ORGANIC AMMONIUM SALTS WITH TRACEABILITY AND DETERGENT DISPERSANT PROPERTIES TO LIQUID FUELS AND PROCESSES FOR THEIR SYNTHESIS

Abstract

The present invention is related to a process for obtaining organic ammonium salts (OAS) and their derivatives, supramolecular surfactants (SS), which simultaneously present the properties of traceability and detergents dispersant of organic scales. Organic ammonium salts (OAS) and their derivatives supramolecular surfactants (SS) have applications as differentiators, markers, or tracers in fuels derived from hydrocarbons; and also to disperse organic scales or inhibit the gums precipitation both in injectors and intake valves of automotive vehicle engines. Organic ammonium salts (OAS) are obtained through an acid-base reaction between a molecule from the azo family and an amine. Once the OAS is obtained, it reacts with an organic compound (OC) so that through non-covalent interactions, a self-assembly process occurs that gives rise to the SS. Said process is based on green chemistry, that is, in the absence of solvents. These OAS and SS are quantified through the analytical techniques of ultraviolet-visible (UV-VIS) and high-performance liquid chromatography (HPLC) through a calibration curve. Additionally, its performance as a gum-dispersing agent in a single-cylinder engine is evaluated.

Claims

1. An organic ammonium salt of an AZO type compound and an A type compound, wherein: the AZO type compound has structural formula (4): ##STR00013## wherein: R.sub.1: is a linear or branched alkyl or alkenyl chain ranging from C.sub.1 to C.sub.30 or a cycloalkyl or aryl group from C.sub.5 to C.sub.12. It can also be aromatic, benzyls, naphthols, naphthylamines, or dimethyl anilines substituted with electron donors such as NH.sub.2, OH, alkyl, and/or electro-attractors such as COOR (ester), CO (ketone), COOH, CN, NO.sub.2, SO.sub.3H; Ar: aromatic, such as an aryl, naphthol, naphthylamide, dimethylaniline, indole, pyrrole, pyrazolone, or substituted quinolones; and R.sub.2: is a substituent of a protic and/or acidic nature, such as COOH, SO.sub.3H, OH; and the A type compound has structural formula (5): ##STR00014## wherein: R.sub.3: is H or a linear or branched alkyl or alkenyl chain from C.sub.1 to C.sub.32, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12, or aromatics, benzyls, naphthols, naphthylamines, or substituted dimethyl anilines; R.sub.4: is H, or a linear or branched alkyl or alkenyl chain from C.sub.1 to C.sub.32, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12 or aromatics, benzyls, naphthols, naphthylamines or substituted dimethyl anilines; and R.sub.5: can be a linear or branched alkyl or alkenyl chain from C.sub.1 to C.sub.32, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12, or primary, secondary or tertiary amino alcohols, linear or branched, cyclic or aromatics and/or derived from poly-isobutenyl-succinic anhydrides, poly-isobutylene, poly-isobutenylphenols or Mannich bases.

2. The organic ammonium salt according to claim 1, wherein the AZO type compound is selected from: tartrazine (CI acid yellow 23), methyl red, eriochrome black (acid and base form), orange II (CI acid orange 7), Dark Benzo Green B (CI Direct Green I), Congo Red (CI Direct Red 28), Acid Blue 113 (CI Acid Blue 113), Direct Orange 18, Acid Brown 145, Acid Red 183, Methyl Orange, Sudan Red G, Sudan III, DC Red 7, flamingo red, FDC, red 40, carmoisine, sunset yellow, citrus red 2, chocolate brown, PN black, oil red O, methanol yellow, oil orange SS, Sudan IV, amaranth (acid and basic form), orange yellow S, red 2G, tartrazine (tris-acid, bis-acid and mono-acid forms), bis-azo dyes with acid groups, and any other molecule that satisfies the structural formula (4).

3. The organic ammonium salt according to claim 1, wherein the salt is an AZO:A salt of structural formula (13): ##STR00015##

4. A process to prepare the organic ammonium salt of claim 1, wherein the process comprises an acid-base reaction between an AZO type compound of structural formula (4) and an A type compound of structural formula (5) without solvents.

5. The process, according to claim 4, wherein the organic ammonium salt is obtained in a single step with no byproducts.

6. The process according to claim 4, wherein the process comprises mixing the AZO type compound and the A type compound in a stoichiometric ratio.

7. The process of claim 6, wherein the process further comprises stirring and agitating for 10-240 minutes, preferably from 20-120 minutes, at a temperature from 10-120? C., preferably from 10-90? C.

8. A supramolecular surfactant of structural formula (14): ##STR00016## wherein the surfactant comprises an AZO:A organic ammonium salt according to claim 3, non-covalently interacting with an organic compound CO of structural formula (6), ##STR00017## wherein: R.sub.6: is hydrogen, or a linear or branched alkyl or alkenyl chain ranging from C.sub.1 to C.sub.32, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12, or substituted aromatic and/or derived from poly-isobutenyl-succinic anhydrides, poly-isobutylene, poly-isobutenylphenols or Mannich bases; R.sub.7: is a linear or branched alkyl or alkenyl chain ranging from C.sub.1 to C.sub.32, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12, or substituted aromatic; R.sub.8: is hydrogen, or a linear or branched alkyl or alkenyl chain ranging from C.sub.1 to C.sub.32, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12, or substituted aromatic with OH and NH.sub.2 groups; n: it has values between zero and four; D.sub.1: nitrogen with substituents R.sub.6 and R.sub.7; and D.sub.2: is selected from oxygen, nitrogen, or sulfur as a substituent of the R.sub.8 group.

9. The supramolecular surfactant of claim 8, wherein the surfactant comprises the AZO:A organic ammonium salt according to claim 3 and the OC organic compound of structural formula (6) in a stoichiometric ratio from 4:1 to 1:4, and preferably in the interval from 1.1 to 1:2.

10. A process for the preparation of a supramolecular surfactant according to claim 8, wherein the process can comprise either Route 1 or Route 2 ##STR00018## Route 1: mixing an AZO type compound, and an A type compound in a stoichiometric ratio, and adding an organic compound CO in a stoichiometric ratio of 1 to 4 relative to the AZO molecule, preferably 1 to 2; then agitating the mixture for 10-240 minutes, preferably from 20-120 minutes, at a temperature from 10-120? C., preferably from 10-90? C.; Route 2: mixing an organic ammonium salt OAS of claim 3 with an organic compound OC, in stoichiometric ratio from 4:1 to 1:4, preferably a ratio of 1:1 to 1:2; then agitating and homogenizing the mixture mechanically for 10-240 minutes, preferably between 20-120 minutes, at a temperature from 10-120? C., preferably from 10-90? C.

11. The process of claim 10, Route 1 or Route 2 are mass reactions without solvents.

12. The process of claim 10, wherein Route 1 or Route 2 occurs in the presence of an organic solvent, selected from benzene, xylene, xylenes, toluene, light aromatic naphtha, heavy aromatic naphtha, diesel, gasoline, chloroform, and aromatics mixture.

