WO2024208675A1 - Surfactant composition based on a mixture of dibasic amino acid ester and glycine betaine ester, and uses thereof - Google Patents

Abstract

The present invention relates to a surfactant composition based on at least one glycine betaine ester salt and at least one dibasic amino acid ester salt, to the process for preparing same by co-esterification of glycine betaine and at least one dibasic amino acid, and to the uses thereof, in particular for producing a spreading or coating emulsion that can be used in the preparation of a road surface.

Description

Surfactant composition based on a mixture of dibasic amino acid ester and glycine betaine ester and its uses

SUBJECT OF THE INVENTION

The present invention relates to a surfactant composition based on at least one glycine betaine ester salt and at least one dibasic amino acid ester salt, its preparation process by co-esterification of glycine betaine and at least one dibasic amino acid and its uses, in particular for manufacturing a spreading or coating emulsion which can be used in the preparation of a road surface.

BACKGROUND OF THE INVENTION

Surfactants are essential raw materials for the manufacture of a variety of products. Among these, cationic surfactants represent, admittedly, a less extensive market than that of anionic or nonionic surfactants, but they are nevertheless of interest in multiple applications, particularly in the manufacture of detergent and cosmetic products, as well as in water treatment.

Due to their toxicity, some surfactants such as dimethyldialkylammonium salts, present in most fabric softeners, are seeing their use limited or even abandoned in some European countries such as Germany and the Netherlands. Under pressure from ecology, surfactant producers must offer products that are less polluting, more biodegradable and have the lowest possible ecotoxicity. In addition to environmental constraints, consumers want products that are as natural as possible.

In this context, novel bio-sourced and biodegradable cationic surfactants based on glycine betaine ester salts have been proposed in patent US-7,829,521, in the publication of F. Goursaud et al in Green Chem., 2008, 10, 310-320 and in patent application WO2020/109710. These surfactants are prepared by esterification of glycine betaine in the presence of an organic acid and a fatty alcohol.

However, it appeared to the Applicant that these surfactants did not always have a sufficiently hydrophilic character in an acidic medium and/or the capacity to develop sufficient electrostatic interactions with a substrate, which may constitute a disadvantage. in certain applications, particularly to protect a substrate against corrosion or to make it water-repellent.

Furthermore, it has been suggested to use the above surfactants in bitumen emulsions (US-7,662,225). Bituminous binder emulsions, in particular bitumen emulsions, are commonly used for various road applications, where they can be spread alone to obtain for example bonding layers or impregnation layers, or in the presence of aggregates to produce surface wear coatings.

For a bitumen emulsion to be suitable for these spreading applications, it is necessary for it to have a rapid or even controlled break, in order to destabilize quickly after application and thus offer rapid curing and resumption of traffic. The emulsion must also have good storage stability, to avoid premature breakage in tanks or trucks and finally adhere effectively to most aggregates.

Bitumen emulsions are obtained by dispersing binder droplets in an aqueous phase. The binder droplets are stabilized in the continuous phase by surfactant compounds that are predominantly cationic in nature. Indeed, cationic surfactants are more versatile compared to anionic surfactants because they allow the manufacture of bitumen emulsions that can be used with a wide range of aggregates (solid mineral particles), specifically aggregates that contain different concentrations of silica. Materials composed of silica mainly carry negative charges on their surface and cationic bitumen emulsions are therefore favored due to the positive charge of the bitumen droplets which allows an attraction of the droplets to the surface of the aggregates. This attraction allows rapid breaking kinetics (demulsification) and thus a rapid reopening of the coating to traffic.

However, it appeared to the Applicant that surfactants based on glycine betaine esters are in a pasty form requiring heating to implement them, whereas it would be useful to have a grade that is fluid at room temperature or even at low temperature. Above all, their stability in an emulsion containing 69% of binder consisting of 70/100 bitumen, or even harder bitumen, is not satisfactory, whereas this is the type of binder most used in spreading. It is therefore necessary to add a flux which increases the manufacturing cost of these emulsions.

After much research, it appeared to the Applicant that a mixture of some of these glycine betaine esters with at least one dibasic amino acid ester made it possible to to overcome the deficiencies of glycine betaine esters in the various applications mentioned above.

These surfactants indeed have a sufficiently hydrophilic character in an acidic medium and/or a capacity to develop sufficient electrostatic interactions with a substrate, in particular with a view to protecting a substrate against corrosion or making it water-repellent. In addition, they make it possible to obtain a stable bituminous emulsion, with rapid or controlled breaking, having good adhesiveness to most aggregates and compatible with polymers, latexes and plant binders likely to be used in spreading compositions. This emulsion is in particular well suited to the formulation of a binder consisting not only of soft bitumen, but also of hard bitumen and is therefore more versatile. The proposed surfactant composition is also simpler to implement than that described in US-7,662,225, since it is not necessarily useful to heat it before forming the emulsion. This surfactant composition can also be used in a smaller quantity than that of the prior art.

SUMMARY OF THE INVENTION

Thus, the invention relates to a surfactant composition containing:

(a) at least one glycine betaine ester salt of formula (1): X ⁿ [(CH3)3N ⁺ -CH2-COO-R] _n ,

(b) at least one salt of a dibasic amino acid ester and a fatty alcohol of formula R-OH, where R is a mono- or polyunsaturated alkenyl group containing from 16 to 20 carbon atoms or a linear or branched alkyl group containing from 12 to 24 carbon atoms, X is an organic or inorganic anion and n is 1 or 2.

It also relates to a process for preparing this surfactant composition comprising the reaction of a reaction mixture containing at least one dibasic amino acid and glycine betaine or one of their salts with at least one mono- or polyunsaturated alcohol containing from 16 to 20 carbon atoms or a linear or branched, saturated alcohol containing from 12 to 24 carbon atoms (R-OH), in the presence of at least one organic or inorganic acid (X-H) and in the absence of organic solvent, at a temperature between 130 and 180°C.

The synthesis process implemented according to the invention is environmentally friendly, without solvent or polluting discharge, and easily transposable on a large scale industrial. It allows a particularly high-performance surfactant composition to be obtained in a single step.

The invention also relates to a spreading or coating emulsion, comprising:

(a) a hydrocarbon binder,

(b) the aforementioned surfactant composition, and

(c) water.

