WO2018055262A1 - Bitumen emulsions comprising one or more particular additives - Google Patents

Abstract

The invention relates to a bitumen emulsion comprising at least one bitumen, at least one emulsifier, phosphoric acid or one of the derivatives thereof, at least one aqueous phase, and at least one particular additive. The invention further relates to a method for producing the emulsion, as well as to the use of the emulsion in order to improve the ravelling resistance of a cold mix.

Description

 Bituminous emulsions comprising one or more particular additives

The present invention relates to a bituminous emulsion comprising at least one bitumen, an emulsifier, phosphoric acid, an aqueous phase and one or more particular additives, for the preparation of cold-poured mixes. The present invention also relates to a process for preparing said emulsion.

In the field of the road industry, bituminous coatings are generally prepared according to two techniques: so-called "hot" techniques, in which the bitumen is heated to high temperatures (typically 150 ° C-170 ° C) and so-called "cold" techniques, based on the use of aqueous bitumen emulsions, at much lower temperatures (typically 30 ° C to 60 ° C).

These bitumen emulsions are commonly used for various road applications, where they can be spread alone to obtain, for example, bonding layers, impregnation layers and spot repairs (joints, cracks, and blockages). others), or in the presence of aggregates to make surface coatings. They can also be mixed with aggregates to obtain cold mixes, either just before laying (cold-poured mixes or ECF), or in asphalt mixing plants (severe-emulsions, bituminous concretes with emulsion, etc.). .

It is also known to use various additives in bitumen to improve performance, control their viscosity, adjust their degree of coating on inorganic aggregates to form asphalt, and others.

 Among the additives commonly used in bitumens, surfactants now occupy a very prominent place in most techniques for the preparation of bitumens and bituminous mixes:

 for the so-called "hot" techniques, the surfactants can be added directly to the bitumen to improve the adhesiveness properties of the bitumen on the granulate, or to obtain a mix at a lower temperature (so-called "Lukewarm");

 for so-called "emulsion" techniques, the use of one or more surfactants used as emulsifying agents is necessary to form the emulsions.

As regards the so-called "emulsion" techniques, in which the bitumen is emulsified with an aqueous phase, there are nonionic, anionic and cationic emulsions. Nonionic emulsions use uncontained surfactants (emulsifiers) (of the polyalkoxylated fatty alcohol type, polyalkoxylated nonylphenol or other polyalkoxylated compounds, alkyl polyglucosides and others). The emulsion can be carried out at neutral, basic or acidic pH.

 Anionic emulsions use anionic surfactants, that is to say emulsifiers carrying sulphate groups, sulfonates, carboxylates and others. Before the formation of the emulsion itself, the aqueous phase can be treated if necessary with a strong base in order to salify the acid functions, so that the surfactant, and therefore the droplets of bitumen in the emulsion, are negatively charged. . In this case, the anionic emulsion has a basic pH.

 [0009] Cationic emulsions use cationic surfactants, that is to say emulsifiers carrying amine, quaternary ammonium and other functions. Before the formation of the emulsion itself, the aqueous phase can be treated if necessary with a strong acid, so that the surfactant, and therefore the droplets of bitumen in the emulsion, are positively charged. In this case, the cationic emulsion has an acidic pH. When the surfactant is in the form of the quaternary ammonium salt, in which the nitrogen atom (s) is positively charged permanently, the resulting emulsion can thus be used without adjustment of pH.

Currently the vast majority of surfactants used to make anionic bitumen emulsions is derived from the chemistry of fatty acids and polyacids, such as for example Stabiram ^® EB marketed by CECA SA

[0011] For cationic bitumen emulsions, commercial surfactants are derived from the chemistry of fatty polyamines and fatty polyamines alkoxylated, such as for example Dinoram ^® S Dinoram ^® SL POLYRAM ^® S and POLYRAM ^® SL marketed by CECA SA as well as products resulting from the condensation of mono- or poly-fatty acids with polyethylenepolyamines or polyethanolamines, such as, for example, Emulsamine ^® L60, Emulsamine ^® L70 and Emulsamine ^® LZ marketed by CECA SA.

It is known to those skilled in the art that cationic emulsions lead to good adhesion of bitumen on acid aggregates whose surface is negatively charged (eg quartz, silicates, and others). It should be noted that this is particularly true for the amine surfactants which do not have quaternary ammonium functions. The water sensitivity of the latter makes the bitumen / aggregates adhesion less robust.

In the general case of cold mixes, the applicators seek not only a good coating of the aggregate by the bitumen, in all stages of the process, but also good bitumen adhesiveness properties / aggregates, and cohesion sufficient to open quickly to traffic, without degradation (tearing, cracking and others).

 In the particular case of cold-poured mixes (ECF), the applicators seek not only good bitumen / aggregate adhesion properties and a sufficient mixing time for correct laying, but also rapid setting of the asphalt mix. .

 By cold-cast asphalt (ECF) is meant according to the present invention a material prepared on site by specific machines such as those proposed by Breining, and placed in the fluid state as described in the note of information from SETRA (Roads and Highways Technical Studies Department), "Dependence Roads", No. 102, June 1997. Another description of this type of material can be found in the guidelines published in 2003 by ISSA (" International Slurry Seal Association "in Annapolis, MD, USA). ECFs are understood here as all variants of this technology, such as bituminous grouts (also described in the SETRA note) and international names such as "Microsurfacing" and "Slurry Seal". Another name for these materials recently appeared in France with the acronym MCBF (Cold-Poured Bituminous Materials).

 Any otherwise equal parameter (aggregates, and emulsifier system), it is known to those skilled in the art that a bitumen naphthenic type allows a cohesion of the asphalt much faster than a bitumen type paraffinic. A distinction between naphthenic bitumens and paraffinic bitumens can be made by measuring the carbonyl function rate as reported by E. Gasthauer et al. in "Fuel", 87, (2008), pages 1428-1434. Naphthenic bitumens derived from petroleum crude oil from Venezuela are for example marketed in Europe by the company Nynas AB. In countries where naphthenic bitumen is available, ECFs are therefore prepared with this type of bitumen, which allows reopening to very fast traffic, typically from 15 minutes to 30 minutes after spreading.

