WO2025027177A1

WO2025027177A1 - Polyisobutenyl succinimide-based compounds

Info

Publication number: WO2025027177A1
Application number: PCT/EP2024/071940
Authority: WO
Inventors: Marco BERNABEI; Héctor LOZANO ORDÓÑEZ; Fermín OLIVA MIÑANA; Beatriz DOMÍNGUEZ JIMENO; Guillermo REVILLA LÓPEZ; Mario FRANCO FERNÁNDEZ; Ramón Jesús GÓMEZ ARRAYÁS; Shin-Ho KIM LEE; Roi NAVEIRO; Nuria E. CAMPILLO
Original assignee: Repsol SA
Current assignee: Repsol SA
Priority date: 2023-08-03
Filing date: 2024-08-02
Publication date: 2025-02-06
Anticipated expiration: 2026-02-03
Also published as: MX2026001214A

Abstract

The present invention relates to new polyisobutenyl succinimide-based compounds which are useful as a component of an engine oil additive package composition or as a component of a fuel additive package composition, particularly in gasoline and diesel fuel compositions.

Description

Polyisobutenyl succinimide-based compounds

[0001].. This application claims the benefit of the European Patent Application 23382811 .0 filed on 03.08.2023.

[0002].. The present invention relates to improved additives for fuel compositions and oil-based lubricating compositions.

BACKGROUND ART

[0003].. Carbon-based deposits formed in fuel compositions and oil-based lubricant compositions due to the degradation of the fluid molecules under high temperature conditions pose a serious maintenance problem.

[0004].. This formation can lead to larger aggregates clogging the smaller diameter pipelines, and to avoid this aggregation, dispersant additives are used in both lubricants and fuels to prevent this formation.

[0005].. The use of additives to try improving the performance of fuel compositions and oil-based lubricating compositions is well known in the art. [0006].. Additives, or additive packages, may be used for a number of purposes, such as to improve detergency, reduce engine wear, stabilize lubricating oils against heat and oxidation, inhibit corrosion and reduce mechanical friction losses.

[0007].. Among other components in the additive packages, dispersants are used to maintain said carbon-based deposits formed by oxidation and other mechanisms within the oil, to prevent sludge flocculation and their precipitation. Other functions of the dispersant include the prevention of soot particle agglomeration, providing soothed oil rheology control, and the prevention of deposit formation on the engine pistons.

[0008].. Among other components in the additive packages, dispersants are used to maintain said carbon-based deposits formed by surface deposition, oxidation and other mechanisms within the fuel injector system, exhaust recirculation system and combustion chamber. Dispersants prevent these phenomenon and soot particle agglomeration in specific engine parts, which can affect to the engine performance.

[0009].. The chemical form of these dispersant additives can vary, but they retain their polymeric and amphipathic nature, which includes amphipathic nature comprising a long non-polar polymeric "tail" and a polar "head". The design of both parts and especially of the polar "head" allows modulation of the molecule's activity as a dispersant, thus improving both its efficacy and optimizes the dose used.

[0010].. Thus, a well-known class of dispersants in use today are polyisobutenyl succinimide-based dispersants (also referred herein as PIBSI- based dispersants) which are obtainable by successive reaction of highly reactive polyisobutene (PIB) with maleic anhydride (MA) and subsequent reaction of the reaction product obtained with alcohols, amines or aminoalcohols. These dispersants customarily have polyisobutenyl radicals having an average molecular weight in the range from 500 to 20000 daltons. [0011].. Thus, it is well known in the art the use of PIBSA-based dispersants containing different alkylamines, such as octylamine, hexamethylenediamine (HMDA), diethylenetriamine, diethylenetetramine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) y aminoethylpiperazine (AEP), among others.

[0012].. US2010205852 refers to polyisobutenyl succinimide-based dispersants having a linear polyamine having at least one terminal secondary or tertiary amine function.

[0013].. US2003192233 refers to polyisobutenyl succinimide-based dispersants obtained as the reaction product of a hydrocarbyl substituted succinic acylating agent and one or more polyalkylene polyamines.

[0014].. EP3680312 refers to polyisobutenyl succinimide-based dispersants obtained as the reaction product of a hydrocarbyl substituted succinimide or succinimide dispersant with an oxazoline.

[0015].. Due to their polarity, they can interact with other components of the additive package, reducing both its own dispersing efficiency and the function of the other components (e.g. anti-wear capacity or other surface properties). Thus, there is still the need to develop efficient dispersant compounds to be used in the preparation of engine oil and fuel compositions.

SUMMARY

[0016].. The inventors have surprisingly found that a compound of formula (I) as depicted below, is useful as a dispersant for the preparation of engine oil and fuel compositions. As is demonstrated in the experimental section, the compounds of formula I of the present invention are suitable in the preparation of dispersant compositions, which may be used both in engine oil composition and in fuel compositions (both diesel and gasoline) to prevent, reduce, or eliminate engine deposits, and/or to improve dispersion of soot and particles, i.e carbonaceous or metallic particles, in a diesel or gasoline engine.

[0017].. In a first aspect, it is provided a compound of formula I

wherein

L is a biradical selected from 0, NH, NCH3, N(CH2)_qNH2, and a biradical of formula II

A is a radical selected form -CH3, -(CH2)t-CH3, -(CH2)u-Z-(CH2)v-NH2, and a

Z is selected from 0, NH, and NCH3; p is an integer selected from 0 and 1 ; q, t, u and v are independently an integer selected from 1 to 4; n, r and w are independently an integer from 10 to 50; m, o, s, x and y are independently an integer selected from 1 to 4; with the proviso that wherein p = 0, then Q is selected from a radical of formula (VI) and (VIII); and wherein p = 1 , then Q is selected from a biradical of formula (IV), (V) and (VII)

wherein z is an integer selected from 1 to 4;

I is an integer selected from 1 to 8; and wherein the wavy lines denote the attaching point.