13. The process of claim 12, wherein the solvent proportion relative to the supramolecular surfactant is from 10 to 80% by weight, preferably from 20-70% by weight.

14. Use of an organic ammonium salt of claim 1 or a supramolecular surfactant derivative thereof as an additive at a concentration of at least 6 ppm, in a liquid fuel, such as gasoline, turbosine, or diesel.

15. The use according to claim 14, wherein said organic ammonium salt or supramolecular surfactant derivative thereof are at a concentration of from 12 and 24 ppm and inhibit gum deposits in a single-cylinder engine by up to 75%.

16. The use according to claim 14, wherein the use is in a gasoline that contains oxygenated compounds such as ethers and/or alcohols.

17. The use according to claim 14 wherein said organic ammonium salts and supramolecular surfactants are employed in: (a) a gasoline-ethanol mixture in volume percentage from 0:100 to 99:2, preferably between 80:20 and 95:5; (b) a gasoline mixture with methanol and isopropanol (2-propanol) in volume percentage ratios gasoline-methanol-isopropanol from 90:2:8 to 94:1:5, preferably between 90:5:5 to 90:1:4.

18. A process to determine the concentration of an organic ammonium salt of claim 1 or a supramolecular surfactant derivative thereof, through UV-VIS spectroscopy, as tracers, markers, differentiators, or dyes in liquid fuels with an error low to 5%, characterized in that it comprises: a) determine the maximum absorbance (A.sub.max) at a wavelength (?.sub.max) of organic ammonium salts and supramolecular surfactants in the presence of liquid fuels as a solvent; b) the additivation of liquid fuel with an organic ammonium salt or supramolecular surfactant at a concentration from 0.5 ppm onwards; c) generate the calibration curve; and d) determine the concentration of organic ammonium salts and/or their derivatives supramolecular surfactants in the liquid fuel employing the calibration curve equation that satisfies the Lambert-Beer's law.

19. The process, conforming to claim 18, characterized in that the liquid fuel is regular gasoline.

20. The process, conforming to claim 18, characterized in that it is done without conditioning or pretreatment of the sample to analyze in the absence and in the presence of additional additives.

21. A process to determine the concentration of an organic ammonium salt according to claim 1 or a supramolecular surfactant derivative thereof through high-performance liquid chromatography, as tracers, markers, differentiators, or dyes in liquid fuels with an error low to 5%, characterized in that comprise: a) the additivation of liquid fuel with organic ammonium salts or supramolecular surfactants in concentrations from 0.5 ppm to 100 ppm; b) in the chromatograph program the detector at 460 nm and inject the samples to obtain the chromatogram; c) determines the retention time from chromatogram and the area under the curve corresponding to the signal of the sample analyzed; d) built the corresponding calibration curve with the values of the area under the curve at the retention time determined; e) determine the concentration of the organic ammonium salts and/or their derivatives supramolecular surfactants in the liquid fuel employing the calibration curve equation that satisfies the Lambert-Beer's law.

22. The process according to claim 21, characterized in that the liquid fuel is regular gasoline.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Drawings that accompany the present invention are described below to have a better understanding of the objects without thereby limiting their scope.

[0048] FIG. 1 shows the spectrum and representative FT-IR bands of supramolecular surfactant 1 (SS-1).

[0049] FIG. 2 shows the comparative NMR .sup.13C (CDCl.sub.3) spectra of methyl red (AZO), oleylamine (A), oxazolidine derived from poly alkenyl N-hydroxyalkyl succinimide (OC), and supramolecular surfactant 1 (SS-1).

[0050] FIG. 3 presents the spectrum and representative FT-IR bands of supramolecular surfactant 2 (SS-2).

[0051] FIG. 4 shows representative .sup.13C NMR (CDCl.sub.3) spectra of methyl red (AZO), hydroxy-ethylamine-ethyl poly alkenyl succinimide (A), the oxazolidine derived from poly alkenyl N-hydroxyalkyl succinimide (OC), and supramolecular surfactant 2 (SS-2).

[0052] FIG. 5 illustrates the comparative FT-IR spectra and bands of phenol (OC), organic ammonium salt 1 (OAS-1), and supramolecular surfactant 3 (SS-3).

[0053] FIG. 6 shows representative chemical shifts in ? (ppm) in .sup.13C NMR (CDCl.sub.3) of phenol (OC), organic ammonium salt 1 (OAS-1), and supramolecular surfactant 3 (SS-3).

[0054] FIG. 7 shows the calibration curve, A.sub.max vs. concentration of organic ammonium salt 1, OAS-1.

[0055] FIG. 8 shows the calibration curve, A.sub.max vs. concentration of organic ammonium salt 1, OAS-4.

[0056] FIG. 9 illustrates the calibration curve, A.sub.max vs. concentration of supramolecular surfactant SS-1.

[0057] FIG. 10 exhibits the calibration curve, A.sub.max vs. concentration of supramolecular surfactant SS-2.

[0058] FIG. 11 shows the calibration curve, A.sub.max vs. concentration of supramolecular surfactant SS-3.

[0059] FIG. 12 shows the calibration curve obtained by HPLC of organic ammonium salt 1, OAS-1, in regular gasoline.

DETAILED DESCRIPTION OF THE INVENTION

[0060] The present invention describes the process for obtaining organic ammonium salts (OAS) and their corresponding supramolecular surfactants (SS) derivatives with traceability properties, which can be applied in liquid hydrocarbons as a tracer, marker, differentiator, or dyes. Besides, these organic ammonium salts and their supramolecular surfactant derivatives also function as detergent-dispersant agents of organic deposits (organic scales) and/or gums in storage tanks and pipes, as well as in auto motor vehicles components, such as intake and injection valves. These organic scales typically are generated in liquid hydrocarbons from an olefin compounds polymerization process and organic compounds containing donor atoms or heteroatoms such as nitrogen and sulfur in their structure. And are present in these liquid hydrocarbons, whereby these OAS and SS are ideal for solving the technical problems mentioned before.

[0061] Such organic ammonium salts (OAS) and their supramolecular surfactant derivatives (SS) are multifunctional by presenting the following functions: traceability, which permits marking in liquid hydrocarbons; and detergent dispersant of organic scales and gums, which allows having intake and injection valves free of deposits of motor vehicles. Said characteristics made these organic ammonium salts and their supramolecular surfactants derivatives of the present invention novelty and different to additive packs, additive kits, or formulations or synergistic formulations described in the background.

[0062] It also is highlighted that through analytic techniques of UV-VIS (ultraviolet-visible spectroscopy) and HPLC (high-performance liquid chromatography), it is feasible to detect and quantify the organic ammonium salts and their supramolecular surfactant derivatives in liquid hydrocarbons object of the present invention, as much as in the absence and presence of additional additives that, traditionally, are added to liquid hydrocarbons. Additional additives may include corrosion inhibitors, demulsifiers, oxygen agents, anti-polymerizers, octane enhancers, detergents, and/or co-detergents. Which ones do not have interference in the quantification of the organic ammonium salts and their supramolecular surfactant derivatives with traceability and detergent dispersant properties. That represents an advantage that permits determining if an additive fuel with organic ammonium salts and/or their supramolecular surfactants has suffered some adulteration type, the object of the present invention.

