Surfactant composition based on glycine betaine amide salts, its preparation process and its uses

Abstract

The present invention relates to a surfactant composition based on glycine betaine amide salt, as well as a process for its preparation. It also relates to its use as a wetting agent, particle dispersant and / or corrosion inhibitor and / or for improving the disinfecting power and / or the persistence of the disinfecting effect of antimicrobial substances and / or the insecticidal effect and / or the persistence of insecticidal substances, as well as in the manufacture of various products for the treatment and / or cleaning of the body, plants or hard surfaces, for water treatment or for oil extraction.

Description

Title of the invention: Surfactant composition based on glycine betaine amide salts, its preparation process and its uses SUBJECT OF THE INVENTION

[0001] The present invention relates to a surfactant composition based on glycine betaine amide salts, as well as its preparation process. It also relates to its use as a wetting agent, particle dispersant and / or corrosion inhibitor and / or for improving the disinfecting power of antimicrobial substances and / or the effect of insecticidal substances, as well as in the manufacture of various products intended for the treatment and / or cleaning of the body, plants or hard surfaces, for water treatment or for oil extraction. BACKGROUND OF THE INVENTION

[0002] Surfactants are essential raw materials for the manufacture of a variety of products. Among these, cationic surfactants certainly represent a smaller market than that of anionic or non-ionic 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.

[0003] Biodegradable cationic surfactants based on glycine betaine amides have been proposed in patent US-7,829,521 and WO 2013 / 188508, as well as their preparation process. The latter consists of protonating glycine betaine using an acid, then esterifying it using a short alcohol, before carrying out an aminolysis reaction of this product using at least one fatty amine, which may in particular be of plant origin. It thus makes it possible to access cationic amphiphilic molecules without the conventional step of quaternization of a tertiary amine using generally toxic methylating agents. Other similar surfactants are presented in the publication of F. Goursaud et al in Green Chem., 2008, 10, 310-320.

[0004] By modifying the operating conditions described in WO 2013 / 188508, the Applicant was able to obtain a surfactant composition enriched in glycine betaine amide and depleted in alkylammonium salts, which proved to have a lower surface tension than the surfactant compositions described in this document and a better environmental profile. This surfactant composition, described in application EP 3 584 303, is therefore suitable for numerous applications.

[0005] However, it was observed that the surfactant compositions of the prior art contained a residual short alcohol (such as butanol or hexanol), as well as esters and ethers of this alcohol, in addition to the desired glycine betaine amide salt, the residual glycine betaine and possibly the residual acid and an ammonium salt of the fatty amine involved. These alcohols, ethers and esters constitute poorly, or even not at all, water-soluble compounds, which lead to difficulties in formulating these surfactants, resulting in the appearance of a supernatant.

[0006] To overcome this drawback, it has been considered to remove the residual alcohol by distillation before the aminolysis step. This expensive solution is however not satisfactory from an industrial point of view. Furthermore, it does not allow all of the alcohol to be removed, since, under the neutral or basic pH conditions in which this surfactant composition is typically used, the aforementioned ester tends to hydrolyze to release additional alcohol.

[0007] In this context, the Applicant has developed an improved process for the synthesis of glycine betaine amides which is not only environmentally friendly and capable of being implemented on an industrial scale under economically acceptable conditions, but which is also easier to formulate in an aqueous medium.

[0008] The process according to the invention comprises a first step of esterification of glycine betaine using a polyol, in particular glycerol. Although this step is known per se (C. Joumoux et al., Green Chemistry, 19(23), 2017), it has never been envisaged that it could be included in a more global process for the preparation of glycine betaine amides, a fortiori with a view to solving the aforementioned problem. Summary of the invention

[0009] The subject of the invention is a process for preparing a surfactant composition, comprising the successive steps consisting of:

[0010] (1) reacting glycine betaine or one of its salts with at least one polyol, in presence of an organic or inorganic acid, at a temperature of 100 to 180°C;

[0011] (2) cooling the reaction medium;

[0012] (3) adding one or more alkylamines containing from 8 to 36 carbon atoms to the reaction medium; and

[0013] (4) recovering the surfactant composition thus obtained.

[0014] The method according to the invention does not require, unlike the methods of the art prior art, of a distillation step to remove the residual alcohol from step (1), nor of equipment to distill the water during step (1) without simultaneously removing the alcohol, which is volatile. It therefore also does not require control pressure during this step. It follows that this process is economically more attractive than known processes for the synthesis of glycine betaine amides.

[0015] The invention also relates to a surfactant composition which can be obtained according to this process and containing:

[0016] (a) at least one glycine betaine amide salt of formula (1): Xn [(CH3)3N+-CH2- CONH-R]n ;

[0017] (b) at least one polyol;

[0018] (c) glycine betaine of formula (2): (CH3)3N+-CH2-COO;

[0019] (d) optionally, at least one salt of glycine betaine ester and polyol, of formula (3): Xn [(CH3)3N+-CH2-COOR']n where R' is a polyol residue; and

[0020] (e) optionally, at least one alkylammonium salt of formula (4): Xn [NH3+R]n And

[0021] (f) optionally an organic or inorganic acid salt,

[0022] where:

[0023] R is a saturated or unsaturated linear alkyl group comprising from 8 to 36 carbon atoms,

[0024] X is an organic or inorganic anion,

[0025] and n is 1 or 2.

[0026] In addition to its biodegradability (according to OECD standard 310), its low surface tension and its good foaming power, comparable to those of the surfactants obtained according to the processes of the prior art, the surfactant composition according to the invention has the advantage of being more soluble in water.

[0027] The invention also relates to the use of the above-mentioned surfactant composition as a wetting agent, particle dispersant and / or corrosion inhibitor and / or for improving the disinfecting power and / or the persistence of the disinfecting effect of antimicrobial substances and / or for improving the effect and / or the persistence of insecticidal substances.

[0028] It also relates to the use of this composition for the manufacture of plastics or products intended:

[0029] - for the treatment and / or cleaning of the body, plants or hard surfaces, in in particular cosmetic products, vehicle washing products, household products, industrial cleaning products, fiber sizing products and phytosanitary products;

[0030] - to water treatment;

[0031] - to the extraction of oil. DETAILED DESCRIPTION Surfactant composition

[0032] The method according to the invention comprises the successive steps consisting of:

[0033] (1) reacting glycine betaine or one of its salts with at least one polyol, in presence of an organic or inorganic acid, at a temperature of 100 to 180°C;

[0034] (2) cooling the reaction medium;

[0035] (3) adding one or more alkylamines containing from 8 to 36 carbon atoms to the reaction medium; and

[0036] (4) recovering the surfactant composition thus obtained.

[0037] The first step of this process consists of esterifying glycine betaine, or trimethylglycine. Glycine betaine can be of plant or synthetic origin. Although glycine betaine exists on the market in protonated form (as hydrochloride), it is preferable to use, according to the invention, glycine betaine in zwitterionic form. It is then necessary to protonate it, in the process according to the invention, using an organic or inorganic acid. The acid can 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 alkyl sulfuric acids, for example decyl or lauryl sulfuric acid; aryl sulfonic acids, such as benzene sulfonic acid, paratoluene sulfonic acid; alkyl sulfonic acids, such as triflic acid, methanesulfonic acid, ethanesulfonic acid, decylsulfonic acid, lauryl sulfonic acid or camphorsulfonic acid; sulfosuccinic acid; and mixtures thereof. Lewis acids may also be used. Preferably, it is an organic acid, more preferably an alkyl sulfonic acid and in particular methanesulfonic or ethanesulfonic acid.

[0038] During the esterification, the acid function of the salified betaine is reacted with a polyol, to produce an ester of glycine betaine and polyol, which is in the form of a salt. By "polyol" is meant a saturated, linear, cyclic or branched monomeric or polymeric compound, containing at least two alcohol functions (OH). Advantageously, the polyol used according to the invention consists of a hydrocarbon chain optionally interrupted by one or more oxygen atoms and carrying at least two alcohol functions. By "hydrocarbon chain" is meant a structure comprising only carbon and hydrogen atoms. The polyol according to the invention generally comprises at least one primary and / or secondary alcohol function; preferably, it comprises at least one primary alcohol function.Advantageously, the polyol has a melting point of at most 180°C, preferably at most 160°C and, better still, at most 150°C, as measured by differential scanning calorimetry according to OECD standard 102. In addition, it is preferred that the polyol has a solubility in water at 25°C of at least 25g / L.