[0018].. A second aspect relates to a composition comprising a compound of formula I as defined herein, together with engine oil, fuel oil or engine or fuel oil additives.

[0019].. A third aspect relates to the use of a compound of formula I as defined in the first aspect of the invention or the composition as defined in the second aspect of the invention, as a component in an engine oil additive package composition.

[0020].. A further aspect relates to an engine oil additive package composition comprising the compound of formula I as defined in the first aspect or the composition as defined in the second aspect of the invention.

[0021].. An additional aspect relates to an engine oil composition comprising the engine oil additive package composition as defined herein.

[0022].. Another aspect relates to an engine oil additive package composition as defined herein in the form of an engine oil finished fluid for an internal combustion engine. The oil additive package further comprising at least one other additive selected from antioxidants, detergent, antiwear, friction modifier, corrosion inhibitor, among others, and mixtures thereof.

[0023].. Another aspect relates to an internal combustion engine lubricated with an engine oil composition as defined herein.

[0024].. Another aspect relates to the use of a compound of formula I as defined herein, as an additive for diesel or gasoline compositions.

[0025].. Another aspect relates to the composition as defined herein, which is a fuel additive package composition comprising a compound of formula I as defined herein, or the composition as defined in the second aspect of the invention. The fuel additive package composition may be used as an additive package composition of a fuel composition selected from gasoline and diesel; the additive package further comprising at least one other additive selected from antioxidants, detergents, antiwear, friction modifiers, corrosion inhibitors, and mixtures thereof.

[0026].. In another aspect, it is provided a fuel composition comprising a major proportion of a fuel oil and a minor proportion of the fuel additive package composition as defined above.

[0027].. In another aspect, it is provided the use of an engine oil additive package composition as defined herein to lower soot and sludge deposits in an internal combustion engine.

[0028].. In another aspect, it is provided the use of a fuel additive composition as defined herein to improve dispersion of soot in a gasoline or diesel engine.

[0029].. In another aspect, it is provided the use of a fuel additive composition as defined herein to reduce and/or prevent internal deposits in an engine operated with a fuel, wherein the fuel is gasoline or diesel.

DETAILED DESCRIPTION

[0030].. To facilitate understanding of the disclosure set forth herein, a number of terms are defined below. Unless defined otherwise, all technical and scientific terms used herein generally have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

[0031].. As used herein, the term "initiator residue" refers to a monovalent, divalent, or polyvalent moiety that is bonded to one, two, or more polymer groups. In certain embodiments, the initiator residue is derived from an initiator. In certain embodiments, the initiator residue is the portion of an initiator that remains after forming one, two, or more carbocations and reacting with a monomer or comonomer during a polymerization.

[0032].. As used herein, the term "monomer" refers to a compound that is capable of forming one of the two or more repetitive units of a polymer. In certain embodiments, the monomer is an olefin. In certain embodiments, the monomer is isobutene.

[0033].. As used herein, the terms "polyisobutylene," "polyisobutylene group," and "PIB" refer to a polymer comprising two or more monomeric isobutylene units. In certain embodiments, the polyisobutylene comprises an initiator residue. In certain embodiments, the polyisobutylene is a homopolyisobutylene. In certain embodiments, the polyisobutylene is a polyisobutylene copolymer.

[0034].. In some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, the polyisobutylene moiety may have a molecular weight of from 500 Da to 5000 Da, preferably from 500 Da to 4500 Da; more preferably from 600 Da to 4000 Da, even more preferably from 800 Da to 3500 Da, being particularly preferred from 1000 Da to 3000 Da. Particularly preferred are those wherein the polyisobutylene moiety have a molecular weight of 1000 Da or 2300 Da.

[0035].. The molecular weight of each of the polyisobutylene moieties present in the formula I depends on the n, r, and w values, which are each independently an integer from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0036].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, p = 1 ; A is selected from -CH₃, -(CH₂)-CH₃, -(CH₂)₂-CH₃, -(CH₂)₃-CH₃, -(CH₂)₂-O- (CH₂)₂-NH₂, -CH₂-O-CH₂-NH_2I -(CH₂)₂-O-CH₂-NH_2I -CH₂-O-(CH₂)₂-NH_2I -(CH₂)₂-NH-(CH₂)₂-NH_2I -CH₂-NH-CH₂-NH_2I -(CH₂)₂-NH-CH₂-

NH_2I -CH₂-NH-(CH₂)₂-NH_2I -(CH₂)₂-NCH₃-(CH₂)₂-NH₂ , -CH₂-NCH₃-CH₂-

NH_2I -(CH₂)₂-NCH₃-CH₂-NH_2I -CH₂-NCH₃-(CH₂)₂-NH_2I and a radical of formula III; and n, r and w are each independently an integer from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0037].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, p = 1 ; A is selected from -CH₃, -(CH₂)-CH₃, -(CH₂)₂-CH₃, -(CH₂)₂-O-(CH₂)₂-NH₂, -(CH₂)₂-NH-(CH₂)₂-NH₂, -(CH₂)₂-NCH₃-(CH₂)₂-NH_2I and a radical of formula III; and n, r and w are each independently an integer from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0038].. The integers q, s, t, u, v, x, y and z are each independently selected from 1 , 2, 3 and 4; preferably 2 and 3; more preferably 2. Whereas the integer I may be selected from 1 , 2, 3, 4, 5, 6, 7, and 8; preferably 2, 3, 4, 5, and 6; more preferably 2, 3, and 4.

[0039].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is O; p=1 ; and Q is selected from a biradical of formula (V) and (VII).