 In contrast, in countries where the naphthenic bitumens are not or not available, and where the ECF are prepared with paraffinic bitumens, reopening times to traffic are much longer, which makes this technique unacceptable . There remains a need for ECFs prepared with paraffinic bitumens that can be used under the same conditions as ECFs prepared with naphthenic bitumens.

Even if the difference is less marked for other types of cold mixes, the performance obtained with naphthenic bitumen in terms of cohesion is greater. The applicators are thus looking for a more robust solution that allows them to use not only cold mixes prepared with paraffinic bitumens, but also to work with any type of bitumen, especially to prepare asphalt mixes. cold, while retaining the same application properties, typically allowing a very fast reopening to the traffic.

 The international application WO2005 / 012433 proposes a mixture for emulsions which contains an emulsifier (surfactant) and a demulsifier. This mixture develops a rapid break and rise in cohesion. By "rupture" is meant the destabilization of the emulsion with the separation of water and bitumen. The "rise in cohesion" results in the hardening of the coating under the effect of the bonding of the granular structure by the bitumen released during the rupture of the emulsion.

 The emulsifier is a diamine salt with a polyvalent phosphoric acid. Polyphosphoric acid is more specifically mentioned. The demulsifier is based on cement.

The preferred diamines as disclosed in this document are tertiary diamines, that is to say totally substituted. It is known to those skilled in the art that this type of emulsifier does not exhibit sufficient active adhesiveness in the presence of water because the tertiary amines are less basic than the others, therefore the affinity with the acid granules is less important.

 Active adhesiveness means the ability for an emulsifier to move the water film present on the surface of a granulate and make it hydrophobic to allow the bitumen to wet the granulate in place of the water.

 Thus, the system described in this document leads to the production of cold-poured mixes whose resistance to water and stripping in the first hours after installation, is insufficient.

 The patent US5096495 describes a "slurry seal" with an increase in cohesion improved through the joint use of a specific emulsifier and an additive introduced into the wetting water aggregates. The introduction of said additive into the wetting water of aggregates is impractical because it requires the adaptation of machines and may interfere with the use of control additives which are commonly used in these techniques to provide flexibility in terms of maneuverability in the field.

Furthermore, patent FR2930253 describes the improvement of the cohesion with paraffinic bitumen by adding a polymerized fatty acid in the bitumen before emulsification.

The polymerized fatty acids are acids derived from the polymerization of the side chains of at least one unsaturated fatty acid. Unsaturated fatty acids allowing to obtain the polymerized fatty acids, are unsaturated fatty acids C4-C24, preferably C11-C22, more preferably C16-C18.

 There is therefore currently no technical solution leading to the production of bituminous emulsions comprising at least one emulsifier with phosphoric acid, to obtain a rapid cohesion of the mixes manufactured without that said mixes have weakness in terms of adhesiveness or resistance to moisture.

 The invention therefore relates to a bituminous emulsion comprising at least one bitumen, at least one emulsifier, phosphoric acid or a derivative thereof, at least one aqueous phase, and at least one additive of formula (I ) next :

in which :

R 1 and R 2, which are identical or different, represent, independently of one another, a group chosen from a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon-based chain, in the form of C 1 -C 30, a group A1) qi-S (0) 20Rs, a - (A2) _2-q P (0) (OR _{9) 2,} a group - (A3) _q3-C (0) ORIO, and a group - (A4) q ₄ -C (O) NH (Rn NH) _n H,

• Re, R9 and R10, identical or different, representing, independently of one another, a hydrogen atom or a hydrocarbon chain, linear or branched, saturated or unsaturated, C 1 -C 22,

 R11 representing a hydrocarbon chain, linear or branched, saturated or unsaturated, C1-C10,

 A1, A2, A3 and A4, which may be identical or different, represent, independently of one another, a linear or branched C1-C22, preferably C1-C12, and preferably C1-C12, alkylene radical; cs

 Q1, q2, q3 and q4, identical or different, representing, independently of one another, an integer equal to 0 or 1, and

 Where n is an integer ranging from 1 to 6,

or R 1 and R 2 together with the carbon atoms to which they are attached form a 5-membered heterocycle, it being understood that at least one of the groups R 1 and F¾ represents a group chosen from the group - (A1) _q iS (O) ₂ OR ₈ , the group - (A2) _q 2 -P (O) (OR ₉ ) 2 , the group - (A3) _q3 - C (0) ORIO, and the group - (A4) q ₄ -C (0) NH (Rn NH) _n H;

 B represents a group selected from a group OR3 and a group -N R12R121,

Wherein R 3 represents a group chosen from a hydrogen atom and a linear or branched, saturated or unsaturated C 1 -C 22 hydrocarbon-based chain,

 • R12 and R121, identical or different, being chosen, independently of one another, from a hydrogen atom, a group R3 and a hydrocarbon chain, linear or branched, saturated or unsaturated, C 2 -C 30, comprising optionally one or more rings, said chain being interrupted and / or terminated by at least one nitrogen atom;

R ₄ and R ₅ , which may be identical or different, represent, independently of one another, a hydrogen atom or a linear or branched, saturated or unsaturated C ₁ -C ₂₂ hydrocarbon-based chain;

R 6 and R ₇ , which may be identical or different, represent, independently of each other, a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon-based chain, Ci-C ₄ , preferably C 1 or C2 or C3,

 D represents a hydrogen atom or a linear or branched, saturated or unsaturated C 1 -C 22 hydrocarbon-based chain;

 G represents a linear or branched, saturated or unsaturated C 1 -C 22 alkylene radical; and

 p is an integer of 0 or 1.

The emulsion according to the invention provides significantly better performance than those obtained under the same conditions without additive. These emulsions are of particular interest with a view to their use for preparing cold-cast asphalts, since they give the said coatings a very rapid cohesion increase, adhesiveness properties and improved water-resistance properties, whatever the emulsifying system and the nature of the aggregates.

 It is specified that the expressions "from ... to ..." used in the present description must be understood as including each of the mentioned terminals.

Emulsifier in the present invention means a compound or a mixture of compounds suitable for forming and / or stabilizing an emulsion.

Heterocycle in the present invention means a ring structure comprising at least one heteroatom selected from O, N and S. By emulsion in the present invention is meant a heterogeneous system with two or more liquid phases, consisting of a continuous liquid phase and at least a second liquid phase, dispersed in the first, in the form of fine droplets.

