EP4634340A1 - Composition, procédé et utilisation - Google Patents

Composition, procédé et utilisation

Info

Publication number
EP4634340A1
EP4634340A1 EP23828233.9A EP23828233A EP4634340A1 EP 4634340 A1 EP4634340 A1 EP 4634340A1 EP 23828233 A EP23828233 A EP 23828233A EP 4634340 A1 EP4634340 A1 EP 4634340A1
Authority
EP
European Patent Office
Prior art keywords
acid
group
substituted
alkyl
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23828233.9A
Other languages
German (de)
English (en)
Inventor
Nigel Broom
Peter Knight
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Innospec Ltd
Original Assignee
Innospec Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB2218664.7A external-priority patent/GB202218664D0/en
Application filed by Innospec Ltd filed Critical Innospec Ltd
Publication of EP4634340A1 publication Critical patent/EP4634340A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0259—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines

Definitions

  • the present invention relates to fuel compositions, and to methods and uses relating thereto.
  • the invention relates to additives for reducing particulate emissions in spark ignition engines.
  • SI spark ignition
  • performance fuel additives have been developed to minimise wear and deposit build-up phenomena. Examples include anti valve seat recession additives to reduce wear and detergents to reduce deposit build-up.
  • Engine designers have developed high performance engines which include injection systems where the fuel is injected directly into the cylinder. Such engines are alternatively known as direct injection spark ignition (DISI), direct injection gasoline (DIG), gasoline direct injection (GDI), etc.
  • DISI direct injection spark ignition
  • DIG direct injection gasoline
  • GDI gasoline direct injection
  • Various additives have been developed for such engines to reduce wear and for deposit control. Considerable work has also been carried out to control emissions from such engines, especially carbon monoxide and NO X in exhaust gases.
  • catalytic converters in the exhaust system of a direct injection gasoline engine. These typically include three way catalytic converters which reduce the concentrations of hydrocarbons, carbon monoxide and NO X species released into the atmosphere.
  • diesel engines it is common to include a diesel particulate filter in the exhaust system.
  • a diesel particulate filter in the exhaust system.
  • the emission of particulates from direct injection gasoline engines is not routinely monitored and many direct injection gasoline engines do not include gasoline particulate filters.
  • Direct Injection Spark Ignition engines do however produce particulates, albeit in a lower concentration than many diesel engines. These particulates are known to be harmful to human health and to have a detrimental environmental impact. Some direct injection spark ignition engines are fitted with particulate filters. However this is not mandated for all vehicles. Furthermore current guidelines only require the emissions of particulates having a diameter of at least 2.5 microns to be measured. However it is known that particulates having a smaller diameter are also emitted, and some of these may pass through particulate filters (when fitted) on exhaust systems.
  • Particulates having a diameter of less than 2.5 microns can be highly damaging to human health. Fine particulate matter can accumulate in the lungs causing increasing damage over time. Ultrafine particles are also able to enter the bloodstream. Additionally particulates having a diameter of less than 2.5 microns are very damaging to the environment.
  • WO2019/186125 describes additives for reducing the particulate emissions from direct injection gasoline engines.
  • the prior art does not describe reducing the emission of particulates having a diameter of less than 2.5 microns, which particulates are most damaging to human health and the environment.
  • a method of reducing the emission of particulates having a diameter of less than 2.5 microns from a direct injection spark ignition engine comprising combusting in the engine a gasoline composition comprising as an additive one or more quaternary ammonium compounds.
  • a second aspect of the present invention there is provided the use of one or more quaternary ammonium compounds as an additive in a gasoline composition to reduce the emission of particulates having a diameter of less than 2.5 microns from a direct injection spark ignition engine.
  • the present invention relates to a method and a use involving one or more quaternary ammonium compounds as a fuel additive.
  • the additive may be referred to herein as “the additive of the present invention”, “the quaternary ammonium compound” or as “the quaternary ammonium salt additive”.
  • the quaternary ammonium salt additive may comprise a single compound. In some embodiments mixtures containing more than one quaternary ammonium compound may be used. Thus the present invention may involve the use of one quaternary ammonium compound, or a mixture of two or more quaternary ammonium compounds. References herein to “an additive” of the invention or “the additive” include embodiments in which mixtures of two or more quaternary ammonium compounds are used.
  • the or each quaternary ammonium compound is suitably the reaction product of a nitrogencontaining species having at least one tertiary amine group and a quaternising agent.
  • the nitrogen-containing species having at least one tertiary amine group may be selected from any compound including a tertiary amine functional group.
  • the nitrogen-containing species having at least one tertiary amine group may be selected from:
  • a tertiary amine of formula R 5 R 6 R 7 N wherein each of R 5 , R 6 and R 7 is independently an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl group;
  • the nitrogen-containing species having at least one tertiary amine group is reacted with a quaternising agent. Any suitable quaternising agent may be used.
  • the nitrogen-containing species having at least one tertiary amine group is (i) the reaction product of a hydrocarbyl-substituted acylating agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group.
  • Suitable hydrocarbyl substituted acylating agents for use herein include fatty acids, i.e. compounds of formula RCOOH in which R is an alkyl or alkenyl group having 6 to 36 carbon atoms, preferably 8 to 30 carbon atoms or 12 to 24 carbon atoms.
  • R is an alkyl or alkenyl group having 6 to 36 carbon atoms, preferably 8 to 30 carbon atoms or 12 to 24 carbon atoms.
  • One preferred fatty acid is oleic acid.
  • the hydrocarbyl substituted acylating agent may be based on a hydrocarbyl substituted mono- di- or polycarboxylic acid or a reactive equivalent thereof.
  • the hydrocarbyl substituted acylating agent is a hydrocarbyl substituted succinic acid compound, for example a hydrocarbyl substituted succinic acid or succinic anhydride.
  • the hydrocarbyl substituent preferably comprises at least 10, more preferably at least 12, for example 30 or 50 carbon atoms. It may comprise up to about 200 carbon atoms.
  • the hydrocarbyl substituent has a number average molecular weight (Mn) of between 170 to 2800, for example from 250 to 1500, preferably from 450 to 1500 and more preferably 450 to 1100. An Mn of 700 to 1300 is especially preferred.
  • the hydrocarbyl based substituents may be made from homo- or interpolymers (e.g. copolymers, terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms, for example ethylene, propylene, but-1-ene, isobutene, butadiene, isoprene, 1 -hexene, 1 -octene, etc.
  • these olefins are 1 -monoolefins.
  • the hydrocarbyl substituent may also be derived from the halogenated (e.g. chlorinated or brominated) analogs of such homo- or interpolymers.
  • the substituent may be made from other sources, for example monomeric high molecular weight alkenes (e.g. 1-tetra-contene) and chlorinated analogs and hydrochlorinated analogs thereof, aliphatic petroleum fractions, for example paraffin waxes and cracked and chlorinated analogs and hydrochlorinated analogs thereof, white oils, synthetic alkenes for example produced by the Ziegler-Natta process (e.g. poly(ethylene) greases) and other sources known to those skilled in the art. Any unsaturation in the substituent may if desired be reduced or eliminated by hydrogenation according to procedures known in the art.
  • component (i) comprises the reaction product of a hydrocarbyl- substituted succinic acid derivative and an alcohol or amine also including a tertiary amine group.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include:
  • hydrocarbon groups that is, aliphatic (which may be saturated or unsaturated, linear or branched, e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
  • substituted hydrocarbon groups that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (e.g. chloro, fluoro or bromo), hydroxy, alkoxy (e.g. Ci to C4 alkoxy), keto, acyl, cyano, mercapto, amino, amido, nitro, nitroso, sulfoxy, nitryl and carboxy);
  • substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (e.g. chloro, fluoro or bromo), hydroxy, alkoxy (e.g. Ci to C4 alkoxy), keto, acyl, cyano, mercapto, amino, amido, nitro, nitroso, sulfoxy, nitryl and carboxy);
  • hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
  • Heteroatoms include sulphur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
  • no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.
  • references to optionally substituted alkyl groups may include aryl-substituted alkyl groups and references to optionally-substituted aryl groups may include alkyl-substituted or alkenyl-substituted aryl groups.
  • hydrocarbyl-based substituents are poly-(isobutene)s. Such compounds are known in the art.
  • the hydrocarbyl substituted acylating agent is a polyisobutenyl substituted succinic acid or succinic anhydride.
  • Polyisobutenyl substituted succinic anhydrides are especially preferred.
  • polyisobutenyl substituted succinic anhydrides PIBSA
  • Suitable processes include thermally reacting polyisobutenes with maleic anhydride (see for example US-A-3,361 ,673 and US-A-3, 018,250), or reacting a halogenated, in particular a chlorinated, polyisobutene (PIB) with maleic anhydride (see for example US-A-3, 172,892).
  • the polyisobutenyl succinic anhydride can be prepared by mixing the polyolefin with maleic anhydride and passing chlorine through the mixture (see for example GB-A- 949,981).
  • polyisobutenes and so-called "highly-reactive" polyisobutenes are suitable for use in the invention.
  • Highly reactive polyisobutenes in this context are defined as polyisobutenes wherein at least 50%, preferably 70% or more, of the terminal olefinic double bonds are of the vinylidene type as described in EP0565285.
  • Particularly preferred polyisobutenes are those having more than 80 mol% and up to 100% of terminal vinylidene groups such as those described in EP1344785.
  • reaction mixtures include some unreacted PIB, some PIBSA from the reaction of PIB with one MA (monomaleated PIBSA) and some PIBSA from the reaction of PIB with two MA (bismaleated PIBSA).
  • the fraction of bismaleated product as a proportion of the total PIBSA product may be referred to as the bismaleation level (BML).
  • Suitable PIBSAs for use in preparing additive (i) may have a BML of up to 90%, suitably up to 70%, for example 1 to 50% or 2 to 30%.
  • hydrocarbyl groups include those having an internal olefin for example as described in the applicant’s published application W02007/015080.
  • An internal olefin as used herein means any olefin containing predominantly a non-alpha double bond, that is a beta or higher olefin.
  • such materials are substantially completely beta or higher olefins, for example containing less than 10% by weight alpha olefin, more preferably less than 5% by weight or less than 2% by weight.
  • Typical internal olefins include Neodene 1518 IO available from Shell.
  • Internal olefins are sometimes known as isomerised olefins and can be prepared from alpha olefins by a process of isomerisation known in the art, or are available from other sources. The fact that they are also known as internal olefins reflects that they do not necessarily have to be prepared by isomerisation.
  • the additive of the present invention comprises the quaternised reaction product of an alcohol or amine including a tertiary amino group and an optionally substituted succinic acid or anhydride thereof of formula (A1) or (A2):
  • R 1 is an optionally substituted hydrocarbyl group.
  • R 1 is an optionally substituted alkyl or alkenyl group.
  • R 1 may be substituted with one or more groups selected from halo (e.g. chloro, fluoro or bromo), nitro, hydroxy, mercapto, sulfoxy, amino, nitryl, acyl, carboxy, alkyl (e.g. Ci to C4 alkyl), alkoxyl (e.g. Ci to C4 alkoxy), amido, keto, sulfoxy and cyano.
  • halo e.g. chloro, fluoro or bromo
  • R 1 is an unsubstituted alkyl or alkenyl group.
  • the substituted succinic acid or anhydrides may suitably be prepared by reacting maleic anhydride with an alkene.
  • R 1 has a number average molecular weight of from 100 to 5000, preferably from 300 to 4000, suitably from 450 to 2500, for example from 450 to 2000 or from 450 to 1500.
  • the additive of the present invention comprises a quaternary ammonium compound prepared from the reaction product of a hydrocarbyl substituted succinic acid or an anhydride thereof substituted with a polyisobutenyl group having a number average molecular weight of 450 to 1500 and an alcohol or amine which further includes a tertiary amino group.
  • the substituted succinic acid or anhydride thereof may comprise a mixture of compounds including groups R 1 of different lengths.
  • any reference to the molecular weight of the group R 1 relates to the number average molecular weight of all of that group for all compounds in the composition.
  • R 1 is a polyisobutenyl group, preferably having a number average molecular weight of from 100 to 5000, preferably from 200 to 2400, suitably from 450 to 1500.
  • R 1 is an optionally substituted Ci to C500 alkyl or alkenyl group, for example a Cs to C40 alkyl or alkenyl group, suitably C to C36 alkyl or alkenyl group.
  • the additive of the present invention comprises a quaternary ammonium compound prepared from the reaction product of a succinic acid or anhydride having a C10 to C30, preferably a C20 to C24 alkyl or alkenyl group and an amine or alcohol which further includes a tertiary amino group.
  • Preferred hydrocarbyl substituted acylating agents for use herein are polyisobutenyl substituted succinic anhydrides or PIBSAs.