[0040].. In some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is O; Q is a biradical of formula (VII), wherein z is an integer selected from 1 , 2, 3 and 4, preferably z is 2; p = 1 ; A is a radical selected from -(CH2)u-Z-(CH2)v-NH2 and a radical of formula III, wherein Z is 0; and wherein n and w are each independently an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0041 ].. In some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is O; Q is a biradical of formula (VII), wherein z is an integer selected from 1 , 2, 3 and 4, preferably z is 2; p = 1 ; A is a radical selected from -(CH2)2-O-(CH2)2-NH2, -CH2-O-CH2-NH2, -(CH₂)2-O-CH₂-NH₂, -CH₂-O-(CH₂)2-NH₂, -(CH₂)2-NH-(CH₂)2-NH₂, -CH2-NH-CH2-NH2, -(CH₂)2-NH-CH₂-NH₂, -CH₂-NH-(CH₂)2-NH₂, -(CH₂)2-NCH3-(CH₂)2-NH2, -CH2-NCH3-CH2-NH2, -(CH₂)2-NCH3-CH2-NH₂, -CH2-NCH3-(CH₂)2-NH₂, and a radical of formula III, wherein Z is 0; and wherein n and w are each independently an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0042].. In some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is 0; Q is a biradical of formula (V); p = 1 ; A is a radical selected from -CH3, -(CH2)u-Z-(CH2)v-NH2 and a radical of formula III, wherein Z is 0; and wherein n and w are each independently an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0043].. In some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is 0; Q is a biradical of formula (V); p = 1 ; A is a radical selected from -CH₃, -(CH₂)-CH₃, -(CH₂)2-CH₃, -(CH₂)2-O-(CH₂)2-NH₂, -CH2-O-CH2-NH2, -(CH₂)2-O-CH₂-NH₂, -CH₂-O-(CH₂)2-NH₂, -NH-CH₂-NH_2I H₂-NCH₃-CH₂-NH₂,

d a radical of formula III, wherein Z is 0; and wherein n is an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0044].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is a biradical selected from NH, and NCH₃; Q is a biradical of formula (IV).

[0045].. In some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is a biradical selected from NH, and NCH₃; Q is a biradical of formula (IV); p = 1 ; A is a radical selected from -(CH₂)_u-Z-(CH₂)_v-NH₂ and a radical of formula III, wherein Z is selected from NH and NCH₃; and wherein n and w are each independently an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0046].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is a biradical selected from NH, and NCH₃; Q is a biradical of formula (IV); p = 1 ; A is selected from -CH₃, -(CH₂)-CH₃, -(CH₂)₂-CH₃, -(CH₂)₂-O-(CH₂)₂-NH₂,

la III; and n and w are each independently an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0047].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is a biradical selected from NCH₃, N(CH₂)_qNH₂, and a biradical of formula II; q is an integer selected from 1 , 2, 3 and 4, preferably q is 2; Q is selected from a radical of formula (VI) and (VIII); p is 0; and n and r are each independently an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0048].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is a biradical selected from NCH₃, and N(CH₂)₂NH₂; Q is selected from a radical of formula (VI) and (VIII); p is 0; and n is an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30. [0049].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is a biradical selected from NCH3, and N(CH2)2NH2; Q is a radical of formula (VI); p is 0; and n is an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0050].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is a biradical selected from NCH3, and N(CH2)2NH2; Q is a radical of formula (VIII), wherein I is an integer selected from 1 , 2, 3, 4, 5, 6, 7, and 8; preferably I is selected from 2, 3, 4, 5, and 6; p is 0; and n is an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0051 ].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is a biradical of formula II; Q is selected from a radical of formula (VI) and (VIII); p is 0; and n, r and w are each independently an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0052].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is a biradical of formula II; Q is a radical of formula (VIII), wherein I is an integer selected from 1 , 2, 3, 4, 5, 6, 7, and 8; preferably I is selected from 2, 3, 4, 5, and 6; p is 0; and n is an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

[0053].. In accordance with some embodiments, optionally in combination with one or more features of the particular embodiments defined herein, L is a biradical of formula II; Q is a radical of formula (VI); p is 0; and n is an integer selected from 10 to 50, preferably from 12 to 40, more preferably from 15 to 30.

Engine oil compositions

[0054].. The compounds of formula I as described herein may be used in the preparation of dispersant compositions, which may be used both in engine oil composition and in fuel compositions (both diesel and gasoline).

[0055].. The dispersant compositions of the invention may be used in the preparation of an engine oil additive package composition comprising the dispersant composition. The engine oil additive package composition may be used in the form of an engine oil finished fluid for an internal combustion engine. [0056].. Accordingly, provided are engine oil additive package compositions, wherein the additive package composition comprises from 15 to 75 weight percent, preferably from 25 to 60 wt%, of, at least, one dispersant component of formula I as defined herein, based on the total weight of the engine oil additive package composition.

[0057].. Generally, this compound of formula I is previously formulated in a dispersant composition, which it is added as a component in an engine oil additive package composition. The dispersant composition comprises a diluent and at least one compound of formula I. The engine oil additive package composition may comprise a dispersant composition comprising a compound of formula I. The dispersant composition comprises from 25 to 100 wt%, preferably 40 to 100% or at least from 50 to 100% of a compound of formula I as defined herein, based on the total weight of the dispersant composition. Typically, the mixtures contain sufficient diluent to make them easy to handle during shipping, manufacturing, and storage. Suitable diluents for the concentrates include any inert diluent, preferably lubricating baseoil, so that the concentrate may be readily mixed with the other formulation components to prepare finished lubricant compositions.

[0058].. When employed as a component in an engine oil additive package composition, the compounds of formula I are usually present in an engine oil composition in an amount of from 0.5 to 8 percent by weight, preferably from 1 to 5 percent by weight, more preferably from 1.5 to 3 percent by weight, based on the total weight of the engine oil composition.