Bituminous emulsion in the present invention is understood to mean an aqueous dispersion of bitumen optionally comprising one or more additives, surfactants, emulsifiers, viscosifiers, thickeners, fluxing agents, plasticizers and / or any other additive making it possible to adjust the properties of the emulsion.

 In the present invention, the term "chain interrupted by at least one nitrogen atom" means a carbon chain comprising at least one nitrogen atom, said nitrogen atom being between two carbon atoms of said chain. If the chain is interrupted by several nitrogen atoms, said nitrogen atoms are separated by at least one carbon atom of said chain.

 The bitumens used in the present invention are bitumens from different origins. We can first mention bitumen of natural origin, those contained in deposits of natural bitumen, natural asphalt or oil sands.

The bitumens according to the invention are also bitumens from the refining of crude oil. Bitumens come from the atmospheric and / or vacuum distillation of oil. These bitumens can be optionally blown, visbroken and / or deasphalted. The bitumens may be hard grade or soft grade bitumens. The different bitumens obtained by the refining processes can be combined with one another to obtain the best technical compromise.

 Bitumens used may also be fluxed bitumens by addition of volatile solvents, petroleum fluxes, carbochemical fluxes and / or fluxes of vegetable origin.

 Bitumens modified with polymers may also be used. As a polymer, mention may be made, for example, and in an indicative and nonlimiting manner, thermoplastic elastomers such as styrene and butadiene random or block copolymers, linear or star (SBR, SBS) or styrene and isoprene (SIS ), optionally crosslinked, copolymers of ethylene and of vinyl acetate, olefinic homopolymers and copolymers of ethylene (or propylene or butylene), polyisobutylenes, polybutadienes, polyisoprenes, polyvinyl chloride, rubber crumbs or any polymer used for the modification of bitumens and mixtures thereof. In general, a quantity of polymer of 2 to 10% by weight relative to the weight of bitumen is used.

It is also possible to use synthetic bitumens also called clear, pigmentable or colorable bitumens. These bitumens contain little or no asphaltenes and can therefore be colored. These synthetic bitumens are based on petroleum resin and / or indene-coumarone resin and lubricating oil as described for example in patent EP 179510.

 Advantageously, the bitumen is a penetration bitumen measured according to the NF EN 1426 standard of June 2007 ranging from 10 to 300, preferably from 20 to 220, more preferably from 70 to 220.

 Preferably, the bitumen according to the invention is chosen from unmodified crude oil refining bitumens.

 The emulsion according to the invention comprises at least one emulsifier as defined above.

 Preferably, said emulsifier is chosen from an amine, a polyamine, an amide, an alkylamidoamine, an alkylimidazoline, a quaternary ammonium, an amine comprising one or more oxides of ethylene or propylene, and mixtures thereof.

Preferably, said emulsifier is an emulsifier:

 of formula (II) below:

in which R13 represents a linear or branched, saturated or unsaturated, C5-C21, preferably C7-C17, hydrocarbon-based chain, and f represents an integer ranging from 0 to 5; or

Formula

in which :

 R14 represents a hydrocarbon chain, linear or branched, saturated or unsaturated, C6-C22, preferentially Cs-C18;

 R15, R16 and R17, which are identical or different, represent, independently of one another, a group chosen from:

 a hydrogen atom,

 a group - (CHR) C hH, with R a representing a hydrogen atom or a methyl or ethyl radical, and h being an integer ranging from 1 to 10, and

a saturated or unsaturated C 1 -C 4 linear or branched hydrocarbon chain; and j represents an integer ranging from 0 to 4. The emulsifier of formula (II) generally exists in admixture with the linear amide form resulting from the hydrolysis of the emulsifier of formula (II).

 Advantageously, said emulsifier is chosen from fatty alkylimidazopolyamines, fatty alkylamidopolyamines, alkoxylated fatty polyamines, alkylated fatty polyamines and mixtures thereof.

 Even more advantageously, said emulsifier is chosen from mixtures of C16-C18 fatty alkylimidazopolyamines obtained by reaction of fatty acids or of vegetable oil with polyethylenepolyamines such as triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA) and ethoxylated fatty tallow polyamines.

 According to a preferred embodiment of the invention, the amount of said emulsifier is 0.2 to 3% by weight relative to the total weight of the emulsion.

 The phosphoric acid derivatives may be chosen from pyrophosphoric acid and polyphosphoric acids, for example triphosphoric acid.

 Preferably, the emulsion comprises phosphoric acid.

 Preferably, the amount of said phosphoric acid or its derivatives is from 0.1 to 4% by weight relative to the total weight of the emulsion.

 Preferably, the phosphoric acid is in a content such that the pH of the aqueous phase of the bituminous emulsion ranges from 1 to 5, preferably from 1.5 to 4.

 The emulsio ins an additive of formula (I) below:

in which :

R 1 and R 2, which are identical or different, represent, independently of one another, a group chosen from a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon-based chain, in the form of C 1 -C 30, a group A1) qi-S (0) 20Rs, a - (A2) _2-q P (0) (OR _{9) 2,} a group - (A3) _q3-C (0) ORIO, and a group - (A4) q ₄ -C (O) NH (RnNH) _n H,

• Re, R9 and R10, identical or different, representing, independently of one another, a hydrogen atom or a hydrocarbon chain, linear or branched, saturated or unsaturated, C 1 -C 22, Ru represents a hydrocarbon chain, linear or branched, saturated or unsaturated, C 1 -C 10,

 A1, A2, A3 and A4, which may be identical or different, represent, independently of one another, a linear or branched C1-C22, preferably C1-C12, and preferably C1-C12, alkylene radical; cs

 Q1, q2, q3 and q4, identical or different, representing, independently of one another, an integer equal to 0 or 1, and

 Where n is an integer ranging from 1 to 6,

 or R 1 and R 2 together with the carbon atoms to which they are attached form a 5-membered heterocycle,

provided that at least one of Ri and R2 represents a group selected from the group - (A1) _q iS (0) ₂ OR _8, the group - (A2) _q2 -P (0) (OR ₉₎ 2, the group - (A3) _q3-C (0) ORIO, and the group - (A4) q ₄ -C (0) NH (R i NH) _n H;