[0039] Examples of such polyols may be chosen from: linear or branched C2-C6 diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol; triols such as glycerol, trimethylolpropane, 1,2,6-hexanetriol; tetraols such as erythritol; hydrogenated sugars such as sorbitol, xylitol, mannitol and maltitol; polyglycerols, preferably having a molar mass ranging from 106 to 8000 g / mol, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, PEG-32, PEG-75 and PEG-180; and mixtures thereof. Glycerol is preferred for use in this invention.Glycerol is in fact a bio-sourced reagent which is readily available and less expensive than certain alcohols of petrochemical origin.

[0040] The introduction of the reactants during the first step is not critical. Thus, in one embodiment of the invention, the polyol is mixed with the glycine betaine before the introduction of the acid. The polyol may in fact constitute a co-product of the extraction of sugar beet vinasse used to produce the glycine betaine. Such a mixture is notably available from the company ALTILIS under the commercial reference Betafin® LQDGL. In another embodiment, the glycine betaine is first reacted with the acid before introduction of the polyol.

[0041] The esterification reaction is generally carried out in the absence of any solvent, the polyol constituting both the reactant and the medium. It is generally possible to use from 1.0 to 4 equivalents, for example from 1.2 to 2 equivalents, of polyol and / or from 1.0 to 1.5 equivalents of acid, for example from 1.0 to 1.2 equivalents of acid, per 1 equivalent of glycine betaine. The esterification can be carried out at a temperature of 100 to 180°C, preferably from 120 to 170°C, more preferably from 140 to 160°C under atmospheric pressure or under reduced pressure (for example from 30 to 200 mbar), for a period generally ranging from 2 hours to 10 hours, preferably from 5 hours to 8 hours. Unlike prior art processes using butanol or hexanol instead of a polyol, there is no need for a Dean-Starck arrangement or precise pressure control, as polyols are not volatile.The reduction in pressure is only intended to distill the water to shift the equilibrium of the reaction.

[0042] During this reaction, one or more of the alcohol functions (hydroxyl groups) of the polyol is esterified by glycine betaine. In addition, oligomerization of the polyol can occur. It is thus possible to obtain a mixture of glycine betaine esters resulting from the reaction of different alcohol functions of the polyol, or even of these oligomers. The conversion rate of glycine is advantageously measured betaine to glycine betaine ester, by 'H NMR. The esterification reaction is typically stopped when a conversion of at least 90%, usually 95% to 99%, has been reached.

[0043] At the end of this esterification step, it is possible to neutralize the reaction medium, in order to prevent the amine added in the following step from forming an ammonium salt in the presence of the residual acid or the residual protonated glycine betaine. The formation of this ammonium salt in fact makes the fatty amine less available for the aminolysis reaction and its presence in the surfactant composition obtained at the end of the process may not be desirable due to environmental constraints.

[0044] After cooling the reaction medium (neutralized or not), for example to 20-100°C, one or more C8-C36 alkylamine(s) are then added to the reaction medium. Examples of such amines are: dodecylamine (or laurylamine), tetradecylamine, hexadecylamine, octadecylamine, oleylamine, docosanylamine, eicosanylamine, dimer diamines (derived from fatty acid dimers), in particular C36 (such as those available from CARGILL under the commercial reference Priamine®), and mixtures thereof. Examples of such mixtures are amines derived from coconut oil.

[0045] In this step, the alkylamine is advantageously used in molten form. The amount of alkylamine(s) added may, for example, represent from 0.9 to 1.5 equivalents and preferably from 1.0 to 1.2 equivalents per 1 equivalent of glycine betaine initially used. This aminolysis reaction is typically carried out at a temperature of 50 to 180°C and preferably from 80 to 120°C, at atmospheric pressure. Since the reaction medium does not contain alcohol, it is not necessary, in parallel with the aminolysis reaction, to remove the alcohol by distillation under reduced pressure, unlike the methods of the prior art. The aminolysis reaction may be carried out for a period of 0.5 to 7 hours, in particular 1 to 3 hours.

[0046] The surfactant composition thus obtained is then recovered, which can optionally be diluted in water before use.

[0047] This process makes it possible to obtain a surfactant composition comprising, and preferably consisting of:

[0048] (a) at least one glycine betaine amide salt of formula (1): Xn [(CH3)3N+-CH2- CONH-R]n ;

[0049] (b) at least one polyol;

[0050] (c) glycine betaine of formula (2): (CH3)3N+-CH2-COO;

[0051] (d) optionally, at least one salt of glycine betaine ester and polyol, of formula (3): Xn [(CH3)3N+-CH2-COOR']n where R' is a polyol residue; and

[0052] (e) optionally, at least one alkylammonium salt of formula (4): Xn [NH3+R]n And

[0053] (f) optionally an organic or inorganic acid salt,

[0054] where:

[0055] R is a saturated or unsaturated linear alkyl group comprising from 8 to 36 carbon atoms,

[0056] X is an organic or inorganic anion,

[0057] and n is 1 or 2.

[0058] By "polyol residue" is meant the unit derived from the polyol which is incorporated into the polyol ester salt after esterification of the polyol by glycine betaine.

[0059] Compound (f) is present in the case where the process according to the invention comprises a neutralization step using a base and is the reaction product of this base with the acid used in the esterification step.

[0060] This surfactant composition generally contains and is preferably constituted by:

[0061] (a) from 40 to 75% by weight, preferably from 50 to 70% by weight of amide salt of glycine betaine,

[0062] (b) from 8 to 40% by weight, preferably from 10 to 35% by weight, of polyol,

[0063] (c) from 0.5 to 5% by weight, preferably from 1 to 3% by weight of glycine betaine,

[0064] (d) optionally, from 0.1 to 10% by weight of glycine betaine ester and polyol,

[0065] (e) optionally, from 0.1 to 30% by weight, in particular from 1 to 20% by weight, of salt alkylammonium, and

[0066] (f) optionally, from 0.1 to 5% by weight of an organic or inorganic acid salt,

[0067] relative to the total dry weight of the surfactant composition.

[0068] It is preferred in all cases that the surfactant composition according to the invention contains less than 5% by weight, advantageously less than 3% by weight, more preferably less than 1% by weight, or even none at all, of linear or branched (preferably linear), saturated or unsaturated alcohol, comprising from 8 to 36 carbon atoms. Uses

[0069] The surfactant composition according to the invention can be used in a variety of applications as a wetting agent, particle dispersant and / or corrosion inhibitor and / or to improve the disinfectant power of antimicrobial substances and / or the effect of insecticidal substances. It can in particular be used for the manufacture of plastics or various products intended in particular:

[0070] - for the treatment and / or cleaning of the body, plants, textiles or surfaces hard, in particular cosmetic products, such as shampoos, liquid soaps, bubble baths and shower gels; vehicle washing products such as cars, trucks, trains, buses or airplanes; household products such as detergents for windows, wall surfaces, floors or dishes; laundry detergents or fabric softeners; industrial cleaning products; fiber sizing products; plant protection products; pigmented products such as paints or varnishes;

[0071] - to water treatment;

[0072] - to the extraction of oil.

[0073] In the case where it is used in the cleaning of hard surfaces, such as windows or bodywork surfaces, or even textiles, it has in particular been observed that the composition according to the invention accelerates the subsequent drying of the surface without leaving traces of limescale upon drying. In addition, when the surface is a vehicle, it has been observed that the cleaning of fine brake particles on the wheels was improved compared to conventional cationic surfactants. Finally, the effectiveness of the composition according to the invention in an alkaline medium makes it possible to avoid the disadvantages linked to the use of acid compositions, in particular their corrosive effect.

[0074] 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.

[0075] In cosmetic applications, the composition according to the invention is compatible with conventional anionic surfactants and makes it possible to improve the creamy character of the foam they generate. It also protects iron aerosol devices against corrosion.

[0076] 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 capabilities given its bio-sourced nature.

[0077] 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 to 25% in water, at a rate of 0.4% by weight, to a product containing a neutral or alkaline medium, for example.

[0078] 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. In this application, it can be added to the oil at a level of 500 to 1000 ppm, for example.

[0079] The products described above, comprising a composition according to the invention, may also include at least one compound chosen from: anionic surfactants, non-ionic surfactants, antimicrobial agents and / or insecticidal substances and mixtures thereof. Examples of anionic surfactants are: ethoxylated fatty alcohol sulfate salts, sulfosuccinates, sarcosinates, alkyl- and dialkylphosphates, fatty acid soaps and mixtures thereof.The nonionic surfactants may, for example, be chosen from: fatty acid and polyol esters such as optionally polyethoxylated fatty acid and glycerol esters, optionally polyethoxylated fatty acid and sorbitan esters, polyoxyethylene fatty acid and sucrose esters, such as sucrose stearate; polyoxyethylene fatty alcohol ethers, sugar fatty alcohol ethers, in particular alkylpolyglucosides (APG), polyether-modified polysiloxanes, and mixtures thereof. The antimicrobial agents may be selected from quaternary ammoniums, aldehydes (such as glutaraldehyde and formaldehyde), ethanol, halogenated derivatives, oxidants, phenolic compounds, parabens, isothiazolones (or isothiazolinones), benzoates, imidazoline, hydantoin, guanidine, organic acids such as lactic acid, and mixtures thereof.The insecticidal substances may be selected from organosphosphorus agents (such as acephate, chlorpyrifos or bromophos), nicotinoids, pyrethroids (such as permethrin, bifenthrin or fenvalerate), monoterpenes (such as p-menthane-3,8-diol), organohalogenated compounds (such as lindane, dicofol or toxaphene), N,N-diethyl-3-methylbenzamide, pyrethrum derivatives (such as Pyrethrin I, Pyrethrin II or Jasmoline I), sulfones, sulfonates, formamidines, benzoylureas, rotenones, alkaloids, quassine, ryanidone, aconitine, geraniol and mixtures thereof.Depending on the intended application, these products may also include at least one ingredient chosen from: phytosanitary or cosmetic active ingredients, enzymes, chelating agents, thickeners, fatty substances (oils, waxes and / or pastes), fillers, preservatives, pigments and dyes, antioxidants, optical brighteners, and mixtures thereof.

[0080] 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 12, in particular from 8 to 12 and preferably from 9 to 11. These products can be packaged in any device suitable for the intended use and in particular in a pump bottle, a tube, a pot, an aerosol device or a wipe.

[0081] 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

[0082] [Fig.l] illustrates the appearance of a 5% solution in water of a surfactant composition according to the invention (right) and of a comparative surfactant composition (left). EXAMPLES

[0083] 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.

[0084] Example 1: Synthesis of a surfactant composition based on betainylaminododecane salt

[0085] The production of betainylaminododecane mesylate is carried out from glycine betaine in a one-pot process involving two reaction steps, as illustrated below:

[0086] [Chem.l]

[0087] Example 1-1: Synthesis from glycine betaine and glycerol

[0088] Glycerol (15.725 g, 170.8 mmol, 2.0 eq) and glycine betaine (10.001 g, 85.4 mmol, 1.0 eq) are introduced into a 100 mL two-necked flask equipped with a distillation assembly. The set temperature is set at 150°C and the pressure is reduced to 200 mbar. Once the temperature and pressure conditions are reached, a 70% methanesulfonic acid solution (11.839 g, 86.2 mmol, 1.01 eq) is introduced. Once the introduction is complete, the pressure is gradually decreased to 30 mbar. The conversion rate is monitored by 'H NMR analyses. At 6 hours of reaction, the conversion rate is 95%.

[0089] The set temperature is set at 100°C. Once the mixture is at 100°C, the assembly is returned to atmospheric pressure and the previously melted dodecylamine (16.005 g, 86.3 mmol, 1.01 eq) is added. The reaction mixture is then heated to 100°C with vigorous stirring at atmospheric pressure for 1 h 30 min. The reaction mixture is then recovered and has the composition indicated in Table 1.

[0090] [Tables 1] Constituent Molar mass (g / mol) % by weight Betainylaminododecane mesylate 380.588 57.2% Dodecylammonium mesylate 281.455 8.5% Glyceryl betainate mesylate 287.327 0.7% Glycine betaine 117.148 2.2% Glycerol 92.094 31.3%

[0091] Example 1-2: synthesis from sugar beet vinasses

[0092] In a 50 mL flask equipped with a distillation assembly is introduced Betafin® LQD GL [10.0 g containing: glycerol (31.2 mmol, 1.46 eq); glycine betaine (21.3 mmol, 1.0 eq)] and a 70% methanesulfonic acid solution (3.481 g, 25.4 mmol, 1.2 eq). The mixture is stirred and the set temperature is set at 160°C. The pressure is reduced to 30 mbar in 35 min. The conversion rate is monitored by 'H NMR analyses. At 7h30 of reaction, the conversion rate is 96%.

[0093] The set temperature is set at 100°C. Once the mixture is at 100°C, the assembly is returned to atmospheric pressure and the previously melted dodecylamine (5.099 g, 27.5 mmol, 1.3 eq) is added. The reaction mixture is then heated to 130°C with vigorous stirring at atmospheric pressure for 2 hours. The reaction mixture is then recovered and has the composition indicated in Table 2.

[0094] [Tables2] Constituent Molar mass (g / mol) % by weight Betainylaminododecane mesylate 380.588 64.2% Dodecylammonium mesylate 281.455 13.8% Glyceryl betainate mesylate 287.327 0.0% Glycine betaine 117.148 2.7% Glycerol 92.094 19.4%

[0095] Example 2: Synthesis of a surfactant composition based on C12-C18 betainylaminoalkane salts

[0096] Glycerol (117.056 g, 1.271 mol, 2.0 eq) and glycine betaine (74.450 g, 0.636 mol, 1.0 eq) are introduced into a 1 L reactor equipped with a distillation assembly. The mixture is stirred and heated to 150°C at a pressure of 200 mbar. Once the temperature and pressure conditions are reached, an acid solution 70% methanesulfonic acid (88.100 g, 0.642 mmol, 1.01 eq) is introduced into the reactor. Once the introduction is complete, the pressure is gradually decreased to 30 mbar. The conversion rate is monitored by 'H NMR analyses. After 5h30 of reaction, the conversion rate is 99%.

[0097] The reaction mixture is cooled to 100°C. Once the mixture is at 100°C, the reactor is returned to atmospheric pressure and the previously melted Coco amine (114.100 g, 0.580 mmol, 0.91 eq) and octadecyl amine (17.131 g, 0.064 mol, 0.1 eq) are added. The reaction mixture is then heated to 150°C with vigorous stirring at atmospheric pressure for 1 hour. The reaction mixture is then recovered by draining the reactor and has the composition shown in Table 3.

[0098] [Tables3] Constituent Molar mass (g / mol) % by weight Betainylaminoalkane mesylate 399.216 51.4% Alkylammonium mesylate 300.083 12.0% Glyceryl betainate mesylate 287.327 6.6% Glycine betaine 117.148 2.0% Glycerol 92.094 28.1%

[0099] Example 3: Synthesis of a surfactant composition based on betainylaminooctadec-9-ene salt

[0100] Betafin® LQD GL [100.478 g containing: glycerol (336.7 mmol, 1.57 eq); glycine betaine (214.4 mmol, 1.0 eq)] is introduced into a 250 mL reactor equipped with a distillation assembly. The mixture is stirred and heated to 90°C at atmospheric pressure. Once the temperature is reached, a 70% methanesulfonic acid solution (35.2 g, 256.4 mmol, 1.2 eq) is introduced into the reactor. Once the introduction is complete, the set temperature is set at 150°C and the pressure is gradually decreased. After 1 h 15 min of reaction, the pressure is 60 mbar. The conversion rate is monitored by 'H NMR analyses. At 7 h of reaction, the conversion rate is 93%.

[0101] The reaction mixture is cooled to 100°C. Once the mixture is at 100°C, the reactor is returned to atmospheric pressure and the previously melted oleylamine (74.155 g, 277.2 mmol, 1.29 eq) is added. The reaction mixture is then heated to 150°C with vigorous stirring at atmospheric pressure for 2 hours. The reaction mixture is then recovered by draining the reactor and has the composition shown in Table 4.

[0102] [Tables4] Constituent Molar mass (g / mol) % by weight Betainylaminooctadec-9-ene mesylate 462.734 62.7% Oleylammonium mesylate 363.601 18.9% Glyceryl betainate mesylate 287.327 1.3% Glycine betaine 117.148 2.4% Glycerol 92.094 14.7%

[0103] Example 4: Properties of surfactant compositions 4-1#: Surface tension

[0104] The surface tension of the surfactant compositions of Examples 1-1 to 3 was measured using a goniometer, according to the hanging drop method described in EN ISO 19403-3 (2020).

[0105] Results:

[0106] [Tables5] Example Surface tension at 1% w / w (mN / m) 1-1 37.3 1-2 32 2 35.6 3 34.3 4-2#: Solubility in water

[0107] The solubility in water of a surfactant according to the invention (TA1), having the following composition, was evaluated: [Table 6] Mass composition Betainylaminododecane mesylate 58.4% Laurylammonium mesylate 9.5% Glyceryl betaine mesylate 0.0% Glycine betaine 3.1% Glycerol 29.0%

[0108] by comparison with a surfactant of the prior art (TA2) obtained from hexanol and having the following composition:

[0109] [Tables?] Mass composition Betainylaminododecane mesylate 56.9% Laurylammonium mesylate 9.9% Hexyl betainate mesylate 3.3% Glycine betaine 1.0% Hexanol 29.0%

[0110] These surfactants TA1 and TA2 were diluted at a rate of 5% by weight in water.

[0111] As shown in [Fig.l], the solution obtained using the surfactant TA1 (at right) remained clear, while that obtained using the TA2 surfactant (left) presented suspended particles indicating poor solubilization of the surfactant in water.

[0112] Example 5: Formulations

[0113] Several types of products can be prepared using the surfactant compositions according to the invention where CTx denotes the surfactant composition prepared according to Example x above. Household detergent

[0114] Lactic acid 80% 2.00%

[0115] CT1-1 0.40%

[0116] Hydroxyethyl cellulose 0.30%

[0117] Chelating agent 0.20%

[0118] Perfume 0.20%

[0119] Colorant 0.01%

[0120] Deionized water qsp 100.00%

[0121] This product can be used for cleaning hard surfaces. Body shampoo

[0122] CT2 3-5%

[0123] Ethoxylated alcohol 0-5%

[0124] Chelating agent* 5-10%

[0125] Soda 0.5-2%

[0126] Water qsp 100%

[0127] * Dissolvine® GL from AKZO NOBEL or Trilon® M from BASF

[0128] This product can be applied to a vehicle and then, after a 5-minute application time, rinsed under high pressure. Water treatment

[0129] MEA (monoethanol amine) 5-10%

[0130] CT3 20-25%

[0131] Antiredeposition polymer 10-25%

[0132] Water qsp 100%

[0133] Hair conditioner

[0134] [Tables8] Ingredients % CT2 Material 4% Olive Oil 5.00% Cetearyl Alcohol 3% Panthenol 0.15% Citric Acid Perfume 0.05% Preservative 0.01% Demineralized Water qsp 100%

Claims

Claims

1. A process for preparing a surfactant composition, comprising the successive steps of: (1) reacting glycine betaine or one of its salts with at least one polyol, in the presence of an organic or inorganic acid, at a temperature of 100 to 180°C; (2) cooling the reaction medium to a temperature of 20 to 100°C; (3) adding one or more alkylamines containing from 8 to 36 carbon atoms to the reaction medium; and (4) recovering the surfactant composition thus obtained.

2. Process according to claim 1, characterized in that the polyol consists of a hydrocarbon chain optionally interrupted by one or more oxygen atoms and carrying at least two alcohol functions, preferably at least one primary alcohol function.

3. Process according to claim 1 or 2, characterized in that the polyol is chosen from: linear or branched C2-C6 diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol; triols such as glycerol, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol; tetraols such as erythritol; hydrogenated sugars such as sorbitol, xylitol, mannitol and maltitol; polyglycerols, preferably having a molar mass ranging from 106 to 8000 g / mol, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, PEG-32, PEG-75 and PEG-180; and mixtures thereof, preferably the polyol is glycerol.

4. Method according to any one of claims 1 to 3, characterized in that the acid is chosen: from inorganic acids, such as hydrochloric acid, sulfuric acid, perhalohydric acids, such as perchloric acid, and mixtures thereof; organic acids, such as alkyl sulfuric acids, for example decyl or lauryl sulfuric acid; arylsulfonic acids, such as benzene sulfonic acid, paratoluene sulfonic acid; alkylsulfonic acids, such as triflic acid, methanesulfonic acid, ethanesulfonic acid, decylsulfonic acid, laurylsulfonic acid or camphorsulfonic acid; sulfosuccinic acid; and mixtures thereof; or Lewis acids, preferably the acid is an organic acid, more preferably an alkylsulfonic acid and in particular methanesulfonic or ethanesulfonic acid.

5. Process according to any one of claims 1 to 4, characterized in that the alkylamine is chosen from: dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, docosanylamine, eicosanylamine, C36 diamine dimers and mixtures thereof, in particular derived from coconut oil.

6. Surfactant composition obtainable according to the process according to any one of claims 1 to 5, characterized in that it comprises, and is preferably constituted by: (a) at least one glycine betaine amide salt of formula (1): X" [(CH3)3N+-CH2-CONH-R]n; (b) at least one polyol; (c) glycine betaine of formula (2): (CH3)3N+-CH2-COO; (d) optionally, at least one glycine betaine ester and polyol salt, of formula (3): Xn [(CH3)3N+-CH2-COOR']n where R' is a polyol residue; and (e) optionally, at least one alkylammonium salt of formula (4): Xn [NH3+R]n and (f) optionally an organic or inorganic acid salt, where: R is a saturated or unsaturated linear alkyl group comprising from 8 to 36 carbon atoms, X is an organic or inorganic anion, and n is 1 or 2.

7. Composition according to claim 6, characterized in that it contains, and is preferably constituted by: (a) from 40 to 75% by weight, preferably from 50 to 70% by weight of glycine betaine amide salt, (b) from 8 to 40% by weight, preferably from 10 to 35% by weight, of polyol, (c) from 0.5 to 5% by weight, preferably from 1 to 3% by weight of glycine betaine, (d) optionally, from 0.1 to 10% by weight of glycine betaine ester and polyol, (e) optionally, from 0.1 to 30% by weight, in particular from 1 to 20% by weight, of alkylammonium salt, (f) optionally, from 0.1 to 5% by weight of an organic or inorganic acid salt, relative to the total dry weight of the surfactant composition.

8. Composition according to claim 6 or 7, characterized in that it contains less than 5% by weight, advantageously less than 3% by weight, more preferably less than 1% by weight, or even none at all, of linear or branched (preferably linear), saturated or unsaturated alcohol, comprising from 8 to 36 carbon atoms.

9. Use of the composition according to any one of claims 6 to 8 as a wetting agent, particle dispersant and / or corrosion inhibitor and / or for improving the disinfecting power and / or the persistence of the disinfecting effect of antimicrobial substances and / or the effect of insecticidal substances.

10. Use of the composition according to any one of claims 6 to 8 for 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, household products, industrial cleaning products, fiber sizing products and phytosanitary products; - for water treatment; - for oil extraction.

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