[0059].. The lubricating oil in these compositions may be any lubricating oil type according to the general and well-established classification of groups for the lubricating base oil and the other co-additives usually present in commercial lubricating oils. The lubricating oils may be derived from synthetic or petroleum sources. Mineral base oils from petroleum source can include paraffinic, naphthenic and other base oils that are ordinarily used in lubricating oil compositions, with a given viscosity. Synthetic oils include hydrocarbon synthetic base oils such as poly alpha olefins and synthetic esters. Other additive in the formulations include thickeners of different chemistries to formulate to the target viscosity.

[0060].. The skilled person in the art knows how to select the lubricating oil and, when necessary, the appropriate diluent for the preparation of the lubricating oil composition and/or the lubricating oil concentrate.

[0061].. Other additives that can be included in the engine oil additive package composition include antioxidants, friction modifiers, detergents, antiwear, and a variety of other well-known additives.

Fuel Compositions

[0062].. The compounds of formula I described herein may also be used as fuel additives. Thus, the compounds of formula I as described herein may be used as an additive for diesel or gasoline compositions. Further, the dispersant compositions containing the compounds of formula I may be formulated as an additive package composition for dispersion of a fuel compositions (both diesel and gasoline compositions).

[0063].. When used in fuels, the proper concentration of the additive necessary in order to achieve the desired detergency is dependent upon a variety of factors including the type of fuel used, the presence of other detergents or dispersants or other additives, etc. Generally, the range of concentration of the compounds of formula I in the base fuel may be from 5 to 1000 mg/kg, preferably from 25 to 350 mg/kg, based on the fuel quantity. [0064].. The compounds of formula I according to the present invention may be formulated in a fuel additive package, in other words, the compounds of formula I may be used as a component in an additive package composition for dispersion of a fuel composition. The fuel additive package composition, in addition to the compound of formula I, may comprise other well-known additives e.g. aromatic solvents, defoamers, alcoholic stabilizers, demulsifiers, antioxidants, metal deactivators, corrosion inhibitors, and a variety of other well-known additives. The skilled person in the art knows how to select and properly formulate the components to prepare fuel additive packages to be used in fuel (diesel or gasoline) compositions.

[0065].. Generally, the range of concentration of the compounds of formula I in the fuel additive package may be from 1 to 80 weight percent, preferably from 5 to 50 weight percent, based on the total weight of the fuel additive package.

[0066].. The fuel utilized in the practice of this disclosure can be traditional blends or mixtures of hydrocarbons in the gasoline boiling range, or they can contain oxygenated blending components such as alcohols and/or ethers having suitable boiling temperatures and appropriate fuel solubility, such as methanol, ethanol, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and mixed oxygen-containing products formed by "oxygenating" gasolines and/or olefinic hydrocarbons falling in the gasoline boiling range.

[0067].. The fuel utilized in the practice of this disclosure can be traditional blends or mixtures of hydrocarbons in the diesel boiling range, or they can contain oxygenated blending components such as esters having suitable boiling temperatures and appropriate fuel solubility, such as Fatty Acid Methyl Esther (FAME) or Fatty Acid Ethyl ester (FAEE), or paraffinic hydrocarbons such us X-To-Liquid fuels or Hydrotreated Vegetable Oil (HVO) falling in the diesel boiling range.

[0068].. When formulating the fuel compositions of this invention, the fuel additive package comprising at least one compound of formula I as described herein, is employed in amounts sufficient to prevent, reduce, or eliminate engine deposits, and/or to improve dispersion of soot and particles, i.e carbonaceous or metallic particles, in a diesel or gasoline engine. Operated with a fuel, wherein the fuel is gasoline or diesel.

[0069].. Although only a number of examples have been disclosed herein, other alternatives, modifications, uses and/or equivalents thereof are possible. Furthermore, all possible combinations of the described examples are also covered. Thus, the scope of the present disclosure should not be limited by particular examples but should be determined only by a fair reading of the claims that follow.

[0070].. Throughout the description and claims the word "comprise" and variations of the word, are not intended to exclude other technical features, additives, components, or steps. Furthermore, the word “comprise” encompasses the case of “consisting of”. Additional objects, advantages and features of the invention will become apparent to those skilled in the art upon examination of the description or may be learned by practice of the invention. The following examples are provided by way of illustration, and they are not intended to be limiting of the present invention. Furthermore, the present invention covers all possible combinations of particular and preferred embodiments described herein.

[0071].. The measures of the dispersing activity are carried out by means of standardized tests for lubricants and diesel:

-Blotter spot (measured according to CEC L-48-00 standard - Measurement of dispersion on an oxidized sample of lubricant, the higher its value, in a standard sample in which only the dispersant used changes, the higher the power of dispersion of said dispersant.

-HLPS: Hot Liquid Process Simulation measured according to ASTM D-3241 test in which the sample recirculation time is up to a maximum of 4 hours. In this test is measured the filterability of a diesel fuel that is subjected to a controlled heat treatment process. According to the pressure drop measured during the process the tendency to form deposits, TFD, is deduced. The lower the TFD, the lower the tendency to form deposits of a standard sample of diesel fuel with or without deposit control additives (DCA). Then, with HLPS test is possible to quantify the activity of the dispersant additive.

EXAMPLES

, , portionwise to ethylenediamine (15 mL, 225 mmol) in a 50 mL sealed tube under stirring over approximately 2 minutes (temperature increase was observed). The mixture was stirred at 120 °C for 18 h. The excess of ethylenediamine was removed using a Kugelrohr system. The remaining semi-solid residue was further purified by ultrasound-assisted trituration with CH2CI2 for about 1 h. The resulting yellowish suspension was filtered, and the solid residue was triturated again with CH2CI2 in an ultrasound bath. The combined filtrates were concentrated to give PA1 as a yellow oil; yield: 761 mg (30%).

¹H NMR (300 MHz, D₂O): 5 7.39-7.29 (m, 4 H), 3.75 (s, 4H), 2.92-2.65 (s, 8H).

