Mixtures of cleavable quaternary ammonium compounds useful as surfactants

Abstract

The present invention relates to novel mixtures of quaternary ammonium compounds having surfactant properties and improved biodegradability.

Description

[Technical field]

[0001] The present invention relates to mixtures of ammonium compounds, in particular quaternary ammonium compounds derivable from internal ketones, which are themselves obtained from mixtures of fatty acids or their derivatives, to processes for making such mixtures and to the use of these mixtures as surfactants, alone or in admixture with other surfactants.

[0002] Ammonium compounds which have surfactant properties and can be used for each application are described in the literature and are commercially available in a variety of different types from various suppliers.

[0003] Japanese Patent No. 3563473 describes the formula R1R2R3N + -(CH2) n -COO-(AO) m discloses a quaternary ammonium salt represented by the formula -CHR4R5, where R1, R2 and R3 are each an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, R4 and R5 are each a linear or branched alkyl or alkenyl group having 7 to 35 carbon atoms, A is a linear or branched alkanediyl group having 2 to 3 carbon atoms, X is an anionic group, n is an integer of 1 to 6, and m is a number of 0 to 20 indicating the average mole number of alkylene oxide. R4 and R5 can be pentadecyl, heptadecyl or a mixture thereof. The surfactant is said to be usable to impart softness to fibers while having good biodegradability.

[0004] The alkoxylated quaternary ammonium salts presented in the Japanese document are poor performance products with hydrolytic stability problems, and furthermore, the manufacture of such products induces the formation of by-products such as dioxane, which are toxic, suspected to be carcinogenic, and difficult to degrade, and therefore under strong regulatory pressure. With regard to the above quaternary ammonium compounds with m=0 as surfactants, the applicant has found it difficult to find a good combination of surfactant properties on the one hand and biodegradability on the other hand. Biodegradability has become more important in recent years due to customer demands for more environmentally friendly products. The improvement of biodegradability should not have a negative effect on the surfactant properties.

[0005] It was therefore an object of the present invention to provide a new solution which has good surfactant properties and excellent biodegradability.

[0006] This object is achieved with specific mixtures of compounds of formula I as defined below. Summary of the Invention

[0007] A first object of the present invention is to provide a compound of formula I [ka] wherein the R groups, which may be the same or different in each occurrence, are 15 Or C 17 is an aliphatic group, Y is a divalent C1-C6 aliphatic group; R', R'' and R''', which may be the same or different, are hydrogen or a C1-C4 alkyl group; X n- teeth, Halide (n=1), formula R a -O-SO2-O - (In the formula, R a is C1-C, which may be optionally halogenated 20 , preferably a C1-C6 hydrocarbyl group), formula R a-SO2-O - (In the formula, R a is C1-C, which may be optionally halogenated 20 , preferably a C1-C6 hydrocarbyl group), Formula SO4 2- Sulfate anion (n=2) Formula HSO4 - of hydrogen sulfate (i.e., bisulfate) anine (n=1), formula CO3 2- Carbonate anion (n=2), Formula HCO3 - hydrogen carbonate (i.e., bicarbonate) anion (n=1), Formula H2PO4 - dihydrogen phosphate anion (n=1), Formula HPO4 2- Hydrogen phosphate anion (n=2), formula PO4 3- phosphate anion (n=3), formula R a (CO2 - ) n (In the formula, R a is a C1-C alkyl group which may be optionally substituted with a heteroatom-containing group; 20 , preferably a C1-C6 hydrocarbyl group), and A mixture of them and a counter anion selected from the group consisting of n is an integer equal to 1, 2 or 3 depending on the nature of the counter anion. A mixture of compounds according to the invention having the formula I, 15 The mixture contains compounds having an aliphatic group.

[0008] Another object of the present invention is a method for preparing a mixture of compounds of formula I above, comprising the steps of: 15 Or C 17 The mixture of fatty acids is prepared by mixing 45 to 98 mol % of R-COOH (wherein R is an aliphatic radical), and the mixture of fatty acids is mixed with 45 to 98 mol % of R-COOH (wherein R is15 aliphatic groups).

[0009] The present invention also relates to the use of the mixture of compounds of formula (I) as above as surfactants.

[0010] All preferred embodiments of the present invention are detailed herein below and apply to all categories of claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The aliphatic group R may not contain any double bonds and may not contain any triple bonds. Alternatively, the aliphatic group R may contain at least one -C=C- double bond and / or at least one -C≡C- triple bond.

[0012] The aliphatic radicals R are advantageously selected from alkyl, alkenyl, alkandienyl, alkanetrienyl and alkynyl radicals.

[0013] The aliphatic group R can be linear or branched, preferably linear.

[0014] Preferably, the aliphatic groups R are independently selected from alkyl and alkenyl groups.

[0015] More preferably, the aliphatic groups R are independently selected from straight chain alkyl groups and alkenyl groups.

[0016] Unsaturation on the R group (R=alkenyl group) is rather favorable for biodegradability.

[0017] Acyclic aliphatic groups, more preferably straight-chain aliphatic groups, even more preferably straight-chain alkyl groups may be mentioned as preferred examples of the substituent R. Excellent results have been obtained when R is a straight-chain alkyl group.

[0018] R' is preferably H or a C1-C4 alkyl group, preferably methyl or ethyl, more preferably methyl. Similarly, R'' is preferably H or a C1-C4 alkyl group, preferably methyl or ethyl, more preferably methyl. Similarly, R''' is preferably H or a C1-C4 alkyl group, preferably methyl or ethyl, more preferably methyl. Preferably, at least one, more preferably at least two, more preferably all three of R', R'' and R''' are H or a C1-C4 alkyl group, preferably methyl or ethyl, most preferably methyl.

[0019] Y is preferably an acyclic divalent C1-C6 aliphatic group, more preferably a saturated acyclic divalent C1-C6 aliphatic group, and even more preferably a straight chain alkanediyl (commonly known as "alkylene") C1-C6 group. Furthermore, Y preferably has 1 to 4 carbon atoms. Exemplary Y are methanediyl (commonly known as "methylene"), ethane-1,2-diyl (commonly known as "ethylene"), and ethane-1,1-diyl. Excellent results have been obtained when Y is a methylene group.

[0020] Preferred X n- is a halide such as chloride, fluoride, bromide or iodine, methyl sulfate, i.e., methosulfate anion (CH3-OSO3 - ), methanesulfonate anion (CH3-SO3 - ), sulfate anion, hydrogen sulfate anion (HSO4 - ), carbonate anion, bicarbonate anion (HCO3 - ), dihydrogen phosphate anion (H2PO4 2- ), hydrogen phosphate anion (HPO4 2- ), phosphate anion or an organic carboxylate anion such as acetate, propionate, benzoate, tartaric acid, citrate, lactate, maleate or succinate anion.

[0021] Counteranion X n- are halides, sulfate anions, carbonate anions, and bicarbonate anions (HCO3 -), hydrogen sulfate anion, dihydrogen phosphate anion, hydrogen phosphate anion or phosphate anion, if inorganic in nature, do not alter the biodegradation behavior of the corresponding quaternary ammonium compound.

