AU2019201700B2 - Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants - Google Patents

Abstract

Abstract The invention relates to novel quaternized nitrogen compounds, to the production thereof, and to the use thereof as fuel additives and lubricant additives, such as in particular detergent additives, additive packages that contain said compounds, and fuels and lubricants to which said additive packages have been added. The invention further relates to the use of said quaternized nitrogen compounds as a fuel addition for reducing or preventing deposits in the injection systems of direct injection diesel engines, in particular in common-rail injection systems, for reducing the fuel consumption of direct-injection diesel engines, in particular diesel engines having common-rail injection systems, and for minimizing the power loss in direct-injection diesel engines, in particular in diesel engines having common-rail injection systems.

Description

Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants

This application is a divisional application of Australian Patent Application No. 2016273853, which in turn is a divisional application of Australian Application No. 2012277805. AU2012277805 claims priority from EP Application No. 11171763.3. The specification for each of these applications is entirely incorporated herein by reference.

The present invention relates to novel quaternized nitrogen compounds, to the preparation thereof and to the use thereof as a fuel and lubricant additive, more particularly as a detergent additive, to additive packages which comprise these compounds; and to fuels and lubricants thus additized. The present invention further relates to the use of these quaternized nitrogen compounds as a fuel additive for reducing or preventing deposits in the injection systems of directinjection diesel engines, especially in common-rail injection systems, for reducing the fuel consumption of direct-injection diesel engines, especially of diesel engines with common-rail injection systems, and for minimizing power loss in directinjection diesel engines, especially in diesel engines with common-rail injection systems.

State of the art:

In direct-injection diesel engines, the fuel is injected and distributed ultrafinely (nebulized) by a multihole injection nozzle which reaches directly into the combustion chamber of the engine, instead of being introduced into a prechamber or swirl chamber as in the case of the conventional (chamber) diesel engine. The advantage of the direct-injection diesel engines lies in their high performance for diesel engines and nevertheless low fuel consumption. Moreover, these engines achieve a very high torque even at low speeds.

At present, essentially three methods are being used to inject the fuel directly into the combustion chamber of the diesel engine: the conventional distributor injection pump, the pump-nozzle system (unit-injector system or unit-pump system) and the common-rail system.

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1a

In the common-rail system, the diesel fuel is conveyed by a pump with pressures up to 2000 bar into a high-pressure line, the common rail. Proceeding from the common rail, branch lines run to the different injectors which inject the fuel directly into the combustion chamber. The full pressure is always applied to the common rail, which enables multiple injection or a specific injection form. In the other injection systems, in contrast, only smaller variation in the injection is possible. The injection in the common

8429357_1 (GHMatters) P95787.AU.1

PF 000007'1427 SE/Ab rail is divided essentially into three groups; (1.) pre-injection, by which essentially softer combustion is achieved, such that harsh combustion noises (nailing) are reduced and the engine seems to run quietly; (2,) main injection, wnich is responsible especsahy for a good torque profile; and (3,) post-injection, which especially ensures a low NO* value.

in this post-injection, the fuel is generally not combusted, but instead evaporated by residual heat in ths cylinder. The exhaust gas/fuel mixture formed is transported to the exhaust gas system, where the fuel, in the presence of suitable catalysts, acts as a reducing agent for the nitrogen oxides NO*.

The variable, cylindeMndWuai injection In the common-rail injection system can positively influence the pollutant emission of the engine, for example the emission of nitrogen oxides (NO*), carbon monoxide (CO) and especially of particulates (soot). This makes it possible, for example, that engines equipped with common-rail injection systems can meet the Euro 4 standard theoretically even without additional particulate filters.

In modem common-rail diesel engines, under particular conditions, for example when biodiesel-containing fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds are used, deposits 20 can form on the injector orifices, which adversely affect the injection performance of the fuel end hence impair the performance of the engine, i.e, especially reduce the power, but in some cases also worsen the combustion. The formation of deposits is enhanced further by further developments in the injector constructton, especially by the change rn the geometry of the nozzles (narrower, conical orifices with rounded outlet). For lasting 25 optimal functioning of engine and injectors, such deposits in the nozzle orifices must be prevented or reduced by suitable fuel additives.

in the injection systems of modem diesel engines, deposits cause significant performance problems. It is common knowledge that such deposits in the spray 30 channels can lead to a decrease in the fuel flow and hence to power toss. Deposits at th© injector tip., in contrast, impair the optimal formation of fuel spray mist and, as a result, cause worsened combustion and associated higher emissions and Increased fuel consumption, in contrast to these conventional ‘'external deposition phenomena, IntemaF deposits (referred to collectively as internal diesel injector deposits (IDiD)) in

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2019201700 13 Mar 2019 particular parts of the injectors, such as at the nozzle needle, at the control piston, at the valve piston, at the valve seat, in the control unit and in the guides of these components, also increasingly cause performance problems. Conventional additives exhibit inadequate action against these IDIDs.

US 4,248,719 describes quatemized ammonium salts which are prepared by reacting an alkenylsuccinimide with a monocarboxyltc ester and find use as dispersants in lubricant oils for prevention of sludge formation. More particularly, for example, the reaction of polyisobutylsuccinic anhydride (PIBSA) with Ν,Ν-dimethylsminopropylamine (DMAPA) and qustemlzation with methyl salicylate is described. However, use in fuels, 10 more particularly diesel fuels, is not proposed therein. The use of PISS A with low bismaleation levels of < 20% is not described therein. .

US 4,171,959 describes quatemized ammonium salts of hydrocartayl-substituted succinimides, which are suitable as detergent additives for gasoline ruel compositions.

For quatemizatfon, preference is given to using alkyl halides. Also mentioned are organic CrCrhydrocarbyl carboxylates and sulfonates. Consequently, the quatemized ammonium salts provided according to the teaching therein have, as a counterion, either a halide or a Ca-Crhydrocarbyl carboxylate or a CrCrhydrocarbyl sulfonate group, The use of PIBSA with low bismaleation levels of < 20% is likewise not described therein.

EP-A-2 033 945 discloses cold flow improvers which are prepared by quaternizing specific tertiary monoamines bearing at least one Cs-C^p-alkyl radical with a Cr Chalky I ester of specific carboxylic acids. Examples of such carboxylic esters are dimethyl 25 oxalate, dimethyl maleate, dimethyl phthalate and dimethyl fumarate. Applications other than that of improving the CFPP value of middle distillates are not demonstrated in EP-A-2 033 945.

WO 2006/135881 describes quatemized ammonium salts prepared by condensation of a hydrocarbyl-substituted acylating agent and of an oxygen or nitrogen atom-containing compound with a tertiary amine group, and subsequent quatemization by means of hydrocarbyl epoxide In the presence of stoichiometric amounts of an acid, especially acetic acid. Further quaternizing agents claimed in WO 2006/135881 are dialkyi

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2019201700 13 Mar 2019 sulfates, benzyl halides and hydrocarbyl-substltuted carbonates, and dimethyl sulfate, benzyl chloride and dimethyl carbonate have been studied experimentally.

The quatemizing agents used with preference in WO 2006/135881, however, have serious disadvantages such as: toxicity or carcinogenicity (for example in the case of dimethyl sulfate and alkylene oxides and benzyl halides), no residue-free combustion (for example in the case of dimethyl sulfate and alkyl halides), and inadequate reactivity which leads to incomplete quatemization or uneconomic reaction conditions (long reaction times, high reaction temperatures, excess or quaternlzing agent; for example in the case of dimethyl carbonate).

It. was therefore an object of the present invention to provide improved qua tern Ized fuel additives, especially based on hydrocarbyl-substltuted polycarboxylic acid compounds, which no longer have the disadvantages of the prior art mentioned.

' Brief description of the invention:

It has now been found that, surprisingly, the above object is achieved by providing specific quaternized nitrogen compounds and fuel and lubricant compositions additized 20 therewith.

Surprisingly, the inventive additives thus prepared are superior In several ways to the prior art additives prepared in a conventional manner: they have low toxicity (caused by the specific selection of the quatemizing agent, bum ashtessly, exhibit a high content of 25 quatemized product, and allow an economic reaction regime in the preparation thereof, and surprisingly have improved handling properties, such as especially improved solubility, such as especially in diesel performance additive packages. At tne same time, the inventive additives exhibit Improved action with regard to prevention of deposits in diesel engines, as especially illustrated by the use examples appended.

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Detailed deacrjpHon of the invention:

A1) Specific embodiments

Ths present Invention relates especially to the following specific embodiments:

1. A fuel ar lubricant composition, especially fuel composition, composing, rn a majority of a customary fuel or lubricant, a proportion (especially an effective amount) of at least one reaction product comprising a quaternized nitrogen compound (or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification),, said reaction product being obtainable by

a. reading a high molecular weight hydrocarbyl-substituted poiycarboxylic add compound with a compound comprising at least one oxygen or nitrogen group reactive (especially capable of addition or condensation) with the poiycarboxylic acid, and comprising at least one quatemizable amino group, to obtain a quatemizable hydrocarbyl’Substituted poiycarboxylic acid compound (by addition or condensation), and b, subsequent reaction thereof with a quatemizing agent which converts the at least one hereafter quatemizable, for example tertiary, amino group to a quaternary ammonium group, said quatemizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono* or poiycarboxylic add (especially of a mono* or dicarboxylic acid) or of an aliphatic poiycarboxylic add (especially dicarboxylic acid).

2. A fuel or lubricant composition, especially fuel composition, comprising, in a majority of a customary fuel or lubricant. a proportion (especially an effective amount) of at least one reaction product comprising a quatemized nitrogen compound (or a fraction thereof which comprises a quatemized nitrogen compound and is obtained from the reaction product by purification), said reaction product being obtainable by reacting a quatemizable high molecular weight hydrocarbyl-substituted poiycarboxylic 30 add compound comprising at least one quatemizable amino group with a quatemizing agent which converts the at least one hereafter quatemizable, for example tertiary, amino group to a quaternary ammonium group,

M/51320-PCT

PF 0000071427 SE/Ab said quaternlzing agent being the alkyl eater of a cycloaromatic or cycloaliphatic monoor polycarboxy Ila acid (especially of a mono* or dicarboxylic acid) or of an aliphatic poly carboxylic acid (especially dicarboxylic acid).

3. The fuel composition according to either of the preceding claims, wherein about 1.1 to about 2.0 or about 1.25 to about 2.0 equivalents, for example 1.3, 1.4, 1.5.1.6, 1J, 1,8 or 1.9 equivalents, of quatemizing agent are used per equivalent of quatemlzable tertiary nitrogen atom. By increasing the proportion of quatemizing agent within the range claimed, distinct Improvements in product yields can be achieved.

4. The fuel composition according to any of the preceding claims, wherein the hydrocarbyl-substltuted polycarboxylic acid compound is a polylsobutenylsuccinic add or an anhydride thereof, said add having a bismaleation level of equal to or less than about 20% or equal to or less then about 15%, tor example 15,14,13,12,11,10, 9, 8, 7, 6, 5, 4, 3, 2,1 or 0.1%.

Lower levels of bismaleation can contribute to a distinct improvement in the solubility of the additive and/or compatibility of the constituents in the formulation of additive packages.

5. The fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quatemizing agent is a compound of the general formula 1

RtOCORs (1) in which r, is a low molecular weight hydrocarbyi radical, such as alkyl or alkenyl radical, especially a lower alkyl radical, such as especially methyl or ethyl, and r₂ is an optionally substituted monocyclic hydrocarbyi radical, especially an aryl or cycloalkyl or cycloalkenyl radical, especially aryl such as phenyl, where the substituent is selected from OH, NHs, NCh, C(O)OR& and RiOC(O)-, in which Ri is as defined above and Rg is H or R?, where the substituent is especially OH. More particularly, the quatemizing agent is a phthalate or a salicylate, such as dimethyl phthalate or methyl salicylate.

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6, Th© fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quatemlzing agent is a compound of the general formula 2

RsOC(O)-A-C(O)ORi_B (2) in which

Ri and Ri_e are each independently a low molecular weight hydrocarbyl radical, such as an alkyl or alkenyl radical, especially a lower alkyl radical and

A is hydrocarbylene (such as especially Ci«Cralkylene or CrCralkenyiene).

7. The fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quatemlzed nitrogen compound has a number-average molecular weight in the range from 400 to 5000, especially 800 to 3000 er 900 to 1500.

8., The fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quatemlzing agent is selected from alkyl salicylates, dialkyi phthalates and dialkyi oxalates; particular mention should be made of alkyi salicylates, especially lower alkyl salicylates, such as methyl, ethyl and n· propyl salicylates.

9, The fuel or lubricant composition, especially fuel composition, according to embodiment 1, wherein the compound which is reactive (capable of addition or condensation) with the polycarboxylic acid and comprises an oxygen or nitrogen group and at. least one quatemizable amino group is selected from a, hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable primary, secondary or tertiary amino group;

b, straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary amino group and having at least one quatemizable primary, secondary or tertiary amino group;

c, piperazines, end particular mention should be made of group a.

