Surfactant composition based on glycine betaine amide salts, method for preparing same and uses thereof

Abstract

The present invention relates to a surfactant composition based on a glycine betaine amide salt, as well as to the method for preparing same. 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 remanence of the disinfectant effect of antimicrobial substances and / or the insecticidal effect and / or the remanence 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, the treatment of water and the extraction of oil.

Description

[0001] Surfactant composition based on glycine betaine amide salts, its preparation process and its uses

[0002] SUBJECT OF THE INVENTION

[0003] The present invention relates to a surfactant composition based on glycine betaine amide salts, 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 disinfectant power of antimicrobial substances and / or the effect 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.

[0004] BACKGROUND OF THE INVENTION

[0005] Surfactants are essential raw materials for the manufacture of a variety of products. While cationic surfactants represent a smaller market than anionic or non-ionic surfactants, they are nevertheless of interest in a wide range of applications, particularly in the manufacture of detergents and cosmetics, as well as in water treatment.

[0006] 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 be of plant origin. It thus provides access to cationic amphiphilic molecules without the classic step of quaternization of a tertiary amine using generally toxic methylating agents. Other similar surfactants are presented in the publication by F. Goursaud et al in Green Chem., 2008, 10, 310-320.

[0007] 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. However, it has been 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 compounds that are weakly, or not at all, water-soluble, which leads to difficulties in formulating these surfactants, resulting in the appearance of a supernatant.

[0008] 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 the elimination of all the alcohol, 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.

[0009] 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 also leads to surfactants which are easier to formulate in an aqueous medium.

[0010] 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. Journoux 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.

[0011] SUMMARY OF THE INVENTION

[0012] The subject of the invention is a process for preparing a surfactant composition, comprising the successive steps consisting of:

[0013] (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;

[0014] (2) cooling the reaction medium; (3) adding one or more alkylamines containing from 8 to 36 carbon atoms to the reaction medium; and

[0015] (4) recovering the surfactant composition thus obtained.

[0016] The process according to the invention does not require, unlike the processes of the prior art, a distillation step aimed at removing the residual alcohol from step (1), nor equipment for distilling the water during step (1) without simultaneously removing the alcohol, which is volatile. It therefore also does not require pressure control during this step. It follows that this process is economically more attractive than the known processes for the synthesis of glycine betaine amides.

[0017] The invention also relates to a surfactant composition which can be obtained according to this process and containing or consisting of:

[0018] (a) from 40 to 75% by weight of glycine betaine amide salt of formula (1): X n [(CH3)3N + -CH2- CONH-R] n ,

[0019] (b) from 8 to 40% by weight of polyol,

[0020] (c) from 0.5 to 5% by weight of glycine betaine of formula (2): (CH3)3N + -CH2-C00',

[0021] (d) optionally, from 0.1 to 10% by weight of glycine betaine ester salt and polyol of formula (3): X I1- [(CH3)3 N + -CH2-COOR'] n where R' is a polyol residue,

[0022] (e) optionally, from 0.1 to 30% by weight of alkyl ammonium salt of formula (4): X 11 ' [NH3 + R] n,

[0023] (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, where:

[0024] R is a saturated or unsaturated linear alkyl group comprising from 8 to 36 carbon atoms,

[0025] X is an organic or inorganic anion, and n is 1 or 2.

[0026] In addition to its biodegradability (according to OECD 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. 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 disinfectant power and / or the persistence of the disinfectant effect of antimicrobial substances and / or for improving the effect and / or the persistence of insecticidal substances.

[0027] It also relates to the use of this composition for the manufacture of plastics or products intended for:

[0028] - the treatment and / or cleaning of the body, plants or hard surfaces, in particular cosmetic products, vehicle washing products, household products, industrial cleaning products, fibre sizing products and plant protection products;

[0029] - water treatment;

[0030] - to oil extraction.

