WO2024013445A1

WO2024013445A1 - Alkoxylated ammonium salts with hydrotropic and detergent properties

Info

Publication number: WO2024013445A1
Application number: PCT/FR2023/051037
Authority: WO
Inventors: Jean-Philippe Gillet; Carl Bouret
Original assignee: Arkema France
Priority date: 2022-07-13
Filing date: 2023-07-06
Publication date: 2024-01-18
Also published as: FR3137921A1

Abstract

The present invention relates to a compound of formula (1), wherein the variables R, X, l, R ¹, R ², A, n and R ³ are as defined in the description. The invention also relates to the use of the compound of formula (1) as a surfactant.

Description

DESCRIPTION TITLE: ALKOXYLATED AMMONIUM SALTS WITH HYDROTROPIC AND DETERGENT PROPERTIES

[0001] The present invention relates to the field of surfactants and more precisely to the field of biodegradable and environmentally friendly surfactants, and more particularly used in detergency formulations and in particular the detergency of hard surfaces ("Hard Surface Cleaning” in English).

[0002] A class of surfactants widely used today, in particular in the field of detergency, is the class of surfactants comprising ammonium salts, and more specifically that of ammonium salts, and in particular alkoxylated ammonium salts, recognized for their hydrotropic and/or detergent properties. Regulation No. 648/2004 of the European Parliament and of the Council signed on March 31, 2004 and relating to detergents, however, no longer allows the supply of certain products which are not considered biodegradable by the definitions of this regulation.

[0003] A lot of research has therefore been carried out in order to offer surfactants meeting the aforementioned European requirements. Thus, for example, patent JP4683605 B2 describes quaternary ammonium chlorates, hydrochlorides, sulfonates and perchlorates used as antistatic and plasticizer agents in PVC compositions. Application JPH9-95471 describes mono-ethoxylated quaternary ammonium mesylates which can be used as antistatic agents for different polymers and different uses.

[0004] Application W02006079598 discloses compounds with an ethoxylated quaternary amine structure with a C to C22 alkyl chain without amide function, with an anion of halide or methyl sulfate type. These compounds can be implemented in the form of formulations with other components, formulations which can be used for the detergency of hard surfaces, for example for automobile cleaning or for dishwashers.

[0005] Application WO2019129710 describes a process for preparing a quaternary ammonium compound which requires between 2 to 20% water and approximately 15% of a solvent poorly miscible with water. The amount of water must be adjusted to minimize the amount of water present in the reaction medium, while still allowing the amine to react at the desired rate.

[0006] There therefore remains a need for surfactants that are even more respectful of the environment, and advantageously biodegradable and non-ecotoxic. There also remains a need for surfactants that are easy to prepare and in particular which do not generate significant consumption of organic solvent or water. Yet another objective is to offer surfactants containing no or little water, more particularly to offer surfactants free of water.

[0007] The industry has in fact a significant need for surfactants making it possible to improve the application performance of formulations containing surfactants in various fields and in particular the fields of detergents, cosmetics, health products. maintenance and personal care, human and animal food, lubricants and in particular for cutting fluids and drilling fluids, agrochemistry and in particular for fertilizer coatings and phytosanitary formulations, ore flotation, adjuvants for road or waterproofing bituminous applications, de-inking, depollution, in the electrical and electronic fields, and in particular for the manufacture of electrodes, membranes and electrolytes for batteries and cells , coating in general (“coating” in English) and in particular paint-type coatings, polyols, emulsion polymerization and so-called “oil & gas” applications, for example for stimulation by foaming, for hydraulic fracturing , for acidification, drilling, completion, production with corrosion protection, against deposits, for demulsification and emulsification, for gas hydrate processing, as well as enhanced oil recovery application and gas, to delay or disperse gas hydrates, or as an emulsifier in emulsion polymerization, as antistatic additives, hydrotropic additives, to name only the main uses targeted by the invention.

[0008] Still other objectives will appear during the presentation of the invention which follows. The inventors have in fact discovered in a completely surprising manner that the surfactants of the invention make it possible to compensate for the defects encountered in the prior art and that the aforementioned objectives are achieved in full, or at least in part.

Thus, and according to a first aspect, the present invention relates to a compound of formula (1) below:

in which :

- A represents a divalent hydrocarbon radical comprising 1, 2, 3 or 4 atoms of carbon, and optionally one or more, preferably optionally a hydroxyl group (-OH),

- R represents a hydrocarbon radical comprising from 4 to 22 carbon atoms, linear, branched and/or comprising one or more cycles, unsaturated or partially or totally saturated, including aromatic(s),

- R ¹ and R ² , identical or different, represent, independently of each other, the hydrogen atom or a hydrocarbon radical comprising from 1 to 20 carbon atoms, preferably from 1 to 16 carbon atoms , linear, branched and/or comprising one or more cycles, unsaturated or partially or totally saturated, including aromatic(s), and very preferably from 1 to 4 carbon atoms, linear, branched and/or comprising one or more cycles, unsaturated or partially or totally saturated,

- R ³ represents R ⁴ or OR ⁴ , where R ⁴ represents a hydrocarbon radical comprising from 1 to 20 carbon atoms, preferably from 1 to 16 carbon atoms, linear, branched and/or comprising one or more cycles, unsaturated ( s) or partially or totally saturated, including aromatic(s),

- or comprising one or more rings, unsaturated or partially or totally saturated, including aromatic(s),

- “/” represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably “/” represents 1, and

- “n” represents a number between 2 and 20, limits included, preferably between 3 and 20, limits included, more preferably between 3 and 10, limits included.

[0010] According to a first preferred embodiment of the invention, the radical R' is chosen from the hydrogen atom and the methyl, ethyl or propyl radicals, and more preferably the radical R' represents the atom d 'hydrogen.

[0011] According to another preferred embodiment of the invention, A is a divalent radical chosen from the divalent radicals -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH(CH3) -, CH2-CH2-CH2-CH2-, -(CH ₃ ) ₂ C-CH ₂ -, -CH ₂ -C(C ₂ H ₅ )H-, -CH(CH ₂ OH)-CH ₂ - and - CH ₂ -CH(OH)- CH ₂ -, preferably from -CH2-CH2-, -CH ₂ -CH(CH ₃ )-, -CH ₂ -C(C ₂ H ₅ )H-,

-CH(CH2OH)-CH2- and -CH2-CH(OH)-CH2, and more preferably among the divalent radicals -CH2-CH2- and -CH ₂ -CH(CH ₃ )-.

[0012] It should be understood that the -AO- motifs repeated n times may be identical or different and, when they are not all identical, may be distributed in such a manner. randomly, in blocks or in a sequenced manner, that is to say in any order. However, we prefer a distribution by blocks.

According to another preferred embodiment of the invention, the radical R is a linear or branched hydrocarbon radical, saturated or aromatic or partially or totally saturated, preferably totally saturated or comprising one or two double bonds. In a preferred embodiment, the radical R is a radical originating from a fatty acid, preferably chosen from fatty acids of natural origin well known to those skilled in the art, and for example the fatty acid is chosen from heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, undecylenic acid, dodecanoic acid, coconut fatty acid, palmitic acid, to name but a few as the main ones of them.

According to yet another preferred aspect, the radical R represents a linear or branched hydrocarbon radical, saturated or comprising one or two double bonds and comprising from 6 to 20 carbon atoms.

[0015] In yet another preferred embodiment, the radicals R ¹ and R ² , identical or different, are chosen, independently of one another, from the hydrogen atom, the methyl radical, the radical ethyl, the n-propyl radical, the /so-propyl radical, the n-butyl radical, the /so-butyl radical and the tert-butyl radical, preferably from the hydrogen atom, the methyl radical, the radical ethyl, the /so-propyl radical, the /so-butyl radical and the tert-butyl radical, more preferably from among the hydrogen atom, the methyl radical, the ethyl radical and the /so-propyl radical.

When the radical R ³ represents R ⁴ , it is then preferred that R ⁴ represents the methyl radical. In this preferred embodiment, the counterion (anion) in the compound of formula (1) is methane sulfonate (or mesylate). Likewise, the R4 radical can be preferably chosen from the ethyl radical, so that the counterion is the ethane-sulfonate (or esylate) ion, the tosyl radical, so that the counterion is the toluene-sulfonate, and the dodecyl radical, so that the counterion is dodecylsulfonate. Very preferably, when R ³ represents R ⁴ , then R ⁴ represents the methyl radical.