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10. The fuel or lubricant composition according to embodiment 9, wherein the compound which is reactive, especially capable of addition or condensation, with the poiycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizable amine group is selected from a, hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines,

b. straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one secondary amino group; di- or poiyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary amino group;

and particular mention should be made of group a.

11. The fuel composition according to any of the preceding embodiments, selected from diesel tesla, biodiesel fuels, gasoline fuels and aikanol-containing gasoline fuels.

12. The fuel or lubricant composition., especially fuel composition, according to any of the preceding embodiments, wherein the hydrocarbyl-substituted poiycarboxylic acid compound Is a poly isobutenyl succinic acid or an anhydride (PIBSA) thereof, said acid having a low bismaieation level, especially 10% or less than 10%, for example 2 to 9 or 3 to 7%. More particularly, such PIBSAs are derived from HR-PIB with an Mn in the range from about 40Q to 3000.

More particularly, the above compositions are fuel compositions, in particular diesel fuels.

13.. The reaction product obtainable by a process as defined in any of the preceding embodiments, especially according to embodiment 3, 4, 5, 6 and In particular embodiment 8, 9 or 10, or quaterrtized nitrogen compound obtained from the reaction product by partial or fell purification.

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In a particular configuration (A) of the Invention, quaternized reaction products which are prepared proceeding from polyisobutenyisucddc acid or an anhydride thereof are provided, this compound having a bismaleatton level of equal to or less than about 20% or equal to or less than about 15%, for example 15_s 14, 13,12., 11, 10, 9, 8, 7, 6, S, 4,

S 3, 2., 1, or 0,1%. This polyisobutenylsucclnic add compound is reacted (especially by addition or condensation) with a compound comprising at least one oxygen or nitrogen group reactive (addable or condensable) with the polyisobutenylsuccinic acid compound and containing at least one quatemizable amino group, and then quaternized,

In a particular configuration (B) of the invention, quatemized reaction products which are obtained by quaternlzation using an excess of quaternizing agent are provided.

More particularly, about 1.1 to about 2,0 or about 1.25 to about 2.0 equivalents, for example 1.3, 1.4, 1..5, 1.6, 1.7, 1.8 or 1.9, equivalents of quaternizing agent are used 15 per equivalent of quatemizable tertiary nitrogen atoms. Particularly useful quaternizing agents are those of the formula (1), especially the lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and η-, i- or tertbutyl salicylate.

in a further particular configuration (C)_t configurations (A) and (B) are combined, i.e.. the quatemizable compounds prepared from the above polyisobutenylsuccinic acid compounds according to configuration (A) are quatemized according to configuration (B).

14, A process for preparing a quaternized nitrogen compound according to embodiment 13, comprising the reaction of a quatemizable hydrocarbyksubstituted poiycarboxyllc add compound comprising at least one tertiary quatemizable amino group with a quaternizing agent which converts the at least one tertiary amino group to a quaternary 30 ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic monoor poiycarboxyllc acid (especially of a mono* or dicarboxylic acid) or of an aliphatic poiycarboxyllc acid (especially dicarboxylic acid).

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15.. The use of a reaction product or of a quaternized nitrogen compound according to embodiment 13 or of a compound prepared according to embodiment 14 as a fuel additive or iubricant additive, especially fuel additive, especially diesel fuel additive.

16. The use according to embodiment 15 as an additive for reducing the fuel consumption of direct-injection diesel engines, especially of diesei engines with common-rail injection systems, as determined, tor example, in an XUDd test to CEC-F23*01, and/or for minimizing power loss in dlrect4njection diesel engines, especially in 10 diesel engines with common-rail injection systems, as determined, for example, In a

DW10 test based on CEC-F-OS8-08.

17.. . The use according to embodiment 15 as a gasoline fuel additive for reducing the level of deposits in the intake system of a gasoline engine, such as especially DISS (direct injection spark ignition) and PFl (port fuel injector) engines,

IS. The use according to embodiment 15 as a diesel fuel additive, especially as a cold flow improver, as a wax antisettllng additive (WASA) or as an additive for reducing the level of and/or preventing deposits in the intake systems, such as especially the 20 internal.diesel injector deposits (IDIDs), and/or valve sticking in direct-injection diesel engines, especially in common-rail injection systems,

19* An additive concentrate comprising, in combination with further diesel fuel or gasoline fuel additives, especially diesei fuel additives, at least one quaternized 25 nitrogen compound as defined in embodiment 13 or prepared according to embodiment

14,

A2) General definitions

A condensation or condensation reaction in the context of the present invention describes the reaction of two molecules with elimination of a relatively small molecule, especially of a water molecule. When such an elimination is not detectable analytically, more particularly not detectable In stoichiometric amounts, and the two molecules react

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2019201700 13 Mar 2019 nevertheless, for example with addilion_s the reaction in question of the two molecules Is without condensation.

In the absence of statements to the contrary, the following general conditions apply:

’’Hydrocarbyr can be interpreted widely and comprises both long-chain and shortchain, straight-chain and branched hydrocarbon radicals, which may optionally additionally comprise hetsroatoms, for example Ο, N, NH, S, in the chain thereof.

’'Long-chain or high molecular weight” hydrocarbyl radicals have a number-average molecular weight (Μ_δ) of 85 to 20 000, for example 113 to 10 000, or 200 to 10 000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. More particularly, they are formed essentially from Cjm, especially Cjm, monomer units such as ethylene, propylene, n- or isobutylene or mixtures thereof,, where the different monomers may be copolymerized in random distribution or as blocks. Such long-chain hydrocarbyl radicals are also referred to as polyalkylene radicals or poljHW or polyCs^-alkyiene radicals. Suitable long-chain hydrocarbyl radicals and the preparation thereof are also described, for example, in WO 2006/135581 and the literature cited therein,

Examples of particularly useful polyalkylene radfoals are polyisobutenyl radicals derived from ^,shigh-readivity polyisobutenes (HR-PIB) which are notable for a high content of terminal double bonds (cf., for example, also Rath et al., Lubrication Science (1999), 11-2, 175Ί85). Terminal double bonds are alpha-olefinic double bonds of the type

Polymer

which are also referred to collectively as vinylidene double bonds. Suitable high30 reactivity polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, especially greater than 80 mol% or greater than 85 mol%. Preference is given especially to poiyisobutenes which have homogeneous polymer structures. Homogeneous polymer structures are possessed

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2019201700 13 Mar 2019 especially by those polyisobutenes formed from isobutene unite to an extent of at least 85% by weight, preferably to ar? extent of at least 00% by weight and more preferably to an extent of at least 95% by weight Such high-readivity polyisobutenes preferably have s number-average moieouter weight within the abovementioned range. In 5 addition, the high-reactivity polyisobutenes may have a polydlspersfty In the range from

1,05 to 7, especially of about 1.1 to 2.5, for example of less than 1.9 or less than 1.5. Polydispersity is understood to mean the quotient of weight-average molecular weight Mw divided by the number-average molecular weight Mn.

Particularly suitable high-reactivity polyisobutenes are, for example, the Glisscpal brands from BASF SE, especially Gllssopal® 1000 (Μη» 1000), Giissopal® V33 (Mn-550).,. Gllssopal® 1300 (Mn- 1300) and Gllssopal® 2300 (Mn-2300)_! and mixtures thereof. Other number-average molecular weights can be established in a manner known In principle by mixing polyisobutenes of different number-average molecular weights or by extractive enrichment of poiylsobutenes of particular molecular weight ranges.

PIBSA is prepared in a manner known In principle by reacting PIB with maleic anhydride (MAA), in principle forming a mixture of PIBSA and bismaieated PIBSA (BM

PIBSA, cf. scheme 1, below), which is generally not separated but used as such in further reactions. The ratio of the two components to one another can be reported via the “bfsmaleation level (BML). The BML is known per se (see also US 5,883,198). The BML can also be determined by the following formula:

BML ” 100% ^x [(wt-%(BM PIBSA))/(wt-%(BM PIBSA>wt-%(PIBSA))] where wt-% (X) represents the proportion by weight of component X (X “ PIBSA or BM

PIBSA) in the reaction product of PIB with MSA.

Scheme 1

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Hydracarbyl-substituted poly carboxylic acid compound with a “low bismaieation level, 5 especially corresponding polyisobutenyisucoinlc acids or anhydrides thereof (also referred to overall as PIBSA) are known from the prior art. Especially advantageous are bismaieation levels of 20% or less, or 15% or less, for example 14, 13, 12 or 10%; or 10% or less, for example 2-0, 3-8, 4-7, 5 or 6%. The controlled preparation thereof is described, for example, in US 5,883,196. Suitable for preparation thereof are especially 10 the above high-reactivity polyisobutenes with an Mn in the range from about 500 to

2500,. for example 550 to 3000, WOO to 2000 or 1000 to 1500,

A nonlimiting example of a corresponding PIBSA is Glissopal® SA, derived from HR-PIB (Mn - WOO), with a bismaieation level of 9%.

Short-chain hydrocarbyT or low molecular weight hydrocarbyT’ is especially straightchain er branched alkyl or alkenyl,, optionally interrupted by one or more, for example 2, 3 or 4, heteroatom groups such as -O- or -NH-, or optionally mono- or polysubstitirted, for example di-, tri- or tetrasubstituted.

Alkyl or lower alkyl” represents especially saturated, straight-chain or branched hydrocarbon radicals having 1 to 4,1 to 5, 1 to 8, or 1 to 10 or 1 to 20, carbon atoms, for example methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, .2methylpropyl, 1,1-dlmethylethyl, n-pentyi, 1 «methylbutyl, 2-methylbutyl, 3-methylbutyl, 25 2,2-dimethylpropyf, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyipentyi, 1,1-dimethyibutyl, 1..2dimethylbutyi, 1,3-dimethylbutyl, 2,2-dimsthyibutyl, 2,3-dirnethylbutyl, 3,3-dirnethylbutyl,

-ethy footy 1, 2-ethyi butyl, 1,1,2-tr imethy I propy 1, 1,2,2»tr methyipropyl, 1 -ethyl-1 methyipropyl and 1-ethyl-2-methylprepyi; and also n«heptyl, n-octyl_t n-nonyl and n30 decyl, and the singly or multiply branched analogs thereof.

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WWalkyi’ raprenm* especially the mono- or p_O|yhy<fraxy|_ata!j, especially monohydrcxyiated, analog of the above afcyi _fa<tols, _{for exampte fhe} monohydroxylated analogs of the above straight-chain or branched alkyl radicals, _fer 5 example the linear hydroxyalkyl groups with a primary hydroxyl group, such as hydroxymethyl. 2-hydroxyethyl, 3-hydroxypropyt 4-hydroxybutyl

Afenyr represents mono- or palyunsatureted, especially monounsatorated. straightchain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or .2 or to 1u 20 carbon atoms and a double bond in any position, for example C₂-C«-alkenyl such as ethenyl, 1 -propenyl. 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, U methyM-propenyl, 2-methyM -propenyl, 1-methyi-2-propenyl, 2-methyl-2-propenyl_t 1pentenyi, 2-pentenyl, 3-pentenyi. 4-pentenyl, 1-methyl-1-butenyl, 2-methyM-butenyl. 3methyl-1-butenyl, 1-methyf-2-butenyl. 2-methyF2-butenyh 3-methyl-2-butenyl, 1-methyf15 3-butewi₍ 2-methyf-3-butenyl S-msthyM-butwl, tl-dimelhyi-2-propenyl, l₍2dimethyl-1 -propenyl, 1»2-dimetoyl-2-propenyl, 1 -ethyl-1-propenyl, l-ethyl-2-propenyl, 1hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl. 5-hexenyl, 1 -methyl- 1-pentenyl. 2-methyMpentenyl, 3-methyM-pentenyl, 4~methyl-1-pentenyi, 1-methyl-2-pentenyl, 2-methyl-2pentenyi, 3-methy!-2-pentenyl, 4-methy!-2-pentenyl, i-methyl-3-pentonyl, 2-methyl-320 pentenyl, 3^ethyl-3^entwl_t 4-methyi~3-pentonyl_< 1-methyM-pentenyl. 2-methyMpentenyl, 3-methyM-pentenyl. l-methyl^-pentenyl, 1,1 -dimethyl-Mutenyl, .l-dimethyl-S-butenyi, l,2-dimethyl-1-butenyf, 1,2-dim^hy!-2-butenyl, 1,2foimethyl-3butenyl, 1,3-dlmethyM-butenyl, 13-cfimethyi-2-butenyl_t 1 .S-dimetoyl^-butenyi, 2,2dimethyl-3-butenyl, 2.3-dimethyM-butenyi. 2.3-dlmethyi-2-butenyl, 2,3-dimefhyl-325 butenyl, 3,3-dlmethyl-1-buteny|, 3,3-dlm^hyJ-2-butenyl, 1-ethyM-butenyl, 1-ethyl-2butenyl, l-dhyl-3-butenyl, 2-othyM-butenyl_s 2-ethyi2-butenyi, 2-ethyl-3-butenyi, 1,1,2tomethyk2-propenyt 1-ethyM -methyl-2-propenyl, 1 -efryl-2-methyM -propenyl and 1 -etoyI-2-methyl-2-propenyl.