 B represents a group selected from a group OR3 and a group -N R12R121,

Wherein R 3 represents a group chosen from a hydrogen atom and a linear or branched, saturated or unsaturated C 1 -C 22 hydrocarbon-based chain,

 • R12 and R121, identical or different, being chosen, independently of one another, from a hydrogen atom, a group R3 and a hydrocarbon chain, linear or branched, saturated or unsaturated, C 2 -C 30, comprising optionally one or more rings, said chain being interrupted and / or terminated by at least one nitrogen atom;

R ₄ and R ₅ , which may be identical or different, represent, independently of one another, a hydrogen atom or a linear or branched, saturated or unsaturated C ₁ -C ₂₂ hydrocarbon-based chain;

R 6 and R ₇ , which may be identical or different, represent, independently of each other, a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon-based chain, Ci-C ₄ , preferably C 1 or C2 or C3,

 D represents a hydrogen atom or a linear or branched, saturated or unsaturated C 1 -C 22 hydrocarbon-based chain;

 G represents a linear or branched, saturated or unsaturated C 1 -C 22 alkylene radical; and

 p is an integer of 0 or 1.

Preferably, the groups R 1 and R 2 of the additive, which are identical or different, represent, independently of one another, a group chosen from a hydrogen atom, a saturated or unsaturated hydrocarbon-based chain, linear or branched, in C1-C30, a group - (A1) _q iS (O) 20Rs, a group - (Α2) _ς2 -Ρ (O) (Οί¾) 2, and a group - (A3) _q- C (O) OR10, provided that at least one of Ri and R2 represents a group selected from the group - (A1) _q iS (0) 20Rs, the group - (A2) _q2 -P (0) (OR9) 2, and the group - (A3) _q 3-

Advantageously, the groups R 1 and R 2 of the additive, which are identical or different, represent, independently of one another, a group chosen from a hydrogen atom, a hydrocarbon chain, saturated or unsaturated, linear or branched C1-C30, and a grouping (A3) _q 3-C (0) ORIO, provided that at least one of Ri and R2 represents the group - (A3) _q 3-C (0) ORIO .

 Preferably, the group B of the additive represents a group OR 3, R 3 being chosen from a hydrogen atom, and a hydrocarbon chain, linear or branched, saturated or unsaturated, C 1 -C 22.

According to a particularly preferred embodiment, the groups R 1 and R 2 of the additive, which are identical or different, represent, independently of one another, a group chosen from a hydrogen atom, a hydrocarbon chain, saturated or unsaturated, linear or branched C1-C30, a group - (A1) _q iS (O) 20R8, a group - (A2) _q 2 -P (O) (OR9) 2, and a group - (A3 ) _q 3-C (0) ORIO, provided that at least one of Ri and R2 represents a group selected from the group - (A1) _q iS (0) 20R8, the group - (A2) _2-q P (0) (ORg) 2, and the group - (A3) _q 3-C (O) OR 10; and the group B of the additive represents a group OR 3, R 3 being chosen from a hydrogen atom, and a hydrocarbon chain, linear or branched, saturated or unsaturated, C1-C22.

According to another particularly preferred embodiment, the groups R 1 and R 2 of the additive, which may be identical or different, represent, independently of one another, a group chosen from a hydrogen atom, a hydrocarbon-based chain saturated or unsaturated, linear or branched C1-C30, and a group - (A3) _q 3-C (0) ORIO, provided that at least one of Ri and R2 represents the group - (A3) _q 3-C (O) OR10; and the group B of the additive represents a group OR 3, R 3 being chosen from a hydrogen atom, and a hydrocarbon chain, linear or branched, saturated or unsaturated, C1-C22.

According to another particular embodiment of the invention, the groups R 1 and R 2 of the additive form, with the carbon atoms to which they are attached, a group of formula (IV) below:

Preferably, the group R 3 of the additive designates the hydrogen atom. Advantageously, the groups Rs, R9 and R10 of the additive designate the hydrogen atom.

 According to a particular embodiment of the invention, the group B of the additive represents the OH group.

 Advantageously, the groups R12 and R121 are chosen from the groups:

 -NH- (CH 2 -CH 2 -NH) mi-R 3, where m 1 is an integer from 1 to 6 and R 3 is as previously defined,

-NH- (CH ₂ -CH ₂ ) m2-N (CH ₂ -CH ₂ ) 2 -NH, where m2 is an integer ranging from 1 to 6 and R ₃ is as defined above,

-NH-CH ₂ -CH ₂ -CH ₂ -N (R ₃ ) 2, and

-NH-CH ₂ -CH ₂ -CH ₂ -NH-CH ₂ -CH ₂ -CH ₂ -N (R ₃ ) 2.

Preferably, the groups R ₄ and R ₅ of the additive simultaneously denote the hydrogen atom.

Preferably, the groups R 6 and R ₇ of the additive, which may be identical or different, represent, independently of one another, the hydrogen atom, the methyl radical or the ethyl radical, more preferably , R6 and R ₇ denote simultaneously hydrogen.

Preferably, D represents a hydrocarbon chain, linear or branched, preferably linear, saturated or unsaturated, Ci-Ci ₄ .

Preferably, D represents a linear hydrocarbon chain, saturated or unsaturated, C 1 -C 22, preferably C 1 -C ₄ .

 According to a particular embodiment of the invention, p is equal to 0.

According to another particular embodiment of the invention, p is equal to 1.

According to a particular embodiment of the invention, p is equal to 1 and G represents a linear or branched, preferably linear, saturated or unsaturated alkylene radical,

Advantageously, the total number of carbon atoms of groups D and G ranges from 2 to 31, preferably from 6 to 17, more preferably from 1 to 13.

According to a particular embodiment of the invention, the additive of formula (I) is obtained by means of a Diels-Alder reaction between a diene compound and a dienophile compound (for more information, see Breuer, TE (2000), "Dimer Acids", Kirk-Othmer Encyclopedia of Chemical Technology).

 [0075] Advantageously, said diene compound is a polyunsaturated fatty acid, that is to say having at least two double bonds.

Said polyunsaturated fatty acids are preferably polyunsaturated fatty acids comprising from 2 to 5 unsaturations, preferably from 2 to 4 unsaturations and from more preferably 2 or 3 unsaturations, C5-C36, preferentially C5-C24, more preferably C10-C22, even more preferably C16-C18, and particularly preferably Cis.

