AU2016273853B2 - 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

This application is a divisional application of Australian Application No. 2012277805, which in turn claims priority from EP Application No. 11171763.3, the specification for 5 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 10 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 direct-injection 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 15 injection systems, and for minimizing power loss in direct-injection 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, 30 the pump-nozzle system (unit-injector system or unit-pump system) and the commonrail system.

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2016273853 12 Dec 2016

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 0000071427 SB'Ab

2016273853 12 Dec 2016 rail is divided essentially Into three groups; (1.) pre4njectfon, 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, which is responsible especially for a good torque profile; and (3.) post-injection, which especially ensures a low NOx value.

in this post-injection, the fuel is generally not combusted, but instead evaporated by residual heat in the cylinder. The exhaust gas/fue! 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 amission 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 modern 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 canpounds are used, deposits 20 can form on the injector orifices, which adversely affect the injection performance of the fuel and hence Impair the performance of the engine, l.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 construction, especially by the change in 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 loss. Deposits at the 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 “extemaP deposition phenomena, ^eintemar deposits (referred to collectively as internal diesel injector deposits (IDID)) in

W5132OPCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 particular parts of th© 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 quaternized ammonium salts which are prepared by reacting an alkenylsuccinimide with a monocarboxyiic ester and find use as dispersants In lubricant oils for prevention of sludge formation. More particularly, for example, the reaction of polyisobutylsuccinlc anhydride (PIBSA) with Ν,Ν-dimethylaminopropylamine (DMAPA) and quatemization 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 4,17'1,959 describes quaternized ammonium salts of hydrocarfoyl-substituted succinimides, which are suitable as detergent additives for gasoline fuel com positions.

For quatemizaticn, proference is given to using alkyl halides. Also mentioned are organic CrCrhydracarbyl carboxylates and sulfonates. Consequently, the quatemized ammonium salts provided according to the teaching therein have, as a counterion, either a halide or a CrCrhydrocarbyl carboxylate or a CrCrhydrocarbyl sulfonate group, The use of P IBS A 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-Gse-alkyl radical with a Cr Ch-alky I ester of specific carboxylic acids. Exampies of such carboxylic esters are dimethyl 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 quaternized ammonium salts prepared by condensation of 30 a hydrocarbyl-substituted acylating agent and of an oxygen or nitrogen atom-containing compound with a tertiary amino group, and subsequent quatsmization 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 dialkyl

M/5132C-PCT

2016273853 26 Sep 2018 sulfates, benzyl halides and hydrocarbyl-substituted carbonates, and dimethyl sulfate, benzyl chloride and dimethyl carbonate have been studied experimentally.

The quaternizing agents used with preference in WO 2006/135881, however, have 5 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 quaternization or uneconomic reaction conditions (long reaction times, high reaction temperatures, excess of quaternizing agent; for 10 example in the case of dimethyl carbonate).

Advantageously, the present invention may provide improved quaternized fuel additives, especially based on hydrocarbyl-substituted polycarboxylic acid compounds, which no longer have the disadvantages of the prior art mentioned.

Brief description of the invention:

The invention provides fuel compositions comprising specific quaternized nitrogen compounds . Also disclosed are lubricant compositions comprising the quaternised 20 nitrogen compounds.

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 quaternizing agent, burn ashlessly, exhibit a high content of 25 quaternized 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 the 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 description of the invention:

A1) Specific embodiments

In a first aspect, there is provided 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 a1) 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;

wherein in step a1) hydrocarbyl-substituted polycarboxylic acid compound is reacted with the quaternizable nitrogen compound in a small molar excess over equimolar amounts.

In a second aspect, there is provided the use of a reaction product obtainable by a process of the first aspect or of quaternized nitrogen compound obtained from the reaction product.

Also described herein are the following embodiments:

1. 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 quaternized nitrogen compound (or a

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2016273853 26 Sep 2018 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 high molecular weight hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one oxygen or nitrogen group reactive (especially capable of addition or condensation) with the polycarboxylic acid, and comprising at least one quaternizable amino group, to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid compound (by addition or condensation), and

b. subsequent reaction thereof with a quaternizing agent which converts 10 the at least one hereafter quaternizable, for example tertiary, 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 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 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 high molecular weight hydrocarbyl-substituted polycarboxylic acid compound comprising at least one quaternizable amino group with a quaternizing agent which converts the at least one hereafter quaternizable, for example tertiary, amino group to a quaternary ammonium group,

10621324_1 (GHMatters) P95787.AU.1

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 said quatemizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic monoor polyoarboxylic acid (especially of a mono- or dicarboxylic acid) or of an aliphatic polycarboxylic add (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, 17, 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-substituted 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

RnOCORi (1) in which

R? is a low molecular weight hydrocarbyl radical, such as alkyl or alkenyl radical, especially a lower alkyl radical, such as especially methyl or ethyl, and

Rs is an optionally substituted monocyclic hydrocarbyl radical, especially an aryl or cycloalkyl or cycloalkenyl radical, especially aryl such as phenyl, where the substituent is selected from OH, NHs, NOs, 0(0)0¾ 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 quatemizing agent is a compound of the general formula 2

R$OC(O)~A-C(O)ORi_e (2) in which

Ri and Ru are each independently a low molecuiar weight hydrocarbyi radical,, such as 10 an alkyl or alkenyl radical, especially a lower alkyl radical and

A is hydrocarbylene (such as especially Ci«Cralkylene or C^Cralkenylene).

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

8., The fuel or lubricant composition, especially fuel composition,, according to any of the preceding embodiments, wherein the quatemizing agent is selected from 20 alkyl salicylates, dialkyl phthalates and dialkyl oxalates; particular mention should be made of alkyl salicylates, especially lower alkyi salicylates, such as methyi, ethyl and n· propyl salicylates.

9, The fuel or lubricant composition, especially fuel composition, according to 25 embodiment 1_f 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 qustemizable 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 on© quaternizable primary, secondary or tertiary amino group;

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

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2016273853 12 Dec 2016

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 qu stern iza ble ami no g rou p is selected from a, hydroxyalkyl-substltuted primary, secondary or tertiary monoamines and hydroxyalky I-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;

and particular mention should be made of group a.

11. The fuel composition according to any of the preceding embodiments, selected from diesel fuels, biodiesel fuels, gasoline fuels and aikanoi-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 polyisobutenyteuccinic 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 ere 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 quaternized nitrogen compound obtained from the reaction product by partial or mil purification.

M/5132OPCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

In a particular configuration (A) of the Invention, quaternized reaction products which are prepared proceeding from polyisobutenyisucdnic acid or an anhydride thereof are provided, this compound having a bismaleation level of equal to or less than about 20% or equal to or less than about 15%, for example 15_s Ί4, 13,12., 11, 10, 9, 8, 7, 6, S, 4, δ 3, 2., 1, or 0,1%. This polyisobutenylsuccinic add compound is reacted (especially by addition or condensation) with a compound comprising at least one oxygen cr nitrogen group reactive (addable or condensable) with the polytsobutenylsucdnlc acid compound and containing at least one quatemizable amino group, and then quatemized,

In a particular configuration (B) of the invention, quatemized reaction products which are obtained by quaternization using an excess of quatemlzing 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 quaternlzing agent are used 15 per equivalent of quatemizable tertiary nitrogen atoms. Particularly useful quaternlzing agents are those of the formula (1), especially the lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, m end i-pmpyl 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 polylsobutenyisuccinic acid compounds according to configuration (A) are quatemized according to configuration (B).

14.. A process for preparing a quaternizad nitrogen compound according to embodiment 13, comprising the reaction of a quatemizable hydrocarbyksubstituted polycarboxyllc 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 ammonium group, said quaternlzing agent being the alkyl ester of a cycloaromatic or cycloaliphatic monoor polycarbcxylic acid (especially of a mono* or dicarboxylic add) or of an aliphatic polyoarboxylio acid (especially dfoarboxylic acid).

