EP2643384A1 - Sels d'ammonium quaternaire de polyester - Google Patents

Sels d'ammonium quaternaire de polyester

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Publication number
EP2643384A1
EP2643384A1 EP11791398.8A EP11791398A EP2643384A1 EP 2643384 A1 EP2643384 A1 EP 2643384A1 EP 11791398 A EP11791398 A EP 11791398A EP 2643384 A1 EP2643384 A1 EP 2643384A1
Authority
EP
European Patent Office
Prior art keywords
acid
carbon atoms
polyester
tertiary amino
quaternized
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.)
Withdrawn
Application number
EP11791398.8A
Other languages
German (de)
English (en)
Inventor
Hannah Greenfield
Dean Thetford
Joanne Jones
David J. Moreton
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.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
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Filing date
Publication date
Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP2643384A1 publication Critical patent/EP2643384A1/fr
Withdrawn legal-status Critical Current

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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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/265—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen and/or sulfur bonds

Definitions

  • the invention relates to polyester quaternary ammonium salts, including amine, amide, and ester salts, processes for making them, and their use as additives, including their use in fuels, such as diesel fuel and fuel oils.
  • the invention particularly relates to the use of polyester quaternary ammonium salts as detergents in fuels and the methods of making them.
  • Hydrocarbon fuels generally contain numerous deposit-forming substances. When used in internal combustion engines (ICEs), deposits tend to form on and around constricted areas of the engine which are in contact with the fuel. In automobile engines deposits can build up on engine intake valves leading to progressive restriction of the gaseous fuel mixture flow into the combustion chamber and to valve sticking. There are two general types of inlet valve deposits, heavy deposits and thin deposits. These different types of deposits affect the performance of the fuel and the engine in slightly different ways. Heavy deposits are carbonaceous and oily in appearance. They cause flow restriction past the valves, which in turn reduces the maximum power of the engine, decreasing fuel economy and increasing emissions. Thin deposits tend to cause problems on starting the engine and increasing emissions.
  • polyisobutylsuccinimide-derived quater- nized PIB/amine and/or amide dispersants/detergents as additives in fuel compositions.
  • Polyisobutylsuccinimides may also be described as polyisobutylene succinimides.
  • These quaternized dispersants/detergents are derived from traditional PIB/amine and/or amide fuel additive compounds that have pendant tertiary amine sites which can be alkylated, i.e. quaternized, by a quaternizing agent, such as propylene oxide. Examples of these additives are disclosed in U.S. patent application US 2008/0307698.
  • the present invention deals with a new class of detergents which offer significant improvements over traditional PIB/amine detergents, including polyisobutylsuccinimide-derived quaternized detergents.
  • a new class of polyester quaternized salts have now been discovered. These polyester quaternized salts have polyester-based hydrocarbyl groups and provide improved viscosity profiles and material handling properties compared to polyisobutylsuccinimide- derived quaternized detergents and related materials.
  • the polyester quaternized salts of the invention provide equivalent detergency and thermal stability performance as other quaternized detergents but also provide the improved viscosity profiles and material handling properties described above
  • the present invention provides a composition containing a quater- nized polyester salt derived from the reaction of a polyester that contains a tertiary amino group and a quaternizing agent suitable for converting the tertiary amino group to a quaternary nitrogen.
  • the quaternizing agent may be a dialkyl sulfate, a benzyl halide, a hydrocarbyl substituted carbonate, a hydrocarbyl epoxide, or some combination thereof. Any of the quaternizing agents described, particularly the hydrocarbyl epoxide, may be used in combination with an acid, for example acetic acid.
  • the invention provides for quaternized polyester salts where the polyester used in their preparation is itself the reaction product of a fatty car- boxylic acid containing at least one hydroxyl group and a compound having an oxygen or nitrogen atom capable of condensing with said acid and further having a tertiary amino group.
  • the invention further provides for the polyester reactant to be a polyester amide containing a tertiary amino group.
  • the invention further provides for fuel compositions that include the quaternized polyester salts described herein and a fuel which is liquid at room temperature. Additional fuel additives may also be present.
  • the invention provides for methods of fueling an internal combustion engine comprising the steps of supplying to the engine a fuel which is liquid at room temperature and a composition comprising one or more of the quaternized polyester salts described herein.
  • the invention also provides for a process of making a quaternary ammonium salt detergent comprising the steps of reacting (a) a polyester con- taining a tertiary amino group; and (b) a quaternizing agent suitable for converting the tertiary amino group to a quaternary nitrogen.
  • the quaternizing agent may be selected from the group consisting of dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates; hydrocarbyl epoxides in combination with an acid or mixtures thereof.
  • the described process results in the quaternized dispersants described herein.
  • the polyester quaternary salts detergents of the invention include quaternized polyester amine, amide, and ester salts.
  • the additives may also be described as quaternary polyester salts.
  • the additives of the invention may be described as the reaction product of: a polyester containing a tertiary amino group; and a quaternizing agent suitable for converting the tertiary amino group to a quaternary nitrogen.
  • the quaternizing agent may be selected from the group consisting of dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates; hydrocarbyl epoxides in combination with an acid or mixtures thereof.
  • polyester containing a tertiary amino group used in the preparation of the additives of the invention may also be described as a non-quaternized polyester containing a tertiary amino group.
  • the polyester is the reaction product of a fatty carboxylic acid containing at least one hydroxyl group and a compound having an oxygen or nitrogen atom capable of condensing with said acid and further having a tertiary amino group.
  • Suitable fatty carboxylic acids that may used in the preparation of the polyesters described above may be represented by the formula:
  • R 1 is a hydrogen or a hydrocarbyl group containing from 1 to 20 carbon atoms and R is a hydrocarbylene group containing from 1 to 20 carbon atoms.
  • R 1 contains from 1 to 12, 2 to 10, 4 to 8 or even 6 carbon atoms, and R contains from 2 to 16, 6 to 14, 8 to 12, or even 10 carbon atoms.