1.2 Synthesis of 2-(2-(4-methylpiperazin-1-yl)ethoxy)ethan-1 -amine (PA2)

[0073].. To a solution of NaNs (7 g, 111 mmol) and Nal (2.8 g, 18.6 mmol) in a 2:1 mixture of H2O/DMF (30 mL) in a sealed tube at room temperature (rt), was added 2-(2-chloroethoxy)ethan-1-ol (4 mL, 37.2 mmol). The mixture was stirred at 90 °C for 24 h before it was allowed to reach rt and concentrated. The residue was dissolved in EtOAc (30 mL) and extracted with H2O (2 x 30 mL). The organic phase was dried (MgSCU) and concentrated to give 2-(2- azidoethoxy)ethan-1-ol as a yellowish liquid; yield: 2.93 (60%). To a solution of this product (2.93 g, 22.3 mmol) in CH2CI2 (130 mL), cooled to 0 °C, was successively added imidazole (1 .97 g, 29 mmol), PPhs (7.6 g, 29 mmol), and I2 (7.36 g, 29 mmol). The mixture was stirred at 0 °C for 30 min (orange color), and at rt for 1 h. Then, a 10% aq. soln of NaHSOs 10% (150 mL) was added and the mixture was vigorously stirred for 10 min (color changed to yellow). The aqueous phase was extracted with CH2CI2 (2 x 50 mL) and the combined organic phase was dried (MgSCU), and concentrated. The solid residue was triturated with an 8:1 cyclohexane/Et2O mixture (200 mL), the solid was filtered off and the filtrate was concentrated. The residue was purified through a short pad of silica gel (cyclohexane/Et2O 8:1 ) to give 1 -azido-2-(2- iodoethoxy)ethane as a colorless liquid; yield: 4.84 g (90%). To a suspension of 1 -methylpiperazine (2.4 g, 24.2 mmol) and K2CO3 (3.33 g, 24.2 mmol) in anhyd DMF (40 mL) was added 1 -azido-2-(2-iodoethoxy)ethane (4.84 g, 20.1 mmol). The mixture was stirred at 90 °C for 18 h under Ar before it was concentrated. The residue was dissolved in EtOAc (30 mL) and the solution was extracted with 1 M NaOH (2 x 30 mL). The combined organic phase was dried (MgSO4) and concentrated to give 1-(2-(2-azidoethoxy)ethyl)-4- methylpiperazine as a colorless oil; yield: 3.85 g (90%). A mixture of this product (3.85 g, 18.1 mmol) and Pd/C (300 mg, 15 mol%) in MeOH (100 mL) was stirred under H2 (1 atm) at rt for 18 h before it was filtered through celite and concentrated to give PA2 as a colorless liquid, which was kept under Ar to prevent carbonation; yield: 3.0 g (90%).

¹H NMR (300 MHz, CDCI3): 5 3.58 (t, J = 5.9 Hz, 2H), 3.52 (t, J = 5.8 Hz, 2H), 2.85 (t, J = 5.9 Hz, 2H), 2.58 (t, J = 6.0 Hz, 2H), 2.67-2.48 (m, 8H), 2.27 (s, 3H), 1.9 (bs, 2H).

1 .3 Synthesis of 2,2'-(((ethane-1 ,2-diylbis(piperazine-4, 1 -diyl))bis(ethane-2, 1 - diyl))bis(oxy))bis(ethan-1 -amine) (PA3)

[0074].. 1 -azido-2-(2-iodoethoxy)ethane was obtained as described in 1 .2 above. To a suspension of 1 -Boc-piperazine (4.5 g, 24.2 mmol) and K2CO3 (3.33 g, 24.2 mmol) in anhyd DMF (40 mL) was added 1-azido-2-(2- iodoethoxy)ethane (4.84 g, 20.1 mmol). The mixture was stirred at 60 °C for 18 h under Ar before it was concentrated. The residue was dissolved in EtOAc (30 mL) and the solution was extracted with 1 M NaOH (2 x 30 mL). The organic phase was dried (MgSCU) and concentrated to give fe/Y-butyl 4-(2-(2- azidoethoxy)ethyl)piperazine-1 -carboxylate as a colorless oil; yield: 5.4 g (89%). To a solution of this product (5.4 g, 18.1 mmol) in MeOH (150 mL) was slowly added oxalyl chloride (4.65 mL, 54.3 mmol, bubbling and increase of temperature was observed) and the mixture was stirred at rt for 6 h. H2O (150 mL) was slowly added to the resulting milky-white solution before it was extracted with CH2CI2 (2 x 300 mL). The combined organic phase was washed with H2O (2 x 200 mL), dried (MgSO4) and concentrated to give 1 -(2-(2- azidoethoxy)ethyl)piperazine as a colorless oil; yield: 3.53 g (98%). To a solution of this product (3.53 g, 17.7 mmol) in MeOH (70 mL) was added glyoxal (1.2 mL, 9.74 mmol) and the mixture was stirred for 10 min at rt. Then, NaBHsCN (1 .33 g, 21 .2 mmol) was added, and the mixture was stirred at rt for 18 h before it was concentrated. The residue was dissolved in CH2CI2 (50 mL) and extracted with 1 M NaOH (2 x 50 mL). The combined organic phase was washed with H2O (2 x 30 mL), then dried (MgSO4) and concentrated to give 1 ,2-bis(4-(2-(2-azidoethoxy)ethyl)piperazin-1 -yl)ethane as a colorless oil; yield: 3.0 g (80%). A mixture of this product (3.0 g, 7.1 mmol) and Pd/C (250 mg, 15 mol%) in MeOH (100 mL) was stirred under H2 (1 atm) at rt for 18 h before it was filtered through celite and concentrated to give PA3 as a colorless liquid, kept under Ar to prevent carbonation; yield: 2.38 g (90%).

¹H NMR (300 MHz, CDCI3): 5 3.58 (m, 4H), 3.45 (m, 4H), 2.84 (m, 4H), 2.67- 2.44 (28H), 1.76 (bs, 4H).