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PF 0000071427 SE/Ab

2016273853 12 Dec 2016

15.. The use of a reaction product or of a quatemized nitrogen compound according to embodiment 13 or of a compound prepared according to embodiment 14 as a fuel additive or lubricant 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 diesel 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 direct-injection 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 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,

19* An additive concentrate comprising, in combination with further diesel fuel or gasoline fuel additives, especially diesel fuel additives, at least one quatemized 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 molecutes 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

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 nevertheless, for example with addition, 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-drain and branched hydrocarbon radicals, which may optionally additionally comprise heteroatoms, for example Ο, N, NH, S, in the chain thereof,

Tong-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 ©thytene, 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 poljMW or polyC^-alkylene radicals. Suitable long-chain hydrocarbyl radicals and the preparation thereof are also described, for example, in WO 2006/135881 and the literature cited therein,

Examples of particularly useful polyalkylene radicals are polyisobutenyl radicals derived from hlgh-reactivity 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 hlgh30 reactivity polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, especially greater than 80 moi% or greater than 85 mol%. Preference is given especially to poiyisobutenes which have homogeneous polymer structures. Homogeneous polymer structures are possessed

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 especially by those polyisobutenes formed from isobutene units to an extent of at least 85% by weight, preferably to ar? extent of at least 00% by weight and preferably to an extent of at least 95% by weight Such high-reactivity polyisobutenes preferably have a number-average molecular weight within the abovementioned range, in 5 addition, the high-reactivity polyisobutenes may have a polydispersfty in the range from

1,05 to 7 ₍ especially of about 1.1 to 2.5, for example of tees 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 Glissopal brands from BASF SE, especially Glissopal® 1000 (Μη» 1000), Glissopal® V33 (Mn~550), Glissopal® 1300 (Mn = 1300) and Glissopal® 2300 (Mn*2300), and mixtures thereof Other number-average molecular weights can be established in a manner known In principle by mixing poly isobutenes of different number-average 15 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 PlBSA and bismaleated PI BSA (BM 20 PIBSA, ct 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 ts known per se (see also US 5,883,198). The

BML can also be determined by the following formula:

BML “ 100% * t(wt-%(BM PiBSA))/(wt-%(BM PIBSA)nvt-%(PlBSA))] where wt-% (X) represents the proportion by weight of component X (X “ PIBSA or BM PIBSA) In the reaction product of FIB with MSA.

Scheme 1

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PIBSA

BM P®SA

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Hydracarbyl-substituted poly carboxylic acid compound with a “low bismaleation level, especially corresponding polyisobutenylsuccinlc adds or anhydrides thereof (also referred to overall as PIBSA) are known from the prior art. Especially advantageous are bismaleation levels of 20% or fess, 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 5,833,196. 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 = 1000), with a. bismaleation level of 9%.

Short-chain hydrocarbyl*¹ or low molecular weight hydrocarbyl” is especially straightchain or 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 tetrasubsffiuted.

* 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-botyl, 1-methylpropyl, .2methylpropyl, 1,1-dlmethylathyl, n-pentyt 1»methy1butyl, 2-methylbutyl, 3-methylbutyl, 25 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethytpropyl, 1,2-dimethylpropyl, 1methylperrtyl, 2-methylpentyl, 3-methylpenfyl, 4-methylpentyl, 1,1-dlrnathylbutyi, 1,.2dimethylbutyi, 1,3-dlmethylbutyl, 2,2-dimethylbutyl, 2,3-dirnethylbutyl, 3,3-dirnethylbutyl, 1-ethyibutyl 2-ethylbutyl, 1,1,2-trimethylpropyi, 1,2,2-trimethylpropyl, 1-ethyl·!methyipropyl and 1-eihyl-2-methylprepyi; and also n-heptyl, n-octyl, n-nonyl and n30 decyl, and the singly or multiply branched analogs thereof.

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Hydroxyalkyl¹’ represents especially the mono- or poiyhydroxylatad, especially monohydroxylated, analogs of the above alkyl radicals, for example the monohydroxylated analogs of the above straight-chain or branched alkyl radicals, for 5 example the linear hydroxyalkyl groups with a primary hydroxyl group, such as hydroxymethyl,. 2-hydroxyethyl, 3-hydroxypropyL 4-hydroxybvtyL ’‘Alkenyl* represents mono- or polyunsaturated, especially monounsaturated, straightchain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or 2 or to 10 20 carbon atoms and a double bond in any position, for example Ci-Cralkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-msthytethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1meth yM-propenyl, Z-methyl-t-propenyl, 1-methyi-2-propenyi, 2-rnethyfr2-propenyl, 1pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyM-butenyl, 2-mathyM-butenyi, 3methyl-1-butenyl, l-meihyl-2-butanyl, 2-methyl-2-butenyl, S-methyl-2-butenyl, 1-methyl15 3-butenyl, 2-methyl-3-butenyl, 3-msthyl-3-butenyl, 1,1-dimethyi-2-propenyl, 1,2dimethyl-1 -propenyl, 1,2-dimethyl-2-propenyl, 1-ethyM -propenyl, 1-ethyl-2-propenyi, 1hexenyi, 2-hexenyl, 3-hexenyk 4-hexenyl, 5-hexenyl, 1-methyM-pentenyl, 2-methyMpentenyl, 3-methyM -pentenyl; 4-methyl-t-pentenyl, 1-methyi-2-pentenyl, 2-methyl-2pentenyi, 3-methyi-2-pentenyl, 4-methy!-2-pentenyl, i-methyl-3-pentenyl, 2-methyl«320 pentenyl, 3-methyl-3-pentenyi, 4-methyl~3-pentenyl, 1-methyM-pentenyl, 2-methyMpentenyl, 3-methyM-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl*2-butenyl, 1,1 -dimethyl-3-butenyi, 1,2-dimethyM -butenyl, 1,2-dimethyl-2-butenyl, 1,2-dlmethyi-3butenyl, 1,3-dfmethyM-butenyl, 1_t3-dimethyl-2-birtenyl, 1,3-dimethyl-3-butenyi, 2,2dimethyl-3-butenyl, 2,3-dimethyM -butenyl, 2,3-dlmethyl-2-butenyl, a^-dlmethyl-S25 butenyl, 3,3-dimeihyM-butenyl, 3,3-dlm^hyl-2-butenyl, 1-ethyM-butenyl, l-ethykabutenyl, l-ethyi-3-butenyi, 2-ethyM-butenyi, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2frimethyl-2-propenyi, 1-efoyM-methyl-2-propenyl, 1-ethyl-2-methyM -propenyl and 1 -ethyi-2-methyl-2-propenyl.

“Alkylene* represents straight-chain or mono- or polybranched hydrocarbon bridge groups having 1 to TO carbon atoms, for example CrCralkylene groups selected from -CH_r, -(CHsh-, “(CH2)_a-, -CH₂-CH(CH_S)-, -CH(QH₃)-CH^, (CH_S)4-, -(CH₂)rCH(CHs)-, -CH₂-CH(CH3)-CHr, (CH₂>, -(CHjJr, -(CH₂)_e, -CH(CH₃)-CH2-CH2-CH(CH_S)or -CHCCHiJ-CHrCHrCHrCHCCHs)- or CrC4-alkylene groups selected from -CHr·, M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

“Aikenylene” represents th® mono- or polyunsaturated, especially monounsaturated, analogs of the above alkylene groups having 2 to 10 carbon atoms, especially C2-C7alkenylenes or CrC<-elkenylenes, such as -CH-QH-, -CHsrCH»CH“.

Cyclic hydrocarbyl radicals’* comprise especially:

cycloalkyl: carbocyclic radicals having 3 to 20 carbon atoms, for example Cs-Cticycloalkyl such as cyclopropyl, cyclobutyl, cydopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyciododecyl; preference is given to cyclopentyl, cyclohexyl, cycloheptyl, and also to cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyi, cydopentylmethyl, cyclopentylethyl, cyclohexylmethyl, or Cs-Cr-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, cyclopropylethyl, cyclobutyl methyl, cyclopentyleihyl, 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-S-yl, cyclohexen-1-yl, cydohexen-S-yl and cyclohexen-4-yl;

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, Indenyi 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, selected from keto groups, -COOH, -COO-alkyl, -OH, -SH_f -CN, amino, -NO?, alkyl, or alkenyl groups..

The term about' 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

2016273853 12 Dec 2016 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) Polycarboxylic acid compounds and hydrocarbyFsubstituted polycarboxylfc acid compounds:

The polycafooxylic acid compounds used are aliphatic di- or polybaslc (for example trior tetrabaslc), especially from di-, tri- or teiraearboxylic acids and analogs thereof, such as anhydrides or tower alkyl esters (partially or completely estertfled), and Is optionally 10 substituted by one or more (for example 2 or 3), especially a long-chain alkyl radical and/or a high molecular weight hydrocafoyl radical, especially a polyalkylene radical. Examples are Cs-Cis poiyearboxylic acids, such as the dicarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic add, suberic acid, azelaic add and sebacic add, and the branched analogs thereof; and the tricarboxylic add citric add; 15 and anhydrides or lower alkyl esters thereof of The polycarboxylic 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 adds are fumaric add, maleic add, Itaconic add.

The hydrophobic long-chain or high molecular weight hydrocarbyi radical which ensures sufficient solubility of the quaternlzed product In the fuel has a numberaverage molecular weight (M4 of 85 to 2Q 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 25 1500. Typical hydrophobic hydrocarbyi radicals include polypropenyl, polybutenyl and polylsobutenyl 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 hydrocarbyi-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/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 can be reacted independently with the quaternlzable nitrogen compound in the preparation process according to the invention.

A4) Quaternizing agents:

Useful quaternizing agents are in principle al! alkyl esters which are suitable as such and are those of a cyctoaromatic or cycloaliphatic mono- or polycarboxylic acid (especially of a mono- or dicarboxylic acid) or of an aliphatic polycarboxylic add (especially dicarboxylic add),

W

In a particular embodiment, however, the at feast one quatemlzabie tertiary nitrogen atom Is quaternized with at least one quaternizing agent selected from

a) compounds of the general formula 1

RiOCCOJR? (1) in which

Rt is a lower alkyl radical and

Rs is an optionally substituted monocyclic aryl or cycioalkyl radical, where the substituent is selected from OH_S NHi, NOs, 0(0)01¾ and RuOC(0)-, In which Ru is as defined above for Ri and Rg is H or Rfo .25 and

b) compounds of the general formula 2

RiOC(O)-A-C(O)OR_?e (2) in which

Ri and Ru are each Independently a lower alkyl radical and

A. Is hydrocarbylene (such as alkylene or aikenyiene).

Particularly suitable compounds of the formula 1 are those in which

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

Ri is a Cr, Cr or Cr-alkyl radical and

R? is a substituted phenyl radical, where the substituent is HO* or an ester radical of the formula RuOCfO)- which Is in the para, meta or especially ortho position to the RiOC(0> radical on the aromatic ring,

Especially suitable quaternizing agents are the lower alkyl esters of salicylic add, such as methyl saficylate, ethyl salicylate, n* and i-prcpyl salicylate, and η», i- or tert-butyt salicylate.

AS) Quaternized or quatemlzabie nitrogen compounds:

The quatemizable nitrogen compounds reactive with the polyoarboxyiic acid compound are selected from

a. hydroxyalkyl-substltoted mono* or pofyamlnes having at least one quaternized (e.g. choline) or quaternlzable primary, secondary or tertiary amino group;

b. straight«chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary (anhydride-reactive) amino group and having at least one quaternized or quatemteabl® primary, secondary or tertiary amino group;

c. piperazines.

The quaternlzable nitrogen compound is especially selected from

d. hydroxyalkyl-substituted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyl-substituted primary, secondary, tertiary 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 least one secondary amino group; di* or polyamines having at least one primary and at least one tertiary amino group; dk or poiyamines having at least one primary and at least one quaternary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic pofyamines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary amino· group.

M/51320-PCT

W

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

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

Examples of hydroxyal kyl-substituted monoamines’* include: N-hydroxyalkyl monoamines, N,N-di hydroxyalkyl monoamines and Ν,Ν,Ν-trihydroxyalkyl monoamines, where the hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl is especially 2-hydroxy ethyl, 3-hydroxy propyl or 4-hydroxy butyl

For example, the following hydroxyalkyl-substituted polyamines'’ and especially hydroxyaikyl-substltuted diamines may be mentioned: (N-hydroxyalkyl)alkylenediamines, Ν,Ν-dihydraxyalkylalkylenediamines, where the hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl is especially 2« 15 hydroxyethyl, 3-hydroxypropyt or 4-hydroxybutyl; alkylene Is especially ethylene, propylene or butylene.

Suitable diamines’* are alkylenediamines, and the N-alkyl-substltuted analogs thereof, such as N-monoalkylated alkylenediamines and the N,N- or Ν,Ν’-dialkylated 20 alkylenediamines. Alkylene is especially straight-chain or branched Cw or Cm.

alkylene as defined above. Alkyl is especially C-M-alkyt as defined above. Examples are especially ethylenediamine, 1,2-propylenedlamine, 1,3-propylenediamine, 1,4butylenedlamine and isomers thereof, pentanediamine and isomers thereof, hexanediamine 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-di methylaminoethylamine.

Suitable straight-chain polyamines” are, for example, dialkylenetriamine, trialkyfeneteternine, tetraaikylenepentsmine, pentaalkylenehexamine, and the N-aikylsubstituted analogs thereof, such as N-monoalkylated and the N,N- or Ν,Ν'-dlalkylated alkylenepolyamines. Alkylene is especially straight-chain or branched Cvr- or Cmalkylene as defined above. Alkyl is especially Ci-alkyl as defined above.

M/51.32C-PCT especial ly diethyl® netriam in e, pentaethylenehexamine, tetrapropytenepentamins, tributyl® netetram Ine,

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

Examples are tetraethylenepentam ine. tripropylsnetetra mine, dlbutyienetriamine, triethyienetetramine, dipropylenetria mine, penta propy tenehexam in®, tetrabutyienepenta mine, pentabutylenehexamine; and the Ν,Ν-dialkyi derivatives thereof, especially the Ν,Μ-diCm-alkyl derivatives thereof. Examples include; Ν,Ν-dlmethyidimethylenetriamine, N,N-diethyldimetoyleneti1amine, N,N-dippopyldimeth^enetriamine, N, Ndimethyldiethylene-1,2-triamlne, N,N-diethyidiethylene-1 ,24riamlne, N,Ndipropyldfethylene-1,2-triamine, N.H-dimethyldipropyiene-ES-trismine (i.e. DMAPAPA), N, N-dtethyldi propylene-1,3-triamin e, dimethyldibutylene-l^-triamlne, dipropyld'lbutyi en a-1,4-triamine, dtethyldlpentytene-1,5-tria m in®, d Im ethyldihexylene-1,6-triamine, dipropyidihexylene-1,6-tria mine.

N, M-d ipropy Id [propylene-1,3-triam he, N ,N -dlethyidibu tylene-1,4-triami ne,

N, N-dimethyldlpentytene*1 ,5-tnamine,

N, N-dipropyldipentyle ne-1,5-trfem foie, N,N’dieihyldihexyfene~1 ,6-triamlne and ’’Aromatic carbocyclic diamines” having two primary amino groups are the dlamino* substituted derivatives of benzene, biphenyl, naphthalene, tetrahydronaphthaiene, 20 fluorene, indene and phenanthrene.

Aromatic or nonsromatic heterocyclic polyamines” having two primary amino groups are the derivatives, substituted by two amino groups, of the following heterocycles:

- 5- or 6-membered, saturated or monounsaturated heterocycles comprising one to two nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms as ring members, for example tetrahydrofuran, pyrrolidine, isoxazolidine, isothlazolidine, pyrazoiidine, oxazoltdine, thlazoiidine, imidazolidtne, pyrroline, piperidine, pipsridlnyi, ij-dioxane, tetrahydropyran, hexahydropyridazine, 30 hexahydropyrimidine, 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, Wane, pyrrole, pyrazole., oxazole, thiazote., imidazole 35 and 1,3,4-titazote; isoxazole, isothiazote, thladiazoie, oxadiazole;

W51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

6-membered heterocycles comprising, In addition to carbon atoms, one or two, or one, two or three, nitrogen atoms as ring members, for example pyridinyl, pyridazme, pyrimidine, pyrazlnyl, 1,2,4^riaztne, 1,3,5-triadn-2-yl

Aromatic or nonaromatic heterocycles having one primary and one tertiary amino group” are, for example, the abovementioned N-heterocydes 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-heterocydes which ar® hydroxyalkylated on at least one ring nitrogen atom, and espedaliy bear a hydroxy-C?. «-alkyl group.

Mention should be made especially of foe following groups of individual classes of quatemizable nitrogen compounds:

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

Group 1:

Ethylenediamine

1,3-Propylenediamfoe

1,3-Pentylened famine

I

Di et h yienetriam foe (D ET A)

Dipropylenetriemine (DPTA), 3,3'iminobis( N ,N-d imethyi pro pyfomfoe)

NAME

FORMULA

Pentasthvle nehexam me | 1,2*Propylenediamme $

isomeric butylenediamines, for example

H-hL

Isomeric hexanediamines, for example

Isomeric heptanediamfoes, for example

I DA andpo/yamtoes wtfto a secopdaiy.eecoffd pto^gen atom

Triethytenelefoamfoe (TETA) ^Nx/^

T etraethytenepentamine (ΤΕΡΑ)

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

IjFleierogycto

ΓΆ /

j 3»DimethyJamlno-1-pn>pyJamine (DMAPA) | Aromaffps

I Diaminpbenzenes, for example

N-Methyl-S-am iwM -propham ine

Bfsnexamelhylenetdamine j Dsamioopyridines, for example

Group 2:

FORMULA | 1 -(3’AminopropyOimidazote

I 4-(3-Am inepropylJnwpbolrne

-(2-Amlnoeihylpipertdine) j 2<1-Piperazinyl)ethytamine (AEP)

N-Ffethylpipe mzi ne j 3,3-Diam im-N'HTi ethyld ipropylam me

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

I | N, N-Dlethylemirtepropylam ine

N Dimstoyiam inoeth y la m Ine

Group 3:

Γ.. Z 7 JAME Z '7 I 1.4/co/jofe twffi a primary amf secohday amfae | Etharolamlne [ 3-Hydroxy-t-propytem ine

H_aN

FORMULA ^_0H | Diethanolamine

I Diisopropanolamrne

I

J N-(2“Hydroxyethy)ethyle nsdiam ine

J Atoohofc with a tertiary amine

I | Triethanolamine, (2,2\2LNiirilatriethanol)

HO'

OH “(3-Hydnoxyprop^)lmldazols

W51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 p

T risfhydroxymethyl

3-Dlm e thy la m inc-1 -propanol

3-Diethylam lno-1 -propa not | 2-Dimethylamino-1 -ethanol

4-Diethyf am ino-1 -butanol

A6) Preparation of Inventive additives:

a) Reaction with oxygen or nitrogen group

The hydrocarbyl-substitufed polycarboxylic acid compound can be reacted with the quatemizable nitrogen compound according to the present invention under thermally 10 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 1G to 80*C, especially 20 to 60*C or 30 to 80*0. 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 15 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 20 promote condensation, for example in the range from 90 to 100’C or 100 to 170*C.

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

The 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.

The reactants are initially charged especially in about equimolar amounts; optionally, a small molar excess of the polycarboxylic add compound, for example a 0.05- to 0.5fold. for example a Q.i- to 0.3-fold, excess, Is desirable. If required, the reactants can be initially 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 aiso serve, for example, to remove water of condensation azeotropicaily from the reaction mixture. More particularly, however, the reactions are performed without solvent.

The reaction product thus formed can theoretics ily be purged 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) Qusternizatton

The quatemlzation in reaction step (b) is then carried out In a manner known per se.

To perform the quaternizatlon, 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 quatemlzation. It is possible to use, for example, 0.1 to 2.0, 0.2 to 1,.5 or 0.5 to 1,.25 equivalents, of quaternlzing agent per equivalent of quatemizabte 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 quatemize a 30 secondary or primary amine group. In a further variant., the quaternlzing agent is added in excess, for example 1.1 to 2.0, 1.25 to 2 or 1.25 to 1.75 equivalents of quaternlzing agent per equivalent of quaternizable tertiary nitrogen atom.

Typical working temperatures here are in the rang® from 50 to l80^eC, for example from 35 90 to ifMFC or 100 to 140°C. The reaction time may be in the range of a few minutes

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 or a 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 at about standard pressure.

If required, the reactants can be initially charged for the quaternization in a suitable inert organic aliphatic 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 quatemization can, however, also be performed in the absence of a solvent.

To perform the quatemlzation, the addition of catalytically active amounts of an acid may be appropriate. Preference is given to aliphatic monccarboxytic acids, for example CrC«-monooarboxylic acids such as especially lauric acid, isononanoic add or naodecanoic add, The quatemlzation can also be performed in the presence of a 15 Lewis acid. The quaternization can, however, also be performed in the absence of any acta.

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 th® Solvesso series, 2-ethylhexanol, or essentially aliphatic solvents. Usually, however, this Is not absolutely necessary, and so the reaction product is usable without further 25 purification as an additive, optionally after blending with further additive components (see below).

B) Further additive components

The fuel additized with the inventive quatemized additive is a gasoline fuel or especially a middle distillate fuel, in particular a diesel fuel

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

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 in the case of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, antifoams, cetane number improvers, combustion Improvers, antioxidants or stabilizers, antistats, metallocenes, metal deactivators, dyes and/or solvents.

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

Typical examples of suitable coadditives ar® listed in the following section:

S1) Detergent additives

The customary detergent additives are preferably amphiphilic substances which possess at least one hydrophobic hydrocarbon radical with a number-average molecular weight (Μ?>) of 85 to 20 000 and at least one polar moiety selected from:

(Da) mono· or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;

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

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

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

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

(Of) polyoxy-C?- to C^-alkylene moieties terminated by hydroxyl groups, mono- or polysmlno groups, at least one nitrogen atom having basic properties, or by carbamate groups;

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 (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 (Di) mofettes 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 (Ms) of 85 to 20 000, preferably of 113 to 10 000, more preferably of 300 to 5000, even more preferably of 300 to 3000, even more especially preferably of 500 to 2500 and especially of 700 to 2500, in particular of 800 to 1500.. As typical hydrophobic hydrocarbon radicals, especially in conjunction with the polar especially poiypropenyl, polybutenyl and polylsobutenyl radicals with a number-average molecular weight of preferably in each case 300 to 5000, mar® 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:

Additives comprising mono- or polyamino groups (Da) are preferably polyalkenemonoor polyalkenepolyamines based on polypropene or on high-reactivity (i.e. having predominantly terminal double bonds) or conventional (Le, having predominantly interns! double bonds) polybutene or polyisobutene having Mn ^a 300 to 5000, more preferably 500 to 2500 and especially 700 to 2500. Such additives based an highreactivity polyisobutene, which can be prepared from the polyisobutene which may comprise up to 20% by weight of n-butene unite by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylsminopropylamin e, ethyleBedlamine, diethylenetriamine, triethylenetetramine or tetraethytenepentamine, are known especially from EP-A. 244 616. When polybutene or polyisobutene having predominantly internal double bonds (usually In the β and γ positions) are used as starting materials in the preparation of the additives, a possible

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 preparative route is by chlorination and subsequent 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 polyamines, Corresponding additives based on polypropene are described in particular in WO-A 94/24231.

Further particular additives comprising monoamino groups (Da) are the hydrogenation products of the reaction products of poiyisobutenes having an average degree of 10 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 poiyisobutenes having an average degree of polymerization P ® 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 96/03367 and in WO-A 96/03479. These reaction products are generally mixtures of pure nitropolyisobutenes (e.g. α,β-dinitiopoiyisobutene) and mixed hydrexynitropo^isobutenes (e.g. a-nitro-βh ydroxypo ly Isobutene).

Additives 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_n - 300 to 5000, with ammonia or mono- or polyamines, as described in particular in EP-A

476 485.

Additives comprising carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copolymers of Cr to C^oleflns with maleic anhydride which have a 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

2016273853 12 Dec 2016 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 EP A 307 816. 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)butensamines or poiyetheramines.

Additives comprising sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) are preferably alkali meta or alkaline earth metal salts of an alkyl suifosuccinate, as described in particular in EP A 639 632, 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-C2*C4*alkylene moleties (Df) are preferably polyethers or 15 polyetheramines which are obtainable by reaction of Cr to Cetralkanois, C«- to C^~ alkanedials, mono or dl-Cr to Cgg-alkylamines, Cr to C^-alkyicyclohexanols or Ci- to Csiralkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, In the case of the poiyetheramines, by subsequent reductive amination with ammonia, monoamines or 20 polyamines. Such products are described in particular In ERA. 310 875, EP-A 356 725,

EP-A 700 985 and USA 4 877 416. in the case of polyethers, such products also have carrier oil properties. Typical examples of these are tridecanol butoxylstes, Isoirtdecanol butoxylates, isononyiphenoi butoxylates and polylsobutenol 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 mrrF/s at 100’C, as described In particular in DEA 38 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids, arid 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 trimellitetes of isooctanol, of isononanol, of isodecanol and of Isotridecanol. Such products also have carrier oil properties.

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

Additives comprising moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or especially Imrdo groups (Oh) are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and especially the corresponding derivatives of polyisobutenylsucdnic anhydride which are obtainable by reacting conventional or high-reactivity polyisobutene having ~ preferably 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2500, even mere especisliy preferably 700 to 2500 and especially SOO to 1500, with maleic anhydride by a thermal route in an ene reaction or via the chlorinated polyisobutene. The moieties having hydroxyl and/or amino and/or amido and/or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which, in addition to the amide function, also have free amine groups, succinic acid derivatives having an acid and an amide function, carijoxlmides with monoamines, carboximides with di- or polyamines which, in addition to the Imide function, also have free amine groups, or diimides which are formed by the reaction of di- or polyamines with two succinic acid derivatives, in the presence of imido moieties D(h)_k the further detergent additive in the context of the present invention is, however, used only up to a maximum of 100% of the weight of compounds with betaine structure. Such fuel additives are common knowledge and are described, for example, in documents (1) and (2), They are preferably the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof wife amines and more preferably the reaction products of polyisobutenyl-substitirted succinic acids or derivatives thereof with amines. Of particular interest in this context are reaction products with aliphatic polyamines (polyalkyleneimines) such as especially .25 ethylenediamine, diethyfenetriamine, triethytenetetramine, tetraethylenepentamlne, pentaethyienehexamine and hexaethyleneheptamine, which have an Imide structure.

Additives comprising moieties (Di) obtained by Mannidi reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentemine or dimethylaminopropylamine. The polyisobutenyl-substitoted phenols may stem from conventional or high-reactivity polyisobutene having = 300 to 5000, Such polyisobutene Mannfch bases are described in particular in EP-A 831 141.

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2016273853 12 Dec 2016

One ar more of the detergent additives mentioned can be added to the fuel in such an amount that the dosage of these detergent additives is preferably 25 to 2500 ppm by weight especially 75 to 1500 ppm by weight in particular 150 to 1000 ppm by weight

B2) Carrier oils

Carrier oils additionally used may be of mineral or synthetic nature. Suitable mineral carrier oils are the fractions obtained in crude oil processing, such as brightstock or 10 base oils having viscosities, for example, from the SIM 500 to 2000 class; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols, Likewise useful is a fraction which is obtained in the refining of mineral oil and is known as hydracrack oil (vacuum distillate cut having a boiling range from about 360 to 500’0, obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized under high pressure and also deparaffinlzed). Likewise suitable are mixtures of the abovementioned mineral carrier oils.

Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyintemalotefins), (polyjesters. (polyjalkoxylates, polyethers, aliphatic poiyether20 amines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic esters of long-chain alkanols.

Examples of suitable polyolefins are olefin polymers having M_s« 400 to 1800, in particular based on polybutene or polyisobirtene (hydrogenated or unhydrogenated).

Examples of suitable polyethers or pdyetheramines are preferably compounds comprising polyoxy-C2- to Chalkylene moieties which are obtainable by reacting Ca- to Caralkanols, C«- to C^-alkanedtols, mono- or di-Cz- to Cge-alkylamines, Ch- to Ca>alkyicyclohexanols or Or to Csa-alkylphenols with 1 to 30 mol of ethylene oxide and/or 30 propylene oxide and/or butylene oxide per hydroxyl group or amino group, and, in the case of the poiyetheramines. by subsequent reductive amination with ammonia, monoamines or polyamlnes, Such products are described in particular in EP-A 310 875, EP-A 356 725. EP-A 700 985 and US-A 4,877.416. For example, the poiyetheramines used may be poly-Cr to C^-alkytene oxide amines or functional

M/5132D-PCT

PF 000007142?SBAb

2016273853 12 Dec 2016 derivatives thereof. Typical examples thereof are tridecanol butoxylates or isotridecanol butoxylates, Isononyfphenol butoxylates and also polyisobutenoi butoxylates and propoxylates, and also the corresponding reaction products with ammonia.

Examples of carboxylic esters of long-chain alkanols are In particular esters of mono-, di* or tricarboxylic acids with long-chain alkanols or polyols, as described In particular In DE-A 38 38 9IS, The mono-, di* or tricarboxylic acids used may be aliphatic or aromatic acids; suitable ester alcohols or polyols are in particular long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trlmeUitates of isooctanol, isononanol, isodeoanol and Isotridecanol, for example di(n- or Isotridecyi) phthalate.

Further suitable carrier oil systems are described, for example, in DE-A 38 26 60S,

DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 817.

Examples of 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 Crolkyiene oxide units, for example selected from propylene oxide, n* 20 butylene oxide and isobutylene oxide units, or mixtures thereof, per alcohol molecule.

Nonlimiting 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 Cr to Cis-alkyl radical. Particular examples include tridecanol and nonylphenol Particularly preferred ataGhokstarted polyethers are ths reaction products (polyetherffication products) of monohydric aliphatic Cr to Cisalcohols with Cs- to CraMene oxides. Examples of monohydric aliphatic CtrCir alcohols are hexanol, heptanol, octanof, 2-ethylhexanol, nonyl alcohol, decanol, 3propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol.

hexadecanol, octadecanol and the constitutional and positional isomers thereof. The 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 Cs- to Cr alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentyiene oxide and hexylene oxide. Particular preference among these is given to CsM/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 to C^sikyteae oxides, i.e. propylene oxide such as 1 ,.2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Especially butylene oxide is used.

Further suitable synthetic carrier oils are alkoxytated aikylphenols, as described in DE-A 10 102 913.

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

The carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably 1 to WOO ppm by weight, more preferably of 10 to 500 ppm by weight and especially of 20 to 100 ppm by weight.

B3) Cold How improvers

Suitable cold flow improvers are in principle ail organic compounds which are capable of improving the flow performance of middle distillate fuels or diesel fuels under cold conditions. For the intended purpose, they must have sufficient oil solubility. in particular, useful cold flow improvers for this purpose are the cold flow improvers (middle distillate flow improvers, MDFIs) typically used to the case of middle distillates of fossil origin, Le. in the case of customary mineral diesel fuels. However, It is also possible to use organic compounds which partly or predominantly have the properties of a wax antisettling additive (WAS A) when used in customary diesel fuels. They can also act partly or predominantly as nucleators. It Is, though, also possible to use mixtures of organic compounds effective as MDFis and/or effective as WASAs and/or effective as nucleators.

The cold flow improver is typically selected from (KI) copolymers of a Ca- to C^rofefin with at least one further ethyienicalfy unsaturated monomer;

(K2) comb polymers;

(K3) polyoxyaikylenes;

(K4) polar nitrogen compounds;

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 (KS) suifbcarboxyiic acids or sulfonic adds or derivatives thereof; and (K6) poly(meth)acrylic esters.

It is passible 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 C46-olefin 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-oleflns, more preferably aolefins having 2: to 8 carbon atoms, for example propene, 1-butene, 1 -pentene, 1hexene and in particular ethylene.

In the copolymers of class (Kt), the at least one further ethylenically unsaturated monomer is preferably selected from alkenyl carboxylates, (meth)acrylfc esters and further cteftos.

When further olefins are also ^polymerized, they are preferably higher in molecular weight than the abovemenfibned Cr to C^rolefin base monomer. When, for example, the olefin base monomer used Is ethylene or propene, suitable further olefins ere in particular Cir to C-w-a-oleflns. Further olefins are In most cases only addittansily copolymerized when monomers with carboxylic ester functions are also used.

Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic add with Cr to Cag-alkanols, especially Cr to C^-alkanofs, in particular with methanol, ethanol, propanol, rsopropanol, n-butenol, seo-butenol, Isobutanol, tert-butanol, pentanol, hexanol, heptenol, octanol, 2-ethylhexanol, nonanol 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 adds having 2 to 21 carton atoms, whose hydrocarbon radical may be linear or branched. Among these, preference is given to

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 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 chcarbon atom more preferably being tertiary, i.e. the carboxylic acid befog a socalled neocarboxylic add. However, the hydrocarbon radical of the carboxylic acid is preferably linear.

Examples of suitable alkenyl carboxylates are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and th® corresponding propenyl esters, preference 10 being given to the vinyl esters. A particularly preferred alkenyl carboxylate is vinyl acetate; typical copolymers of group (K1) resulting therefrom are ethylene-vinyl acetate copolymers (“EVAs), which are soma 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 Gopolymerized 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 (methjacryiic 20 ester in copolymerized form.

Terpolymers of a Cr to C^-a-otefln, a Cr- to C^-alkyl ester of an ethytenically unsaturated monocarboxyllc 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

2006/054314. A typical terpolymer of this kind is formed from ethylene, 2-ethylhexyi acrylate and vinyl acetate.

The at least one or the further ethylenlcally unsaturated monom@r(s) are copoiymenzed 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 C? to C-w base olefins.

M/51320-PCT rr uvuuu/HZ/ tsfc/Ab

2016273853 12 Dec 2016

SB

The copolymers of class (KI) preferably have a number-average molecular weight M_B of 1000 to 20 000, more preferably 1000 to 10 000 and in particular 1000 to 8000.

Typical comb polymers of component (K2) are, for example, obtainable by the copolymerization of maleic anhydride or fumaric acid with another ethytonically unsaturated monomer, for example with an α-olefin or an unsaturated ester, such as vinyl acetate, and subsequent, esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms. Further suitable comb polymers are copolymers of a-oleflns and esterified comonomers, for example esterified copolymers 10 of styrene and mefefc anhydride or esterified copolymers of styrene and fumaric acid.

Suitable comb polymers may also be polyfumarates or poly maleates,. Homo- and copolymers of vinyl ethers are also suitable comb polymers. Comb polymem suitable as components of class (K2) are, for example, also those described in WO 2004/035715 and in Comb-Like Polymers. Structure and Properties, N. A.. Plate and 15 V. P, Shibaev, J. Poly» Sol. Macromolecular Revs, 8, pages 117 to 253 (1974/.

Mixtures of comb polymers are also suitable.

Poiyoxyalkylenes suitable as components of class (K3) are, for example, polyoxyalkylene esters,, polyoxyalkylene ethers, mixed polyoxyalkyiene ester/ethers 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 polyoxyalkyiene group having a number-average molecular weight of up to 5000. Such polyoxyalkyiene 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 100 to 5000. Additionally suitable are polyoxyalkyiene mono- and dfesters of fatty acids having 10 to 30 carbon sterns, such as stearic add or behenic acid.

Polar nitrogen compounds suitable as components of class (K4) may be either ionic or nonionic 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 R^? is a Cr to C^-hydrocarbon radical. The nitrogen substituents may also be quaternized, i.e. be in cationic form, An example of such nitrogen compounds is that of ammonium salts and/or amides which are obtainable by the reaction of at least one

MZ5132O-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 amine substituted by at least one hydrocarbon radical with a carboxylic add having 1 to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably comprise at least one linear Cr to C-walkyl radical· Primary amines suitable for preparing the polar nitrogen com pounds mentioned are, for example, cctylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and foe higher linear homologs. Secondary amines suitable for this purpose are, for example, dtoctadecylsmine 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, aliphatic chapter. Adds suitable for the reaction are, for example, cyclohexane*! ,2-dicarbcxylic acid, cyclo hexene-1,2-dica.rboxylic acid, cyclopentane-! ,2-dlcarboxyilc add, naphthalenedfcarboxylrc acid, phthalic acid, isophthalic acid, 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-carbsxylic acids) having at least one tertiary amino group with primary or secondary amines. The polyfCr to Cso-carboxyllc adds) which have at least one tertiary amino group and form foe basis of this reaction product comprise preferably at 20 least 3 carboxyl groups, especially 3 to 12 and In particular 3 to 5 carboxyl. groups. The carboxylic add units in the polycarboxylic adds have preferably 2 to 10 carbon atoms, and are especially acetic add units. The carboxylic add units are suitably bonded to· the polycarboxylic adds, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in foe 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^e-carboxyllc adds) which have at least one tertiary amino group and are of the general formula Ha er lib

HOOCT .CQQH

S B

HOQC.„zN. _Λ A_,COOH

Ο ·ΓΊ· O / i ] A

M/5132Q.-PCT

2016273853 12 Dec 2016 hoqc^bn'^bcooh

I

A ''COOH in which the variable A Is a straight-chain or branched C2» to Cg-afkylene group or the moiety of ths formula III

HGOCT⁸’ _HXH_rCH_£CH,_rCH._f (Hi) and the variable 8 is a Cr to Ciralkylene group. The compounds of the general formulae Ila and lib especially have the properties of a WASA,

Moreover, the preferred oil-soluble reaction product of component (K4), especially that of the general formula Ila or fib, is an amide, an amide-ammonlum salt or an ammonium salt in which no, one or more carboxylic acid groups have been converted to amide groups.

Straight-chain or branched to Cg-alkylene groups of the variable A ate, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, ^-methyl-ta-propytene, 1,5-pentylene, 2-methyM ,4-butylene, 2,2«dsmethyM,3propylene, 1,6-hexylene (hexamethylene) and in particular 1,2-ethylene. The variable A 20 comprises preferably 2 to 4 and especially 2 or 3 carbon atoms.

Cr to Cirelkyiene groups of the variable B ©re, for example, 1,2*ethylene,

1,3-propylene, 1,4-butylene, hexamethyiene. octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethyiene, odadecamethylene, 26 nonadecamethyfene and especially methylene. The variable 8 comprises preferably 1 to 10 and especially 1 to 4 carbon atoms.

The primary and secondary amines as a reaction partner tor the polycarboxylic acids to form component (K4) are typically monoamines, especially aliphatic monoamines.

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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These parent amines of the oil-soluble reaction products of component (K4) are usually secondary amines and have the general formula HN(R^S^ in which the two variables R® are each independently straight-chain or branched Cw- to Cstralkyl radicals, especially

Cm- to Chalky! radicals. These relatively· long-chain alkyl radicals are preferably straight-chain 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 polyoarboxylic 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 in the form of the amide structures.

Typical examples of such components (K4) are reaction products of nitrltotriacetic acid, of ethylenediaminetetraacetic acid or of propylene-1,2-diamlnetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, ©specially 0.8 to 1.2 mol per carboxyl group, of dioleyiamin®, dlpalmitinamine, dlcoconut fatty amine, distearylamine, dibeheny[amine or especially ditallow fatty amine, A particularly preferred component (K4) is the reaction product of 1 moi of ethylenedlaminetetraacetic acid and 4 mol of hydrogenated ditaltow fatty amine.

Further typical examples of component (K4) Include the Ν,Ν-dlalkylammonium salts of 2-N\N’-dialkylamidobenzoates, 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 ditai 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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Sulfbcarboxytic 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 ortho-suifobenzolc acid, tn which the sulfonic acid function is present as a sulfonate with alkyFsubstituted ammonium cations, as described In EP-A 261 957.

Poly (meth)acry lie esters suitable as co id flow improvers of class (K6) are either homo or 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 estariffed alcohol.

The copolymer optionally comprises another different oleflnlcally 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 acid groups having been neutralized with hydrogenated tallamine. Suitable poly(meth)acrylic esters are described, for example, in WO 00/44857.

The cold flow improver or the mixture 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.

84} Lubricity improvers

Suitable lubricity improvers or friction modifiers are based typically on fatty acids or fatty add esters. Typical examples are tail oil fatty acid, as described, for example, in WO 98/004656, and glyceryl monooleate. The reaction products, described in US 6 743 266 B2, of natural or synthetic oils, for example triglycerides, and alkanolamines 30 are also suitable as such lubricity improvers.

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2016273853 12 Dec 2016

B5) Corrosion inhibitors

Suitable corrosion inhibitors ere, for example, succinic esters, in particular with polyols, fatty add derivatives, for example oleic esters, oligomerized fatty acids, substituted ethanolamines, and products sold under ths trade name RC 4801 (Rhein Chemi® Mannheim, Germany) or HtTEC 536 (Ethyl Corporation).

BB) 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 sails of fatty adds, and also neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol atocylates, e.g, tert-buiylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkjdphenols, 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 polysiloxanes.

67} Dehazers

Suitable dehazers are, for example, alkoxylated phenolformaldehyde condensates, for example the products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).

B8) Antifoams

Suitable antifoams are, for example, polyether-modffied polysiloxanes, for example the products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSiL (Rhone Poulenc).

89) Cetane number improvers

Suitable cetane number improvers are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyelohexyl nitrate and peroxides such as di-tert-btayl peroxide.

M/51320-PCT

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2016273853 12 Dec 2016

BIO) Antioxidants

Suitable antioxidants are, for example substituted phenols, such as 2,6-dl-tertbutylphenol and 6*dl-tert*but^-3-methylphenol, and also phenylenedfamines such as 5 N,N'-di*seo-butyl-p-phenylenediamine.

Si 1) Metal deactivators

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

N,N’’disalicyiidene’1 ,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 Dutch/Shell Group) and EXXSOL (ExxonMobil), and also polar organic solvents, for example, alcohols such as 2-ethylhexanol, decanol and isoindecanol Such solvents are usually added to the diesel feel together with the aforementioned additives and coadditives, which they are intended to dissolve or dilute for better handling,

C) Fuels

The inventive additive is outstandingly suitable as a feel additive and can be used in principle in any fuels. It brings about a whole series of advantageous effects in the 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,.

with a content of the inventive quatemized additive which is effective as an additive for achieving 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 weight, preferably 20 to 1500 ppm by weight, especially

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 to iOOO ppm by weight, in particular 30 to 750 ppm by weight, based in each 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 360^eC 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 a 95% point of, for example, 285^eC and a sulfur content of not more than 0.001% by

W weight. In addition to the mineral middle distillate fuels or diesel fuels obtainable by refining, those obtainable by coal gasification or gas liquefaction (“gas io liquid (GTL) fuels] or by biomass liquefaction (“biomass to liquid (8TL) fuels] are also suitable. Also suitable are mixtures of the aforementioned middle distillate fuels or diesel fuels with renewable fuels, such as biodiesel or bloethanoL

The qualities of the heating oils and diesel fuels are laid down In detail, for example, in DIN 51603 end EM 590 (of. also Ullmann’s Encyclopedia of industrial Chemistry, 5th edition, Volume A12, p, 617 <), 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 quaternlzed additive can also be used tn mixtures of such middle distillates with biofuel oils (biodiesel). Such mixtures are also encompassed by the term ‘'middle distillate fuel” in 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 fatty 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 CrQ-alkyl esters, which are obtainable by transesterifying the glycerides which occur in vegetable and/or animat oils and/or fats, especially triglycerides, by means of lower alOThols, far example ethanol or in particular methanol (FAME). Typical lower alkyl esters based

M/&1320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 on vegetable and/or animal oils and/or fats, which tied use as a biofuel oil or components thereof,, are, for example, sunflower methyl eater, palm oil methyl ester fPME”), soya oil methyl ester (’SME*) and especially rapeseed oil methyl ester CRME”).

The middle distillate fuels or diesel fuels are more preferably those having a tow sulfur content, i.e.. 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 sulfur.

Useful gasoline fuels include all commercial gasoline fuel compositions. One typical representative which shall be mentioned here is the Eurosuper base fuel to EM 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 forth© present 15 Invention.

The inventive quatemized additive is especially suitable as a fuel additive in fuel compositions, especially in diesel fuels, for overcoming the problems outlined at the outset In direct-injection diesel engines, in particular In those with common-rail injection 20 systems.

The 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 at the description and can be employed generally in the 25 context of the present invention.

A. General test methods

Engine test b1) XUD9 test™ determination of flow restriction

The procedure was according to the standard stipulations of CE.C F-23-01.

M/5132Q-PCT

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2016273853 12 Dec 2016 b2) DW10 ™ keep clean test

To examine the influence of the Inventive compounds on the performance of directinjection diesel engines, the power toss 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.

The keep clean test la based on CEC test procedure FO08-08 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 injectors were used. The cleaning time in an ultrasound bath in 15 water at 60*C + 10% Superdecontamine (intersclenoes, Brussels) was 4 h.

b) Test run tiroes the test period was 12 h without shutdown phases. The one-hour test cycle (see table below) from CEC F-098O8 was run through 12 times.

Torque

W51320-PCT

Duration | Engine spe (rpm) +/-20

Charge air temperature downstream of charge run coater (*C)+/«3

1750

4000

PF 0000071427 SE/Ab

2016273853 12 Dec 2016

for range to be. expected see CE 0098-08 target value

c) Power determination

e.

The initial power (P«, KC (kWJ) is calculated from the measured torque at full load 4000/min directly after the test has started and the engine has warmed up. The procedure is described in Issue 5 of the test procedure CEC F-08-08. The same test setup and the PEUGEOT DWW engine type are used.

The final power (Ρ®*, KC) is determined in the 12th cycle in stage 12. (see table above). Here too, foe operating point Is full load 4000/min, P^, KC [kWJ is calculated from the measured torque.

The power loss in KC is calculated as follows:

power foss, KC [%] ® (1 - P_8taJ,KC / P₆,KC) x 100

The fuel used was a commercial diesel fuel from Haltermann (RF-06-03). To 20 synthetically induce the formation of deposits at the injectors, 1 ppm of zinc was added thereto in the form of a zinc neodecanoate solution,.

B. Preparation examples:

Reactants used:;

PISS A: Prepared from maleic anhydride and FIB 1000 in a known manner. For the inventive preparation examples and comparative examples which follow, qualities with hydrolysis numbers in the region of 84-95 mg KOH/g were used. DMAPA was used 30 with the particular PIBSA quality in a motor ratio of 1:1 according to the hydrolysis number. The PIBSA qualities used had bismaieafion levels (BML) of less than 15%.

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2016273853 12 Dec 2016

4®

DMAPAi M - 102.18 methyl salicylate.: M 152,14 dimethyl phthalate: M ~ 194.19 dimethyl oxalate: M ~ 118.09 dimethyl sulfate: M ~ 126.13 dimethyl carbonate M ~ 90.08

Preparation example 1: Synthesis of an inventive quatemlzed succinimide 10 (PIBSA/DMAPA/dlmethyl phthalate)

Polyisobutylenesuccinic anhydride (1659 g) is dissolved in Solvent Naphtha Heavy fSAW, Exron WM (1220 g), and 3-dimethylsmino-l -propylamine (DMAPA; 153 g) is added. The reaction solution is stirred at 17O‘C for 8 h, in the 15 course of which water of condensation formed is distilled off continuously. This affords tiie PIBSA-DMAPA succinimide as a solution In Solvent Naphtha Heavy (TBN 0.557 mmol/g).

A portion of this solution of the PIBSA-DMAPA succinimide (181 g) is added to 20 dimethyl phthalate (19,4 g), and the resulting reaction solution Is stirred at 120*C for

1'1 h and then at 150*C for 24 h. After coding to room temperature, the product obtained is the ammonium carboxyiate as a solution in Solvent Naphtha Heavy, Ή NMR analysis confirms the quatemization.

Preparation example 2: Synthesis of an inventive quatemtzed succinimide (PIBSA/DMAPA/methyl salicylate)

Polyisobutylenesuccinic anhydride (PiBSA; 2198 g) is heated to 11D’C_S and 3* dimethylsmlnO’l-prapylamine (DMAPA; 182 g) is added within 40 min, In the course of 30 which the reaction mixture heats up to 140*0. The reaction mixture is heated to 170’C and held at this temperature for 3 h_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 mmoVg).

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2016273853 12 Dec 2016

A mixture of this PIBSA-DMAPA succinimide (284,5 g), methyl salicylate (65.5 g) (i.e. about 2 equivalents of methyl salicylate per equivalent of tertiary amino group) and 3,3,54rimethylheptenoic add (from BASF) (0.75 g) is hosted 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 quatemlzation. By adding Pitot 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 (PIBSA/DMAPA/dimethyl oxalate)

Polyisobutylertesuccinic anhydride (PIBSA; 2198 g) is heated to 110’C, and 3dimethylamino-1 -propylamine (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 this 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 (p ™ 5 mbar) at 12O*C. The product obtained is the ammonium methyl oxalate as a viscous oil. ¹H NMR analysis confirms the· quatemlzation.

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*C. 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 150°C and the mixture is then kept at this temperature

M/51320-PCT

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2016273853 12 Dec 2016 for 3 h, in the course of which the water of reaction which forms is distilled off. After cooling to room temperature, the PISSA-DMAPA suodnimlde is obtained as a solution in Pilot SOO oil (TEN 0.62 mmol/g).

A portion of foe PiBSA-DMAPA succinimide thus obtained as a solution in Pilot 900 oil, Petrachem Carless Ltd., (354 g) is initially charged and heated to 90’C. Dimethyl sulfate (26..3 g) is metered in, in the course of which foe reaction temperature rises to 112’C. Subsequently, the readion mixture is stirred at 100’C for 3h. After cooling to room temperature, the quaternlzed PIBSA-DMAPA succinimide is obtained as a 10 solution in Pilot 900 oil. Ή NMR confirmed the quaternization. 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 quaternlzed succinimide (comparative example) (Example 4 from WO 2006/135881)

A solution of PI8SA (420.2 g) tn Pilot 900 oil, Petrochem Carless Ltd., (51.3 g) is initially charged and heated to 110*0. DMAPA (31.4 g) is metered In within 50 minutes, in foe course of which a slightly exothermic readion is observed. Within 80 minutes, the reaction mixture is heated to 150*G and the mixture is then kept at this temperature 20 for 3 h, in foe course of which the water of reaction which forms is distilled off. After cooling to room temperature, the PIBSA-DMAPA succinimide is obtained as a solution in Pilot 900 oil (T8N 0.62 mmol/g).

A portion of the PIBSA-DMAPA succinimide thus obtained as a solution in Pitot 900 oil,

Petrochem Carless Ltd., ¢130 g), dimethyl carbonate (20 g) and methanol (17.4) are charged into an autoclave and inertteed with nitrogen, and a starting pressure of 1.3 bar is established. Subsequently, the reaction mixture is stirred under autogenous pressure first at 90’C for 1 h, then at 140®C for 24 h. After cooling to room temperature, the autoclave is decompressed and the contents are rinsed out completely with a little toluene as a solvent. All low-boiling constituents are subsequently removed on a rotary evaporator under reduced pressure to obtain the quaternlzed' PIBSA-DMAPA succinimide as a solution in Pilot 900 oli. ¹H NMR analysis confirmed the partial quaternization. The output is adjusted to an active ingredient content of 50% by weight by adding Pilot 900 oil.

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C. Use examples:

in the us® examples which follow, the additives are used either as a pure substance {as synthesized in 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)

M3; 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) XUD9 Teste

Fuel used: RF-06-03 (reference diesei, Haltermann Products, Hamburg)

The resuite are compiled in tobte 1:

Table 1: X.UD9 tests |ex. j Name #3 [m1 , according to preparation example 2

M2, according to j preparation example 4

I M3, according to __[preparation example 5 j

I Dosage according to | Flow restriction I j preparation example 10.1 mm needle g/kg] | stroke [%] win- ttv.ww rown . .ie-xiv.

10..7

20.8

M/51320-PCT

PF 0000071427 SE/Ab

2016273853 12 Dec 2016 ft was found that the inventive additive M1, with the same dosage, has an improved effect compared to the 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-093-08 as described above. The power loss is a direct measure of formation of deposits in the Injectors. A conventional direct-injection diesel engine with a comm on10 rail system was used.

The fuel used was a commercial diesel fuel from Haltermann (RF-06-03). To synthetically induce the formation of deposits at the injectors, 1 ppm by weight of zinc in the form of a anc didodecanoate solution was added thereto.

The table below shows the results of tee determinations of the relative power loss at 4000 rpm after 12 hours of sustained operation without interruption. The value Ps gives the power after 10 minutes and the value Ρ«χΐ the power at the end of the measurement:

The test results are shown in table 2,

Table 2: Results of the DW10 test [Baseyaiue, , I 0 [12 | 99,3 pH3~T J>0%~ |M1, according to preparation Itill l_ex8mp,_e2 I 160J 12 | 98.7 | 97.4 |1.32% [m2, Mconflna to preparation , I I| |«»m».4 j ¹⁶⁰ I « | »1

UrnpteS _______[ J⁸⁰ | ⁹⁸·¹ ' ^SS·⁷ I

0.9% .25 It was found that the inventive additive M1 has an improved effect compared to the base value and has an improved effect at least compared to example M3.

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Oss example 2: Determinate of the sduM'ity properties

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

M 4 (Inventive) | Substance Content [ppm]

Additive aco. to preparation example 2	160.00
Dehazer, commercial	3.00
Antifoam, silicone-based. commercial	6.00
Solvent Naphtha Heavy	30.00
Total	249.00

M 5 (comparative, dimethyl sulfete)

Substance J Content [ppm]

[Additive acc. to preparation example 4	160.00
Dehazer, commercial	3.00
Antifoam, silicone-based, commercial	e.od
iSolvent Naphtha Heavy	420.00
Total	§39.00
M 6 (comparative, dimethyl carbonate)
Substance	Content [ppm]
Additive acc. to preparation example 5	160.00
Dehazer (commercial)	3.00
Antifoam, silicone-based, commercial	6.00
Solvent Naphtha Heavy	150.00
Total	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, clear 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

2016273853 26 Sep 2018

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 20 preclude the presence or addition of further features in various embodiments of the invention.

Claims (20)

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

5 fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, said reaction product being obtainable by a1) reacting a hydrocarbyl-substituted polycarboxylic acid compound with a 10 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

15 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;

20 wherein in step a1) hydrocarbyl-substituted polycarboxylic acid compound is reacted with the quaternizable nitrogen compound in a small molar excess over equimolar amounts.

2. A fuel composition according to Claim 1 wherein in step a1) the molar excess of 25 hydrocarbyl-substituted polycarboxylic acid compound over the quaternizable nitrogen compound is 0.05 to 0.5-fold over equimolar amounts.

3. A fuel composition according to Claim 1 wherein in step a1) the molar excess of hydrocarbyl-substituted polycarboxylic acid compound over the quaternizable nitrogen

30 compound is 0.1 to 0.3-fold over equimolar amounts.

4. A fuel composition according to any one of Claims 1-3 wherein in step a1) the molar excess of hydrocarbyl-substituted polycarboxylic acid compound over the quaternizable nitrogen compound is calculated on the basis of the hydrolysis number of

35 the hydrocarbyl-substituted polycarboxylic acid compound.

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2016273853 26 Sep 2018

5. A fuel composition according to any one of the preceding claims wherein the hydrocarbyl-substituted polycarboxylic acid compound has a bismaleation level of less than 20%.

5

6. A fuel composition according to Claim 1, wherein the hydrocarbyl radical of the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutene radical having a proportion of vinylidene double bonds of greater than 80 mol%.

7. A fuel composition according to Claim 1, wherein the hydrocarbyl radical of the 10 hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutene radical having a polydispersity in the range of from 1.1 to 2.5.

8. A fuel composition according to Claim 1, wherein the hydrocarbyl radical of the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutene radical

15 having an Mn of 500 to 2500.

9. The fuel composition according to any one of the preceding claims, wherein the compound comprising at least one oxygen or nitrogen group is reactive with the polycarboxylic acid by addition or condensation.

10. The fuel composition according to any one of the preceding claims, wherein said quaternizing agent is an alkyl ester of a cycloaromatic or cycloaliphatic mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid.

25

11. The fuel composition according to any one of the preceding claims, wherein about 1.25 to about 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom.

12. The fuel composition according to claim 1, wherein the hydrocarbyl-substituted 30 polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, said acid having a bismaleation level of 2 to 15% by weight.

13. 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)

10621324_1 (GHMatters) P95787.AU.1 in which

Ri is a lower alkyl radical and

R2 is an optionally substituted monocyclic aryl or cycloalkyl radical, where the

5 substituent is selected from OH, NH2, NO2, C(O)OR3, and RiOC(O)-, in which R1 is as defined above and R3 is H or R1.

2016273853 26 Sep 2018

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

RiOC(O)-A-C(O)ORia (2) in which

R1 and Ria are each independently a lower alkyl radical and

15 A is hydrocarbylene.

15. 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.

16. 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.

25

17. The fuel composition according to any one of the preceding claims, 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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18. The fuel composition according to any one of the preceding claims, selected from diesel fuels, biodiesel fuels, gasoline fuels and alkanol-containing gasoline fuels.

19. The use of a reaction product obtainable by a process as defined in any one of

5 the preceding claims or of quaternized nitrogen compound obtained from the reaction product, as a fuel additive.

20. The use according to claim 19 as:

a. an additive for reducing the fuel consumption of direct-injection diesel

10 engines, or diesel engines with common-rail injection systems, and/or for minimizing power loss in direct-injection diesel engines, or in diesel engines with common-rail injection systems;

b. 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

15 injector) engines; and/or

c. a diesel fuel additive, a cold flow improver, a wax antisettling additive (WASA) or 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

20 systems.