  • PIBSAs are those having a PIB molecular weight (Mn) of from 300 to 2800, preferably from 450 to 2300, more preferably from 500 to 1300.
  • the hydrocarbyl substituted succinic acid derived acylating agent is suitably prepared by reacting maleic anhydride with an alkene, for example a polyisobutene.
  • the product obtained (such as a PIBSA) still includes a double bond.
  • the maleic anhydride is present in the resultant molecule as a succinic acid moiety.
  • This initial product is a monomaleated PIBSA.
  • the monomaleated PIBSA may have the structure (A) or (B):
  • the double bond in the monomaleated product can react with a further molecule of maleic anhydride to form a bismaleated PIBSA having the structure (C) or (D):
  • a hydrocarbyl group which is substituted with more than one succinic acid moiety.
  • hydrocarbyl substituted succinic acid derived acylating agents used in the invention typically comprise mixtures of compounds, for example mixtures of monomaleated and bismaleated PIBSAs.
  • the PIBSAs may be defined in terms of their level of bismaleation.
  • One way in which this may be determined is by calculating the average number of succinic acid moieties per molecule of acylating agent.
  • a monomaleated PIBSA has one succinic acid moiety per module.
  • a bismaleated PIBSA has two succinic acid moieties per molecule.
  • a mixture comprising monomaleated PIBSA and bismaleated PIBSA in a 1 :1 molar ratio would comprise an average of 1 .5 succinic acid moieties per molecule of PIBSA.
  • P value The average number of succinic acid moieties per molecule of acylating agent is sometimes referred to in the art as “P value”.
  • the or each quaternary ammonium compound is prepared from a hydrocarbyl substituted succinic acid derived acylating agent comprising on average from 1 to 2 succinic acid moieties per molecule.
  • the present invention may involve the use of quaternary ammonium compounds derived from hydrocarbyl substituted acylating agents which include an average of at least 1 .2 succinic acid moieties per molecule.
  • a single molecule cannot have 1 .2 succinic acid moieties. What is meant by at least 1 .2 succinic acid moieties is the mean number of succinic acid moieties per molecule of acylating agent as the sum of all the succinic acid moieties present in a sample divided by the total number of molecules of acylating agent having one or more succinic acid moieties present in the sample.
  • the hydrocarbyl substituted succinic acid derived acylating agent comprises on average at least 1 .21 succinic acid moieties per molecule, more preferably at least 1 .22 succinic acid moieties per molecule.
  • the hydrocarbyl substituted succinic acid derived acylating agent may comprise at least 1 .23 or at least 1 .24 succinic acid moieties per molecule.
  • the hydrocarbyl substituted succinic acid derived acylating agent may comprise at least 1 .25, at least 1 .26 or at least 1 .27 succinic acid moieties per molecule.
  • the hydrocarbyl substituted succinic acid derived acylating agent may comprise at least 1 .28, at least 1 .29 or at least 1 .30 succinic acid moieties per molecule.
  • succinic acid moiety we mean to include residues of succinic acid present in diacid or anhydride form.
  • the hydrocarbyl substituted acylating agent is reacted with a compound able to react with said acylating agent and which includes a tertiary amine group.
  • the tertiary amine group is quaternised to provide the quaternary ammonium salt.
  • suitable compounds able to react with the hydrocarbyl substituted succinic acid derived acylating agent and which include a tertiary amine group can include but are not limited to: N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dimethylamino ethylamine.
  • the nitrogen or oxygen containing compounds capable of condensing with the acylating agent and further having a tertiary amino group can further include amino alkyl substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3- aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, and 3'3-aminobis(N,N-dimethylpropylamine).
  • amino alkyl substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3- aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, and 3'3-aminobis(N,N-dimethylpropylamine).
  • alkanolamines including but not limited to triethanolamine, trimethanolamine, N,N- dimethylaminopropanol, N,N-dimethylaminoethanol, N,N-diethylaminopropanol, N,N- diethylaminoethanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N- tris(hydroxymethyl)amine, N,N,N-tris(aminoethyl)amine, N,N-dibutylaminopropylamine and N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethylether; N,N-bis(3-dimethylaminopropyl)-N- isopropanolamine ; N-(3-dimethylaminopropyl)-N- isopropanolamine ; N-(3-dimethylaminopropyl)
  • Preferred nitrogen-containing species having at least one tertiary amino group of types (i) are formed by the reaction of a hydrocarbyl-substituted acylating agent and an amine of formula (B1) or (B2): wherein R 1 is a Ci to C36 alkyl, aryl, alkaryl or aralkyl group; R 2 and R 3 are the same or different alkyl groups having from 1 to 36 carbon atoms; X is an alkylene group having from 1 to 20 carbon atoms; n is from 0 to 20; m is from 1 to 5; and R 4 is hydrogen or a Ci to C36 alkyl group.
  • quaternary ammonium salt additives of the present invention a quaternising agent may be reacted with a compound formed by the reaction of a hydrocarbyl substituted acylating agent and an amine of formula (B1) or (B2).
  • R 4 is preferably hydrogen or a Ci to Cw alkyl group, preferably a Ci to Cw alkyl group, more preferably a Ci to Ce alkyl group.
  • R 4 is alkyl it may be straight chained or branched. It may be substituted for example with a hydroxy or alkoxy substituent.
  • R 4 is not a substituted alkyl group. More preferably R 4 is selected from hydrogen, methyl, ethyl, propyl, butyl and isomers thereof. Most preferably R 4 is hydrogen.
  • each R 4 is preferably hydrogen or a Ci to Ce alkyl group. More preferably each R 4 is selected from hydrogen, methyl, ethyl, propyl, butyl and isomers thereof. Most preferably each R 4 is hydrogen or methyl.
  • n is preferably from 0 to 15, preferably 0 to 10, more preferably from 0 to 5. Most preferably n is 0 and the compound of formula (B2) is an alcohol.
  • hydrocarbyl substituted acylating agent is reacted with a diamine compound of formula (B1).
  • R 2 and R 3 are the same or different alkyl, alkenyl or aryl groups having from 1 to 22 carbon atoms. In some embodiments R 2 and R 3 may be joined together to form a ring structure, for example a piperidine or imidazole moiety. R 2 and R 3 may be branched alkyl or alkenyl groups. Each may be substituted, for example with a hydroxy or alkoxy substituent. R 2 and R 3 may each independently be a Ci to C alkyl group, preferably a Ci to C10 alkyl group.
  • R 2 and R 3 may independently be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or an isomer of any of these.
  • R 2 and R 3 is each independently Ci to C4 alkyl.
  • R 2 is methyl.
  • R 3 is methyl.
  • X is a bond or alkylene group having from 1 to 20 carbon atoms. In preferred embodiments when X is an alkylene group this group may be straight chained or branched.
  • the alkylene group may include a cyclic structure therein. It may be optionally substituted, for example with a hydroxy or alkoxy substituent. In some embodiments the alkylene group may be optionally interrupted with one or more heteroatoms, for example O, NH or N-alkyl.
  • X is preferably an alkylene group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, for example 2 to 6 carbon atoms or 2 to 5 carbon atoms. Most preferably X is an ethylene, propylene or butylene group, especially a propylene group.
  • Examples of compounds of formula (B1) suitable for use herein include 1-aminopiperidine, 1-(2- aminoethyl)piperidine, 1- (3-aminopropyl)-2-pipecoline, 1-methyl-(4-methylamino)piperidine, 4- (1 -py rro lid iny I) pi pe rid i n e , 1 -(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)-1 - methylpyrrolidine, N,N-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-dibutylethylenediamine, N,N- diethyl-l,3-diaminopropane, N,N-dimethyl-1 ,3-diaminopropane, N,N,N'- trimethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N-diethyl-N
  • the compound of formula (B1) is selected from from from N,N- dimethyl-1 ,3-diaminopropane, N,N-diethyl-1 ,3- diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, or combinations thereof.
  • An especially preferred compound of formula (B1) is dimethylaminopropylamine.
  • Examples of compounds of formula (B2) suitable for use herein include alkanolamines including but not limited to triethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N- diethylaminobutanol, triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2- (dimethylamine)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N- butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethyl amino- ethanol, 2-dimethylamino- 2-methyl-1 -propanol; trimethanolamine, N,N,N-tris(hydroxymethyl)amine, N,N,N- tris(aminoethyl)amine, N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine and N-(3-
  • the compound of formula (B2) is selected from N, N- dimethylaminopropanol, triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2- (dimethylamine)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N- butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylaminoethanol, 2-dimethylamino-2- methyl-1 -propanol, or combinations thereof.
  • An especially preferred compound of formula (B2) is dimethylaminopropanol.
  • Some preferred acylating agents for use in the preparation of the quaternary ammonium salt additives of the present invention are polyisobutene-substituted succinic acids or succinic anhydrides.
  • a compound of formula (B2) is reacted with a succinic acylating agent the resulting product is a succinic ester.
  • a succinic acylating agent is reacted with a compound of formula (B1) in which R 4 is hydrogen the resulting product may be a succinimide or a succinamide.
  • a succinic acylating agent is reacted with a compound of formula (B1) in which R 4 is not hydrogen the resulting product is an amide.
  • component (i) may be the reaction product of a succinic acid derivative and an amine or alcohol which is an ester or an amide and which also includes a further unreacted carboxylic acid group.
  • This further carboxylic acid functional group can react with another amine or alcohol when an excess is used to form a diester or the diamide.
  • succinic esters include the monoester compounds having the general formula (C1) and the diester compounds having the general formula (C2); succinimides have the general formula (C3); and succinamides include the monoamide compounds having the general formula (C4) and the diamide compounds having have the general formula (C5):
  • the groups R’ shown in figures (C1) to (C5) include a tertiary amino group. This group may be quaternised by reaction with a quaternising agent. For compounds of formula (C2) or (C5) which include two tertiary amino groups, each of these may be reacted with a quaternising agent to provide a diquaternary ammonium compound including two cationic moieties. Compounds of this type to provide a diquaternary ammonium compound including two cationic moieties. Compounds of this type are described (for use as diesel detergents) in US9365787.
  • mixtures of compounds having formula (C1) and (C2) or mixtures containing compounds (C3) and/or (C4) and/or (C5) may be used.
  • a succinic acid derivative is reacted with an amine (also including a tertiary amine group) under conditions to form a succinimide.
  • the acid/anhydride and the alcohol/amine are reacted in a molar ratio of from 10:1 to 1 :10, preferably from 5:1 to 1 :5, more preferably from 2:1 to 1 :2, for example from 1.5:1 to 1 :1.5.
  • the acid/anhydride and the alcohol/amine are reacted in an approximately 1 :1 molar ratio, for example from 1 .2:1 to1 :1 .2.
  • the quaternary ammonium salt additive of the present invention comprises a compound prepared from the reaction product of an optionally substituted succinic acid or anhydride thereof, preferably a hydrocarbyl substituted succinic acid or anhydride thereof, and an alcohol or amine selected from dimethylaminopropanol, dimethylaminopropylamine, N,N-diethyl-1 ,3- diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N- dibutylethylenediamine, 3-(2-(dimethylamino)ethoxy)proylamine or combinations thereof.
  • the quaternary ammonium salt additives of the present invention comprise quaternary ammonium compounds prepared from tertiary amines (i) wherein the tertiary amine is prepared from an amine which includes a tertiary amino group (for example dimethylamino propylamine) and a polyisobutylene-substituted succinic anhydride.
  • the number average molecular weight of the polyisobutylene substituent is preferably from 450 to 1300, more preferably from 900 to 1100.
  • the quaternary ammonium salt additives of the present invention comprising compounds derived from tertiary amines (i) may be prepared by any suitable method. Such methods will be known to the person skilled in the art and are exemplified herein. Typically the quaternary ammonium compounds will be prepared by heating the quaternising agent and a compound prepared by the reaction of a hydrocarbyl substituted acylating agent with an amine of formula (B1) or (B2) in an approximate 1 :1 molar ratio, optionally in the presence of a solvent. The resulting crude reaction mixture may be added directly to a gasoline fuel, optionally following removal of solvent.
  • the present invention may provide a gasoline fuel composition
  • a gasoline fuel composition comprising the reaction product of a quaternising agent and the reaction product of a hydrocarbyl substituted acylating agent and an amine formula (B1) or (B2).
  • the quaternary ammonium compounds for use in the present invention are the quaternised reaction product of a fatty acid (for example oleic acid) and a compound of formula (B1) or (B2) (for example dimethylaminopropyl amine).
  • the nitrogen-containing species having at least one tertiary amine group may be (ii) a Mannich reaction product including a tertiary amine.
  • the preparation of quaternary ammonium salts formed from nitrogen-containing species including component (ii) is described in US2008/0052985.
  • the Mannich reaction product having a tertiary amine group is prepared from the reaction of a hydrocarbyl-substituted phenol, an aldehyde and an amine.