  • the fatty carboxylic acid used in the preparation of the polyester is 12-hydroxystearic acid, ricinoleic acid, 12-hydroxy dodecanoic acid, 5-hydroxy dodecanoic acid, 5-hydroxy decanoic acid, 4- hydroxy decanoic acid, 10-hydroxy undecanoic acid, or combinations thereof.
  • the compound having an oxygen or nitrogen atom capable of condensing with said acid and further having a tertiary amino group is represented by the formula: R 3 H
  • R 3 is a hydrocarbyl group containing from 1 to 10 carbon atoms
  • R 4 is a hydrocarbyl group containing from 1 to 10 carbon atoms
  • R 5 is a hydrocarbyl ene group containing from 1 to 20 carbon atoms
  • X 1 is O or NR 6 where R 6 is a hydrogen or a hydrocarbyl group containing from 1 to 10 carbon atoms.
  • R 3 contains from 1 to 6, 1 to 2, or even 1 carbon atom
  • R 4 contains from 1 to 6, 1 to 2, or even 1 carbon atom
  • R 5 contains from 2 to 12, 2 to 8 or even 3 carbon atoms
  • R 6 contains from 1 to 8, or 1 to 4 carbon atoms.
  • formula (II) becomes:
  • nitrogen or oxygen containing compounds capable of condensing with the acylating agents, which also have a tertiary amino group, or compounds that can be alkylated into such compounds include but are not limited to: 1-aminopiperidine, l-(2-aminoethyl)piperidine, l -(3-aminopropyl)-2- pipecoline, 1 -methyl-(4-methylamino)piperidine, 4-(l -pyrrolidinyl)piperidine, 1 -(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)- 1 -methylpyrrolidine, N,N- diethylethylenediamine, ⁇ , ⁇ -dimethylethylenediamine, N,N- dibutylethylenediamine, N,N-diethyl-l ,3-diaminopropane, N, N- dimethyl -1 ,3- diaminopropane,
  • the nitrogen or oxygen containing compounds may further include aminoalkyl substituted heterocyclic compounds such as l-(3- aminopropyl)imidazole and 4-(3-aminopropyl)morpholine.
  • alkanolamines including but not limited to triethanolamine, ⁇ , ⁇ -dimethylaminopropanol, N,N- diethylaminopropanol, ⁇ , ⁇ -diethylaminobutanol, triisopropanolamine, l -[2- hydroxyethyljpiperidine, 2-[2-(dimethylamine)ethoxy]-ethanol, N- ethyldiethanolamine, N-methyldiethanol amine, N-butyldiethanolamine, N,N- diethylaminoethanol, ⁇ , ⁇ -dimethyl aminoethanol, 2-dimethylamino-2-methyl- 1 -propanol.
  • the resulting additive includes a quaternary
  • the nitrogen or oxygen containing compound is triisopropanolamine, l-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamino) ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N- butyldiethanolamine, ⁇ , ⁇ -diethylaminoethanol, N,N-dimethylaminoethanol, 2- dimethylamino-2-methyl-l -propanol, or combinations thereof.
  • the compound having an oxygen or nitrogen atom capable of condensing with said acid and further having a tertiary amino group comprises ⁇ , ⁇ -diethylethylenediamine, N,N-dimethylethylenediamine, ⁇ , ⁇ -dibutylethylenediamine, N,N-dimethyl-l ,3-diaminopropane, N,N-di ethyl - 1 ,3-diaminopropane, N,N-dimethylaminoethanol, ⁇ , ⁇ -diethylaminoethanol, or combinations thereof.
  • the quaternized polyester salt can be a quaternized polyester amide salt.
  • the polyester containing a tertiary amino group used to prepare the quaternized polyester salt is a polyester amide containing a tertiary amino group.
  • the amine or aminoalcohol is reacted with a monomer and then the resulting material is polymerized with additional monomer, resulting in the desired polyester amide which may then be quaternized.
  • the quaternized polyester salt includes an cation represented by the following formula:
  • R 1 is a hydrogen or a hydrocarbyl group containing from 1 to 20 carbon atoms and R is a hydrocarbylene group containing from 1 to 20 carbon atoms;
  • R 3 is a hydrocarbyl group containing from 1 to 10 carbon atoms;
  • R 4 is a hydrocarbyl group containing from 1 to 10 carbon atoms;
  • R 5 is a hydrocarbylene group containing from 1 to 20 carbon atoms;
  • R 6 is a hydrogen or a hydrocarbyl group containing from 1 to 10 carbon atoms;
  • n is a number from 1 to 20 or from 1 to 10;
  • R 7 is hydrogen, a hydrocarbonyl group containing from 1 to 22 carbon atoms, or a hydrocarbyl group containing from 1 to 22 carbon atoms; and
  • X is a group derived from the quaternizing agent.
  • R 6 is hydrogen.
  • R 1 contains from 1 to 12, 2 to 10, 4 to 8 or even 6 carbon atoms, and R contains from 1 or even 2 to 16, 6 to 14, 8 to 12, or even 10 carbon atoms, R contains from 1 to 6, 1 to 2, or even 1 carbon atom, R 4 contains from 1 to 6, 1 to 2, or even 1 carbon atom, R 5 contains from 2 to 12, 2 to 8 or even 3 carbon atoms, and R 6 contains from 1 to 8, or 1 to 4 carbon atoms.
  • n may be from 2 to 9, or 3 to 7, and R 7 may contain from 6 to 22, or 8 to 20 carbon atoms.
  • R 7 may be an acyl group.
  • the quaternized polyester salt is essentially capped with a C I -22, or a C8-20, fatty acid.
  • suitable acids include oleic acid, palmitic acid, stearic acid, erucic acid, lauric acid, 2-ethylhexanoic acid, 9, 1 1 -linoleic acid, 9, 12-linoleic acid, 9,12, 15-linolenic acid, abietic acid, or combinations thereof.