[0063] Organic ammonium salts and/or their supramolecular surfactants can be employed in different fuel types, such as types of gasoline, mixtures of gasoline-ethanol in volume percentages between 0:100 until 99:2, preferably between 80:20 and 95:5; blends of gasoline with methanol or isopropanol (2-propanol) in % volume gasoline-methanol-isopropanol ratios from 90:2:8 to 94:1:5, preferably between 90:5:5 to 90:1:4.

[0064] The liquid fuels do not need any conditioning, pretreatment, or other preparation to quantify the organic ammonium salts and/or their supramolecular surfactants to be evaluated in this process. Therefore, the detection and quantification process can be done directly in the liquid fuels additived with organic ammonium salts and/or their supramolecular surfactant derivatives, objects of the present invention.

[0065] The organic ammonium salts (OAS) of the present invention are the product of an acid-base reaction between an azo compound that contains in its chemical structure protic functional groups, such as acids (carboxylic, sulphonic or similar) and alcohols (AZO type compounds) with amines and/or amino alcohols (A), wherein the acid and protic groups in the azo type compounds (AZO) are preferably selected of the chemical family COOH, SO.sub.3H, OH; while the amines (A) can be primary, secondary, and/or tertiary with linear and/or branched hydrocarbon chains and/or with an alkenyl chain from C.sub.1 to C.sub.32 and/or derived from poly-isobutenyl-succinic anhydrides, poly-isobutylene, poly-isobutenylphenols or Mannich bases; and the amino alcohols can be primary, secondary or tertiary, linear or branched, cyclic or aromatic and/or derived from poly-isobutenyl-succinic anhydrides, poly-isobutylene, poly-isobutenylphenols or Mannich bases.

[0066] Ammonium salts (OAS) have the general formula AZO:A, which allows them to have the capacity to form intermolecular interactions with organic compounds (CO) that contain heteroatoms or donor atoms in their structure, preferably oxygen, nitrogen, and sulfur: of the chemical families of phenols, oxazolidines, succinimides, imidazolines and naphthols, which, when interacting with AZO type compounds and A type compounds, give rise to their corresponding supramolecular surfactants (SS).

[0067] Said supramolecular surfactants are formed through hydrogen bonding, Van der Waals forces, dipole-dipole, ion-dipole, ion-ion, ?-?, and ?-cation interactions. Providing to the supramolecular surfactant has traceability properties with improved detergency properties and dispersion of organic incrustations and gums.

[0068] Organic ammonium salts (OAS) have the general formula AZO:A. Supramolecular surfactants (SS) derived from organic ammonium salts (OAS) and organic compounds (CO) have the general formula OAS:CO in a stoichiometric ratio that can vary from 4:1 to 1:4, preferably in the range from 1:1 to 1:2, where OAS contains the AZO and A groups.

[0069] Next, Scheme 2 describes the synthesis route for organic ammonium salts (OAS) consisting of an acid-base reaction between the AZO type compound and the A type compound. And Scheme 3 exposes the synthesis routes corresponding to supramolecular surfactants (SS) with traceability, marker, differentiator, or dye properties that can be used in hydrocarbon-derived liquid fuels and which is based on self-assembly by non-covalent interactions, which gives rise to a surfactant supramolecular.

##STR00002##

##STR00003##

wherein:

[0070] An AZO type compound is a compound from the azo family of structural formula (4):

##STR00004##

wherein: [0071] R.sub.1: is a linear or branched alkyl or alkenyl chain ranging from C.sub.1 to C.sub.30 or a cycloalkyl or aryl group from C.sub.5 to C.sub.12. It can also be aromatic, benzyls, naphthols, naphthylamines, or dimethyl anilines substituted with electron donors such as NH.sub.2, OH, alkyl, and/or electro-attractors such as COOR (ester), CO (ketone), COOH, CN, NO.sub.2, SO.sub.3H; [0072] Ar: is aromatic, such as an aryl, naphthol, naphthylamide, dimethylaniline, indole, pyrrole, pyrazolone, or substituted quinolones groups; [0073] R.sub.2: is a substituent of a protic and/or acidic nature, such as COOH, SO.sub.3H, OH.

[0074] Among the AZO-type compounds (or molecules) that satisfy these conditions are the following: tartrazine (CI acid yellow 23), methyl red, eriochrome black (acid and base form), orange II (CI acid orange 7), Dark Benzo Green B (CI Direct Green I), Congo Red (CI Direct Red 28), Acid Blue 113 (CI Acid Blue 113), Direct Orange 18, Acid Brown 145, Acid Red 183, Methyl Orange, Sudan Red G, Sudan III, DC Red 7, flamingo red, FDC, red 40, carmoisine, sunset yellow, citrus red 2, chocolate brown, PN black, oil red O, metanil yellow, oil orange SS, Sudan IV, amaranth (acid and basic form), orange yellow S, red 2G, tartrazine, bis-azo dyes with acid groups and any other molecule that satisfies the chemical description of the AZO-type molecule, which does not limit the scope of this invention.

[0075] Type A compounds are compounds of structural formula (5), which can include primary, secondary, or tertiary amines, or alkyl, cyclic, linear, or branched amino alcohols:

##STR00005##

wherein: [0076] R.sub.3: is H or a linear or branched alkyl or alkenyl chain from C.sub.1 to C3.sub.2, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12. They can also be aromatic groups, such as benzyls, naphthols, naphthylamines, or substituted dimethyl anilines; [0077] R.sub.4: is H, or a linear or branched alkyl or alkenyl chain from C.sub.1 to C.sub.32, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12. They can also be aromatic groups, such as benzyls, naphthols, naphthylamines or substituted dimethyl anilines, or groups derived from poly-isobutylene, poly-isobutenyl-succinimides, poly-isobutenyl-amines, poly-isobutenyl-phenols, or poly-isobutenyl-phenol-amines; [0078] R.sub.5: can be a linear or branched alkyl or alkenyl chain from C.sub.1 to C.sub.32, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12, or a hydroxyalkyl group, wherein the length of the alkyl group is from C.sub.2 to C.sub.6.

[0079] Organic Compounds (OC) are compounds of structural formula (6) that contain in their chemical structure heteroatoms or donor atoms (D):

##STR00006##

wherein: [0080] R.sub.6: can be hydrogen, or a linear or branched alkyl or alkenyl chain ranging from C.sub.1 to C.sub.32, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12, or substituted aromatic and/or derived from poly-isobutenyl-succinic anhydrides, poly-isobutylene, poly-isobutenylphenols or Mannich bases; [0081] R.sub.7: can be a linear or branched alkyl or alkenyl chain ranging from C.sub.1 to C.sub.32, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12, or substituted aromatic;

[0082] R.sub.8: can be hydrogen, or a linear or branched alkyl or alkenyl chain ranging from C.sub.1 to C.sub.32, or a cycloalkyl or aryl group from C.sub.5 to C.sub.12, or substituted aromatic;

[0083] n: can have values between zero and four;

[0084] D.sub.1: nitrogen with substituents R.sub.6 and R.sub.7;

[0085] D.sub.2: can be oxygen, nitrogen, or sulfur as a substituent for the R.sub.8 group.