'Alkylene” represents straight-chain or mono- or pelybranched hydrocarbon bridge groups having 1 to 10 cafoon atoms, for example CrCralkylene groups selected from -CHr, ^CH^HCl-frh-, -CHi-CHCCHs)-, -CH(QH₃)-CH.-, (ChW, -CHj-CHCCHsKHr, (CH₃>. -(CH₂)₅-_f -(CH₂)e, -(CH_a)r_:, ’CH(CH₃)-CH_S-CH₂-CH(CH3)or CHCuHij-CHi-CHrCHrCHiCHli- or CrC^-alkylene groups selected from -CHs-. M/51320-PCT

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2019201700 13 Mar 2019 (CHg>, -<CH₃)s- -CH₂-CH(CH₃)-_t -CH(GHa)-CHr> -(CH₂>CH(CH₃h -CHr CH(CH₃>CH2-.

“Alkenylene** represents th® mono- or polyunsaturated, especially monounsaturated, 5 analogs of the above alkylene groups having .2 to 10 carbon atoms, especially Ca-Cjalkenylenes or CrC^-elkenylenes, such as -CH»CH-, -CH^CH»CH-,

-CH=CH-CH2-CHi-, -CHi-CH=CH-CH_r, -CH^CHa-CH-CH-, -CH(CH₃>0H~CH-,

-CHH3(CH₃^CH-.

Cyclic hydrocarbyl radicals’* comprise especially:

- cycloalkyl: carbocyclic radicals having 3 to 20 carbon atoms, for example Cs-Cticydoalkyl such as cydopropyl, cyclobutyl, cydopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cydodecyl, cycloundecyl and cydododecyl; preference is given to cydopentyl, cyclohexyl, cycloheptyl, and also to cyclopropylmethyl, cyclopropylethyl.

cyclobutylmethyl, cyclobutylethyl, cydopentylmethyl, cyclopentylethyl, cyclohexy Im ethyl, or Cs-Cr-cycloalkyl such as cyclopropyl, cydobutyi, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylm ethyl, cyclopropylethyl, cyclobutylmethyi, cydopentyfeftyl, cyclohexylmethyl, where the bond to the rest of the molecule may be via any suitable carbon atom.

- cycloalkenyl: monocyclic, monounsaturated hydrocarbon groups having 5 to 8, preferably up to 6, carbon ring members, such as cyclopenten-1-yl, cydopenten»3-yl, cydohex.en-1-yl, cydohexen-3-yl and cyclohexen-4-yh

- aryl: mono- or polycyclic, preferably mono- or bicyclic, optionally substituted aromatic radicals having 6 to 20,. for example 6 to 10, ring carbon atoms, for example phenyl, biphenyl, naphthyl such as 1- or 2«naphthyl, tetrahydronaphthyl, fluorenyl,

Indenyl and phenanthrenyl. These aryl radicals may optionally bear 1, 2., 3, 4, 5 or 6 identical or different substituents.

“Substituents’* for radicals specified herein are especially, unless stated otherwise, 30 selected from keto groups, -COOH, -COO-alkyl, -OH, -SH_f -CN, amino, -NO& alkyl, or alkenyl groups.

The term about'¹' in the context of a stated figure or of a value range denotes deviations from the specifically disclosed values. These are usually customary deviations. These

M/51320-PCT

PF 0000071427 SE/'Ab may differ, for example, by ± 10% to ±0.1% from the specific values. Typically, such deviations are about ± 8% to ± 1% or ± 5%, ± 4%,. ± 3% or ± 2%,

A3) PolycarboxyliG acid compounds and hydrocarbyl-substituted polycarboxylfc acid compounds:

The polycarboxylic acid compounds used are aliphatic di- or polybaslc (for example trier tetra basic), especially from di-, tri- or tefracarboxylic acids and analogs thereof, such as anhydrides or lower alkyl esters (partially or completely esterifled), and Is optionally substituted by one or more (for example 2 or 3), especially a long-chain alkyl radical and/or a high molecular weight hydrocarbyl radical, especially a poiyalkylene radical. Examples are Cj-Cw polyearboxylic acids, such as the dicarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pi malic add, suberic acid, azelaic acid and sebadc acid, and the branched analogs thereof; and the tricarboxylic acid citric acid; and anhydrides or lower alkyl esters thereof of. The poly carboxy lie acid compounds can also be obtained from the corresponding monounsaturated acids and addition of at least one long-chain alkyl radical and/or high molecular weight hydrocarbyl radical. Examples of suitable monounsaturated acids are fumaric add, maleic add, Itaconic acid.

The hydrophobic long-chain” or high molecular weight hydrocarbyl radical which ensures sufficient solubility of the quaternized product In the fuel has a numberaverage molecular weight (Μ») of 85 to 20 000, for example 113 to 10 000, or 200 to 10 000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. Typical hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and polyisobutenyl radicals, for example with a number-average molecular weight of 3500 to 5000, 350 to 3000, 500 to 2500, 700 to 2500 and 800 to 1500.

Suitable hydrocarbyl-substituted compounds are described, for example, in

DE 43 19 572 and WO 2008/138836.

Suitable hydrocarbyl-substituted polycarboxylic acid compounds also comprise polymeric, especially dimeric, forms of such hydrocarbyl-substituted polycarboxylic add compounds. Dimeric forms comprise, for example, two add anhydride groups which

M/5132Q-PCT

PF 0000071427 SEiAb

2019201700 13 Mar 2019 can te reacted Mependenuy _{with she quatemizabte nitrog8n oompound jn fte} preparation process according to the invention.

A4) QuatemlzlHg agents:

UseM quatemteing agents _are |_{n prtn{;ipte a}„ _{8t|!yJ es(efs wf)fch} and are those of a cydoaromatlc _or cycloaliphatic mono- or polycartwxyfc add (especially of a mono, or dicarboxylte acid) or of _{an aWlic p0}|y_{raf(wfc asW} (especially dicarboxylic add),

W

In a particular embodiment, however, the at feast one quaternizebie tertiary nitrogen atom is guaternizsd with at feast one quatemfeing agent selected from

a) compounds of the general formula 1

RiOC(O)R? (1) in which

Rf & g lower alkyl radical and

R« Is an optionally substituted monocyclic aryl or eyctoalkyl rafatl. where the substituent is selected from OH, Wfe NO₂, C(O)OR_S, and R,„OC(0)-, in which R„ is as defined above for Fh and Rg is H or P_q;

and

b) compounds of the general formula 2

R_?0C(O)-A-C(O)OR,₈ (2) in which

Ri and R_1a are each independently a lower alkyl radical and

A Is hydrocarbylene (such as alkylene or alkenylene).

Particularly suitable compounds of the formula 1 are those in which

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019

Ri ® a Cr, C?- or C^alkyl radical and (¾ e a substituted phsnyl radical, where the substituent is HO- or an ester radical of the fomiule R_WOC(OJ- which Is in the para, meta or especially ortho position to the RiOC(O)- radical on the aromatic ring.

Especially suitable quaternizing agents are the lower alkyl esters of salicylic add, such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and π-, i- or tert-butyl salicylate.

υ AS) Quatemtzed or quaternlzabte nitrogen compounds:

The quatemizable nitrogen compounds reactive with the polycarboxylic acid compound are selected from * a. hydroxyalkyl-substiteted mono- or polyamines having at least one quatemized (e.₉. choline) or quatemizable primary, secondary or tertiary amino group;

, straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic pdyammes having at least one primary or secondary (anhydride-reactive) amino * group and having at least one quatemized or quatemteable primary, secondary or 20 terttery amino group;

piperazines,, he quatemizable nitrogen compound is especially selected from ^d' hydroxyelkyPsubstltuted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyksubstituted primary, secondary, ternary or quaternary diamines; '

e. straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at feast one secondary amino group; di- or polyamines having at least one primary and at feast one tertiary amino group; di- or polyamines having at feast one primary and at feast one quaternary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic pofyamines having two primary amino groups; aromatic or nonaromatic heterocydes having one primary and one tertiary amino· group.

M/51320-PGT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019

Examples of suitable hydroxyalkyl-subsfituted mono- or polyamines” are those provided with at least one hydroxyalkyi substituted, for example 1, 2, 3, 4, 5 or 8 hydroxyslkyi substituted.

Examples of hydroxyal kyl-substituted monoamines’* Include: Nnhydroxyeikyl monoamines, Ν,Ν-dihydroxyalkyl monoamines and Ν,Ν,Ν-trihydroxyalkyl monoamines, where the hydroxyalkyl groups are the same or different and are also as defined above. Hyciroxyalkyi is especially 2-hydroxyethyl, 3-hydroxy propyl or 4-hydroxy butyl.

For example, the following hydroxyalkyksubstituted polyamines'’ and especially hydroxyalkyl-substituted diamines may be mentioned: (N-hydroxyalkyl)alkylenedlamines, Ν,Ν-dihydraxyalkyiaikylenediamines, where the hydroxyslkyl groups are the same or different and are also as defined above. Hydroxyalkyl Is especially 2« 15 hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyh alkylene Is espscisiiy ethylene, propylene or butylene.

Suitable diamines’* are alkylenediamines, and the N-alkyl-substituted analogs thereof, such as N-monoalkylated alkylenediamines and the N,N- or N,N’-dialkyiated 20 alkylenediamines. Alkylene is especially straight-chain or branched Cw or Cmalkylene as defined above. Alkyl is especially Cm-alkyt as defined above. Examples are especially ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4butyienedlamine and isomers thereof, pentanediamine and isomers thereof, hexanedlamine and isomers thereof, heptanediamine and isomers thereof, and singly 25 or multiply, for example singly or doubly, CrO-alkylated, for example methylated, derivatives of the aforementioned diamine compounds such as 3-dlmethylamino-lpropylamine (DMAPA), Ν,Ν-diethylaminopropylamine and N,N-dimethylamlnoethylamine,

Suitable straight-chain polyamines” are, for example, dialkylenetriamine, trialkylenetetramine, tetraalkylenepentamine, pentaalkylenehexamine, and the N-alkylsubstituted analogs thereof, such as N-monoalkylated and the N_:,.N- or Ν,Ν'-dlalkylated alkylenepolyemines. Alkylene is especially straight-chain or branched Cm- or Cmalkylene as defined above. Alkyl Is especially Cm-alkyl as defined above.

M/51.320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019

Examples ere tetraethyienepentam he , tripropylenetetra mine, dibutyienetriamine, pentabuty lenehexsm In e;

especial |y d iethy i© netriam in e, pentaethylenehexam Ins, tetrapropy lenepenta mine, tributyienetetram he, triethyisnetetra mine, dipropylenetrla mine, penta propytenehexam ine, tetrabutyienepenta mine, and the Ν,Ν-dialkyi derivatives thereof, especially the N.N-diCM-ajkyl derivatives thereof. Examples include; N,N-dimethyldimethylen®triamine, N,N-dlethyldlmethylenetriamine, Ν,Ν-dipropyldimethylenetriamine, N,Ndimethyldietnylene-1,2-trlamlne, N,N-diethyldiethy1ene-1,2-triamine, N.Ndlpropyldtethytene-4,2-triamine, N^-dimethyidipropyiene-l^-triamine (i.e. DMAPAPA). N, N-diethyidi propylene-1,3-triamln e, ‘ dimethyldibutylene-1,4-triamlne, dipropyldlbutylen e-1 ,4-triamlne, diethyldipentylene-1, δ-tria m he, d Im ethyldihexylene-1,6-tria m ine, dipropyldihexylene-1,6-tria m he.

N, N-d ipropy Id [propylene-1,3-trlam he,

N, N-d lethyldlbu tylene-1,4-triami ne, N, N-dimethyldipentylene»1 ,5-triamine, N, N-d ipropyldipentyle ne-1,5-tri am ine,

N, N -dtethyidihexyfene-1 , 6-triamlne an d

H_hMN.NN,NN,NN,NAromatic carbocyclic diamines” having two primary amino groups are the diamino» substituted derivatives of benzene, biphenyl, naphthalene, tetrahydronaphthaiene. 20 fluorene, indene and phenanthrene.

Aromatic or nonaromatic heterocyclic polyamines⁸ having two primary amino groups are the derivatives, substituted by two amino groups, of the fol lowing heterocycles:

2b - 5- or 6-membered, saturated or monounsaturated heterocycles comprising one to two nitrogen atoms and/or one oxygen or suiter atom or one or two oxygen and/or sulfur atoms as ring members, for example tetrahydroteran, pyrrolidine, isoxazolidine, isothiazolidine, pyrazolidine, oxazoiidine, thteiidm imidazoildine, pyrroline, pperiome. pipendmyi, 1,3-dioxane, tetrahydropyran, hexahydropyridazine, 30 hexahydropyrimidhe, piperazine;

- 5-membered aromatic heterocycles comprising, in addition to carbon atoms, two or three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members, for example furan, thiane, pyrrole, pyrazoie., oxazole, thiazole, imidazole 35 and 1,3,4-triazole; isoxazole, isothiazole, thladiazoie, oxadiazofe;

W51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019

- 6-membered heterocycles comprising, In addition to carbon atoms, one or two, or one, two or three, nitrogen atoms as ring members, for example pyrldinyl, pyridazine, pyrimidine, pyrazinyl, 1,2,4-triazlne, 1,3,5-triazin-2-yL “Aromatic or nonaromatic heterocycles having one primary and one tertiary amino group” are, for example, the abovementioned N-heterocycies which are aminoalkylated on at least one ring nitrogen atom, and especially bear an amlno-Cw-alkyl group.

