by VFT France (Adheflux®).

Such fluxes of petroleum origin are very satisfactory in terms of results. In fact, when they are added to a hydrocarbon binder, they make it possible to temporarily lower the viscosity while generally ensuring that the mechanical performance of the bituminous product based on this fluxed hydrocarbon binder is not appreciably deteriorated and thus makes them clean for their road use, in particular with a sufficient increase in cohesion.

These fluxes of petroleum origin are volatile products: after their incorporation into the hydrocarbon binder where they ensure the desired reduction in viscosity, they evaporate, whereby the binder substantially regains its primary characteristics. These released fluxes, however, have many negative environmental impacts. In addition, their use is dangerous and uncomfortable (harmful and unpleasant vapors and danger of flammability).

Other volatile fluxing agents are fluxes of carbochemical origin which are products resulting from the pyrolysis of coal, having undergone at least one distillation operation, which have the major drawback of being recognized as carcinogens.

To replace the aforementioned volatile fluxing agents, fluxes of natural non-fossil origin (plant or animal origin) have been proposed, which make it possible to avoid the release of harmful volatile organic compounds. A non-fossil natural flux is a natural non-fossil oil, one of its derivatives such as fatty acid esters, or a mixture of two or more of these oils and / or oil derivatives. Mention may in particular be made of vegetable oils such as sunflower, rapeseed, peanut, coconut, linseed, palm, soy, olive, castor, corn, squash, seed oil. grapes, jojoba, sesame, walnuts, hazelnuts, Chinese wood, tall oil (their tall oil), their derivatives, as well as their mixtures. Most of these oils mainly contain fatty acids at least C ₁₆ unsaturated. Such fluxing agents are for example described in applications FR 2 910 477, EP 0 900 822, FR 2 721 043 or FR 2 891 838.

With non-volatile fluxes of the type of the aforementioned oils, the increase in consistency of the binder in the final product (after spreading or after coating) does not occur by evaporation, unlike the case of volatile fluxes, but rather by crosslinking, typically following radical reactions, the unsaturated fatty chains reacting in the presence of oxygen in the air. These reactions, which can be catalyzed by adding drying agents such as metal salts, include the formation of peroxide -O-O- bridges on the unsaturated chains. These bridges are unstable and lead to the formation of free radicals which themselves will react with other unsaturations of other chains. This flux crosslinking technique thus only applies to unsaturated compounds. The fluxing agent is selected on the basis of the iodine index which characterizes the rate of unsaturation of a compound and therefore its capacity to react by siccativation.

Although they have less impact on the environment and on the well-being and health of the manipulators, fluxes of natural non-fossil origin are, however, less satisfactory than fluxes of petroleum origin in terms of results. In fact, the results of the increase in cohesion are less good. They most often lead to disorders in the event of showers, heat or traffic that is too dense, clouding problems, linked in particular to poor adhesion of the hydrocarbon binder fluxed onto the solid mineral particles.

Bituminous products based on bitumen fluxed with fluxes of non-fossil natural origin are currently considered not to be suitable for moderate to heavy traffic and climatic variations.

An object of the invention is to provide a solution:

allowing the viscosity of a hydrocarbon binder to be lowered making it possible to have a hydrocarbon binder of wettability well suited with respect to mineral solid particles without having the aforementioned drawbacks

To this end, it is proposed according to the present invention to use as fluxes, particular compounds, the inventors of which have now discovered, in the context of the work which led to the present invention, (1) that they are include interesting volatile fluxes which make it possible, once incorporated into compositions comprising a hydrocarbon binder and before their evaporation, to reduce the viscosity of the hydrocarbon binder, which can therefore be used more easily, but without having the drawbacks of fluxes usual volatiles in terms of environmental impact and toxicity for their handler; and (2) that they also induce for the composition a satisfactory wettability with respect to the mineral solid particles, of the same order as those of the best fluxing agents currently used, such as Greenflux® SD, which in particular makes it possible to adhere properly to solid mineral particles.

A more specific subject of the invention is the use, as fluxing agent, of at least one compound corresponding to formula (I)

Fri-XRYR ² (I) where:

R ¹ and R ² , identical or different, are hydrocarbon chains, linear or branched, in C2-C11;

each of -X- and -Y-, identical or different, is a group -O- (C = O) -;

- (C = O) -O-; -NR '- (C = O) - with R' representing a hydrogen atom or an alkyl radical Ci-C _4, or (C = O) -NR'- with R 'representing a hydrogen atom or a alkyl radical _C-4, the group -R- is a divalent hydrocarbon chain, C1-C10 linear or branched and optionally interrupted by one or more oxygen atoms in a composition comprising a hydrocarbon binder for the preparation of a bituminous product based on mineral solid particles in contact with said hydrocarbon binder, wherein said compound of formula (I) is present in said composition when said composition is brought into contact with said mineral solid particles.

A single compound of formula (I) can be used according to the invention or a mixture of several compounds of formula (I).

The compounds of formula (I), alone or in mixtures, turn out to be compounds the work of the inventors of which have shown that they are volatile within a bitumen-type hydrocarbon binder and that they therefore provide a similar effect. fluxes of petroleum origin, but without the issues of their impact on the environment and toxicity for the operator.

Furthermore, the compounds of formula (I), before their volatilization, ensure not only a specific reduction in the viscosity of the binder, but also a wettability of the solid mineral particles by the binder of the same order as that of the best fluxing agents currently used.

The compound of formula (I) as it is used according to the invention is not only used to reduce the viscosity of the hydrocarbon binder, but also, more specifically to ensure good wettability of the solid mineral particles by the composition comprising the binder. To this end, the compound of formula (I) is present in the bituminous composition during all or part of the time period when the composition is brought into contact with the solid mineral particles. In practice, the compound of formula (I) can in particular be added to the composition comprising the hydrocarbon binder according to one and / or the other of the following 3 compatible variants:

variant 1: the compound of formula (I) is added at least in part (if variant 2 and / or 3 is also used), or even entirely (if not), to the composition comprising the hydrocarbon binder, then the composition comprising the compound of formula (I) is brought into contact with the solid mineral particles before complete evaporation of the compound of formula (I) from the composition (in other words, said compound of formula (I) is still present at least partly in the composition when brought into contact with the solid mineral particles, preferably in an amount sufficient in the composition to ensure a fluxing role therein);

and or

variant 2: the compound of formula (I) is added at least in part (if variant 1 and / or 3 is also used), or even entirely (if not), at the same time as the solid mineral particles to the composition comprising the hydrocarbon binder and / or

- variant 3: the compound of formula (I) is added at least in part (if variant 1 and / or 2 is also used), or even entirely (if not), to a premix containing the solid particles minerals and the composition comprising the hydrocarbon binder

Note that when variant 2 and / or 3 is used, it may well be envisaged to use, in a prior step (E0), compounds of formula (I) as fluxes in the composition based on binder (for example to make a composition of bitumen emulsion type), then allow the compounds of formula (I) used to evaporate completely. In this case, to implement variant 2 or 3, compounds of formula (I), identical or different from those used in the previous step (E0), will be introduced jointly and / or after mixing the composition with solid mineral particles.

The compounds of formula (I) according to the invention make it possible to lower the viscosity of the hydrocarbon binder, to which they are added, while ensuring good wettability of the mineral solid particles by the composition comprising the binder.

Advantageously, the compounds of formula (I) according to the invention also make it possible to obtain a high-performance binder after stabilization (these performances are seen through the results of penetrability, ball-ring temperature, possibly of Fraass point of weakness)

Preferably, the compounds of formula (I) according to the invention allow a reduction in the viscosity of the hydrocarbon binder during its implementation without affecting its performance and its capacity to wet the solid mineral particles.

In a variant of the invention, the composition also comprises a compound corresponding to formula (II)

Ff-XRYR ² (II) where:

R ¹ and R ² , identical or different, are hydrocarbon chains, linear or branched, in Ci-Cn, preferably in Q-Cg; and where at least one of R ¹ , R ² is a methyl radical

-X- and -Y-, -R- are as defined for formula (I).

A single compound of formula (II) or a mixture of several compounds of formula (II) can be used according to the invention.