[0031] DETAILED DESCRIPTION surfactant

[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 the 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 in this process is to esterify glycine betaine, or trimethylglycine. Glycine betaine can be of plant or synthetic origin. Although glycine betaine is available on the market in protonated form (as hydrochloride), it is preferable to use glycine betaine in zwitterionic form according to the invention. 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, decyl sulfonic 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 esterification, the acid function of the salified betaine is reacted with a polyol, to produce a glycine betaine and polyol ester, which is in salt form. The term "polyol" means 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. The term "hydrocarbon chain" means 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 102. Furthermore, it is preferred that the polyol has a solubility in water at 25°C of at least 25 g / 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; polyethylene glycols, 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 petrochemical alcohols.

[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 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 glycine betaine. Such a mixture is notably available from the company ALTILIS under the commercial reference Betafin® LQD GL. In another embodiment, the glycine betaine is first reacted with the acid before the 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 time generally ranging from 2 h to 10 h, preferably from 5 h to 8 h. 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 pressure reduction is only intended to distill the water to shift the reaction equilibrium.

[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 betaine to glycine betaine ester is advantageously measured by NMR 1H. The esterification reaction is typically stopped when a conversion rate of at least 90%, generally 95% to 99%, has been reached. At Tissue of this esterification step, it is possible to neutralize the reaction medium, in order to avoid or limit the formation of an ammonium salt between the amine added in the following step and 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 Tissue of the process may not be desirable due to environmental constraints.

[0043] This neutralization step may be carried out by adding any suitable base to the reaction medium, such as an organic or inorganic sodium salt, in particular sodium carbonate, sodium hydrogen carbonate or calcium carbonate. In this step, the reaction medium may be heated to a temperature of 40 to 150°C, for example 60 to 80°C.

[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, toleylamine, docosanylamine, eicosanylamine, dimer diamines (derived from fatty acid dimers), in particular C36 (such as those available from CARGILL under the trade name 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 from 1 to 3 hours. In one embodiment of the invention, the neutralization step described above may alternatively be carried out at the end of the aminolysis step.In this case, sodium ethanolate is advantageously used as the base or any other base having a pKa high enough to deprotonate the fatty amine salt.

[0046] Thus, the method according to the invention advantageously comprises an additional step of adding a base between steps (2) and (3) or between steps (3) and (4).

[0047] The surfactant composition thus obtained is then recovered, which can optionally be diluted in water before use.

[0048] This process makes it possible to obtain a surfactant composition comprising, and preferably consisting of:

[0049] (a) from 40 to 75% by weight, preferably from 50 to 70% by weight of glycine betaine amide salt of formula (1): X n -[(CH3)3N + -CH2-CONH-R] n ,

[0050] (b) from 8 to 40% by weight, preferably from 10 to 35% by weight, more preferably from 25 to 35% by weight, of polyol,

[0051] (c) from 0.5 to 5% by weight, preferably from 1 to 3% by weight of glycine betaine of formula (2): (CH3)3N + -CH2-COO-,

[0052] (d) optionally, from 0.1 to 10% by weight of glycine betaine ester salt and polyol of formula (3): X"'[(CH3)3N + -CH2-COOR'] n where R' is a polyol residue,

[0053] (e) optionally, from 0.1 to 30% by weight, in particular from 1 to 20% by weight or from 0.1 to 0.5% by weight, of alkylammonium salt of formula (4): X"'[NH3R] n ,

[0054] (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, 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, and n is 1 or 2

[0057] By "polyol residue" is meant the unit derived from the polyol which is incorporated into the polyol ester salt after esterification of the polyol with glycine betaine. 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.

[0058] In all cases, it is preferred 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.

[0059] Uses

[0060] 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:

[0061] - for the treatment and / or cleaning of the body, plants, textiles or hard surfaces, 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;

[0062] - water treatment;

[0063] - to oil extraction.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] These products are advantageously presented in the form of an aqueous solution or aqueous gel. Alternatively, they may be presented 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 may 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.

[0072] 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

[0073] Figure 1 illustrates the appearance of a 5% solution in water of a surfactant composition according to the invention (right) and a comparative surfactant composition (left).

[0074] EXAMPLES

[0075] 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.

[0076] Example 1: Synthesis of a surfactant composition based on bctainylaminododccanc salt

[0077] The production of betainylaminododecane mesylate is carried out from glycine betaine in a one-pot process involving two reaction steps, as illustrated below:

[0078] Example 1-1: Synthesis from glycine betaine and glycerol

[0079] 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. After 6 hours of reaction, the conversion rate is 95%. 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 hour 30 minutes.The reaction mixture is then recovered and has the composition indicated in Table 1.

[0080] SUBSTITUTION SHEET (RULE 26) [Table 1]

[0081] Example 1-2: Synthesis from sugar beet vinasse

[0082] 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) are introduced into a 50 mL flask equipped with a distillation assembly. The mixture is stirred and the set temperature is set at 160°C. The pressure is decreased to 30 mbar in 35 min. The conversion rate is monitored by NMR analyses. 1H. At 7h30 of reaction, the conversion rate is 96%. 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.

[0083] [Table 2] Example 2: Synthesis of a surfactant composition based on C12-C18 betainylaminoalkane salts

[0084] 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, a 70% methanesulfonic acid solution (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 NMR analyses. 1 H. At 5h30 of reaction, the conversion rate is 99%.

[0085] The reaction mixture is cooled to 100°C. Once the mixture reaches 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.

[0086] [Table 3]

[0087] Example 3: Synthesis of a surfactant composition based on betainylaminooctadec-9-ene salt

[0088] 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 hL of reaction, the pressure is 60 mbar. The conversion rate is monitored by NMR analyses. 1 H. At 7:00 of reaction, the conversion rate is 93%.

[0089] The reaction mixture is cooled to 100°C. Once the mixture reaches 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.

[0090] [Table 4] : Synthesis of a surfactant composition based on betainylaminododecane salt

[0091] The production of betainylaminododecane mesylate is carried out from glycine betaine in a one-pot process involving three reaction steps, as illustrated below:

[0092] The experiment is carried out in a 100 mL tank with counter-blades, equipped with a turbine-shaped stirring blade, a temperature probe and a distillation setup. Glycerol (23.58 g, 0.256 mol, 2.0 eq) and glycine betaine (15.00 g, 0.128 mol, 1.0 eq) are introduced into the tank. The set temperature of the reaction mixture 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 (17.75 g, 0.129 mol, 1.01 eq) is introduced via an addition funnel fixed on one of the necks of the tank lid. Once the introduction is complete, the pressure is gradually decreased to 30 mbar. The conversion rate is monitored by NMR analyses 1 H. At 6 hours of reaction, the conversion rate is 97.7%.

[0093] The set temperature is set at 70°C. Once the mixture is at 70°C, the assembly is returned to atmospheric pressure and sodium carbonate (0.27 g, 2.6 mmol, 0.02 eq) is added. The reaction mixture is then heated to 70°C with vigorous stirring at atmospheric pressure for 30 minutes.

[0094] Dodecylamine (21.36 g, 0.115 mol, 0.9 eq) previously melted is then added. The reaction mixture is then heated to 100°C with vigorous stirring at atmospheric pressure for 5 h. The reaction mixture is then recovered and has the composition indicated in Table 5 below.

[0095] [Table 5] : Synthesis of a surfactant composition based on betainylaminododecane salt The production of betainylaminododecane mesylate is carried out from glycine betaine using a one-pot process involving three reaction steps, as illustrated below:

[0096] The experiment is carried out in a 100 mL tank with counter-blades, equipped with a turbine-shaped stirring blade, a temperature probe and a distillation setup. Glycerol (23.597 g, 0.2562 mol, 2.0 eq) and glycine betaine (15.001 g, 0.1280 mol, 1.0 eq) are introduced into the tank. The set temperature of the reaction mixture 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 (17.775 g, 0.1295 mol, 1.01 eq) is introduced via an addition funnel fixed on one of the necks of the tank lid. Once the introduction is complete, the pressure is gradually decreased to 30 mbar. The conversion rate is monitored by NMR analyses 1 H.

[0097] After 7 hours of reaction, the set temperature of the reaction mixture is set at 100°C. Once the mixture is at 100°C, the assembly is returned to atmospheric pressure and the previously melted dodecylamine (21.369 g, 0.1153 mol, 0.9 eq) is added. The reaction mixture is then heated to 100°C with vigorous stirring at atmospheric pressure for 3 hours.

[0098] The set temperature of the reaction mixture is set at 70°C. Once the mixture is at 70°C, a first addition of sodium ethanolate (21% solution, 5.73 mL, 0.0154 mol, 0.12 eq) is made. After 1 h of reaction, a second addition of sodium ethanolate (21% solution, 2.39 mL, 0.0064 mol, 0.05 eq) is made. After 1 h of reaction, a third addition of sodium ethanolate (21% solution, 1.43 mL, 0.0038 mol, 0.03 eq) is made. After 1 h of reaction, the reaction mixture is concentrated under vacuum to distill off the ethanol. The mixture obtained then has the composition indicated in Table 6 below.

[0099] [Table 6]

[0100] Example 6: Properties of surfactant compositions

[0101] 6-1: Surface tension 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).

[0102] Results :

[0103] [Table 71

[0104] 6-2: Solubility in water

[0105] The solubility in water of a surfactant according to the invention (TA1), having the following composition, was evaluated:

[0106] [Table 8] by comparison with a surfactant of the prior art (TA2) obtained from hexanol and having the following composition:

[0107] [Table 9]

[0108] These surfactants TA1 and TA2 were diluted at a rate of 5% by weight in water.

[0109] As shown in Figure 1, the solution obtained using surfactant TA1 (right) remained clear, while that obtained using surfactant TA2 (left) presented suspended particles indicating poor solubilization of the surfactant in water. Formulations

[0110] 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.

[0111] Household detergent

[0112] Lactic acid 80% 2.00%

[0113] CT1-1 0.40%

[0114] Hydroxy ethyl cellulose 0.30%

[0115] Chelating agent 0.20%

[0116] Perfume 0.20%

[0117] Colorant 0.01%

[0118] Deionized water qsp 100.00%

[0119] This product can be used for cleaning hard surfaces. body

[0120] CT2 3-5%

[0121] Ethoxylated alcohol 0-5%

[0122] Chelating agent* 5-10%

[0123] Soda 0.5-2%

[0124] Water qsp 100%

[0125] * Dissolvine® GL from AKZO NOBEL or Trilon® M from BASF

[0126] This product can be applied to a vehicle and then, after a 5-minute application time, rinsed under high pressure.

[0127] Water treatment

[0128] MEA (monoethanol amine) 5-10%

[0129] CT3 20-25%

[0130] Anti-redeposition polymer 10-25%

[0131] Water qsp 100%

[0132] Hair conditioner

[0133] [Table 10]

Claims

CLAIMS 1. 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. Method 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. Method 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; polyethylene glycols, 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; acids 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. Method according to any one of claims 1 to 5, characterized in that it further comprises a step of adding a base between steps (2) and (3) or between steps (3) and (4).

7. Surfactant composition capable of being obtained according to the process according to any one of claims 1 to 6, characterized in that it comprises, and is preferably constituted by: (a) from 40 to 75% by weight, preferably from 50 to 70% by weight of glycine betaine amide salt of formula (1): X n -[(CH3)3N + -CH2-CONH-R] n , (b) from 8 to 40% by weight of polyol, (c) from 0.5 to 5% by weight of glycine betaine of formula (2): (CH3)3N + -CH2-C00', (d) optionally, from 0.1 to 10% by weight of glycine betaine ester salt and polyol of formula (3): X"'[(CH3)3N + -CH2-COOR'] n where R' is a polyol residue, (e) optionally, from 0.1 to 30% by weight of alkyl ammonium salt of formula (4): X' 1- [NH3 + R] n , (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, 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 8. Composition according to claim 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 claim 7 or 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 claim 7 or 8 for the manufacture of plastics or products intended: - the treatment and / or cleaning of the body, plants or hard surfaces, in particular cosmetic products, vehicle washing products, household products, industrial cleaning products, fibre sizing products and plant protection products; - water treatment; - to oil extraction.

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