1.4 Synthesis of N1-(2-aminoethyl)-N1 -(2-morpholinoethyl)ethane-1 ,2-diamine

(PA4)

, dropwise to a solution of diethylenetriamine (2.1 mL, 19.42 mmol) and triethylamine (8.1 mL, 58.2 mmol) in anhyd THF (100 mL) under N2. After stirring at 0 °C for 1 h, and at rt for 2 h, the mixture was concentrated. The residue was dissolved in CH2CI2 (100 mL) and washed with 5% aq. NaOH (2 x 100 mL), H2O (100 mL) and brine (100 mL), then dried (Na2SO4) and concentrated to give the diprotected amine as an oil; yield: 5.56 g (95%). This product (5.56 g, 18.3 mmol) was added to a mixture of 4-(2- chloroethyl)morpholine hydrochloride (4.1 g, 22 mmol), K2CO3 (5.8 g, 42.1 mmol) , and Nal (1 .65 g, 11 mmol) in dry DMF (40 mL). The mixture was stirred at 90 °C for 18 h and concentrated. The residue was dissolved in EtOAc (10 mL) and successively washed with 5% aq. NaOH (2 x 100 mL), H2O (100 mL) and brine (100 mL), then dried (Na2SO4) and concentrated to give the N¹-(2-morpholi noethylated product as an oil; yield: 6.1 g (80%). To a solution of this product (6.1 g, 14.6 mmol) in 1 ,4-dioxane (50 mL) was added 3 M HCI (50 mL) and the mixture was stirred at 60 °C for 18 h. The solvent was concentrated, and the residue was dissolved in deionized water (50 mL) before it was washed with AcOEt (50 mL). The aqueous phase was brought to pH 14 by adding 8 M NaOH at 0 °C dropwise while stirring, and then lyophilized. The product was extracted from the mixture by stirring with CH2CI2. The combined organic phase was dried (Na2SO4) and concentrated to give PA4; yield: 3.0 g (95%). The product was kept under a nitrogen atmosphere to avoid its possible carbonation.

¹H NMR (300 MHz, D₂O): 5 3.41 (m, 4H), 3.19 (t, J = 6.7 Hz, 8H), 3.08 (m, 4H), 2.93 (t, J = 6.7 Hz, 8H).

1 .5 Synthesis of 4,7, 10, 13-tetramethyl-1 ,4,7, 10, 13-pentaazatetradecane

[0076].. To a solution of tetramethylenepentamine (6 mL, 31 .5 mmol) in CH2CI2 (100 mL) at 0 °C, was added a solution of trityl chloride (1 .95 g, 7 mmol) in CH2CI2 (20 mL). The mixture was stirred at 0 °C for 3 h and then at rt for 18 h before it was washed with 1 M NaOH (2 x 100 mL) and H2O (2 x 50 mL). The organic phase was dried (MgSO4) and concentrated to give the 1- tritylated 1 ,4,7, 10,13-pentaazatridecane a white solid; yield: 2.1 g (70%). To a solution of this product (2.1 g, 4.9 mmol) in MeOH (40 mL) was added a 37% aq. formaldehyde solution (2.55 mL, 34.3 mmol). Upon stirring at rt for 10 min, NaBHsCN (2.16 g, 34.3 mmol) was added, and the mixture was stirred for additional 18 h. Then, it was concentrated, the residue was dissolved in CH2CI2 (50 mL), and the solution was successively washed with 1 M NaOH (2 x 50 mL) and H2O (2 x 30 mL). The combined organic phase was dried (MgSCU) and concentrated to give the 1 -tritylated-4,7,10,13,13-pentamethyl- 1 ,4,7, 10, 13-pentaazatridecane as a viscous solid; yield: 2.3 g (95%). To a solution of this product (2.3 g, 4.6 mmol) in 1 ,4-dioxane (20 mL) was added 3 M HCI (20 mL). The mixture was stirred at 60 °C for 16 h before it was concentrated and the residue treated with H2O (30 mL) and Et20 (30 mL), and vigorously stirred for 5 min at rt. To the aqueous phase at 0 °C was added 8 M NaOH dropwise until pH > 12, before the mixture was lyophilized. The remaining residue was then triturated with CH2CI2 (100 mL), and the filtrate was concentrated to give the product as a colorless oil; yield: 1.1 g (95%). ¹H NMR (300 MHz, D₂O): 5 2.85-2.35 (m, 18H), 2.28-2.18 (m, 15H).

PA5 is also denoted as N'-[2-[2-[2-(dimethylamino)ethyl-methylamino]ethyl- methylamino]ethyl]-N'-methylethane-1 ,2-diamine (IUPAC name), with PubChem ID 87239535.

1 .6 TEPA: 1,4, 7, 10, 13-pentaazatridecane (PA6)

[0077].. Tetraethylenepentamine (TEPA, IUPAC name N'-[2-[2-(2- aminoethylamino)ethylamino]ethyl]ethane-1 ,2-diamine) was purchased from Aldrich and used as received. This sample was analyzed by quantitative ¹³C NMR and it was found that this commercial TEPA is a mixture of four ethyleneamines with close boiling points including linear (TEPA, CAS #000112-57-2, 1 ,4,7,10,13-pentaazatetradecane), branched (AETETA, CAS #031295-46-2, N¹,N¹,N²-tris(2-aminoethyl)ethane-1 ,2-diamine), and two cyclic products (APEEDA (CAS #031295-54-2, 1 -(2-aminoethyl)-4-[(2- aminoethyl)amino]ethyl]-piperazine) & PEDETA (CAS #031295-49-5, 1 -[2-[[2- [(2-aminoethyl)amino]ethyl]-amino]ethyl]-piperazine). The relative ratio of these four components in the mixture was found to be: TEPA/AETETA/APEEDA/PEDETA = 60:17:18:5). 2. Imidization of PIBSA with polyamines (synthesis of PIBSI derivatives)