Aromatic or nonaromatic heterocycles having a tertiary amino group and a hydroxyalkyl group” are, for example, the abovementioned N-heterocycles which are hydroxyalkylated on at least one ring nitrogen atom, and especially bear a hydroxy-Ct4’Slkyi group.

Mention should be made especially of the following groups of individual classes of quatemizabie nitrogen compounds:

M/51320-PCT

PF 0000071427 SE/Ab

Group 1:

NA^E .-- .......„ , , SSSSSSSSSSSSS.... I I I

Djawnes with primary second mTrogen atom

Ethylenediamine |

FORMULA

H,N nh₂

1,2-Propytonediamine

NH₂

1,3-Propylenediamlne

H₂Ns^

,.nh₂

Isomeric butytenedlamines, for example

1,5-Penty toned tornlne ,nh₂

Isomeric pentenediamines, for example

M.Ns

NH,

Isomeric hexanediamines, for example

MH,

Isomsbc heptanediamlnes, for example

H₃Ns.

nh₂

OF andpo/yammesmTha secondary second ndrog^

Dieth ylenetriam sne (D ET A)

Dipropyienetriamine (DPTA), 3,3' iminobisf N ,N-d imethyi pro p^amlne)

_xNH₂

T riethylenele (ram i ne (TETA)

T etraethylenepentamine (ΤΕΡΑ)

Pentasf hyle nehexam hie

NH, nh₂

H N,..

h₂n >

HbK

H ,-hk λ. .

Ν'

H

M/51320-PCT

PF 0000071427 SE/Ab

N-MethyF3-am irw~1 -propham ins

NH,

Bfehexarnethylenetdarnirte

H

N.

nh₂.

'nh₂

I Dsaminobenzenes. for example | DiafTsinopyridines. for example h₂n.

Group 2:

NAME

H₂N' n

FORMULA | 1 -(3’Aminopropyi)imidazole

N' ) .

I 4-(3-Ammopropyljmorph<)Hri® .NH.

-(2-AmtaoeihylpipeHdine) v /-W,

N— j 2rt1-Piperazinyi)etoylamine (AEP)

N-Methylpiperazine \

N“ j 3,3-Dsam mo-N-m ethyld Ipropylam me

H.N

NH,

3-Dimethylamho-1 -propylamine (DMAPA) J

M/51320-PCT

PF 0000071427 SE/Ab

N, N-Diethyleminopropylam ine

KN

I N, NOimethylam inoethyla m Ine

H₂N

Group 3:

L_...... ........ „ NAME 2 ΞΖΓΖΖΤ j Afcg/?Qfe _a pnfffia/y arrtfsecoridary am/ne'™

FORMULA j Ethanolamine

H,K

3-Hydroxy-1 -propytem ins

H₂N

Diethanolamine

HO

OH

Diisopropanolamrn®

HO ‘OH

H2“Hydroxy^hyl)eth^ensdiafRine

NH

HO

OH

J

I Triethanolamine, (2,2^2^a-Niirilotriethanol)

ΌΗ

H 3-Hyd roxypropyijlm idazols

W51320-PCT

PF 0000071427 SE/Ab

Γ ~~

I Tris(hydroxyrn$thyi Jamine

3-Dim e thy la m ino-1 -propanol

3“Di6thylam ino-1 -props nd

| g-Dimdhylamlino-l -ethanol

H------—--_

A6) Preparation of Inventive additives:

a) Reaction with oxygen or nitrogen group

Th© hydrocarbyi-substitufed poiycarboxylic acid compound can be reacted with the quatemizable nitrogen compound according to the present invention under thermally controlled conditions, such that there is essentially no condensation reaction. More particularly, no formation of water of reaction is observed in that case, More particularly, such a reaction is effected at a temperature in the range from 10 to 80*0, especially 20 to 60*C or 30 to 50*C. The reaction time may be in the range from a few minutes or a few hours, for example about 1 minute up to about 10 hours. The reaction can be effected at a pressure of about 0.1 to 2 atm, but especially at approximately standard pressure, For example, an inert gas atmosphere, for example nitrogen, is appropriate,

More particularly, the reaction can also be effected at elevated temperatures which promote condensation, for example in the range from 90 to 100'C or 100 to 170^eC.

M/5132Q-PCT

PF 0000071427 SBAb

2019201700 13 Mar 2019

Ths reaction time may be in the region of a few minutes or a few hours, for example about 1 minute up to about 10 hours. The reaction can be effected at pressure at about 0:.1 to 2 atm, but especially at about standard pressure.

o The reactants are initially charged especially in about equimolar amounts; optionally, a small molar excess of the poiycarboxyllc acid compound, for example a 0.05- to 0.5fold. for example a 0.1-to 0.3-fold, excess, Is desirable. If required, the reactants can be sretiaily charged In a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are, for example, solvents of the Solvesso series, toluene or 10 xylene. The solvent can also serve, for example, to remove water of condensation azeotropfcahy from the reaction mixture. More particularly, however, the reactions are performed without solvent.

The reaction product thus formed can theoretically be purified further, or the solvent 15 can be removed. Usually, however, this is not absolutely necessary, such that the reaction step can be transferred without further purification into the next synthesis step, the quaternization.

b) Quaternization he quatemtzation in reaction step (b) is then carried out In a manner known per se.

To perform the quaternization, the reaction product or reaction mixture from stage a) is admixed with at least one compound of the above formula 1 or 2, especially in the 25 stoichiometric amounts required to achieve the desired quatemizafion. It fs possible to use, for example, 0.1 to 2.0, 0.2 to 1.5 or 0.5 to 1.25 equivalents, of quatemizing agent per equivalent of quafernlzabfe tertiary nitrogen atom. More particularly, however, approximately equimolar proportions of the compound are used to quatemize a tertiary amine group.. Correspondingly higher use amounts are required to quaternize a 30 secondary or primary amine group, in a further variant, the quatemizing agent is added in excess, for example 1.1 to 2.0, 1,25 to 2 or 1.25 to 1.75 equrvalente of quatemizing agent per equivalent of quaternizable tertiary nitrogen atom.

Typical working temperatures here are in the range from 50 to 180^eC, for example from 35 00 to 1S0^eC or 100 to 140°C. The reaction time may be in the range of a few minutes

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 or e few hours, for example about 10 minutes up to about 24 hours. The reaction can be effected at a pressure of about 0.1 to 20 bar, for example 1 to 10 or 1.5 to 3 bar, but especially et about standard pressure.

b If requhed, the reactants can be initially charged for the quaternization in a suitable inert organic ahphatic or aromatic solvent or a mixture thereof, or a sufficient proportion of solvent from reaction step a) is still present Typical examples are, for example, solvents of the Solvesso series, toluene or xylene. The quaternization can, however, also be performed in the absence of a solvent io

To perform the quaternlzation, the addition of catalytically active amounts of an acid may be appropriate. Preference is given to aliphatic monocarboxylic acids, for example vrCirmonocsrboxyHc acids such as ©specially fa uric acid, isononanolc acid or neodecanolc add, The quaternlzation can also be performed in the presence of a 15 Lewis acid. The quaternization can, however, also be performed in toe absence of any acid.

c) Workup of the reaction mixture

The reaction end product thus formed can theoretically be purified further, or the solvent can be removed. In order to Improve the further processability of the products, however, it is also possible to add solvent after the reaction, for example solvents from the Solvesso series, 2-ethylhexanol. or essentially aliphatic solvents. Usually, however, this is not absolutely necessary, and so the reaction product is usable without further purification as an additive, optionally after blending with further additive components (see below).

B) Further additive components

The fuel addltlzed with toe inventive quatemlzed additive is a gasoline fuel or especially a middle distillate fuel, in particular a diesei fuel

The fuel may comprise further customary additives to Improve efficacy and/or suppress wear.

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019

In the case of diesel fuels, these are primarily customary detergent additives, carrier oOs, cold how Improvers, lubricity improvers, corrasion Inhibitors, demulsifiers, denazers, antifoams, cetane number impravers, combustion improvers, antioxidants or 5 stabilizers, antistats, metallocenes, metal deactivatore, dyes and/or solvents.

In the case of gasoline fuels, these are in particular lubricity impravers (friction modifiers), corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion impravers, antioxidants or stabilizers, antistats, metallocenes, metal deactivators, dyes '10 and/or solvents.

Typical examples of suitable coadditives are listed In trie following section:

81) Detergent additives

The customary detergent additives are preferably amphiphilic substances which possess at feast one hydrophobic hydrocarbon radical with a number-average molecuiar weight (M„) of as to 20 000 and at ieast one polar moiety selected from20 (Da) mono- or polyamino _Br_Otlps havl_{ni up to} θ _{nHroem g(} atom having basic properties;

(Db) nitro groups, optionally in combination with hydroxyl groups;

(De) hydroxyl groups in combination with mono- or polyamino groups, at feast on© nitrogen atom having basic properties;

(Dd) carboxyl groups or their alkali metal or alkaline earth metal safe;

(De) sulfonfc acid groups or their alkali metal or alkaline earth metal salts;

(Of) polyoxy-O to C^-alkyiene moieties terminated by hydroxyl groups, mono- or poiyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups; *

M/51320-PCT

PF 0000071427 SE/Ab (Dg) carboxylic ester groups;

(Dh) mofettes derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups; and/or (Dr) motets obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.

The hydrophobic hydrocarbon radical in the above detergent additives, which ensures the adequate solubility in the fuel, has a number-average molecular weight M) of 85 to 000, preferably of 113 to 10 QOO, more preferably of 300 to 5000 even more preferably of 300 to 3000, even more especially preferably of 500 to 2500 and especlaify of 700 to 2500, in particular of 800 to 1500.. As typical hydraphobic > 5 hydrocarbon radicals, especially in conjunction with the polar especially polypropenyl, polybutenyi and polyisobutenyi radicals with a number-average molecular weight M, of preferably in each case 300 to 5000, more preferably 300 to 3000, even more ' preferably 500 to 2500, even more especially preferably 700 to 2500 and especially 800 to 1500 into consideration,

Examples of the above groups of detergent additives include the following;

Aodtevas comprising mono- or polyamino groups (Da) are preferably poly alkenemono or polyalkenepolyamlnes based on polypropene or on high-reactivity (i.e* having 25 predominantly terminal double bonds) or conventional (ire, having predominancy internal double bonds) polybutane or polyisobutene having M_n - 300 to 5000, more preferably 500 to 2500 and especially 700 to 2500. Such additives based on highreactivity polyisobutene, which can be prepared from the polyisobutene which may comprise up to .20% by weight of π-butene units by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimetnylamsnopropytemlne, ethylenediamine, diethylenetriamine, triethyleneteframine or tetraethyfenepentamins, are known especially from EP-A244 616. When poiybutene or polyisobutene having predominantly Internal double bonds (usually in the β and y positions) are used as starting materials in the preparation of the additives, a possible

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 preparative route is by chtodnatkm and sequent amination or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent amination under .reductive (hydrogenating) conditions. The amines used here for the amination may be, for example, ammonia, monoamines or the abovementioned polysmines. Corresponding additives based on polypropene are described in particular in WO-A 94/24231. >

Further particular adrtlttves comprise monoamino groups (Oa) are the hydrooenation products of the reaction products of polyisobutenes haying an average degree of polymerization P . 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 97/03946.

Further particular additives comprising monoamino groups (Da) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262. '

Additives comprising nitro groups (Db), optionally in combination with hydroxyl groups are preferably reaction products of polyisobutenes having an average degree of 20 polymerization P - 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxKtes and oxygen, as described in particular in WO-A 96/03367 and in WO-A WJ3479. These reaction products are generally mixtures of pure nftropolyisobutenes (e.g.. α,β-dWtropolyisGbutene) and mixed hydroxynltropoMsobutenes (e.g. α-ηίίτο-βh ydroxypo ly isobutene).

Adortrees comprising hydroxyl groups in combination with mono- or polyamino groups (De) are in particular reaction products of polyisobutene epoxides obtainable from polyisobutene having preferably predominantly terminal double bonds and M„ = 300 to 5000, with ammonia or mono- orpotyamines, as described in oarticular in EP-A 30 470485. '

Additive comprising carboxyl groups or their atell metal or atallne earth metal selts (Od) are preferably copolymers of Cr to Ce-olefins with maleic anhydride which have e total molar mass of 500 to 20 000 and some or all of whose carboxyl groups have been

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 converted to the alkali metal or alkaline earth metal salts and any remainder of the carboxyl groups has been reacted with alcohols or amines. Such additives are disclosed in particular by ΕΡΆ 307 81 δ. Such additives serve mainly to prevent valve seat wear and can, as described in WO A 87/01126, advantageously be used in combination with customary fuel detergents such as poly(iso)buteneam ines or poiyetheramines.