  • the hydrocarbyl substituent of the hydrocarbyl substituted phenol can have 6 to 400 carbon atoms, suitably 30 to 180 carbon atoms, for example 10 or 40 to 110 carbon atoms.
  • This hydrocarbyl substituent can be derived from an olefin or a polyolefin.
  • Useful olefins include alpha-olefins, such as 1 -decene, which are commercially available.
  • the polyolefins which can form the hydrocarbyl substituent can be prepared by polymerizing olefin monomers by well known polymerization methods and are also commercially available.
  • Some preferred polyolefins include polyisobutylenes having a number average molecular weight of 400 to 3000, in another instance of 400 to 2500, and in a further instance of 400 or 450 to 1500.
  • the hydrocarbyl-substituted phenol can be prepared by alkylating a phenol with an olefin or polyolefin described above, such as, a polyisobutylene or polypropylene, using well-known alkylation methods.
  • the phenol may include a lower molecular weight alkyl substituent for example a phenol which carries one or more alkyl chains having a total of less 28 carbon atoms, preferably less than 24 carbon atoms, more preferably less than 20 carbon atoms, preferably less than 18 carbon atoms, preferably less than 16 carbon atoms and most preferably less than 14 carbon atoms.
  • a lower molecular weight alkyl substituent for example a phenol which carries one or more alkyl chains having a total of less 28 carbon atoms, preferably less than 24 carbon atoms, more preferably less than 20 carbon atoms, preferably less than 18 carbon atoms, preferably less than 16 carbon atoms and most preferably less than 14 carbon atoms.
  • a monoalkyl phenol may be preferred, suitably having from 4 to 20 carbons atoms, preferably 6 to 18, more preferably 8 to 16, especially 10 to 14 carbon atoms, for example a phenol having a C12 alkyl substituent.
  • the aldehyde used to form the Mannich detergent can have 1 to 10 carbon atoms, and is generally formaldehyde or a reactive equivalent thereof such as formalin or paraformaldehyde.
  • the amine used to form the Mannich detergent can be a monoamine or a polyamine.
  • monoamines include but are not limited to ethylamine, dimethylamine, diethylamine, n-butylamine, dibutylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, diethanolamine, morpholine, and octadecylamine.
  • Suitable polyamines may be selected from any compound including two or more amine groups.
  • Suitable polyamines include polyalkylene polyamines, for example in which the alkylene component has 1 to 6, preferably 1 to 4, most preferably 2 to 3 carbon atoms.
  • Preferred polyamines are polyethylene polyamines.
  • the polyamine has 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, more preferably 2 to 8 nitrogen atoms.
  • the amine used to form the Mannich detergent comprises a diamine.
  • it includes a primary or secondary amine which takes part in the Mannich reaction and in addition a tertiary amine.
  • component (ii) comprises the product directly obtained from a Mannich reaction and comprising a tertiary amine.
  • the amine may comprise a single primary or secondary amine which when reacted in the Mannich reaction forms a tertiary amine which is capable of being quaternised.
  • the amine may comprise a primary or secondary amine capable of taking part in the Mannich reaction and also a tertiary amine capable of being quaternised.
  • component (ii) may comprise a compound which has been obtained from a Mannich reaction and subsequently reacted to form a tertiary amine, for example a Mannich reaction may yield a secondary amine which is then alkylated to a tertiary amine.
  • the nitrogen-containing species comprising at least one tertiary amine group is (iii) a polyalkylene substituted amine having at least one tertiary amine group.
  • the polyalkene-substituted amines having at least one tertiary amino group of the present invention may be derived from an olefin polymer and an amine, for example ammonia, momoamines, polyamines or mixtures thereof. They may be prepared by a variety of methods such as those described and referred to in US2008/0113890.
  • Suitable preparation methods include, but are not limited to: reacting a halogenated olefin polymer with an amine; reacting a hydroformylated olefin with a polyamine and hydrogenating the reaction product; converting a polyalkene into the corresponding epoxide and converting the epoxide into the polyalkene substituted amine by reductive animation; hydrogenation of a p- aminonitrile; and hydroformylating an polybutene or polyisobutylene in the presence of a catalyst, CO and H2 at elevated pressure and temperatures.
  • the olefin monomers from which the olefin polymers are derived include polymerizable olefin monomers characterised by the presence of one or more ethylenically unsaturated groups for example ethylene, propylene, 1 -butene, isobutene, 1 -octene, 1 ,3-butadiene and isoprene.
  • the olefin monomers are usually polymerizable terminal olefins.
  • polymerizable internal olefin monomers can also be used to form the polyalkenes.
  • terminal and internal olefin monomers which can be used to prepare the polyalkenes according to conventional, well-known polymerization techniques include: ethylene; propylene; butenes, including 1 -butene, 2-butene and isobutylene; 1 -pentene; 1 -hexene; 1- heptene; 1 -octene; 1 -nonene; 1 -decene; 2-pentene; propylene-tetramer; diisobutylene; isobutylene trimer; 1 ,2-butadiene; 1 ,3-butadiene; 1 ,2-pentadiene; 1 ,3-pentadiene; 1 ,4- pentadiene; isoprene; 1 ,5-
  • the polyalkene substituent of the polyalkene-substituted amine is derived from a polyisobutylene.
  • the amines that can be used to make the polyalkene-substituted amine include ammonia, monoamines, polyamines, or mixtures thereof, including mixtures of different monoamines, mixtures of different polyamines, and mixtures of monoamines and polyamines (which include diamines).
  • the amines include aliphatic, aromatic, heterocyclic and carbocylic amines.
  • the monomers and polyamines suitably include at least one primary or secondary amine group.
  • Suitable monoamines are generally substituted with a hydrocarbyl group having 1 to about 50 carbon atoms, preferably 1 to 30 carbon atoms. Saturated aliphatic hydrocarbon radicals are particularly preferred.
  • Suitable monoamines include methylamine, ethylamine, diethylamine, 2- ethylhexylamine, di-(2-ethylhexyl)amine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine and oleylamine.
  • Aromatic monoamines include those monoamines wherein a carbon atom of the aromatic ring structure is attached directly to the amine nitrogen.
  • aromatic monoamines include aniline, di(para-methylphenyl)amine, naphthylamine, and N-(n-butyl)aniline.
  • Examples of aliphatic substituted, cycloaliphatic-substituted, and heterocyclic-substituted aromatic monoamines include: para-dodecylaniline, cyclohexyl-substituted naphthylamine, and thienyl-substituted aniline respectively.
  • Hydroxy amines are also included in the class of useful monoamines.
  • Examples of hydroxylsubstituted monoamines include ethanolamine, di-3-propanolamine, 4-hydroxybutylamine; diethanolamine, and N-methyl-2-hydroxypropylamine.
  • the amine of the polyalkene-substituted amine can be a polyamine.
  • the polyamine may be aliphatic, cycloaliphatic, heterocyclic or aromatic.
  • suitable polyamines include alkylene polyamines, hydroxy containing polyamines, arylpolyamines, and heterocyclic polyamines.
  • Ethylene polyamines are especially useful for reasons of cost and effectiveness. Suitable ethylene polyamines are described in relation to the first aspect.
  • Suitable hydroxy containing polyamines include hydroxyalkyl alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms and can be prepared by reacting alkylenepolyamines with one or more alkylene oxides.
  • suitable hydroxyalkylsubstituted polyamines include: N-(2-hydroxyethyl)ethylene diamine, N,N-bis(2- hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl) piperazine, monohydroxypropl-substituted diethylene triamine, dihydroxypropyl-substituted tetraethylene pentamine, propyl and N-(3- hydroxybutyl)tetramethylene diamine.
  • Suitable arylpolyamines are analogous to the aromatic monoamines mentioned above except for the presence within their structure of another amino nitrogen.
  • Some examples of arylpolyamines include N,N’-di-n-butyl-para-phenylene diamine and bis-(para- aminophenyl)methane.
  • heterocyclic mono- and polyamines will be known to the person skilled in the art.
  • specific examples of such heterocyclic amines include N-aminopropylmorpholine, N- aminoethylpiperazine, and N,N’-diaminoethylpiperazine.
  • Hydroxy heterocyclic polyamines may also be used for example N-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine, parahydroxy-aniline and N-hydroxyethylpiperazine.
  • polyalkene-substituted amines can include: poly(propylene)amine, poly(butene)amine, N,N-dimethylpolyisobutyleneamine; N-polybutenemorpholine, N- poly(butene)ethylenediamine, N-poly(propylene) trimethylenediamine, N- poly(butene)diethylenetriamine, N’,N’-poly(butene)tetraethylenepentamine, and N,N-dimethyl- N’poly(propylene)-1 ,3 propylenediamine.
  • the number average molecular weight of the polyalkene-substituted amines can range from 500 to 5000, or from 500 to 3000, for example from 1000 to 1500.
  • the nitrogen-containing species having at least one tertiary amine group is (iv) a tertiary amine of formula R 5 R 6 R 7 N, wherein each of R 5 , R 6 and R 7 is independently an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl group.
  • the tertiary amine of formula R 5 R 6 R 7 N may be a small compound of low complexity and low molecular weight. In some embodiments the tertiary amine may be a complex molecule and/or a molecule of high molecular weight which includes a tertiary amine group.
  • the tertiary amine compounds of formula R 5 R 6 R 7 N preferably do not include any primary or secondary amine groups. In some embodiments they may be derived from compounds including these groups but preferably these have been subsequently reacted to form additional tertiary amine species.
  • the tertiary amine compound formula R 5 R 6 R 7 N may contain more than one tertiary amine group. However tertiary amine compounds including primary or secondary amine groups are within the scope of the invention provided these groups do not prevent quaternisation of the tertiary amine species.
  • Tertiary amines (iv) for use herein are preferably compounds of formula R 5 R 6 R 7 N, wherein each of R 5 , R 6 and R 7 is independently an optionally substituted alkyl, alkenyl, aryl, aralkyl or alkaryl group.
  • R 5 , R 6 and R 7 may be the same or different. In some preferred embodiments R 5 and R 6 are the same and R 7 is different.
  • each of R 5 and R 6 is independently an optionally substituted alkyl, alkenyl, aryl, aralkyl or alkaryl group having from 1 to 50 carbon atoms, preferably from 1 to 40 carbon atoms, more preferably from 1 to 30 carbon atoms.
  • R 5 and R 6 may be optionally substituted with one or more groups selected from halo (especially chloro and fluoro), hydroxy, alkoxy, keto, acyl, cyano, mercapto, alkylmercapto, dialkylamino, nitro, nitroso, and sulphoxy.
  • halo especially chloro and fluoro
  • each of R 5 and R 6 is independently an optionally substituted alkyl or alkenyl group.
  • each of R 5 and R 6 is independently an optionally substituted alkyl group.
  • each of R 5 and R 6 is independently an optionally substituted alkyl or alkenyl group having from 1 to 50 carbon atoms, preferably from 1 to 40 carbon atoms, more preferably from 1 to 30 carbon atoms, suitably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, more preferably from 1 to 10 carbon atoms, suitably from 1 to 8 carbon atoms, for example from 1 to 6 carbon atoms.
  • R 5 is an optionally substituted alkyl or alkenyl group, preferably having from 1 to 10, preferably from 1 to 4 carbon atoms.
  • R 5 is an alkyl group. It may be a substituted alkyl group, for example a hydroxy substituted alkyl group.
  • R 5 is an unsubstituted alkyl group.
  • the alkyl chain may be straight-chained or branched.
  • R 5 is selected from methyl, ethyl, propyl and butyl, including isomers thereof. Most preferably R 5 is methyl.
  • R 6 is an optionally substituted alkyl or alkenyl group, preferably having from 1 to 10, preferably from 1 to 4 carbon atoms.
  • R 6 is an alkyl group. It may be a substituted alkyl group, for example a hydroxy substituted alkyl group.
  • R 6 is an unsubstituted alkyl group.
  • the alkyl chain may be straight-chained or branched.
  • R 6 is selected from methyl, ethyl, propyl and butyl, including isomers thereof. Most preferably R 6 is methyl.
  • R 7 is an optionally substituted alkyl or alkenyl group having from 1 to 50 carbon atoms, preferably from 1 to 40 carbon atoms, more preferably from 1 to 30 carbon atoms, suitably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, more preferably from 1 to 10 carbon atoms, suitably from 1 to 8 carbon atoms, for example from 1 to 6 carbon atoms.
  • Suitable substituents include halo (especially chloro and fluoro), hydroxy, alkoxy, keto, acyl, cyano, mercapto, alkylmercapto, amino, alkylamino, nitro, nitroso, sulphoxy, amido, alkyamido, imido and alkylimido.
  • the alkyl groups of these substituents may be further substituted.