The compounds of formula (II), alone or as mixtures, turn out to be compounds which the work of the inventors have shown to be volatile within a bitumen-type hydrocarbon binder.

This compound of formula (II) may advantageously be introduced as a mixture with the compound of formula (I), according to one or other of the variants 1, 2 and / or 3 above or during step (E0). More generally, a fluxing agent and / or one or more compounds of formula (II) may be added to the composition before and / or during and / or after (and preferably before and / or during) the contacting of the solid mineral particles with the composition, regardless of the time of introduction of the compound of formula (I). According to a particular embodiment, at least part of the compounds of formula (I) and at least part of the compounds of formula (II) are present simultaneously in the composition, preferably at least for part of the time when the composition is in contact with mineral solid particles.

The following definitions will be adopted throughout this description:

Hydrocarbon binder:

The term “hydrocarbon binder” is understood to mean any hydrocarbon binder of fossil or vegetable origin usable for the production of so-called “bituminous” products, this hydrocarbon binder can typically be bitumen or not, and be pure or modified, in particular by adding polymer (s) .

The binder may be a soft to hard binder, advantageously of a grade ranging from 10/20 to 160/220.

The hydrocarbon binder can be a bitumen, pure or modified by polymers.

The bitumen-modifying "polymer" referred to here can be chosen from natural or synthetic polymers. It is, for example, a polymer from the family of elastomers, synthetic or natural, and in an indicative and nonlimiting manner:

- random, multi-block or star copolymers of styrene and butadiene or isoprene in all proportions (in particular block copolymers of styrene-butadiene styrene (SBS), of styrene-butadiene (SB, SBR for styrene-butadiene rubber ), styrene isoprene-styrene (SIS)) or the copolymers of the same chemical family (isoprene, natural rubber, etc.), optionally crosslinked in situ,

- copolymers of vinyl acetate and ethylene in all proportions,

- copolymers of ethylene and of esters of acrylic, methacrylic acid or maleic anhydride, copolymers and terpolymers of ethylene and glycidyl methacrylate) and polyolefins.

The bitumen-modifying polymer can be chosen from recovery polymers, for example “rubber crumbs” or other compositions based on rubber reduced in pieces or in powder, for example obtained from used tires or other waste to based on polymers (cables, packaging, agricultural, ...) or any other polymer commonly used for the modification of bitumens such as those mentioned in the Technical Guide written by the International Road Association (PIARC) and published by the Central Laboratory of Bridges and Roads Use of Modified Bituminous Binders, Special Bitumens and Bitumens with Additives in Road Pavements (Paris, LCPC, 1999), as well as any mixture in any proportion of these polymers.

The composition comprising the binder may be in the form of an anhydrous binder or in the form of an emulsion (typically bitumen emulsion).

The emulsion is a dispersion of the binder (bitumen, synthetic binder or vegetable binder) in a continuous phase, typically an aqueous phase, for example water. A surfactant can be added to the emulsion, which in particular makes it possible to stabilize it.

During the manufacture of an emulsion, the binder is dispersed in fine droplets in water, for example by mechanical action. The addition of a surfactant forms a protective film around the droplets, preventing them from agglomerating and thus making it possible to keep the mixture stable and to store it for a certain time. The amount and type of surfactant added to the mixture determines the stability of the emulsion during storage and influences the curing time at the time of application. The surfactant can be positively charged, negatively charged, amphoteric or non-ionic.

The surfactant is advantageously of petroleum, vegetable or animal origin and their mixtures (for example the surfactant can be of vegetable and petroleum origin). The surfactant can be an alkaline soap of fatty acids: sodium or potassium salts of an organic acid (resin for example). The emulsion is then anionic. The surfactant can be an acid soap, which is generally obtained by the action of hydrochloric acid on one or two amines. The emulsion is then cationic. Among the surfactants relevant in road application, mention may be made of: the surfactants marketed by Akzo NOBEL (Redicote® E9, Redicote® EM 44, Redicote® EM 76), the surfactants marketed by CECA (Dinoram® S, Polyram® S, Polyram® L

80), the surfactants marketed by Meadwestvaco (Indulin® R33, Indulin® R66, Indulin® W5). One or more of these surfactants may be used, alone or in mixtures.

The emulsion may contain synthetic or natural latex. By latex is meant a dispersion of polymers (polyisoprene, SBS, SB, SBR, acrylic polymers, etc.) crosslinked or not in the aqueous phase. This latex is incorporated into the aqueous phase before emulsification or online during the manufacture of the emulsion, or even after manufacture of the emulsion.

The composition comprising the binder may be in whole or in part in the form of a foam typically obtained a method of injecting into the binder arrival a quantity of water, and optionally air, the water being pure or may include additives making it possible to modify the adhesiveness or even rheological properties of the binder.

Whatever its form, the composition comprising the binder, typically within the binder, additives commonly used in the road sector, such as compositions based on powdered rubber (“rubber crumbs”), vegetable waxes or of petrochemical origin, dopes of adhesiveness.

Mineral solid particles

By mineral solid particles is meant in the present description all solid particles which can be used for the production of bituminous products in particular for road construction, comprising in particular the natural mineral aggregates (gravel, sand, fines) from quarry or gravel pit, the products of recycling such as asphalt aggregates resulting from the recycling of materials recovered during road repairs as well as surplus coating plants, manufacturing waste, “shingles” (from the recycling of roofing membranes), aggregates from the recycling of road materials including concrete, slag, in particular slag, shale in particular bauxite or corundum, rubber crumbs from tire recycling in particular, artificial aggregates of all origins and originating for example of household waste incineration bottom ash (MIOM), as well as their mixtures in all proportions.

Natural mineral aggregates include:

elements less than 0.063 mm (filler or fines) of sand whose elements are between 0.063 mm and 2 mm;

gravel, the elements of which have dimensions o of between 2 mm and 6 mm; o greater than 6 mm;

The size of the mineral aggregates is measured by the tests described in standard NF EN 933-2 (May 1996 version).

“Asphalt mixes” are understood to mean asphalt mixes (mixture of aggregates and bituminous binders) coming from milling of asphalt layers, crushing of sheets extracted from asphalt pavements, pieces of mix sheets, waste from asphalt. '' asphalt mix or asphalt production surpluses (production surpluses are materials coated or partially coated at the plant resulting from transitional manufacturing phases). These elements and other recycling products can reach dimensions up to 31.5 mm.

“Mineral solid particles” are also designated by the terms “O / D mineral fraction”. This mineral fraction 0 / D can be separated into two particle sizes: the mineral fraction 0 / d and the mineral fraction d / D.

The finest elements (the mineral fraction 0 / d) will be those in the range between 0 and a maximum diameter that can be set between 2 and 6 mm (from 0/2 to 0/6), advantageously between 2 and 4 mm. The other elements (minimum diameter greater than 2, 3, 4, 5 or 6 mm; and approximately up to 31.5 mm) constitute the mineral fraction d / D.

Compound of formula (I)

A compound or mixture of compounds is used in the invention, corresponding to the formula (I) R ¹ -XRYR ² (I) where:

R ¹ and R ² , identical or different, are hydrocarbon chains, linear or branched, of C2-C11, preferably of C ₂ -C ₉ ;

each of -X- and -Y-, identical or different, is a group -O- (C = O) -; - (C = O) -O-;

-NR '- (C = O) - with R' representing a hydrogen atom or an alkyl radical Ci-C _4, or (C = O) -NR'- with R 'representing a hydrogen atom or a alkyl radical _C-4, the group -R- is a hydrocarbon chain C1-C10 divalent linear or branched and optionally interrupted by one or more oxygen atoms.

It is noted that according to a variant of the invention, the compound of formula (I) can be in the form of a mixture comprising different compounds of formula (I). In the application, unless explicitly mentioned in the presence of at least two compounds, a compound may denote a single compound corresponding to formula (I) or a mixture or a combination of several compounds corresponding to formula (I).

In the compounds of formula (I) used according to the invention, the total number of carbon atoms is preferably between 7 and 16. According to one embodiment, the total number of carbon atoms is greater than or equal to 8, or even 9. According to a particular mode, the number of carbon atoms is greater than or equal to 10, for example to 11, and in particular, greater than or equal to 12. Furthermore, it is generally preferred that the total number of carbon atoms is less than or equal to 15, for example less than or equal to 14. Thus, for example, the total number of carbon atoms can be between 10 and 15, for example between 10 and 12 or between 12 and 14.