Additives comprising sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as described in particular in EP-A 030 632, Such additives serve mainly to prevent valve seat wear and can be used advantageously in combination with customary fuel detergents such as poly(iso)buteneamines or polyetheramines.

Additives comprising polyoxy-Cs-C^alkylene moieties (Df) are preferably polyethers or 15 polyetheramlnes which are obtainable by reaction of Cr to Ce«ralkanols, Cs- to C®»alkanediols, mono- or dl-Cr to C^j-alkylamines, Cr to C^-alkyicyclohexanols or Ci- to Csiralkylphenols with 1 to 30 moi of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described in particular In EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A4 877 416. in the case of polyethers, such products also have carrier oil properties. Typical examples of these are tridecanol butoxylates, Isotrtdecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and also the corresponding reaction products with ammonia.

Additives comprising carboxylic ester groups (Dg) are preferably esters of mono», di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mm®/s at 100’C, as described In particular in DE-A 38 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids, and 30 particularly suitable ester alcohols or ester polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates,, isophthalates, terephthalates and trimellltates of Isooctanol, of isononanol, of isodecanol and of isotridecanol. Such products also have carrier oil properties.

M/51320-PCT

PF 0000071427 SEZAb

2019201700 13 Mar 2019

Additives comprising moieties derived from succinic anhydride and having hydroxyl snd/or amino and/or amido andfor especially Imido groups (Dh) are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and especially the corresponding derivatives of poiyisobutenylsucdnic anhydride which are Obtainable by reading conventional or high-reactivity polyisobutene having M, = praferaw 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2500, even more especially preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride by a thermal route in an ene reaction or via the chlorinated potyisobutene. The moieties having hydroxyl and/or amino and/or amido and/or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, add amides of o or polyamines which, In addition to the amide function, also have free amine groups, succinic acid derivatives having an acid and an amide function, „ carboximides with monoamines, carboximides with di- or polyamines which, in addition 1b to the Imide function, also have free amine groups, or diimides which are formed by the reaction of dh or pofyamlnes with two succinic acid derivatives, in the presence of ’ imido moieties D(h). ths further detergent additive in the context of the present invention is, however, used only up to a maximum of W0% of the weight of compounds with betaine structure. Such fuel additives are common knowledge and are described 20 for example, in documents (1) and (2). They are preferably the reaction products of ’ alkyl· or alkenyInstituted succinic adds or derivatives thereof with amines and more preferably the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines. Of particular interest in this context are reaction products with aliphatic polyamines (polyalkyleneimines) such as especially ethylenediamine, diethyfenetriamine. triethytenetetramine, tetraethyleneoen famine, pmitaethytenehexamkte and hexasthyfeneheptemine, which have an imide structure.

Additives comprising moieties (Di) obtained by Mannich reaction of substituted phenols _ with aldehydes and mono- or polyamines are preferably reaction products of 30 polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethytenediamine, diethyienetrismine, triethylenetetramine, tetraathytenepentemine or dimethyiaminopropytamme. The polyisobutenyi-substiteted phenols may stem from conventional or high-reactivity poiyisobbtene having M_n. = 300 to 5000, Such potyisobutene Mannich bases are described in particular in EP-A 831 141.

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PF 0000071427 SE/Ab

2019201700 13 Mar 2019

One or more of the detergent additives mentioned can be added to the fuel in such an anoint that the dosage of these detergent additives is preferably 25 to 2500 ppm bv ₅ wetght, especially 75 to ,500 ppm by weight. _in ,_{50 t(J 10M ppm}

B2) Cam'er oils

Carrier oils additionally used may be of mineral or synthetic nature. Suitable mineral carrier oils are the fractions obtained in crude oft prating, such as brightstock or 1Q case otis naving vIscoslties, for example. from the SM 500 to 2000 ofa_ss- but also aromatic hydrocarbons, paraffinic hydrocarbons and altoxyalkanote. Likewise useful fe a fraction which is obtained in the refining of mineral oil and is known as «hydrocrack oil (vacuum dfsWIste cut having a boiling range from about 360 to 500’C, obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized 15 under high pressure and also deparaffinized). Likewise suitable are mixtures of the abovementioned mineral carrier oils.

Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins or polymtemalolefins), (polyJesters. (poly)alkoxylatss, polyethers, aliphatic pofyetiw20 amines, «WtenoLstoted polyethara, alkyiphenol-sterted polyetheramines end carboxylic esters of long-chain alkanols.

Examples of suitable polyolefins are olefin polymere having M. - 400 to 1800, in particular based on polybutene or polytobuteno (hydrogenated or unhydrogenated).

Examples of suitable polyethers or pdyetheramines are preferably compounds comprising pofyoxy^ to Cralkylene moietles which are obtainable by reacting C> to C^alkanols, C_r to C^alkanedtols, mono- or di-C₂- to C_3(S-alkylamlnes, Ch- to alxylcycfohexanols or to C^-alkylphenois with 1 to 30 mol of ethylene oxide and/or prepytene oxide andfor butylene oxide per hydroxyl group or amino group, and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described In particular in EP-A 310 875, EP-A 366 725. EP-A ZOO 985 and US-A 4,877,416. For example the polyetheramines used may be poly-c,- to C.-alkyiene oxkfe amines _or functional

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 derive thereof. Typical examples thereof are tridecanol bufoxyiates or isotridecanol outoxytates, Isononyfphenol bufoxyiates and also polyisobutenol butoxyfates and propoxylates, and also the corresponding reaction products with ammonia.

o Examples of carboxylic esters of long-chain alkanols are in particular esters of mono-, dF or tricarboxylic acids with long-chain alkanols or polyols, as described In particular In DE-A 38 38 918. The mono-, di- or tricarboxylic acids used _{may be} sllphatic or aromatic acids; suitable ester alcohols or polyols are in particular long-chain representatives having, for example, 8 to 24 carbon atoms. Typical representatives of the esters ate adipates, phthalates, Isophthalates, terephthalates and trlmellltetes of isooctanol, isononanol, isodecanol and Isotridecanol, for example di(n- or isotridecyn phthalate, '

Further suitable carrier oil systems are described, for example, in DE-A 38 26 608. 15 DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617. ’ examples or particularly suitable synthetic carrier oils are alcohoi-started polyethers having about 5 to 35, preferably about 5 to 30, more preferably 10 to 30 and especially 15 to 30 Ca- to Cralkylene oxide units, for example selected from propylene oxide, n20 butylene oxide and isobutylene oxide units, or mixtures thereof, per alcohol molecule.

Nonllmitlng examples of suitable starter alcohols are long-chain alkanols or phenols substituted by long-chain alkyl in which the long-chain alkyl radical is in particular a straight-chain or branched to C_isralkyi radical. Particular examples include ~ tridecanol and nonylphenok Particuteriy preferred alcohol-started polyethers are the 2t> reaction products (polyetherffication products) of monohydric aliphatic C_r to C_ir alcohois with C₃- to C_ralkyfene oxides. Examples of monohydric aliphatic Ca-Cir alcohols are hsxanol, heptanol, octanol, 2-dhy I hexanol, nonyl alcohol, decanol, 3propyiheptanol, undecanal, dodeasnol, tridecanol, tetradecanol, pentadeoano), ~ hexadecanol, octadecanol and the constitutional and positional isomers thereof. The u0 alcohols can be used either in the form of the pure isomers or in the form of technical grade mixtures. A particularly preferred alcohol is tridecanol. Examples of C₃- to C₆alkyiene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylens oxide, isobutylene oxide or tetrahydrofuran, pentyiena oxide and hexylene oxide. Particular preference among these is giv^ _to C.M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 to Ο,-elkylene oxides, I.e. propylene oxide «ch « 1,2-propylene _{oxWe 3nd buSyfeoe} ox.de such as 1,2-butylane oxide, 2.3-butyiene oxide and Isobutylene _oxide. a-*** butylene oxide is used,

Further suitable synthetic carrier oils are aitoxyiafed alkylphenols, as described i_n DE-A W 102 913. ‘

Particular carrier oils are synthetic carrier oils, particular preference being given to the above-described alcohoFsterted polyethers.

IO ’

The carrier oil or the mixture of different oils is added to the tel h « _{sraount of} preferably 1 to WOO ppm by weight, more pr_efe_rab|y of w to 500 ppm by weight end especially of 20 to 100 ppm by weight,

B3) Cold fiow improvers

«.table cold flow improvers are in principle all organic compounds which are capable οι improving the flow performance of middle distillate tels or diesel tele under cold commons. For the Mended purpose, they must have sufficient oil solubility i_R particular, _useM cold _&w improvers _{for Ws} (middle distillate flow Improvers, MDHs) typically used _h the case of middle distillates of fossil origin, i.e. in the case of customary mineral diesel fuels. However, It Is also possible to use organic compounds which party or predominantly have ths properties « a wax antisettling additive (WASA) when used ip customary diesel fuels. Thev can 25 also act partly or predominantly as nucleators. It Is. though, also possible to use mixtures of organic compounds effective as MDFIs and/o- effective as WASAs andfer effective as nucleators. ’

The cold flow improver is typically selected frc-m •Λ) (KI> cop_wsy_s»»ers of a Cs- to C^otefin with at feast one further ethytenicalfy unsaturated monomer;

(K2) comb pofyrnerc;

(K3) polyoxyalkytenes;

(K4) peter nitrogen com pounds;

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 (K5) suifocarboxylic acids or sulfonic adds or derivatives thereof· and (K6) poly(meth)acrylic esters.

It is possible to use either mixtures of different representatives from one of the particular classes (KI) to (K6) or mixtures of representatives from different classes (Kt) to (K6). '

Suitable Cr to C^lefin monomers for the copolymers of class (Ki) are, for example, those having 2 to 20 and especially 2 to 10 carbon atoms, and 1 to 3 and preferably 1 10 or 2 carbon-carbon double bonds, especially having one carbon-carbon double bond.

In the latter case, the carbon-carbon double bond may be arranged either terminally (aolefins) or internally. However, preference is given to α-olefins, more preferably aolefins having 2 to e carbon atoms, for example propene, 1-butene, 1-pentene,. 1hexene and in particular ethylene.

In the copolymers of class (K1), the at least one further ethylenlcally unsaturated monomer is preferably selected from alkenyl carboxylates, (meth)acrylic esters and further olefins.

When further olefins are also copolymerized, they are preferably higher in molecular weight than the abovementioned Cr to C^-olefin base monomer. When, for example, the olefin base monomer used is ethylene or propene, suitable further olefins are in particular Ow- to C-w-a-oleflns. Further olefins are in most cases only additionally copolymerjzed when monomers with carboxylic ester functions are also used.

Suitable (metn)acryhc esters are, for example, esters of (meth)acrylic acid with Cr to C^j-adtenols, especially Gt- to G?a-alkanofs, in particular with methanol, ethanol, propanol, rsopropanol, n-butanol, seo-butanol, isobutanol, tert-butanol, pentanol hexanol, heptanol, octanol, 2-ethylhexanol, nonanoi and decanol, and structural isomers thereof.

Suitable alkenyl carboxylates are, for example, Or to C«-alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carton atoms, whose Hydrocarbon radical may be linear or branched. Among these, preference is given to

M/51320-PCT

FF 0000071427 SE/Ab

2019201700 13 Mar 2019 the vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical, preference is given to those whose branch is in the oposition to the carboxyl group, the o-carbon atom more preferably being tertiary, i.e. the carboxylic acid being a socalled neocarboxylic add. However, the hydrocarbon radical of the carboxylic add is preferably linear.

Examples of suitable alkenyl carboxylates are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoste, vinyl hexanoate, vinyl neonone noate, vinyl neodecanoate and th© corresponding propenyl esters, preference 10 being given to the vinyl esters. A particularly preferred alkenyl carbonate Is vinyl acetate; typical copolymers of group (K1) resulting therefrom are ethylene-vinyl acetate copolymers CEVAs), which are some of the most frequently used. Ethylene-vinyl acetate copolymers usable particularly advantageously and their preparation are described in WO 99/29748.

Suitable copolymers of class (K1) are also those which comprise two or more different alkenyl carboxylates in copolymerized form, which differ in the alkenyl function and/or in the carboxylic acid group. Likewise suitable are copolymers which, as well as the alkenyl carboxylate(s), comprise at least one olefin and/or at least one (meth)acrylic 20 ester in copolymerized form.

Terpolymers of a Cr to C^-a-olefin, a Ci- to C^-aikyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a Cr to Gw-alkenyl ester of a saturated monocarboxylic add having 2 to· 21 carbon atoms are also suitable 25 as copolymers of class (K1), Terpolymers of this kind are described in WO

2005/054314. A typical terpolymer of this kind is formed from ethylene, 2-ethylhexyl acrylate and vinyl acetate.

The at least one or the further ethyleuicaiiy unsaturated monomers) are copolymerized 30 in the copolymers of class (KI) in an amount of preferably 1 to 50% by weight, especially 10 to 45% by weight and in particular 20 to 40% by weight, based on the overall copolymer. The main proportion In terms of weight of the monomer units in the copolymers of class (KI) therefore originates generally from the C₂ to base olefins.

