Surfactant composition based on glycine betaine amide salts, process for their preparation and use thereof

Abstract

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

Description

Technical Field

[0001] This invention relates to a surfactant composition based on glycine betaine amide salt and a method for its preparation. The invention also relates to the use of said composition as a wetting agent, particulate dispersant, and / or corrosion inhibitor, and / or for improving the disinfection capabilities of antimicrobial substances and / or the effectiveness of insecticides, as well as for use in the manufacture of various products intended for use in treating and / or cleaning bodies, plants, or hard surfaces, for water treatment, or for use in oil extraction. Background Technology

[0002] Surfactants are indispensable raw materials in the manufacture of a wide variety of products. Among them, cationic surfactants, although smaller in market size than anionic or nonionic surfactants, are still of great interest in various applications, especially in the manufacture of detergents and cosmetics, as well as in water treatment.

[0003] Patents US-7,829,521 and WO 2013 / 188508 disclose biodegradable cationic surfactants based on glycine betaine amides and methods for their preparation. The latter involves: protonating glycine betaine with an acid, then esterifying it with a short-chain alcohol, followed by ammonolysis of the product with at least one aliphatic amine (particularly of plant origin). Therefore, this method allows the acquisition of cationic amphiphilic molecules without the conventional step of quaternizing tertiary amines with typically toxic methylating agents. F. Goursaud et al., Green Chem. Other similar surfactants are described in publications 310-320, October 2008.

[0004] By modifying the operating conditions described in WO 2013 / 188508, the applicant has obtained a surfactant composition rich in glycine betaine amide and poor in alkyl ammonium salts, which has been found to have lower surface tension and better environmental friendliness than the surfactant composition described in that document. Therefore, this surfactant composition (described in application EP3 584 303) is suitable for a variety of applications.

[0005] However, it has been observed that prior art surfactant compositions, in addition to containing the desired glycine betaine amide salt, residual glycine betaine, and possibly residual acid and ammonium salt of the fatty amine used, also contain residual short-chain alcohols (e.g., butanol or hexanol), as well as esters and ethers of these alcohols. These alcohols, ethers, and esters are poorly or even completely insoluble in water, which makes the formulation of these surfactants difficult, resulting in the formation of supernatants.

[0006] To overcome this drawback, it has been envisioned to remove residual alcohols by distillation prior to the ammonolysis step. However, this expensive solution is not satisfactory from an industrial perspective. Furthermore, it cannot remove all alcohols because, under the neutral or alkaline pH conditions typically used in this surfactant composition, the aforementioned esters tend to hydrolyze, releasing additional alcohols.

[0007] Against this backdrop, the applicant has developed an improved method for synthesizing glycine betaine amide, which is not only environmentally friendly and can be implemented on an industrial scale under acceptable economic conditions, but also yields a surfactant that is easier to formulate in an aqueous medium.

[0008] The method according to the invention includes a first step of esterifying glycine betaine with the aid of a polyol (particularly glycerol). While this step is known in itself (C. Journoux et al., Green Chemistry , 19(23), 2017), but it was never conceived that it could be incorporated into a more comprehensive method for preparing glycine betaine amide, let alone to address the aforementioned problems. Summary of the Invention

[0009] The subject of this invention is a method for preparing a surfactant composition, the method comprising the following sequential steps: (1) In the presence of organic or inorganic acids, at a temperature of 100 to 180°C, glycine betaine or its salt is reacted with at least one polyol. (2) Cool the reaction medium; (3) Adding one or more alkylamines containing 8 to 36 carbon atoms to the reaction medium; and (4) The surfactant composition obtained therefrom is recovered.

[0010] Compared to existing methods, the method according to the present invention does not require a distillation step aimed at removing residual alcohol from step (1), nor does it require any equipment capable of distilling water during step (1) without simultaneously removing volatile alcohol. Therefore, no pressure control is required during this step. Consequently, this method is economically more attractive than known methods for synthesizing glycine betaine amides.

[0011] The subject of this invention also relates to a surfactant composition obtainable according to the method, said composition comprising or consisting of the following components: Relative to the total dry weight of the surfactant composition, (a) Formula (1) from 40% to 75% by weight: X n- [(CH3)3N + -CH2-CONH-R] n The glycine betaine amide salt shown is... (b) 8% to 40% by weight of polyols, (c) 0.5 wt% to 5 wt% of formula (2): (CH3)3N + -CH2-COO - The glycine betaine shown, (d) Optionally, 0.1% to 10% by weight of formula (3): X n- [(CH3)3N + -CH2-COOR'] n The polyol glycine betaine ester salt shown is an example of a polyol residue. (e) Optionally, 0.1% to 30% by weight of formula (4): X n- [NH3 + R] n The alkylammonium salt shown, (f) Optionally, 0.1% to 5% by weight of organic acid or inorganic acid salt, in: R is a saturated or unsaturated straight-chain alkyl group containing 8 to 36 carbon atoms. X is an organic or inorganic anion, and n is 1 or 2.

[0012] In addition to its biodegradability (according to OECD 310 standards), low surface tension, and good foaming ability (comparable to surfactants obtained according to prior art methods), the surfactant compositions according to the invention also have the advantage of being more soluble in water.

[0013] Another subject of the present invention is the use of the above-mentioned surfactant composition as a wetting agent, particulate dispersant and / or corrosion inhibitor, and / or for improving the disinfection ability and / or durability of disinfection effect of antimicrobial substances and / or for improving the effect and / or durability of insecticides.

[0014] The subject of this invention also lies in the use of the composition in the manufacture of plastics or products intended to: - Used for treating and / or cleaning the body, plants or hard surfaces, especially cosmetics, car wash products, household products, industrial cleaning products, fiber sizing products and plant protection products; - Used for water treatment; - Used for oil extraction. Detailed Implementation

[0015] Surfactant Composition

[0016] The method according to the present invention comprises the following sequential steps: (1) In the presence of organic or inorganic acids, at a temperature of 100 to 180°C, glycine betaine or its salt is reacted with at least one polyol. (2) Cool the reaction medium; (3) Adding one or more alkylamines containing 8 to 36 carbon atoms to the reaction medium; and (4) The surfactant composition obtained therefrom is recovered.

[0017] The first step of this method is the esterification of glycine betaine or trimethylglycine. Glycine betaine can be of plant or synthetic origin. Although protonated forms of glycine betaine (such as hydrochloride) are commercially available, zwitterionic forms are preferred according to the invention. Then, in the method according to the invention, it needs to be protonated using an organic or inorganic acid. The acid may be particularly selected from inorganic acids, such as hydrochloric acid, sulfuric acid, perhalic acids such as perchloric acid, and mixtures thereof. In one variant, the acid may be selected from organic acids, such as alkyl sulfuric acids, such as decyl sulfuric acid or lauryl sulfuric acid; aryl sulfonic acids, such as benzenesulfonic acid, p-toluenesulfonic acid; alkyl sulfonic acids, such as trifluoromethanesulfonic 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, the acid is an organic acid, more preferably an alkyl sulfonic acid, particularly methanesulfonic acid or ethanesulfonic acid.

[0018] During esterification, the acid functional group of the salt-forming betaine reacts with the polyol to generate the polyol glycine betaine ester in salt form. The term "polyol" is understood to refer to a straight-chain, cyclic, or branched saturated monomer or polymer compound containing at least two alcohol (OH) functional groups. Advantageously, the polyol used according to the invention consists of a hydrocarbon chain optionally interrupted by one or more oxygen atoms and containing at least two alcohol functional groups. "Hydrocarbon chain" is understood to refer to a structure containing only carbon and hydrogen atoms. The polyol according to the invention typically contains at least one primary alcohol and / or secondary alcohol functional group; preferably, it contains at least one primary alcohol functional group. Advantageously, the melting point of the polyol, measured by differential scanning calorimetry according to OECD 102 standards, is at most 180°C, preferably at most 160°C, more preferably at most 150°C. Furthermore, the solubility of the polyol in water at 25°C is preferably at least 25 g / L.

[0019] Examples of such polyols may be selected from: straight-chain 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, neopentanediol, 1,6-hexanediol, and 3-methyl-1,5-pentanediol; triols, such as glycerol, trimethylolpropane, and 1,2,6-hexanetriol; tetraols, such as erythritol; hydrogenated sugars, such as sorbitol, xylitol, mannitol, and maltitol; polyglycerol; polyethylene glycol, preferably polyethylene glycol with a molar mass in the range of 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 in this invention. Glycerol is a bio-based reactant that is readily available and cheaper than some petrochemically derived alcohols.

[0020] The introduction of reactants during the first step is not critical. Therefore, in one embodiment of the invention, the polyol is mixed with glycine betaine before the acid is introduced. In practice, the polyol can be a co-product of beet molasses extract used to produce glycine betaine. Such a mixture is available, in particular, from Altilis under the trade name Betafin® LQD GL. In another embodiment, glycine betaine is reacted with the acid first, followed by the introduction of the polyol.

[0021] Esterification reactions are typically carried out in the absence of any solvent, with the polyol serving as both a reactant and a medium. Generally, 1.0 to 4 equivalents (e.g., 1.2 to 2 equivalents) of polyol and / or 1.0 to 1.5 equivalents of acid, such as 1.0 to 1.2 equivalents, can be used relative to 1 equivalent of glycine betaine. Esterification can be carried out at a temperature of 100 to 180°C, preferably 120 to 170°C, more preferably 140 to 160°C, under atmospheric or reduced pressure (e.g., 30 to 200 mbar), for a duration typically ranging from 2 to 10 h, preferably 5 to 8 h. Compared to existing methods using butanol or hexanol instead of polyols, there is no need for a Dean-Stark apparatus or precise pressure control because the polyols are non-volatile. The sole purpose of reducing the pressure is to distill off water to shift the reaction equilibrium.

[0022] During this reaction, one or more alcohol functional groups (hydroxyl groups) of the polyol are esterified with glycine betaine. Additionally, oligomerization of the polyol may occur. Thus, a mixture of glycine betaine esters produced from different alcohol functional groups of the polyol, or even from the reaction of these oligomers, can be obtained. The conversion of glycine betaine to glycine betaine esters is advantageously measured by ¹H NMR. The esterification reaction typically stops when at least 90% (typically 95% to 99%) of the conversion is reached.

[0023] At the end of this esterification step, the reaction medium can be neutralized to avoid or limit the formation of ammonium salts between the amine added in the next step and the residual acid or residual protonated glycine betaine. This is because the formation of such ammonium salts reduces the availability of the fatty amine to the ammonolysis reaction, and its presence in the surfactant composition obtained at the end of the method may be undesirable due to environmental constraints.

[0024] This neutralization step can be achieved by adding any suitable base (e.g., an organic or inorganic sodium salt, particularly sodium carbonate, sodium bicarbonate, or calcium carbonate) to the reaction medium. In this step, the reaction medium can be heated to a temperature of 40 to 150°C, for example, 60 to 80°C.

[0025] After cooling the reaction medium (whether or not neutralized), for example to 20-100°C, one or more C8-C36 alkylamines are then added to the reaction medium. Examples of such amines include: dodecylamine (or laurylamine), tetradecylamine, hexadecylamine, octadecylamine, oleylamine, docosylamine, eicosylamine, and dimeramines (derived from dimer fatty acids), especially C8-C36 alkylamines. 36 Dimeric diamines (such as those available from Cargill under the trade name Priamine®) and mixtures thereof. Examples of such mixtures are amines derived from coconut oil.

[0026] In this step, the alkylamine is advantageously used in molten form. The amount of alkylamine added can be, for example, 0.9 to 1.5 equivalents, preferably 1.0 to 1.2 equivalents, relative to 1 equivalent of the initially used glycine betaine. The ammonolysis reaction is typically carried out at atmospheric pressure at a temperature of 50 to 180°C, preferably 80 to 120°C. Since the reaction medium is alcohol-free, it is indeed unnecessary to remove alcohol by vacuum distillation during the ammonolysis reaction, in contrast to prior art methods. The ammonolysis reaction can proceed for 0.5 to 7 hours, particularly 1 to 3 hours.

[0027] In one embodiment of the invention, the above-described neutralization step may be performed in a variant manner at the end of the ammonolysis step. In this case, sodium ethoxide or any other base with a sufficiently high pKa to deprotonate the aliphatic amine salt is advantageously used as the base.

[0028] Therefore, the method according to the invention advantageously includes an additional step of adding alkali between steps (2) and (3) or between steps (3) and (4).

[0029] The resulting surfactant composition is then recovered and may optionally be diluted with water before use.

[0030] This method enables the preparation of a surfactant composition comprising, and preferably consisting of, the following components: Relative to the total dry weight of the surfactant composition, (a) 40% to 75% by weight, preferably 50% to 70% by weight of formula (1): X n- [(CH3)3N + -CH2-CONH-R] n The glycine betaine amide salt shown is... (b) 8% to 40% by weight, preferably 10% to 35% by weight, more preferably 25% to 35% by weight of polyols. (c) 0.5% to 5% by weight, preferably 1% to 3% by weight of formula (2): (CH3)3N + -CH2-COO - The glycine betaine shown, (d) Optionally, 0.1% to 10% by weight of formula (3): X n- [(CH3)3N + -CH2-COOR'] n The polyol glycine betaine ester salt shown is an example of a polyol residue. (e) Optionally, from 0.1% to 30% by weight, particularly from 1% to 20% by weight or from 0.1% to 0.5% by weight of formula (4): X n- [NH3 + R] n The alkylammonium salt shown, (f) Optionally, 0.1% to 5% by weight of organic acid or inorganic acid salt, in: R is a saturated or unsaturated straight-chain alkyl group containing 8 to 36 carbon atoms. X is an organic or inorganic anion, and n is 1 or 2.

[0031] "Polyol residues" are understood to refer to units derived from polyols, which are incorporated into polyol ester salts after the polyol is esterified with glycine betaine.

[0032] In the case where the method according to the invention includes a neutralization step using a base, compound (f) is present and is the product of the reaction of the base with the acid used in the esterification step.

[0033] In all cases, the surfactant composition according to the invention preferably contains less than 5% by weight, advantageously less than 3% by weight, more preferably less than 1% by weight, or even completely free of C8 to C36 saturated or unsaturated straight-chain or branched (preferably straight-chain) alcohols.

[0034] use

[0035] The surfactant compositions according to the invention can be used in a variety of applications as wetting agents, particulate dispersants, and / or corrosion inhibitors, and / or to improve the disinfecting ability of antimicrobial substances and / or the effectiveness of insecticidal substances. It is particularly suitable for use in the manufacture of plastics or various products, which are specifically designed to: - Products for treating and / or cleaning the body, plants, textiles, or hard surfaces, especially cosmetics such as shampoos, liquid soaps, bubble baths, and shower gels; vehicle (e.g., car, truck, train, bus, or airplane) cleaning products; household products such as detergents for windows, walls, floors, or dishes; laundry detergents or fabric softeners; industrial cleaning products; fiber sizing products; plant protection products; coloring products such as paints or varnishes; - Used for water treatment; - Used for oil extraction.

[0036] When used to clean hard surfaces (such as windows or vehicle body surfaces) or textiles, it was particularly observed that the compositions according to the invention accelerated subsequent drying of the surface without leaving scale marks during drying. Furthermore, when the surface is a vehicle, improved cleaning of fine brake dust on wheels was observed compared to conventional cationic surfactants. Finally, the effectiveness of the compositions according to the invention in alkaline media allows avoidance of the disadvantages of using acidic compositions, particularly their corrosive effects.

[0037] In water treatment applications, the compositions according to the invention enable the separation of biofilms without compromising the effectiveness of ion exchange resins, in contrast to conventional cationic surfactants, which have a significant environmental impact due to their lack of biodegradability or slow biodegradability. This ability to separate biofilms can also be applied to oil extraction processes.

[0038] In cosmetic applications, the compositions according to the invention are compatible with conventional anionic surfactants, thereby improving the creamy feel of the foam produced. They also protect ferrous aerosol devices from corrosion.

[0039] In plastic manufacturing, the compositions according to the invention enable the imparting of electrostatic properties to the surface of plastics without affecting their recyclability, as they possess bio-based properties.

[0040] When used in the manufacture of plant protection products, the composition according to the invention improves the persistence of the active ingredient and the water resistance of the product (e.g., herbicides, insecticides, or plant growth regulators), thus allowing these products to be used in small quantities. Therefore, the composition can be added, for example, to products containing neutral or alkaline media in a 0.4% by weight aqueous solution diluted to 25%.

[0041] The compositions according to the invention can also be used in the extraction, storage, intermediate storage, or refining processes of petroleum to limit equipment corrosion. In this application, for example, they can be added to petroleum in amounts up to 500 to 1000 ppm.

[0042] The products comprising the compositions according to the present invention may further include at least one compound selected from: anionic surfactants, nonionic surfactants, antimicrobial agents and / or insecticides, and mixtures thereof. Examples of anionic surfactants are: ethoxylated fatty alcohol sulfates, sulfosuccinates, sarcosinates, alkyl and dialkyl phosphates, fatty acid soaps, and mixtures thereof. Nonionic surfactants may be selected, for example, from: fatty acid esters of polyols, such as optionally polyethoxylated glycerol fatty acid esters, optionally polyethoxylated sorbitan fatty acid esters, polyoxyethylene fatty acid esters, sucrose fatty acid esters such as sucrose stearate; fatty alcohol polyoxyethylene ethers, fatty alcohol sugar ethers, especially alkyl polyglucosides (APG), polyether-modified polysiloxanes, and mixtures thereof. Antimicrobial agents may be selected from quaternary ammonium salts, aldehydes (e.g., glutaraldehyde and formaldehyde), ethanol, halogenated derivatives, oxidants, phenolic compounds, p-hydroxybenzoates, isothiazolones (or isothiazolinones), benzoates, imidazolines, hydantoin, guanidine, organic acids such as lactic acid, and mixtures thereof. Insecticides may be selected from organophosphates (e.g., acephate, chlorpyrifos, or bromoxynil), neonicotinoids, pyrethroids (e.g., permethrin, bifenthrin, or cypermethrin), monoterpenes (e.g., p-menthane-3,8-diol), organohalogen compounds (e.g., lindane, trichlorfon, or toxaphene), N,N-diethyl-3-methylbenzamide, pyrethroid derivatives (e.g., pyrethroid I, pyrethroid II, or jasmine I), sulfones, sulfonates, formamidins, benzoylurea, rotenone, alkaloids, quassinolide, rysantheminone, aconitine, geraniol, and mixtures thereof. Depending on the intended application, these products may also contain at least one ingredient selected from: plant protection or cosmetic surfactants, enzymes, chelating agents, thickeners, fatty substances (oils, waxes, and / or pastes), fillers, preservatives, pigments and dyes, antioxidants, optical brighteners, and mixtures thereof.

[0043] These products are advantageously in the form of aqueous solutions or hydrogels. In one variant, they may be in the form of oil-in-water or water-in-oil emulsions or even pastes. In any case, the aqueous phase present in these products advantageously has a pH in the range of 1 to 12, particularly 8 to 12, preferably 9 to 11. These products can be packaged in any device suitable for the intended use, particularly in pump bottles, tubing, cans, aerosol devices, or wet wipes.

[0044] They advantageously contain 0.1% to 25% by weight, for example 1% to 10% by weight, of the surfactant composition according to the invention. Attached Figure Description

[0045] Figure 1 The appearance of a 5% aqueous solution of the surfactant composition according to the invention (right) and a comparative surfactant composition (left) is shown.

[0046] Example

[0047] The invention will be better understood through the following examples, which are for illustrative purposes only and are not intended to limit the scope of the invention as defined by the appended claims.

[0048] Example 1 Synthesis of surfactant compositions based on betaine aminododecane salt

[0049] Betaine aminododecane methanesulfonate is prepared from glycine betaine in a one-pot process involving two reaction steps, as follows:

[0050] Example 1-1 Synthesized from glycine betaine and glycerol

[0051] Glycerol (15.725 g, 170.8 mmol, 2.0 equivalents) and glycine betaine (10.001 g, 85.4 mmol, 1.0 equivalents) were added to a 100 mL double-necked round-bottom flask equipped with a distillation apparatus. The set temperature was fixed at 150 °C, and the pressure was reduced to 200 mbar. Once the temperature and pressure conditions were reached, a 70% methanesulfonic acid solution (11.839 g, 86.2 mmol, 1.01 equivalents) was introduced. After the addition was complete, the pressure was gradually reduced to 30 mbar. The conversion was monitored by ¹H NMR analysis. At a reaction time of 6 h00, the conversion was 95%.

[0052] The set temperature was fixed at 100 °C. Once the mixture reached 100 °C, the assembly was restored to atmospheric pressure, and pre-melted dodecylamine (16.005 g, 86.3 mmol, 1.01 equivalents) was added. The reaction mixture was then heated vigorously at 100 °C for 1 h30 under atmospheric pressure. The reaction mixture was then recovered, and its composition is shown in Table 1.

[0053] [Table 1]

[0054] Examples 1-2 Synthesized from beet molasses

[0055] Betafin® LQD GL [10.0 g, containing: glycerol (31.2 mmol, 1.46 equivalents); glycine betaine (21.3 mmol, 1.0 equivalents)] and 70% methanesulfonic acid solution (3.481 g, 25.4 mmol, 1.2 equivalents)] were added to a 50 mL round-bottom flask equipped with a distillation apparatus. The mixture was stirred, and the set temperature was maintained at 160 °C. The pressure was reduced to 30 mbar over 35 minutes. The conversion was monitored by ¹H NMR analysis. At a reaction time of 7 h30, the conversion was 96%.

[0056] The set temperature was fixed at 100°C. Once the mixture reached 100°C, the assembly was restored to atmospheric pressure, and pre-melted dodecylamine (5.099 g, 27.5 mmol, 1.3 equivalents) was added. The reaction mixture was then heated vigorously at 130°C for 2 hours under atmospheric pressure. The reaction mixture was then recovered, and its composition is shown in Table 2.

[0057] [Table 2]

[0058] Example 2 Synthesis of surfactant compositions based on C12-C18 betaine aminoalkane salts

[0059] Glycerol (117.056 g, 1.271 mol, 2.0 equivalent) and glycine betaine (74.450 g, 0.636 mol, 1.0 equivalent) were charged into a 1 L reactor equipped with a distillation apparatus. The mixture was stirred and heated to 150 °C at 200 mbar. Once the temperature and pressure conditions were reached, a 70% methanesulfonic acid solution (88.100 g, 0.642 mol, 1.01 equivalent) was introduced into the reactor. After the addition was complete, the pressure was gradually reduced to 30 mbar. The conversion was monitored by ¹H NMR analysis. The conversion was 99% at a reaction time of 5 h 30.

[0060] The reaction mixture was cooled to 100°C. Once the mixture reached 100°C, the reactor was restored to atmospheric pressure, and pre-melted coconut oil amine (114.100 g, 0.580 mol, 0.91 equivalents) and octadecylamine (17.131 g, 0.064 mol, 0.1 equivalents) were added. The reaction mixture was then heated vigorously at 150°C for 1 hour under atmospheric pressure. The reaction mixture was then recovered by evacuating the reactor; its composition is shown in Table 3.

[0061] [Table 3]

[0062] Example 3 Synthesis of surfactant compositions based on betaine aminooctadecyl-9-ene salt

[0063] Betafin® LQD GL [100.478 g, containing: glycerol (336.7 mmol, 1.57 equivalents); glycine betaine (214.4 mmol, 1.0 equivalents)] was charged into a 250 mL reactor equipped with a distillation apparatus. The mixture was stirred and heated to 90 °C at atmospheric pressure. Once this temperature was reached, a 70% methanesulfonic acid solution (35.2 g, 256.4 mmol, 1.2 equivalents) was introduced into the reactor. After the addition was complete, the set temperature was fixed at 150 °C, and the pressure was gradually reduced. After 1 h 15, the pressure was 60 mbar. The conversion was monitored by ¹H NMR analysis. At a reaction time of 7 h 00, the conversion was 93%.

[0064] The reaction mixture was cooled to 100°C. Once the mixture reached 100°C, the reactor was restored to atmospheric pressure, and pre-melted oleylamine (74.155 g, 277.2 mmol, 1.29 equivalents) was added. The reaction mixture was then heated vigorously at 150°C for 2 hours under atmospheric pressure. The reaction mixture was then recovered by evacuating the reactor; its composition is shown in Table 4.

[0065] [Table 4]

[0066] Example 4 Synthesis of surfactant compositions based on betaine aminododecane salt

[0067] Betaine aminododecane methanesulfonate is prepared from glycine betaine in a one-pot process involving three reaction steps, as follows:

[0068] The experiment was conducted in a 100 mL container with baffles, equipped with a turbine stirrer, temperature probe, and distillation assembly.

[0069] Glycerol (23.58 g, 0.256 mol, 2.0 equivalent) and glycine betaine (15.00 g, 0.128 mol, 1.0 equivalent) were added to the container. The reaction mixture was set to a temperature of 150 °C and the pressure was reduced to 200 mbar. Once the temperature and pressure conditions were reached, a 70% methanesulfonic acid solution (17.75 g, 0.129 mol, 1.01 equivalent) was introduced through a dropping funnel attached to a neck of the container lid. After the addition was complete, the pressure was gradually reduced to 30 mbar. The conversion was monitored by ¹H NMR analysis. At a reaction time of 6 h00, the conversion was 97.7%.

[0070] The set temperature was fixed at 70°C. Once the mixture reached 70°C, the assembly was restored to atmospheric pressure and sodium carbonate (0.27 g, 2.6 mmol, 0.02 equivalent) was added. The reaction mixture was then heated vigorously at 70°C under atmospheric pressure for 30 minutes with stirring.

[0071] Then, pre-melted dodecylamine (21.36 g, 0.115 mol, 0.9 equivalents) was added. The reaction mixture was then vigorously stirred and heated to 100 °C at atmospheric pressure for 5 h. The reaction mixture was then recovered, and its composition is shown in Table 5 below.

[0072] [Table 5]

[0073] Example 5 Synthesis of surfactant compositions based on betaine aminododecane salt

[0074] Betaine aminododecane methanesulfonate is prepared from glycine betaine in a one-pot process involving three reaction steps, as follows:

[0075] The experiment was conducted in a 100 mL container equipped with a baffle, a turbine stirrer, a temperature probe, and a distillation assembly. Glycerol (23.597 g, 0.2562 mol, 2.0 equivalent) and glycine betaine (15.001 g, 0.1280 mol, 1.0 equivalent) were added to the container. The reaction mixture was set to a temperature of 150 °C and the pressure was reduced to 200 mbar. Once the temperature and pressure conditions were reached, a 70% methanesulfonic acid solution (17.775 g, 0.1295 mol, 1.01 equivalent) was introduced through a dropping funnel attached to a neck of the container lid. After the addition was complete, the pressure was gradually reduced to 30 mbar. The conversion was monitored by ¹H NMR analysis.

[0076] The reaction mixture was kept at a set temperature of 100°C for 7 hours. Once the mixture reached 100°C, the assembly was restored to atmospheric pressure and pre-melted dodecylamine (21.369 g, 0.1153 mol, 0.9 equivalents) was added. The reaction mixture was then heated vigorously at 100°C for 3 hours under atmospheric pressure.

[0077] The reaction mixture was kept at a constant temperature of 70°C. Once the mixture reached 70°C, a first addition of sodium ethoxide (21% solution, 5.73 mL, 0.0154 mol, 0.12 equivalents) was made. After 1 h of reaction, a second addition of sodium ethoxide (21% solution, 2.39 mL, 0.0064 mol, 0.05 equivalents) was made. After 1 h of reaction, a third addition of sodium ethoxide (21% solution, 1.43 mL, 0.0038 mol, 0.03 equivalents) was made. After 1 h of reaction, the reaction mixture was concentrated under vacuum to distill off the ethanol. The composition of the resulting mixture is shown in Table 6 below.

[0078] [Table 6]

[0079] Example 6 Properties of surfactant compositions

[0080] 6-1: Surface tension

[0081] The surface tension of the surfactant compositions of Examples 1-1 to 3 was measured using a goniometer according to the pendant drop method described in standard EN ISO 19403-3 (2020).

[0082] result: [Table 7]

[0083] 6-2: Solubility in water

[0084] The solubility of the surfactant (TA1) according to the present invention in water was evaluated, having the following composition: [Table 8]

[0085] Compared with a prior art surfactant (TA2) obtained from hexanol, which has the following composition: [Table 9]

[0086] These surfactants TA1 and TA2 were diluted in water at a ratio of 5% by weight.

[0087] like Figure 1 As shown, the solution obtained using surfactant TA1 (right side) remains clear, while the solution obtained using surfactant TA2 (left side) shows suspended particles, reflecting the poor solubility of the surfactant in water.

[0088] Example 7 :preparation

[0089] Various types of products can be prepared using the surfactant compositions according to the present invention, wherein CTx represents the surfactant composition prepared according to Example x above.

[0090] Household detergents

[0091] This product can be used to clean hard surfaces.

[0092] Vehicle body shampoo

[0093] The product can be applied to vehicles, followed by a 5-minute rinse with high-pressure water.

[0094] Water treatment

[0095] conditioner

[0096] [Table 10]

Claims

1. A method for preparing a surfactant composition, the method comprising the following sequential steps: (1) In the presence of organic or inorganic acids, at a temperature of 100 to 180°C, glycine betaine or its salt is reacted with at least one polyol. (2) Cool the reaction medium to a temperature of 20 to 100°C; (3) Adding one or more alkylamines containing 8 to 36 carbon atoms to the reaction medium; and (4) The surfactant composition obtained therefrom is recovered.

2. The method according to claim 1, characterized in that, The polyol consists of a hydrocarbon chain that is optionally interrupted by one or more oxygen atoms and has at least two alcohol functional groups, preferably at least one primary alcohol functional group.

3. The method according to claim 1 or 2, characterized in that, The polyol is selected from: straight-chain 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, neopentanediol, 1,6-hexanediol, and 3-methyl-1,5-pentanediol; triols, such as glycerol, trimethylolpropane, 1,2,6-hexanetriol, and 1,2,4-butanetriol; tetraols, such as erythritol; hydrogenated sugars, such as sorbitol, xylitol, mannitol, and maltitol; polyglycerol; and polyethylene glycol, preferably with a molar mass of 10⁶ to 8000. Polyethylene glycol in the range of 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. The method according to any one of claims 1 to 3, characterized in that, The acid is selected from: inorganic acids, such as hydrochloric acid, sulfuric acid, perhalic acids such as perchloric acid and mixtures thereof; organic acids, such as alkyl sulfuric acid, such as decyl sulfuric acid or lauryl sulfuric acid; aryl sulfonic acids, such as benzenesulfonic acid or p-toluenesulfonic acid; alkyl sulfonic acids, such as trifluoromethanesulfonic acid, methanesulfonic acid, ethanesulfonic acid, decyl sulfonic acid, lauryl sulfonic acid or camphorsulfonic acid; sulfosuccinic acid; and mixtures thereof; or Lewis acids; preferably, the acid is an organic acid, more preferably an alkyl sulfonic acid, especially methanesulfonic acid or ethanesulfonic acid.

5. The method according to any one of claims 1 to 4, characterized in that, The alkylamine is selected from: dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, docosylamine, eicosylamine, C 36 Dimeric diamines and mixtures thereof, especially coconut oil derivatives.

6. The method according to any one of claims 1 to 5, characterized in that, The method further includes the step of adding an alkali between steps (2) and (3) or between steps (3) and (4).

7. A surfactant composition obtainable by the method according to any one of claims 1 to 6, characterized in that, The composition comprises, and preferably consists of, the following components: Relative to the total dry weight of the surfactant composition, (a) 40% to 75% by weight, preferably 50% to 70% by weight of formula (1): X n- [(CH3)3N + -CH2-CONH-R] n The glycine betaine amide salt shown is... (b) 8% to 40% by weight of polyols, (c) 0.5 wt% to 5 wt% of formula (2): (CH3)3N + -CH2-COO - The glycine betaine shown, (d) Optionally, 0.1% to 10% by weight of formula (3): X n- [(CH3)3N + -CH2-COOR'] n The polyol glycine betaine ester salt shown is an example of a polyol residue. (e) Optionally, 0.1% to 30% by weight of formula (4): X n- [NH3 + R] n The alkylammonium salt shown, (f) Optionally, 0.1% to 5% by weight of organic acid or inorganic acid salt, in: R is a saturated or unsaturated straight-chain alkyl group containing 8 to 36 carbon atoms. X is an organic or inorganic anion, and n is 1 or 2.

8. The composition according to claim 7, characterized in that, The composition contains less than 5% by weight, advantageously less than 3% by weight, more preferably less than 1% by weight, or even completely free of C8 to C36 saturated or unsaturated straight-chain or branched (preferably straight-chain) alcohols.

9. Use of the composition according to claim 7 or 8 as a wetting agent, particulate dispersant and / or corrosion inhibitor, and / or use for improving the disinfection ability and / or the durability of disinfection effect of antimicrobial substances and / or the effect of insecticidal substances.

10. Use of the composition according to claim 7 or 8 in the manufacture of plastics or products, wherein the products are intended to: - Used for treating and / or cleaning the body, plants or hard surfaces, especially cosmetics, car wash products, household products, industrial cleaning products, fiber sizing products and plant protection products; - Used for water treatment; - Used for oil extraction.

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