[0086] Among the compounds that satisfy the OC characteristics are amino alcohols of the aromatic type, which can be derivatives of aminophenol in its different substitutions, aminonaphthol derivatives, aminoquinoline, amino resorcinol, and aromatic rings with OH and NH.sub.2 substituents. This is not limited to the families described here but also to their derivatives containing the mentioned characteristics.

[0087] The obtention process of the organic ammonium salts (OAS) and their supramolecular surfactants (SS) derivatives from (OAS) of the present invention was carried out according to the following procedures:

[0088] Synthesis of OAS: Through an acid-base mass reaction and in the absence of solvents, the stoichiometric quantity in mol of the compounds AZO and A is placed in a reactor, following scheme (2). The reaction occurs at a temperature between 15-100? C., preferably between 20-80? C., with constant mechanical stirring to homogenize the mixture. This process takes approximately 30 minutes to 4 hours, preferably between 1-3 hours.

[0089] Synthesis of SS (Route 1): Through a mass reaction and without solvents, the stoichiometric amount in mol of the AZO, A compounds are placed in a reactor. Finally, the organic compound CO is added in a stoichiometric ratio in mol with respect to the AZO compound that can vary from 1:4 to 4:1, preferably in the range from 1:1 to 1:2, following scheme (3). The reaction occurs at a temperature between 15-150 ? C., preferably between 20-100? C., with constant mechanical stirring to homogenize the mixture. This process takes approximately 30 minutes to 4 hours, preferably between 0.1-3 hours. In the end, a product with the appearance of a paste or a highly viscous liquid is obtained.

[0090] Synthesis of SS (Route 2): Through a mass reaction and in the absence of solvents, the stoichiometric amount of the OAS and CO compounds are placed in a reactor with a stoichiometric ratio in mol that can vary from 4:1 to 1:4, preferably in the range from 1:1 to 1:2, following scheme (3). The reaction occurs at a temperature between 15-150? C., preferably between 20-100? C., with constant mechanical stirring to homogenize the mixture. This process takes approximately 30 minutes to 4 hours, preferably between 0.1-3 hours. In the end, a product with the appearance of a paste or a highly viscous liquid is obtained.

[0091] No solvents are used during the synthesis of OAS and SS. It is a mass reaction that does not generate byproducts, which makes this process friendly to the environment and is within the field of green chemistry.

[0092] Nevertheless, said products can also be obtained in the presence of solvents without affecting the final products' performance and properties. If necessary, the solvents used for these purposes can be polar: primary, secondary, tertiary, or aromatic alcohols; ketone, tetrahydrofuran, dioxane, ethyl acetate, acetic anhydride, and acetonitrile. Solvents can be non-polar: chloroform, pentane, hexane, heptane, octane, cyclohexane, types of gasoline, kerosene, light or heavy aromatic naphtha, benzene, toluene, and xylenes, as well as the corresponding mixtures in any proportion between polar and non-polar. It is not even limited to using water and its combinations with alcohols.

[0093] The characterization of the OAS and the SS is carried out through FT-IR spectroscopy, and the shift of the vibration frequencies where the characteristic bands of the functional groups of the AZO, A, and CO type compounds appear, which can be determined supramolecular interactions between these molecules. These displacements have been studied and evidenced in several scientific articles as proof that a supramolecular assembly has occurred (J. Donon, S. Habka, T. Very, F. Charnay-Pouget, M. Mons, D. J. Aitken, V. Brenner, E. Gloaguen. Chem. Phys. Chem. 2021, 22, 2442; S. Habka, T. Very, J. Donon, V. Vaquero-Vara, B. Tardivel, F. Charnay-Pouget, M. Mons, D. J. Aitken, V. Brenner. E. Gloaguen. Phys. Chem. Chem. Phys. 2019, 21, 12798; C. Chi, X. Li, Y. Zhang, L. Li, Z. Wang. Food Funct. 2017, 8, 720; M. Shirakawa, S. I. Kawano, N. Fujita, K. Sada, S. Shinkai. J. Org. Chem. 2003, 68, 5037; MX338862). Also, through the .sup.1H and .sup.13C Nuclear Magnetic Resonance technique, supramolecular assemblies can be characterized through the variations in chemical shifts (8 in ppm) of the corresponding functional groups with respect to the original raw materials, which gives experimental evidence supporting the FTIR finding that supramolecular assembly has occurred (A. Pastor, E. Martinez-Viviente. Coord. Chem. Rev. 2008, 252, 2314; P. S. Denkova, L. Van Lokeren, I. Verbruggen, R. Willem. J. Phys. Chem. B 2008, 112, 10935; M. Pons, P. Bernardo. Supramolecular Chemistry in Encyclopedia of Nuclear Magnetic Resonance, John Wiley & Sons. Ltd. Chichester, 2002, MX338862). Additionally, through UV-VIS, the absorption maximum and the absorptivity coefficient (?) can be calculated, which is a unique parameter that distinguishes one substance from another. The change in this coefficient ? is derived from the formation of charge transfer complexes due to supramolecular interactions, which is due to changes in the absorption band's intensity or the displacement of its wavelength (Spectroscopy Studies of Macrocyclic Supramolecular Assembly. 2019 In: Liu Y., Chen Y., Zhang H Y. (eds) Handbook of Macrocyclic Supramolecular Assembly. Springer, Singapore; Analytical Methods in Supramolecular Chemistry 2007. Ed. By C. Schalley, Wiley-VCH).

[0094] Examples. The following examples are presented to illustrate the process of obtaining and using organic ammonium salts (OAS) and supramolecular surfactants (SS) that have traceability and dispersant detergency properties for liquid fuels. These examples should not be considered as limiting what is claimed here.

[0095] Example 1. Synthesis of the organic ammonium salt, OAS-1. The organic ammonium salt 1 (OAS-1) is prepared through a reaction without solvents. 2 g of methyl red (AZO type compound) and 2 g of oleylamine (type A compound) are placed in a reactor, using the general formula AZO:A for organic ammonium salts in a molar ratio 1:1. It is mixed at 80? C. with mechanical stirring for 30 minutes. The final product (OAS-1) is obtained as a red paste and is soluble in hydrocarbons (7).

[0096] The characterization of the organic ammonium salt 1 (OAS-1) derived from this process is shown below:

[0097] Representative FT-IR bands (cm.sup.?1): 3369, 3055, 3002, 2921, 2852, 1599, 1559, 1515, 1465, 1363, 1311, 1247, 1230, 1140, 1089, 1064, 946, 849, 821, 761, 725, 665.

[0098] Representative chemical shifts ? (ppm) in .sup.1H NMR (600 MHZ, CDCl.sub.3): 7.79, 7.67, 7.61, 7.33, 7.27, 6.90, 6.58, 5.34, 2.91, 2.44, 1.98, 1.27, 1.20, 1.09, 0.99, 0.87.

[0099] Representative chemical shifts ? (ppm) in .sup.13C NMR (151 MHZ, CDCl.sub.3): 174.70, 152.43, 150.02, 143.52, 129.86, 129.83, 128.83, 125.39, 116.72, 111.55, 40.16, 39.73, 31.91, 29.79, 29.76, 29.35, 29.33, 27.24, 22.69, 14.14.

##STR00007##

[0100] Example 2. Synthesis of the organic ammonium salt, OAS-2. The organic ammonium salt 2 (OAS-2) is prepared through a reaction without solvents in a molar ratio of 1:1 at 40? C. and mechanical stirring for 60 minutes. The reaction occurs between methyl red and N-benzyl ethanolamine. The final product is obtained as an orange-red paste and is soluble in methanol (8).

[0101] The characterization of the OAS-2 derived from this process is shown below:

[0102] Representative FT-IR bands (cm.sup.?1): 3234, 2930, 2796, 2657, 1601 1597, 1451, 1370, 1310, 1239, 1144, 1087, 949, 823, 771, 704, 665.

[0103] Representative chemical shifts ? (ppm) in .sup.1H NMR (600 MHZ, MeOD): 7.79, 7.74, 7.72, 7.53, 7.52, 7.39, 7.31, 7.25, 7.23, 6.65, 6.63, 3.94, 3.62, 3.20, 2.93, 2.84, 1.17.

[0104] Representative chemical shifts ? (ppm) in .sup.13C NMR (151 MHz, MeOD): 177.54, 154.08, 150.42, 145.02, 140.77, 134.16, 130.70, 130.01, 130.01, 129.97, 129.30, 128.19, 126.28, 117.41, 112.47, 79.44, 58.55, 52.31, 50.17, 40.42.

##STR00008##

[0105] Example 3. Synthesis of the organic ammonium salt, OAS-3. It is prepared through a reaction without solvents in a molar ratio of 1:1 at 40?C and mechanical stirring for 60 minutes. The reaction occurs between methyl red and decylamine. The final product is obtained as a yellow paste and is soluble in hydrocarbons (9).

[0106] The characterization of the organic ammonium salt 3 (OAS-3) derived from this process is shown below:

[0107] Representative FT-IR bands (cm.sup.?1): 3433, 3054, 2918, 2851, 1628, 1603, 1522, 1411, 1395, 1368, 1316, 1231, 1144, 1093, 947, 850, 821, 757, 663, 542.

[0108] Representative chemical shifts ? (ppm) in .sup.1H NMR (600 MHz, CDCl.sub.3): 7.80, 7.78, 7.66, 7.65, 7.61, 7.60, 7.34, 7.33, 7.32, 7.28, 7.27, 7.25, 6.58, 6.56, 2.90, 2.44, 2.43, 2.42, 1.28, 1.27, 1.26, 1.24, 1.19, 1.17, 1.16, 1.14, 1.06, 0.97, 0.88, 0.87, 0.86, 0.85.

[0109] Representative chemical shifts ? (ppm) in .sup.13C NMR (151 MHZ, CDCl.sub.3): 177.86, 152.38, 150.04, 143.56, 128.83, 128.78, 128.24, 125.34, 116.75, 111.54, 40.14, 39.63, 31.92, 29.55, 29.47, 29.30, 29.04, 28.59, 22.70, 14.16.

##STR00009##

[0110] Example 4. Synthesis of the organic ammonium salt, OAS-4. The organic ammonium salt 4 (OAS-4) is prepared through a reaction without solvents in a 1:1 molar ratio at 100? C. and mechanical stirring for 30 minutes. The reaction occurs between methyl red and a hydroxy-ethylamine-ethyl-polyisobutenyl succinimide with an average molecular weight of 1168 Da; organic ammonium salt 4 (OAS-4) is obtained as a dark red paste at room temperature and is soluble in hydrocarbons (10).

[0111] The characterization is shown below:

[0112] Representative FT-IR bands (cm.sup.?1): 3489, 2952, 1773, 1704, 1603, 1528, 1468, 1389, 1366, 1312, 1276, 1230, 1165, 1146, 1113, 1086, 943, 889, 818, 764.

[0113] Representative chemical shifts ? (ppm) in .sup.1H NMR (600 MHZ, CDCl.sub.3): (d)8.20, (d)7.90, (d)7.79, (t)7.56, (t)7.46, (d)6.74, (m)5.16, 4.79, 3.65, 3.13, (m)2.92, (m)2.82, 1.41, 1.33, (m)1.10, (m)0.99.

[0114] Representative chemical shifts ? (ppm) in .sup.13C NMR (151 MHZ, CDCl.sub.3): 180.22, 177.16, 168.92, 153.71, 150.25, 143.54, 142,29, 139.46, 135.43, 132.59, 131.63, 129.69, 126.65, 115.83, 111.74, 59.88, 59.46, 59.33, 58.77, 58.15, 57.11, 50.97, 50.29, 46.19, 40.30, 39.82, 38.68, 38.10, 38.02, 37.82, 37.73, 37.55, 36.42, 34.22, 32.54, 32.41, 32.40, 31.20, 31.13, 31.12, 30.75, 29.24, 28.98, 18.95, 16.70.

##STR00010##

[0115] Example 5. Synthesis of the supramolecular surfactant, SS-1. Supramolecular surfactant-1 (SS-1) is prepared through a without-solvents reaction using synthesis route 1. Take 2 g of methyl red (AZO type compound) and 2 g of oleylamine (A type compound) are placed in a reactor in the presence of 8.95 g of an oxazolidine derived from poly alkenyl N-hydroxyalkylsuccinimide with an average molecular weight of 1,000 Da (OC type compound), at 80? C. and mechanical agitation for 30 minutes. The final product (SS-1) contains the AZO, A, and OC molecules with a 1:1:1 molar ratio in their structure. Wherein AZO and A are components of the organic ammonium salt 1 (OAS-1), in such a way that the supramolecular surfactant remains with a formula OAS: OC in a 1:1 molar ratio and it is obtained as a red paste and is hydrocarbons soluble; which also has a supramolecular surfactant structure (11).

##STR00011##

[0116] The characterization is shown below:

[0117] Representative FT-IR bands (cm.sup.?1): 3455, 2926, 1774, 1705, 1602, 1517, 1468, 1389, 1366, 1231, 1147, 1089, 947, 849, 764, 665. In the FT-IR spectrum of SS-1 (FIG. 1), the quaternization band of the oleic amine appears at 3455 cm.sup.?1; in addition, two carbonyl group signals are also observed: the first appear at 1774 cm.sup.?1 and correspond to succinimide; while the other band appears at 1705 cm.sup.?1 and corresponds to the methyl red carboxylate group, which is displaced regarding organic ammonium salt 1 (which is discussed in example 1). In such a way, these displacements concerning the original methyl red (1714 cm.sup.?1) and OAS-1 (1599 cm.sup.?1) can be deduced that a supramolecular surfactant has been formed that corresponds to SS-1.

[0118] Representative chemical shifts ? (ppm) in .sup.1H NMR (600 MHZ, CDCl.sub.3): (d)7.80, (d)7.67, (td)7.39, (t)7.32, (d)6.63, (m)5.34, 4.83, 4.26, (m)3.64, 3.36, 2.98, 2.89, 2.79, 2.49, 2.39, 2.30, (m)1.99, 1.41, (m)1.28, (m)1.10, (m)0.99.

[0119] Representative chemical shifts ? (ppm) in .sup.13C NMR (151 MHZ, CDCl.sub.3): 180.23, 177.16, 173.28, 152.72, 150.08, 143.54, 143.24, 139.45, 135.44130.44, 130.32, 130.18, 130.10, 129.88, 129.82, 129.79, 129.75, 129.03, 128.03, 127.91, 127.88, 127.67, 125.66, 116.50, 115.86, 111.58, 74.64, 59.51, 59.47, 59.33, 59.14, 59.05, 58.77, 58.16, 52.83, 50.94, 50.53, 40.20, 40.00, 39.87, 38.67, 38.21, 38.10, 38.08, 37.98, 37.94, 37.90, 37.83, 37.73, 37.57, 37.05, 36.43, 34.20, 32.62, 32.54, 32.41, 32.28, 31.91, 31.89, 31.77, 31.21, 31.13, 31.08, 31.01, 10.93, 30.73, 29.76, 29.73, 29.69, 29.66, 29.63, 29.60, 29.55, 29.52, 29.49, 29.44, 29.39, 29.36, 29.33, 29.31, 29.25, 29.17, 29.13, 29.11, 29.07, 28.98, 27.58, 27.52, 27.21, 27.18, 26.60, 22.67, 22.55, 14.13, 14.09, 13.73

[0120] In the .sup.13C NMR spectrum of SS-1 (FIG. 2), three characteristic carbonyl group signals are observed: the first two at 180.23 and 177.16 ppm corresponding to the succinimide fragment of oxazolidine derived from poly alkenyl N-hydroxyalkylsuccinimide (OC), which initially appeared at 179.81 and 176.62 ppm. Also, in SS-1, a third carbonyl signal appears at 173.28 ppm, corresponding to the carbonyl group of methyl red, which is now in the carboxylate form, while in the raw material, it appeared at 167.35 ppm. Additionally, in the spectrum of supramolecular surfactant 1, other displaced signals correspond to the aromatic groups of methyl red since they move from 154.10, 150.39, and 142.13 ppm (in the raw material) to 152.72, 150.08, and 143.24 ppm. These chemical shifts are a consequence of the supramolecular interaction between the components methyl red (AZO), oleylamine (A), and the oxazolidine derived from poly alkenyl N-hydroxyalkylsuccinimide (OC) that give rise to supramolecular surfactant 1 (SS-1).

[0121] Example 6. Synthesis of the supramolecular surfactant, SS-2. Supramolecular surfactant 2 (SS-2) was prepared through a without-solvents reaction using synthesis route 2 shown in scheme (3). 3.0000 g of organic ammonium salt 4 (OAS-4) are placed in a reactor, then 2.4730 g of an oxazolidine derived from poly alkenyl N-hydroxyalkylsuccinimide with an average molecular weight of 1,000 Da (OC type compound) are added. The reaction mixture is heated to a temperature of 100? C. and mechanical stirring for 30 minutes. The final product (SS-2) has a formula OAS:OC with a 1:1 molar ratio and contains the AZO, A, and OC molecules in a 1:1:1 ratio. SS-2 is obtained as a paste at room temperature and is soluble in hydrocarbons, which shows a supramolecular assembly (12).

##STR00012##

[0122] The characterization is shown below:

[0123] Representative FT-IR bands (cm.sup.?1): 3304, 2951, 1896, 2734, 1773, 1704, 1603, 1528, 1471, 1390, 1366, 1277, 1230, 1165, 1147, 819, 765, 688. In the FT-IR spectrum (FIG. 3) of supramolecular surfactant 2 (SS-2), the band corresponding to OH is observed at 3304 cm.sup.?1. If we compare this band with the same one from OAS-4 that appeared at 3489 cm.sup.?1, it can be seen that it moves. It is important to note that Organic Ammonium Salt 4 (OAS-4) is a precursor of Supramolecular Surfactant 2 (SS-2); therefore, the difference is that Quaternary Salt 4 has a supramolecular assembly. Other displaced bands appear at 1773 and 1704 cm.sup.?1 corresponding to the carbonyl groups of hydroxy-ethylamine-ethyl poly alkenyl succinimide (A) and oxazolidine derived from poly alkenyl N-hydroxyalkylsuccinimide (OC).

[0124] Representative chemical shifts ? (ppm) in .sup.1H NMR (600 MHZ, CDCl.sub.3): (d)8.20, (d)7.90, (d)7.79, (t)7.56, (t)7.46, (d)6.74, (m)5.16, 4.79, 3.65, 3.13, (m)2.92, (m)2.82, (m)1.41, (m)1.33, (m)1.10, (m)0.99.

[0125] Representative chemical shifts ? (ppm) in .sup.13C NMR (151 MHZ, CDCl.sub.3): 180.01, 176.02, 168.24, 153.69, 150.13, 143.39, 142.29, 139.46, 135.28, 132.59, 131.63, 129.79, 126.65, 115.83, 111.63, 59.88, 59.46, 59.33, 58.77, 58.15, 50.97, 50.29, 46.19, 40.30, 38.10, 38.02, 36.42, 34.22, 32.40, 31.20, 31.13, 31.12, 30.75, 29.74, 28.98, 18.95. In the .sup.13C NMR spectrum of SS-2 (FIG. 4), three carbonyl signals are observed at 180.01 and 176.02 ppm that correspond to the carbonyls of the succinimide groups of A and OC type compounds; the third carbonyl signal appears at 168.24 ppm corresponding to the carboxylate group of the AZO type molecule. Initially, these signals appeared in the corresponding raw materials with different chemical shifts: 180.17 and 177.07 ppm for the A type compound and 179.81 and 176.62 ppm for the Ar type compound. The displacement of the carbonyl signal of methyl red (AZO type compound) is also observed since it appeared as the carbonyl of a carboxylic acid at 167.35 ppm, and in the quaternary salt, it seems to carboxylate at 168.24 ppm. In addition, shifts are observed in the aromatic signals that appear between 154-130 ppm in methyl red (AZO type compound), and in quaternary salt 4, these signals also appear shifted. These displacements confirm what was observed in FT-IR and show that quaternary salt 4 has a supramolecular assembly.

[0126] Example 7. Synthesis of the supramolecular surfactant, SS-3. Supramolecular surfactant 3 (SS-3) is prepared through a reaction without solvents using the synthesis route 2 of the scheme (3). 4.0000 g of organic ammonium salt 1 (OAS-1) are placed in a reactor, then 0.6989 g of phenol (OC type compound) is added. The reaction mixture is brought to a temperature of 40? C. and mechanical stirring for 30 minutes. The final product (SS-3) has a formula SAO:OC with a 1:1 molar ratio and contains the AZO, A, and OC molecules in a 1:1:1 ratio. SS-3 is obtained as a highly viscous liquid at room temperature and is soluble in hydrocarbons, which shows a supramolecular assembly similar to (12).

[0127] Representative FT-IR bands (cm.sup.?1): 3190, 3049, 3011, 2922, 2852, 1598, 1521, 1468, 1406, 1365, 1309, 1250, 1139, 1089, 1033, 946, 852, 823, 759, 695, 666. In the FT-IR spectrum of SS-3 (FIG. 5), two bands that appear at 3190 and 3049 cm.sup.?1 are observed and correspond to the NH (ammonium) and OH groups, respectively. On the one hand, the OH band in phenol (OC) originally appeared at 3307 cm.sup.?1, and in SAO-1, these bands appeared at 3369 and 3055 cm.sup.?1, respectively. The displacement of these bands in SS-3, concerning the signals in the raw materials, is evidence of the supramolecular interactions of the product.

[0128] Representative chemical shifts ? (ppm) in .sup.1H NMR (600 MHZ, CDCl.sub.3): 7.78, 7.76, 7.70, 7.69, 7.65, 7.64, 7.35, 7.06, 7.05, 6.76, 6.75, 6.57, 5.56, 5.34, 5.33, 2.92, 2.45, 2.44, 2.43, 2.01, 2.00, 1.96, 1.95, 1.27, 1.27, 1.22, 1.21, 1.09, 1.08, 0.98, 0.97, 0.87, 0.86.

[0129] Representative chemical shifts ? (ppm) in .sup.13C NMR (151 MHZ, CDCl.sub.3): 175.92, 157.92, 152.50, 149.80, 143.55, 135.99, 129.96, 129.32, 129.48, 129.30, 129.04, 128.06, 125.38, 119.24, 117.07, 115.72, 111.59, 40.16, 39.77, 31.90, 29.78, 29.75, 29.54, 29.37, 2934, 29.32, 29.24, 28.98, 28.98, 28.49, 27.23, 26.49, 22.68, 14.13. In the .sup.13C NMR spectrum of SS-3 (FIG. 6), a signal is observed at 175.92 ppm corresponding to the AZO compound's carboxylate group into the organic ammonium salt 1 (OAS-1). That same signal appears at 174.70 ppm in the OAS-1 spectrum, which shows that this carboxylate group has shifted its signal and participates in a supramolecular interaction. On the other hand, the four aromatic phenol (OC) aromatic signals initially appear at 155.31, 129.72, 120.86, and 115.39 ppm, and in the spectrum of SS-3, they appear displaced at 157.92, 129.32, 119.24, and 115.72 ppm, respectively. These displacements indicate that the aromatic part of phenol (OC) is forming x-type interactions with quaternary ammonium salt 1 (OAS-1) to give rise to the formation of supramolecular surfactant 3 (SS-3).

[0130] Example 8. Determination of traceability properties through UV-VIS spectroscopy. The traceability property of some prepared organic ammonium salts (OAS) and supramolecular surfactants (SS) were evaluated. This is done through the UV-VIS technique, using gasoline as a solvent. The procedure consists of building the calibration curve of each material to be analyzed. Later, through the absorbance reading of a test sample, the absorbance value is interpolated in said calibration curve to know the concentration of the substance with traceability properties.

[0131] Equipment: UV-VIS spectrophotometer, magnetic stirrer, and analytical balance.

[0132] Materials: Volumetric flasks, volumetric pipettes, glass vials, and quartz cells with a light path length of 1 cm.

[0133] Sample to analyze: Organic ammonium salt (OAS), supramolecular surfactant (SS), solutions of known concentration of the mentioned products dissolved in regular gasoline.

Test Procedure:

[0134] a) In a 100 mL volumetric flask, prepare a standard solution at 10 000 ppm of the product to be analyzed. To do this, 0.0250 g of OAS or SS is weighed and later placed in a 25 mL volumetric flask, and regular gasoline is used as a solvent to reach the volume graduation mark. [0135] b) An aliquot of the standard solution is taken and diluted in regular gasoline to obtain at least five or more solutions in concentrations ranging from 0.5 ppm to 100 ppm. [0136] c) Next, in the UV-VIS spectrophotometer and using a quartz cell, the UV-VIS spectrum of each sample is obtained in a spectral window from 350 to 600 nm. [0137] d) In each UV-VIS spectrum, the absorbance maximum (Amax) and the wavelength at which this occurs (maximum absorption wavelength, Amax) are determined. With these A.sub.max values, a calibration curve of absorbance as a function of concentration (A.sub.max vs. concentration) is built, representing a straight line that must comply with the Lambert-Beer law. [0138] e) With the calibration curve, the specific absorptivity constant (?) is calculated at the maximum absorption wavelength value (?.sub.max). The slope of the linear fit equation corresponds to the value of the specific absorptivity constant (?). The calibration curve is done for each OAS and SS to be analyzed.

[0139] FIGS. 7, 8, 9, 10, and 11 show the linear range of absorbance as a function of the concentration of some OAS and SS, which demonstrates that organic ammonium salts (OAS) and supramolecular surfactants (SS) of the present invention can be detected as tracers, dyes, markers or differentiators in fuels in concentrations ranging from 0.5 ppm onwards, through the UV-VIS spectroscopy technique.

[0140] Table 1 shows the values obtained for the specific absorptivity constant of the ammonium salts OAS-1 and OAS-4 and the supramolecular surfactants SS-1, SS-2, and SS-3.

TABLE-US-00001 TABLE 1 Specific absorptivity constant, ? Product ?.sub.max (nm) (mL .Math. g.sup.?1 .Math. cm.sup.?1) OAS-1 461 29.7 OAS-4 464 12.5 SS-1 461 9.7 SS-2 460 5.3 SS-3 461 17.6 [0141] f) Determination of the concentration of a test sample. To show that it is feasible to determine the concentration of OAS and SS in gasoline through the determination of absorbance through the UV-Vis spectroscopy technique and the use of the generated equations, it was prepared for the case of the products OAS-1, OAS-4, SS-1, SS-2 and SS-3 a sample in Mexican gasoline of the PEMEX-Magna type free of additives with a known concentration, or of reference, at 10 ppm; subsequently, its absorbance was determined at the wavelength established in Table 2 (?.sub.max), and the concentration of product in each of the test samples were calculated though the corresponding equation. The obtained absorbance values (A.sub.max) and the calculated concentrations for the products OAS-1, OAS-4, SS-1, SS-2, and SS-3 are shown in Table 2.

[0142] The comparison of the absorbance value obtained against that calculated for the products OAS-1, OAS-4, SS-1, SS-2, and SS-3 shows that the absolute maximum error obtained is 4.3% (less than 5%), which confirms that the procedure through UV-VIS spectroscopy allows to reliably quantify the concentration of organic ammonium salt (OAS) and supramolecular surfactant (SS) in gasoline.

TABLE-US-00002 TABLE 2 Concentration Error % respect to the Product A.sub.max found (ppm) reference concentration OAS-1 0.2763 10.16 1.6 OAS-4 0.1119 10 0 SS-1 0.0971 10.39 3.9 SS-2 0.0507 10.43 4.3 SS-3 0.1501 9.96 1.19

[0143] Example 9. Determination of traceability properties through high-performance liquid chromatography. The High-Performance Liquid Chromatography (HPLC) technique can also determine the traceability property so that a calibration curve must be built at different concentrations of the substance to be determined, in this case, OAS or SS. Later, this calibration curve is then used to determine the OAS or SS concentration in unknown or test samples.

[0144] Equipment: High-performance liquid chromatograph (HPLC) with diode array detector and Nova-Park HR C18 column, 6 ?m, 60?, 3.9?300 mm; analytical balance. Solvents: Acetonitrile and methanol (mobile phase), regular gasoline.

[0145] Materials: Volumetric flasks, volumetric pipettes, glass vials and micropipettes, magnetic stirrer.

[0146] Sample to analyze: Organic ammonium salt (OAS) or supramolecular surfactant (SS). Solutions of known concentration of the mentioned products dissolved in regular gasoline.

Test Procedure:

[0147] a) Prepare a standard solution of OAS or SS to be studied at 200 ppm of concentration dissolved in regular gasoline. [0148] b) An aliquot of the standard solution is taken and diluted in regular gasoline to obtain at least five or more solutions in concentrations ranging from 0.5 ppm to 100 ppm. [0149] c) In the HPLC, the detector is programmed at 460 nm, and the samples are injected to obtain their corresponding chromatogram. The chromatogram determines the retention time and the area under the curve corresponding to the signal of the analyzed sample. [0150] d) With the values of area under the curve for the different concentrations, the calibration curve is built, plotting area under the curve vs. concentration, [0151] e) Following the procedure described, the calibration curve shown in FIG. 12 was obtained for the case of organic ammonium salt OAS-1 in regular gasoline. [0152] f) Determination of the concentration of a test sample. To demonstrate that it is feasible to determine the concentration of OAS and/or SS in gasoline through the determination of the area under the curve of chromatograms obtained through the HPLC technique and the use of the generated equations for the case of the OAS-1 product was prepared a sample in Mexican gasoline of the PEMEX-Magna type free of additives with a known concentration, or reference, of 10 ppm, later the area under the curve was determined in the obtained chromatogram, and the concentration of the product in the test samples was calculated through the corresponding equation. The value obtained for the area under the curve was 42.83 milli-absorbance units (mAU), corresponding to a calculated concentration of 10.25 ppm and leading to an absolute error of 2.49% concerning the reference concentration. The result confirms that the HPLC procedure allows us to reliably quantify the concentration of organic ammonium salt (OAS) and/or supramolecular surfactant (SS) in gasoline.

[0153] Example 10. Evaluation as a dispersant detergent for the control of deposits through the single-cylinder engine test. The purpose of this method is to evaluate the formation of deposits in the intake valve of a 4 HP single-cylinder internal combustion engine; in this way, it is possible to determine the performance of OAS and SS as gum dispersant detergents for gasoline. Each run has a time of 16 hours, a total of 20 liters of additive-free PEMEX-Magna gasoline is consumed, and the engine speed is adjusted to 2100?100 rpm. The amount of deposits obtained in the intake valve is quantified in milligrams, and the efficiency of the OAS and SS that are evaluated, are determined, taking as reference the deposits that are obtained when using gasoline without additives. It must have a minimum efficiency of 75% to pass this test.

[0154] The results of the efficiency of the deposits control obtained for the case of the organic ammonium salts OAS-1 and OAS-4, and the supramolecular surfactants SS-1 and SS-2 of the present invention in the presence of Mexican gasoline of the PEMEX-type Magna free of additives are shown below in Table 3.

TABLE-US-00003 TABLE 3 Deposits control Deposits on Deposits on Supramolecular Concentration the reference the run Efficiency surfactant (ppm) (ppm) (mg) (%) OAS-1 24 3.1 1.9 38.7 18 3.1 2.1 32.2 12 3.1 1.7 45.1 6 3.1 1.5 51.6 OAS-4 24 3.1 0.4 87 18 3.1 0.5 83.8 12 3.1 0.7 77.4 6 3.1 0.9 70.9 SS-1 24 3.1 0.6 80.6 18 3.1 1.1 64.5 12 3.1 1.5 51.6 6 3.1 1.9 38.7 SS-2 24 3.1 0.4 87.1 18 3.1 0.8 74.2 12 3.1 1.2 61.3 6 3.1 1.7 45.2

[0155] The results in Table 3 show that the organic ammonium salt OAS-4 passes the test for deposits control in a single-cylinder engine from concentrations of 12 ppm, while the supramolecular surfactants SS-1 and SS-2 pass the test from concentrations of 24 ppm.

[0156] Likewise, it is observed that OAS-1 does not pass the deposit control test in a single-cylinder engine at the concentrations that its performance was evaluated and that at concentrations of 24 ppm, its deposit removal efficiency was 38.7%. This fact is relevant because SS-1, which passes the single-cylinder engine test at 24 ppm, is derived from OAS-1 and demonstrates the flexibility of our invention to obtain novel products that have traceability and detergent-dispersant properties simultaneously.

[0157] It is important to highlight that the organic ammonium salts (OAS) and supramolecular surfactants (SS) of the present invention have several advantages over oxazolidines derived from polyalkyl or poly alkenyl N-hydroxyalkyl succinimides protected in Mexican patent MX269419 and the formulations of hydroxylated polyisobutylene-succinimides and polyethers that are covered in the Mexican patent MX234498. Since the organic ammonium salts (SAO) and the supramolecular surfactants (SS) of the present document simultaneously present traceability and dispersing detergents properties, while the oxazolidines derived from polyalkyl or poly alkenyl N-hydroxyalkyl succinimides of the Mexican patent MX269419 and the formulations of hydroxylated polyisobutylene succinimides and polyethers that are protected in Mexican patent MX234498 only have dispersant detergent properties. In addition to this, the Mexican patent MX269419 shows that to pass the deposit control test in a single-cylinder engine, concentrations of at least 85 ppm of oxazolidines derived from polyalkyl or poly alkenyl N-hydroxyalkyl succinimides are required, while in the present invention, it requires dosages of organic ammonium salts (OAS) or supramolecular surfactants (SS) of at least 12 and 24 ppm, respectively; which represents a great competitive advantage of our organic ammonium salts (OAS) and supramolecular surfactants (SS) object of the present invention concerning the oxazolidines derived from polyalkyl or poly alkenyl N-hydroxyalkyl succinimides of patent MX269419.

[0158] Likewise, Mexican patent MX234498 shows that concentrations of at least 165 ppm are required to pass the deposit control test in a single-cylinder engine of the formulations of hydroxylated polyisobutylene succinimides and polyethers, which demonstrates the competitive advantage of our organic ammonium salts (OAS) and supramolecular surfactants (SS) object of the present invention concerning the formulations of hydroxylated polyisobutylene succinimides and polyethers.

[0159] The evidence presented shows that it is feasible to apply our organic ammonium salts (OAS) and supramolecular surfactants (SS) as differentiators, markers, tracers, or dyes for fuels that can simultaneously prevent and control the formation of deposits in internal combustion engines.