M/51320-PCT rr uuuuuroezr tsfc/AP

2019201700 13 Mar 2019

The copolymers of class (KI) preferably have a number-average molecular weight M. of WOO .o J3 Ου0, more preferably 1000 to 10 000 and in particular 1000 to 8000.

Typical comb polymers of component (K2) ere, for example, obtainable by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an arofefin or an unsaturated ester, such as vinyl acetate, and subsequent esteriffcatbn of the anhydride or acid function with an alcohol having at least 10 carbon atoms. Further suitable comb polymere are copolymers of a-olefins and esteriflad comonomers, for example esterifed copolymers 10 of styrene and maiete anhydride or esterjfied copolymers of styrene and fumaric acid.

Suitable comb polymere may also be polylumarates or polymaleates. Homo- and copolymers of vinyl ethers are also suitable comb polymere. Comb polymere suitable as components of class (K2) are, for example, also those described in WQ 2004/035715 and In “Comb-Like Polymere. Structure and Properties, M, A.. Plate and 15 V. P. Shibaev. J. Poly, Scl. Macromolecular Revs, 8, pages 117 to 253 (W74).

Mixtures of comb polymers are also suitable.

Polyoxyalkylene® suitable as components of class (K3) are, for example, polyoxyalkylene estere, polyoxyalkylene ethers, mixed poiyoxyalkytene esterfethers 20 and mixtures thereof. These polyoxyalkylene compounds preferably comprise at least one linear alkyl group, preferably at least two linear alkyl groups, each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number-average molecular weight of up to 5000,. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and also in US 4,491,455. Particular polyoxyalkylene compounds are based 25 on polyethylene glycols and polypropylene glycols having a number-average molecular weight of wo to 5000. Additionally suitable are polyoxyalkylene mono- and diestere of fatty acids having W to 30 carbon atoms, such as stearic add or behenic sold.

Polar nitrogen compounds suitable as components of class (K4) may be either ionic or 30 nonionlc and preferably have at least one substituent, in particular at least two substituents, in the form of a tertiary nitrogen atom of the general formula >NR? In which R⁷ is a C_r to ^-hydrocarbon radical. The nitrogen substituents may also be quatemlzed, Le. be in cationic form. An exampte of such nitrogen compounds is that of ammonium salts and/or amides which are obtainable by the reaction of at least one

M/51320-PCT

PF 0000071427 SE/Ab amine substituted by at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof The amines preferably comprise at least one linear Ca- to C-walkyl radical· Primary amines suitable for preparing the polar nitrogen compounds mentioned are, for example, cctylamine, nonylamln®, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs. Secondary amines suitable for this purpose are, for example, dtoctadecylamine and methylbehenylamine. Also suitable for this purpose are amine mixtures, in particular amine mixtures obtainable on the industrial scale, such as fatty amines or hydrogenated tallamlnes, as described, for example, In Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Amines, aliphatic¹’ chapter. Adds suitable for the reaction are, for example, cyclohexane^ ,2-dicarbcxylic acid, cycl o hexene-1,2-dicarboxylio acid, cyclopentane-1,2-dicarboxyilc acid, naphthalenedfcarboxylrc acid, phthalic acid, isophthalic add, terephthalic add, and succinic acids substituted by long-chain hydrocarbon radicals.·

In particular, the component of class (K4) Is an oil-soluble reaction product of poly (Cato· Cga-carbsxyiic acids) having at. least one tertiary amino group with primary or secondary amines. The poiyfCr to Cso-carboxyllc adds) which have at least one tertiary amino group and form the basis of this reaction product comprise preferably at least 3 carboxyl groups, espedatly 3 to 12 and in particular 3 to 5 carboxyl. groups. The carboxylic add units in the polycarboxyllc adds have preferably 2 to 10 carbon atoms, and are especially acetic add units. The carboxylic acid units are suitably bonded to· the polycarboxyllc adds, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in the case of a plurality of nitrogen atoms, are bonded via hydrocarbon chains.

The component of class (K4) is preferably an oil-soluble reaction product based on poly(Cr to C^-carboxylic adds) which have at least one tertiary amino group and are of the general formula Ila or lib

HOOCb .CQQH B B

HOQC.^zN. _A A_n,COOH

B A B (Ila)

M/51320-PCT rr bfc/AP

2019201700 13 Mar 2019

ΗΟ0Τ^Βγ%00Η

B ⁿcooh (lib) in which the variable A is a sWght-ctain or branched C₂- to Ce-alkylene grauc or the moiety of the formula ill ' hqoc' rsi' ^CHr^CH2‘

ChL_fCH._f (Hl) and the variable S is a to C_1g-aikylene group. The compounds of the general formulae I fa and ifo especially have the properties of a WASA ’

Moreover, the preferred o^oluble reaction product of component (K4), especially that of the general formula Ila or fib, fo an amide, an amid^ammcnium salt or an ammonium salt in which no, one or more carboxylic add groups have been converted to amide groups.

StraighUharn or branched to C^alkylene groups of the variable A are, for example 1.1-ethytene, 1,2-propyierie, 1,3-propytene, 1,2-butylene, 1,3-butylene, 1,4-butylene. ’ 2-methyM,3-propylene, 1,5-pentylene, 2-methyM ,4-butyfene, 2.2-dimethyM 3propylene, tOexylene (hexamethylene) and in particular 1,2-ethyiene. The ImWeA 20 comprises preferably 2 to 4 and especially 2 or 3 carbon atoms.

Ci~ to C^kylene groups of the variable B are, for example, 1 ^ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethytene, decamethylene, dodecamethytene, tetradecamethylene, hexadecam ethylene, octadeca methane, 25 nonadeca methylene end especially methylene. The variable 8 comprises preferably 1 to 10 and especially 1 to 4 carbon atoms.

The primary _and secondary amines _{Bs a} reaction _{partner for polyOBriKS<yfc acWs to} „ form component (K4) are typically monoamines, especially aliphatic monoamines. 30 These primary and secondary amines may be selected from a multitude of amines which bear hydrocarbon radicals which may optionally be bonded to one another.

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2019201700 13 Mar 2019

These parent amines of the oil-soluble reaction products of component (K4) are usually secondary amines and have the general formula HN(R^ in which the two variables R« are each independently straight-chain or branched C_iS- to Cstralkyl radicals, especially 5 Cu- to C?4-alkyl radicate. These relatively tong-chain alkyl radicals are preferably strasght-chaln or only slightly branched. In general, the secondary amines mentioned, with regard to their relatively long-chain alkyl radicals, derive from naturally occurring fatty add and from derivatives thereof. The two R® radicals are preferably identical.

The secondary amines mentioned may be bonded to the poiycarboxylic acids by means of amide structures or in the form of the ammonium salts; It Is also possible for only a portion to be present as amide structures and another portion as ammonium salts. Preferably only few, if any, free acid groups are present The oil-soluble reaction products of component (K4) are preferably present completely tn the form of the amide structures.

Typical examples cf such components (K4) are reaction products of nitrltotriacetic acid, of ethylenediaminetetraacetic acid or of propylene-1,2-diaminetetraacetic sold with in each case 0.5 to 1.5 mol per carboxyl group, especially 0.8 to 1.2 mol per carboxyl 20 group, of dioleylamine, dips! mitinam foe, dicoconut fatty amrne, disfearylamine, dibehenylamine or especially ditallow fatty amine. A particularly preferred component (K4) is the reaction product of 1 moi of ethylenediaminetetraacetic acid and 4 mol of hydrogenated ditallw fatty amine.

Further typical examples of component (K4) include the Ν,Ν-dfsikylammonlum salts of 2-N’,N’-dialkylamidobenzcates, for example the reaction product of 1 mol of phthalic, anhydride and 2 mol of ditallow fatty amine, the latter being hydrogenated or unhydrogenated, and the reaction product of 1 mol of an alkenylspirobislactone with 2 mol of a dialkylamine, for example ditel low fatty amine and/or tallow fatty amine, the last two being hydrogenated or unhydrogenated,

Further typical structure types for the component of class (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic add-containing polymers, as described in WO 93/18115..

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Sulfocarboxylic acids, sulfonic acids or derivatives thereof which are suitable as cold flow improvers of class (K5) are, for example, the oil-soluble carboxamides and carboxylic esters of oriho-sulfobenzoic add, In which the sulfonic add function is present as a sulfonate with aikyLsubstituted ammonium cations, as described In EP-A 261 957.

Poly(meth)acrylie esters suitable as cold flow improvers of class (K6) are either homoor copolymers of acrylic and methacrylic esters. Preference is given to copolymers of at 10 least two different (methacrylic esters which differ with regard to the esteriffed alcohol

The copolymer optionally comprises another different olefinlcally unsaturated monomer in copolymerized form. The weight-average molecular weight of the polymer is preferably 50 000 to 500 000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic esters of saturated Cm and alcohols, the add groups having been neutralized with hydrogenated tellamine. Suitable poly(meth)acrylic esters are described, for example, in WO 00/44857.

The cold flow improver or the mixta re of different cold flow improvers is added to the middle distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by 20 weight, more preferably of 20 to 2000 ppm by weight even more preferably of 50 to

1000 ppm by weight and especially of 100 to 700 ppm by weight, for example of 200 to 500 ppm by weight.

B4) Lubricity improvers

Suitable lubricity improvers or friction modifiers are based typically on fatty acids or tatty acid esters. Typical examples are tail oil tatty acid, as described, far example, In WO 98/004656, and glyceryl monooleate. The reaction products, described In US 6 743 266 B2_S of natural or synthetic ells, for example triglycerides, and alkanoiamlnes 30 are also suitable as such lubricity improvers.

M/51320-PCT

PF 0000071427 SE/Ab

B5) Corrosion inhibitors

Suitable corrasion inhibitors are, for example, succinic esters, In particular with polyols, fatty acid derivatives, for example oleic esters, oligomerized fatty acids, substituted ethanolamines, and products· sold under ths trade name RC 4801 (Rhein Chemi® Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).

86) Demulsifiers

Suitable demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol- and naphthatenesulfonates and the alkali metal or alkaline earth metal salts of tatty adds, and also neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkuxylates, e.g. tert-buiylphenoi ethoxylate or tert-pentylphenol ethoxylate, fattyacrds, alkyiphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), for example including in the form of EO/PO block copolymers, polyethylene! mines or else poiysiloxanes.

B7) Dehazers

Suitable dehazers are, for example, alkoxylated phenolformaldehyde condensates, for example the products available under the trade names NALCO 7D07 (Naico) and TOLAD 2633 (Petrolite).

88) Antifoams

Suitable antifoams are, for example, polyether-modified poiysiloxanes, for example the products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Coming) and RHODOSIL (Rhone Poulenc).

89) Cetane number improvers

Suitable cetane number improvers are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyctohexyi nitrate and peroxides such as dhtert-butyi peroxide.

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PF 0000071427 SE/Ab

2019201700 13 Mar 2019

BW) Antioxidants

Suitable antioxidants are, for example substituted phenols, such as 2,.6tol-tertbutyfphenol and 6-dMert-butyi-3-methyiphenol, and also phsnyienedfamines such as δ N, N’-dt-seo-buty l-p-pheny lenediami ne.

811) Mete I deactivators

Suitable metal deactivated are, for example, salicylic acid derivatives such as

Ν,Ν’-disaiicyildene-l ,2-propanedlamine.

812) Solvents

Suitable solvents are, for example, nonpolar organic solvents such as aromatic and aliphatic hydrocarbons. for example toluene, xylenes, white spirit and products sold under the trade names SHELLSOL (Royal Dufch/Sheli Group) and EXXSOL (ExxonMobil), and also polar organic solvents, for example, alcohols such as 2-ethy?hexano?, decanol and isotridecanoi. Such solvents are usually added to the diesel fuel together with the aforementioned additives and coadditives, which they are 20 intended to dissolve or dilute for better handling,

C) Fuels

The inventive additive is outstandingly suitable as a fuel additive and can be used in 25 principle in any fuels.. It brings _{about a} whole _{of advam}^_{s effecfe jft} operation of Internal combustion engines with fuels. Preference is given to using the Inventive quatemized additive in middle distillate fuels, especially diesel fuels. '

The present invention therefore also provides fuels, especially middle distillate fuels, 30 with a content of the inventive quatemized additive which is effective as an additive for achrevmg advantageous effects in the operation of internal combustion engines, for example of diesel engines, especially of direct-injection diesel engines, in particular of diesel engines with common-rail injection systems. This effective content (dosage) is generally 10 to 5000 ppm by wight, preferably 20 to 1500 ppm by weight, especially

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 to 1000 ppm by weight. In particular 30 to 750 _ppn, _{by we}|_oM, _{basM h case} on the total amount of fuel.