[0022] Counteranion X n- is methyl sulfate, i.e., methosulfate anion (CH3-OSO3 - ), methanesulfonate anion (CH3-SO3 - ) or "short-chain" organic carboxylate anions (R a (CO2 - ) n ), e.g. acetate anion (R a =CH3-, n=1), propionic acid (R a =CH3-CH2-, n=1), tartaric acid (R a =-CH(OH)-CH(OH)-, n=2), citric acid (R a =-CH2-C(OH)(-)-CH2-, n=3), lactic acid (R a =CH3-CH(OH)-, n=1), maleic acid (R a =-CH=CH-, n=2) or succinic acid (R a For organic salts such as aryl anions (e.g., n=-CH2-CH2-, n=2), it is not expected that biodegradability will be significantly affected since the hydrogen and carbon content in the anion represents a small percentage of the total hydrogen and carbon content of the whole salt (especially for polyanions). a (CO2 - ) n For the organic carboxylate anion, R a is preferably C1 to C6, more preferably C1 to C4. a is preferably linear and may be unsaturated, as unsaturation is advantageous for biodegradability.

[0023] Counteranion X n- A preferred list of - ), fluoride (F - ), bromide (Br - ) or iodine (I -), methyl sulfate, i.e., methosulfate anion (CH3-OSO3 - ), methanesulfonate anion (CH3-SO3 - ), sulfate anion (SO4 2- ), hydrogen sulfate anion (HSO4 - ), carbonate anion (CO3 2- ), bicarbonate anion (HCO3 - ), dihydrogen phosphate anion (H2PO4 2- ), hydrogen phosphate anion (HPO4 2- ), phosphate anion (PO4 3- ) or acetate anion (CH3-COO - ) can be cited.

[0024] According to a preferred embodiment, X n- is a halide, preferably chloride, with n=1.

[0025] In the mixture according to the invention, the R group is C 15 Or C 17 alkyl group, and the mixture is 20 to 95 mole percent of a cyclic alkyl group of formula I, 15 It is advantageous to include compounds in which the aryl group is an alkyl group.

[0026] The best results are obtained with the mixtures according to the invention in which the R group is C 15 Or C 17 linear alkyl group, and the mixture comprises 20 to 95 mole % of a compound of formula I, 15 This is obtained when the compound contains a straight chain alkyl group.

[0027] As shown in the experimental section below, the mixture contains less than 20 mol % of a compound of formula I, where both R groups are C 15When the 95% limit is exceeded, the biodegradability performance is not reached. Experiments have also demonstrated that above the 95% limit, the hydrophobicity of the mixture is affected, which will reduce its performance as a surfactant in certain applications. Since both biodegradability and surfactant performance are required, the optimum balance is not easy to achieve. In fact, when the 95% limit is exceeded, the biodegradability performance is not reached. 17 Without the minimum compound containing the linear alkyl group, the CMC (critical micelle concentration) would be high and a higher amount of surfactant would need to be introduced into the target formulation to reach performance in the application.

[0028] In the mixtures according to the invention, excellent results have been obtained when the mixtures contain from 20 to 60 mol %, preferably from 30 to 50 mol %, of a compound of formula I, in which both R groups are C 15 This is obtained when the mixture contains compounds with an aliphatic group, preferably an alkyl group, especially a linear alkyl group.

[0029] According to a preferred embodiment, the mixture according to the invention comprises: 20 to 95 mol %, preferably 20 to 60 mol %, more preferably 30 to 50 mol % of the cyclic amine of formula I (wherein both R groups are C 15 a straight chain alkyl group, 4.9 to 50 mol %, preferably 35 to 50 mol %, more preferably 41 to 50 mol % of a compound of formula I (wherein one R group is C 15 is a straight chain alkyl group, and the other R groups are 17 is a straight chain alkyl group, and 0.1 to 31 mol %, preferably 5 to 31 mol %, more preferably 9 to 20 mol % of the compound of formula I, in which both R groups are C 17 A compound of Includes.

[0030] The mixture according to the invention comprises less than 5 mol %, preferably less than 2 mol %, of the compound of formula I, in which at least one of the R groups, which may be the same or different in each occurrence, is a C7-C 13These products are by-products derived from the raw materials used. In fact, the fatty acid cuts used as starting materials may contain compounds with C7-C 13 If it contains a low amount of one or more fatty acids based on an aliphatic group, it may be used in combination with any fatty acids contained in the cut, such as C7-C 13 Any possible internal ketones that can be obtained by coupling with any of this one or more fatty acids based aliphatic groups are brought about during the decarboxylative ketonization step.

[0031] The mixture according to the invention comprises less than 5 mol %, preferably less than 2 mol %, of the compound of formula I, in which at least one of the R groups, which may be the same or different in each occurrence, is C 19 ~C 21 These products are by-products derived from the raw materials used. As explained previously, the fatty acid cuts used as starting materials may further include compounds of C 19 ~C 21 C when it contains a low amount of one or more fatty acids based on aliphatic groups 19 ~C 21 Any possible internal ketones that can be obtained by coupling any of this one or more fatty acids based on an aliphatic group with any fatty acid contained in the cut are brought about during the step of decarboxylative ketonization (see step a. below in this description).

[0032] According to a particular embodiment of the invention, the mixture of compounds of formula I is a compound of formula I, wherein the R groups, which may be the same or different in each occurrence, are 15 Or C 17 The compound essentially contains compounds of the formula (I) (wherein the alkyl group is a straight chain alkyl group), which means that other compounds represent less than 2 mol %, preferably less than 1 mol %.

[0033] The above defined mixtures according to the invention exhibit, on the one hand, good surfactant properties and, on the other hand, good biodegradability.

[0034] In the experimental part, it is shown that by careful control of the average hydrocarbon chain length (R-CH-R), especially by careful selection of the starting fatty acid, it is possible to achieve a good balance between surfactant properties on the one hand and biodegradability on the other. For example, C 16 :C 18 Starting with a fatty acid mixture, the minimum amount of C is selected to achieve ready biodegradability for the final compound. 16 is required in the starting fatty acid. At the same time, a minimum amount of C is required to achieve surfactant properties for the final compound. 18 is also required in the starting fatty acid.

[0035] In addition, at least for industrial applications, the starting raw materials for the mixtures of the present invention are derived from renewable resources, typically both C 16 and C 18 It is important to point out that the fatty acids are derived from the fatty acids of coconut oil cuts that contain fatty acids. 16 and C 18 Fatty acids are very difficult to isolate from one another, which is energy intensive, costly and makes no sense from an industrial point of view.

[0036] The mixture of compounds of formula I according to the invention can be obtained by various methods. A preferred method for preparing the compounds of the invention comprises the reaction of an internal ketone of formula VI: RC(=O)-R (VI), which can preferably be obtained by decarboxylative ketonization of a mixture of fatty acids, fatty acid derivatives or mixtures thereof. A suitable method for the preparation of an internal ketone according to this route is disclosed in US Patent Application Publication No. 2018 / 0093936, to which reference is made for further details. In any case, such a mixture of compounds of formula I as defined above can advantageously be prepared by the reaction of a fatty acid R-COOH (wherein R is C 15 Or C 17 aliphatic radicals), and said mixture of fatty acids is obtained by a process starting from a mixture of R-COOH (wherein R is C 15 aliphatic groups).

[0037] The method comprises the steps of: 15 Or C 17 The mixture of fatty acids preferably contains 45 to 78 mol %, more preferably 55 to 71 mol % of R-COOH (wherein R is a straight chain alkyl group), and the mixture of fatty acids preferably contains 45 to 78 mol %, more preferably 55 to 71 mol % of R-COOH (wherein R is 15 It is particularly preferred that the alkyl group contains a straight chain alkyl group.

[0038] The process of the present invention may be a process comprising: 1) Piria ketonization (i.e., decarboxylative ketonization) of the mixture of fatty acids described above; 2) ketone hydrogenation to a mixture of secondary fatty alcohols; 3) alcohol esterification, especially with chloroacetic acid (where Y is methylene); 4) condensation of the mixture of monoesters, especially chloroesters, with an amine; and 5) optionally anion exchange to provide the desired quaternary ammonium mixture of compounds of formula I.

[0039] The method starts with a pyria ketonization, followed by hydrogenation and esterification to obtain a mixture of monoesters. The esterification reaction step is followed by an amine condensation step to convert the monoesters to a mixture of compounds that can conform to formula I or can be further reacted by anion exchange to conform to formula I. This is a multi-step process that is linked to the pyria technology. It has the advantage of being salt-free and relying on chemical transformations that can be easily performed if no step of anion exchange is performed.

[0040] The overall method according to the present invention comprises the following steps: a. Fatty acid R-COOH (wherein R is C 15 Or C 17 aliphatic groups), where R is C 15 decarboxylating a mixture containing 45-98 mol % of the aliphatic radical R-COOH in the presence of a metal catalyst, thereby obtaining a mixture of internal ketones of formula VI: RC(=O)-R (VI), in which the R radicals, which may be the same or different in each occurrence, are as defined above; b. hydrogenating the mixture of internal ketones of formula VI obtained in step a. in the presence of H and a catalyst, thereby obtaining a mixture of secondary alcohols of formula V: R-CH(OH)-R (V), in which the R groups, which may be the same or different in each occurrence, are as defined above; c. reacting the mixture of secondary alcohols of formula V obtained in step b. with a secondary alcohol of formula IV: [LY-CO2H] (t-1)- [U u+ ] (t-1) / u (IV) (wherein L is a leaving group; t is an integer equal to 1 or greater than 2; U u+ is a cation, u is an integer that fixes the positive charge of the cation, Y is as defined in claim 1 or 4, and The R group is as described above. to a carboxylic acid reagent of formula III: [ka] (In the formula, R 、 Y, L, t, U, and u are as defined above. obtaining a mixture of monoesters of d. Condensing the mixture of monoesters of formula III obtained in step c. with an amine of formula R'R''R'''N, where R', R'' and R''', which may be the same or different, are hydrogen or C1-C4 alkyl groups, to obtain a monoester of formula II: [ka] (In the formula, R, R', R'', R''', Y, L and t are as defined above.) obtaining a mixture of compounds of e. Optionally, the mixture of compounds of formula II obtained in step d. is treated with L t- X n- If different, X n- By L t- To replace the formula [U'u’+ ] n / u’ X n- where X and n are as defined in any one of the preceding claims, and U' u’+ is a cation and u' is an integer which fixes the positive charge of the cation; f. recovering the mixture of compounds of formula I as defined above; may include.

[0041] Further details regarding this method are provided below.

[0042] Method for the synthesis of a mixture of compounds of formula I a. Pyriaketonization The basic reaction in the first step is: [ka] wherein the R group has the same meaning as defined above. It is.

[0043] This reaction is described in detail in U.S. Pat. No. 10,035,746, WO 2018 / 087179 and WO 2018 / 033607, to which reference is made for further details.

[0044] b. Hydrogenation The internal ketone mixture of formula VI is then subjected to a hydrogenation reaction: [ka] The resulting product is subjected to hydrogenation, which can be carried out under standard conditions known to those skilled in the art.

[0045] The hydrogenation reaction is carried out by contacting the internal ketone mixture of formula VI with hydrogen in an autoclave reactor at a temperature ranging from 15°C to 300°C and a hydrogen pressure ranging from 1 bar to 100 bar. The reaction can be carried out in the presence of an optional solvent, but the use of such a solvent is not essential and the reaction can also be carried out without the addition of any solvent. Examples of suitable solvents include methanol, ethanol, isopropanol, butanol, THF, methyl-THF, hydrocarbons, water or mixtures thereof. A suitable catalyst based on a transition metal should be used for this reaction. Examples of suitable catalysts include heterogeneous transition metal catalysts such as supported dispersed transition metal catalysts or homogeneous organometallic complexes of transition metals. Examples of suitable transition metals are Ni, Cu, Co, Fe, Pd, Rh, Ru, Pt, Ir. Examples of suitable catalysts include Pd / C, Ru / C, Pd / Al2O3, Pt / C, Pt / Al2O3, Raney nickel, Raney cobalt, etc. At the end of the reaction, the desired alcohol mixture of formula V can be recovered after appropriate workup.Those skilled in the art are aware of representative techniques, and therefore no further details need to be provided here.Details of this process step can be found, for example, in US Patent No. 10035746, which is referred to herein.

[0046] A person skilled in the art will select suitable reaction conditions based on their professional experience and taking into account the specific target compound to be synthesized, and therefore no further details need be described here.

[0047] C.Esterification Esterification of the above obtained alcohol mixture of formula V can then be carried out by reacting said alcohol mixture of formula V with a carboxylic acid reagent of formula IV to obtain an ester of formula III: [ka] The mixture of monoester compounds of the formula: [ka] wherein whenever present in the above compound, L is a leaving group, t is an integer equal to 1 or greater than 2; U u+ is a cation, u is an integer that fixes the positive charge of the cation, and R and Y are as defined above.

[0048] The esterification is carried out by reacting the alcohol mixture of formula V with an alcohol mixture of formula IV: [LY-CO2H] (t-1)- [U u+ ] (t-1) / u (IV) (In the formula, L, Y, t, U u+ and u are as previously described. This is carried out by contacting the reaction with a carboxylic acid reagent of

[0049] When t is equal to 1, the cation is absent. Otherwise, the esterification reaction proceeds by converting the alcohol to the formula: LY-CO2H This is carried out by contacting the compound with a carboxylic acid of

[0050] If the leaving group L is already negatively charged in the carboxylic acid reagent (this is the case when (t-1) is 1 or more, i.e., t is 2 or more), U u+ A cation, denoted as (u is preferably 1, 2 or 3, more preferably 1), must be present in the reactants to ensure electrical neutrality. This cation can be, for example, H, to name a few. + , alkali metal cations (e.g., Na + Or K + ), alkaline earth metal cations (e.g., Ca 2+ ), Al 3+ and ammonium.

[0051] The nature of the leaving group L is not particularly limited, provided that the next reaction step (i.e. the amine condensation as detailed below) can take place. The leaving group L is advantageously a nucleofugic leaving group. It is especially - halogen, - Formula R a -O-SO2-O-(wherein, R a is C1-C, which may be optionally halogenated 20 (hydrocarbyloxysulfonyl)oxy group, - Formula R a -SO2-O-(wherein, R a is C1-C, which may be optionally halogenated 20 (hydrocarbylsulfonyl)oxy groups (such as in CF3-SO2-O-), which represent a hydrocarbyl group; and - expression - The oxysulfonyloxy group of O-SO2-O- (which is a leaving group L that already bears one negative charge on the terminal oxygen atom) You can choose from.

[0052] Hydrocarbyl Group R a wherever present in the preceding formula, may in particular be an aliphatic group or an optionally substituted aromatic group such as phenyl or p-tolyl. a is typically a C1-C6 alkyl group which may be linear or branched; it is often a straight chain C1-C4 alkyl such as methyl, ethyl or n-propyl.

[0053] The leaving group L is preferably - halogens, such as fluorine, chlorine, bromine or iodine, - Formula R such as CH3-SO3 a -SO3-(wherein, R a is C1~C 20 (hydrocarbyloxysulfonyl)oxy groups, and - expression - O-SO2-O-oxysulfonyloxy group is selected from.

[0054] An example of a compound where t is equal to 1 is CH3-O-SO3-CH2-COOH, which may be referred to as 2-((methoxysulfonyl)oxy)acetic acid. Further examples of compounds where t is equal to 1 and thus no cation is present include chloroacetic acid, bromoacetic acid, and 2-chloropropionic acid. Chloroacetic acid is a preferred reagent of formula IV.

[0055] An example where t is equal to 2 is [LY-COOH] (t-1)- [U u+ ] (t-1) / u [O-SO2-O-CH2-COOH] - [Na + ] is sodium carboxymethyl sulfate.

[0056] The reaction carried out during the esterification step c. can be carried out in the presence of a solvent. However, the presence of such a solvent is not essential and the reaction can also be carried out without adding any solvent. Examples of suitable solvents include toluene, xylene, hydrocarbons, DMSO, Me-THF, THF or mixtures thereof.

[0057] The reaction is advantageously carried out under an inert atmosphere, such as a nitrogen or noble gas atmosphere. An argon atmosphere is an example of a suitable inert atmosphere.

[0058] The reaction can be carried out in the absence of any catalyst. A catalyst can also be used in the reaction, and a suitable catalyst is a Bronsted acid catalyst or a Lewis acid catalyst. Preferred examples of catalysts include H2SO4, para-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, HCl or heterogeneous acid resins such as Amberlite® resin, AlCl3, FeCl3, SnCl4, etc.

[0059] The total number of moles of the carboxylic acid reagent of formula IV contacted with the alcohol of formula V during the entire course of the reaction is advantageously more than half the total number of moles of the alcohol; it is preferably at least the same as the total number of moles of the alcohol, and it is more preferably at least twice the total number of moles of the alcohol. Moreover, the total number of moles of the carboxylic acid reagent contacted with the alcohol during the entire course of the reaction is advantageously at most 10 times the total number of moles of the alcohol.

[0060] The reaction is advantageously carried out in a reactor in which the alcohol is in the molten state. It has also been found to be advantageous to carry out the reaction in a reactor in which the carboxylic acid reagent of formula IV is in the molten state. Preferably, the reaction is carried out in a reactor in which both the alcohol and the carboxylic acid reagent are in the molten state.

[0061] The esterification reaction can be carried out in the presence of an optional solvent, generally at a temperature ranging from about 20°C to about 200°C. To allow for a sufficient reaction rate, the reaction is preferably carried out at a temperature that is at least 60°C, more preferably at least 80°C, even more preferably at least 100°C. On the other hand, the applicant has surprisingly found that carrying out the reaction at high temperatures leads to the formation of internal olefins as dehydration by-products and color build-up. Therefore, the reaction is preferably carried out at a temperature that is less than 180°C, more preferably less than 160°C, even more preferably at most 150°C.

[0062] The overall reaction can be carried out at atmospheric pressure or below atmospheric pressure to aid in water removal and drive the equilibrium to completion. Preferably, it is carried out at atmospheric pressure or under vacuum, i.e., at a pressure between 10 kPa and atmospheric pressure (about 1 atm = 101.325 kPa). More preferably, it is carried out at atmospheric pressure.

[0063] At the end of the reaction, the desired mixture of monoester compounds of formula III can be recovered after suitable work-up, and those skilled in the art are aware of the representative techniques, so no further details are required here.For example, a suitable work-up can consist of distilling excess carboxylic acid reagent under vacuum.Alternatively, excess carboxylic acid reagent can be removed by simple extraction of crude organic mixture with aqueous solution.

[0064] D. Amine condensation The mixture of monoester compounds of formula III can be prepared according to the following reaction scheme: [ka] wherein R, R', R'', R''', Y, L, U, t and u are as previously described herein. can be converted to the mixture of compounds of formula II by

[0065] The amine condensation reaction is carried out by contacting the mixture of intermediate monoester compounds of formula III with ammonia or an amine of formula NR'R''R'', where R', R'' and R''', which may be the same or different, are hydrogen or C1-C4 alkyl groups, and preferred R', R'' and R''' are exactly as defined above in connection with the ammonium compounds of formula I.

[0066] The reaction can be carried out in the presence of a suitable solvent at a temperature ranging from 15° C. to 250° C. Examples of suitable solvents include THF, Me-THF, methanol, ethanol, isopropanol, butanol, ethyl acetate, DMSO, toluene, xylene or mixtures thereof. Alternatively, the reaction can be carried out in the absence of any added solvent.

[0067] During this reaction, L in the monoester (t-1)- There is nucleophilic attack of ammonia or amine to replace L (t-1)- acts as a leaving group. t-becomes the counter anion of the final ammonium compound. If the leaving group is already negatively charged in the monoester (which is the case when (t-1) is 1 or greater or when t is 2 or greater), a by-product of the reaction is produced, which has the general formula [U u+ ] t / u [L t- ] salts may also be formed.

[0068] e. Optional Anion Exchange In a preferred embodiment, L t- X n- (in other words, X is equal to L), which means that the compound of formula II is equal to the compound of formula I.

[0069] In this case, the counterion X of formula I n- is in fact derived from the leaving group L of the previous step. This is especially true for X n- is a halide, sulfate, hydrogen sulfate, methanesulfonate, methosulfate, p-toluenesulfonate, dihydrogen phosphate, hydrogen phosphate, phosphoric acid, or an organic carboxylate.

[0070] In another embodiment, the method of the present invention includes a step e. of anion exchange. For example, X n- When is a carbonate or bicarbonate, the mixture of compounds of formula I may be t- X n- This is obtained in an additional step e. of anion exchange to replace

[0071] For the phosphate and carboxylate anions, both options are possible.

[0072] The anion exchange reaction in step e. is carried out by displacing the mixture of compounds of formula II obtained at the end of step d., which is essentially a compound of formula I, but with the addition of an anion L t- X n- Instead of one of the products of the anion exchange reaction (X as counter anion) to drive the equilibrium to completion. n- The novel compounds of formula I or salt by-products [U' u’+ ]t / u’ L t- (either U' u’+ ] n / u’ X n- This can be achieved by contacting the compound with a salt of U' u’+ is a cation and u' is an integer that fixes the positive charge of the cation. The cation can be, for example, H + , alkali metal cations (e.g., Na + Or K + ), alkaline earth metal cations (e.g., Ca 2+ ), Al 3+ , Ag + and ammonium.

[0073] Examples of solvents include water, methanol, ethanol, isopropanol, butanol, DMSO, acetone, acetonitrile, ethyl acetate, and mixtures thereof.

[0074] f. Recovering the mixture of compounds of formula I The final mixture of compounds of formula I can be recovered following appropriate work-ups known in the prior art.

[0075] A particularly preferred method according to the present invention comprises the following steps: a. Fatty acid R-COOH (wherein R is C 15 Or C 17 aliphatic groups), where R is C 15 decarboxylating a mixture containing 45-98 mol % of the aliphatic radical R-COOH in the presence of a metal catalyst, thereby obtaining a mixture of internal ketones of formula VI: RC(=O)-R (VI), in which the R radicals, which may be the same or different in each occurrence, are as defined above; b. hydrogenating the mixture of internal ketones of formula VI obtained in step a. in the presence of H and a catalyst, thereby obtaining a mixture of secondary alcohols of formula V: R-CH(OH)-R (V), in which the R groups, which may be the same or different in each occurrence, are as defined above; c. Esterification of the mixture of secondary alcohols of formula (V) obtained in step b. with a carboxylic acid reagent of formula (IV), which is chloroacetic acid, thereby obtaining a compound of formula (III') [ka] (wherein the R group is as defined above). obtaining a mixture of monoesters of d. Condensing the mixture of monoesters of formula (III') obtained in step c. with an amine of formula R'R''R'''N, where R', R'' and R''', which may be the same or different, are hydrogen or a C1-C4 alkyl group, to obtain the compound of formula (I'): [ka] (wherein the R group is as defined above). and directly obtaining a mixture of compounds of The method includes:

[0076] This preferred method is salt-free and allows for easy chemical transformations.

[0077] Other methods for preparing mixtures of compounds of formula I according to the invention An alternative method for preparing a mixture of compounds of formula I, comprising the steps of: 15 wherein the mixture containing the compound of formula I is a simple mixture of a defined ratio of quaternary ammonium compounds of formula I.

[0078] C 15 and C 17 It is also possible to start from a mixture of symmetrical ketones of formula VI RC(=O)-R, where the R groups are as defined above, with a defined proportion of aliphatic groups, followed by a hydrogenation step (as described above in step b), then an esterification step (as described above in step c) and a condensation step (as described above in step d), optionally followed by steps e and f.

[0079] For the same reason, it is possible to start with a mixture of secondary alcohols of formula V in the correct proportions and then carry out the esterification (step c), the condensation (d) and optionally steps e and f.

[0080] It is also possible to start from a mixture of monoesters of formula III as described above in the correct proportions and then carry out the condensation (d) and optional steps e and f.

[0081] The exemplary methods described above are examples of suitable methods, i.e., there may be other suitable methods for synthesizing the compounds according to the present invention. Therefore, the methods described herein above are not limiting as far as the methods for producing the compounds according to the present invention are concerned.

[0082] The mixture of compounds of formula I can be used as surfactants.Surfactants are compounds that reduce the surface tension (or interfacial tension) between two immiscible liquids, between a liquid and a gas, or between a liquid and a solid.Surfactants can function as detergents, wetting agents, emulsifiers, foaming agents, and dispersants.

[0083] Surfactants are organic compounds that are usually amphiphilic, meaning that they contain both hydrophobic groups (their tails) and hydrophilic groups (their heads). Thus, surfactants contain both water-insoluble (or oil-soluble) and water-soluble components. Surfactants will diffuse in water and, when water is mixed with oil, will adsorb at the air-water interface or the oil-water interface. The water-insoluble hydrophobic groups can extend from the bulk water phase into the air or oil phase, while the water-soluble head groups can remain in the water phase.

[0084] The adsorption of cationic surfactants to negatively charged surfaces is an important property for such surfactants. This property is usually associated with the minimum concentration of surfactant required to bring about the aggregation of negatively charged cellulose nanocrystals (CNCs, often used as reference material) suspensions in aqueous media. The continuous change in size can be monitored and followed by dynamic light scattering (DLS).

[0085] Following the protocol described by EKOikonomou et al., J. Phys. Chem. B, 2017, 121(10), 2299-307, the adsorption properties of ammonium compounds can be studied by monitoring the ratio X = [surfactant] / [CNC] or the mass fraction M = [surfactant] / ([surfactant]+[CNC]), at immobilized [surfactant]+[CNC]=0.01 wt% in aqueous solution, which is required to induce aggregation of cellulose nanocrystals.

[0086] The biodegradability of the compounds of the present invention can be measured according to procedures described in the prior art and known to those skilled in the art. Details regarding one such method, OECD Standard 301, are described in the experimental section herein below.

[0087] The mixture of compounds of formula I exhibits outstanding surfactant properties and biodegradability.

[0088] It can be used in a variety of aqueous or hydroalcoholic formulations as the only ammonium compound exhibiting surfactant properties, i.e., without other monoammonium compounds exhibiting surfactant properties and without di- or higher ammonium compounds exhibiting surfactant properties being present in these formulations.

[0089] The applicant has observed that in aqueous or hydroalcoholic formulations, mixtures of compounds of formula I are generally structured in the form of lamellae, such as multilamellar vesicles.This lamellar structure generally results in aqueous or hydroalcoholic formulations based on ammonium surfactants that exhibit substantially higher viscosities than the same formulations, but are structured in the form of micelles.This higher viscosity is well suited for some applications, while for some other applications a somewhat lower viscosity is desired.

[0090] As in the examples below, throughout this description, any developed formula should be understood to include, where appropriate, all potential enantiomers and diastereoisomers. Unless a specific stereochemistry is intended and specifically mentioned, each chiral molecule presented is in the form of its racemic mixture.

[0091] To the extent that the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the statements of this application to the extent that any term may be unclear, the statements of this application shall control. EXAMPLES

[0092] Example (Comparative) 1) C 16 :C 18 = 33.7:65.3% by weight C 16 ~C 18 Mixture of fatty acids (or in other words R = C 15 :R=C 17 =33.7:65.3 wt.% mixture of R-COOH, 13 mol. % of formula I, where both R groups are C 15 Synthesis of mixed compounds of formula I having a compound of formula (I) in which the aliphatic group is All reactions are carried out under an inert argon atmosphere.

[0093] Steps a. and b.: Pyriaketonization and hydrogenation The two initial steps (pyria and hydrogenation) were carried out according to the protocol described in Example 12 of published patent application WO 2020 / 254337.

[0094] Step c.: Esterification of secondary alcohols with chloroacetic acid In a three-necked 500 mL round bottom flask equipped with a magnetic stirring device, heater, thermometer probe, and distillation apparatus connected to a receiving flask, 50 g (0.102 mol, 1 eq.) of secondary alcohol C 31 ~C 35 mixture 39.1 g of chloroacetic acid (0.41 mol, 4 eq.) Add the following.

[0095] The reaction mixture is then heated to 120° C. and stirring is commenced (900 rpm stirring speed) as soon as the reaction mixture is completely melted (approximately 105° C.).

[0096] The reaction mixture is then allowed to stir at 120° C. and the progress of the reaction is followed by 1H NMR spectroscopy.

[0097] After 1 h00 stirring at 120° C., NMR analysis indicates a conversion level of 82%. A slight vacuum is applied to the reactor (800 mbar) to effectively remove the water co-generated during the reaction and to shift the equilibrium towards the completion of the esterification.

[0098] After an additional 2 h00 of stirring at 120° C. under 800 mbar, NMR analysis of the reaction crude indicates a conversion level of 96%.

[0099] The reactor pressure is then reduced to 30 mbar and the temperature of the reaction medium is further increased to 140° C. in order to distill off the excess chloroacetic acid.

[0100] Distillation is carried out at 140° C. and 30 mbar until complete disappearance of chloroacetic acid as evidenced by 1H NMR analysis of the crude (less than 0.3 mol % residual chloroacetic acid in the crude).

[0101] At the end of the reaction, the pressure is restored to 1 atm. and the reaction medium is allowed to cool to room temperature.

[0102] 56.7 g of product are recovered as a beige wax of the following composition: 98.9% by weight of mixture of chloroacetic esters, 1% by weight of starting mixture of fatty alcohols, 0.04% by weight of residual chloroacetic acid.

[0103] The esterification yield, taking into account the purity, is 97%.

[0104] The crude product is then used in the subsequent quaternization step. 1 H NMR(CDCl3,400MHz)δ(ppm):4.93(quint,J=6.0Hz,1H),4.01(s,2H),1.64-1.46(m,4H),1.45-1.05(m,57H(average number)),0.86(t,J=6.8Hz,6H). 13 C NMR(CDCl3,101MHz)δ(ppm):167.32,77.21,41.37,34.17,32.16,29.93,29.90,29.87,29.79,29.72,29.69,29.60,25.42,22.92,14.33.

[0105] Step d.: Quaternization of chloroacetate with trimethylamine A 1 L double jacketed reactor equipped with a mechanical stirrer (propeller with four pitched plows), a thermometer probe, a condenser and two successive traps connected thereto, each containing an aqueous solution of HCl (0.1 M) and activated carbon, was 56 g (0.099 mol, 1 eq.) of the mixture of chloroacetates obtained from step c. 212 mL (180.6 g, 0.397 mol, 4 eq.) of trimethylamine / THF solution (13 wt%, approx. 2 mol / L) Add the following.

[0106] The reaction mixture is then left stirring at 40° C. (stirring speed of 700 rpm) and the progress of the reaction is followed by 1H NMR spectroscopy.

[0107] After 2 h of stirring at 40° C., the conversion level of the mixture of chloroacetates is about 66%.

[0108] After 4 h00 stirring at 40° C., the conversion level increased to 85%.

[0109] To increase the reaction rate, the temperature of the reaction medium was further increased to 55° C. and after an additional 2 hours of stirring at 55° C., the conversion level reached 94%.

[0110] The reaction mass is then left to stir at 55° C. for an additional 6 h00 in order to complete the reaction.

[0111] At this stage, the reaction crude composition is 98 mol % of the mixture of glycine betaine esters of formula I and 0.7 mol % of the starting mixture of chloroacetate esters.

[0112] The reaction medium is then allowed to cool to room temperature and all volatile substances are removed under vacuum to obtain 61.41 g of crude product as a beige wax of the following composition: 98.2% by weight of a mixture of glycine betaine esters of formula I, corresponding to a yield of 97.4% taking into account the purity, 0.9% by weight of a mixture of fatty secondary alcohols and 0.8% by weight of a mixture of chloroacetic esters. 1 H NMR(CD3OD,400MHz)δ(ppm):5.02(quint,J=6.0Hz,1H),4.41(s,2H),3.35(s,9H),1.68-1.52(m,4H),1.50-1.05(m,57H(average number)),0.87(t,J=7.2Hz,6H). 13 C NMR(CD3OD,101MHz)δ(ppm):165.46,78.81,63.98,54.43,34.59,32.83,30.56,30.53,30.49,30.44,30.34,30.24,26.07,23.53,14.54.

[0113] Example 2) C 16 :C 18 = 60.9:38.2% by weight C 16 ~C18 Mixture of fatty acids (or in other words R = C 15 :R=C 17 =60.9:38.2 wt.% mixture of R-COOH, 41 mol. % of formula I, where both R groups are C 15 Synthesis of a mixture of compounds of formula I having a compound of formula (I) in which the group is an aliphatic group. All reactions are carried out under an inert argon atmosphere.

[0114] Steps a. and b.: Pyriaketonization and hydrogenation The two initial steps (pyria and hydrogenation) were carried out according to the protocol described in Example 13 of published patent application WO 2020 / 254337.

[0115] Step c.: Esterification of secondary alcohols with chloroacetic acid In a three-necked 500 mL round bottom flask equipped with a magnetic stirring device, heater, thermometer probe, and distillation apparatus connected to a receiving flask, 82 g (0.173 mol, 1 eq.) of secondary alcohol C 31 ~C 35 mixture 66.2 g of chloroacetic acid (0.693 mol, 4 eq.) Add the following.

[0116] The reaction mixture is then heated to 120° C. and stirring is commenced (1200 rpm stirring speed) as soon as the reaction mixture is completely melted.

[0117] A slight vacuum (800 mbar) is applied to remove the water co-produced by the reaction and to shift the equilibrium towards complete esterification.

[0118] The reaction mixture is left stirring at 120° C., 800 mbar for 3 h40 and the progress of the reaction is followed by 1H NMR spectroscopy.

[0119] After 3 h00 reaction time, NMR analysis indicates a conversion level of 96%.

[0120] The pressure is then reduced to 10 mbar in order to distill off the excess chloroacetic acid and distillation is carried out until complete disappearance of chloroacetic acid (less than 0.3 mol % residual chloroacetic acid in the crude) as evidenced by 1H NMR analysis of the crude.

[0121] At the end of the distillation, the pressure is restored to 1 atm. and the reaction medium is allowed to cool to room temperature.

[0122] 95 g of product are recovered as a beige wax of the following composition: 98.3% by weight of the mixture of chloroacetic esters and 1.7% by weight of the starting mixture of fatty alcohols.

[0123] The esterification yield, taking into account the purity, is 98%.

[0124] The crude product is then used in the subsequent quaternization step. 1 H NMR(CDCl3,400MHz)δ(ppm):4.93(quint,J=5.6Hz,1H),4.01(s,2H),1.62-1.46(m,4H),1.33-1.16(m,54.8H(average number)),0.86(t,J=6.8Hz,6H).

[0125] Step d.: Quaternization of chloroacetate with trimethylamine A 1 L double jacketed reactor equipped with a mechanical stirrer (propeller with four pitched plows), a thermometer probe, a condenser and two successive traps connected thereto, each containing an aqueous solution of HCl (0.1 M) and activated carbon, was 95 g (98.3% by weight purity, 0.17 mol, 1 eq.) of the mixture of chloroacetates obtained from step c. 364 mL (309 g, 0.68 mol, 4 eq.) of trimethylamine / THF solution (13 wt%, approx. 2 mol / L) Add the following.

[0126] The reaction mixture is then left to stir at 55° C. (stirring speed of 1200 rpm) and the progress of the reaction is followed by 1H NMR spectroscopy.

[0127] After 3 h30 of stirring at 55° C., the conversion level of the mixture of chloroacetates is about 87%.

[0128] After stirring for 5 h45 at 55° C. the conversion level increased to 97%.

[0129] The reaction mass is then left to stir at 55° C. for an additional 6 h00 in order to complete the reaction.

[0130] At this stage, the reaction crude composition is 98 mol % of the mixture of glycine betaine esters of formula I and 0.2 mol % of the starting mixture of chloroacetate esters.

[0131] The reaction medium is then allowed to cool to room temperature and all volatile substances are removed under vacuum to obtain 103 g of crude product as a beige wax of the following composition: 98.3% by weight of a mixture of glycine betaine esters of formula I, corresponding to a yield of 98%, 1.5% by weight of a mixture of fatty secondary alcohols and 0.2% by weight of a mixture of chloroacetic esters. 1 H NMR(CD3OD,400MHz)δ(ppm):4.97(quint,J=6.0Hz,1H),4.38(s,2H),3.36(s,9H),1.65-1.46(m,4H),1.45-1.05(m,54.8H(average number)),0.84(t,J=6.8Hz,6H). 13 C NMR(CD3OD,101MHz)δ(ppm):164.81,78.67,63.64,54.28,34.12,32.36,30.11,30.08,30.05,30.02,29.90,29.81,29.78,25.66,23.10,14.38.

[0132] Biodegradability Assessment: The ready biodegradability of the test substances was determined according to the 301 F OECD protocol.

[0133] A measured amount of inoculated mineral medium containing a known concentration of the test substance to reach approximately 50-100 mg ThOD / l (theoretical oxygen demand) as the nominal sole source of organic carbon is stirred in a closed flask (oxitop™ respirometry flask) at a constant temperature (20±2°C) for up to 28 days. Oxitop™ respirometry bottles were used in this test to access the biodegradability of the test samples: a sealed incubation BOD flask was used at a temperature of 20±2°C throughout the 28 days.

[0134] The evolved carbon dioxide is absorbed by sodium or potassium hydroxide pellets present in the headspace of the bottle. The amount of oxygen taken up by the microbial population during the biodegradation process (biological oxidation of the test substance) (=oxygen consumption in mg / l) reduces the headspace pressure (ΔP measured by a pressure switch) and is mathematically converted into mgO2 / liter consumed. The inoculum is washed in a mineral medium (ZW medium) to reduce the DOC (dissolved oxygen carbon) content, corresponding to municipal activated sludge. A control solution containing the reference substance sodium acetate and also a toxicity control solution (test substance + reference substance) were used for validation purposes.

[0135] The reference substance, sodium acetate, was tested in one bottle at a nominal concentration of 129 mg / l (corresponding to 100 mg ThOD / l) to check the viability of the inoculum. The toxicity control corresponded to a mixture of the substance reference and the test substance; it would check whether the test substance was toxic to the inoculum (if so, the test must be repeated with a lower test substance concentration, if possible in relation to the sensitivity of the method).

[0136] Since the test substances are, for the most part, poorly soluble in water (if they are soluble in water, their metabolites after hydrolysis containing alkyl chains often have very low solubility in water), a specific protocol was used, named the "emulsion protocol", which allows the bioavailability of poorly water-soluble substances to be improved in the aqueous phase with the inoculum.

[0137] The emulsion protocol consisted of adding the test substance in a bottle vial as an emulsified stock solution.

[0138] The emulsions were a 50 / 50 v / v mixture of stock solutions of the test substances dissolved in a non-biodegradable surfactant-containing aqueous solution (Synperonic PE 105, at 1 g / l) then mixed with mineral silicone oil AR 20 (Sigma).

[0139] Initial dissolution of the test articles into the aqueous solutions containing the non-biodegradable surfactants often required magnetic stirring followed by sonication.

[0140] Once dissolved, the aqueous solution is mixed with mineral silicone oil in a 50 / 50 volume / volume ratio. The emulsion is maintained by magnetic stirring and sampled for addition to the corresponding bottles to achieve the required test article concentration.

[0141] Of course, two emulsion controls are run in parallel during the study to eliminate those values ​​coming from the emulsion bottles containing the test article added with the emulsion concentrate.

[0142] The results of the biodegradability tests are summarized in Table 1 below.

[0143] [Table 1]

[0144] As can be seen in the table above, C 16 :C 18 = 60.9:38.2% by weight C 16 ~C 18 The mixture of quaternary ammonium compounds of formula I derived from a mixture of fatty acids showed a final biodegradation rate of 67.5% and can therefore be considered readily biodegradable. 16 :C 18= 33.7:65.3% by weight C 16 ~C 18 The mixture of quaternary ammonium compounds of formula I derived from a mixture of fatty acids exhibited a lower biodegradation rate of 50.4% and cannot be considered readily biodegradable.

[0145] These results clearly show that the hydrocarbon chain length distribution in the final mixture of compounds of formula I (and therefore in the starting mixture of fatty acids) has a dramatic effect on biodegradability.

[0146] Further Experiments Additional mixtures of quaternary ammonium compounds of formula I were prepared by mixing the previous mixtures obtained in Examples 1 and 2 in two different ratios (one according to the invention, the other as a comparison), and biodegradability assessment was carried out according to the same method as above, the results of which are shown in Table 2 below.

[0147] [Table 2]

[0148] Conclusion: The ready biodegradation (meaning in this case 60% for BOD>DThO after 28 days) for the mixture of quaternary ammonium compounds of formula I is 16 ~C 18 C in the starting fatty acid material of 45 mol% or more for fatty acid mixture raw material 16 C at 20 mol% or more of the hydrocarbon chain length distribution corresponding to the fatty acid content 31 Content (31 mol% or less of C 35 The results are obtained in terms of the content.

[0149] In other words, ready biodegradation occurs when the average hydrocarbon chain length in the mixture of quaternary ammonium compounds of formula I is less than or equal to C 33 is obtained with respect to

Claims

1. Formula I 【Chemical 1】 (In the formula, the R groups, which may be the same or different in each occurrence, are C １５ or C １７ aliphatic groups, Y is a divalent C １ to C ６ aliphatic group, The R', R'', and R''' groups, which may be the same or different, are hydrogen or C １ to C ４ alkyl groups, X ｎ－ is halide (n = 1), the formula R ａ -O-SO ２ -O － (wherein R ａ is a C １ to C ２０ which may be optionally halogenated, preferably C １ to C ６ hydrocarbyl group) of hydrocarbyl sulfate anion (n = 1), the formula R ａ -SO ２ -O － (wherein R ａ is a C １ to C ２０ which may be optionally halogenated, preferably C １ to C ６ hydrocarbyl group) of hydrocarbyl sulfonate anion (n = 1), the formula SO ４ ２－ of sulfate anion (n = 2), the formula HSO ４ － of hydrogen sulfate (i.e., bisulfate) anion (n = 1), the formula CO ３ ２－ of carbonate anion (n = 2), the formula HCO ３ － of hydrogen carbonate (i.e., bicarbonate) anion (n = 1), the formula H ２ PO ４ － the dihydrogen phosphate anion (n = 1), the formula HPO ４ ２－ the hydrogen phosphate anion (n = 2), the formula PO ４ ３－ the phosphate anion (n = 3), the formula R ａ (CO ２ － ) ｎ (wherein R ａ is a C １ to C ２０ hydrocarbyl group optionally substituted by a heteroatom-containing group, preferably a C １ to C ６ hydrocarbyl group) of the organic carboxylic acid anion (n = 1, 2 or 3), and these mixtures is a counter anion selected from the group consisting of, n is an integer equal to 1, 2 or 3 depending on the nature of the counter anion) a mixture of compounds of, 20 to 95 mol% of the compound of formula I (wherein both R groups are C １５ an aliphatic group).

2. The R group is a C １５ or C １７ alkyl group, and the mixture comprises 20 to 95 mol% of the compound of formula I (wherein both R groups are C １５ an alkyl group), the mixture according to claim 1.

3. The R group is a C １５ or C １７ linear alkyl group, and the mixture comprises 20 to 95 mol% of the compound of formula I (wherein both R groups are C １５ a linear alkyl group), the mixture according to claim 1 or 2.

4. Y is a methylene group, the mixture according to claim 1 or 2.

5. The mixture according to claim 1 or 2, wherein R’, R’’ and R’’’ are methyl.

6. X ｎ－ is a halide with n = 1, the mixture according to claim 1 or 2.

7. 20 to 60 mol%, preferably 30 to 50 mol% of a compound of formula I (wherein both R groups are C １５ an aliphatic group, preferably an alkyl group, especially a straight-chain alkyl group), the mixture according to claim 1 or 2.

8. ・ 20 to 95 mol%, preferably 20 to 60 mol%, more preferably 30 to 50 mol% of a compound of formula I (wherein both R groups are C １５ a straight-chain alkyl group), ・ 4.9 to 50 mol%, preferably 35 to 50 mol%, more preferably 41 to 50 mol% of a compound of formula I (wherein one R group is C １５ a straight-chain alkyl group and the other R group is C １７ a straight-chain alkyl group), and ・ 0.1 to 31 mol%, preferably 5 to 31 mol%, more preferably 9 to 20 mol% of a compound of formula I (wherein both R groups are C １７ a straight-chain alkyl group) comprising the mixture according to claim 1 or 2.

9. Less than 5 mol%, preferably less than 2 mol% of a compound of formula I (wherein at least one of said R groups, which may be the same or different in each occurrence, is C ７ to C １３ an aliphatic group and / or C １９ to C ２１ an aliphatic group), further comprising the mixture according to claim 1 or 2.

10. A process for producing a mixture of compounds of formula I according to claim 1 or 2, starting from a mixture of fatty acids R-COOH (wherein R is C １５ or C １７ an aliphatic group), and said mixture of fatty acids comprises 45 to 98 mol% of R-COOH (wherein R is C １５ A method comprising an aliphatic group). Claim 11 Fatty acids R-COOH (wherein R is C １５ or C １７ Starting from a mixture of linear alkyl groups), and the mixture of fatty acids is 45 to 78 mol%, more preferably 55 to 71 mol% of R-COOH (wherein R is C １５ A linear alkyl group), the method according to claim 10. Claim 12 The following steps: a. A mixture of fatty acids R-COOH (wherein R is C １５ or C １７ An aliphatic group), a mixture containing 45 to 98 mol% of R-COOH in which R is an aliphatic group is decarboxylative ketonized in the presence of a metal catalyst, thereby obtaining a mixture of internal ketones of formula VI: R-C(=O)-R (VI) (wherein the R groups, which may be the same or different in each occurrence, are as defined above); １５ b. The mixture of internal ketones of formula VI obtained in step a is hydrogenated in the presence of H and a catalyst, thereby obtaining a mixture of secondary alcohols of formula V: R-CH(OH)-R (V) (wherein the R groups, which may be the same or different in each occurrence, are as defined above); ２ c. The mixture of secondary alcohols of formula V obtained in step b is reacted with a compound of formula IV: [L-Y-CO H] ２ [U （ｔ－１）－ ] ｕ＋ ](IV) （ｔ－１）／ｕ (wherein L is a leaving group, t is an integer equal to 1 or greater than or equal to 2, U is a cation, ｕ＋ u is an integer that fixes the positive charge of the cation, Y is as described in claim 1, and the R groups are as described above). Esterify with a carboxylic acid reagent, thereby obtaining a mixture of monoesters of formula III: 【Chemical Formula 2】 (wherein R 、 Y, L, t, U and u are as described above) to obtain a mixture of monoesters of formula III; and d. Condensing the mixture of monoesters of formula III obtained in step c. with an amine of the formula R', R'', R''', N (wherein R', R'' and R''', which may be the same or different, are hydrogen or C １ ~C ４ alkyl group) to obtain a mixture of compounds of formula II: 【Chemical Formula 3】 (wherein R, R', R'', R''', Y, L and t are as described above) to obtain a mixture of compounds of formula II; and e. Optionally, when L ｔ－ is different from X ｎ－ , anion exchange by contacting with a salt of the formula [U' ｎ－ ｔ－ X ｕ’＋ (where X and n are as described in claim 1, and U' ｎ／ｕ’ is a cation and u' is an integer that fixes the positive charge of the cation) to replace L ｎ－ with X ｕ’＋ ; and f. Recovering the mixture of compounds of formula I according to claim 1 The method according to claim 10, comprising

13. L ｔ－ is equal to X ｎ－ as described in claim 1, and the compound of formula II is equal to the compound of formula I, the method according to claim 12

14. The method according to claim 12, comprising the step e. of anion exchange

15. Use of the mixture of compounds of formula I according to claim 1 or 2 as a surfactant

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