  • the number average molecular weight (Mn) of the quaternized polyester salts of the invention may be from 500 to 3000, or from 700 to 2500.
  • the polyester useful in the present invention can be obtained by heating one or more hydroxycarboxylic acids or a mixture of the hydroxycar- boxylic acid and a carboxylic acid, optionally in the presence of an esterification catalyst.
  • the hydroxycarboxylic acids can have the formula HO-X-COOH wherein X is a divalent saturated or unsaturated aliphatic radical containing at least 8 carbon atoms and in which there are at least 4 carbon atoms between the hydroxy and carboxylic acid groups, or from a mixture of such a hydroxycar- boxylic acid and a carboxylic acid which is free from hydroxy groups.
  • This reaction can be carried out at a temperature in the region of 160 C to 200 C, until the desired molecular weight has been obtained.
  • the course of the esterification can be followed by measuring the acid value of the product, with the desired polyester, in some embodiments, having an acid value in the range of 10 to 100 mg KOH/g or in the range of 20 to 50 mg KOH/g.
  • the indicated acid value range of 10 to 100 mg KOH/g is equivalent to a number average molecular weight range of 5600 to 560.
  • the water formed in the esterification reaction can be removed from the reaction medium, and this can be conveniently done by passing a stream of nitrogen over the reaction mixture or, by carrying out the reaction in the presence of a solvent, such as toluene or xylene, and distilling off the water as it is formed.
  • a solvent such as toluene or xylene
  • the resulting polyester can then be isolated in conventional manner; however, when the reaction is carried out in the presence of an organic solvent whose presence would not be harmful in the subsequent application, the result- ing solution of the polyester can be used.
  • the radical represented by X may contain from 12 to 20 carbon atoms, optionally where there are between 8 and 14 carbon atoms between the carboxylic acid and hydroxy groups.
  • the hydroxy group is a secondary hydroxy group.
  • hydroxycarboxylic acids include ricinoleic acid, a mixture of 9- and 10-hydroxystearic acids (obtained by sulphation of oleic acid followed by hydrolysis), and 12-hydroxystearic acid, and especially the commercially available hydrogenated castor oil fatty acid which contains in addition to 12-hydroxystearic acid minor amounts of stearic acid and palmitic acid.
  • the carboxylic acids which can be used in conjunction with the hydroxycarboxylic acids to obtain these polyesters are preferably carboxylic acids of saturated or unsaturated aliphatic compounds, particularly alkyl and alkenyl carboxylic acids containing a chain of from 8 to 20 carbon atoms.
  • carboxylic acids there may be mentioned lauric acid, palmitic acid, stearic acid and oleic acid.
  • the polyester is derived from commercial 12- hydroxy-stearic acid having a number average molecular weight of about 1600. Polyesters such as this are described in greater detail in U.K. Patent Specification Nos. 1373660 and 1342746.
  • the components used to prepare the additives described above are substantially free of, essentially free of, or even completely free of, non-polyester-containing hydrocarbyl substituted acylating agents and/or non-polyester-containing hydrocarbyl substituted diacylating agents, such as for example polyisobutylene succinic anhydride.
  • the excluded hydrocarbyl-substituted acylating agent is a dicarboxylic acylating agent. In some of these embodiments, the excluded hydrocarbyl-substituted acylating agent is polyisobutylene succinic anhydride.
  • the components of the present invention are primarily composed of materials other than hydrocarbyl substituted acylating agents described above such that these agents are not significantly involved in the reaction and the compositions of the invention do not contain significant amounts of additives derived from such agents.
  • the components of the invention, or the compositions of the invention may contain less than 10 percent by weight of these agents, or of the additives derived from these agents.
  • the maximum allowable amount may be 5, 3, 2, 1 or even 0.5 or 0.1 percent by weight.
  • One of the purposes of these embodiments is to allow the exclusion of agents such as polyisobutylene succinic anhydrides from the reactions of the invention and so, to also allow the exclusion of quaternized salt detergent additive derived from agents such as polyisobutylene succinic anhydrides.
  • the focus of this invention is on polyester, or hyperdispersant, quaternary salt detergent additives.
  • the quaternized salt detergents of the present invention are formed when the non-quaternized detergents described above are reacted with a quater- nizing agent.
  • Suitable quaternizing agents include selected dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates; hydrocarbyl epoxides in combination with an acid or mixtures thereof.
  • the quaternizing agent can include alkyl halides, such as chlorides, iodides or bromides; alkyl sulphonates; dialkyl sulphates, such as, dimethyl sulphate; sultones; alkyl phosphates; such as, C I- 12 trial- kylphosphates; di C l -12 alkylphosphates; borates; C l-12 alkyl borates; alkyl nitrites; alkyl nitrates; dialkyl carbonates; alkyl alkanoates; 0,0-di-Cl -12 alkyldithiophosphates; or mixtures thereof.
  • alkyl halides such as chlorides, iodides or bromides
  • alkyl sulphonates such as, dimethyl sulphate
  • dialkyl sulphates such as, dimethyl sulphate
  • alkyl phosphates such as, C I- 12 trial- kylphosphate
  • the quaternizing agent may be derived from dialkyl sulphates such as dimethyl sulphate, N-oxides, sultones such as propane and butane sultone; alkyl, acyl or araalkyl halides such as methyl and ethyl chloride, bromide or iodide or benzyl chloride, and a hydrocarbyl (or alkyl) substituted carbonates. If the alkyl halide is benzyl chloride, the aromatic ring is optionally further substituted with alkyl or alkenyl groups.
  • dialkyl sulphates such as dimethyl sulphate, N-oxides, sultones such as propane and butane sultone
  • alkyl, acyl or araalkyl halides such as methyl and ethyl chloride, bromide or iodide or benzyl chloride, and a hydrocarbyl (or alkyl) substituted
  • 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.
  • 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.
  • the quaternizing agent can be a hydrocarbyl epoxide, as represented by t la, in combination with an acid:
  • R 1 , R 2 , R 3 and R 4 can be independently H or a hydrocarbyl group contain from 1 to 50 carbon atoms.
  • hydrocarbyl epoxides include: ethylene oxide, propylene oxide, butylene oxide, styrene oxide and combinations thereof.
  • the quaternizing agent does not contain any styrene oxide.
  • the acid used with the hydrocarbyl epoxide may be a separate component, such as acetic acid.
  • the hydrocarbyl acylating agent is a dicarboxylic acylating agent
  • the detergent may be prepared by combining reactants which are essentially free of, or even free of, a separate acid component, such as acetic acid, and rely on the acid group of the hydrocarbyl acylating agent instead.
  • a small amount of an acid component may be present, but at ⁇ 0.2 or even ⁇ 0.1 moles of acid per mole of hydrocarbyl acylating agent.
  • These acids may also be used with the other quaternizing agents described above, including the hydrocarbyl substituted carbonates and related materials described below.
  • the quaternizing agent of the invention does not contain any substituent group that contains more than 20 carbon atoms.
  • the long substituent group that allows for the resulting additive to be organic soluble and thus useful for the purposes of this invention is not provided by the quaternizing agent but instead is brought to the additive by the non-quaternized detergents described above.
  • the molar ratio of detergent having an amine functionality to quaternizing agent is 1 :0.1 to 2, or 1 : 1 to 1.5, or 1 : 1 to 1.3.
  • the quaternizing agent can be an ester of a carboxylic acid capable of reacting with a tertiary amine to form a quaternary ammonium salt, or an ester of a polycarboxylic acid.
  • ester of a carboxylic acid capable of reacting with a tertiary amine to form a quaternary ammonium salt
  • polycarboxylic acid an ester of a polycarboxylic acid.
  • such materials may be described as compounds having the structure:
  • R 19 -C( 0)-0-R 20 (IX) where R 19 is an optionally substituted alkyl, alkenyl, aryl or alkylaryl group and R 20 is a hydro carbyl group containg from 1 to 22 carbon atoms.
  • Suitable compounds include esters of carboxylic acids having a pKa of 3.5 or less.
  • the compound is an ester of a carboxylic acid selected from a substituted aromatic carboxylic acid, an a-hydroxycarboxylic acid and a polycarboxylic acid.
  • the compound is an ester of a substituted aromatic carboxylic acid and thus R 19 is a subsituted aryl group.
  • R may be a substituted aryl group having 6 to 10 carbon atoms, a phenyl group, or a naph- thyl group.
  • R may be suitably substituted with one or more groups selected from carboalkoxy, nitro, cyano, hydroxy, SR " or NR R " where each of R “ and R “ may independently be hydrogen, or an optionally substituted alkyl, alkenyl, aryl or carboalkoxy groups.
  • R “ and R " are each independently hydrogen or an optionally substituted alkyl group containing from 1 to 22, 1 to 16, 1 to 10, or even 1 to 4 carbon atoms.
  • R 19 in the formula above is an aryl group substitut- ed with one or more groups selected from hydroxyl, carboalkoxy, nitro, cyano and
  • R 19 may be a poly-substituted aryl group, for example trihydroxyphenyl, but may also be a mono-substituted aryl group, for example an ortho substituted aryl group.
  • R 19 may be substituted with a group selected from OH, NH 2 , N0 2 , or COOMe.
  • R 19 is a hydroxy substituted aryl group.
  • R 19 is a 2-hydroxyphenyl group.
  • R 20 may be an alkyl or alkylaryl group, for example an alkyl or alkylaryl group containing from 1 to 16 carbon atoms, or from 1 to 10, or 1 to 8 carbon atoms.
  • R 20 may be methyl, ethyl, propyl, butyl, pentyl, benzyl or an isomer thereof. In some embodiments R is benzyl or methyl. In some embodiments the quaternizing agent is methyl salicylate.
  • the quaternizing agent is an ester of an alpha- hydroxycarboxylic acid.
  • suitable compounds which contain the residue of an alpha-hydroxycarboxylic acid include (i) methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of 2-hydroxyisobutyric acid; (ii) methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of 2-hydroxy-2-methylbutyric acid; (iii) methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, phenyl
  • the quaternizing agent comprises an ester of a polycarboxylic acid.
  • the esters are alkyl esters with alkyl groups that contain from 1 to 4 carbon atoms. Suitable example include diesters of oxalic acid, diesters of phthalic acid, diesters of maleic acid, diesters of malonic acid or diesters or triesters of citric acid.
  • the quaternizing agent is an ester of a carboxylic acid having a pKa of less than 3.5.
  • the quaternizing agent 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 quaternizing agent includes dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.
  • Suitable acids include carboxylic acids, such as acetic acid, propionic acid, 2-ethylhexanoic acid, and the like.
  • the quaternized salt detergents of the present invention may be used as an additive in various types of compositions, including fuel compositions and additive concentrate compositions.
  • the quaternized detergents of the present invention may be used as an additive in fuel compositions.
  • the fuel compositions of the present invention comprise the quaternized detergent additive described above and a liquid fuel, and is useful in fueling an internal combustion engine or an open flame burner. These compositions may also contain one or more additional additives. These optional additives are described below.
  • the fuels suitable for use in the present invention include any commercially available fuel, and in some embodiments any commercially available diesel fuel and/or biofuel.
  • Fuels suitable for use in the present invention are not overly limited. Generally, suitable fuels are normally liquid at ambient conditions e.g., room temperature (20 to 30°C) or are normally liquid at operating conditions.
  • the fuel can be a hydrocarbon fuel, non-hydrocarbon fuel, or mixture thereof.
  • the hydrocarbon fuel can be a petroleum distillate, including a gasoline as defined by ASTM specification D4814, or a diesel fuel, as defined by ASTM specification D975.
  • the liquid fuel is a gasoline, and in another embodiment the liquid fuel is a non-leaded gasoline.
  • the liquid fuel is a diesel fuel.
  • the hydrocarbon fuel can be a hydrocarbon prepared by a gas to liquid process to include for example hydrocarbons prepared by a process such as the Fischer-Tropsch process, and option- ally hydro-isomerized.
  • the fuel used in the present invention is a diesel fuel, a biodiesel fuel, or combinations thereof.
  • Suitable fuels also include heavier fuel oils, such as number 5 and number 6 fuel oils, which are also referred to as residual fuel oils, heavy fuel oils, and/or furnace fuel oils. Such fuels may be used alone or mixed with other, typically lighter, fuels to form mixtures with lower viscosities. Bunker fuels are also included, which are generally used in marine engines. These types of fuels have high viscosities and may be solids at ambient conditions, but are liquid when heated and supplied to the engine or burner it is fueling.
  • the non-hydrocarbon fuel can be an oxygen containing composition, often referred to as an oxygenate, which includes alcohols, ethers, ketones, esters of a carboxylic acids, nitroalkanes, or mixtures thereof.
  • oxygenate which includes alcohols, ethers, ketones, esters of a carboxylic acids, nitroalkanes, or mixtures thereof.
  • Non-hydrocarbon fuels can include methanol, ethanol, methyl t-butyl ether, methyl ethyl ketone, transesterified oils and/or fats from plants and animals such as rapeseed methyl ester and soybean methyl ester, and nitromethane.
  • Mixtures of hydrocarbon and non-hydrocarbon fuels can include, for example, gasoline and methanol and/or ethanol, diesel fuel and ethanol, and diesel fuel and a transesterified plant oil such as rapeseed methyl ester and other bio-derived fuels.
  • the liquid fuel is an emulsion of water in a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof.
  • the liquid fuel can have a sulphur content on a weight basis that is 50,000 ppm or less, 5000 ppm or less,
  • the liquid fuel of the invention is present in a fuel composition in a major amount that is generally greater than 95% by weight, and in other embod- iments is present at greater than 97% by weight, greater than 99.5% by weight, greater than 99.9% by weight, or greater than 99.99% by weight.
  • Additive concentrates are compositions that contain one or more additives and which may also contain some amount of fuel, oil, or a diluent of some type. These concentrates can then be added to other compositions as a convenient way to handle and deliver the additives, resulting in the final compositions such as the fuel compositions described above.
  • the additive concentrate compositions of the present invention contain one or more of the quaternized detergents described above and an optional diluent, which may be any of the fuels described above, a solvent, a diluent oil, or similar material. These compositions may also contain one or more of the additional additives described below.
  • compositions of the present invention include the quaternized detergents described above and may also include one or more additional additives.
  • additional performance additives can be added to any of the compo- sitions described depending on the results desired and the application in which the composition will be used.
  • any of the additional performance additives described herein can be used in any of the compositions of the invention, the following additional additives are particularly useful for fuel compositions: antioxidants, corrosion inhibitors, detergent and/or dispersant additives other than those described above, cold flow improvers, foam inhibitors, demulsifiers, lubricity agents, metal deactivators, valve seat recession additives, biocides, antistatic agents, deicers, fluidizers, combustion improvers, seal swelling agents, wax control polymers, scale inhibitors, gas-hydrate inhibitors, or any combination thereof.
  • Suitable antioxidants include for example hindered phenols or derivatives thereof and/or diarylamines or derivatives thereof.
  • Suitable deter- gent/dispersant additives include for example polyetheramines or nitrogen containing detergents, including but not limited to PIB amine deter- gents/dispersants, succinimide detergents/dispersants, and other quaternary salt detergents/dispersants including polyisobutylsuccinimide-derived quaternized PIB/amine and/or amide dispersants/detergents.
  • Suitable cold flow improvers include for example esterified copolymers of maleic anhydride and styrene and/or copolymers of ethylene and vinyl acetate.
  • Suitable demulsifiers include for example polyalkoxylated alcohols.
  • Suitable lubricity agents include for example fatty carboxylic acids.
  • Suitable metal deactivators include for example aromatic triazoles or derivatives thereof, including but not limited to benzotria- zole.
  • Suitable valve seat recession additives include for example alkali metal sulfosuccinate salts.
  • Suitable foam inhibitors and/or antifoams include for example organic silicones such as polydimethyl siloxane, polyethylsiloxane, polydiethylsiloxane, polyacrylates and polymethacrylates, trimethyl-triflouro- propylmethyl siloxane and the like.
  • Suitable fluidizers include for example mineral oils and/or poly(alpha-olefms) and/or polyethers.
  • Combustion improvers include for example octane and cetane improvers.
  • the additional performance additives which may be present in the compositions of the invention, also include di-ester, di-amide, ester-amide, and ester-imide friction modifiers prepared by reacting a dicarboxylic acid (such as tartaric acid) and/or a tricarboxylic acid (such as citric acid), with an amine and/or alcohol, optionally in the presence of a known esterification catalyst.
  • a dicarboxylic acid such as tartaric acid
  • a tricarboxylic acid such as citric acid
  • These friction modifiers often derived from tartaric acid, citric acid, or derivatives thereof, may be derived from amines and/or alcohols that are branched, resulting in friction modifiers that themselves have significant amounts of branched hydrocarbyl groups present within it structure.
  • suitable branched alcohols used to prepare such friction modifiers include 2-ethylhexanol, isotridecanol, Guerbet alcohols, and mixtures thereof.
  • the additional performance additives may comprise a high TBN nitrogen containing detergent/ dispersant, such as a succinimide, that is the condensation product of a hydrocarbyl-substituted succinic anhydride with a poly(alkyleneamine).
  • a high TBN nitrogen containing detergent/ dispersant such as a succinimide
  • succinimide that is the condensation product of a hydrocarbyl-substituted succinic anhydride with a poly(alkyleneamine.
  • Succinimide detergents/dispersants are more fully described in U.S. patents 4,234,435 and 3, 172,892.
  • Another class of ashless dispersant is high molecular weight esters, prepared by reaction of a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol such as glycerol, pentaerythri- tol, or sorbitol. Such materials are described in more detail in U.S. Patent 3,381 ,02
  • Mannich bases Another class of ashless dispersant is Mannich bases. These are materials which are formed by the condensation of a higher molecular weight, alkyl substituted phenol, an alkylene polyamine, and an aldehyde such as formal- dehyde and are described in more detail in U.S. Patent 3,634,515.
  • Other disper- sants include polymeric dispersant additives, which are generally hydrocarbon- based polymers which contain polar functionality to impart dispersancy charac- teristics to the polymer.
  • An amine is typically employed in preparing the high TBN nitrogen-containing dispersant.
  • One or more poly(alkyleneamine)s may be used, and these may comprise one or more poly(ethyleneamine)s having 3 to 5 ethylene units and 4 to 6 nitrogen units.
  • Such materials include tri ethyl en etet- ramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA).
  • TETA tri ethyl en etet- ramine
  • TEPA tetraethylenepentamine
  • PEHA pentaethylenehexamine
  • Such materials are typically commercially available as mixtures of various isomers containing a range number of ethylene units and nitrogen atoms, as well as a variety of isomeric structures, including various cyclic structures.
  • the poly(alkyleneamine) may likewise comprise relatively higher molecular weight amines known in the industry as ethylene amine still bottoms.
  • Dispersants can also be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in U.S. Patent 4,654,403.
  • compositions of the invention may include a detergent additive, different from the quaternized salt additive of the invention.
  • a detergent additive used in the field of engine lubrication obtain most or all of their basicity or TBN from the presence of basic metal-containing compounds (metal hydroxides, oxides, or carbonates, typically based on such metals as calcium, magnesium, or sodium).
  • Such metallic overbased detergents also referred to as overbased or superbased salts, are generally single phase, homogeneous Newtonian systems characterized by a metal content in excess of that which would be present for neutralization according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
  • the overbased materials are typically prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid such as carbon dioxide) with a mixture of an acidic organic compound (also referred to as a substrate), a stoichiometric excess of a metal base, typically in a reaction medium of an one inert, organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for the acidic organic substrate. Typically also a small amount of promoter such as a phenol or alcohol is present, and in some cases a small amount of water.
  • the acidic organic substrate will normally have a sufficient number of carbon atoms to provide a degree of solubility in oil.
  • Patents describing techniques for making basic metallic salts of sulfonic acids, carboxylic acids, phenols, phos- phonic acids, and mixtures of any two or more of these include U.S. Patents 2,501 ,731 ; 2,616,905; 2,616,91 1 ; 2,616,925; 2,777,874; 3,256, 186; 3,384,585; 3,365,396; 3,320, 162; 3,318,809; 3,488,284; and 3,629, 109.
  • Salixarate detergents are described in U.S. patent 6,200,936.
  • Antioxidants encompass phenolic antioxidants, which may comprise a butyl substituted phenol containing 2 or 3 t-butyl groups. The para position may also be occupied by a hydrocarbyl group or a group bridging two aromatic rings. The latter antioxidants are described in greater detail in U.S. Patent 6,559, 105. Antioxidants also include aromatic amines, such as nonylated diphenylamine. Other antioxidants include sulfurized olefins, titanium compounds, and molybdenum compounds. U.S. Pat. No. 4,285,822, for instance, discloses lubricating oil compositions containing a molybdenum and sulfur containing composition.
  • antioxidants will, of course, depend on the specific antioxidant and its individual effectiveness, but illustrative total amounts can be 0.01 to 5, or 0.15 to 4.5, or 0.2 to 4 percent by weight. Additionally, more than one antioxidant may be present, and certain combinations of these can be synergistic in their combined overall effect.
  • Viscosity improvers may be included in the compositions of this invention.
  • Viscosity improvers are usually polymers, including polyisobutenes, polymethacrylates (PMA) and polymethacrylic acid esters, hydrogenated diene polymers, polyalkylstyrenes, esterified styrene-maleic anhydride copolymers, hydrogenated alkenylarene-conjugated diene copolymers and polyolefins.
  • PMA's are prepared from mixtures of methacrylate monomers having different alkyl groups.
  • the alkyl groups may be either straight chain or branched chain groups containing from 1 to 18 carbon atoms.
  • PMA's are viscosity modifiers as well as pour point depressants.
  • Multifunctional viscosity improvers which also have dispersant and/or antioxidancy properties are known and may optionally be used.
  • Dispersant viscosity modifiers are one example of such multifunctional additives. DVM are typically prepared by copolymerizing a small amount of a nitrogen- containing monomer with alkyl methacrylates, resulting in an additive with some combination of dispersancy, viscosity modification, pour point depressan- cy and dispersancy.
  • Vinyl pyridine, N-vinyl pyrrolidone and ⁇ , ⁇ '- dimethylaminoethyl methacrylate are examples of nitrogen-containing monomers.
  • Polyacrylates obtained from the polymerization or copolymerization of one or more alkyl acrylates also are useful as viscosity modifiers.
  • Anti-wear agents can in some embodiments include phosphorus- containing antiwear/extreme pressure agents such as metal thiophosphates, phosphoric acid esters and salts thereof, phosphorus-containing carboxylic acids, esters, ethers, and amides; and phosphites.
  • a phosphorus antiwear agent may be present in an amount to deliver 0.01 to 0.2 or 0.015 to 0.15 or 0.02 to 0.1 or 0.025 to 0.08 percent by weight phosphorus.
  • the antiwear agent is a zinc dialkyldithiophosphate (ZDP).
  • ZDP zinc dialkyldithiophosphate
  • suitable amounts may include 0.09 to 0.82 percent by weight.
  • Non-phosphorus- containing anti-wear agents include borate esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfu- rized olefins.
  • the fuel compositions of the invention are free of phosphorus-containing antiwear/extreme pressure agents.
  • any of the additional performance additives described above may be added to the compositions of the present invention. Each may be added directly to the additive and/or the compositions of the present invention, but they are generally mixed with the additive to form an additive composition, or concentrate, which is then mixed with fuel to result in a fuel composition. These various types of compositions are described in more detail above.
  • the amount of additional additives in the present composition can typically be 1 to 10 weight percent, or 1.5 to 9.0 percent, or 2.0 to 8.0 percent, all expressed on an oil-free basis.
  • the present invention provides a process of preparing quaternized amide and/or ester detergent where the process includes: reacting (a) a polyester containing a tertiary amino group; and (b) quaternizing agent suitable for converting the tertiary amino group to a quaternary nitrogen, thereby obtaining the quaternized dispersant.
  • the quaternizing agent may be selected from the group consisting of dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates; hydrocarbyl epoxides in combination with an acid or mixtures thereof.
  • the processes of the present invention may also be described as a process for preparing a quaternized detergent comprising the steps of: (1) mixing (a) a polyester containing a tertiary amino group, (b) a quaternizing agent and optionally (c) a protic solvent; (2) heating the mixture to a tempera- ture between 50°C to 130°C; and (3) holding for the reaction to complete; thereby obtaining the quaternized detergent.
  • the reaction is carried out at a temperature of less than 80°C, or less then 70°C.
  • the reaction mixture is heated to a temperature of about 50°C to 120°C, 80°C, or 70°C.
  • the reaction temperature may be 70°C to 130°C.
  • the reaction temperature may be 50°C to 80°C or 50°C to 70°C.
  • the processes of the present invention are free of the addition of any acid reactant, such as acetic acid.
  • the salt product is obtained in these embodiments despite the absence of the separate acid reactant.
  • the non-quaternized polyester containing a tertiary amino group is the condensation product of a fatty carboxylic acid containing at least one hydroxyl group and a compound having an oxygen or nitrogen atom capable of condensing with said acid and further having a tertiary amino group, thereby obtaining the polyester containing a tertiary amino group.
  • the compound having an oxygen or nitrogen atom capable of condensing with said acid and further having a tertiary amino group is a diamine containing a tertiary amino group and a primary or secondary amino group.
  • the additives of the present invention may be derived in the presence of a protic solvent.
  • Suitable protic solvents include solvents that have dielectric constants of greater than 9.
  • the protic solvent includes compounds that contain 1 or more hydroxyl (-OH) functional groups, and may include water.
  • the solvents are glycols and glycol ethers.
  • Glycols containing from 2 to 12 carbon atoms, or from 4 to 10, or 6 to 8 carbon atoms, and oligomers thereof (e.g., dimers, trimers and tetramers) are generally suitable for use.
  • Illustrative glycols include ethylene glycol, propylene glycol, di ethylene glycol, dipropylene glycol, 1 ,4-butanediol, 2-methyl- l ,3-propanediol, neopentyl glycol, triethylene glycol, polyethylene glycol and the like and oligomers and polymeric derivative and mixtures thereof.
  • Illustrative glycol ethers include the Ci-C 6 alkyl ethers of propylene glycol, ethylene glycol and oligomers thereof such as di-, tri- and tetra glycol ethers of methyl, ethyl, propyl, butyl or hexyl.
  • Suitable glycol ethers include ethers of dipropylene glycol, tripropylene glycol diethylene glycol, triethylene glycol; ethyl diglycol ether, butyl diethyleneglycol ether, methoxytriethyleneglycol, ethoxytriethy- leneglycol, butoxytriethyleneglycol, methoxytetraethyleneglycol, butoxytetra- ethyleneglycol.
  • Suitable solvents for use in the invention also include alcohols from C I -20 including branched hydrocarbyl alcohols.
  • suitable alcohols include 2-methylheptanol, 2-methyldecanol, 2-ethylpentanol, 2-ethylhexanol, 2- ethylnonanol, 2-propylheptanol, 2-butylheptanol, 2-butyloctanol, isooctanol, dodecanol, cyclohexanol, methanol, ethanol, propan-l-ol, 2-methylpropan-2-ol, 2-methylpropan-l -ol, butan-l-ol, butan-2-ol, pentanol and its isomers, and mixtures thereof.
  • the solvent of the present invention is 2- ethylhexanol, 2-ethyl nonanol, 2-propylheptanol, or combinations thereof. In one embodiment the solvent of the present invention includes 2-ethylhexanol.
  • the solvent can be any of the commercially available alcohols or mixtures of such alcohols and also includes such alcohols and mixtures of alcohols mixed with water.
  • water is the only solvent used.
  • the amount of water present may be above 1 percent by weight of the solvent mixture.
  • the solvent mixture may contain traces of water, with the water content being less than 1 or 0.5 percent by weight.
  • the alcohols can be aliphatic, cycloaliphatic, aromatic, or heterocyclic, including aliphatic-substituted cycloaliphatic alcohols, aliphatic-substituted aromatic alcohols, aliphatic-substituted heterocyclic alcohols, cy clo aliphatic - substituted aliphatic alcohols, cycloaliphatic-substituted aromatic alcohols, cycloaliphatic-substituted heterocyclic alcohols, heterocyclic-substituted aliphatic alcohols, heterocyclic-substituted cycloaliphatic alcohols, and heterocyclic-substituted aromatic alcohols.
  • a polar protic solvent (which may include water) is required in order to facilitate the dissociation of the acid into ions and protons.
  • the dissociation is required to protonate the ion formed when the detergent having an amine functionality initially reacts with the quaternizing agent.
  • the quaternizing agent is an alkyl epoxide the resulting ion would be an unstable alkoxide ion.