Middle distillate fuels such as diesel fuels or heating oils are preferably mineral oil raffinates which typically have a boiling range from 100 to 400“C. These are usually distillates having a 95% point up to 300«C or even higher. These may also be so-called ultra low sulfur diesel” or city diesel, characterized by a 95% point of, for example, not more than 345’C and a sulfur content of not more than 0,005% by weight or by s -5 A point of, for example, 235“C and a sulfur content of not more than 0.001% by weight, in addition to the mineral middle distil late fuels or diesel fuels obtainable by refining, those obtainable by coal gasification or gas liquefaction [“gas to liquid (GTL) fuelsj or by biomass liquefaction [“biomass to liquid (BTL) fuels] are also suitable. Also suitable are mixtures of the aforementioned middle distillate fuels or diesel fuels with renewable fuels, such as biodiesel or bfoethanoL

The qualities of the heating oils and diesel fuels are laid down in detail, for example. In DIN 51603 and EN 590 (of. also UHmann’s Encyclopedia of Industrial Chemistry, 5th edition, Volume A12, p, 617 ff,).

.20 in addition to the use thereof in the abovementioned middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, the inventive quaternized additive can also be used in mixtures of such middle distillates with biofuel oils (biodiesel). Such mixtures are also encompassed by the term middle distillate fuel m the context of the present invention. They are commercially available and usually comprise the biofuel oils In minor amounts, typically in amounts of 1 to 30% by weight, especially of 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil..

Biofuel oils are generally based on fetty acid esters, preferably essentially on alkyl esters of fatty acids which derive from vegetable and/or animal oils and/or fats, Alkyl esters are typically understood to mean lower alkyl esters, especially C_rQ-aikyl esters, whicn are obtainable by transesterifying the glycerides which occur in vegetable and/or animal oils and/or fete, especially triglycerides, by means of lower alcohols, for example ethanol or in particular methanol (TAMS’). Typical lower alkyl estera based

M/S132G-PCT

PF 0000071427 SE/Ab on vegetable and/or animal oils and/or fats, which find use as a biofuel oil or components thereof,, are, for example, sunflower methyl ester, palm oil methyl ester CPME-), soya oil methyl ester (SME) and especially rapeseed oil methyl ester C’RME”). '

The miodie distillate fuels or diesel fuels are more preferably these having a low sulfur content, having a sulfur content of less than 0,05% by weight, preferably of less than 0.02% by weight, more particularly of less than 0.005% by weight and especially of less than 0.001 % by weight of sulfo r. '

Useful gasoline feels include ail commercial gasoline fuel compositions. One typical representative which shall be mentioned here Is the Eurosuper base feel to EN 228, which is customary on the market, in addition, gasoline fuel compositions of the ’ specification according to WO 00/47698 are also possible fields of use for the present invention.

The Inventive quaternszed additive Is especially suitable as a feel additive in fuel compositions, especially in diesel fuels., far overcoming the problems outlined at the outset In direct-injection diesei engines. in particular In those with common-rail injection systems.

r he invention is now illustrated in detail by the working examples which follow. The test methods described herein are not restricted to the specific working examples, but are part of the general disclosure of the description and can be employed generally in the context of the present invention.

Experimental section:

A. General test method^

Engine test b1) XUD9 test - determination of flow re st notion s he procedure was according to the standard stipulations of CEC F-23-01

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82) DW10 - keep clean test

To examine the influence of the Inventive compounds on the performance of directinjection diesel engines, the power loss was determined on the basis of the official test 5 method CEC F-098-08. The power loss is a direct measure of formation of deposits in the Injectors.

Tne keep ciean test is based on CEC test procedure F-098-08 issue 5. The same test setup and engine type (PEUGEOT DW10) as in the CEC procedure are used.

Special features of the test used;

a) Injectors ~ in the tests, cleaned injectora were used. The cleaning time in an ultrasound bath in 15 water at 60*C + 10% Superdecontamine (interaciences, Brussels) was 4 h.

b) Test run times the test p-enod was 12 h without shutdown phases. The one-hour test cycle (see table below) from CEC F-O98-08 was run through 12 times. ~

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c) Power determination

The >nitial power (Pa, KC [kW]) is calculated from the measured torque st fuP load AOOOMn directly after the tert has started and the engine _{tes warmed The} procedure is described in issue 5 of the test procedure CEC F-98-oa. The same test setup and the PEUGEOT DWW engine type are used ' ' '

The final power (P«, KC) Is ««mined in the 12th cycle in stage 12. _(m above). Here too, toe operating point |_{s U} 4000/mln. _{Kc (kwJ js ca|oulated} from the measured torque.

The power loss in KC is calculated as follows:

power loss, KC [%] - 0 . p_8tHj>Kc / p_{6(KC) χ 10}θ

The fuel used _{ws a} commercial diesel fuel from Hattermsnn (RR06-03). To 20 ^svnthetically Induce the formation nf Λλ , '

- .wnawn OT Uwpo&ts at the mjectora, 1 ppm of zinc was added thereto in the form of a zinc neodecanoate solution,.

B. Preparation examples:

Reactants used:

PIBSA: Prepared from maleic anhydride and P® 1000 In a known manner. For the inventive preparation examples and comparative examples which follow, qualities hydrolysis numbers in the region of 8445 m₈ KOW₈ were _used. _{0MW>A was} * »* the particular PIBSA quality In a molar _{raUo of} ,., _{accor(fcg !o lh(j hvdro|ysjs} number. The PIBSA qualities used had blsmaleation levels (BML) of less than 15%,’

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DMAPA: M= 102.18 methyl salicylate: M « 152., 14 d Im ethyl phthalate: M ~ 194,19 dimethyl oxalate: M - 118.09 dimethyl sulfete: M - 126.13 dimethyl carbonate M~ 90.08 preparation example _1; Synthesis _{of an} |_{nveniive quatemizad succjnimide} (PI B SA/DMAP A/dlmethyl phthalate)

Polyisobutylenesuccinic anhydride (1659 g) |_S dissolved in Solvent Naphtha Heavy W to O4S^Z^4) (1220 g), and 3-dimethyiamino-1-propytemine (DIMAPA; 153 g) is added. The reaction solution is stirred at 17O‘C for 8 h, in the 5 course of which water of condensation formed is distilled off continuously. This affords the PIBSA-DMAPA succinimide as a solution In Solvent Naphtha Heavy (TBN 0.557 mmoi/g).

A portion of this solution of the PISSA-DMAPA succinimide (181 g) is added to 20 dimethyl phthalate (19.4 g)_s and the resulting reaction solution is stirred at 12O*C for h and then at 150*C ter 24 h. After cooling to room temperature, the product obtained is the ammonium carboxylate as a solution in Solvent Naphtha Heavy. Ή NMR analysis confirms the quatemlzation.

2S Preparation example 2: Synthesis of _an inventive _{quaternfeed succWmMe} (PiBSA/DMAPA/methyl salicylate)

Pclyisobutytenesuccinic anhydride (PIBSA; 2198 g) is healed to 11OW_S and 3dimethylsmlnO’l-prapylsmine (DMAPA; 182 g) to added within 40 min, In the course of 3u Ahich the rw&Uion mixture heats up to 14(TC. The reaction mixture is heated to 17O”C and held at this temperature for 3h_f in the course of which 28 g of distillate are collected. This affords the PIBSA-DMAPA succinimide as a viscous oil (TBN 0,735 mmol/g).

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A mixture of this PIBSA-DMAPA succinimide (284,5 g), methyl sal icy late (65.5 g) (j._e< about 2 equivalents of methyl salicylate per equivalent of tertiary amino group) and 3,3,5-frlmetnyiheptenoic add (from. BASF) (0.75 g) is heated to 140-150* and the reaction mixture is stirred at this temperature for 6 h. After cooling to room temperature, 5 the product obtained Is the ammonium salicylate as a viscous oil. Ή NMR analysis confirms the quatemlzatlon. By adding Pilot 900 oil, Petrochem Carless Ltd., the active ingredient content of the solution is adjusted to 50% by weight

Preparation example 3: Synthesis of an inventive quaternized succinimide 10 (PISSA/DMAPAMimethyl oxafete)

Polyisobutylenesuccinic anhydride (PISSA; 2198 g) is heated to WC, and 3dlmethylamino-1-propylamlne (DMAPA; 182 g) is added within 40 min, in the course of which the reaction mixture heats, up to 140’C. The reaction mixture is heated to 170’C 15 and held at tn is temperature for 3h, In the course of which 28 g of distillate are collected. This affords the PIBSA-DMAPA succinimide as a viscous oil (TBN 0.735 mmol/g).

A mixture of this PIBSA-DMAPA succinimide (211 g), dimethyl oxalate (34.5 g) and 20 lauric acid (4.9 g) is heated to 120*C and then stirred at this temperature for 4 h.

Excess dimethyl oxalate is removed on a rotary evaporator under reduced pressure Φ - 5 mbar) at 12O*C. The product obtained is the ammonium methyl oxalate as a viscous oil, 1H NMR analysis confirms the quaternization.

For comparison with the prior art, Examples 2 and 4 from WO 2006/135881 were worked up.

Preparation example 4: Synthesis of a known quaternized succinimide (comparative example) (Example 2 from WO 2006/135881)

A solution of PIBSA (420.2 g) in Pilot 900 oil, Petrochem Cariess Ltd., (51.3 g) is initially charged and heated to 110*0.. DMAPA (31.4 g) is metered In within 50 minutes, in the course of which a slightly exothermic reaction is observed. Within SO minutes, the reaction mixture is heated to 15O°C and the mixture is then kept at this temperature

M/51320-PCT

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2019201700 13 Mar 2019 tor 3 h, in the course of which the water of reaction which forms _{is dwned off Afcf} ooolha to room temperature, the PIBSA-DMAPA mmm _is obtained _{as a s0)u)fan} in Pilot 900 oil (TBN 0.62 mmd/g).

A portion of the PIBSA-DMAPA succinimide thus obtained as a solution In Pilot 900 oil mrochem Cartess Ito,, (3S4 g) to i»y charged end heated to 9DX Dimethyl suifete (26..3 g) is metered to, in the course of which the reaction temperature rises to 112 C. Subsequently, the reaction mixture is stirred at lOO’C for 3 h. After cooling to room temperature, the quaternized PIBSA-DMAPA succinimide is obtained as a 10 solution in Pitot 900 oil Ή NMR confirmed the quaternion. The output was adjusted to an active ingredient content of 50% by weight by adding Pilot 900 oil >

Preparation example 5: Synthesis of a known quaternized wcoinimide (comparative example) (Exam pie 4 from WO 2006/135381)

A solution Of PIBSA (426.2 s) in Pilot 900 oil. Petrochem Carte Ltd., _(S1._{3 g) fe} initially charged and heated to 110*C. DMAPA (31.4 _s) Is metered In within 50 minute, m the course of which a slightly exothermic reaction is observed. Within 80 minutes _r the reaction mixture Is heated to 160'C and the mixture Is then kept at this temperature 20 for 3 h, in the course of which the water of reaction which forms is distilled off. After cooling to room temperature, the PIBSA-DMAPA succinimide _!s obtained as a solution in Pitot 900 oil (TSM 0.52 mmoi/g).

A portion of the PIBSA-DMAPA succinimide thus obtained as a solution in Pilot 900 oit, 25 Petrwhem Carte Ltd., (130 _S), dimethyl carbonate (2S g) and methanol (17.4) are charged into _an autoclave and Inerted with nitrogen, and a starting pressure of 1.3 bar is established. Subsequently, the reaction mixture is stirred under autogenous pressure first at so°c for 1 h unm *« .· , ^{1 n}’ ^k‘^{,en a 140 c tor} ^⁴ h. After cooling to room temperature, the autoclave is decompressed and the contents are rinsed out completely with a tittle 30 towne as a solvent. All low-boiling constituents are subsequently removed on a rotary evaporator under reduced pressure to obtain the quaternized PIBSA-DMAPA succinimide as a solution in Pilot SOO oil. Ή NMR analysis confirmed the partial quatemization. The output is adjusted to an active Ingredient content of 50% by welaht by adding Pitot 900 oil ~

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C> Use examples:

In the use examples which follow, the additives are used either as a pure substance (as synthesized m the above preparation examples) or in the form of an additive package.

Ml: Additive according to preparation example 2 (Inventive, quaternized with methyl salicylate) ’

M2: Additive according to preparation example 4 (comparative, quaternized with dimethyl sulfate)

MS. Additive according to preparation example 5 (comparative, quaternized with dimethyl carbonate)

Use example 1: determination of the additive action on the formation of deposits in diesel engine injection nozzles

a) XU DO Teste

Fuel used: RF-06-03 (reference diesel, Haitermann Products. Hamburg)

The results are compiled in table 1:

Table 1: XU DO tests

Name | Dosage according to ] Flow restriction I preparation example 10.1 mm needle W&g] | stroke [%] #1 j M1, according to >

_ preparation example 2

M2, according to :

^preparation exam pie 4 j | M3, according to i #3

10..7

20.8

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2019201700 13 Mar 2019 it was found that the inventive additive M1, with the same dosage, has an improved effect compared to toe prior art (M2, M3).

b) DW10 test

To study the influence of the inventive compound on the performance of direct-injection diesel engines, the power loss was determined based on the official test method CEC F-09O8 as described above. The power foss is a direct measure of formation of deposits m the Injectors. A conventional direct-injection diesel engine with a common10 rail system was used.