It also relates to the use of this emulsion in the formation of a road surface, in particular a surface wear coating, a bonding layer, a sealing veil, a sealing coating, paving joints or an impregnation layer, a bituminous grout or a cold-poured asphalt, preferably in the formation of a surface wear coating or a bonding layer.

It also relates to a process for preparing a road surface, comprising:

- a step of application by spreading this emulsion, either on the surface of a layer comprising solid particles, such as gravel, or on the surface of a support, followed by the application of a layer of solid particles, such as coatings, or

- a step of applying to a support a bituminous grout or a cold-poured coating comprising this emulsion.

The invention also relates to the use of this surfactant composition for the manufacture of a hydrocarbon binder emulsion, in particular a spreading or coating emulsion, in particular a bituminous emulsion.

Another subject of the invention relates to the use of the above-mentioned surfactant composition as a wetting agent, dispersant, flotation agent, lubricant, corrosion inhibitor, solubilizer, antistatic and/or detangling agent and/or for improving the effect and/or persistence of insecticidal substances and/or for improving the disinfectant power and/or persistence of the disinfectant effect of antimicrobial substances. DETAILED DESCRIPTION

The present invention relates to a surfactant composition comprising salts of glycine betaine ester and dibasic amino acid ester. These two compounds will now be described in more detail, as well as the process for preparing the surfactant composition.

Surfactant composition

The surfactant composition according to the invention contains precisely:

(a) at least one glycine betaine ester salt of formula (1): X ⁿ [(CH3)3N ⁺ -CH2-COO-R] _n ,

(b) at least one salt of a dibasic amino acid ester and a fatty alcohol of formula R-OH, where R is a mono- or polyunsaturated alkenyl group containing from 16 to 20 carbon atoms or a linear or branched alkyl group containing from 12 to 24 carbon atoms, X is an organic or inorganic anion and n is 1 or 2.

In the remainder of this description, the term "dibasic amino acid" means one or more amino acids having at least two protonatable groups, in particular chosen from lysine, histidine, arginine and mixtures thereof. According to the invention, it is preferred to use lysine. Furthermore, the expressions "the dibasic amino acid ester salt", "the dibasic amino acid salt" and "the dibasic amino acid" used in this description refer to both a single one of these compounds and to mixtures thereof. The same applies to the expressions "the glycine betaine ester salt" and "the glycine betaine salt".

In formula (1) above, X is an inorganic anion, in particular chloride, sulfate or perchlorate; or an organic anion, in particular an alkyl sulfate ion, in particular decyl sulfate or lauryl sulfate, an aryl sulfonate ion, in particular benzene sulfonate or paratoluene sulfonate, an alkyl sulfonate ion, in particular triflate, methanesulfonate, ethanesulfonate, decyl sulfonate, laurylsulfonate, camphorsulfonate, or a sulfosuccinate ion. It is preferred according to the invention that X is chosen from alkyl sulfonates and aryl sulfonates, in particular from methanesulfonate, ethanesulfonate, triflate, paratoluenesulfonate and camphorsulfonate ions. It is advantageously the methanesulfonate or ethanesulfonate ion.

The radical R can for its part be chosen from the groups cetyl (C16:0), stearyl (Cl 8:0), behenyl (C22:0), 2-hexyldecyl (C16R:0), 2-octyldodecyl (C20R:0), 2-decyltetradecyl (C24R:0), palmitoleyl (C16:1), oleyl (C18:1), linoleyl (C18:2), linolenyl (C18:3), and arachidonyl (C20:4), preferably R is a mono- or polyunsaturated alkenyl group. containing from 16 to 18 carbon atoms or a branched alkyl group containing from 16 to 20 carbon atoms, such as a 2-hexyldecyl or oleyl group, more preferably an oleyl group.

It is understood that the surfactant composition according to the invention may comprise several salts of esters of dibasic amino acid and glycine betaine. When this composition is obtained by co-esterification of glycine betaine and a dibasic amino acid, as described below, several fatty alcohols may in fact be used in the esterification reaction. This may in particular be the case when oleic alcohol is used, which is commercially available in a mixture with minor quantities of linear fatty alcohols.

The surfactant composition according to the invention advantageously also contains:

(c) at least one fatty alcohol of formula R-OH,

(d) optionally, at least one organic or inorganic acid of formula XH,

(e) optionally, at least one dibasic amino acid salt,

(f) optionally, at least one glycine betaine salt of formula (2): X ⁿ [(CH3)3N ⁺ -CH2- COOH]n'

(g) optionally, at least one ether of formula R-O-R,

(h) optionally, at least one chloroalkane and/or chloroalkene,

(i) optionally, at least one branched fatty alcohol or branched fatty alkane containing from 16 to 24 carbon atoms, when constituent (c) is a linear, saturated or unsaturated fatty alcohol.

In one embodiment, it contains:

(a) from 5 to 60% by weight of glycine betaine ester salt of formula (1),

(b) from 10 to 70% by weight of dibasic amino acid ester salt,

(c) from 5 to 35% by weight of fatty alcohol R-OH,

(d) from 0 to 20% by weight of organic or inorganic acid,

(e) from 0 to 15% by weight of dibasic amino acid salt,

(f) from 0 to 5% by weight of glycine betaine salt,

(g) from 1 to 20% by weight of ether,

(h) from 0 to 10% by weight of chloroalkane and/or chloroalkene,

(i) from 0 to 20%, preferably from 10 to 15%, of branched fatty alcohol or branched fatty alkane containing from 16 to 24 carbon atoms, when constituent (c) is a linear, saturated or unsaturated fatty alcohol. In a preferred embodiment, the surfactant composition according to the invention contains from 75 to 100%, preferably from 90 to 100%, of constituents (a) to (h).

The weight ratio of the dibasic amino acid ester salt to the glycine betaine ester salt may for example be between 15:85 and 95:5. It is preferably from 20:80 to 90:10 and more preferably from 70:30 to 90:10 for use in the manufacture of a spreading or coating emulsion. In other applications, the weight ratio of the dibasic amino acid ester salt to the glycine betaine ester salt is generally between 50:50 and 95:5, preferably between 65:35 and 95:5, more preferably between 75:25 and 95:5 and, more preferably, between 80:20 and 95:5.

Process of

The surfactant composition according to the invention can be prepared by simple mixing of the two ester salts which it contains, or by salification of a mixture of these two esters.

However, in a preferred embodiment of the invention, the surfactant composition is obtained according to a co-esterification process comprising the reaction of a reaction mixture containing at least one dibasic amino acid or one of its salts and glycine betaine with at least one mono- or polyunsaturated alcohol containing from 16 to 20 carbon atoms or a linear or branched, saturated alcohol containing from 12 to 24 carbon atoms (R-OH), in the presence of at least one organic or inorganic acid (X-H) and in the absence of organic solvent, at a temperature between 130 and 180°C.

The glycine betaine used in this process may be of plant or synthetic origin and in the form of a salt. For its part, the dibasic amino acid may be used in the form of a salt, typically hydrochloride. It is necessary to protonate them beforehand using an organic or inorganic acid. The acid may in particular be chosen from inorganic acids such as hydrochloric acid, sulfuric acid, perhalohydric acids, such as perchloric acid, and mixtures thereof. Alternatively, it may be chosen from organic acids, such as alkylsulfuric acids, for example decyl or lauryl sulfuric acid; arylsulfonic acids, such as benzenesulfonic acid, paratoluenesulfonic acid; alkylsulfonic acids, such as triflic acid, methanesulfonic acid, ethanesulfonic acid, decylsulfonic acid, laurylsulfonic acid or camphorsulfonic acid; sulfosuccinic acid; and mixtures thereof. Lewis acids may also be used. Preferably, it is an alkylsulfonic acid and in particular ethanesulfonic acid, since it is readily biodegradable, or methanesulfonic acid.

In one embodiment of the invention, the method further comprises a step of adding a chloride ion precursor to the reaction medium, in particular a hydrogen chloride or an alkali or alkaline-earth metal chloride, preferably calcium chloride or sodium chloride. It has in fact been observed that this compound makes it possible to improve the fluidity of the reaction mixture at high temperature.

During esterification, the acid functions of the protonated glycine betaine and dibasic amino acid react with a fatty alcohol (R-OH), to yield esters of glycine betaine and dibasic amino acid in the form of salts. This fatty alcohol is chosen from a mono- or polyunsaturated alcohol containing from 16 to 20 carbon atoms or a linear or branched, saturated alcohol containing from 12 to 24 carbon atoms, such as: cetyl alcohol (C16:0), stearyl alcohol (Cl 8:0), behenyl alcohol (C22:0), 2-hexyldecanol (C16R:0), 2-octyldodecanol (C20R:0), 2-decyltetradecanol (C24R:0), oleyl alcohol (C18:1), linoleyl alcohol (C18:2), linolenic alcohol (C18:3), arachidonic alcohol (C20:4) and mixtures thereof, preferably 2-hexyldecanol or oleyl alcohol. It is preferred that these alcohols do not represent more than 2 molar equivalents, for one molar equivalent of mixture of glycine betaine and dibasic amino acid. Mixtures of fatty alcohols can be used. Oleic alcohol exists for example in commercial form in mixture with saturated linear alcohols, in a ratio of unsaturated or branched alcohols to saturated alcohols ranging from 80:20 to 95:5. It is however preferred that the reaction mixture contains less than 10% and for example from 0 to 5% by weight of saturated linear alcohols.

The esterification reaction is carried out in any case in the absence of solvent, under pressure and temperature conditions making it possible to distill the water produced during the reaction and to shift the equilibrium of the reaction until a conversion rate of at least 75 and 80%, or even at least 80 and 85% or even at least 85 and 90%, respectively into salts of dibasic amino acid esters and glycine betaine is reached. To do this, the temperature is advantageously set at 130-180°C, preferably 145-170°C. The reaction can be carried out under atmospheric pressure or preferably under reduced pressure, for example at a pressure of 10 to 600 mbar. The esterification reaction is carried out in the presence of at least one organic acid or inorganic acid that serves as a catalyst and which can be the one used to protonate the reactants (which is in this case introduced in excess), or another acid. In particular, a combination of hydrochloric acid and methanesulfonic acid can be used.

For the implementation of the esterification reaction, one can for example use:

- from 0.1 to 1.0 molar equivalent, preferably from 0.1 to 0.2 molar equivalent of glycine betaine,

- from 0.2 to 1.0 molar equivalent, for example from 0.7 to 0.9 molar equivalent, of dibasic amino acid or one of its salts, the sum of the molar equivalents of glycine betaine and dibasic amino acid being equal to 1 and the mass ratio glycine betaine / dibasic amino acid being preferably greater than or equal to 10%,

- from 1.0 to 2.2 molar equivalents, preferably from 1.8 to 2.0 molar equivalents, of fatty alcohol (R-OH),

- from 1.5 to 3.0 molar equivalents, preferably from 1.8 to 2.2 molar equivalents, of acid (X- H),

- optionally, from 0.01 to 0.4 molar equivalents, preferably from 0.1 to 0.3 molar equivalents of chloride ion precursor.

In one embodiment of the invention, when the esterification product contains a glycine betaine ester salt of formula (1): X ⁿ [(CH3)3N ⁺ -CH2-COO-R] _n , where R is a mono- or polyunsaturated alkenyl group containing from 16 to 20 carbon atoms or a linear alkyl group containing from 12 to 24 carbon atoms, X is an organic or inorganic anion and n is 1 or 2, the process advantageously further comprises a step consisting in adding to the product resulting from the esterification a fluidizer, i.e. a non-volatile solvent, liquid at room temperature and which is not capable of destabilizing an emulsion incorporating the surfactant composition according to the invention. Examples of such solvents may be chosen from branched fatty alcohols and branched fatty alkanes containing from 16 to 24 carbon atoms, such as 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, isoparaffins such as isohexadecane and isododecane, and mixtures thereof. It is preferably 2-hexyldecanol. This solvent is preferably used in an amount of 5 to 15% by weight, more preferably 10 to 15% by weight, relative to the total weight of this solvent and the esterification product. It is generally added to the surfactant composition after cooling, generally at a temperature of 20 to 90°C, for example 70 to 80°C. In a preferred embodiment, the surfactant composition according to the invention contains at least 75% by weight, preferably at least 80% by weight, or even at least 90% by weight, of ingredients of natural origin, as calculated according to the ISO-16128 standard.