The total number of carbon atoms defined in the preceding paragraph is particularly valid when the groups R, R ¹ and R ² are saturated, linear or branched groups, and in particular when they are saturated and branched groups.

When the compounds of formula (I) have linear chains, the groups R ¹ and R ² are typically saturated groups, generally identical, and comprising from 2 to 5 carbon atoms, and advantageously 3 or 4 carbon atoms. In this case, the saturated group R generally contains from 1 to 8 carbon atoms, for example between 2 and 7, in particular between 2 and 6, with a total number of carbon in the compound of formula (I) which may be between 10 and 16, for example between 10 and 12 or between 12 and 14.

The compounds of formula (I) moreover preferably have a molecular mass of between 180 g / mol and 280 g / mol, more advantageously between 190 g / mol and 275 g / mol, even more advantageously between 200 g / mol and 265 g / mol.

The compounds of formula (I) appear to be volatile in most hydrocarbon binders and in particular in bitumen, that is to say that over time they will evaporate from the bituminous compositions comprising them, thus allowing a increase in cohesion of bituminous products based on said bituminous compositions.

R ′ advantageously represents a hydrogen atom or a methyl group or an ethyl group.

The groups R ¹ and R ² , which may be identical or different, advantageously represent an alkyl, aryl, alkyaryl or arylalkyl group, linear or branched, cyclic or non-cyclic, saturated or unsaturated and most often saturated, in C2-C11, typically in C ₂ -C ₉ .

The groups R ¹ and R ² , which may be identical or different, can in particular be chosen from ethyl, n-propyl, isopropyl, benzyl, phenyl, n-butyl, isobutyl, n-pentyl, isoamyl, cyclohexyl, hexyl, n-hexyl groups. , heptyle, isooctyle, 2-ethylhexyle, 2-propylhexyle.

R ¹ and R ² each advantageously contain from 2 to 5 carbon atoms, for example from 3 to 5 carbon atoms. Typically (in particular for reasons of ease of synthesis) R ¹ and R ² are identical and are chosen from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isoamyl, in particular isobutyl groups.

The group R advantageously represents alkanediyl radical Ci-Ci ₀ linear or branched alkenediyl radical C2-C10 linear or branched, or an alkoxylated chain, especially ethoxylated and / or propoxylated C2-C10.

Use may be made, as compounds of formula (I), of compounds in which R is as defined in one of the following modes, or a mixture of compound (s) according to these embodiments:

Mode 1: R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 8 inclusive. In particular, R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive.

Preferably, R is chosen so that the compound can be a mixture of adipate derivative (r = 4), glutarate derivative (r = 3), and succinate derivative (r = 2).

Mode 2: R is a branched C3-C10 alkanediyl radical. R can in particular be a C ₃ C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C _{9 group} , or a mixture. It is preferably a C _{4 group} .

The group R is preferably chosen from the following groups:

the group R _M g of formula -CH (CH ₃ ) -CH2-CH2-,

- the group R _E s of formula -CH (C ₂ H ₅ ) -CH ₂ -, and

- their mixtures.

Such mixtures, as well as suitable production methods, are in particular described in documents WO 2007/101929; WO 2007/141404; WO 2008/009792; WO 2008/062058.

Mode 3: R is a linear or branched C ₂ -C ₈ alkenediyl radical, advantageously C ₂ C ₄ .

The group R is preferably chosen from the following groups:

- the group of formula -CH = CH-, the double bond being of configuration Z

- the group of formula -CH = CH-, the double bond being of configuration E

- the group of formula -CH (CH ₂ ) -CH2-, and

- their mixtures.

Mode 4: R is a radical - (OE / OP) _n - where OE / OP are alkoxy groups, preferably chosen from ethoxy, propoxy groups and ethoxy / propoxy mixtures and n an average number between 1 and 5 inclusive and with a total carbon number of 10 in group R.

In particular in the above modes 1 to 4, X and Y are advantageously esters, preferably esters of diacids (-X- = -O- (C = O) -; and Y = - (C = O) -O- ) or diol esters (-X- = - (C = O) -O- and Y = -O- (C = O) -)

Advantageously,

R ¹ and R ² are the same or different and are each chosen from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isoamyl, hexyl, nhexyl, isooctyl, 2-ethylhexyl, 2-propylhexyl groups; in particular isobutyl;

X and Y are advantageously esters, preferably esters of diacids (X- = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols (- X- = - (C = O) -O- and -Y- = -O- (C = O) -)

R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. Preferably, R is chosen so that the compound can be a mixture of adipate diesters (r = 4), glutarate diesters (r = 3), and succinate diesters (r = 2).

Advantageously, the compound (I) used in the present invention is chosen from diisobutyl adipate, diisobutyl glutarate or diisobutyl succinate, and mixtures thereof.

A suitable mixture can for example comprise, by weight relative to the total weight of the mixture, a mixture of 5 to 29% by weight of diisobutyl adipate (typically measured by gas chromatography), from 50 to 72% by weight of diisobutyl glutarate , and from 10 to 32% by weight of diisobutyl succinate.

Use may be made, as compound (I), of the solvent sold by Solvay under the name Rhodiasolv® DIB.

Compound of formula (II)

A compound corresponding to formula (II) can be used in the invention

Fri-XRYR ² (II) where:

R ¹ and R ² , identical or different, are linear or branched hydrocarbon chains, of C1-C12, preferably of C1-C10; and where at least one of R ¹ , R ² is a methyl radical

-X- and -Y-, -R- are as defined for formula (I).

It is noted that according to a variant of the invention, the compound of formula (II) can be in the form of a mixture of different compounds of formula (II). In the application, unless explicitly mentioned in the presence of at least two compounds, a compound may denote a single compound corresponding to formula (II) or a mixture or a combination of several compounds corresponding to formula (II).

The compounds of formula (II) advantageously have a molecular mass of between 130 g / mol and 290 g / mol, more advantageously between 140 g / mol and 250 g / mol, even more advantageously between 150 g / mol and 200 g / mol.

In the compounds of formula (II) used according to the invention, the total number of carbon atoms is preferably between 5 and 12. According to one embodiment, the total number of carbon atoms is greater than or equal to 6 Furthermore, it is generally preferred that the total number of carbon atoms is less than or equal to 11, for example less than or equal to 10. Thus, for example, the total number of carbon atoms can be between 6 and 11, for example between 6 and 8.

The total number of carbon atoms defined in the previous paragraph is particularly valid when the groups R, R ¹ and R ² are saturated, linear or branched groups

-X- and -Y-, -R- are as defined for formula (I), including the various variants.

The groups R ¹ and R ² , identical or different, advantageously represent an alkyl, aryl, alkyaryl or arylalkyl group, linear or branched, cyclic or non-cyclic, saturated or unsaturated and most often saturated, in Ci-Cn, typically in C1-C9. At least one of R ¹ , R ² is a methyl radical.

The groups R ¹ and R ² , which may be identical or different, can in particular be chosen from the methyl, ethyl, n-propyl, isopropyl, benzyl, phenyl, n-butyl, isobutyl, n-pentyl, isoamyl, cyclohexyl, hexyl, n groups. -hexyle, heptyle, isooctyle, 2-ethylhexyle, 2-propylhexyle. At least one of R ¹ , R ² is a methyl radical.

Advantageously, R ¹ , R ² both represent a methyl radical.

A compound of formula (II) according to the invention can for example be chosen from dimethyl adipate, dimethyl glutarate, dimethyl succinate, and mixtures thereof.

A suitable mixture can for example comprise, by weight relative to the total weight of the mixture, a mixture of dimethyl adipate (for example from 4 to 22% by weight, by gas chromatography), of dimethyl glutarate (for example from 55 to 77% by weight), and dimethyl succinate (for example from 12 to 32% by weight).

As solvent (II), the solvent sold by Solvay under the name Rhodiasolv® RPDE can be used.

Another possible compound of formula (II), which can be used alone or as a mixture with the previous one, is a compound for which R ¹ and R ² both represent a methyl radical and the group R is chosen from the following groups:

- the group R _M g of formula -CH (CH ₃ ) -CH ₂ -CH ₂ -,

- the group R _E s of formula -CH (C ₂ H ₅ ) -CH ₂ -, and

- their mixtures.

-X- and -Y- are advantageously esters, preferably esters of diacids (-X- = -O- (C = O) -; and -Y- = - (C = O) -O-) or diol esters (-X- = - (C = O) -O- and -Y- = -O- (C = O) -).

As solvent (II), the solvent sold by Solvay under the name Rhodiasolv® IRIS can be used.

Bituminous products

By “bituminous product” in the present invention is meant a product based on a hydrocarbon binder and inorganic solid particles. Mention may in particular be made of coatings, emulsion mixes, storable mixes, hot mixes, warm mixes with controlled workability which are described in more detail below.

Bituminous products may contain significant contents (ranging from 0% to 100% by weight, advantageously from 20% to 50% by weight, relative to the total weight) of recycling products (asphalt product aggregates, asphalt aggregates) .

Coatings

A surface coating, within the meaning of the present description, designates a layer consisting of superposed layers of a hydrocarbon binder and of solid mineral particles. It is typically obtained by spraying a hydrocarbon binder and then spreading on this binder mineral solid particles, in one or more layers. The whole is then compacted. A surface coating requires not only a binder which is sufficiently fluid to be able to be sprayed but also a binder which allows good bonding of the solid mineral particles on the support.

Thus, the flux added to the binder must make it possible to soften it without penalizing the wetting of the solid mineral particles by the binder. In addition, the fluxing agent must make it possible to soften the binder during its spraying, but once sprayed the binder must harden quickly to also meet the criterion of increase in cohesion. If the binder does not properly wet the solid mineral particles, the adhesion of this binder on these particles will not be satisfactory or even unacceptable.

The binder - mineral solid particles affinity is determined by the possibility of wetting the mineral solid particles with the binder, which is assessed by means of the test for determining the adhesiveness of binders-aggregates by measuring the cohesion Vialit (NF EN 12272-3, 2003-07-01).

It has been discovered that the compounds of formula (I) make it possible to effectively flux the binder, with a satisfactory increase in cohesion, without penalizing the affinity binder - mineral solid particles.

The compound or compounds of formula (I) are advantageously added in full to the composition comprising the hydrocarbon binder then the composition comprising the hydrocarbon binder and the compound or compounds of formula (I) is sprayed onto the mineral solid particles before complete evaporation of the compound of formula (I) outside the composition. In other words, said compound of formula (I) is still present at least in part when the fluxed binder is brought into contact with the solid mineral particles, preferably in an amount sufficient in the composition to allow good adhesion of the binding to solid mineral particles.

In an embodiment adapted to coatings, in formula (I)

R ¹ and R ² are identical and are each chosen from the groups ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl, 2-propylhexyl, in particular isobutyl;

X and Y are advantageously esters, preferably esters of diacids (X- = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols (- X- = - (C = O) -O- and -Y- = -O- (C = O) -)

R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. Preferably, R is chosen so that the compound can be a mixture of adipate diesters (r = 4), glutarate diesters (r = 3), and succinate diesters (r = 2).

Advantageously, the compound (I) used in a coating is diisobutyl adipate, diisobutyl glutarate or diisobutyl succinate, and their mixtures.

A suitable mixture can for example comprise, by weight relative to the total weight of the mixture, a mixture of 5 to 29% by weight of diisobutyl adipate (typically measured by gas chromatography), from 50 to 72% by weight of diisobutyl glutarate , and from 10 to 32% by weight of diisobutyl succinate

Use may be made, as compound (I), of the solvent sold by Solvay under the name Rhodiasolv® DIB.

The solid mineral particles used in a coating advantageously belong to the following granular classes (d / D): 4 / 6.3, 6.3 / 10, 10/14.

The total content of hydrocarbon binder in a coating will be adapted according to the structure of the coating (mono- or bi-layer, type of gravel), the nature of the binder and the size of the aggregates, by following for example the recommendations of the document "Surface wear plasters - Technical guide, May 1995".

The hydrocarbon binder used for the manufacture of a coating may be in the form of an anhydrous binder or in the form of an emulsion binder.

In one embodiment, the hydrocarbon binder is used in the form of an anhydrous binder during the manufacture of the coating. In this mode, the hydrocarbon binder advantageously comprises, relative to the total weight of the hydrocarbon binder, from 3% to 18% by weight of said compound of formula (I).

In one embodiment, the hydrocarbon binder is an emulsion binder. In this mode, the hydrocarbon binder advantageously comprises, relative to the total weight of the hydrocarbon binder, 0.1 to 10% by weight of said compound of formula (I), more advantageously 0.5 to 8% by weight, even more advantageously 1 at 6% by weight.

Bituminous concrete with emulsion

Bituminous emulsion concretes, also called emulsion mixes, are hydrocarbon mixes produced cold from aggregates and a hydrocarbon binder in emulsion. The aggregates can be used without drying and prior heating or undergo partial hot pre-lacquering. It may sometimes be necessary to reheat the product after its manufacture, during its implementation.

This technique, called cold technique, has the important environmental advantage of not producing smoke emissions, which reduces the nuisance of workers and residents. Bituminous emulsion concretes consist of a mixture of solid mineral particles including aggregates, bitumen emulsion (modified or not), and additives.

However, the quality of the coating can be poor, with the observation of a coating phenomenon: poor distribution of the bitumen film over the entire granular fraction, all the more so as the fluxing or fluidifying content is high. . The more fines the granular fraction contains, the worse the distribution of the binder on the granular fraction (mainly on large elements).

To remedy or limit these problems of loss of compactability and poor distribution of the bitumen film over the entire granular fraction, the step of mixing the granular fractions and the binder, possibly of the fluxing agent, can be sequenced. These sequenced processes involve more steps and therefore are less economical.

It has now been discovered that the compounds of formula (I) make it possible to effectively flux bituminous concretes in the emulsion. The invention can make it possible to dispense with the implementation of sequenced and / or reheating processes.

The compound or compounds of formula (I) is advantageously added to the composition comprising the hydrocarbon binder according to one and / or the other of the 3 variants described above on pages 4 and 5, and thus before and / or during and / or after contacting the binder and mineral solid particles. The compound (s) of formula (I) is introduced at the latest before using the bituminous concrete with the emulsion, and is present at least partly in the composition comprising the binder and the solid mineral particles to allow good adhesion.

In an embodiment suitable for bituminous concretes, the compound or compounds of formula (I) is introduced into the composition comprising the binder in emulsion, then said composition is brought into contact with solid mineral particles (variant 1).

In another embodiment suitable for bituminous concretes, part or all of the compound or compounds of formula (I) is introduced into a premix based on binder in emulsion and inorganic solid particles (variant 3). The resulting composition also comprises a sufficient amount of compound of formula (I) for using bituminous concrete in the emulsion.

In yet another embodiment suitable for bituminous concretes, in the formula (D

R ¹ and R ² are identical and are each chosen from the groups ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl, 2-propylhexyl in particular isobutyl;

X and Y are advantageously esters, preferably diacid esters (X- = -O- (C = O) -; and -Y- = - (C = O) -0-) or diol esters (- X- = - (C = O) -O- and -Y- = -O- (C = O) -)

R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. Preferably, R is chosen so that the compound can be a mixture of adipate diesters (r = 4), glutarate diesters (r = 3), and succinate diesters (r = 2).

Advantageously, the compound (I) used for bituminous concretes in the emulsion is diisobutyl adipate, diisobutyl glutarate or diisobutyl succinate, and their mixtures.

A suitable mixture can for example comprise, by weight relative to the total weight of the mixture, a mixture of 5 to 29% by weight of diisobutyl adipate (typically measured by gas chromatography), from 50 to 72% by weight of diisobutyl glutarate , and from 10 to 32% by weight of diisobutyl succinate.

Use may be made, as compound (I), of the solvent sold by Solvay under the name Rhodiasolv® DIB.

Advantageously, for a bituminous concrete in the emulsion, a compound of formula (II) of the aforementioned type is also added.

In a first embodiment suitable for bituminous concrete with emulsion, in formula (II):

R ¹ and R ² are identical and are each methyl;

X and Y are advantageously esters, preferably esters of diacids (X- = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols (- X- = - (C = O) -O- and -Y- = -O- (C = O) -)

R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. Preferably, R is chosen so that the compound can be a mixture of adipate diesters (r = 4), glutarate diesters (r = 3), and succinate diesters (r = 2).

Advantageously, the compound (II) used for the bituminous concretes in the emulsion is dimethyl adipate, dimethyl glutarate, dimethyl succinate, and their mixtures.

A suitable mixture can for example comprise, by weight relative to the total weight of the mixture, a mixture of 4 to 22% by weight of dimethyl adipate (typically measured by gas chromatography), from 55 to 77% by weight of dimethyl glutarate , and from 12 to 32% by weight of dimethyl succinate).

As solvent (I), the solvent sold by Solvay under the name Rhodiasolv® RPDE can be used.

In a second embodiment suitable for bituminous concrete with emulsion, in formula (II):

R ¹ and R ² are identical and are each methyl;

X and Y are advantageously esters, preferably esters of diacids (X- = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols (- X- = - (C = O) -O- and -Y- = -O- (C = O) -)

R is chosen from the following groups: o the group R _M g of formula -CH (CH ₃ ) -CH ₂ -CH ₂ -, o the group R _E s of formula -CH (C ₂ H ₅ ) -CH ₂ - , and o their mixtures.

In particular, the product sold by Solvay under the name of Rhodiasolv® IRIS can be used as the compound of formula (II) for bituminous concrete with an emulsion.

The solid mineral particles for bituminous concrete with emulsion advantageously comprise:

elements less than 0.063 mm (fHier or fine) of sand whose elements are between 0.063 mm and 2 mm;

gravel, the elements of which have dimensions ranging from 2 mm to 6, 10 or 14 mm.

The hydrocarbon binder used for the synthesis of bituminous concretes in the emulsion is in the form of binder in emulsion. The total content of hydrocarbon binder in said emulsion is typically from 2 to 8 ppc (part percent by weight), advantageously 3 to 7 ppc, more advantageously 3.5 to 5.5 ppc, relative to the weight of the solid mineral particles . This binder content corresponds to the quantity of binder introduced as such (filler binder) plus the quantity of binder recovered from the asphalt aggregates forming part of the solid mineral fraction.

The hydrocarbon binder in an emulsion used for making bituminous concrete with the emulsion advantageously comprises, relative to the total weight of the hydrocarbon binder, 1 to 25% by weight of said compound of formula (I), more advantageously 2 to 15 % by weight, even more advantageously 3 to 10% by weight. These contents are calculated whether the compound of formula (I) is actually added to the binder before being brought into contact with mineral solid particles or whether it is added to the composition comprising the binder and the mineral solid particles.

The hydrocarbon binder in an emulsion used for making bituminous concrete with the emulsion may optionally comprise a compound of formula (II), advantageously 0.1 to 5% by weight of said compound of formula (II), relative to the total weight of the hydrocarbon binder. These contents are calculated whether the compound of formula (II) is actually added to the binder before being brought into contact with mineral solid particles or whether it is added to the composition comprising the binder and the mineral solid particles.

The bituminous concretes obtained according to the invention with the emulsion can be used for the production of storable mixes.

In this embodiment, the hydrocarbon binder advantageously comprises, relative to the total weight of the hydrocarbon binder, 10 to 30% by weight of said compound of formula (I), more advantageously 15 to 25% by weight, even more advantageously 17 to 22 % in weight.

Cold-poured bituminous materials

Cold-poured bituminous materials are asphalt mixes for surface layers made up of undried aggregates coated with bitumen emulsion and continuously poured in place using specific equipment.

After its implementation and rupture of the emulsion, this cold-cast coating in very small thickness (generally 6 to 13 mm thick per layer) must reach its final consistency (increased in cohesion) very quickly. The two essential parameters governing the formulation, manufacture and use of cold-cast bituminous materials are:

- the workability of the aggregates / emulsion mixture: optimization of the proportions of the various constituents (water, additives, formulation of the emulsion) to obtain sufficient processing time and thus allow the aggregates to be mixed with the emulsion in the mixer.

- the kinetics of cohesion rise: the cold-poured bituminous material, after application on the road, must acquire a cohesion rise as quickly as possible for the opening to traffic. For ripening temperatures ranging from 7 to 40 ° C., a period of 30 minutes is considered relevant for those skilled in the art to meet the most stringent specifications.

It has been discovered that the compounds of formula (I) make it possible to efficiently flow cold-poured bituminous materials.

In an embodiment suitable for cold-poured bituminous materials, the compound or compounds of formula (I) is introduced into the composition comprising the emulsion binder (in practice, the compound or compounds of formula (I) is typically introduced into the binder then the binder is emulsified in a continuous aqueous phase), then said composition is brought into contact with solid mineral particles (variant 1)

In an embodiment suitable for cold-poured bituminous materials, in formula (I)

R ¹ and R ² are identical and are each chosen from the groups ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, isoamyl, isobutyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl, 2-propylhexyl in particular isobutyl;

X and Y are advantageously esters, preferably esters of diacids (X- = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols (- X- = - (C = O) -O- and -Y- = -O- (C = O) -)

R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. Preferably, R is chosen so that the compound can be a mixture of adipate diesters (r = 4), glutarate diesters (r = 3), and succinate diesters (r = 2).

Advantageously, for cold-poured bituminous materials, the compound (I) used in the present invention is diisobutyl adipate, diisobutyl glutarate or diisobutyl succinate, and mixtures thereof.

A suitable mixture can for example comprise, by weight relative to the total weight of the mixture, a mixture of 5 to 29% by weight of diisobutyl adipate (typically measured by gas chromatography), from 50 to 72% by weight of diisobutyl glutarate , and from 10 to 32% by weight of diisobutyl succinate.

Use may be made, as compound (I), of the solvent sold by Solvay under the name Rhodiasolv® DIB.

Advantageously, for a cold-poured bituminous material, a compound of formula (II) is also added.

In a first embodiment, in formula (II):

R ¹ and R ² are identical and are each methyl;

X and Y are advantageously esters, preferably esters of diacids (X- = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols (- X- = - (C = O) -O- and -Y- = -O- (C = O) -)

R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. Preferably, R is chosen so that the compound can be a mixture of adipate diesters (r = 4), glutarate diesters (r = 3), and succinate diesters (r = 2).

Advantageously, the compound (II) used for cold-poured bituminous materials is dimethyl adipate, dimethyl glutarate, dimethyl succinate, and their mixtures.

A suitable mixture can for example comprise, by weight relative to the total weight of the mixture, a mixture of 4 to 22% by weight of dimethyl adipate (typically measured by gas chromatography), from 55 to 77% by weight of dimethyl glutarate , and from 12 to 32% by weight of dimethyl succinate.

As solvent (II), the solvent sold by Solvay under the name Rhodiasolv® RPDE can be used.

In a second embodiment suitable for cold-poured bituminous materials, in formula (II):

R ¹ and R ² are identical and are each methyl;

X and Y are advantageously esters, preferably diacid esters (X- = -O- (C = O) -; and -Y- = - (C = O) -0-) or diol esters (- X- = - (C = O) -O- and -Y- = -O- (C = O) -)

R is chosen from the following groups:

o the group R _M g of formula -CH (CH ₃ ) -CH ₂ -CH ₂ -, o the group R _E s of formula -CH (C ₂ H ₅ ) -CH ₂ -, and o their mixtures.

In particular, a compound of formula (II) suitable for cold-poured bituminous materials is the product sold by Solvay under the name Rhodiasolv® IRIS.

The solid mineral particles used for cold-poured bituminous materials advantageously include:

elements less than 0.063 mm (filler or fines) of sand whose elements are between 0.063 mm and 2 mm;

o gravel, the elements of which have dimensions ranging from 2 mm to 6, 10 or 14 mm.

The hydrocarbon binder used for the manufacture of cold-cast bituminous materials is in the form of an emulsion binder.

In this emulsion, the content of binder advantageously varies from 50 to 75% by weight of binder, relative to the total weight of the emulsion, more advantageously from 55 to 70% by weight, even more advantageously from 60 to 65% by weight .

The hydrocarbon binder suitable for cold-poured bituminous materials advantageously comprises, relative to the total weight of the hydrocarbon binder, 0.1 to 6% by weight of said compound of formula (I), more advantageously 0.1 to 3% by weight of said compound of formula (I).

The hydrocarbon binder suitable for cold-poured bituminous materials advantageously comprises, relative to the total weight of the hydrocarbon binder, 0.1 to 3% by weight of said compound of formula (II).

Hot or warm asphalt mixes

Hot bituminous mixes are obtained by hot mixing of aggregates and a binder. This binder can be a pure or modified bitumen (addition for example of polymer (s), fluxes of petroleum or vegetable origin), a pure or modified vegetable binder or a synthetic binder of petroleum origin. The aggregates are heated, as a rule at a temperature above 100 ° C.

Warm asphalt mixes are mixes used at temperatures of around 30 to 50 ° C lower than the temperatures used for hot mixes.

It has been discovered that the compounds of formula (I) make it possible to efficiently flux hot or warm hydrocarbon mixes, with a satisfactory increase in cohesion, and good wettability of the solid mineral particles.

The compound or compounds of formula (I) is advantageously added to the composition comprising the hydrocarbon binder according to one and / or the other of the 3 variants described above on pages 4 and 5, and thus before and / or during and / or after contacting the binder and mineral solid particles. The compound (s) of formula (I) is introduced at the latest before using hot or warm hydrocarbon mixes, and is present at least partly in the composition comprising the binder and the solid mineral particles to allow good adhesion.

In a suitable embodiment, the compound or compounds of formula (I) is introduced into the composition comprising the binder, then said composition is brought into contact with solid mineral particles (variant 1).

In one embodiment, suitable for hot or warm asphalt mixes, in formula (I)

R ¹ and R ² are identical and are each chosen from the groups ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl, 2-propylhexyl in particular isobutyl;

X and Y are advantageously esters, preferably esters of diacids (X- = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols (- X- = - (C = O) -O- and -Y- = -O- (C = O) -)

R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. Preferably, R is chosen so that the compound can be a mixture of adipate diesters (r = 4), glutarate diesters (r = 3), and succinate diesters (r = 2).

Advantageously, the compound (I) used in the present invention is diisobutyl adipate, diisobutyl glutarate or diisobutyl succinate, and mixtures thereof.

A suitable mixture can for example comprise, by weight relative to the total weight of the mixture, a mixture of 5 to 29% by weight of diisobutyl adipate (typically measured by

Gas Chromatography), from 50 to 72% by weight of diisobutyl glutarate, and from 10 to 32% by weight of diisobutyl succinate.

As solvent (I), the solvent sold by Solvay under the name Rhodiasolv® DIB can be used

Advantageously, for hot asphalt mixes, a compound of formula (II) of the above type is also added.

In a first embodiment suitable for hot bituminous mixes, in formula (II):

R ¹ and R ² are identical and are each methyl;

X and Y are advantageously esters, preferably esters of diacids (X- = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols (- X- = - (C = O) -O- and -Y- = -O- (C = O) -)

R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. Preferably, R is chosen so that the compound can be a mixture of adipate diesters (r = 4), glutarate diesters (r = 3), and succinate diesters (r = 2).

Advantageously, the compound (II) used for hot bituminous mixes is dimethyl adipate, dimethyl glutarate, dimethyl succinate, and their mixtures.

A suitable mixture can for example comprise, by weight relative to the total weight of the mixture, a mixture of 4 to 22% by weight of dimethyl adipate (typically measured by gas chromatography), from 55 to 77% by weight of dimethyl glutarate , and from 12 to 32% by weight of dimethyl succinate.

As solvent (II), the solvent sold by Solvay under the name Rhodiasolv® RPDE can be used.

In a second embodiment suitable for hot bituminous mixes, in formula (II):

R ¹ and R ² are identical and are each methyl;

X and Y are advantageously esters, preferably diacid esters (X- = -O- (C = O) -; and -Y- = - (C = O) -0-) or diol esters (- X- = - (C = O) -O- and -Y- = -O- (C = O) -)

R is chosen from the following groups: o the group R _M g of formula -CH (CH3) -CH ₂ -CH ₂ -, o the group R _E s of formula -CH (C ₂ H ₅ ) -CH ₂ -, and o their mixtures.

In particular, the product sold by Solvay under the name Rhodiasolv® IRIS can be used as the compound of formula (II) for hot hydrocarbon mixes.

The mineral solid particles are as defined above and advantageously comprise:

elements less than 0.063 mm (fHier or fine) of sand whose elements are between 0.063 mm and 2 mm;

o gravel, the elements of which have dimensions ranging from 2 mm to 6, 10 or 14 mm.

The hydrocarbon binder is in the anhydrous form.

The total content of hydrocarbon binder is 3 to 7 ppc (part weight percent), advantageously 3.5 to 6 ppc relative to the weight of the solid mineral particles.

This binder content corresponds to the quantity of binder introduced as such (filler binder) plus the quantity of binder recovered from the asphalt aggregates forming part of the solid mineral fraction.

For hot or warm hydrocarbon mixes, the hydrocarbon binder advantageously comprises, relative to the total weight of the hydrocarbon binder, 1 to 30% by weight of said compound of formula (I).

For hot bituminous mixes, the hydrocarbon binder can also advantageously comprise, relative to the total weight of the hydrocarbon binder, 1 to 30% by weight of said compound of formula (II).

The fluxing content is adjusted as a function of the time between manufacture and implementation.

When hot or warm hydrocarbon mixes are used quickly after manufacture, for example for the manufacture of wearing courses, the hydrocarbon binder advantageously comprises, with respect to the total weight of the hydrocarbon binder, 0.1 to 6% by weight of said compound. formula (I).

When hot bituminous mixes are used quickly after manufacture, for example for the manufacture of wearing courses, the hydrocarbon binder may also comprise, relative to the total weight of the hydrocarbon binder, 0.1 to 6% by weight of said compound of formula (II).

These hot or warm hydrocarbon mixes can be used for the production of storable mixes.

In this embodiment, the hydrocarbon binder advantageously comprises, relative to the total weight of the hydrocarbon binder, 15 to 30% by weight of said compound of formula (I), more advantageously 15 to 25% by weight, even more advantageously 17 to 22% in weight.

For hot bituminous mixes, the hydrocarbon binder can also comprise, relative to the total weight of the hydrocarbon binder, 15 to 30% by weight of said compound of formula (II), more advantageously 15 to 25% by weight, even more advantageously 17 at 22% by weight.

EXAMPLES

Description of test methods:

Stabilization of fluxed binders: This is a method of obtaining a thin layer of binder. Stabilization is carried out according to standard NF EN 13074 1,2 (April 2011) by leaving the bitumen fluxed for 24 hours at laboratory temperature then transferred to a ventilated oven for 24 hours at 50 ° C, and finally 24 hours at 80 ° C in order to to allow the fluxing agent to evaporate.

STV pseudo-viscosity: This is a method of measuring the viscosity of a bitumen fluxed by determining the flow time of the product at 40 ° C or 50 ° C through a 10mm orifice. The pseudo-viscosity STV is measured according to standard NF EN 12846-2 (April 2011).

Penetration: Penetration corresponds to the consistency expressed as the depth, in tenths of a millimeter, corresponding to the vertical penetration of a reference needle in a test sample of the material, under prescribed conditions of temperature, load and duration of application of the load. The penetration test is carried out according to standard NF EN 1426 (June 2007). In the examples, the measurements were carried out at 25 ° C., for a load of 100 g and a duration of 5 s.

Ball-ring temperature: This is the temperature at which the binder reaches a precise consistency under the reference conditions of the test. Two horizontal bitumen discs, molded in shoulder brass rings, are heated in a stirred liquid (water) bath with a controlled temperature rise rate (5 ° C / min, initial bath temperature of (5 ± 1) ° C), while each supports a steel ball. The softening point noted must correspond to the average of the temperatures at which the two discs soften enough to allow each ball, wrapped in bituminous binder, to descend from a height of (25,0 ± 0.4) mm. The measurement is carried out according to standard NF EN 1427 (June 2007). FRAASS point of weakness: This test consists in measuring the temperature at which cracks appear on a film spread on a blade subjected to successive bending. The higher the FRAASS point, the more fragile the bitumen. The measurement is carried out according to standard NF EN 12593 (August 2015).

Weight loss after stabilization: Weight loss after stabilization is measured as the mass difference between the binder deposited at the start of the stabilization procedure and the mass of binder actually measured after the stabilization step (standard NF EN 13074 1 , 2, April 2011)

Evaporation curves (thermobalance): This is a measure of the mass loss of a bitumen fluxed as a function of time at a fixed temperature of 85 ° C. The test is carried out using a thermobalance and makes it possible to evaluate the kinetics of evaporation of a fluxing agent.

Adhesiveness: This is a method for determining the adhesion of binder aggregates and the influence of additives on the characteristics of this adhesiveness (Standard NF EN 12272-3, July 2003). The quantity of binder required is heated to the spreading temperature, then applied uniformly to a steel plate. The test is carried out at (5 ± 1) ° C. 100 calibrated gravel are distributed over the binder, then cylindrical. The plate thus prepared is turned over and then placed on a support with three points. A steel ball falls on the plate from a height of 500 mm, three times in 10 s.

Description of the compounds tested:

The following compounds have been tested:

Compounds of formula (I): Rhodiasolv® DIB. This compound is called "DIB" in the tables which follow.

Compounds of formula (II):

1. Rhodiasolv® RPDE. This compound is called “RPDE” in the tables which follow.

2. Rhodiasolv® IRIS. This compound is called "IRIS" in the tables which follow.

The physico-chemical properties of these compounds are reported in the following table:

Mw (g / mol) Voltage of steam (Pa) Flash point in closed cup (° C) Density at 20 ° C (g / cm ³ ) Interval boiling point (° C) RPDE 159 9.4 99 1.0915 195 - 216 IRIS 174 6.3 98 1.055 215 DIB 244 0.4 134 0.959 250 - 285

Table 1

Description of the figures:

Figure 1: mass percentage loss of volatile compound (Rhodiasolv® RPDE (solid line),

Rhodiasolv® DIB (dotted line) and Greenflux® SD (broken line - dashes)) as a function of time at 85 ° C in the binder of Example 1

Figure 2: mass percentage loss of volatile compound (Rhodiasolv® RPDE (solid line), Rhodiasolv® DIB (dotted line) and Greenflux® SD (broken line - dashes)) as a function of time at 85 ° C in the binder 'example 2

Figure 3: mass percentage loss of volatile compound (Rhodiasolv® DIB (dotted line) and Rhodiasolv® IRIS (broken line - dashes / dots)) as a function of time at 85 ° C in the binder of Example 3

Example 1: fluxed binders for surface coatings

The following binders are prepared:

T0 Cl C2 L1 bitumen Provider ESSO Grade 70/100 fluxing Last name - Oil (1) RPDE DIB Content (% by weight relative to binder weight) 0 6.2 4.5 6.2 Dope of membership Last name - Impact 9000 (2) Content (% by weight relative to binder weight) 0 0.3 0.3 0.3

Table 2 (1) Greenflux® SD marketed by TOTAL (2) tall oil fatty amides, N - [(dimethylamino) -3propyl] marketed by INGEVITY

The TO binder is a non-fluxed binder, which serves as a control allowing the performance of the binder according to the invention to be compared with the binder without addition of compound according to the invention. Binders C1 and C2 are fluxed binders, which serve as comparative examples. The binder L1 is a binder according to the invention.

The properties of the binders before / after stabilization and the results of adhesiveness of the binders to the aggregates are reported in the following table:

T0 Cl C2 L1 Before stabilization Pseudo-viscosity STV 40 ° C, 10mm, s - 440 484 459 Penetration at 25 ° C, 1/10 mm 78 - - - Ball-Ring temperature, ° C 46.2 - - - After stabilization Weight loss after stabilization - 3.0% 3.9% 4.9% Penetration at 25 ° C, 1/10 mm - 124 62 92 Ball-Ring temperature, ° C - 43.0 51.0 45.4 Adhesion to the Vialit plate 5 ° C + viadop PX10051 40 g / m ² Aggregates 6/10 La Meilleraie - washed dry Fallen not stained - 7 8 5 Fallen stained - 39 90 42 Glued to the plate - 54 2 53

Table 3

Stabilization of fluxed bitumens is carried out according to the protocol described in standard NF EN 13074 1,2 (April 2011). All the tests are carried out according to the protocols described in the standards cited in references and explained above.

It is found that the binder according to the invention makes it possible to obtain satisfactory results in terms of adhesiveness and fluxing (seen through the viscosity).

In addition, the binder according to the invention regains its properties before fluxing, seen through the penetrability and the ball-ring temperature.

These results show that the binder according to the invention makes it possible to obtain hard surface coatings in a short time, which allows rapid re-traffic.

By way of comparison, it should be noted that Rhodiasolv® RPDE which does not correspond to formula (I), although it is a volatile compound, does not make it possible to obtain suitable adhesiveness. In fact, only 2% of the aggregates remain stuck to the plate. The binder C2 does not have a consistency allowing it to properly wet the aggregates.

The evaporation curves (mass loss of fluxing agent as a function of time) for the binders C 1, C2 and L1 without stabilization are reproduced in FIG. 1. It can be seen that the kinetics of evaporation of the binders Cl and L1 are similar whereas in the binder C2, the flux evaporated very quickly.

EXAMPLE 2 Binders-Fluxed Polymers for Surface Coatings

The following binders are prepared:

C3 C4 L2 Bitumen polymer Provider Eurovia (1) Grade bitumen 50/70 comprising 3% by weight, per based on total weight, of SBS polymer linear, cross-linked by sulfur fluxing Last name Oil (2) RPDE DIB Content (% by weight per relative to the weight of the binder) 15.0 12.0 13.5 Dope of membership Last name Impact 9000 (3) Content (% by weight per relative to the weight of the binder) 0.3 0.3 0.3

Table 4 (1) this binder has a cohesion greater than or equal to 1.3 J / cm ² as measured according to standard NF EN 13588 of July 2008 after stabilization according to standards NF EN 13074-1 and 13074-2 (2) Greenflux® SD marketed by TOTAL (3) tall oil fatty amides, N - [(dimethylamino) -3propyl] marketed by INGEVITY

Binders C3 and C4 are fluxed polymer binders, which serve as comparative examples. The binder L2 is a binder according to the invention.

The properties of the binders before / after stabilizations are given in the following table:

C3 C4 L2 Specifications (EN 15332, August 2013) Before stabilization Pseudo-viscosity STV 50 ° C, 10mm, s 83 82 84 After stabilization Weight loss after stabilization 11.0% 11.1% 10.2% Penetration at 25 ° C, 1/10 mm 114 46 119 <120 Ball-Ring temperature, ° C 51.2 60.8 49.5 > 49 FRAASS point of weakness, ° C - - -18 <-15

Table 5

Stabilization of fluxed bitumens is carried out according to the protocol described in standard NF EN 13074 1,2 (April 2011). All the tests are carried out according to the protocols described in the standards cited in references and explained above.

It can be seen that even for strongly modified binders, the evaporation of the flux is suitable and makes it possible to obtain stabilized binders meeting the specifications according to the standard.

EN 15322 of August 2013.

The evaporation curves (mass loss of fluxing agent as a function of time) for the binders C 3, C4 and L2 without stabilization are shown in FIG. 2. It can be seen that the kinetics of evaporation of the binders C3 and L2 are similar whereas in the binder C4, the flux evaporated very quickly.

EXAMPLE 3 Binders-Fluxed Polymers for Surface Coatings

The following binders are prepared:

C5 L3 bitumen Provider Eurovia (1) Grade bitumen 70/100 comprising 3% by weight, per based on total weight, of SBS polymer linear, cross-linked by sulfur fluxing Last name IRIS DIB Content (% by weight per relative to the weight of the binder) 7.0 8.02 Dope of membership Last name Impact 9000 (1) Content (% by weight per relative to the weight of the binder) 0.3 0.3

Table 6 (1) this binder has a cohesion greater than or equal to 1 J / cm ² as measured according to standard NF EN 13588 of July 2008 after stabilization according to standards NF EN 13074-1 and

13074-2 (2) tall oil fatty amides, N - [(dimethylamino) -3propyl] marketed by INGEVITY

The binder C5 is a fluxed polymer binder, which serves as a comparative example. The binder L3 is a binder according to the invention.

The properties of the binders before / after stabilization and the results of adhesiveness of the binders to the aggregates are reported in the following table:

C5 L3 Specifications EN 15322, August 2013 Before stabilization Pseudo-viscosity STV 40 ° C, 10mm, s 379 367 250 - 500 After stabilization Weight loss after stabilization 5.8% 5.9% Penetration at 25 ° C, 1/10 mm 62 84 <150 Ball-Ring temperature, ° C 50.4 48.4 > 43 FRAASS point of weakness, ° C -13 -15 <-14 (own specifications) Adhesion to the Vialit plate 5 ° C + viadop PX10051 40 g / m ² ESCHAU 6/10 aggregates - dry washed Fallen not stained 63 11 Fallen stained 37 20 Glued to the plate 0 69

Table 7

Stabilization of fluxed bitumens is carried out according to the protocol described in standard NF EN 13074 1,2 (April 2011). All the tests are carried out according to the protocols described in the standards cited in references and explained above.

It is found that the binder according to the invention makes it possible to obtain satisfactory results in terms of adhesiveness and fluxing (seen through the viscosity). In addition, the binder according to the invention has properties of penetrability, ball-ring temperature and FRAASS point of fragility in accordance with the specifications. These results show that the binder modified according to the invention makes it possible to obtain hard surface coatings in a short time, which enables rapid re-traffic.

By way of comparison, it should be noted that Rhodiasolv® IRIS, which does not correspond to formula (I), although it is a volatile compound, does not make it possible to obtain suitable adhesiveness. In fact, no aggregates remain stuck to the plate and 63% of the aggregates fall unstained. The binder C5 does not have a consistency allowing it to properly wet the aggregates. However, if we compare the evaporation curves for C5 and L3, the IRIS and DIB compounds have similar behaviors (Figure 3). These results show that the evaporation curve of the compounds in the bitumen is not the only parameter which makes it possible to choose a fluxing agent which makes it possible to achieve the objectives of the invention.

Claims (15)

1. Use as fluxing agent of at least one compound corresponding to formula (I) R ^ xRYR ² (I) where: R ¹ and R ² , identical or different, are hydrocarbon chains, linear or branched, in C2-C11; each of -X- and -Y-, identical or different, is a group -O- (C = O) -; - (C = O) -O-; -NR '- (C = O) - with R' representing a hydrogen atom or an alkyl radical CiC _4, or - (C = O) -NR'- with R 'representing a hydrogen atom or a radical C1-C4 alkyl, the group -R- is a divalent hydrocarbon chain, C1-C10, linear or branched, and optionally interrupted by one or more oxygen atoms in a composition comprising a hydrocarbon binder for the preparation of a bituminous product based on mineral solid particles in contact with said hydrocarbon binder, wherein said compound of formula (I) is present in said composition when said composition is brought into contact with said mineral solid particles. 2. Use according to claim 1, characterized in that the compound of formula (I) is added to the composition comprising the hydrocarbon binder according to one and / or the other of the following 3 compatible variants: variant 1: the compound of formula (I) is added at least in part (if variant 2 and / or 3 is also used), or even entirely (if not), to the composition comprising the hydrocarbon binder, then the composition comprising the compound of formula (I) is brought into contact with the solid mineral particles before complete evaporation of the compound of formula (I) out of the composition, (in other words, said compound of formula (I) is still present at least partly in the composition when brought into contact with the solid mineral particles, preferably in an amount sufficient in the composition to ensure a fluxing role); and or variant 2: the compound of formula (I) is added at least in part (if variant 1 and / or 3 is also used), or even entirely (if not), at the same time as the solid mineral particles to the composition comprising the hydrocarbon binder; and or - variant 3: the compound of formula (I) is added at least in part (if variant 1 and / or 2 is also used), or even entirely (if not), to a premix containing the solid particles minerals and the composition comprising the hydrocarbon binder. 3. Use according to claim 1 or 2, characterized in that the composition also comprises a compound corresponding to the formula (II) fU-XRYR ² (II) where: R ¹ and R ² , identical or different, are hydrocarbon chains, linear or branched, Ci-Cu; and where at least one of R ¹ , R ² is a methyl radical -X- and -Y-, -R- are as defined for formula (I) in claim 1. 4. Use according to any one of the preceding claims, characterized in that the bituminous product is a surface coating. 5. Use according to claim 4, characterized in that in formula (I): - R ¹ and R ² are identical and are each chosen from ethyl, npropyl, isopropyl, n-butyl, isobutyl, n-pentyl, isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl, 2-propylhexyl groups; - X and Y are advantageously esters, preferably esters of diacids (-X = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols ( -X- = - (C = O) -O- and -Y- = -O (C = O) -) - R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. 6. Use according to any one of claims 1-3, characterized in that the bituminous product is a bituminous concrete with emulsion. 7. Use according to claim 6, characterized in that in formula (I): - R ¹ and R ² are identical and are each chosen from ethyl, npropyl, isopropyl, n-butyl, isobutyl, n-pentyl, isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl, 2-propylhexyl groups; - X and Y are advantageously esters, preferably esters of diacids (-X = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols ( -X- = - (C = O) -O- and -Y- = -O (C = O) -) - R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. 8. Use according to claim 6 or 7, characterized in that the composition also comprises a compound of formula (II), in particular with - R ¹ and R ² are identical and are each methyl; - X and Y are advantageously esters, preferably esters of diacids (-X = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols ( -X- = - (C = O) -O- and -Y- = -O (C = O) -) - R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. 9. Use according to any one of claims 6 to 8, characterized in that the composition also comprises a compound of formula (II), in particular with - R ¹ and R ² are identical and are each methyl; - X and Y are advantageously esters, preferably esters of diacids (-X = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols ( -X- = - (C = O) -O- and -Y- = -O (C = O) -) the group R is chosen from the following groups: the group R _M g of formula -CH (CH ₃ ) -CH ₂ -CH ₂ -, the group R _E s of formula -CH (C ₂ H ₅ ) -CH ₂ -, and mixtures thereof. 10. Use according to any one of claims 6 to 9, characterized in that the hydrocarbon binder comprises 1 to 25% by weight of said compound of formula (I), relative to the total weight of the hydrocarbon binder and, where appropriate, 0.1 to 5% by weight of said compound of formula (II), relative to the total weight of the hydrocarbon binder. 11. Use according to any one of claims 1-3, characterized in that the bituminous product is a hot mix or a warm mix. 12. Use according to claim 11, characterized in that in formula (I) 5 - R ¹ and R ² are identical and are each chosen from ethyl, npropyl, isopropyl, n-butyl, isobutyl, n-pentyl, isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl, 2-propylhexyl groups; - X and Y are advantageously esters, preferably esters of diacids (-X = -O- (C = O) -; and -Y- = - (C = O) -O-) or esters of diols ( -X- = - (C = O) -O- and -Y- = -O10 (C = O) -) - R is a radical of formula - (CH ₂ ) _r -, where r is an average number between 2 and 4 inclusive. 13. Use according to claim 11 or 12, characterized in that the hydrocarbon binder 15 comprises 1 to 30% by weight of said compound of formula (I), relative to the total weight of the hydrocarbon binder. 14. Use according to any one of claims 1-3, characterized in that the bituminous product is a storable mix. 15. Use according to any one of claims 1-3, characterized in that the bituminous product is a cold-cast bituminous material. 1/2 tsp ro x M— eu Z5 ÇT l / l <Si ro eu + - L_ had o. sp OS time (min) Fig. i 90.0% fluxing mass loss 60.0 Greenflux® SD · * ·· Rhodiasolv® DIB ^^ - Rhodtaso1v®RPOE “'“ 30.0 time (min)