2.1 General procedure for the monoimidization of PIBSA with polyamines

[0078].. A 250 mL round bottom flask was charged with PIBSA-1000 (i.e. a polyisobutylene succinic anhydride having a molecular weight of 1000) (15.3 g, 13.9 mmol) or PIBSA-2300 (i.e. a polyisobutylene succinic anhydride having a molecular weight of 2300) (15.3 g, 6.36 mmol) and xylene (15 mL). The flask was fitted with a Dean-Stark apparatus connected with a reflux condenser. The whole system was purged with a N2 stream and maintained under N2 atmosphere. The mixture was stirred with a magnetic stirrer at 70 °C until the PIBSA was completely dissolved. At that point, the polyamine (13.9 mmol for the PIBSA-1000 and 6.36 mmol for the PIBSA-2300) was added, and the resulting mixture was stirred at 190 °C for 24 h. Then, it was allowed to reach room temperature and the crude mixture was passed through a pad of silica gel, eluting with cyclohexane and a 20:1 mixture of CH2Cl2/MeOH. The filtrate was concentrated, and the residue was purified by repeated precipitations from cyclohexane into anhydrous acetone followed precipitations from cyclohexane into anhydrous MeOH and then concentrated. The resulting thick dark orange oil was dried in an oven at 80 °C for 48 h, until no solvents remain upon checking by ¹H NMR. The purity of the product was determined by ¹H NMR via integration ratio of the protons corresponding to the polyamine protons (from 2.0 ppm to 4.0 ppm) with those of the PIB chain (from 1.0 to 2.0 ppm, ca. 150 H, and the signal at 4.7-4.9 ppm corresponding to the two alkenyl CH2 protons), as well as by the observation of the formation of a single C=O band at 1700 cm^-1 (succinimide) in the IR spectrum.

[0079].. The following compounds were prepared following the above- mentioned general procedure:

2.2 General procedure for the diimidization of PIBSA with polyamines

[0080].. A 250 mL round bottom flask was charged with PIBSA-1000 (15.3 g, 13.9 mmol) or PIBSA-2300 (15.3 g, 6.36 mmol) and xylene (15 mL). The flask was fitted with a Dean-Stark apparatus connected with a reflux condenser. The whole system was purged with a N2 stream and maintained under N2 atmosphere. The mixture was stirred with a magnetic stirrer at 70 °C until the PIBSA was completely dissolved. At that point, the polyamine (7.25 mmol for the PIBSA-1000 and 3.45 mmol for the PIBSA-2300) was added before the reaction was stirred at 190 °C for 24 h. Then, the reaction was allowed to reach room temperature and the crude mixture was passed through a pad of silica gel, eluting with cyclohexane and a 20:1 mixture of CH2Cl2/MeOH. The filtrate was concentrated, and the residue was purified by repeated precipitations from cyclohexane into anhydrous acetone followed precipitations from cyclohexane into anhydrous MeOH and then concentrated. The resulting thick dark orange oil was dried in an oven at 80 °C for 48 h, until no solvents remain upon checking by ¹H NMR. The purity of the product was determined by ¹H NMR via integration ratio of the protons corresponding to the polyamine protons (from 2.0 ppm to 4.0 ppm) with those of the PIB chain (from 0.6 to 2.0 ppm, ca. 300 H, and the signal at 4.7-4.9 ppm corresponding to the four alkenyl CH2 protons), as well as by the observation of the formation of a single C=O band at 1700 cm^-1 (succinimide) in the IR spectrum.

[0081 ].. The following compounds were prepared following the above- mentioned general procedure:

n=30 QR52b-2300 Example 3.- Detergent capacity evaluation using Hot Liquid Process Simulator (HLPS)

[0082].. The goal of the test procedure is to evaluate the fouling formation capacity of different Diesel fuels, with or without Deposit Control Additives (DCA). Then, it can compare the performance of different DCA and/or dosage levels to reduce the fouling trend of the Diesel fuel.

Testing conditions:

• Temperature: 280 °C

• Fuel volume: 110 mL

• Fuel flow: 4.5 mL/min

• Pressure: 550 psi

Fuel preparation

[0083].. First, fuel was filtered through 0.45 pm paper filter according to DIN 51419. If the DCA is to be contained in the fuel, it will be added before filtering.

Test procedure

[0084].. All the components were cleaned previously with a proper solvent (heptane, toluene, and methanol blend) and with acetone.

[0085].. The aluminum probe was weighted in a mass balance with a precision level of 0.0001 mg. Later, the probe was fitted properly in the HLPS equipment.

[0086].. The exact quantity of the testing fuel was incorporated inside the fuel recipient of HLPS equipment (volumetric measurement).

[0087].. The pressure transducer indicator was changed to ON. PUMP was ON with a fuel rate adjusted to 4.5 mL/min and nitrogen at 550 psi, start the heater and START the test.

[0088].. During the test, pressure measurements were registered every 5 minutes.

[0089].. Once the pressure difference was equal or higher than 25 mmHg (dP > 25 mm Hg) the time was recorded, and the test was finished. In this case, TFD (Trend to Form Deposits) is calculated as follows:

TFD = 2401 time (min)

[0090].. If the test arrives to 240 minutes without increase enough the pressure (dP < 25 mm Hg), then the pressure was registered at 240 minutes. In this case, TFD is calculated as follows:

TFD = dP (mm Hg ) / 25 [0091].. Finally, testing was stopped and cooled. The aluminum probe was removed, cleaned with hexane and weighted in the same balance at room temperature. The weigh was recorded.

Results: [0092].. Results in table below for the tested new compounds, were obtained adding the same additive dose (mg/kg) on a diesel fuel of reference.

[0093].. A TFD value lower than 0.1 refers to an excellent dispersant function of the additive. The results obtained for the tested compounds demonstrates that all of them show an excellent dispersant function.

Example 4.- Blotter Spot

[0094].. Samples were subjected to oxidation conditions by heating in an oil bath a fresh oil sample to a specified temperature, and flowing air through it at a specified flow rate during a specified period.

[0095].. It was used apparatus referred as “B according to CEC L-48-00 standard,” where usual specifications are shown below:

[0096].. Concretely for this set of tests, it was conducted the following conditions:

• Temperature: 170°C

• Time: 192 h duration

• Air flow rate: 5L/h

[0097].. After the test, certain fresh oil properties were compared with the aged oil ones, such as kinematic viscosity at 40°C and 100°C, quantitative area variation in the infrared band between 1650 and 1820 cm^-1 (typical of oxidized compounds), TBN, TAN, etc. Also, heptane insoluble content of the oil was measured by filtration on a pre-weighed filter, by weighing the sample flask before and after test, or qualitative sludge rating according to the guidelines of CEC L-48-00 standard.

[0098].. In order to evaluate the dispersant capacity of the formulation, on top of that, Blotter Spot test, based on the standardized norm ASTM D7899, was conducted by dropping a sample of aged oil after oxidation test on a paper filter placed in a petri dish, and heating it in an oven during 1h at 100°C. [0099].. After this time a spot with 2 concentrical rings were formed. The rating of the blotter spot, N, was calculated by measuring the areas inner and outer rings following to the equation: N = F2/F1 *100. Where F2 is the area of the inner ring and F1 the area of the outer one.

[00100].. The higher the value of N is, the better the dispersant capacity of the formulation.

[00101].. Our method only differs from the standardized norm ASTM D7899 in that the measure of areas is made manually instead of using a calibrated device.

[00102].. Results of the Blotter Spot Test, a test for dipersancy, clearly highlight: P I BSI-TE PA-2300, QR47b-2300 and QR52-with the highest dispersant power. A clear trend is detected for the size of the polymer chain which suggest that in the tested engine oil lubricants longer polymer confers a higher activity whereas this is not detected for gasoil fuel.

REFERENCES CITED IN THE APPLICATION CEC L-48-00 standard

ASTM D7899

ASTM D-3241

Claims

wherein

L is a biradical selected from 0, NH, NCH3, N(CH2)_qNH2, and a biradical of

A is a radical selected form -CH3, -(CH2)t-CH3, -(CH2)u-Z-(CH2)v-NH2, and a radical of formula III

Z is selected from 0, NH, and NCH3; p is an integer selected from 0 and 1 ; q, t, u and v are each independently an integer selected from 1 to 4; n, r and w are each independently an integer from 10 to 50; m, o, s, x and y are each independently an integer selected from 1 to 4; with the proviso that wherein p = 0, then Q is selected from a radical of formula (VI) and (VIII); and wherein p = 1 , then Q is selected from a biradical of formula (IV), (V) and (VII)

wherein z is an integer selected from 1 to 4;

I is an integer selected from 1 to 8; and wherein the wavy lines denotes the attaching point.

2. The compound according to claim 1 , wherein L is 0; p=1 ; and Q is selected from a biradical of formula (V) and (VII).

3. The compound according to any one of claims 1 -2, wherein L is 0; Q is a biradical of formula (VII), wherein z is an integer selected from 1 , 2, 3 and 4, preferably z is 2; p = 1 ; A is a radical selected from -(CH2)u-Z-(CH2)v-NH2 and a radical of formula III, wherein Z is 0; and wherein n and w are each independently an integer selected from 15 to 30.

4. The compound according to any one of claims 1 -2, wherein L is 0; Q is a biradical of formula (V); p = 1 ; A is a radical selected from -CH3, -(CH2)u-Z- (CH2)v-NH2 and a radical of formula III, wherein Z is 0; and wherein n and w are each independently an integer selected from 15 to 30.

5. The compound according to claim 1 , wherein L is a biradical selected from NH, and NCH3; Q is a biradical of formula (IV).

6. The compound according to claim 5, wherein L is a biradical selected from NH, and NCH3; Q is a biradical of formula (IV); p = 1 ; A is a radical selected from -(CH2)u-Z-(CH2)v-NH2 and a radical of formula III, wherein Z is selected from NH and NCH3; and wherein n and w are each independently an integer selected from 15 to 30.

7. The compound according to claim 1 wherein L is a biradical selected from NCH3, N(CH₂)_qNH₂, and a biradical of formula II; q is an integer selected from 1 , 2, 3 and 4; Q is selected from a radical of formula (VI) and (VIII); p is 0; and n and r are each independently an integer selected from 15 to 30.

8. The compound according to claim 7 wherein L is a biradical selected from NCH3, and N(CH2)2NH2; Q is a radical of formula (VI); p is 0; and n is an integer selected from 15 to 30.

9. The compound according to claim 7, wherein L is a biradical selected from NCH3, and N(CH2)2NH2; Q is a radical of formula (VIII), wherein I is an integer selected from 1 , 2, 3, 4, 5, 6, 7, and 8; p is 0; and n is an integer selected from 15 to 30.

10. The compound according to claim 7, wherein L is a biradical of formula II; Q is selected from a radical of formula (VI) and (VIII); p is 0; and n, r and w are each independently an integer selected from 15 to 30.

11. The compound according to claim 10, wherein L is a biradical of formula II; Q is a radical of formula (VI); p is 0; and n is an integer selected from 15 to 30.

12. An engine oil additive package composition comprising a compound of formula I as defined in any one of claims 1 to 11 .

13. An engine oil composition comprising the engine oil additive package composition as defined in claim 12.

14. A fuel additive package composition comprising a compound of formula I as defined in any one of claims 1 to 11 .

15. A fuel composition comprising the fuel additive package composition as defined in claim 14.