In addition to its low surface tension, the surfactant composition according to the invention has the advantage of being biodegradable (according to OECD standard 301), and slightly toxic to the environment (according to OECD standards 201, 202 and 203).

Re emulsion

The surfactant composition according to the invention may in particular be included in a spreading or coating emulsion further comprising a hydrocarbon binder and water. The surfactant composition generally represents from 0.1 to 1% by weight and preferably from 0.2 to 0.5% by weight, relative to the total weight of the emulsion.

The term "hydrocarbon binder" as used in this description designates any hydrocarbon binder of mineral, vegetable, animal or synthetic origin, usable for the production of road surfaces.

These may be bitumens contained in deposits of natural bitumen, asphalt or oil sands. They may also be bitumens from the refining of crude oil and more particularly from its atmospheric and/or vacuum distillation. These bitumens may possibly be blown and/or deasphalted. Alternatively, synthetic bitumens, also called clear, pigmentable or colourable bitumens, may be used. These bitumens contain little or no asphaltenes and may therefore be coloured. These synthetic bitumens are based on petroleum resin and/or indene-coumarone resin and lubricating oil. According to yet another possibility, the hydrocarbon binder may be a binder of plant origin which may in particular comprise one or more compounds chosen from: an oil, a plant resin, a modified plant resin, a tall oil pitch, a modified tall oil pitch (in particular esterified or epoxidized), a wood gum rosin, a modified rosin (in particular hydrogenated, polymerized or maleized), esters of rosins and glycerol or pentaerythritol which may be modified (in particular hydrogenated, polymerized or maleized), rosin soaps, a terpene, a resin acid, a metal resinate, in particular calcium and/or zinc, a fatty acid, a fatty acid ester, in particular an ester m ethyl fatty acid, a dammar resin, an acroid resin and mixtures thereof. A preferred example of a vegetable binder is tall oil pitch described in patents FR 3 028 862 and FR 2 915 204, which has characteristics similar to those of a soft bitumen. For example, the cold brittleness point of tall oil pitch, as defined by French standard NF EN 12593, is close to -30°C, and its softening point, as defined by French standard NF EN 1427, is approximately 35°C. Tall oil pitch typically comprises: from 5 to 30% free tall oil fatty acids, from 1 to 35% esterified tall oil fatty acids and from 10 to 30% resin acids. The term "hydrocarbon binder" also encompasses combinations of several of the aforementioned binders of mineral, synthetic, animal and/or vegetable origin. In an advantageous embodiment of the invention, the hydrocarbon binder is a bituminous binder comprising bitumen and optionally at least one vegetable binder, in particular tall oil pitch, rosin and/or a fatty acid methyl ester. In another embodiment, the hydrocarbon binder is a vegetable binder.

Advantageously, the bitumen is a bitumen with a penetrability measured according to standard NF EN 1426 ranging from 35/50 to 160/220, preferably from 50/70 to 160/220 and more preferably from 70/100 to 160/220. It is preferred that the emulsion according to the invention comprises from 25 to 75% by weight of hydrocarbon binder, preferably bitumen of grade 160/220 or 70/100, in particular 69% by weight of bitumen of grade 70/100.

The hydrocarbon binder may be pure or modified, in particular by the addition of polymers. As polymers, mention may be made, for example, and in an indicative and non-limiting manner, of thermoplastic elastomers such as statistical or block copolymers of styrene and butadiene (SBR, SBS) or of styrene and isoprene (SIS), optionally crosslinked, copolymers of ethylene and vinyl acetate, homopolymers and olefinic copolymers of ethylene (or propylene, or butylene), polyisobutylenes, polybutadienes, polyisoprenes, poly(vinyl chloride), thermoplastic polyurethanes (TPU) or any polymer used for the modification of bitumens, as well as their mixtures.

The bitumen-modifying polymers may also be chosen from recovered polymers, for example “rubber crumbs” or other compositions based on rubber reduced to pieces or powder, for example obtained from used tires or other polymer-based waste (cables, packaging, agricultural, etc.). Generally, a quantity of polymer of 0.5% to 15% by weight, preferably 1 to 8% by weight, relative to the weight of hydrocarbon binder is used.

Alternatively or additionally, the hydrocarbon binder may be modified by one or more fluxing agents, i.e. compounds for reducing the viscosity of the binder, which are typically derived from the distillation of crude oil (volatile light fractions) and which have optionally undergone a hydrotreatment or thermal cracking and additional distillation operation. Other fluxing agents are vegetable oils containing unsaturated fatty acids or their esters. Examples of fluxing agents are described in particular in patent EP 0900 822. These are alkyl monoesters of C16-C18 fatty acids derived from vegetable oils such as sunflower, linseed, soybean or rapeseed oils, optionally isomerized. An example of such fluxing agents is the product based on methyl esters of vegetable oil marketed under the name Oléoflux®.

Fluxing agents can represent from 2 to 20% by weight, relative to the weight of the hydrocarbon binder.

The spreading or coating emulsion also contains water, generally in an amount of 20 to 70% by weight, preferably 25 to 55% by weight. It may also comprise an acid, such as phosphoric acid, hydrochloric acid, sulfuric acid, acetic acid and mixtures thereof.

It may also include any usual additive, chosen for example from: viscosity agents, setting regulators, calcium, potassium, sodium or magnesium salts.

Alternatively or additionally, the emulsion may contain a synthetic or natural latex. The term "latex" as used in the present description designates a dispersion of polymers (polyisoprene, SB S, SB, SBR, acrylic polymers, etc.) crosslinked or not in aqueous phase. This latex is incorporated into the aqueous phase before emulsification or in line during the manufacture of the emulsion, or even after manufacture of the emulsion.

The spreading or coating emulsion according to the invention can be prepared by any means known to those skilled in the art and in particular by mixing water with the other constituents of the aqueous phase, including the surfactant composition, at a temperature generally ranging from 25 to 40°C, then addition of the hot hydrocarbon binder, possibly with additives (typically brought to 140-160°C), in a device such as a colloidal mill, a turbine or a static mixer, for example.

Uses - road surfaces

As indicated above, the present invention relates to the use of the aforementioned surfactant composition for the manufacture of a hydrocarbon binder emulsion, in particular a bituminous emulsion.

The hydrocarbon binder emulsion according to the invention is preferably a spreading emulsion. The term “spreading” as used in the present description designates the action of applying a hydrocarbon binder emulsion to a surface, before or after application of solid particles. Spreading techniques are thus distinguished from coating techniques in which the emulsion and the solid particles are mixed before application.

The term "solid particles" as used in this description means any solid particles usable for the production of road surfaces. Examples of solid particles include mineral solid particles such as natural mineral aggregates (gravel, sand, fines) for example from quarries or gravel pits, recycled products such as asphalt aggregates, for example resulting from the recycling of materials recovered during road repairs or surplus from asphalt plants, manufacturing waste, "shingles" ("shingles" from the recycling of roofing membranes), aggregates from the recycling of road materials including concrete, slag in particular slag, schists in particular bauxite or corundum, rubber crumb from the recycling of tires in particular, artificial aggregates of any origin and aggregates from for example household waste incineration bottom ash (MIOM), as well as their mixtures in all proportions.

Solid particles, particularly mineral solid particles, e.g. natural mineral aggregates, typically include:

- elements less than 0.063 mm (loads or fines);

- sand with elements between 0.063 mm and 2 mm;

- gravel or aggregates, the elements of which have dimensions between 2 mm and 6 mm or greater than 6 mm. The size of solid particles, in particular mineral solid particles, for example mineral aggregates, is measured by the tests described in standard NF EN 933-2.

The emulsion according to the invention can be used in the preparation of a road surface, according to a process comprising a step of application by spreading of this emulsion before or after application of solid particles, or a step of application on a support of a bituminous slurry or of a cold-poured coating comprising this emulsion.

The process of preparing a road surface includes precisely:

- a step of application by spreading the hydrocarbon binder emulsion, either on the surface of a layer comprising solid particles, such as gravel, or on the surface of a support, followed by the application of a layer of solid particles, such as coatings, or

- a step of applying to a support a bituminous grout or a cold-poured coating comprising the hydrocarbon binder emulsion.

The road surfaces prepared by the method of the invention are typically selected from a surface wear coating, a bonding layer, a sealing veil, a sealing coating, paving joints or an impregnation layer. Alternatively, it may be a bituminous slurry or a cold-poured asphalt.

A surface wear coating refers to one or more layers consisting of a hydrocarbon binder and solid particles, in particular mineral solid particles, forming a so-called wearing course, which generally has a thickness of 0.5 to 1.5 cm. It is typically obtained by spraying a hydrocarbon binder and then spreading mineral solid particles on this binder, in one or more layers. The whole is then compacted. A surface coating requires not only a binder that is sufficiently fluid to be able to be sprayed but also a binder that allows good adhesion of the mineral solid particles to the support, such as a gravel-emulsion base.

Alternatively, the emulsion can be spread using a series of brooms arranged at precise angles on heavily cracked surfaces, in order to seal the cracks and restore the watertightness of the road surface.

Sealers are generally available in layers less than 25 mm thick and can be applied to an existing bituminous surface showing damage due to oxidation of the bitumen, such as small cracks. One type The particular feature of such coatings is the fog seals which also make it possible to restore flexibility to the bitumen that has hardened over time. This technique is also particularly suitable for surfaces with low bitumen content, which can lead to occasional release of gravel. Finally, it makes it possible to give the treated surface a uniform appearance and improve its waterproofing.

The emulsion is spread using a conventional spreader. Optionally, the application can be followed by light sanding in order to preserve the adhesion of the treated surface.

A tack coat is a layer obtained by spraying the hydrocarbon binder emulsion onto a road surface support, in order to consolidate the interface between the support and a subsequently applied road surface layer. The main function of the tack coat is to improve the longevity of a road surface, by avoiding shear between the layers. The conditions at the interfaces of the layers are very important and the optimal dimensioning of the road surface involves effective and lasting bonding of the layers together.

The impregnation layers are intended to be applied to an untreated and previously compacted road surface (gravel), in order to stabilize the gravel and protect it against humidity, but also to reinforce its cohesion until the application of the next road surface layer.

Finally, the joint paving technique is a very old technique that is particularly well suited to the creation of sidewalks, squares and forecourts of listed or historical streets. This technique consists of laying paving stones on a bedding made up of solid mineral particles, preferably sand without fines, while maintaining a spacing of approximately 1 to 2 cm between two paving stones. The spaces between paving stones are then filled with solid mineral particles, generally particles of 2 to 4 mm, then a hydrocarbon binder emulsion is spread in the spaces between paving stones to form the flexible joint.

The constituents of the hydrocarbon binder emulsion according to the invention, as well as their proportions, will be chosen so as to give the latter the desired properties depending on the road surface to be manufactured. In any event, the emulsion according to the invention meets the requirements of CAS, ESU and IMP emulsions of class 2 or 3 as regards is their residue on a 0.5 mm sieve, their storage stability and their rupture index, in accordance with standard NF EN 13808. It also meets the requirements of ESU type emulsions of class 2 or 3 with regard to their adhesion to aggregates.

The invention thus relates to the use of the hydrocarbon binder emulsion described above in the formation of a road surface, in particular a surface wear coating, a bonding layer, a sealing veil, a sealing coating, paving stone joints or an impregnation layer, a bituminous grout or a cold-poured asphalt, preferably in the formation of a surface wear coating or a bonding layer.

Other uses

Alternatively, the surfactant composition according to the invention can be used as a wetting agent, dispersant, flotation agent, lubricant, corrosion inhibitor, solubilizer, antistatic and/or detangling agent and/or to improve the effect and/or persistence of insecticidal substances and/or to improve the disinfectant power and/or persistence of the disinfectant effect of antimicrobial substances.

This composition can thus be used in the manufacture of plastics or products intended for:

- for the treatment and/or cleaning of the body, plants or hard surfaces, in particular cosmetic products, vehicle washing products or water-repellent products for automobiles, household products, industrial cleaning products, fibre sizing products and plant protection products;

- water treatment; or

- to the oil industry.

In the case of water treatment, the composition according to the invention makes it possible to detach the biofilm without destroying the effectiveness of the ion exchange resins, unlike conventional cationic surfactants which also have a significant environmental impact given their lack of biodegradability, or their slower biodegradability. This ability to detach biofilms can also be used in oil extraction processes. In cosmetic applications, the composition according to the invention is compatible with conventional anionic surfactants and makes it possible to improve the creaminess of the foam they generate. It also protects iron aerosol devices against corrosion. The solubilizing power of the composition according to the invention also makes it possible to envisage its use for the solubilization of perfumes or essential oils and its dispersing capacity can make it possible to disperse the pigments present in cosmetic compositions.

In the manufacture of plastics, the composition according to the invention makes it possible to confer electrostatic properties on the surface of the plastic, without affecting its recycling capacities given its bio-sourced nature.

When used in the manufacture of plant protection products, the composition according to the invention makes it possible to improve the persistence of active ingredients and the water resistance of products such as herbicides, pesticides or agents modifying plant growth, which can thus be used in smaller quantities. This composition can thus be added, in a form diluted in water, to a product containing an acidic medium, for example.

The composition according to the invention can also be used in a process for extracting, storing, warehousing or refining oil to limit corrosion of equipment, limit the ingress of water and gas, inhibit certain types of clay, control the formation of paraffin or asphaltene, and participate in the control of sand.

These products are advantageously in the form of an aqueous solution or aqueous gel. Alternatively, they may be in the form of an oil-in-water or water-in-oil emulsion or even a paste. In any event, the aqueous phase contained in these products advantageously has a pH ranging from 1 to 8, in particular from 1 to 5. These products may be packaged in any device suitable for the intended use and in particular in a pump bottle, a tube, a pot, a can, an aerosol device or a wipe. They advantageously contain from 0.1 to 25% by weight, for example from 1 to 10% by weight, of surfactant composition according to the invention.

FIGURES

Figure 1 illustrates a synthesis scheme of a surfactant composition according to the invention, based on 2-hexyldecyl betainate and 2-hexyldecyl lysinate salts.

Figure 2 illustrates a synthesis scheme of a surfactant composition according to the invention, based on oleyl betainate and oleyl lysinate salts. Figure 3] illustrates a synthesis scheme of a comparative surfactant composition, not containing lysine ester.

Figure 4 illustrates the contact angle formed on a glass substrate by a surfactant composition according to the invention, in comparison with a surfactant composition of the prior art.

EXAMPLES

The invention will be better understood in light of the following examples, which are given purely for illustrative purposes and are not intended to limit the scope of the invention, defined by the appended claims.

Example 1: Synthesis of surfactant compositions according to the invention

Example 1-1: Mixture of 2-hexyldecyl betainate and 2-hexyldecyl lysinate salts This synthesis is illustrated in Figure 1.

Glycine betaine (0.5 to 0.61 eq) and lysine hydrochloride (0.39 to 0.50 eq) are introduced into a reactor and dispersed in 2-hexyldecanol alcohol (1.10 to 1.32 eq). The addition of an excess of methanesulfonic acid (1.99 to 2.10 eq) then allows protonation of the substrates and catalysis of the esterification reaction. The set temperature at the mixture level is set at 150 °C and the pressure is reduced to a value of 20 mbar in order to eliminate the water formed during the reaction and to reach a minimum conversion rate of 96% for glycine betaine and 95% for lysine. The reaction mixture is then allowed to cool to 80°C, then the product is recovered, cooled to room temperature, and constitutes the surfactant composition CT according to the invention, which contains the following constituents:

Table 1

Example 1-2: Mixture of oleyl betainate and oleyl lysinate salts

This synthesis is illustrated in Figure 2.

Glycine betaine (0.148 eq) and lysine hydrochloride (0.852 eq) are introduced and dispersed in the presence of oleic alcohol (1.9 eq) in a reactor whose double jacket temperature is set at 170°C. Methanesulfonic acid (2 eq) and hydrochloric acid (0.17 eq) are then added hot to the dispersion. The temperature setpoint is then set to obtain a reaction mixture temperature of 150°C. When the acids are added, the pressure is 200 mbar and is then reduced to 150 mbar after the acids are added. When the reaction mixture tends to become viscous, the pressure is increased to 200 mbar to remove the water and to reach a conversion rate of 91% for glycine betaine and 85% for lysine.

The reaction mixture is then allowed to cool to 90°C, then 10% of 2-hexyldecanol is added in order to fluidify the mixture. Stirring is continued for approximately 1 h, then the product is recovered, cooled to room temperature, and constitutes the surfactant composition C1 according to the invention, which contains the following constituents:

Des mélanges similaires ont été préparés suivant le même procédé, en faisant varier le ratio massique initial lysine/glycine bétaïne de 25/75 à 80/20, excepté qu'il n'a pas été ajouté de 2- hexyldécanol en fin de réaction. On a également fait varier les conditions opératoires de ces synthèses. Table 2

Similar mixtures were prepared using the same procedure, varying the initial lysine/glycine betaine mass ratio from 25/75 to 80/20, except that no 2-hexyldecanol was added at the end of the reaction. The operating conditions of these syntheses were also varied.

The surfactants C2 to C5 thus obtained had the following compositions:

D'autres synthèses (compositions tensioactives C6 et C7) ont par ailleurs été réalisées en faisant plutôt varier le précurseur d'ions chlorure, et en conservant le ratio massique lysine/glycine bétaïne de 90/10 de la composition Cl. On a également fait varier les conditions opératoires de ces synthèses. Les réactifs utilisés et les résultats obtenus sont présentés dans le tableau ci- dessous : Table 3

Other syntheses (surfactant compositions C6 and C7) were also carried out by varying the chloride ion precursor, and by retaining the lysine/glycine betaine mass ratio of 90/10 of composition Cl. The operating conditions of these syntheses were also varied. The reagents used and the results obtained are presented in the table below:

Table 4

Example 2: Synthesis of a comparative surfactant composition

A composition similar to compositions C2 to C5 of Example 1 but not comprising a lysine ester salt was prepared. The synthesis scheme followed is illustrated in Figure 3.

The synthesis consists first of protoning glycine betaine initially in zwitterionic form, then reacting it with oleic alcohol via an esterification reaction. The quantities of reagents used are: glycine betaine (1 eq), oleic alcohol (1.4 eq), methanesulfonic acid (1.6 eq). The use of an excess of methanesulfonic acid is justified by the need to both protonate glycine betaine and catalyze the esterification reaction. This is carried out at 150°C and under reduced pressure in order to eliminate the water formed during the reaction and thus allow the reaction equilibrium to shift. This synthesis is carried out in the absence of any solvent. The reaction lasts 3.5 hours to reach a conversion rate of approximately 90%. This gives a surfactant composition CC.

Example 3: Study of the performance of spreading emulsions

Bituminous emulsions containing the following surfactant compositions were prepared, respectively: Cl; Cl without the use of HCl during synthesis or the addition of 2-hexyldecanol after synthesis (Cl ¹ ); C4; C4 with 10% 2-hexyldecanol (C4 ¹ ); and C6. Tests were then conducted to compare the performance of these bituminous emulsions with those of identical emulsions but comprising the comparative surfactant composition according to Example 2 (CC).

Stability Stability tests were carried out according to the NF EN 1429 - 2013 standard relating to cationic bitumen emulsions, by determining the particle size of the particles present in the emulsion immediately after its formation and after seven days. A visual evaluation by stirring and handling the emulsion over 7 days following manufacture was also carried out. The results of these tests are presented in Tables 5 and 6.

Table 5

OK: stable emulsion, no demixing - KO: broken emulsion, decantation

Table 6

As can be seen from these tables, the surfactant compositions according to the invention make it possible to formulate stable bituminous emulsions, containing bitumens of different grades, unlike the surfactant composition of the prior art. The residue on a sieve of less than 0.5 mm is always less than 0.1% and the residue on a sieve of 0.5 mm after 7 days of storage is always less than 0.5%, or even 0.2% for compositions C1, C1', C4 and C6.

Adhesiveness

The adhesiveness tests were carried out according to the NF EN 13614 standard and consist of reproducing the behavior and the covering capacity of aggregates by the binder after breaking of the emulsion. Aggregates from different quarries and of different mineralogical nature, with a size between 6 and 10 mm, were tested. The results of these tests are presented in Tables 7 and 8.

Table 7

Comme il ressort de ces tableaux, les compositions tensioactives selon l'invention permettent de formuler des émulsions bitumineuses présentant une bonne adhésivité à des granulats de natures minéralogiques variées. Table 8

As can be seen from these tables, the surfactant compositions according to the invention make it possible to formulate bituminous emulsions exhibiting good adhesiveness to aggregates of various mineralogical types.

Breaking Index

The rupture index measurement was carried out according to standard NF EN 13075-1 - 2016.

During the test, dried reference fines are added at a constant speed (0.25 to 0.45 g/sec) to a known quantity of cationic bitumen emulsion (100 g), with manual or mechanical stirring. When the emulsion is completely broken, which is observed by the solidification of the mixture, the quantity of fines added is determined by weighing to the nearest 0.1 g. The mass thus obtained, multiplied by 100 and divided by the mass of the emulsion, gives the breaking index of the cationic emulsion. The higher this index, the more stable the emulsion is in contact with the aggregates: the emulsion will therefore be “slow breaking”. Conversely, a low breaking index will be characteristic of “fast breaking” emulsions.

The results of these tests expressed in forshammer are presented in Table 9.

Table 9

As can be seen from this table, the surfactant compositions according to the invention make it possible to formulate bituminous emulsions having a breaking index which is always less than 110 and even 70, whatever the grade and proportion of bitumen which they contain. Example 4: Corrosion protection test

Tests were conducted to study the gravimetric evolution of a metal nail immersed in a 3 mol/L hydrochloric acid solution in the presence of 0.1% cationic surfactant compared to a control solution without surfactant. The results obtained with the composition Cl described in Example 1, in comparison with the composition CC described in Example 2, are presented in Table 10 below.

Table 10

After only 1 day in the acid and surfactant solution, the nail lost more than half of its mass for composition CC. Furthermore, the nail completely disappeared after 4 days of testing in this case, compared to 6 days for composition Cl.

Example 5: Water repellency test

Water repellency is an interfacial phenomenon that consists of forming spherical drops on a hydrophilic surface. This characteristic finds its application in the automotive field in order to evacuate water, mainly rain, and to dry the components of a motorized vehicle more quickly.

To evaluate this property on a laboratory scale, a glass plate is immersed in an aqueous solution of cationic surfactants at 1% by mass for 10 seconds and then dried. The angle formed by a drop of water on the surface of the glass, or contact angle, is then measured. This angle characterizes the spread of the drop on the surface. The results obtained for compositions Cl and CC are presented in Figure 4. In this Figure, the larger the contact angle between the drop and the surface, the smaller the spread of the drop on the surface, and the more effective the water-repellent effect.

The measurement of contact angles for compositions Cl and CC shows that the former improves the water repellency of the glass after treatment. Example 6: Formulations

6.1. Cleaning composition of a silicon wafer Hydrofluoric acid 6.50%

Oleyl betaine methyl sulfonate 0.50%

Oleyl lysinate methyl sulfonate 0.50%

Nitric acid 0.25%

Water 92.25%

6.2. Concentrated fabric softener

2-Hexyldecyl betaine ethyl sulfonate 5.00%

2-Hexyldecyl lysinate ethyl sulfonate 10.00%

Calcium Chloride 25% 1.50% Perfume 0.70%

Colorant 0.02%

Preservative 0.10%

Water qsp 100.00%

Claims

Claims 1. Surfactant composition containing: (a) at least one glycine betaine ester salt of formula (1): X ⁿ [(CH3)3N ⁺ -CH2-COO-R] _n , (b) at least one salt of a dibasic amino acid ester and a fatty alcohol of formula R-OH, where R is a mono- or polyunsaturated alkenyl group containing from 16 to 20 carbon atoms or a linear or branched alkyl group containing from 12 to 24 carbon atoms, and X is an organic or inorganic anion and n is 1 or 2. 2. Surfactant composition according to claim 1, characterized in that the radical R is chosen from the groups cetyl (C16:0), stearyl (C18:0), behenyl (C22:0), 2-hexyldecyl (C16R:0), 2-octyldodecyl (C20R:0), 2-decyltetradecyl (C24R:0), palmitoleyl (C16:1), oleyl (C18:1), linoleyl (C18:2), linolenyl (C18:3), arachidonic (C20:4), preferably R is a 2-hexyldecyl or oleyl group, more preferably an oleyl group. 3. Surfactant composition according to claim 1 or 2, characterized in that the X ion is chosen from a chloride, a sulfate, a perchlorate, an alkyl sulfate ion, in particular decyl sulfate or lauryl sulfate, an aryl sulfonate ion, in particular benzene sulfonate, paratoluene sulfonate, an alkyl sulfonate ion, in particular triflate, methanesulfonate, ethanesulfonate, decyl sulfonate, laurylsulfonate, camphorsulfonate, or a sulfosuccinate ion, preferably from alkyl sulfonates and aryl sulfonates, more particularly from methanesulfonate, ethanesulfonate, triflate, paratoluenesulfonate and camphorsulfonate ions, better still, X is the methanesulfonate or ethanesulfonate ion. 4. Surfactant composition according to any one of claims 1 to 3, characterized in that it also contains: (c) at least one fatty alcohol of formula R-OH, (d) optionally, at least one organic or inorganic acid of formula XH, (e) optionally, at least one dibasic amino acid salt, (f) optionally, at least one glycine betaine salt of formula (2): X ⁿ [(CH3)3N ⁺ -CH2- COOH]n' (g) optionally, at least one ether of formula R-O-R, (h) optionally, at least one chloroalkane and/or chloroalkene, (i) optionally, at least one branched fatty alcohol or branched fatty alkane containing from 16 to 24 carbon atoms, when component (c) is a linear, saturated or unsaturated fatty alcohol, where R is a mono- or polyunsaturated alkenyl group containing from 16 to 20 carbon atoms or a linear or branched alkyl group containing from 12 to 24 carbon atoms, X is an organic or inorganic anion and n is 1 or 2. 5. Surfactant composition according to claim 4, characterized in that it contains: (a) from 5 to 60% by weight of glycine betaine ester salt of formula (1), (b) from 10 to 70% by weight of dibasic amino acid ester salt, (c) from 5 to 35% by weight of fatty alcohol R-OH, (d) from 0 to 20% by weight of organic or inorganic acid X-H, (e) from 0 to 15% by weight of dibasic amino acid salt, (f) from 0 to 5% by weight of glycine betaine salt of formula (2), (g) from 1 to 20% by weight of R-O-R ether, (h) from 0 to 10% by weight of chloroalkane and/or chloroalkene, (i) from 0 to 20%, preferably from 10 to 15%, of branched fatty alcohol or branched fatty alkane containing from 16 to 24 carbon atoms, when constituent (c) is a linear, saturated or unsaturated fatty alcohol. 6. Surfactant composition according to any one of claims 1 to 5, characterized in that it contains from 75 to 100%, preferably from 90 to 100%, of constituents (a) to (h). 7. Process for the preparation of a surfactant composition according to any one of claims 1 to 6, characterized in that it comprises the reaction of a reaction mixture containing at least one dibasic amino acid or one of its salts and glycine betaine with at least one mono- or polyunsaturated alcohol containing from 16 to 20 carbon atoms or a linear or branched, saturated alcohol containing from 12 to 24 carbon atoms (R-OH), in the presence of at least one organic or inorganic acid (X-H) and in the absence of organic solvent, at a temperature between 130 and 180°C. 8. Method according to claim 7, characterized in that the following are used: - from 0.1 to 1.0 molar equivalent, preferably from 0.1 to 0.2 molar equivalent of glycine betaine, - from 0.2 to 1.0 molar equivalent, for example from 0.7 to 0.9 molar equivalent, of dibasic amino acid or one of its salts, the sum of the molar equivalents of glycine betaine and dibasic amino acid being equal to 1 and the mass ratio glycine betaine / dibasic amino acid being preferably greater than or equal to 10%, - from 1.0 to 2.2 molar equivalents, preferably from 1.8 to 2.0 molar equivalents, of fatty alcohol (R-OH), - from 1.5 to 3.0 molar equivalents, preferably from 1.8 to 2.2 molar equivalents, of acid (X- H), - optionally, from 0.01 to 0.4 molar equivalents, preferably from 0.1 to 0.3 molar equivalents of chloride ion precursor. 9. Spreading or coating emulsion, comprising: (a) a hydrocarbon binder, (b) a surfactant composition according to any one of claims 1 to 6, and (c) water. 10. Use of the emulsion according to claim 9 in the formation of a road surface, in particular a surface wear coating, a bonding layer, a sealing veil, a sealing coating, paving stone joints or an impregnation layer, a bituminous slurry or a cold-poured asphalt, preferably in the formation of a surface wear coating or a bonding layer. 11. Method for preparing a road surface, comprising: - a step of application by spreading this emulsion, either on the surface of a layer comprising solid particles, such as gravel, or on the surface of a support, followed by the application of a layer of solid particles, such as coatings, or - a step of applying to a support a bituminous slurry or a cold-poured coating comprising the emulsion according to claim 9. 12. Use of the surfactant composition according to any one of claims 1 to 6 for the manufacture of a hydrocarbon binder emulsion, in particular a spreading or coating emulsion, in particular a bituminous emulsion. 13. Use of the surfactant composition according to any one of claims 1 to 6 as a wetting agent, dispersant, flotation agent, lubricant, corrosion inhibitor, solubilizer, antistatic and/or detangling agent and/or for improving the effect and/or persistence of insecticidal substances and/or for improving the disinfectant power and/or persistence of the disinfectant effect of antimicrobial substances. 14. Use according to claim 13, characterized in that the surfactant composition is used in the manufacture of plastics or products intended: - for the treatment and/or cleaning of the body, plants or hard surfaces, in particular cosmetic products, vehicle washing products or water-repellent products for automobiles, household products, industrial cleaning products, fibre sizing products and plant protection products; - water treatment; or - to the oil industry.