The fuel used was a commercial diesel fuel from Haltem^rm (RF-06-03). To synthetically induce toe formation of deposits at the injectors, 1 ppm by weight of zinc sn the form of a zinc didodecanoate solution was added thereto ' ^r

The table below shows the results of the determinations of the relative power loss at 400Q rpm after 12 hours of sustained operation without intemjption. The value P_e gives the power after 10 minutes and the value the power at toe end of the measurement:

The test results are shown in table 2,

Table 2: Results of the DWW test

I Additive I Dose | Time] PjTTp

IM1, according to preparation

I example 2 | | 12 |98J I 97.4 | ^M2, according to preparation ' example 4 [M3, accordhglTpre^ratton ϋ example 5

160

I 98.1

0,9¾

160 | 12

Θ5.7 2..4% il was found that the inventive additive Mt has en improved effect compared _to the base vasue and has an improved effect at least compared to example M3.

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Use example 2: Determination of the solubility properties

To determine the solubility properties, the following additive packages were produced and tested:

M 4 (inventive) i Substance. | Content [ppm]

Additive acc. to preparation example 2	160.00
pehazer, commercial	3.0Q
iAntifeam, silicone-based, commercial	mwww ,1 6.00
Solvent Naphtha Heavy	80.00
_____ Total 1,11 L . . . . . . . . .UH I II .I.HXXXXX,·,,· . . ,-.-.-.-.-,-.-.-.-.-.-.- .-.-.-.-.j	249,od

M 5 (comparative, dimethyl sulfate) ' ' ------ΓΧ,-ΛΧΧΧΧΧ^ν^.--------.-.............

Substance

--------__ | Content [ppm]

Μ I Ι«ΑΧΧΧΧΧΧΧΧ·>·>·»~.-.Ί I I , .V.-.X V.XW J

^Additive acc< to preparation example 4	160.00
Denazer, commercial	3.00
Antifoam, silicone-based, commercial	6.00
Solvent Naphtha Heavy	420.00
Total	589.00

M 6 (comparative, dimethyl carbonate) ¹ . ,, I, mxwxwxxxvn __________

J .....L ' 1 ' ' »»«>«>»» ' .L..V.XXX^^_-----^MAVAVAV.V. Substance -------l^XXXXXXXX^-------_________	Content [ppm]
[Additive acc. to preparation example 5	160.00
Dehazer (commercial)	3.00
Antifoam» silicone-based, commercial	L aww.*, v.*., . 11 , ,.,.,.un».v· e.oq
Solvent Naphtha Heavy	15O,od
------™V.XV.XV.W.-_------------------------------ ______ Total 1 1 1 . ...., , , t , ,vxww>>^-------------_.--------------- 1	lAWWWll.V...... 319.00

The result of the solubility tests Is compiled In the table below. The minimum amount of solvent (Solvent Naphtha Heavy) needed to obtain a homogeneous, dear diesel

M/51320-PCT performance package at room temperature with otherwise identical amounts of active substance, Pilot 900, antifoam and dehazer is reported.

Table 3: Determination of the solvent requirement

Additive	Additive package	Minimum amount of solvent needed for a homogeneous package
PIBSA-DMAPA-imide-methyl salicylate	M4	32%
PIBSA-DMAPA-imide-dimethyl sulfate	M5	71%
PIBSA-DMAPA-imide-dimethyl carbonate	M6	47%

It was found that, surprisingly, the additive according to preparation example 2 has the best solubility properties, i.e. requires the least solvent.

Reference is made explicitly to the disclosure of the publications cited herein.

It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.

In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.

Also described herein are the following items 1 to 18:

1. A fuel composition comprising, in a majority of a customary fuel, a proportion of at least one reaction product comprising a quaternized nitrogen compound, or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, said reaction product being obtainable by

a) reacting a hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one oxygen or nitrogen group reactive, especially capable of

8429357_1 (GHMatters) P95787.AU.1 addition or condensation, with the polycarboxylic acid, and comprising at least one quaternizable amino group, to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid compound, and

b) subsequent reaction thereof with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, especially of a mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid, especially dicarboxylic acid.

2. A fuel composition comprising, in a majority of a customary fuel, a proportion of at least one reaction product comprising a quaternized nitrogen compound, or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, said reaction product being obtainable by reacting a quaternizable hydrocarbyl-substituted polycarboxylic acid compound comprising at least one quaternizable amino group with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic monoor polycarboxylic acid, especially of a mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid, especially dicarboxylic acid.

3. The fuel composition according to either of the preceding items, wherein about 1.1 to about 2.0 or about 1.25 to about 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom.

4. The fuel composition according to any of the preceding claims, wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, said acid having a bismaleation level of less than about 20% or less than about 15%.

5. The fuel composition according to any of the preceding items, wherein the quaternizing agent is a compound of the general formula 1

R1OC(O)R2 (1)

8429357_1 (GHMatters) P95787.AU.1 in which

R1 is a lower alkyl radical and

R2 is an optionally substituted monocyclic aryl or cycloalkyl radical, where the substituent is selected from OH, NH2, NO2, C(O)OR3, and R1OC(O)-, in which R1 is as defined above and R3 is H or R1.

6. The fuel composition according to any of the preceding items, wherein the quatemizing agent is a compound of the general formula 2

R1OC(O)-A-C(O)OR1a (2) in which

R1 and R1a are each independently a lower alkyl radical and

A is hydrocarbylene, such as especially alkylene or alkenylene.

7. The fuel composition according to any of the preceding items, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 500 to 5000, especially 800 to 3000 or 900 to 1500.

8. The fuel composition according to any of the preceding items, wherein the quatemizing agent is selected from alkyl salicylates, dialkyl phthalates and dialkyl oxalates.

9. The fuel composition according to item 1, wherein the compound which is reactive, especially capable of addition or condensation, with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizable amino group is selected from

a) hydroxyalkyl-substituted mono or polyamines having at least one quaternizable primary, secondary or tertiary amino group;

b) straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary amino group and having at least one quaternizable primary, secondary or tertiary amino group;

c) piperazines.

8429357_1 (GHMatters) P95787.AU.1

10. The fuel composition according to item 9, wherein the compound which is reactive, especially capable of addition or condensation, with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizable amino group is selected from

a) hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines,

b) straight-chain or branched aliphatic diamines having two primary amino groups; di or polyamines having at least one primary and at least one secondary amino group; di or polyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary amino group.

11. The fuel composition according to any of the preceding items, selected from diesel fuels, biodiesel fuels, gasoline fuels and alkanol-containing gasoline fuels.

12. A reaction product obtainable by a process as defined in any of the preceding items or quaternizable nitrogen compound obtained from the reaction product.

13. A process for preparing a quaternized nitrogen compound according to item 12, comprising the reaction of a quaternizable hydrocarbyl-substituted polycarboxylic acid compound comprising at least one tertiary quaternizable amino group with a quaternizing agent which converts the at least one tertiary amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic monoor polycarboxylic acid, especially of a mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid, especially dicarboxylic acid.

14. The use of a reaction product or of a quaternized nitrogen compound according to item 12 or of a compound prepared according to item 13 as a fuel additive.

15. The use according to item 14 as an additive for reducing the fuel consumption of direct-injection diesel engines, especially of diesel engines with common-rail injection

8429357_1 (GHMatters) P95787.AU.1

2019201700 13 Mar 2019 systems, and/or for minimizing power loss in direct-injection diesel engines, especially in diesel engines with common-rail injection systems.

16. The use according to item 14 as a gasoline fuel additive for reducing the level of 5 deposits in the intake system of a gasoline engine, such as especially DISI (direct injection spark ignition) and PFI (port fuel injector) engines.

17. The use according to item 14 as a diesel fuel additive, especially as a cold flow improver, as a wax antisettling additive (WASA) or as an additive for reducing the level of and/or preventing deposits in the intake systems, such as especially the internal diesel injector deposits (IDIDs), and/or valve sticking in direct-injection diesel engines, especially in common-rail injection systems.

18. An additive concentrate comprising, in combination with further diesel fuel or 15 gasoline fuel additives, especially diesel fuel additives, at least one quaternized nitrogen compound as defined in item 12 or prepared according to item 13.

Claims (22)

1. A fuel composition comprising, in a majority of a customary fuel, a proportion of at least one reaction product comprising a quaternized nitrogen compound, or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, said reaction product being obtainable by al) reacting a hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one oxygen or nitrogen group reactive, with the polycarboxylic acid, and comprising at least one quaternizable amino group, to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid compound, and a2) subsequent reaction thereof with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, or of an aliphatic polycarboxylic acid; or

b) reacting a quaternizable hydrocarbyl-substituted polycarboxylic acid compound comprising at least one quaternizable amino group with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or

cycloaliphatic mono- or polycarboxylic acid polycarboxylic acid, or of an aliphatic wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, prepared by reacting

polyisobutene having a proportion of vinylidene groups of greater than 70 mol% and having a polydispersity in the range from 1.1 to less than 1.9.

2. The fuel composition according to claim 1, wherein the compound comprising at least one oxygen or nitrogen group is reactive with the polycarboxylic acid by addition or condensation.

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2019201700 13 Mar 2019

3. The fuel composition according to claim 1 or 2, wherein said quaternizing agent is an alkyl ester of a cycloaromatic or cycloaliphatic mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid.

4. The fuel composition according to any one of claims 1 to 3, wherein about 1.1 to 2.0 of quaternizing agent are used per equivalent of quatemizable tertiary nitrogen atom.

5. The fuel composition according to any one of claims 1 to 4, wherein about 1.25 to about 2.0 equivalents of quaternizing agent are used per equivalent of quatemizable tertiary nitrogen atom.

6. The fuel composition according to any one of claims 1 to 5, wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, prepared by reacting polyisobutene having a proportion of vinylidene groups of greater than 80 mol% and having a polydispersity in the range from 1.1 to less than 1.9.

7. The fuel composition according to any one of claims 1 to 6, wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, prepared by reacting polyisobutene having a proportion of vinylidene groups of greater than 85 mol% and having a polydispersity in the range from 1.1 to less than 1.9.

8. The fuel composition according to any one of the preceding claims, wherein the quaternizing agent is a compound of the general formula 1

RiOC(O)R₂ (1) in which

R₂ is a lower alkyl radical and

R₂ is an optionally substituted monocyclic aryl or cycloalkyl radical, where the substituent is selected from OH, NH₂, NO₂, C(O)OR₃, and R^C/O)-, in which R₂ is as defined above and R₃ is H or R₂.

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2019201700 13 Mar 2019

9. The fuel composition according to any one of the preceding claims, wherein the quaternizing agent is a compound of the general formula 2

RiOCO-A-COOR^ (2) in which

Riand R_la are each independently a lower alkyl radical and

A is hydrocarbylene.

10. The fuel composition according to any one of the preceding claims, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 500 to 5000.

11. The fuel composition according to any one of the preceding claims, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 800 to 3000.

12. The fuel composition according to any one of the preceding claims, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 900 to 1500.

13. The fuel composition according to any one of the preceding claims, wherein the quaternizing agent is selected from alkyl salicylates, dialkyl phthalates and dialkyl oxalates.

14. The fuel composition according to any one of claims 1 to 13, wherein the compound which is reactive with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizable amino group is selected from

a. hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable primary, secondary or tertiary amino group;

b. straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary amino group and having at least one quaternizable primary, secondary or tertiary amino group;

c. piperazines.

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2019201700 13 Mar 2019

15. The fuel composition according to claim 14, wherein the compound which is reactive with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizable amino group is selected from

a. hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines,

b. straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one secondary amino group; di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary amino group.

16. The fuel composition according to any one of the preceding claims, selected from diesel fuels, biodiesel fuels, gasoline fuels and alkanol-containing gasoline fuels.

17. The use of a reaction product obtainable by a process as defined in any one of the preceding claims or of quaternized nitrogen compound obtained from the reaction product; or of a quaternized nitrogen compound prepared by a process comprising the reaction of a quaternizable hydrocarbyl-substituted polycarboxylic acid compound comprising at least one tertiary quaternizable amino group with a quaternizing agent which converts the at least one tertiary amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid or of an aliphatic polycarboxylic acid; as a fuel additive, and wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, prepared by reacting polyisobutene having a proportion of vinylidene groups of greater than 70 mol% and having a polydispersity in the range from 1.1 to less than 1.9.

18. The use according to claim 17 as an additive for reducing the fuel consumption of direct-injection diesel engines, or diesel engines with common-rail injection systems, and/or for minimizing power loss in direct-

11167196_1 (GHMatters) P95787.AU.2

2019201700 13 Mar 2019 injection diesel engines, or in diesel engines with common-rail injection systems.

19. The use according to claim 17 as a gasoline fuel additive for reducing the level of deposits in the intake system of a gasoline engine, or DISI (direct injection spark ignition) and PFI (port fuel injector) engines.

20. The use according to claim 17 as a diesel fuel additive, as a cold flow improver, as a wax antisettling additive (WASA) or as an additive for reducing the level of and/or preventing deposits in the intake systems, the internal diesel injector deposits (IDIDs), and/or valve sticking in direct-injection diesel engines, or in common-rail injection systems.

21. The use according to any one of claims 17 to 20, wherein about 1.25 to about 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom.

22. The use according to any one of claims 17 to 21, wherein said quaternizing agent is the alkyl ester of a cycloaromatic or cycloaliphatic mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid.