EMULSIFYING COMPOSITION FOR BITUMEN

Description

Technical field

[0001] The present disclosure relates to the field of polymeric emulsifiers. In particular, the present disclosure relates to emulsifying compositions for bitumens incorporating at least one polymeric emulsifier, in particular for the preparation of road bituminous materials. More specifically, the present disclosure belongs to the fields of maintenance and upkeep of road networks with bituminous coatings with bitumen emulsion (ACBE), according to the definition given in point 3.1.9 of standard NF EN 13108-31 of September 2019. Prior art

[0002] There are several techniques for preparing bituminous road materials. They are classified into three main categories: cold techniques, hot techniques, and warm techniques.

[0003] Cold-mixing techniques allow the binder and aggregates to be used at temperatures below 100°C, most often at room temperature. They are based on the use of bitumen emulsions as a binder. The bitumen is then dispersed in the aqueous phase by mechanical action in the presence of surfactants.

[0004] Hot-mix techniques use an anhydrous binder that is made, or kept, fluid by heating, generally to 160°C or more. Hot-mix techniques use aggregates that are heated and dried at high temperatures before being brought into contact with the binder. For example, asphalt can be produced at a temperature of around 160°C, or more depending on the binder's characteristics, by coating aggregates with the binder; this is known as hot-mix asphalt.

[0005] The so-called warm techniques also allow the operations described above to be carried out but at temperatures lower than those used for hot techniques, generally between 100°C and 150°C, in which case we speak of warm asphalt mixes. Some so-called warm techniques can be carried out in the presence of water at a mass percentage of less than 3% relative to the mass of bitumen; in these techniques, the components are dry before the water is added.

[0006] Bitumen emulsions are obtained by hot dispersion of a bituminous binder in an aqueous phase. The production of such emulsions requires mechanical shear energy but also chemical energy. The latter is necessary to reduce the water / bitumen surface tension and to allow the medium-term preservation, i.e. approximately 1 month, of the bitumen in the dispersed state in the aqueous phase. This chemical energy is provided by molecules called surfactants and its intensity is therefore dependent on the family of molecules considered.

[0007] Techniques using bitumen emulsions, in particular so-called cold techniques, can be implemented for different applications such as: coating, including for example “heavy emulsions”, “cold-poured asphalt” (CMA), “dense cold asphalt”, “storable asphalt”; spreading, mainly with “surface coatings”, “sealing coatings”, “impregnation emulsions” and “bonding layers”; sprayed asphalt or “Jet Patching”.

[0008] These three types of road applications require bitumen emulsions whose characteristics are adapted to the intended application. Thus, it is known to the person skilled in the art that to obtain a bitumen emulsion suitable for the cold mix technique, and more precisely a "severe emulsion", a slow-breaking emulsion is required so that it can diffuse into the granular matrix during the coating phase. The emulsion must also be stable during storage to avoid breaking in storage or transport tanks and it must have sufficient adhesiveness to meet the performance criteria for these materials. As a general rule, emulsions that meet these criteria are C60B5 / B7 and / or C65B5 / B7 type emulsions. These names, taken from standard NF EN 13808, define cationic emulsions with medium-slow to slow breaking. The pH of these emulsions is less than or equal to 7.The emulsifiers generally used in these coating techniques are cationic surfactants such as polyamine, polyamidoamine or imidazopolyamine. Amphoteric surfactants are also used in these applications.

[0009] Solutions to improve the adhesion between the bituminous binder and the aggregates have been proposed, including the use of the reaction product of a styrene-maleic anhydride polymer with a polyalkylene amine in anionic bituminous emulsions disclosed in US patent 5,776,234. Anionic emulsions are distinguished from cationic emulsions by their breaking mechanism. In fact, a vast majority of bituminous emulsions for road applications are cationic. Anionic bituminous emulsions are mainly used for industrial applications, such as building waterproofing, for example for foundations or subgrades.

[0010] Substituted styrene-maleimide copolymers have been studied but are not known as surfactants for bitumen emulsions. In particular, Kun et al. investigated the influence of molecular weight of poly(styrene-alt-octadecyl maleimide) as a flow promoter for petroleum (Energy Fuels 2016, 30, 2721-2728; DOI / 10.1021 / acs.energyfuels.5b02946). Also worth mentioning is the study by Qingjun et al. on the influence of the molecular structure poly(styrene-co-octadecyl maleimide) as an asphaltene stabilizer in petroleum (Energy Fuels 2020, 34, 3057-3064; DOI / 10.1021 / acs.energyfuels.9b04372).

[0011] There is a need to propose, for road applications, a new family of surfactant molecules and a new surfactant composition with a view to obtaining bitumen emulsions, in particular cationic bitumen emulsions, having a good binder content, low sieve rejection, a breaking speed adapted to the intended application and good storage stability, and the use of which in cold coating techniques, for example of the emulsion gravel type, makes it possible to obtain materials which have good coating quality, good storability, good workability and improved water resistance.

[0012] Existing technologies can achieve one or more of the four criteria described above, but never all four at the same time. For example, fatty amines provide good water resistance, but a coating of less than 80%; cationic amine-modified lignin-based coatings provide 100% coating but generally provide water resistance below the standard.

[0013] In particular, the present invention aims to improve the water resistance, while maintaining or improving the coating rate, of the materials obtained from a bitumen emulsion and to better control the breaking kinetics. It should be noted that the breaking kinetics is linked to the kinetics of evaporation and drying in the context of the use of anionic emulsifying compositions but linked to the kinetics of chemical reaction in the context of the use of cationic emulsifying compositions. Summary

[0014] This disclosure improves the situation.

[0015] An emulsifying composition is proposed comprising: a copolymer comprising between 10% and 70% by mole of at least one monomeric unit A and between 30% and 90% by mole of at least one monomeric unit B, said monomeric unit B being cationic or cationizable at acidic pH, and at least one emulsifier chosen from the group comprising cationic emulsifiers, non-ionic emulsifiers and amphoteric emulsifiers and mixtures thereof.

[0016] According to another aspect, there is provided a bituminous emulsion comprising a bituminous binder, the emulsifying composition as described above, and water characterized in that the mass percentage of the copolymer of said emulsifying composition, relative to the total weight of the emulsion, is between 0.75% and 3%, more advantageously between 0.9% and 2% and even more advantageously between 1% and 1.4%.

[0017] According to another aspect, the use of a copolymer of formula I, in salified form or not, is proposed: in which: R is a linear or branched, saturated or unsaturated, aliphatic or aromatic monovalent hydrocarbon radical, comprising at most 1000 carbon atoms, preferably between 5 and 25 carbon atoms, which may comprise one or more heteroatoms chosen from nitrogen and oxygen, preferably R is an alkyl chain containing at least one primary, secondary, tertiary or quaternary amine function; X, Y and Z represent the molar fraction of each of the monomeric units, X is less than 0.1, Y is between 0.1 and 0.7 and Z is between 0.3 and 0.9, the sum X + Y + Z being equal to 1; for the preparation of a cationic or non-ionic bituminous emulsion.

[0018] According to another aspect, there is provided a method for preparing a bituminous emulsion as described above, comprising a step of mixing a bituminous binder and an emulsifying composition as described above.

[0019] The features set out in the following paragraphs may, optionally, be implemented, independently of each other or in combination with each other: Detailed description Emulsifying composition

[0020] The invention therefore relates to an emulsifying composition comprising a copolymer comprising between 10% and 70% by mole of at least one monomeric unit A and between 30% and 90% by mole of at least one monomeric unit B, said monomeric unit B being cationic or cationizable at acidic pH, and at least one emulsifier chosen from the group comprising cationic emulsifiers, non-ionic emulsifiers and amphoteric emulsifiers and mixtures thereof.

[0021] For the purposes of the present invention, the term cationizable designates the property of a molecule of being able to carry one or more positive charges depending on its immediate environment. For example, a molecule carrying a primary, secondary or tertiary amine function may be non-ionic at a pH greater than or equal to the pKa of the amine function and cationic at a pH lower than its pKa, it being understood that the level of protonated amine functions increases with the drop in pH.

[0022] An emulsifying composition is a composition capable of forming an emulsion when mixed with another composition such as an oil or bitumen. In some cases, particularly for bitumen emulsions, the addition of shear energy may be necessary. Copolymer

[0023] The copolymer of the emulsifying composition according to the invention is a random, alternating, block or grafted copolymer, preferably the copolymer is an alternating copolymer.

[0024] Advantageously, the copolymer has a weight average molecular weight (Mw) of between 500 and 100,000, more advantageously between 10,000 and 80,000 and even more advantageously between 30,000 and 60,000.

[0025] Advantageously, the monomeric unit A is selected from the group comprising, and more advantageously consisting of, olefins, diolefins, styrenes, vinyl esters, vinyl ethers, acrylates, methacrylates, acrylonitriles and their alkyl or aryl derivatives, adipic acid, benzoic acid, butyl benzoic acid, decadiene, ethylene, isobutene, iso-octylene, (meth)acrylic esters of saturated or unsaturated cyclic or bicyclic alcohols having from 6 to 20 carbon atoms, (meth)acrylic esters, branched-chain alkyl alcohols, neopentyl glycol, octadecene, palmitic acid, pentaerythritol / neopentyl glycol, phthalic anhydride, styrene, trimethylol ethane vinyl acetate or vinyls alkyl ethers and mixtures thereof. Particularly advantageously, the monomeric unit A is styrene.

[0026] The molar percentage of monomeric unit A, relative to the total number of monomeric units in the copolymer, is between 10% and 70%, preferably between 20% and 60%, more preferably between 45% and 65% and even more preferably, the molar percentage of monomeric unit A is 50%.

[0027] The monomeric unit B is cationic or cationizable. In the embodiment in which the monomeric unit B is cationic, said monomeric unit B advantageously comprises a quaternary ammonium. In the embodiment in which the monomeric unit B is cationizable, said monomeric unit B advantageously comprises a primary, secondary or tertiary amine function. In this embodiment, said amine function captures a proton when the copolymer is placed in a medium whose pH is lower than the pKa of said amine function, it being understood that the level of protonated amine functions increases with the decrease in pH.

[0028] The molar percentage of monomeric unit B, relative to the total number of monomeric units in the copolymer, is between 30% and 90%, preferably between 40% and 70%, more preferably between 45% and 65% and even more preferably, the molar percentage of monomeric unit B is 50%.

[0029] In a particularly advantageous embodiment, the emulsifying composition according to the invention is characterized in that the copolymer is of formula I, in salified form or not: in which: R is a linear or branched, saturated or unsaturated, aliphatic or aromatic monovalent hydrocarbon radical, comprising at most 1000 carbon atoms, preferably between 5 and 25 carbon atoms, which may comprise one or more heteroatoms chosen from nitrogen and oxygen, preferably R is an alkyl chain containing at least one primary, secondary, tertiary or quaternary amine function; X, Y and Z represent the molar fraction of each of the monomeric units, X is less than 0.1, Y is between 0.1 and 0.7 and Z is between 0.3 and 0.9, the sum X + Y + Z being equal to 1.

[0030] Advantageously, R is selected from the group comprising, preferably consisting of, 2-ethylhexylamine, N-octylamine, decylamine, octadecylamine, stearylamine, laurylamine, N-methylstearin amine, N-ethyloctadecylamine, N-butyllaurylamine and mixtures thereof.

[0031] X is less than 0.5, advantageously X is less than 0.1 and even more advantageously, X is equal to 0.

[0032] Y is between 0.1 and 0.7, advantageously Y is between 0.2 and 0.6, more advantageously Y is between 0.35 and 0.55 and even more advantageously Y is equal to 0.5.

[0033] Z is between 0.3 and 0.9, advantageously Z is between 0.4 and 0.7, more advantageously Z is between 0.45 and 0.65 and even more advantageously Z is equal to 0.5. Emulsifier

[0034] The emulsifying composition according to the invention comprises at least one emulsifier chosen from the group comprising cationic emulsifiers, non-ionic emulsifiers and amphoteric emulsifiers and mixtures thereof, advantageously the emulsifier is chosen from the group comprising cationic emulsifiers and non-ionic emulsifiers, even more advantageously the emulsifier is a cationic emulsifier.

[0035] Advantageously, the emulsifying composition comprises between 0.5% and 2.5% by weight, relative to the total weight of the emulsion, of emulsifier.

[0036] Advantageously, the emulsifying composition comprises between 50% and 90% by weight, relative to the total weight of the components other than water, of the copolymer of formula I, between 0.1% and 30% by weight, relative to the total weight of the components other than water, of the non-ionic emulsifier and between 0% and 5% by weight, relative to the total weight of the components other than water, of cationic and / or amphoteric emulsifier.

[0037] Advantageously, emulsifiers have an HLB between 10 and 30 according to the 1949 Griffin method.

[0038] Advantageously, the emulsifier comprises at least one amine, polyamine, amide, alkylamidoamine, alkylimidazoline, quaternary ammonium, ethylene oxide and propylene oxide function. Advantageously, the emulsifier comprises at least two different functions chosen from the amine, polyamine, amide, alkylamidoamine, alkylimidazoline, quaternary ammonium, ethylene oxide and propylene oxide functions.

[0039] Advantageously, said emulsifier is chosen from fatty alkylimidazopolyamines, fatty alkylamidopolyamines, fatty polyamines, alkoxylated fatty polyamines, alkylated fatty polyamines and mixtures thereof, more advantageously, said emulsifier is chosen from mixtures of C16-C18 fatty alkylimidazopolyamines obtained by reaction of fatty acids or vegetable oil with polyethylene polyamines such as triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA) and ethoxylated tallow fatty polyamines. Bituminous emulsion

[0040] The invention also relates to a bituminous emulsion comprising a bituminous binder, the emulsifying composition as described above, and water, characterized in that the mass percentage of the copolymer of said emulsifying composition, relative to the total weight of the emulsion, is between 0.75% and 3%, more advantageously between 0.9% and 2% and even more advantageously between 1% and 1.4%.

[0041] Advantageously, the bituminous emulsion has a mass percentage of bituminous binder, relative to the total weight of the emulsion, of between 50% and 80%, preferably between 55% and 75% and more preferably between 60% and 70%. Bituminous Binder

[0042] In the context of the present invention, bituminous binder means all of the following products: natural bitumen, bitumens derived from mineral oil and the resulting mixtures, bitumens obtained by atmospheric distillation, by distillation under reduced pressure, by visbreaking, by cracking, precipitation residues (such as in propane), blown bitumens, tars and the mixtures which may result therefrom, synthetic or plant-based road binders containing modified or unmodified natural resins mixed with petroleum or plant-based oils or their derivatives and bitumens modified by natural or synthetic polymers.As natural or synthetic polymer, we can cite for example, and in an indicative and non-limiting manner, thermoplastic elastomers such as random or block copolymers of styrene and butadiene, linear or star-shaped (SBR, SBS) or of styrene and isoprene (SIS), possibly crosslinked, copolymers of ethylene and vinyl acetate, homopolymers and olefinic copolymers of ethylene, propylene or butylene, polyisobutylenes, polybutadienes, polyisoprenes, polyvinyl chloride, rubber crumb or any polymer used for the modification of bitumens as well as their mixtures. In general, a quantity of polymer of 2 to 10% by weight relative to the weight of bitumen is used. These different polymers are considered without limitation of presentation, whether in anhydrous form (powder, granules or in solution) but also in the form of aqueous dispersion (latex).

[0043] Some synthetic bitumens are also sometimes called clear, pigmentable or colorable bitumens. These bitumens contain little or no asphaltenes and can therefore be colored. These bitumens are based on petroleum resin and / or indene-coumarone resin and lubricating oil as described for example in patent EP 0 179 510.

[0044] Examples of common synthetic binders are Kromatis ®< from Total and / or Bituclair ®< from Colas.

[0045] The bituminous binders that can be used for the invention can also be mixtures of bitumens with hydrocarbon binders from industrial processes such as tall oil pitch (from the paper pulp refining process) or pitch from vegetable oil distillation processes. Such products, bituminous binders from refining or synthetic, can be used as such or made fluid via a mineral or vegetable organic solvent, whether drying or not, for example, for their use as a primer, sealing coating for road tack coat. According to another method of use, they can be dispersed in an aqueous medium and thus give rise to hydrocarbon binders in aqueous phase. These binders, whether anhydrous or aqueous, can be used as such or mixed with mineral materials, for example in the form of aggregates, such as sand, gravel, etc., to obtain bituminous road materials.

[0046] In one embodiment, the bitumens used are bitumens originating from the refining of crude oil, in particular from atmospheric and / or vacuum distillation of oil. These bitumens may optionally be blown, visbroken and / or deasphalted. The bitumens may be hard grade or soft grade bitumens. The different bitumens obtained by the refining processes may be combined with each other to obtain the best technical compromise.

[0047] In another embodiment, the bitumens used are bitumens fluxed by the addition of volatile solvents, fluxes of petroleum origin, carbochemical fluxes and / or fluxes of plant origin.

[0048] Preferably, the bitumen according to the invention is chosen from unmodified crude oil refining bitumens, fluxed or not. Additives

[0049] Generally, for the preparation of bituminous road materials, the bitumens or binders used can be pure or modified by polymers. In the case of using polymers, these can be added to the bitumen in order to obtain bituminous products with improved mechanical properties. These polymer-modified bituminous products are used in road, urban and airport construction using, for example, the techniques mentioned above. Polymers are macromolecules formed by covalent chemical bonds between several repeating units or monomers. The modification of bitumens with linear or branched polymers of high molar masses is used to improve the mechanical properties of the bituminous product.Bitumens modified in this way, called polymer-modified bitumens or BmP, have greater flexibility at low temperatures and better plasticity at high temperatures than their unmodified equivalents. They also have stronger internal cohesion. Finally, BmPs have a higher rigidity modulus, which also improves resistance to rutting of bituminous materials or to the tearing of aggregates from coatings, for example.

[0050] The bituminous emulsion may also include one or more additives to further improve performance.

[0051] The bituminous emulsion according to the invention can be advantageously used to prepare a bituminous coating. A bituminous coating is a mixture between a bituminous binder and one or more granular materials, recycled or native such as gravel or sand. The bituminous emulsion according to the invention is particularly suitable for the preparation of a bituminous coating comprising between 5% and 12% by weight, relative to the total weight of the bituminous coating, of the bituminous emulsion and between 88% and 95% by weight, relative to the total weight of the bituminous coating of granular materials. Other aspects of the invention

[0052] The invention also relates to the use of a copolymer of formula I, in salified form or not: in which: R is a linear or branched, saturated or unsaturated, aliphatic or aromatic monovalent hydrocarbon radical, comprising at most 1000 carbon atoms, preferably between 5 and 25 carbon atoms, which may comprise one or more heteroatoms chosen from nitrogen and oxygen, preferably R is an alkyl chain containing at least one primary, secondary, tertiary or quaternary amine function; X, Y and Z represent the molar fraction of each of the monomeric units, X is less than 0.1, Y is between 0.1 and 0.7 and Z is between 0.3 and 0.9, the sum X + Y + Z being equal to 1; for the preparation of a cationic or non-ionic bituminous emulsion.

[0053] The copolymer of formula I is advantageously obtained by the reaction of a copolymer of formula II in which: X', Y' represent the molar fraction of each of the monomeric units, X' is between 0.3 and 0.9 and Y' is between 0.1 and 0.7, the sum X' + Y' being equal to 1; and an amine of formula III in which: R 1 is a linear or branched, saturated or unsaturated, aliphatic or aromatic monovalent hydrocarbon radical, comprising at most 1000 carbon atoms, preferably between 5 and 25 carbon atoms, which may comprise one or more heteroatoms chosen from nitrogen and oxygen, preferably R 1 is an alkyl chain containing at least one primary, secondary, tertiary or quaternary amine function; R 2 and R 3 , identical or different, are chosen from a hydrogen atom, a linear or branched, saturated or unsaturated, aliphatic or aromatic monovalent hydrocarbon radical, comprising at most 1000 carbon atoms, preferably between 5 and 25 carbon atoms, which may comprise one or more heteroatoms chosen from nitrogen and oxygen, preferably R 2 and / or R 3 is an alkyl chain containing at least one primary, secondary, tertiary or quaternary amine function.

[0054] The invention also relates to a process for preparing a bituminous emulsion as described previously, comprising a step of mixing a bituminous binder and an emulsifying composition as described above. Examples Preparation of bituminous emulsions El1 to EI4, EC1 and EC2 :

[0055] Bituminous emulsions E1 to E14, according to the invention, and EC1 and EC2 (counter-examples) were obtained with a colloidal mill of the Emulbitume brand. The bitumen mass content of the emulsion is 60%. The bitumen used is a paraffinic bitumen with a penetrability of 70 / 100 supplied by the company Total and coming from the Feyzin refinery in France. The temperature of the bitumen during emulsification is 145°C. The bitumen was used fluxed with a petroleum fluxing agent.

[0056] The emulsions were prepared by introducing the aqueous phase emulsifying composition and the bituminous binder into a container. The compositions of the bituminous emulsions are listed in Table 1 below: [Table 1] Components EI1 EI2 EI3 EI4 EC1 EC2 Anhydrous phase: Bitumen 70 / 100 (kg / t) 582 582 582 582 582 582 Fluxant (kg / t) 18 18 18 18 18 18 Aqueous phase: CTA (kg / t) - - - - - 14 CTI (kg / t) 12,9 13 14 18 10,8 - Including TI (kg / t) 7,5 9,3 10 13,8 5,3 - HCl 33% (kg / t) 2,5 2,5 2,5 2,5 2,5 2,5 Water (kg / t) 384,6 384,5 383,5 379,5 386,7 383,5 CTA: emulsifier: INDULIN GEF2 ®<; CTI: emulsifying composition comprising XIRAN 1000IC ®< , SERDOX NSP50 ®< as non-ionic emulsifier and DINORAM O ®< as cationic emulsifier ; TI: XIRAN 1000IC ®< . Evaluation of bituminous emulsions

[0057] The emulsions are analyzed to determine their quality and application properties, according to the criteria of the NE EN 13808 standard of August 2013.

[0058] The binder content of the emulsion is characterized by the desiccant balance method (measured according to standard NF EN 16849 of December 2016).

[0059] The quality of the emulsion is judged by the residue on a 0.5 mm sieve after manufacture (measured according to standard NF EN 1429 of August 2013)

[0060] The quality of destabilization after application is judged using the rupture index measured with Q92 filler expressed in Forshamer according to the operating method described in standard NF EN 13075-1 of December 2016. The lower this index, the more the emulsion will tend to destabilize quickly, leading to a more or less good coating quality.

[0061] The results are listed in Table 2 below: [Table 2] EI1 EI2 EI3 EI4 EC1 EC2 Penetrability of the binder (1 / 10 mm) 218 218 218 218 218 218 pH at 26°C: 2,5 2,6 2,6 2,5 2,1 2,6 Dry extract: IR - 110°C (%) 61,0 61,0 59,4 60,1 58,6 60,2 0.5mm sieve rejection (%) < 0,1 < 0,1 < 0,1 < 0,1 < 0,1 < 0,1 Forshamer Break Index 181 189 199 221 210 183

[0062] All tested emulsions comply with the specifications of standard NF EN 13808 of August 2013. Qualification of emulsions in the Graves Emulsion technique:

[0063] One of the standard criteria for qualifying the performance of cold asphalt techniques is the measurement of water sensitivity. This measurement of sensitivity is codified through the test standard NF P 98 251-4, DURIEZ test developed on cold hydrocarbon mixtures with bitumen emulsion.

[0064] Cold mixes of the "Grave Emulsion" type were formulated with the previous emulsions El1 to EI4, EC1 and EC2, ensuring that a constant residual binder content was maintained in the mixes. The petrographic nature of the materials was analyzed; it is a sericitoschist from the CEYRAT quarry. The formulas of the gravel emulsions are recalled in Table 3 below: [Table 3] GEI1 GEI2 GEI3 GEI4 GEC1 GEC2 GE Sericitoschist 0 / 10: Materials (%) 100 100 100 100 100 100 Emulsion (No. - ppc) 7,2 7,2 7,2 7,2 7,2 7,2 Total water (ppc) 7 7 7 7 7 7

[0065] The EN 13108-31 standard defines the various performance criteria for bitumen emulsion coatings and the performance classes. In this standard, a specific criterion related to coating quality is specified on page 42 and reproduced in Table 4 below. [Table 4] Coating class Minimum binder coverage percentage % C3 >97 C2 90 à 97 C1 75 à <90 C0 <75

[0066] All tested emulsions resulted in a C3 coating level > 97%.

[0067] These mixes were subsequently subjected to the Duriez test according to the NF P 98 251-4 standard. The NF P 98-121 standard defines the performance of bituminous mixes with gravel emulsion type bitumen emulsion, this standard specifies among other things the application thicknesses of such materials, as well as the minimum characteristics to be achieved depending on the type of product formulated. In this standard a summary table presents the minimum performances to be achieved in the Duriez test, the information in this table is reproduced in part in table 5 below. [Table 5] Type of Grave-emulsion Type R Type S class 1 Type S class 2 Compressive strength without immersion (R in MPa) ≥ 1,5 ≥ 2,5 ≥ 3,5 R / R ratio ≥ 55% ≥ 55% ≥ 65%

[0068] The results obtained with the different serious emulsions are recorded in Table 6 below: [Table 6] GEI1 GEI2 GEI3 GEI4 GEC1 GEC2 GE Sericitoschist 0 / 10: r / R (%) 55 61 60 77 33 33 R (MPa) 4,4 4,8 4,5 5,0 2,7 4,4 Internal binder content (%) 3,9 3,9 3,9 3,9 3,9 3,9

[0069] Following these tests, it is observed that the more the proportion of TI increases in the surfactant composition of the invention and therefore in the emulsion, the more the water resistance of the coating increases.

[0070] Thus, the emulsifying composition according to the invention makes it possible to achieve the desired water resistance specifications without degrading the coating quality or the workability of the coating.

Claims

1. Emulsifier composition comprising: - a copolymer of formula I, in salified form or not: in which : - R is a linear or branched, saturated or unsaturated, aliphatic or aromatic monovalent hydrocarbon radical comprising at most 1000 carbon atoms, preferably between 5 and 25 carbon atoms, which may comprise one or more heteroatoms chosen from nitrogen and oxygen, preferably R is an alkyl chain containing at least one primary, secondary, tertiary or quaternary amine function; - X, Y and Z represent the molar fraction of each of the monomer units, X is less than 0.1, Y is comprised between 0.1 and 0.7 and Z is comprised between 0.3 and 0.9, the sum X + Y + Z being equal to 1, - and at least one emulsifier chosen from the group comprising cationic emulsifiers, non-ionic emulsifiers and amphoteric emulsifiers and mixtures thereof.

2. Emulsifying composition according to claim 1, characterized in that R is chosen from the group comprising, preferably consisting of, 2-ethylhexylamine, N-octylamine, decylamine, octadecylamine, stearylamine, laurylamine, N-methylstearin amine, N-ethyloctadecylamine, N-butyllaurylamine and mixtures thereof.

3. Emulsifier composition according to any one of the preceding claims, characterized in that the emulsifier is chosen from fatty alkylimidazopolyamines, fatty alkylamidopolyamines, fatty polyamines, alkoxylated fatty polyamines, alkylated fatty polyamines and mixtures thereof, more advantageously, said emulsifier is chosen from mixtures of C16-C18 fatty alkylimidazopolyamines obtained by reacting fatty acids or vegetable oil with polyethylenepolyamines such as triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA) and ethoxylated tallow fatty polyamines.

4. Bituminous emulsion comprising a bituminous binder, the emulsifying composition according to any one of claims 1 to 3 and water, characterized in that the percentage by weight of the copolymer of said emulsifying composition, relative to the total weight of the emulsion, is comprised between 0.75% and 3%, more advantageously between 0.9% and 2% and even more advantageously between 1% and 1.4%.

5. Bituminous emulsion according to claim 4, characterized in that the percentage by weight of bituminous binder, relative to the total weight of the emulsion, is comprised between 50% and 80%.

6. Use of a copolymer of formula I, in salified form or not : in which : - R is a linear or branched, saturated or unsaturated, aliphatic or aromatic monovalent hydrocarbon radical comprising at most 1000 carbon atoms, preferably between 5 and 25 carbon atoms, which may comprise one or more heteroatoms chosen from nitrogen and oxygen, preferably R is an alkyl chain containing at least one primary, secondary, tertiary or quaternary amine function; - X, Y and Z represent the molar fraction of each of the monomer units, X is less than 0.1, Y is comprised between 0.1 and 0.7 and Z is comprised between 0.3 and 0.9, the sum X + Y + Z being equal to 1; for the preparation of a cationic or non-ionic bituminous emulsion.

7. Use according to claim 6, characterized in that the copolymer is obtained by reacting a copolymer of formula II in which: - X' and Y' represent the molar fraction of each of the monomer units, X' is comprised between 0.3 and 0.9 and Y' is comprised between 0.1 and 0.7, the sum X' + Y' being equal to 1; and a primary amine of formula III in which : - R1 is a linear or branched, saturated or unsaturated, aliphatic or aromatic monovalent hydrocarbon radical comprising at most 1000 carbon atoms, preferably between 5 and 25 carbon atoms, which may comprise one or more heteroatoms chosen from nitrogen and oxygen, preferably R1 is an alkyl chain containing at least one primary, secondary, tertiary or quaternary amine function; - R2 and R3, which may be identical or different, are chosen from a hydrogen atom, a linear or branched, saturated or unsaturated, aliphatic or aromatic monovalent hydrocarbon radical comprising at most 1000 carbon atoms, preferably between 5 and 25 carbon atoms, which may comprise one or more heteroatoms chosen from nitrogen and oxygen, preferably R2 and / or R3 is an alkyl chain containing at least one primary, secondary, tertiary or quaternary amine function.

8. Process for preparing a bituminous emulsion according to any one of claims 4 and 5, comprising a step of mixing a bituminous binder and an emulsifying composition according to any one of claims 1 to 5.