 Among said unsaturated fatty acids, there may be mentioned, for example, sorbic acid and arachidonic, linoleic and linolenic fatty acids. For the latter, the Diels-Alder reaction is then preceded by an intramolecular thermal rearrangement of the double bonds to present a conjugate structure capable of being reacted, according to the conventional techniques known to those skilled in the art.

 As indicated in the document by Breuer, TE, (2000), "Dimer Acids", Kirk-Othmer Encyclopedia of Chemical Technology, the use of oleic acid for this type of reaction is possible despite the presence of a single unsaturation, by catalyzed dimerization using activated clays such as Montmorillonite. One would not depart from the scope of the invention using such a raw material.

 Advantageously, said dienophile compound is chosen from carboxylic, sulfonic, phosphonic and anhydride acids and dicarboxylic acids, said acids and anhydrides comprising at least one double bond, preferably a single double bond.

As the dienophile compound, there may be mentioned, for example, acrylic acid, methacrylic acid, oleic acid, crotonic acid, isocrotonic acid, angelic acids, tiglic acids, acid, and the like. maleic anhydride, vinylsulfonic acid, 2-propene-1-sulfonic acid and vinylphosphonic acid.

Preferably, said additive of formula (I) is chosen from the products obtained by reacting a linoleic acid with acrylic acid, maleic acid, oleic acid or maleic anhydride, or even by reaction of a linolenic acid with acrylic acid, maleic acid, oleic acid or maleic anhydride. It is also possible to envisage reacting one or more diene mixtures, such as, for example, tall oil fatty acid (TOFA) fatty acid mixtures in the English language) with one or more dienophiles. (s), as previously described, for example such as acrylic acid, maleic acid or maleic anhydride.

Preferably, said additive of formula (I) is chosen from 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 5-carboxy-4-hexyl-2-cyclohexene- 1-octanoic, and their mixture; 6-carboxy-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-carboxy-4-pentyl-2-cyclohexene-1-nonanoic acid, and mixtures thereof; 6-carboxy-6-methyl-4-hexyl-2-cyclohexene-1-octanoic acid, 5-carboxy-5-methyl-4-hexyl-2-cyclohexene-1-octanoic acid, and mixtures thereof; 6-carboxy-6-methyl-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-carboxy-5-methyl-4-pentyl-2-cyclohexene-1-nonanoic acid, and mixtures thereof; 6-sulfonic acid-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-acid acid sulfonic-4-pentyl-2-cyclohexene-1-nonanoic acid, and mixtures thereof; 6-phosphonic acid-4-hexyl-2-cyclohexene-1-octanoic acid, 5-phosphonic acid-4-hexyl-2-cyclohexene-1-octanoic acid, and mixtures thereof; 6-phosphonic acid-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-phosphonic acid-4-pentyl-2-cyclohexene-1-nonanoic acid, and mixtures thereof; 5,6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 5,6-carboxy-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-carboxylic acid-5-carboxylic acid; 4-hexyl-2-cyclohexene-1-octanoic acid, 5-pentoxide-4-pentyl-2-cyclohexene-1-nonanoic acid; and mixtures thereof, preferably from 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, and mixtures thereof.

 According to a particular embodiment of the invention, the additive of formula (I) is a polymerized fatty acid.

 Preferably, the polymerized fatty acids are as defined in patent FR2930253.

 Advantageously, the polymerized fatty acid comprises fatty acid monomers, fatty acid dimers, fatty acid trimers and fatty acid tetramers, preferably comprising predominantly fatty acid dimers and trimers of fatty acids.

 Preferably, said fatty acid dimers are obtained by means of a Diels-Alder reaction between two fatty acid monomers. Thus, a fatty acid monomer is preferentially considered to be a diene compound and the other is advantageously considered to be a dienophile compound.

An example of a polymerized fatty acid according to the invention is the polymerized fatty acid Pripol 1017 ^® , marketed by the company Croda, which comprises, according to the technical data sheet of the supplier CRODA, about 2% by weight of monomer of fatty acid, 78% by weight of fatty acid dimer and 20% by weight of fatty acid trimer.

 According to a particular embodiment of the invention, the additive of formula (I) is a reaction product of a fatty acid polymerized with polyalkylene polyamines.

According to a particular embodiment of the invention, the additive of formula (I) is a product obtained by reaction of a polymerized fatty acid as defined above with an amine of formula (V) below: HN R12R121 (V), wherein R12 and R121 are as previously defined.

Thus, the fatty acid dimers are preferably obtained initially by a Diels-Alder reaction between two fatty acid monomers, then the polymerized fatty acid reacts with said amine of formula (V). According to a particular embodiment of the invention, the additive of formula (I) is obtained by reaction of 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, the acid 5 carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 6-carboxy-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-carboxy-4-pentyl-2-cyclohexene-1 acid -nonanoic or mixtures of these acids, in the presence of 0.1 to 2 equivalents of polyethylenepolyamines such as diethylenetriamine (DETA), TETA, TEPA and PEHA.

 According to another particular embodiment of the invention, the additive of formula (I) is obtained by reaction of 5,6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 5,6-carboxy-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-carboxylic acid-4-hexyl-2-cyclohexene-1-octanoic acid, 5-carboxylic acid-4-anhydride pentyl-2-cyclohexene-1-nonanoic acid or mixtures of these acids, in the presence of 0.1 to 3 equivalents of polyethylenepolyamines such as DETA, TETA, TEPA and PEHA.

According to a still more particular embodiment of the invention, the additive of formula (I) is obtained by reaction of polyethyleneopolyamines such as DETA, TETA, TEPA, aminoethylpiperazine (AEP) and PEHA with an acid. polymerized fat, such as Pripol 1017 ^® , marketed by the company Croda.

 Advantageously, the reaction is carried out in the presence of from 0.1 to 1 equivalent, more preferably from 0.3 to 0.7, of polyethylenepolyamine per acid function of the polymerized fatty acid.

 Preferably, the amount of said additive of formula (I) represents from 0.1 to 5% by weight, more preferably from 0.3 to 2% by weight, even more preferably from 0.3 to 1% by weight. , relative to the total weight of the emulsion.

 Preferably, the amount of bitumen represents from 50 to 90% by weight, preferably from 50 to 70%, more preferably from 60 to 70% by weight, relative to the total weight of the emulsion.

 According to a particular embodiment of the invention, the amount of the aqueous phase represents from 10 to 50% by weight, preferably from 30 to 50% by weight, more preferably from 30 to 40% by weight, relative to to the total weight of the emulsion.

Advantageously, the bituminous emulsion according to the invention comprises one or more additives, other than those defined above, commonly used in the field, among which may be mentioned in a non-limiting manner, viscosifiers, natural or synthetic latexes. thickeners, fluxing agents, plasticizers and any other additive making it possible to adjust the properties of the emulsion, such as the process additives mentioned in patent EP1057873, for example lignins, polymers, salification agents, alcohols, especially fatty alcohols, and others. It is understood that the additive (s) mentioned above may be incorporated into the bituminous emulsion at any stage of manufacture according to the methods known to those skilled in the art.

The invention also relates to a method for preparing at least one bituminous emulsion as defined above, comprising at least one mixing step:

 at least one additive of formula (I) as defined above,

 bitumen,

 at least one emulsifier as defined above,

 phosphoric acid or a derivative thereof as defined above, and at least one aqueous phase.

Advantageously, said process for preparing the bituminous emulsion according to the invention is carried out according to the methods well known to those skilled in the art, and for example as described in the manual "Bitumen emulsions" published by the General Review of Roads and Aerodromes (RGRA) (2006).

 According to a preferred embodiment of the invention, said method comprises the following successive steps:

 the mixture of additive and bitumen; then

 mixing the aqueous phase, the emulsifier, the phosphoric acid or one of its derivatives and the bituminous composition obtained after mixing the bitumen and the additive.

 According to an exemplary implementation of the process according to the invention, at room temperature, or under gentle heating (from 40 ° C. to 60 ° C.), a mixture of at least one emulsifier such as previously defined in water, then the phosphoric acid is added to this mixture in order to obtain a final aqueous phase pH ranging from 1 to 5 and preferably from 2 to 4, more preferably 2.

 Is prepared parallel to the aqueous phase, at a temperature where the bitumen used is fluid, typically between 140 and 160 ° C, a mixture between an additive of formula (I) as described above and the bitumen. The mixture maintained in temperature is homogenized by stirring with, for example, a Rayneri type stirrer for 15 minutes.

 The solution obtained at the end of the preparation of the aqueous phase is then mixed under high shear with the mixture of hot bitumen and at least one additive (bitumen temperature ranging, for example, from 140 ° C. to 160 ° C.). VS).

Another object of the invention is a cold-poured mix comprising at least one bituminous emulsion as defined above, and aggregates. Advantageously, said granulates are of any type known to those skilled in the art. Among the granulates that can be used for the cold-poured mixes according to the invention, there may be mentioned, in a nonlimiting manner, aggregates of a mineralogical nature, for example of eruptive nature, such as granites, porphyries, of metamorphic nature, such as shales. , gneisses, and sedimentary type siliceous type, such as flint, quartzite, and carbonated type, such as limestone, dolomite, but also asphalt aggregates (such as recycled pavement, or "recycled asphalt pavement "(RAP) in English), slags, crushed concrete, and others, as well as mixtures of such aggregates. These aggregates can of course be additivés cement and / or lime, according to techniques known to those skilled in the art.

 The invention also relates to the use of an additive according to the invention as defined above for the preparation of a cold-poured mix, as defined above.

 The invention also relates to the use of an additive according to the invention as defined above to improve the resistance to stripping of a cold-poured mix as mentioned above.

 The invention also relates to the use of the emulsion as defined above to improve the resistance to stripping of a cold-poured mix as mentioned above.

 The invention is illustrated by the following non-limiting examples.

EXAMPLES

Example 1

 1. Preparation of four bituminous emulsions

Four bituminous emulsions are manufactured with an emulsification pilot Emulbitume ^® brand equipped with an Atomix C type colloid mill.

The four bituminous emulsions contain 60% by weight of bitumen, penetrability 70/100, from the refinery Total de Feyzin, relative to the total weight of the emulsion.

 The coating emulsions prepared are slow coating emulsions of type C60B6 according to standard NF EN 13808 of August 2013.

The aqueous phase 1 is prepared by mixing:

22 g of fatty amideopolyamine emulsifier of the name Polyram ^® L927 marketed by CECA SA;

 754 g of water;

24 g of 32% hydrochloric acid. The aqueous phase 2 is prepared by mixing:

12 g of tallow diamine of Dinoram S ^® type, marketed by CECA SA, modified with three ethylene oxides per mole of diamine;

8 g of fatty amideopolyamine emulsifier of Polyram ^® L930 name marketed by CECA SA;

 758 g of water;

 22 g of 85% orthophosphoric acid.

 The composition of the four bituminous emulsions is shown in Table 1 below:

 - Table 1 -

The Cecabase ^® FC + additive comprises 45% by weight of oleic acid and 55% by weight of a mixture comprising 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid and the acid. 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid.

The polymerized fatty acid Pripol 1017 ^® comprises, according to the technical data sheet of the supplier CRODA, about 2% by weight of fatty acid monomer, 78% by weight of fatty acid dimer and 20% by weight of trimer of fatty acid.

The additives (the polymerized fatty acid Pripol 1017 ^® for the emulsion 3, and the Cecabase ^® FC + additive for the emulsion 4) are introduced into the hot bitumen, heated to about 140 ° C, with stirring. The mixture is stirred for 15 minutes for homogenization before emulsification.

The emulsification is carried out as standard with an Emulbitume pilot operating continuously at a rate of 60 liters / h. The mixture of bitumen / aqueous phase at a mass ratio (60/40) is introduced into an atomix C by means of two separate circuits fed by two pumps. 2. Preparation of four cold-poured mixes

 Four cold-poured mixes are prepared from the four bituminous emulsions mentioned above.

 The four mixes were prepared with Gneiss type aggregates from the Ambazac quarry. The aggregates are of particle size 0-6 cm.

The amount of water added to the dry aggregates is 6 g and is adjusted according to the system so as to maintain a kneading time around 100 ± 10 seconds.

 It is understood in the present examples, by mixing time, the time during which the mixture described above remains fluid with stirring.

The composition of the four cold-poured mixes is indicated in Table 2 below:

 - Table 2 -

3. Evaluation of the performance of the four cold-poured mixes

The internal cohesion of each of the four mixes is evaluated using the HCT test "Hilt Cohesion Test", described in the guide of the IDRRIM, on "Cold Bituminous Materials", 2015.

 This test makes it possible to evaluate the tensile and flexural strength of the tested mix.

Specimens of MBCF (Cold Cast Bituminous Materials) 120 ^* 120 ^* 15 mm are manufactured by casting 400g of cold-cast asphalt in a mold of 120 ^* 120 mm with removable edges. After taking the mix, the edges of the mold are removed carefully and the test piece is left at room temperature for ripening for a determined time.

The test was performed on a table, the principle being to put half of the test tube in the vacuum while the other half is held on a support. The test piece is positioned at the edge of the table on a plastic support in two equal parts not secured. A counterweight is placed on the part that remains on the table. The other half of the specimen is slid over the void, and the support under this part is removed.

 The time required for the breakage of the asphalt after the half of the test piece has been placed above the vacuum is then measured. The result (in seconds) represents the HCT cohesion value after a defined ripening time under known temperature and hygrometry conditions. The longer the duration is (under equivalent ripening conditions), the colder the cold mix is resistant and therefore the higher the cohesion is advanced.

 The test has been adapted from the IDRRIM guide cited above. The curing time necessary to obtain an 80 second HCT cohesion is evaluated here when 1/3 of the test piece is placed in a vacuum, considered to be a value sufficient for opening to traffic under these test conditions.

In addition, in order to evaluate the adhesiveness of the mixes, the fracture profile is observed after 24 hours of drying in ambient conditions and noted according to the percentage of loosened surface. For example, if 20% of the mineral surfaces are apparent, the adhesiveness will be noted 80%.

 The curing times at 20 ° C to obtain an HCT cohesion of 80 seconds, called open times to traffic, and the results in terms of adhesiveness are shown in Table 3 below:

 - Table 3 -

A mix comprising an emulsion according to the invention has both a low traffic opening time and high adhesiveness. In the case of comparative mixes, either the opening time to the traffic is too high or the adhesiveness is too low.

Example 2

 1. Preparation of four bituminous emulsions

Four bituminous emulsions are manufactured with an Emulbitume ^® brand emulsification pilot equipped with an Atomix C type colloid mill. The four bituminous emulsions contain 60% by weight of paraffinic bitumen, 70/100 penetrability, from the total refinery Grandpuits, relative to the total weight of the emulsion.

 The coating emulsions prepared are slow coating emulsions of type C60B6 according to standard NF EN 13808 of August 2013.

The emulsifier dosage in emulsions 5 and 6 is 5 kg / t of a mixture of amino derivatives of the trade name Polyram L80 ^® , marketed by Ceca SA, and 8 kg / t in emulsions 7. and 8.

 The aqueous phase is identical to that which has been prepared for emulsions 2 to 4 as indicated in Example 1.

 The pH of the aqueous phase was adjusted to 2 with 85% orthophosphoric acid.

 The composition of the four bituminous emulsions is shown in Table 4 below:

 - Table 4 -

The additives (the polymerized fatty acid Pripol 1017 ^® for the emulsion 6, and the Cecabase ^® FC + additive for the emulsion 8) are introduced into the hot bitumen, heated to about 140 ° C, with stirring. The mixture is stirred for 15 minutes for homogenization before emulsification.

The emulsification is carried out as standard with an Emulbitume pilot operating continuously at a rate of 60 liters / h. The mixture of bitumen / aqueous phase at a mass ratio (60/40) is introduced into an atomix C by means of two separate circuits fed by two pumps. 2. Preparation of four cold-poured mixes

 The four mixes were prepared with two types of aggregates: eruptive aggregates from the quarry of Chailloué (granular mixture comprising 50% by weight of aggregates of 0-4 cm size class, and 50% by weight of aggregates of grain size class 4-6 cm) and Gneiss-type aggregates from the Ambazac quarry (aggregates with particle size class 0-6 cm).

 The amount of water added to the dry aggregates varies between 9 and 10 g and is adjusted according to the system so as to maintain a kneading time around 100 ± 10 seconds.

 The composition of the four cold-poured mixes is shown in Table 5 below:

 - Table 5 -

3. Evaluation of wet abrasion resistance of the four cold-cast asphalts

 The resistance to abrasion under humid conditions is evaluated using a test adapted to the NF EN 12274-5 test. This test is described in part in the IDRRIM guide, on "Cold-Rolled Bituminous Materials", 2015.

 This test consists of performing a wear test as described in standard 12274-5 after more severe curing conditions for drying and more representative of reality, namely that the mix is stored for 18 hours. at 55% humidity and at a temperature of 18 ° C., after one hour of maturing at room temperature.

After curing, the test pieces are immersed for 1 hour in water before being abraded under water for 5 minutes at room temperature.

The results in terms of mass loss are presented in Table 6 below: - Table 6 -

The results therefore clearly indicate that the use of an emulsion according to the invention makes it possible to limit the mass loss of the cold-cast mixes, compared with the mixes of the prior art. Thus, the mixes according to the invention have improved moisture resistance properties.