  • R 7 is an optionally substituted alkyl or alkenyl group, preferably having from 1 to 10, preferably from 1 to 4 carbon atoms.
  • R 7 is an optionally substituted alkyl group.
  • R 7 is a substituted alkyl group.
  • Preferred substituents include alkoxy and hydroxyl groups.
  • R 7 is a hydroxyl-substituted alkyl group.
  • the alkyl chain may be straight-chained or branched. Most preferably R 7 is a hydroxyethyl group.
  • Suitable tertiary amine compounds of formula R 5 R 6 R 7 N include simple alkylamino and hydroxyalkylamino compounds; trialkylamino compounds having a high molecular weight substituent; Mannich reaction products including a tertiary amine and substituted acylated amines or alcohols including a tertiary amine.
  • Simple alkylamino and hydroxyalkyl amino compounds are preferably compounds of formula R 5 R 6 R 7 N, wherein each of R 5 , R 6 and R 7 is an alkyl group or a hydroxyalkyl group.
  • Each of R 5 , R 6 and R 7 may be the same or different.
  • each of R 5 , R 6 and R 7 is independently selected from an alkyl or hydroxyalkyl group having 1 to 10, preferably 1 to 6 carbon atoms, for example 1 to 4 carbon atoms.
  • Each of R 5 , R 6 and R 7 may be independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl and hydroxyhexyl.
  • the amine of formula R 5 R 6 R 7 N may be a trialkylamine, a dialkylhydroxyalkylamine, a dihydroxyalkylalkylamine or a trihydroxyalkylamine. There are many different compounds of this type and these will be known to the person skilled in the art.
  • one or two of the groups R 5 , R 6 and R 7 is a short chain alkyl group having 1 to 6, preferably 1 to 4 carbon atoms and the other one or two groups is a longer chain alkyl or group having 6 to 30, preferably 10 to 24 carbon atoms.
  • each of R 5 and R 6 is Ci to C4 alkyl, preferably methyl and R 7 is an alkyl or alkenyl group having 6 to 36, preferably 10 to 30, for example 12 to 24 carbon atoms.
  • Compounds of this type include, for example, dimethyloctadecylamine and hexadecyl dimethyl amine.
  • the hexadecyl dimethyl amine may be quaternised by reaction with propylene oxide (for example 1 to 3 molar equivalent of propylene oxide) and polyisobutylene succinic acid (for example 1 molar equivalent of polyisobutylene succinic acid).
  • propylene oxide for example 1 to 3 molar equivalent of propylene oxide
  • polyisobutylene succinic acid for example 1 molar equivalent of polyisobutylene succinic acid
  • R 5 is Ci to C4 alkyl, preferably methyl and each R 6 and R 7 is an alkyl or alkenyl having 6 to 36, preferably 8 to 30, for example 10 to 24 carbon atoms.
  • Compounds of this type include, for example, hexadecyl dimethyl amine, N-methyl N-N- ditallowamine and dicocomethyl amine.
  • Especially preferred tertiary amine compounds of formula R 5 R 6 R 7 N include N,N-dimethyl ethanolamine, dimethyloctadecylamine and N-methyl N-N-ditallowamine.
  • the nitrogen-containing species having at least one tertiary amine group is (v) a cyclic tertiary amine.
  • Suitable cyclic amines have the formula (D1):
  • R 6 an optionally substituted alkyl, alkenyl, aryl, aralkyl or alkaryl group, and R 9 together with N forms a heterocycle.
  • heterocycle has less than 12 carbon atoms.
  • R 6 has less than 8 carbon atoms.
  • R 6 is an optionally substituted alkyl, alkenyl or aryl group having from 1 to 7 carbon atoms, preferably from 1 to 5 carbon atoms, more preferably from 1 to 4 carbon atoms.
  • R 6 may be optionally substituted with one or more groups selected from halo (especially chloro and fluoro), hydroxy, alkoxy, keto, acyl, cyano, mercapto, alkylmercapto, dialkylamino, nitro, nitroso, and sulphoxy.
  • halo especially chloro and fluoro
  • the alkyl groups of these substituents may be further substituted.
  • R 6 is an optionally substituted alkyl or alkenyl group.
  • R 6 is an optionally substituted alkyl group.
  • R 6 is an optionally substituted alkyl or alkenyl group having from 1 to 7 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 5 carbon atoms, suitably from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, more preferably from 1 to 2 carbon atoms.
  • R 6 is an optionally substituted alkyl or alkenyl group, preferably having from 1 to 6, preferably from 1 to 4 carbon atoms.
  • R 6 is an alkyl group. It may be a substituted alkyl group, for example a hydroxy substituted alkyl group.
  • R 6 is an unsubstituted alkyl group or a hydroxy alkyl group. More
  • R 6 is an unsubstituted alkyl group.
  • the alkyl chain may be straight-chained or branched.
  • R 6 is selected from methyl, ethyl, propyl and butyl, including isomers thereof. Most preferably R 6 is methyl.
  • R 10 , R 11 and N together form an aromatic ring and the cyclic amine may have the structure (D2):
  • the total number of carbon atoms in groups R 10 and R 11 is preferably less than 19.
  • R 9 together with N may form an aliphatic heterocyclic group or an aromatic heterocyclic group. Thus they form a heterocyclic ring. There may be one or more further heteroatoms in the ring. Suitably the ring may include one or more further atoms selected from N, O and S.
  • the heterocyclic group formed by R 9 and N may be substituted or unsubstituted; i.e. there may be one or more substituents bonded to atoms that form the ring.
  • Suitable substituents include halo (especially chloro and fluro); hydroxy, alkoxy, keto, acyl, cyano, mercapto, alkylmercapto, alkyl, alkenyl, aryl, dialkylamino, alkylamino, nitro, nitroso, and sulphoxy.
  • the alkyl, alkenyl and aryl groups of these substituents may be further substituted.
  • the heterocyclic group may be substituted with a further cyclic group i.e. it may be part of a bicyclic heterocyclic group.
  • heterocyclic group formed by N and R 9 is not substituted.
  • the group formed by R 9 and N is a heterocyclic group having from 3 to 12 atoms in the ring.
  • the atoms in the ring include carbon atoms and other atoms.
  • the heterocyclic ring includes 3 to 10 atoms, preferably 4 to 8, more preferably 5 to 7 atoms.
  • the heterocyclic group contains only carbon and nitrogen atoms within the ring.
  • the heterocyclic group formed by R 9 and N may be aliphatic or aromatic.
  • R 9 and N together form an aliphatic or aromatic heterocycle having 5 to 7 atoms in the ring.
  • Suitable aliphatic heterocyclic groups include those based on pyrrolidine, piperidine, morpholine and piperazine. Suitable aliphatic heterocyclic groups include unsaturated heterocycles that are not aromatic, i.e. they may contain one or more double bonds, for example those based on dihydropyrrole.
  • Suitable aromatic heterocyclic groups including those based on pyrrole, pyridine, imidazole, pyrimidine, isoxzole, quinolone, oxazole, and pyrazole.
  • R 9 and N together form an imidazole moiety or a pyrrolidine moiety.
  • R 9 contains 3 to 11 carbon atoms (and optional heteroatoms with the ring), preferably 3 to 10 carbon atoms, preferably 3 to 9 carbon atoms, suitably 3 to 8 carbon atoms, preferably 3 to 7 carbon atoms, more preferably 3 to 6 carbon atoms, for example 3 to 5 or 3 to 4 carbon atoms.
  • R 9 contains less than 8 carbon atoms.
  • the compound of formula (D1) or (D2) is a cyclic tertiary amine.
  • this we mean to refer to an amine group in which the nitrogen atom is part of a heterocyclic ring and is preferably further bonded to another group.
  • the compound of formula (D1) or (D2) is a cyclic tertiary amine having less than 18 carbon atoms. Preferably it has less than 16 carbon atoms, suitably less than 14 carbon atoms, preferably less than 12 carbon atoms, for example less than 10 carbon atoms, less than 8 carbon atoms or less than 6 carbon atoms.
  • the cyclic amine compound is a compound of formula (D1) and is an N-substituted heterocyclic amine.
  • it is an N-alkyl heterocyclic amine having 5 to 7 atoms in the heterocyclic ring.
  • the tertiary amine is an N-methyl cyclic amine wherein the heterocyclic ring moiety may include one or more further heteroatoms such as O, N or S and may be aliphatic or non-aromatic.
  • Suitable cyclic amines for use herein are based on N-alkyl heterocycles, for example N- methyl heterocycles, selected from pyrrolidine, piperidine, morpholine, piperazine, pyrrole, imidazole and dihydropyrrole.
  • Other suitable amines include those based on the above in which the heterocyclic ring includes one or more further alkyl, alkenyl or aryl substituents, provided the total number of carbon atoms in the tertiary amine is less than 19.
  • compounds which include one, two or three methyl groups bonded to carbon atoms within the heterocyclic ring are within the scope of the invention.
  • Suitable cyclic amines for use herein include those based on heterocycles in which R 10 , R 11 and N together form an aromatic ring, for example those based on piperidine, pyrimidine, isoxazole and oxazole.
  • Suitable amines include those based on the above in which the heterocyclic ring includes one or more further alkyl, alkenyl or aryl substituents, provided the total number of carbon atoms in the tertiary amine is less than 19.
  • Tertiary amine compounds including primary or secondary amine groups are within the scope of the invention provided these groups do not prevent quaternisation of the tertiary amine species.
  • the cyclic tertiary amine compounds preferably do not include any free primary or secondary amine groups.
  • Some preferred cyclic amine compounds include 1-methyl pyrrolidine, 1 -methylimidazole, 1 ,2- dimethyl-1 H-imidazole, pyridine and mixtures and isomers thereof. 8-hydroxyquinoline could also be used.
  • tertiary amine compounds include methyl pyrollidine and methyl imidazole.
  • the nitrogen-containing species having at least one tertiary amine group is (vi) a polyetheramine compound.
  • Some preferred polyetheramine compounds are polyoxyalkylene amines.
  • polyetheramine compound has the general formula (D3):
  • R 12 is H or a hydrocarbyl group having from 1 to 30 carbon atoms
  • R 13 and R 14 are each independently hydrogen or lower alkyl having from about 1 to about 6 carbon atoms and each R 13 and R 14 is independently selected in each --O — CHR 13 -CHR 14 -- unit
  • x is an integer of from 1 to 100, preferably 5 to 50
  • A is NR 15 R 16 , NR 17 NR 15 R 16 , OR 17 NR 15 R 16 , OCONR 15 R 16 or a polyamine moiety having about 2 to about 12 nitrogen atoms, about 4 to about 40 carbon atoms and including at least one tertiary amine group
  • each of R 15 and R 16 is independently an alkyl group having about 1 to about 20 carbon atoms in each alkyl group, and R 17 is an alkylene group having 1 to 20 carbon atoms.
  • R 12 is H or a C1-C30 alkyl preferably a C4-C20 alkyl.
  • R 12 is an alkylphenyl group, wherein the alkyl group has from about 1 to about 24 carbon atoms.
  • one of R 13 and R 14 is lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen. More preferably, one of R 13 and R 14 is methyl or ethyl, and the other is hydrogen.
  • each of R 15 and R 16 is an alkyl group having from about 1 to about 20 carbon atoms in each alkyl group, preferably about 1 to about 6 carbon atoms, more preferably about 1 to about 4 carbon atoms.
  • R 17 is an alkyl group having from about 1 to about 20 carbon atoms in each alkyl group, preferably about 1 to about 6 carbon atoms, more preferably about 1 to about 4 carbon atoms.
  • A is a polyamine moiety comprising a tertiary amine group and having from about 2 to about 12 nitrogen atoms and from about 4 to about 40 carbon atoms.
  • the compound of formula (D3) may be derived by alkoxylation of an N,N dialkyl hydroxyalkylamine such as N,N dimethyl aminoethanol or N,N dimethylamino propanol.
  • the compound of formula D4 may be derived by alkoxylation of a C1-C30 alcohol preferably a C4-C20 alcohol followed by amination with ammonia further followed by alkylation of the amine. Such processes are described in US2013225463. Other preferred features of the polyetheramine compound are also described in US2013225463.
  • the quaternary ammonium salt additive of the present invention comprises compounds prepared by the reaction of a quaternising agent and (i) the reaction product of a hydrocarbyl-substituted acylating agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group.
  • the quaternary ammonium salt compounds used in the present invention are prepared by the reaction of a nitrogen-containing species having at least one tertiary amine group and a quaternising agent.
  • Any compound capable of reacting with the tertiary amine group to form a quaternary ammonium cation may be used as the quaternising agent.
  • an ion exchange reaction may be carried out to provide a quaternary ammonium compound having a different anion.
  • the quaternary ammonium compounds used in the present invention may be prepared by reaction of a tertiary amine with a quaternising agent selected from an ester of a carboxylic acid, epoxides optionally in combination with an acid, dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, alkyl halides, alkyl sulfonates, sulfones, hydrocarbyl substituted phosphates, hydrocarbyl substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides or mixtures thereof.
  • a quaternising agent selected from an ester of a carboxylic acid, epoxides optionally in combination with an acid, dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, alkyl halides, alkyl sulfonates, sulfones, hydro
  • quaternising agent containing such an element it may be advantageous to carry out a subsequent reaction to exchange the counterion.
  • a quarternary ammonium salt formed by reaction with an alkyl halide could be subsequently reacted with sodium hydroxide and the sodium halide salt removed by filtration.
  • the quaternising agent can include halides, such as chloride, iodide or bromide; hydroxides; sulphonates; bisulphites, alkyl sulphates, such as dimethyl sulphate; sulphones; phosphates; C1-12 alkylphosphates; di C1-12 alkylphosphates; borates; C1-12 alkylborates; nitrites; nitrates; carbonates; bicarbonates; alkanoates; O,O-di C1-12 alkyldithiophosphates; or mixtures thereof.
  • the quaternising agent is selected from esters of a carboxylic acid, dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides optionally in combination with an acid, alkyl halides, alkyl sulfonates, sulfones, hydrocarbyl substituted phosphates, hydrocarbyl substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or salts thereof, or mixtures thereof.
  • the quaternising agent may be derived from dialkyl sulphates such as dimethyl sulphate, N-oxides, sulphones such as propane and butane sulphone; alkyl, acyl or aralkyl halides such as methyl and ethyl chloride, bromide or iodide or benzyl chloride, and a hydrocarbyl (or alkyl) substituted carbonates. If the quaternising agent is benzyl chloride, the aromatic ring is optionally further substituted with alkyl or alkenyl groups.
  • dialkyl sulphates such as dimethyl sulphate, N-oxides, sulphones such as propane and butane sulphone
  • alkyl, acyl or aralkyl halides such as methyl and ethyl chloride, bromide or iodide or benzyl chloride, and a hydrocarbyl (or alkyl) substituted carbon
  • the hydrocarbyl (or alkyl) groups of the hydrocarbyl substituted carbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atoms per group. In one embodiment the hydrocarbyl substituted carbonates contain two hydrocarbyl groups that may be the same or different. Examples of suitable hydrocarbyl substituted carbonates include dimethyl or diethyl carbonate.
  • Preferred quaternising agents for use herein are esters of a carboxylic acid or an epoxide, optionally in combination with an acid.
  • the quaternising agent is an ester of formula R 18 COOR 19 .
  • R 19 is a Ci to C7 alkyl group and R 18 COO is preferably the residue of a carboxylic acid selected from a substituted aromatic carboxylic acid, an a-hydroxycarboxylic acid and a polycarboxylic acid.
  • Preferred ester quaternising agents are compounds of formula (E): in which R 18 is an optionally substituted alkyl, alkenyl, aryl or alkylaryl group which may comprise a further carboxy derived functional group; and R 19 is a Ci to C22 alkyl, aryl or alkylaryl group.
  • the compound of formula (E) is suitably an ester of a carboxylic acid capable of reacting with a tertiary amine to form a quaternary ammonium compound.
  • Suitable quaternising agents include esters of carboxylic acids having a pKa of 3.5 or less.
  • the compound of formula (E) is preferably an ester of a carboxylic acid selected from a substituted aromatic carboxylic acid, an a-hydroxycarboxylic acid and a polycarboxylic acid.
  • the compound of formula (E) is an ester of a substituted aromatic carboxylic acid and thus R 18 is a substituted aryl group.
  • R 18 is suitably a substituted aryl group having 6 to 10 carbon atoms, preferably a phenyl or naphthyl group, most preferably a phenyl group.
  • R 18 is suitably substituted with one or more groups selected from carboalkoxy, nitro, cyano, hydroxy, SR 20 or NR 21 R 22 .
  • Each of R 21 and R 22 may be hydrogen or optionally substituted alkyl, alkenyl, aryl or carboalkoxy groups.
  • each of R 21 and R 22 is hydrogen or an optionally substituted Ci to C22 alkyl group, preferably hydrogen or a Ci to C alkyl group, preferably hydrogen or a Ci to C10 alkyl group, more preferably hydrogen or a Ci to C4 alkyl group.
  • R 21 is hydrogen and R 22 is hydrogen or a Ci to C4 alkyl group.
  • R 21 and R 22 are both hydrogen.
  • R 18 is an aryl group substituted with one or more groups selected from hydroxyl, carboalkoxy, nitro, cyano and NH2.
  • R 18 may be a poly-substituted aryl group, for example trihydroxyphenyl.
  • R 18 is a mono-substituted aryl group.
  • R 18 is an ortho substituted aryl group.
  • R 18 is substituted with a group selected from OH, NH2, NO2 or COOMe.
  • R 18 is substituted with an OH or NH2 group.
  • R 18 is a hydroxy substituted aryl group.
  • Most preferably R 18 is a 2-hydroxyphenyl group.
  • R 19 is an alkyl or alkaryl group.
  • R 19 may be a Ci to C alkyl group, preferably a Ci to Cw alkyl group, suitably a Ci to Cs alkyl group.
  • R 19 may be Ci to C alkaryl group, preferably a Ci to Cw alkaryl group, suitably a Ci to Cs alkaryl group.
  • R 19 may be methyl, ethyl, propyl, butyl, pentyl, benzyl or an isomer thereor.
  • R 19 is benzyl or methyl. Most preferably R 19 is methyl.
  • esters of salicylic acid such as benzyl salicylate, methyl salicylate, ethyl salicylate, n and /-propyl salicylate, and butyl salicylate.
  • An especially preferred compound of formula (E) is methyl salicylate.
  • the compound of formula (E) is an ester of an a-hydroxycarboxylic acid.
  • R 18 is R 23 CR 24 OH and the compound of formula (E) has the structure: wherein R 23 and R 24 are the same or different and each is selected from hydrogen, alkyl, alkenyl, aralkyl or aryl.
  • R 23 and R 24 are the same or different and each is selected from hydrogen, alkyl, alkenyl, aralkyl or aryl.
  • Examples of compounds of formula (E) in which R 18 COO is the residue of an a- hydroxycarboxylic acid include methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of 2-hydroxyisobutyric acid; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl- , phenyl-, and allyl esters of 2-hydroxy-2-methylbutyric acid; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of 2-hydroxy-2-ethylbutyric acid; methyl-, ethyl- , propyl-, butyl-, pentyl-, hexy
  • the compound of formula (E) is an ester of a polycarboxylic acid.
  • this definition we mean to include dicarboxylic acids and carboxylic acids having more than 2 acidic moieties.
  • R 18 includes a carboxy derived functional group. This is preferably present in the form of an ester, that is the one or more further acid groups present in the group R 18 are in esterified form. Preferred esters are Ci to C4 alkyl esters.
  • Compound (E) may be selected from the diester of oxalic acid, the diester of phthalic acid, the diester of maleic acid, the diester of malonic acid or the diester of citric acid.
  • One especially preferred compound of formula (E) is dimethyl oxalate.
  • the compound of formula (E) is an ester of a carboxylic acid having a pK a of less than 3.5.
  • the compound includes more than one acid group, we mean to refer to the first dissociation constant.
  • Compound (E) may be selected from an ester of a carboxylic acid selected from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid and 2, 4, 6-trihydroxybenzoic acid.
  • the compound of formula (E) may be selected from dimethyl oxalate, methyl 2- nitrobenzoate, dimethylphthalate, dimethyltartrate and methyl salicylate
  • Preferred compounds of formula (E) include dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.
  • ester quaternising agents are dimethyl oxalate and methyl salicylate.
  • the quaternising agent is an epoxide, optionally in combination with an acid.
  • Suitable epoxide compounds are those of formula: wherein each of R 25 , R 26 , R 27 , R 28 is independently selected from hydrogen or an optionally substituted alkyl, alkenyl or aryl group, provided at least one of R 25 , R 26 , R 27 and R 28 is hydrogen.
  • R 25 , R 26 , R 27 and R 28 are hydrogen. Most preferably three of R 25 , R 26 , R 27 and R 28 are hydrogen, of R 25 , R 26 , R 27 and R 28 may be all hydrogen.
  • R 25 and R 26 are interchangeable and thus when these groups are different either enantiomer or diastereomer may be used as component (b).
  • R 27 and R 28 are interchangeable and thus when these groups are different either enantiomer or diastereomer may be used as component (b).
  • R 25 is hydrogen or an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl group.
  • R 25 may suitably be selected from hydrogen and phenyl. Most preferably R 25 is hydrogen.
  • R 26 is hydrogen or an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl group. Most preferably R 26 is hydrogen.
  • R 27 is hydrogen or an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl group. Most preferably R 27 is hydrogen.
  • R 28 is hydrogen or an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl group.
  • R 28 is an optionally substituted aryl group.
  • R 28 may be phenyl.
  • R 28 is an optionally substituted alkyl or alkenyl group.
  • R 28 may be an alkyl group, for example an unsubstituted alkyl group.
  • R 28 may be an alkyl group having 1 to 50 carbon atoms, preferably from 1 to 30 carbon atoms, suitably 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, for example from 1 to 8 or from 1 to 4 carbon atoms.
  • R 28 is hydrogen
  • R 28 is the moiety CH2OR 29 or CH2OCOR 30 wherein each of R 29 and R 30 may be an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl group.
  • R 29 is preferably an optionally substituted alkyl or aryl group, preferably having from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms, suitably from 1 to 12 carbon atoms.
  • R 29 is an alkyl group it may be straight-chained or branched. In some embodiments it is branched.
  • R 29 may be an optionally substituted phenyl group.
  • R 29 is a 2-methyl phenyl group. In another embodiment R 29 is CH 2 C(CH2CH3)CH2CH2CH2CH 3 .
  • R 30 may be an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl group.
  • R 30 is preferably an optionally substituted alkyl or aryl group, preferably having from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms, suitably from 1 to 12 carbon atoms.
  • R 30 is an alkyl group it may be straight-chained or branched. In some preferred embodiments it is branched.
  • R 30 may be an optionally substituted phenyl group.
  • R 30 is C(CH 3 )R2 wherein each R is an alkyl group.
  • the R groups may be the same or different.
  • R 30 is an alkyl group having 1 to 5 carbon atoms.
  • R 30 may include an oxygen atom in the carbon chain, i.e.
  • R 30 may include an ether functional group.
  • Suitable epoxide compounds for use herein as quaternising agents include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, heptylene oxide, dodecylene oxide, alkyl glycidyl ethers, for example 2-ethylhexyl glycidyl ether or isopropyl glycidyl ether, alkyl glycidyl esters styrene oxide, stilbene oxide and other C2 to C30 hydrocarbyl groups.
  • Some preferred epoxide compounds for use herein as quaternising agents include styrene oxide, ethylene oxide, propylene oxide, butylene oxide, stilbene oxide, dodecylene oxide 2- ethylhexyl glycidyl ether and isopropyl glycidyl ether. Styrene oxide, butylene oxide, 2-ethylhexyl glycidyl ether and propylene oxide are especially preferred.
  • epoxide quaternising agents are used in combination with an acid.
  • the nitrogen-containing species having at least one tertiary amine group includes (i) the reaction product of a substituted succinic acid which is an ester or an amide and which also includes a further unreacted carboxylic acid group, an additional acid may be omitted and the hydrocarbyl epoxide may be used alone as the quaternising agent. It is believed that formation of the quaternary ammonium salt is promoted by protonation by the carboxylic acid group also present in the molecule.
  • the quaternary ammonium compound is suitably prepared in a protic solvent.
  • Suitable protic solvents include water, alcohols (including polyhydric alcohols) and mixtures thereof.
  • Preferred protic solvents have a dielectric constant of greater than 9.
  • the epoxide quaternising agent is used in combination with an acid.
  • Any suitable acid may be used.
  • the acid is an organic acid, preferably a carboxylic acid.
  • Suitable carboxylic acids include monocarboxylic acids and polycarboxylic acids.
  • the acid is a monocarboxylic acid or a dicarboxylic acid.
  • the acid suitably activates the epoxide and forms the anionic counterion of the quaternary ammonium compound.
  • a subsequent ion exchange reaction may be carried out but this is not preferred.
  • any compound which includes a carboxylic acid functional group may be used.
  • the acid may be a very small simple molecule.
  • suitable small simple acids include formic acid, acetic acid, propionic acid and butyric acid.
  • the acid may be a simple fatty acid compound. However the acid may also be a more complex molecule including additional acid functional groups. Suitable fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, undecylenic acid and docosahexenoic acid.
  • Suitable fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmi
  • Suitable complex acids include optionally substituted phthalic acids and succinic acid derivatives.
  • hydrocarbyl substituted phthalic acid or succinic acid derivatives are especially preferred.
  • the hydrocarbyl group is preferably a polyisobutenyl group, preferably having a molecular weight of from 100 to 5000, preferably from 300 to 4000, suitably from 450 to 2500, for example from 450 to 2000 or from 450 to 1500.
  • the hydrocarbyl group is an alkyl or alkenyl group having 6 to 30 carbon atoms, preferably 10 to 26 carbon atoms, more preferably 12 to 24 carbon atoms, suitably 16 to 20 carbon atoms, for example 18 carbon atoms.
  • the hydrocarbyl group is an alkyl or alkenyl group having 6 to 50 carbon atoms, preferably 12 to 40 carbon atoms, more preferably 18 to 36 carbon atoms, suitably 24 to 36 carbon atoms, for example 30 carbon atoms.
  • the succinic acid derivative may be polyisobutylene succinic acid (for example which may be used with an epoxide quaternising agent such as propylene oxide).
  • the polyisobutylene succinic acid may form a salt via one or both of its acid groups. When only one of its acid groups is used to form a salt it may maintain a free acid group.
  • the further groups may be present as the free acid or the ester. Where there is more than one free acid group there may be an equivalent number of cations.
  • the quaternary ammonium compound may comprise a dicarboxylate dianion and two quaternary ammonium ions. Compounds of this type are described in EP3024913.
  • Some preferred epoxide quaternising agents for use herein include styrene oxide, butylene oxide, propylene oxide or 2-ethylhexyl glycidyl ether in combination with a monocarboxylic acid, suitably acetic acid.
  • Some preferred epoxide quaternising agents for use herein include styrene oxide, butylene oxide, propylene oxide or 2-ethylhexyl glycidyl ether in combination with a polycarboxylic acid, suitably a polyisobutenyl substituted succinic acid.
  • the quaternising agent is selected from an ester of a carboxylic acid, a quaternising agent optionally in combination with an acid and chloroacetic acid or a salt thereof.
  • the quaternary ammonium compound is the reaction product of a tertiary amine of a tertiary amine of formula R 5 R 6 R 7 N, wherein each of R 5 , R 6 and R 7 is independently an optionally substituted alkyl or alkenyl group having 1 to 40 carbon atoms; an epoxide; and a monocarboxylic acid or a dicarboxylic acid.
  • the quaternary ammonium compound is the reaction product of a tertiary amine of a tertiary amine of formula R 5 R 6 R 7 N, wherein each of R 5 , R 6 and R 7 is an alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms; an epoxide; and a monocarboxylic acid or a dicarboxylic acid.
  • the quaternary ammonium compound is the reaction product of a tertiary amine of a tertiary amine of formula R 5 R 6 R 7 N, wherein one or two of the groups R 5 , R 6 and R 7 is a short chain alkyl group having 1 to 6, preferably 1 to 4 carbon atoms and the other one or two groups is a longer chain alkyl or group having 6 to 30, preferably 10 to 24 carbon atoms; an epoxide; and a monocarboxylic acid or a dicarboxylic acid.
  • the quaternary ammonium compound is the reaction product of a tertiary amine; an epoxide, preferably propylene oxide; and an optionally substituted succinic acid, preferably a polyisobutenyl substituted succinic acid wherein the tertiary amine has the formula R 5 R 6 R 7 N, wherein one or two of the groups R 5 , R 6 and R 7 is a short chain alkyl group having 1 to 6, preferably 1 to 4 carbon atoms and the other one or two groups is a longer chain alkyl or group having 6 to 30, preferably 10 to 24 carbon atoms.
  • Preferred quaternary ammonium salt additives for use in the present invention include at least one reaction product of:
  • quaternising agent selected from: an ester of a carboxylic acid; and an epoxide, optionally in combination with an acid.
  • Preferred quaternary ammonium salt additives for use in the present invention include at least one reaction product of:
  • a quaternising agent selected from: an ester of a carboxylic acid; and an epoxide, optionally in combination with an acid.
  • More preferred quaternary ammonium salt additives of the present invention include at least one reaction product of:
  • a quaternising agent selected from an ester of a carboxylic acid selected from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid and 2, 4, 6-trihydroxybenzoic acid; and an epoxide selected from one or more of ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, heptylene oxide, isopropyl glycidyl ether, styrene oxide, stilbene oxide and other C2 to C30 hydrocarbyl groups, optionally in combination with an acid.
  • Some especially preferred quaternary ammonium salt additives of the present invention include at least one reaction product of:
  • (x) a polyisobutenyl substituted succinic acid or anhydride thereof having a PIB molecular weight of 170 to 2800, preferably 450 to 1500 and an amine or alcohol selected from dimethylaminopropanol, dimethylaminopropylamine, N,N-diethyl-1 ,3- diaminopropane, N,N- dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, or combinations thereof; and
  • a quaternising agent selected from dimethyl oxalate, methyl 2-nitrobenzoate, dimethylphthalate, dimethyltartrate, methyl salicylate; and an epoxide selected from styrene oxide, 2-ethylhexyl glycidyl ether, ethylene oxide, propylene oxide, butylene oxide, 2-ethylhexyl glycidyl ether, stilbene oxide and isopropyl glycidyl ether, in combination with an acid.
  • Some especially preferred quaternary ammonium salt additives of the present invention include at least one reaction product of:
  • (x) a polyisobutenyl substituted succinic acid or anhydride thereof having a PIB molecular weight of 170 to 2800, preferably 450 to 1500 and an amine or alcohol selected from dimethylaminopropanol and dimethylaminopropylamine; and
  • quaternising agent selected from dimethyl oxalate; methyl salicylate; and an epoxide selected from styrene oxide, propylene oxide and butylene oxide, in combination with an acid.
  • quaternary ammonium salt additives of the present invention include at least one reaction product of:
  • (x) a polyisobutenyl substituted succinic acid or anhydride thereof having a PIB molecular weight of 170 to 2800, preferably 450 to 1500 and including an average of at least 1 .2 succinic acid moieties per molecule, and an amine or alcohol selected from dimethylaminopropanol and dimethylaminopropylamine; and
  • (y) a quaternising agent selected from dimethyl oxalate; methyl salicylate; and an epoxide selected from styrene oxide, propylene oxide and butylene oxide, in combination with an acid.
  • the quaternary ammonium salt additives for use in the present invention are the quaternised reaction product of a fatty acid (for example oleic acid) and dimethylaminopropyl amine.
  • the present invention relates to uses of a gasoline fuel composition.
  • gasoline a liquid fuel for use with spark ignition engines (typically or preferably containing primarily or only C4-C12 hydrocarbons) and satisfying international gasoline specifications, such as ASTM D-439 and EN228.
  • the term includes blends of distillate hydrocarbon fuels with oxygenated components such as alcohols or ethers for example methanol, ethanol, butanol, methyl t-butyl ether (MTBE), ethyl t-butyl ether (ETBE), as well as the distillate fuels themselves.
  • oxygenated components such as alcohols or ethers for example methanol, ethanol, butanol, methyl t-butyl ether (MTBE), ethyl t-butyl ether (ETBE), as well as the distillate fuels themselves.
  • MTBE methyl t-butyl ether
  • ETBE ethyl t-butyl ether
  • the present inventors have surprisingly found that even very low concentrations of the quaternary ammonium compound provide a significant reduction in the emission of particulates having a diameter of less than 2.5 microns from a direct injection spark ignition engine.
  • the quaternary ammonium salt additive is present in the gasoline composition in an amount of less than 300 ppm, suitably less than 100 ppm, preferably less than 50 ppm, preferably less than 30 ppm.
  • the quaternary ammonium compound is present in the gasoline composition in an amount of less than 20 ppm, preferably less than 15 ppm, preferably less than 10 ppm, for example less than 8 ppm or even less than 5 ppm.
  • the quaternary ammonium salt additive is present in the gasoline in an amount of from 0.1 to 100 ppm, preferably 0.5 to 50 ppm, preferably 1 to 25 ppm or 1 to 10 ppm.
  • gasoline compositions used in the present invention may comprise a mixture of two or more quaternary ammonium compounds. In such embodiments the above amounts refer to the total amounts of all such compounds present in the composition.
  • the quaternary ammonium salt additive comprises one or more quaternary ammonium compounds.
  • the amounts of quaternary ammonium salt additive referred to herein refer to the total amount of active quaternary ammonium compounds present in the composition.
  • the amounts referred to herein do not include any diluent or carrier and do not include any unreacted starting materials or byproducts. Such components may however be present in the additive composition dosed into a fuel.
  • the crude reaction mixture following the quaternisation reaction may be used as an additive without purification but the amounts referred to herein relate to the active quaternary ammonium compound or compounds.
  • mixtures may arise due to the availability of starting materials or a particular mixture may be deliberately selected to use in order to achieve a benefit.
  • a particular mixture may lead to improvements in handling, a general improvement in performance or a synergistic improvement in performance.
  • the quaternary ammonium salt additives may be used without additional components.
  • the quaternary ammonium salt additive is used with one or more additional components selected from: a) carrier oils b) acylated nitrogen compounds which are the reaction product of a carboxylic acid- derived acylating agent and an amine c) hydrocarbyl-substituted amines wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms d) Mannich base additives comprising nitrogen-containing condensates of a phenol, aldehyde and primary or secondary amine; and e) polyether amines.
  • the ratio of the quaternary ammonium salt additive to additional components (a) to (e) when present is 1 :100 to 100:1 , preferably 1 :50: to 50:1 , preferably 1 :15 to 20:1 preferably 1 :15 to 10:1 preferably 1 :10 to 10:1 preferably 1 :5 to 5:1 .
  • the ratio of the total of the quaternary ammonium salt additive and components b), c), d) and e) to carrier oil a) when present is 1 :100 to 100:1 , preferably 1 :50 : 50:1 , preferably 1 :15 to 20:1 preferably 1 :15 to 10:1 preferably 1 :10 to 10:1 preferably 1 :5 to 5:1 , preferably 1 :2 to 2:1.
  • the carrier oil may have any suitable molecular weight.
  • a preferred molecular weight is in the range 500 to 5000.
  • the carrier oil may comprise an oil of lubricating viscosity.
  • the oil of lubricating viscosity includes natural or synthetic oils of lubricating viscosity, oil derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined and re-refined oils, or mixtures thereof.
  • the carrier oil may comprise a polyether carrier oil.
  • the carrier oil is a polyalkyleneglycol monoether of the formula: where R 31 is a hydrocarbyl group having from 1 to 30 carbon atoms; R 32 and R 33 are each independently hydrogen or lower alkyl having from about 1 to about 6 carbon atoms and each R 32 and R 33 is independently selected in each --O — CHR 32 -CHR 33 -- unit; and x is an integer of from 5 to 100, preferably 10 to 50, preferably 10 to 30, preferably 10-25, more preferably 12 to 25, more preferably 12 to 20.
  • R 31 is a straight chain C1-C30 alkyl, preferably C4-C20 alkyl, preferably C 8 -Ci8 alkyl, and more preferably C12-C18 alkyl or Cs-C alkyl.
  • R 31 is an alkylphenyl group preferably an alkylphenyl group, wherein the alkyl moiety is a straight or branched chain alkyl of from about 1 to about 24 carbon atoms.
  • one of R 32 and R 33 is lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen. More preferably, one of R 32 and R 33 is methyl or ethyl, and the other is hydrogen.
  • the carrier oil is a polypropyleneglycol monoether of the formula (C1) wherein R 31 , and x are as defined above, and in each repeat unit one of R 32 and R 33 are hydrogen and the other is methyl.
  • the polyalkyleneglycol may be an ester.
  • the carrier oil may be a polypropyleneglycol monoester of the formula where R 31 , R 32 , R 33 and x are as defined for (C1) above and R 34 is a C1-C30 hydrocarbyl group, preferably an aliphatic hydrocarbyl group, and more preferably C1-C10 alkyl.
  • R 31 , R 32 , R 33 and x are as defined for (C1) above and R 34 is a C1-C30 hydrocarbyl group, preferably an aliphatic hydrocarbyl group, and more preferably C1-C10 alkyl.
  • the carboxylic derived acylating agent may be a hydrocarbyl substituted acylating agent as described for the guaternary ammonium compounds (i).
  • Amines useful for reaction with these acylating agents include the following:
  • each R 35 is independently selected from a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group containing up to about 30 carbon atoms, with proviso that at least one R 35 is a hydrogen atom, n is a whole number from 1 to 10 and U is a C1-18 alkylene group.
  • each R 35 is independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl and isomers thereof. Most preferably each R 35 is ethyl or hydrogen.
  • U is preferably a C1-4 alkylene group, most preferably ethylene.
  • (poly)alkylene polyamines (1) include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tri(tri-methylene)tetramine, pentaethylenehexamine, hexaethylene-heptamine, 1 ,2-propylenediamine, and other commercially available materials which comprise complex mixtures of polyamines.
  • higher ethylene polyamines optionally containing all or some of the above in addition to higher boiling fractions containing 8 or more nitrogen atoms etc.
  • (poly)alkylene polyamines (1) which are hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl) ethylene diamine, N,N’ -bis(2-hydroxyethyl) ethylene diamine, N-(3-hydroxybutyl) tetramethylene diamine, etc.
  • heterocyclic-substituted polyamines including hydroxyalkyl-substituted polyamines wherein the polyamines are as described above and the heterocyclic substituent is selected from nitrogen-containing aliphatic and aromatic heterocycles, for example piperazines, imidazolines, pyrimidines, morpholines, etc.
  • Ar(NR 35 2 ) y wherein Ar is an aromatic nucleus of 6 to 20 carbon atoms, each R 35 is as defined above including the proviso that at least one R 35 is a hydrogen atom and y is from 2 to 8.
  • the amine reactant may alternatively be a compound of general formula R 35 sN wherein each R 35 is as defined in (1) above including the proviso that at least one R 35 is a hydrogen atom.
  • amines which may be used in this invention include amines selected from ammonia, butylamine, aminoethylethanolamine, aminopropan-2-ol, 5-aminopentan-1-ol, 2-(2-aminoethoxy)ethanol, monoethanolamine, 3-aminopropan-1-ol, 2-((3-aminopropyl)amino)ethanol, dimethylaminopropylamine, and N-(alkoxyalkyl)- alkanediamines including N-(octyloxyethyl)-1 ,2-diaminoethane and N-(decyloxypropyl)-N- methyl-1 ,3-diaminopropane.
  • a preferred acylated nitrogen compound of this class is that made by reacting a poly(isobutene)- substituted succinic acid-derived acylating agent (e.g., anhydride, acid, ester, etc.) wherein the poly(isobutene) substituent has between about 12 to about 200 carbon atoms and the acylating agent has from 1 to 2, preferably predominantly 1 succinic-derived acylating groups; with a mixture of ethylene polyamines having 3 to about 9 amino nitrogen atoms, preferably about 3 to about 8 nitrogen atoms, per ethylene polyamine and about 1 to about 8 ethylene groups.
  • a poly(isobutene)- substituted succinic acid-derived acylating agent e.g., anhydride, acid, ester, etc.
  • acylated nitrogen compounds are formed by the reaction of a molar ratio of acylating agent : amino compound of from 10:1 to 1 :10, preferably from 5:1 to 1 :5, more preferably from 2.5:1 to 1 :2, more preferably from 2:1 to 1 :2 and most preferably from 2:1 to 1 :1 .
  • the acylated nitrogen compounds are formed by the reaction of acylating agent to amino compound in a molar ratio of from 1 .8:1 to 1 :1 .2, preferably from 1 .6:1 to 1 :1 .2, more preferably from 1 .4:1 to 1 :1.1 and most preferably from 1 .2:1 to 1 :1 .
  • acylated amino compound and the preparation thereof is well known to those skilled in the art and are described in the above- referenced US patents.
  • the acylated nitrogen compounds are formed by the reaction of acylating agent to amino compound in a molar ratio of from 2.5:1 to 1 .5:1 , preferably from 2.2:1 to 1 .8:1.
  • Preferred acylated nitrogen compounds for use herein include: the compound formed by reacting a polyisobutylene succinic anhydride (PIBSA) having a PIB molecular weight of 900 to 1100, for example approximately 1000 with aminoethyl ethanolamine or triethylene tetramine; and the compound formed by reacting a PIBSA having a PIB molecular weight of 650 to 850, for example about 750 with tetraethylene pentamine.
  • PIBSA polyisobutylene succinic anhydride
  • the ratio of PIBSA to amine is from 1 .5:1 to 0.9:1 , preferably from 1 .2:1 to 1 :1 .
  • acylated nitrogen compounds for use herein include: the compound formed by reacting a polyisobutylene succinic anhydride (PIBSA) having a PIB molecular weight of 900 to 1100, for example approximately 1000 with tetraethylene pentamine, the ratio of PIBSA to amine being from 2.5:1 to 1 .5:1 , preferably from 2.2:1 to 1.8:1.
  • PIBSA polyisobutylene succinic anhydride
  • Hydrocarbyl-substituted amines suitable for use in the present invention are well known to those skilled in the art and are described in a number of patents. Among these are U.S. Patent Numbers 3275554; 3438757; 3454555; 3565804; 3755433 and 3822209. These patents describe suitable hydrocarbyl amines for use in the present invention including their method of preparation.
  • the hydrocarbyl-substituted amine comprises an amine derivative of polyisobutene.
  • Such materials are commonly referred to as PIBamines.
  • the Mannich additives comprise nitrogen-containing condensates of a phenol, aldehyde and primary or secondary amine. Suitable phenols and aldehydes are as described in relation to nitrogen containing species (ii) a Mannich reaction product comprising a tertiary amine group described above.
  • the amine used to form the Mannich Additive (d) can be a monoamine or a polyamine.
  • monoamines include but are not limited to ethylamine, dimethylamine, diethylamine, n-butylamine, dibutylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, diethanolamine, morpholine, and octadecylamine.
  • Suitable polyamines may be selected from any compound including two or more amine groups.
  • Suitable polyamines include polyalkylene polyamines, for example in which the alkylene component has 1 to 6, preferably 1 to 4, most preferably 2 to 3 carbon atoms.
  • Preferred polyamines are polyethylene polyamines.
  • the polyamine has 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, more preferably 2 to 8 nitrogen atoms.
  • the amine used to form the Mannich detergent comprises a diamine.
  • Polyamines may be selected from any compound including two or more amine groups.
  • the polyamine is a (poly)alkylene polyamine (by which is meant an alkylene polyamine or a polyalkylene polyamine; including in each case a diamine, within the meaning of “polyamine”).
  • the polyamine is a (poly)alkylene polyamine in which the alkylene component has 1 to 6, preferably 1 to 4, most preferably 2 to 3 carbon atoms.
  • the polyamine is a (poly) ethylene polyamine (that is, an ethylene polyamine or a polyethylene polyamine).
  • the polyamine has 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, more preferably 2 to 8 nitrogen atoms.
  • the polyamine may, for example, be selected from ethylenediamine, dimethyl amino propylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, propane-1 ,2-diamine, 2(2-amino- ethylamino)ethanol, and N’,N’-bis (2-aminoethyl) ethylenediamine (N(CH2CH2NH2)3).
  • the polyamine comprises tetraethylenepentamine or ethylenediamine. Preferred Mannich additives of this type are described in US5876468.
  • the primary or secondary amine has only one reactive primary or secondary amine group.
  • Such amines include the monoamines as described above, particularly secondary monoamines and polyamines having only one reactive primary or secondary amine group such as dialkyl alkylene diamines.
  • Preferred Mannich additives of this type are described in US5725612, US5634951 and US6800103. e) polyetheramine
  • polyetheramines function as deposit control additives. It is common for polyetheramines to be used as detergents and/or as carrier oils.
  • Suitable hydrocarbyl-substituted polyoxyalkylene amines or polyetheramines employed in the present invention are described in the literature (for example US6217624 and US4288612) and have the general formula: or a fuel-soluble salt thereof;
  • R 31 , R 32 , R 33 and x are as defined for (C1) above;
  • A is amino, N- alkyl amino having about 1 to about 20 carbon atoms in the alkyl group, N,N-dialkyl amino having about 1 to about 20 carbon atoms in each alkyl group, or a polyamine moiety having about 2 to about 12 amine nitrogen atoms and about 2 to about 40 carbon atoms; and y is 0 or 1 .
  • A is amino, N-alkyl amino having from about 1 to about 20 carbon atoms in the alkyl group, preferably about 1 to about 6 carbon atoms, more preferably about 1 to about 4 carbon atoms; N,N-dialkyl amino having from about 1 to about 20 carbon atoms in each alkyl group, preferably about 1 to about 6 carbon atoms, more preferably about 1 to about 4 carbon atoms; or a polyamine moiety having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms, preferably about 2 to 12 amine nitrogen atoms and about 2 to 24 carbon atoms. More preferably, A is amino or a polyamine moiety derived from a (poly)alkylene polyamine, including alkylene diamine. Most preferably, A is amino or a polyamine moiety derived from ethylene diamine or diethylene triamine.
  • the polyetheramines will generally have a molecular weight in the range from about 600 to about 10,000.
  • the gasoline fuel compositions used in the present invention may contain one or more further additives conventionally added to gasoline, for example other detergents, dispersants, antioxidants, anti-icing agents, metal deactivators, lubricity additives, friction modifiers, dehazers, corrosion inhibitors, dyes, markers, octane improvers, anti-valve-seat recession additives, stabilisers, demulsifiers, antifoams, odour masks, conductivity improvers and combustion improvers.
  • further additives conventionally added to gasoline, for example other detergents, dispersants, antioxidants, anti-icing agents, metal deactivators, lubricity additives, friction modifiers, dehazers, corrosion inhibitors, dyes, markers, octane improvers, anti-valve-seat recession additives, stabilisers, demulsifiers, antifoams, odour masks, conductivity improvers and combustion improvers.
  • Such further ingredients could in principle be added separately to the quaternary ammonium compound(s) but it is preferred for reasons of convenience and consistency of dosing to include all additives in a common additive composition.
  • the fuel compositions of the invention contain the quaternary ammonium salt additive and one or more of a detergent, a friction modifier and a carrier oil.
  • the fuel compositions of the invention contain the quaternary ammonium salt additive and two or more of a detergent, a friction modifier and a carrier oil.
  • the fuel compositions of the invention contain the quaternary ammonium salt additive a detergent, a friction modifier and a carrier oil.
  • the quaternary ammonium salt addtive and further additives (when present) is/are present in the fuel in the fuel storage tank which supplies the engine. Although they could be mixed into the fuel in the storage tank, preferably they are present in bulk fuel which is pumped into the storage tank.
  • the quaternary ammonium salt additives may be added to gasoline fuel at any convenient place in the supply chain.
  • the additives may be added to fuel at the refinery, at a distribution terminal or after the fuel has left the distribution terminal. If the additive is added to the fuel after it has left the distribution terminal, this is termed an aftermarket application.
  • Aftermarket applications include such circumstances as adding the additive to the fuel in the delivery tanker, directly to a customer’s bulk storage tank, or directly to the end user’s vehicle tank.
  • Aftermarket applications may include supplying the fuel additive in small bottles suitable for direct addition to fuel storage tanks or vehicle tanks.
  • the present invention relates to improving the reducing the emission of particulates having a diameter of less than 2.5 microns from a direct injection spark ignition engines by combusting gasoline fuel compositions comprising a quaternary ammonium compound as an additive.
  • particulate emissions we mean that the level of particulates released via the exhaust stream of a direct injection spark ignition on combustion of a gasoline fuel comprising the additive is lower than that achieved on combustion of the same fuel without the additive in the same engine.
  • the level of particulates, such as the level of particulates having a diameter of less than 2.5 microns, released via the exhaust stream may be measured by any suitable means and such means will be known to the person skilled in the art.
  • the number of particulates, such as the number of particulates having a diameter of less than 2.5 microns, in a given volume of exhaust gas is counted.
  • particulate emissions may be measured using a Cambustion® DMS500 exhaust gas analyser, equipped with a Catalytic Stripping Accessory (CSA), by an electrical mobility detection method.
  • CSA Catalytic Stripping Accessory
  • the present invention preferably also reduces the total mass of particulates having a diameter less than 2 microns emitted. In some embodiments the present invention reduces the number of particulates having a diameter less than 2.5 microns emitted per unit volume of exhaust gas.
  • the present invention reduces the total mass of particulates having a diameter less than 2.5 microns emitted per unit volume of exhaust gas.
  • the present invention reduces the total mass and the number of particulates having a diameter less than 2.5 microns emitted per unit volume of exhaust gas.
  • the present invention reduces particulate emissions from a direct injection spark ignition engine.
  • the exhaust gases from the engine may be directed through a particulate filter.
  • the present invention may advantageously reduce the level of particulates in the exhaust gases which pass through the filter. As a result this may extend the life of the particulate filter and/or increase the maintenance intervals and/or increase regeneration intervals.
  • the present invention may provide the use of a quaternary ammonium compound as an additive in a gasoline fuel composition to improve the performance of a particulate filter fitted to the exhaust of a direct injection spark ignition engine wherein the improvement in performance is selected from: increased longevity; an increase in maintenance intervals; and an increase in regeneration intervals.
  • a particular advantage of the present invention is that the emission of very small particulates is reduced, including particulates that may be small enough to pass through exhaust filters.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 2 microns from a direct injection spark ignition engine.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 1 micron from a direct injection spark ignition engine.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 0.5 microns from a direct injection spark ignition engine.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 0.3 microns from a direct injection spark ignition engine.
  • the method and use of the present invention reduce the emission of nanoparticles from a direct injection spark ignition engine.
  • Nanoparticles are particles which have one or more dimensions of the order of 100 nm or less.
  • the size of the nanoparticles may be measured by any suitable method. For example, any of the methods described in PAS 71 :2005 published by British Standards could be used. Preferred methods for the determination of particle size include TEM (Transmission Electron Microscopy, when particles are made of a material that has high contrast with a carbon TEM grid), SEM (Scanning Electron Microscopy) and AFM (Atomic Force Microscopy). If the particles show plasmon resonance then the size can also be determined from the peak in the UV-VIS spectrum. For larger particles having a size of order of magnitude of 10 -8 m or greater, light scattering can be used.
  • method and use of the present invention reduce the emission of particulates having a particle size (as defined above) of between 5 nm and 100 nm, for example between 10 nm and 80 nm.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 2.5 microns from a direct injection spark ignition engine by at least 50%.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 2.5 microns from a direct injection spark ignition engine by at least one order of magnitude.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 2 microns from a direct injection spark ignition engine by at least 50%.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 2 microns from a direct injection spark ignition engine by at least one order of magnitude.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 1 micron from a direct injection spark ignition engine by at least 50%.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 1 micron from a direct injection spark ignition engine by at least one order of magnitude.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 0.5 microns from a direct injection spark ignition engine by at least 50%.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 0.5 microns from a direct injection spark ignition engine by at least one order of magnitude.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 0.3 microns from a direct injection spark ignition engine by at least 50%.
  • the method and use of the present invention reduce the emission of particulates having a diameter of less than 0.3 microns from a direct injection spark ignition engine by at least one order of magnitude.
  • the method and use of the present invention reduce the emission of nanoparticles from a direct injection spark ignition engine by at least 50%.
  • the method and use of the present invention reduce the emission of nanoparticles, preferably having a diameter of 1 to 100 nm from a direct injection spark ignition engine by at least one order of magnitude.
  • the present invention may provide a method of reducing the emission of particulates having a diameter of less than 2.5 microns from a direct injection spark ignition engine, the method comprising the steps of:
  • the method may further comprise comparing the concentration of particulates having a diameter of less than 2.5 microns emitted from the exhaust of the engine during combustion of the gasoline fuel composition comprising the quaternary ammonium compound with the concentration of particulates having a diameter of less than 2.5 microns emitted from the exhaust of the engine during combustion of the gasoline fuel composition without the quaternary ammonium compound.
  • the gasoline fuel composition without the quaternary ammonium compound is suitably otherwise an identical fuel composition.
  • the present invention may provide a method of reducing the emission of particulates having a diameter of less than 0.5 microns from a direct injection spark ignition engine, the method comprising the steps of:
  • the method further comprises comparing the concentration of particulates having a diameter of less than 0.5 microns emitted from the exhaust of the engine during combustion of the gasoline fuel composition comprising the quaternary ammonium compound with the concentration of particulates having a diameter of less than 0.5 microns emitted from the exhaust of the engine during combustion of the gasoline fuel composition without the quaternary ammonium compound.
  • the present invention the use of from 1 to 20 ppm of a quaternary ammonium compound as an additive in a gasoline composition to reduce the emission of particulates having a diameter of less than 0.5 microns from a direct injection spark ignition engine by at least 50%, preferably at least 90% wherein the quaternary ammonium compound is the quaternised reaction product of a hydrocarbyl substituted succinic acid derived acylating agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group wherein hydrocarbyl substituted acylating agent includes an average of at least 1 .2 succinic acid moieties per molecule.
  • Example 1 the reaction product of a hydrocarbyl substituted acylating agent and a compound of formula (B1) was prepared as follows:
  • PIBSA made from 1000 MW PIB and maleic anhydride
  • DMAPA was added over 1 hour and the mixture heated to 140°C for 3 hours, with concurrent removal of water using a Dean-Stark apparatus.
  • PIB herein means polyisobutene
  • PIBSA means polyisobutenyl-substituted succinic anhydride
  • DMAPA means dimethylaminopropylamine
  • Additive B an additive comprising a quaternary ammonium salt additive of the present invention was prepared as follows:
  • additive C an additive comprising a quaternary ammonium salt additive of the present invention was prepared as follows:
  • the reaction mass was cooled to ⁇ 80°C then discharged from the reactor.
  • the resulting PIBSA was charged to a nitrogen flushed, jacketed reactor fitted with an overhead stirrer and heated to 120 °C.
  • 3-(dimethylamino)propylamine (DMAPA) (1 eq relative to anhydride groups) was charged slowly, maintaining the reaction temperature between 120 - 130 °C.
  • DMAPA dimethylamino)propylamine
  • the reaction temperature was increased to 140 °C and held for 3 hrs with concurrent distillation of water.
  • Methyl salicylate (2.1 eq relative to anhydride groups) was added in a single portion and heating was continued at 140 °C for 10 hours.
  • the reaction mass was diluted with Aromatic 150 solvent to provide an overall solids content of 60 wt% prior to discharging from the reactor.
  • Gasoline compositions were prepared comprising additive C (30 mg/kg treat rate of the additive), added to aliquots all drawn from a common batch of base fuel.
  • the base fuel was EN228 compliant and had the specification as shown in Table 1 .
  • the size, number and distribution of emitted particulates was measured using a Cambustion® DMS500 exhaust gas analyser, equipped with a Catalytic Stripping Accessory (CSA).
  • the instrument measures particulate matter having sizes between 5 and 1000 nm using an electrical mobility detection method.
  • DISI direct injection spark ignition
  • GPF gasoline particulate filter
  • a Euro 6 compliant 2.0 litre turbocharged gasoline direct injection (GDI) engine was connected to a test automation system and test bed fitted with an engine dynamometer. The engine was controlled by an ECU supplied by the engine manufacturer. The engine configuration included a GPF and (as set out above) emitted particulates were measured before and after the GPF.
  • GDI turbocharged gasoline direct injection
  • test cycle was 48 hours duration and consisted of a single speed and load point (42% load @ 2000 RPM).
  • the base fuel complied with the specification detailed in Table 1 .
  • Table 2 The results of the engine test are shown in Table 2.
  • the term “average total particulates” refers to the average taken over the entire 48 hour test and includes all measured particulates in the size range 10 to 1000 nm.
  • Additive B Prepared according to examples 1 and 2.
  • Additive D The Mannich reaction product of a polyisobutylene (PIB)-substituted phenol having a PIB number average molecular weight of 1000, formaldehyde and DMAPA reacted in a molar ratio of 1 : 1 : 1 using a procedure analogous to that described in Example 28 of US5634951 .
  • PIB polyisobutylene
  • Additive E A non-quaternized succinimide reaction product of PIBSA having a PIB number average molecular weight of 1000 and an oligomeric mixture of polyethylene polyamines comprising tetraethylene pentamine as its major component.
  • Additive F A commercially available polyetheramine, derived from alkoxylated polyisobutenyl (PIB)-substituted phenol.
  • the additive had number average molecular weight in the range 1400 to1800 and an amine value of 0.5 ⁇ 0.05 mmol/g.
  • Fuel compositions were prepared by dosing additives B, D, E and F into an EN 228 compliant, low sulfur E0 gasoline fuel (Haltermann Carless, DISI TF low sulfur batch 12).

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Abstract

L'invention concerne un procédé de réduction de l'émission de particules ayant un diamètre inférieur à 2,5 microns provenant d'un moteur à allumage commandé et injection directe, le procédé comprenant la combustion dans le moteur d'une composition d'essence comprenant un ou plusieurs composés d'ammonium quaternaire en tant qu'additifs.
EP23828233.9A 2022-12-12 2023-12-12 Composition, procédé et utilisation Pending EP4634340A1 (fr)

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WO2025008645A1 (fr) * 2023-07-06 2025-01-09 Innospec Limited Procédés et utilisations se rapportant à la combustion de compositions de carburant d'essence dans un moteur à allumage par étincelle à injection directe

Family Cites Families (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3444170A (en) 1959-03-30 1969-05-13 Lubrizol Corp Process which comprises reacting a carboxylic intermediate with an amine
DE1248643B (de) 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Verfahren zur Herstellung von öllöslichen aeylierten Aminen
NL124306C (fr) 1959-08-24
NL124842C (fr) 1959-08-24
US3231587A (en) 1960-06-07 1966-01-25 Lubrizol Corp Process for the preparation of substituted succinic acid compounds
NL137371C (fr) 1963-08-02
US3455832A (en) 1963-09-09 1969-07-15 Monsanto Co Schiff bases
US3455831A (en) 1963-09-27 1969-07-15 Monsanto Co Imines containing a polyalkenylsuccinic anhydride substituent
US3310492A (en) 1964-09-08 1967-03-21 Chevron Res Oils for two-cycle engines containing basic amino-containing detergents and aryl halides
NL145565B (nl) 1965-01-28 1975-04-15 Shell Int Research Werkwijze ter bereiding van een smeermiddelcompositie.
US3574576A (en) 1965-08-23 1971-04-13 Chevron Res Distillate fuel compositions having a hydrocarbon substituted alkylene polyamine
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3822209A (en) 1966-02-01 1974-07-02 Ethyl Corp Lubricant additives
GB1282887A (en) 1968-07-03 1972-07-26 Lubrizol Corp Acylation of nitrogen-containing products
US3576743A (en) 1969-04-11 1971-04-27 Lubrizol Corp Lubricant and fuel additives and process for making the additives
US3632511A (en) 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
US3804763A (en) 1971-07-01 1974-04-16 Lubrizol Corp Dispersant compositions
US3755433A (en) 1971-12-16 1973-08-28 Texaco Inc Ashless lubricating oil dispersant
US4288612A (en) 1976-06-21 1981-09-08 Chevron Research Company Deposit control additives
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
DE3826608A1 (de) 1988-08-05 1990-02-08 Basf Ag Polyetheramine oder polyetheraminderivate enthaltende kraftstoffe fuer ottomotoren
JPH0662965B2 (ja) 1990-02-02 1994-08-17 花王株式会社 燃料油添加剤及び燃料油添加剤組成物
GB9208034D0 (en) 1992-04-10 1992-05-27 Bp Chem Int Ltd Fuel composition
US5634951A (en) 1996-06-07 1997-06-03 Ethyl Corporation Additives for minimizing intake valve deposits, and their use
US5725612A (en) 1996-06-07 1998-03-10 Ethyl Corporation Additives for minimizing intake valve deposits, and their use
GB9618546D0 (en) 1996-09-05 1996-10-16 Bp Chemicals Additives Dispersants/detergents for hydrocarbons fuels
US6821307B2 (en) 1997-05-15 2004-11-23 Infineum International Ltd. Oil composition
US6217624B1 (en) 1999-02-18 2001-04-17 Chevron Chemical Company Llc Fuel compositions containing hydrocarbyl-substituted polyoxyalkylene amines
US6800103B2 (en) 2001-02-02 2004-10-05 Ethyl Corporation Secondary amine mannich detergents
US6784317B2 (en) 2001-05-02 2004-08-31 Mitsubishi Gas Chemical Company, Inc Production of quaternary ammonium salt of hydroxycarboxylic acid and quarternary ammonium salt of inorganic acid
DE10211418A1 (de) 2002-03-15 2003-09-25 Bayer Ag Verfahren zur Herstellung hochreaktiver Polyisobutene
GB0515998D0 (en) 2005-08-03 2005-09-07 Ass Octel Fuel additives
US7906470B2 (en) 2006-09-01 2011-03-15 The Lubrizol Corporation Quaternary ammonium salt of a Mannich compound
US20080113890A1 (en) 2006-11-09 2008-05-15 The Lubrizol Corporation Quaternary Ammonium Salt of a Polyalkene-Substituted Amine Compound
GB201113388D0 (en) 2011-08-03 2011-09-21 Innospec Ltd Fuel compositions
US20130225463A1 (en) 2011-11-04 2013-08-29 Markus Hansch Quaternized polyether amines and their use as additive for fuels and lubricants
GB201313423D0 (en) 2013-07-26 2013-09-11 Innospec Ltd Compositions and methods
GB201416088D0 (en) * 2014-09-11 2014-10-29 Bp Oil Int Additive and fuel compositions
GB201705124D0 (en) * 2017-03-30 2017-05-17 Innospec Ltd Composition, method and use
GB201805238D0 (en) * 2018-03-29 2018-05-16 Innospec Ltd Composition, method and use
FR3110914B1 (fr) * 2020-05-29 2023-12-29 Total Marketing Services Utilisation d’une composition de carburant pour nettoyer les parties internes des moteurs essence

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