[0017] When the radical R ³ represents OR ⁴ , it is then preferred that R ⁴ represents the methyl radical. In this preferred embodiment, the counterion (anion) in the compound of formula (1) is methosulfate. Likewise, when R ³ represents OR ⁴ , the R ⁴ radical may preferably represent the ethyl radical, so that the counterion is the ethosulfate ion. Very preferably, when R ³ represents OR ⁴ , then R ⁴ represents the methyl radical.

[0018] In a preferred embodiment, the radical R ³ represents R ⁴ . [0019] We particularly prefer, for the purposes of the invention, the compounds of formula (1) for which -X- represents -O-, and as non-limiting examples, the compounds of formula (1) are esters advantageously chosen from sulfonates (for example mesylate, esylate, dodecylsulfonate or tosylate, preferably mesylate) or sulfates (for example methosulfate or ethosulfate, preferably methosulfate):

- amine ester of octanoic acid and alkoxylated aminoethanol,

- amine ester of copra fatty acid and alkoxylated aminoethanol,

- amine ester of decanoic acid and alkoxylated aminopropanol,

- amine ester of palmitic acid and alkoxylated aminopropanol,

- amine ester of undecylenic acid and alkoxylated 3-dimethylamino 1-propanol,

- amine ester of decanoic acid and alkoxylated 3-dimethylamino 1-propanol,

- amine ester of copra fatty acid and alkoxylated 3-dimethylamino ethanol, and

- amine ester of palmitic acid and alkoxylated 3-dimethylamino ethanol.

[0020] We also prefer, in another embodiment of the invention, the compounds of formula (1) for which -X- represents -NR', and by way of non-limiting examples, the compounds of formula (1 ) are amides advantageously chosen from sulfonates (for example mesylate, esylate, dodecylsulfonate or tosylate, preferably mesylate) or sulfates (for example methosulfate or ethosulfate, preferably methosulfate):

- amido amine, decanoic acid and alkoxylated propylene diamine,

- amido amine of palmitic acid and alkoxylated propylene diamine,

- amido amine, octanoic acid and alkoxylated ethylene diamine,

- amido amine of undecylenic acid and alkoxylated ethylene diamine,

- amido amine of copra fatty acid and alkoxylated dimethyl aminoethylamine,

- amido amine of palmitic acid and alkoxylated dimethylaminoethylamine,

- amido amine of decanoic acid and alkoxylated dimethylaminopropylamine, and

- amido amine of copra fatty acid and alkoxylated dimethyl aminopropylamine.

[0021] In one embodiment of the invention, the value of “I” of the compound of formula (1) is equal to 0, and in this case the compound of formula (1) comprises compounds of the ester type of alkoxylated ethylammonium or alkoxylated amidoethylammonium. Examples of such compounds of formula (1) in which “I” is equal to 0 include, by way of non-limiting examples, compounds chosen from sulfonates (for example mesylate, esylate, dodecylsulfonate or tosylate, preferably mesylate) or sulfates (for example methosulfate or ethosulfate, preferably methosulfate):

- amine ester of decanoic acid and alkoxylated aminoethanol, - amine ester of undecylenic acid and alkoxylated aminoethanol,

- amine ester of octanoic acid and alkoxylated 3,3-dimethylaminoethanol,

- amine ester of decanoic acid and alkoxylated 3-dimethylaminoethanol,

- amidoamine, decanoic acid and alkoxylated ethylenediamine,

- amidoamine of palmitic acid and alkoxylated ethylenediamine,

- amidoamine, octanoic acid and alkoxylated dimethylaminoethylamine, and

- amidoamine, undecylenic acid and alkoxylated dimethylaminoethylamine.

[0022] In another embodiment of the invention, the value of “/” of the compound of formula (1) is equal to 1, and in this case the compound of formula (1) comprises compounds of the ester type of alkoxylated propylammonium or alkoxylated amidopropylammonium. Examples of such compounds of formula (1) in which "I" is equal to 1 include, by way of non-limiting examples, those chosen from sulfonates (for example mesylate, esylate, dodecylsulfonate or tosylate, preferably mesylate) or sulfates (for example methosulfate or ethosulfate, preferably methosulfate):

- amine ester of octanoic acid and alkoxylated aminopropanol,

- amine ester of undecylenic acid and alkoxylated aminopropanol,

- amine ester of copra fatty acid and alkoxylated 3-dimethylamino-1-propanol,

- amine ester of palmitic acid and alkoxylated 3-dimethylamino-1-propanol,

- amidoamine, octanoic acid and alkoxylated propylenediamine,

- amidoamine of undecylenic acid and alkoxylated propylenediamine,

- amidoamine, octanoic acid and alkoxylated dimethylaminopropylamine,

- amidoamine, decanoic acid and alkoxylated dimethylaminopropylamine,

- amidoamine of undecylenic acid and alkoxylated dimethylaminopropylamine, and

- palmitic acid amidoamine and alkoxylated dimethylaminopropylamine.

[0023] Among the compounds of formula (1) according to the present invention, those which meet one, or even two, preferably three, preferably all of the following characteristics are particularly preferred:

- AO represents ethoxy, propoxy, hydroxypropoxy or butoxy, preferably ethoxy or propoxy, more preferably ethoxy,

- R represents a hydrocarbon radical comprising from 4 to 22 carbon atoms, preferably from 6 to 20 carbon atoms, preferably from 8 to 20 carbon atoms, linear, branched, saturated or partially or totally saturated,

- R’ represents the hydrogen atom,

- X represents -O- or -NH-, preferably X represents the oxygen atom,

- “I” represents 0 or 1, and - “n” represents a number between 2 and 20, limits included, preferably between 2 and 15, limits included, more preferably between 2 and 10, limits included, advantageously between 3 and 10, limits included.

The present invention also relates to the process for preparing the compounds of formula (1) as they have just been defined. The process thus comprises a first step a) of reaction between an acid of formula R-COOH, in which R is as defined above, and a compound of formula HX-CH ₂ -(CH ₂ )rCH2-NR ¹ R ² , in which X, I and R ¹ and R ² are as defined above. When X represents oxygen, the reaction consists of an esterification reaction which can be carried out in a conventional manner according to the knowledge of those skilled in the art. When X represents NR'-, the reaction consists of an amidation reaction which can be carried out in a conventional manner, well known to those skilled in the art.

[0025] In this first condensation step, the acid/amine molar ratio can vary in large proportions, and is generally around 1/1. According to a preferred aspect, the reaction between the acid and the amine is generally carried out with an acid/amine molar ratio of between 0.9/1 and 1.1/1, at a temperature generally between 150 and 200°C. , for a variable duration depending on the quantities used and the nature of the reagents, and generally and most often for a few minutes to a few hours, for example between 10 minutes and 10 hours.

The reaction between the acid and the amine of step a) described above is a condensation reaction which generates water, water which is gradually eliminated during the reaction (displacement of equilibrium) according to all techniques known to those skilled in the art, and for example by at least partial evacuation or by bubbling with inert gas, for example by nitrogen sweeping.

The condensation product obtained in step a) is then engaged in step b) with a reagent of formula R ³ -SO ₂ -OH or a reagent of formula R ³ -SO ₂ -OR ⁴ , where R ³ and R ⁴ are as defined previously. The reagent of formula R ³ -SO ₂ -OH is an acid and allows the salification of the condensation product obtained in step a), and preferably the acid is methane sulfonic acid (AMS). The reagent of formula R ³ -SO ₂ -OR ⁴ is an alkylating reagent and allows the N-alkylation of the condensation product obtained in step a), in particular when at least one of R ¹ or R ² represents the hydrogen atom. According to a preferred embodiment, the alkylating reagent is dimethyl sulfate (CH3O-SO ₂ -OCH3).

This step b) can be carried out once or twice, depending on whether the radicals R ¹ and/or R ² represent the hydrogen atom, with identical or different reagents. It is thus possible to carry out a step b) of salification or one of N-alkylation, but also of combine an N-alkylation and salification step. These salification and N-alkylation operations are carried out in a conventional manner, using all techniques well known to those skilled in the art.

It was discovered quite surprisingly that the compounds obtained at the end of step b) and in particular the salts, and more generally the salts of sulfonic acid, are generally and most often solids. whose melting point is equal to approximately 50°C or lower.

As a general rule, the compounds resulting from step b), and in particular the sulfonates and sulfates obtained at the end of step b), without adding water, have a relatively low melting point, and in particular a melting point lower than homologous salts of hydrochloride type or others. For this reason among others, the sulfonates and sulfates obtained in step b) can easily be engaged in the alkoxylation reactions described below, without it being necessary to work in water and/or with one or more. several solvent(s).

The product resulting from step b) is then engaged in step c) of the process in which one or more alkoxylation reactions are carried out, according to techniques well known to those skilled in the art. , and according to the nature of the desired [-AO-] _n group, where A and n are as defined above. Typically, when AO is an ethoxyl, propoxyl, hydroxypropyl or butoxyl group, the alkoxylation can be conventionally carried out from alkoxylation reagents chosen from ethylene, propylene, 3-hydroxypropylene and butylene epoxide, respectively.

As indicated above, step c) can be carried out with a single or a mixture of alkoxylation reagents, and/or be reproduced one or more times, with identical or different alkoxylation patterns.

[0033] Alkoxylation step c) is carried out according to techniques known to those skilled in the art and is generally carried out under pressure generally between 50 hPa and 12,000 hPa and at a temperature generally between 50°C and 100°C. , better between 70°C and 85°C. The salt from step b) can thus be advantageously used in this alkoxylation step in the molten state, without adding water and/or solvent(s), as indicated above. It may prove useful, although this does not constitute a preferred embodiment of the invention, to carry out the alkoxylation reaction(s) in the presence of a more or less significant quantity of water and/or solvent. (s). According to a preferred aspect, the alkoxylation reaction of step c) is optionally carried out in the presence of water, and preferably in a proportion of less than 2% by weight relative to the total weight of the reaction medium. The compounds of formula (1) thus obtained are ammonium salts, the cationic charge being carried by the nitrogen atom carrying the radicals R ¹ and R ² , the negative charge being carried by the conte-ion R ³ SOs'. When the radicals R ¹ and R ² are each different from the hydrogen atom, the alkoxylation reaction of step c) above leads to quaternary ammonium salts. When one of the radicals R ¹ or R ² , or the two radicals R ¹ and R ² , represent(s) the hydrogen atom, it is possible, after the alkoxylation reaction of step c) aforementioned to carry out an alkylation of the nitrogen atom carrying the radicals R ¹ and R ² , according to conventional techniques of those skilled in the art, in order to lead to ammonium salts in which one of the radicals R ¹ or R ² is different from the hydrogen atom or the two radicals R ¹ and R ² are different from the hydrogen atom, in the latter case, the ammonium salts of formula (1) are quaternary ammonium salts.

The process of the present invention thus leads to the compounds of formula (1) as defined above, which are ammonium salts, and are generally in liquid form at room temperature. These salts are in particular liquid at room temperature, particularly when the number of alkoxylated repeating groups “n” is equal to 2 or more, preferably equal to 3 or more.

Another advantage of the process of the present invention is that it is generally carried out without adding water and/or any other reaction solvent, so that the ammonium salts of formula (1) are obtained in concentrated form, without the need for subsequent removal of water and/or solvent(s).

[0037] Likewise, the product obtained from the preparation process described above can be used as is, without any other purification operation. However, it may be desirable or even necessary to carry out a subsequent purification step, which can be carried out according to any method well known to those skilled in the art, for example by distillation or the like.

The compounds of formula (1) as defined above are particularly usable as surfactants and have many advantages over the surfactants known in the prior art. In particular, the compounds of formula (1) are most often and generally present in liquid form at ambient temperature and pressure, that is to say at 25°C, under 1 atmosphere (101325 Pa), and this even for compounds containing only a minimum number of alkoxylated units. Indeed, the compounds of formula (1) are most often in liquid form at ambient temperature and pressure, when n represents a number between 2 and 20, terminals inclusive, preferably between 3 and 20, terminals inclusive, more preferably between 3 and 10, terminals inclusive.

The compounds of formula (1) can be formulated without any particular problem. In fact, the compounds of formula (1) are soluble, in all proportions, in water, and in protic solvents, such as for example alcohols, as well as in practical water/solvent mixtures. Among the preferred alcohols, in which the compounds of formula (1) are soluble, we can cite ethanol and isopropanol, to name the main ones among them.

The compounds of formula (1) find quite advantageous use as surfactants, which can be marketed as such, in non-solvent form, and ready to be, if necessary and if desired, diluted. in an aqueous, organic or hydro-organic solvent.

[0041] Depending on the areas of application envisaged, the compounds of formula (1) which have just been defined can be formulated, if necessary and if desired, with one or more additives and fillers chosen from detergency agents, surfactants, acids, bases, perfumes, dyes, inert fillers, impregnating agents, aqueous, organic, hydro-organic solvents, chosen from water, alcohols, glycols, polyols, mineral oils, vegetable oils, waxes, and others, alone or in mixtures of two or more of them, in any proportion.

[0042] In particular, the compounds of formula (1) can be formulated with one or more additives and fillers well known to those skilled in the art, such as for example, and without limitation, those chosen from anionic surfactants , cationic, amphoteric, non-ionic, rheology modifiers, demulsifiers, foaming agents, antifoaming agents, hydrotropic agents, anti-deposition agents, dispersants, retarders or dispersants of gas hydrates, emulsifiers, particularly in emulsion polymerization , pH control agents, dyes, antioxidants, preservatives, corrosion inhibitors, biocides, and other additives such as for example sulfur, boron, nitrogen, phosphorus, and other products. The natures and quantities of additives and fillers can vary greatly depending on the nature of the application envisaged and can easily be adapted by those skilled in the art.

[0043] Thus, the compounds of formula (1) can be advantageously used as surfactants, hydrotropic agents, or even conditioning agents, in numerous fields of application, and in particular for cleaning, detergency, solvation , interactions with mineral surfaces, metallic surfaces, organic surfaces, and others. [0044] The compounds of formula (1) have shown themselves to be particularly effective as surfactants, hydrotropic agents, or even conditioning agents, as such or formulated in suitable formulations and in particular intended for the detergency as a general rule, for example in car wash shampoos, in dishwasher detergent formulations (detergents or rinse aids), in cosmetic formulations (shampoos, shower gels, soaps , for hair care in general, and others), or for multi-purpose cleaner, for cleaning hard surfaces, for cleaning clothes (“laundry” in English), for cleaning sanitary facilities, for Nettoyage En Place (NEP) or “cleaning in place” in English (CIP), and others.

[0045] Other fields of application can also benefit from the advantages linked to the compounds of formula (1) of the present invention, in particular for their surfactant properties as emulsifier, conditioning agents, wetting agents, solvents. or adjuvants, and in particular in formulations for the flotation of ores, for the treatment of metals (“metal working fluids” in English), for bituminous applications, for deinking, for enhanced gas and mineral recovery applications. petroleum, to delay or disperse gas hydrates, for protection against corrosion, for hydraulic fracturing, for soil remediation, in agrochemistry (for example coatings of granular products, notably fertilizers and phytosanitary products), but also as emulsifiers in emulsion polymerization, anti-foam agents, antistatic agents, paint additives, textile additives, for polyols, for the production of electrodes, membranes and electrolytes for batteries and cells, to name only the areas main applications.

The compounds of formula (1) of the present invention find in particular a very suitable use in the field of detergency and in particular as a detergency agent, and very particularly for washing the bodies of motor vehicles.

[0047] The invention is now illustrated using the examples which follow and which in no way limit the invention, the scope of which is defined by the claims appended to the present description. Examples

Example 1: Synthesis of ethoxylated copra/DMAPA quaternary ammonium mesylate

Amidoamine synthesis

[0048] In a 1 L glass reactor, equipped with mechanical stirring, heating by balloon heater, a Dean Starck type condensation system, a nitrogen inerting system, from an amine introduction system by means of a pump, 486 g (2.53 M) of copra fatty acid are loaded, the average molar mass of which is determined by an acid number measurement . The acid is brought to 180°C and then 258 g (2.53 M) of dimethylaminopropylamine (DMAPA) are slowly introduced with slow stirring and under an inert atmosphere. A release of water is observed. The quantity of DMAPA is optionally adjusted so that the acid number of the reaction medium is less than 5 mg of KOH/g. The residual DMAPA is removed under a stream of nitrogen (nitrogen stripping). The product (702 g) is cooled and drained, which is in orange liquid form.

Synthesis of amidoamine mesylate obtained in Example 1

[0049] In a 1 L glass reactor, equipped with mechanical stirring, heating by a balloon heater, a refrigerant, a nitrogen inerting system, a casting funnel , 657 g (2.28 M) of amidoamine obtained in Step 1 are loaded. The medium is brought to 60° C. with stirring and inerting with nitrogen. 219 g (2.28 M) of 99% methanesulfonic acid are gradually introduced. The medium is cooled to keep the temperature below 90°C. At the end of the reaction, the product is drained. The latter is solid at room temperature. It has a solidification point of 53-54°C.

Synthesis of ethoxylated quaternary ammonium mesylate

[0050] In a clean and dry 6 L autoclave, 710 g (1.85 M) of mesylate obtained in Step 2 and 7 g of water, or 1%, are loaded. The reaction medium is heated to around 70°C and stirred. The gas phase is purged with nitrogen then the leak tests are carried out. A little ethylene oxide (EO) is then added. The reaction medium is heated until the reaction starts. The introduction of ethylene oxide is continued while maintaining the temperature between 70°C and 90°C. In total, 245 g (5.56 M) of ethylene oxide are introduced. [0051] It is maintained at 90° C. for an additional hour and then the residual ethylene oxide is stripped with nitrogen. The reaction medium is then cooled and drained at around 60°C. 945 g of final product ethoxylated with 3 moles of EO are recovered in the form of a clear and viscous liquid. Example 2: Synthesis of an ethoxylated decanoic acid/DMAPA quaternary ammonium mesylate

This synthesis is carried out as indicated in Example 1, replacing the copra fatty acid in Step 1 with decanoic acid.

Example 3: Synthesis of an ethoxylated quaternary ammonium undecylenic acid mesylate/DMAPA

This synthesis is carried out as indicated in Example 1, replacing the copra fatty acid in Step 1 with undecylenic acid.

Example 4: Characterization of the hydrotropic power

[0054] Characterizing the hydrotropic power of a product to be tested consists of heating a solution containing a reference product (isotridecanol ethoxylated at 8 EO) and noting the temperature at which the cloudiness formed by the desolubilization of the reference product in the solution. The hydrotropic power corresponds to this temperature (expressed in °C). The higher this temperature, the more hydrotropic the product.

[0055] In a beaker, a solution containing (mass percentages, unless otherwise indicated) is heated until a persistent cloudiness appears:

• 5% of Surfaline® OX1308L (isotridecanol ethoxylated at 8 EO) and diluted with 15% (by weight) with water, marketed by the company ARKEMA,

• 2% sodium hydroxide,

• 1% active ingredient (product to be tested),

• q.s.p. 100% demineralized water.

[0056] We allow it to cool naturally and we note the temperature at which the disorder disappears. The hydrotropic power corresponds to this temperature (expressed in °C). The higher this temperature, the greater the solubilizing power of the compound tested. The results are presented in Table 1 below:

[Table 1]

* The reference product is a quaternary ammonium chloride of C12-C14- alkyl (hydroxyethyl) dimethyl ethoxylated, marketed by the company Nouryon under the name BEROL® R648.

[0057] These results clearly show the advantage of the compounds of the invention through their better solubilizing power compared to the reference product.

Example 5: performance tests of degreaser sprays

[0058] The performances are measured in accordance with the protocol entitled “Degreasing Power by Pure Product Application and Friction - Performance Test”, communicated by IKW - SÔFW Journal, 144 (2018), 22-28.

[0059] This method makes it possible to evaluate the cleaning performance by direct application of the pure product to encrusted greasy dirt subjected to cleaning by rubbing with a sponge. This test thus makes it possible to be in conditions of use of the product representative of consumer habits.

[0060] The greasy dirt is deposited on stainless steel sheets then cooked and stored before being used to evaluate the cleaning performance. An abrasimeter is used to represent the manual friction carried out by consumers. The number of back and forth movements necessary to completely clean the encrusted dirt highlights the capabilities of the detergent. A total of 8 tests are carried out on each product. It should be noted that two products will be differentiated based on a performance difference at least equal to 10 round trips (= significance threshold).

[0061] The cationic surfactants were compared in the formulation detailed in the following Table 2, where the percentages are given by weight, unless otherwise indicated: [Table 2]

[0062] Four formulations according to the table above are prepared with the products of examples 1, 2 and 3 described above, as well as the reference BEROL® R648, from the company Nouryon. The results are presented in Table 3 below.

[Table 3]

* The reference product is BEROL® R648, identified above.

[0063] This test makes it possible to easily demonstrate the superiority of the formulations based on the compounds according to the invention compared to the reference formulation available today. Indeed, the formulations based on the compounds of the present invention require on average 20 times less, or even more than 20 times less, back and forth, showing their greater degree of degreasing power compared to the formulation based on the reference compound.

Claims

1. Compound of formula (1) following:

in which :

- A represents a divalent hydrocarbon radical comprising 1, 2, 3 or 4 carbon atoms, and optionally one or more, preferably optionally a hydroxyl group (-OH),

2. Compound of formula (1) according to claim 1, in which the radical R' is chosen from the hydrogen atom and the methyl, ethyl or propyl radicals, and preferably the radical R' represents the atom of hydrogen.

3. Compound of formula (1) according to claim 1 or claim 2, in which A is a divalent radical chosen from the divalent radicals -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -(CH ₃ ) ₂ - C-CH ₂ -, -CH ₂ -C(C ₂ H ₅ )H-, -CH(CH ₂ OH)-CH ₂ - and -CH ₂ -CH(OH)-CH ₂ -, preferably from -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ ) -, -CH ₂ -C(C ₂ H ₅ )H-, -CH(CH ₂ OH)-CH ₂ - and -CH ₂ -CH(OH)-CH ₂ , and more preferably among the divalent radicals -CH ₂ -CH ₂ - and -CH ₂ -CH(CH ₃ )-.

4. Compound of formula (1) according to any one of the preceding claims, in which the radical R is a radical originating from a fatty acid chosen from heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, undecylenic acid, dodecanoic acid, copra fatty acid, and palmitic acid.

5. Compound of formula (1) according to any one of the preceding claims, in which the radicals R ¹ and R ² , identical or different, are chosen, independently of one another, from the hydrogen atom , the methyl radical, the ethyl radical, the n-propyl radical, the /so-propyl radical, the n-butyl radical, the /so-butyl radical and the tert-butyl radical, preferably from the hydrogen atom , the methyl radical, the ethyl radical, the /so-propyl radical, the /so-butyl radical and the tert-butyl radical, more preferably from the hydrogen atom, the methyl radical, the ethyl radical and the radical /so-propyl.

6. Compound of formula (1) according to any one of the preceding claims, in which the radical R ³ represents R ⁴ or the radical -OR ⁴ , and R ⁴ is chosen from the methyl radical, the ethyl radical, the tosyl radical , and the dodecyl radical, most preferably, R ⁴ represents the methyl radical, and preferably R3 represents the methyl radical or the -O-methyl radical.

7. Compound of formula (1) according to any one of the preceding claims, meeting one, or even two, preferably three, preferably all of the following characteristics: - AO represents ethoxy, propoxy, hydroxypropoxy or butoxy, preferably ethoxy or propoxy, more preferably ethoxy,

- R’ represents the hydrogen atom,

- X represents -O- or -NH-, preferably X represents the oxygen atom,

- “I” represents 0 or 1, and

- “n” represents a number between 2 and 20, limits included, preferably between 2 and 15, limits included, more preferably between 2 and 10, limits included, advantageously between 3 and 10, limits included.

8. Use of a compound of formula (1) according to any one of the preceding claims, as a surfactant.

9. Use according to claim 8, in formulations intended for detergency, in automobile shampoos, in dishwasher detergent formulations, in cosmetic formulations, or even for multi-purpose cleaning, for cleaning surfaces hard, for cleaning clothes, for cleaning sanitary facilities, for Cleaning In Place, for ore flotation, for metal processing, as emulsifiers in emulsion polymerization, for bituminous applications, for deinking, for applications for enhanced gas and oil recovery, to delay or disperse gas hydrates, for protection against corrosion, for hydraulic fracturing, for soil remediation, in agrochemistry, as an anti-foam agent, anti-static agent, paint adjuvant, textile adjuvant, for polyols, for the production of electrodes, membranes and electrolytes for batteries and cells.

10. Use according to claim 8 or claim 9, in the field of detergency as a detergency agent for washing motor vehicle bodies.