Claims

A bituminous emulsion comprising at least one bitumen, at least one emulsifier, phosphoric acid or a derivative thereof, at least one aqueous phase, and at least one additive of formula (I) below:

in which : R 1 and R 2, which are identical or different, represent, independently of one another, a group chosen from a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon-based chain, in the form of C 1 -C 30, a group A1) qi-S (0) 20Rs, a - (A2) _2-q P (0) (OR _{9) 2,} a group - (A3) _q3-C (0) ORIO, and a group - (A4) q ₄ -C (O) NH (Rn NH) _n H, • Re, R9 and R10, identical or different, representing, independently of one another, a hydrogen atom or a hydrocarbon chain, linear or branched, saturated or unsaturated, C 1 -C 22,  R11 representing a hydrocarbon chain, linear or branched, saturated or unsaturated, C1-C10,  A1, A2, A3 and A4, which may be identical or different, represent, independently of one another, a linear or branched C1-C22, preferably C1-C12, and preferably C1-C12, alkylene radical; cs  Q1, q2, q3 and q4, identical or different, representing, independently of one another, an integer equal to 0 or 1, and  Where n is an integer ranging from 1 to 6,  or R 1 and R 2 together with the carbon atoms to which they are attached form a 5-membered heterocycle, provided that at least one of Ri and R2 represents a group selected from the group - (A1) _q iS (0) ₂ OR _8, the group - (A2) _q2 -P (0) (OR ₉₎ 2, the group - (A3) _q3 - C (0) ORIO, and the group - (A4) q ₄ -C (0) NH (Rn NH) _n H; B represents a group selected from a group OR3 and a group -N R12R121, Wherein R 3 represents a group chosen from a hydrogen atom and a linear or branched, saturated or unsaturated C 1 -C 22 hydrocarbon-based chain,  • R12 and R121, identical or different, being chosen, independently of one another, from a hydrogen atom, a group R3 and a hydrocarbon chain, linear or branched, saturated or unsaturated, C 2 -C 30, comprising optionally one or more rings, said chain being interrupted and / or terminated by at least one nitrogen atom; R ₄ and R ₅ , which may be identical or different, represent, independently of one another, a hydrogen atom or a linear or branched, saturated or unsaturated C ₁ -C ₂₂ hydrocarbon-based chain; R 6 and R ₇ , which are identical or different, represent, independently of each other, a hydrogen atom or a linear or branched, saturated or unsaturated, C 1 -C 4, preferably C 1 or C 2, hydrocarbon-based chain; or in C3,  D represents a hydrogen atom or a linear or branched, saturated or unsaturated C 1 -C 22 hydrocarbon-based chain;  G represents a linear or branched, saturated or unsaturated C 1 -C 22 alkylene radical; and p is an integer of 0 or 1. An emulsion according to claim 1, wherein said emulsifier is selected from an amine, a polyamine, an amide, an alkylamidoamine, an alkylimidazoline, a quaternary ammonium, an amine comprising one or more oxides of ethylene or propylene, and their mixtures. 3. Emulsion according to claim 1 or 2, wherein the amount of said emulsifier is 0.2 to 3% by weight relative to the total weight of the emulsion. 4. Emulsion according to any one of the preceding claims, wherein the groups R 1 and R 2 of the additive form with the carbon atoms to which they are attached, a group of formula IV) following:

5. Emulsion according to any one of the preceding claims, wherein the R3 group of the additive denotes the hydrogen atom. 6. Emulsion according to any one of the preceding claims, wherein the groups R ₄ and R ₅ of the additive simultaneously denote the hydrogen atom. Emulsion according to any one of the preceding claims, in which the groups R 6 and R ₇ of the additive, which are identical or different, represent, independently of one another, the hydrogen atom and the methyl radical. or ethyl, more preferably R6 and R ₇ denote simultaneously hydrogen. An emulsion according to any one of the preceding claims wherein said additive of formula (I) is selected from 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 5-carboxy 4-hexyl-2-cyclohexene-1-octanoic acid, and mixtures thereof; 6-carboxy-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-carboxy-4-pentyl-2-cyclohexene-1-nonanoic acid and mixtures thereof; 6-carboxy-6-methyl-4-hexyl-2-cyclohexene-1-octanoic acid, 5-carboxy-5-methyl-4-hexyl-2-cyclohexene-1-octanoic acid, and mixtures thereof; 6-carboxy-6-methyl-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-carboxy-5-methyl-4-pentyl-2-cyclohexene-1-nonanoic acid and mixtures thereof; 6-sulfonic acid-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-sulfonic acid-4-pentyl-2-cyclohexene-1-nonanoic acid, and mixtures thereof; 6-phosphonic acid-4-hexyl-2-cyclohexene-1-octanoic acid, 5-phosphonic acid-4-hexyl-2-cyclohexene-1-octanoic acid, and mixtures thereof; 6-phosphonic acid-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-phosphonic acid-4-pentyl-2-cyclohexen-1-nonanoic acid, and mixtures thereof; 5,6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 5,6-carboxy-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-carboxylic acid-5-carboxylic acid; 4-hexyl-2-cyclohexene-1-octanoic acid, 5-pentoxide-4-pentyl-2-cyclohexene-1-nonanoic acid; and mixtures thereof, preferably from 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, and mixtures thereof. An emulsion according to any one of the preceding claims, wherein said additive is a polymerized fatty acid, said polymerized fatty acid comprising fatty acid monomers, fatty acid dimers, fatty acid trimers and tetramers of fatty acids, preferably comprising predominantly fatty acid dimers and fatty acid trimers. 10. Emulsion according to any one of the preceding claims, wherein the amount of phosphoric acid or a derivative thereof is from 0.1 to 4% by weight relative to the total weight of the emulsion. 11. Emulsion according to any one of the preceding claims, characterized in that it comprises phosphoric acid. 12. Emulsion according to any one of the preceding claims, wherein the amount of said additive represents from 0.1 to 5% by weight, more preferably from 0.3 to 2% by weight, even more preferably from 0.3 to 1% by weight. % by weight, based on the total weight of the emulsion. 13. Emulsion according to any one of the preceding claims, in which the amount of bitumen represents from 50 to 90% by weight, preferably from 50 to 70%, more preferably from 60 to 70% by weight, relative to the total weight of the emulsion. 14. Process for the preparation of at least one bituminous emulsion as defined in any one of the preceding claims, comprising at least one mixing step:  at least one additive of formula (I) as defined in any one of claims 1 to 13;  bitumen,  at least one emulsifier as defined in any one of claims 1 to 13, phosphoric acid or a derivative thereof as defined in any one of claims 1 to 13, and  at least one aqueous phase. 15. The method of claim 14, comprising the following successive steps: mixing the additive and said bitumen; then  mixing the aqueous phase, the emulsifier, the phosphoric acid or one of its derivatives and the bituminous composition obtained after mixing the bitumen and said additive. 16. Cold-poured mix comprising at least one emulsion as defined in any one of claims 1 to 13, and aggregates. 17. Use of the emulsion as defined in any one of claims 1 to 13 to improve the resistance to stripping of a cold-poured mix as defined in claim 15.