  • the dissociation also provides a counter ion from the acid group of the additive that acts to stabilize the quaternary ammonium ion formed in the reaction, resulting in a more stable product.
  • the process of the present invention produces a quaternized salt detergent.
  • the quaternized detergent can be used as an additive for use in a fuel for use in an internal combustion engine and/or an open flame burner.
  • the internal combustion engine includes spark ignition and compression ignition engines; 2-stroke or 4-stroke cycles; liquid fuel supplied via direct injection, indirect injection, port injection and carburetor; common rail and unit injector systems; light (e.g. passenger car) and heavy duty (e.g. commercial truck) engines; and engines fuelled with hydrocarbon and non-hydrocarbon fuels and mixtures thereof.
  • the engines may be part of integrated emissions systems incorporating such elements as; EGR systems; aftertreatment including three- way catalyst, oxidation catalyst, NOx absorbers and catalysts, catalyzed and non-catalyzed particulate traps optionally employing fuel-borne catalyst; variable valve timing; and injection timing and rate shaping.
  • the open flame burner burning may be any open-flame burning apparatus equipped to burn a liquid fuel. These include domestic, commercial and industrial burners. The industrial burners include those requiring preheating for proper handling and atomization of the fuel. Also included are oil fired combustion units, oil fired power plants, fired heaters and boilers, and boilers for use in ships and marine applications including deep draft vessels. Included are boilers for power plants, utility plants, and large stationary and marine engines.
  • the op en- flame fuel burning apparatus may be an incinerator such as rotary kiln incinerator, liquid injection kiln, fluidized bed kiln, cement kiln, and the like. Also included are steel and aluminum forging furnaces.
  • the open- flame burning apparatus may be equipped with a flue gas recirculation system.
  • 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.
  • hydro- carbyl groups include: hydrocarbon substituents, that is, aliphatic (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 substituents, 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 (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); hetero substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this
  • Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
  • 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 hydro- carbyl group; typically, there will be no non-hydrocarbon substituents in the hydro- carbyl group.
  • hydro carbonyl group or "hydrocarbonyl substituent” means a hydrocarbyl group containing a carbonyl group.
  • a non-quaternized polyester amide is prepared by reacting, in a jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to subline addition pipe, nitrogen line and thermocouple/temperature controller system, 6 moles of 12-hydroxystearic acid and 1 mole of dimethylaminopropylamine where the reaction is carried out at about 130°C and held for about 4 hours.
  • the reaction mixture is then cooled to about 100°C and zirconium butoxide is added, in an amount so that the catalyst makes up 0.57 percent by weight of the reaction mixture.
  • the reaction mixture is heated to about 195°C and held for about 12 hours.
  • the resulting product is cooled and collected.
  • a quaternized polyester amide salt detergent is prepared by reacting, in a jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to subline addition pipe, nitrogen line and thermocouple/temperature controller system, 600 grams of the non-quaternized polyester amide of Example A, 120 grams of 2-ethylhexanol, 18.5 grams of acetic acid, and 32.3 ml of propylene oxide, where the reaction is carried out at about 75°C and the propylene oxide is fed in to the reaction vessel over about 3.5 hours. The reaction mixture is then held at temperature for about 3 hours.
  • TAN, FTIR and ESI-MS analysis confirms to be about 80% by weight quaternized polyester amide salt detergent, with the remaining material being primarily non-quaternized polyester amide.
  • the collected material has a TAN of 1.26 mg KOH/gram, a TBN of 23.82 mg KOH/gram, a kinematic viscosity at 100°C of 28.58 cSt (as measured by ASTM D445), an acetate peak by IR at 1574 cm "1 , and is 1.22% nitrogen.
  • a non-quaternized polyester amide is prepared by reacting, in a jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to subline addition pipe, nitrogen line and thermocouple/temperature controller system, 1300 grams of ricinoleic acid and 73.5 grams of dimethylaminopropylamine where the reaction is carried out at about 130°C, the amine is added dropwise over about 8 minutes, and the reaction mixture held for about 4 hours. The reaction mixture is then cooled to about 100°C and 7.8 grams of zirconium butoxide is added. The reaction mixture is heated to about 195°C and held for about 17 hours. The resulting product is filtered, cooled and collected. 1301 grams of product is collected which has a TAN of 0 mg KOH/gram and shows by IR an ester peak at 1732 cm "1 , an amide peak at 1654 cm “1 , but no acid peak at 1700 cm “1 .
  • a quaternized polyester amide salt detergent is prepared by reacting, in a jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to subline addition pipe, nitrogen line and thermocouple/temperature controller system, 600 grams of the non-quaternized polyester amide of Example C, 123 grams of 2-ethylhexanol, 18.9 grams of acetic acid, and 33.1 ml of propylene oxide, where the reaction is carried out at about 75°C and the propylene oxide is fed in to the reaction vessel over about 3.5 hours. The reaction mixture is then held at tempera- ture for about 3 hours.
  • TAN, FTIR and ESI-MS analysis confirms to be about 70%> by weight quaternized polyester amide salt detergent, with the remaining material being primarily non-quaternized polyester amide.
  • the collected material has a TAN of 0 mg KOH/gram, a TBN of 23.14 mg KOH/gram, a kinematic viscosity at 100°C of 47.0 cSt (as measured by ASTM D445), an acetate peak by IR at 1574 cm "1 .
  • a non-quaternized polyisobutylene monosuccinimide detergent is prepared by reacting, in a jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to subline addition pipe, nitrogen line and thermocouple/temperature controller system, 100 pbw polyisobutylene succinic anhydride (which is itself prepared from 1000 number average molecular weight high vinyli- dene polyisobutylene and maleic anhydride reaction in a 1 : 1.2 molar ratio) 13 pbw tetraethylenepentamine, where the anhydride is preheated to about 80°C, the amine is added to the system over about 8 hours, where the reaction mixture temperature is kept below 120°C. The reaction mixture is then heated to 170°C and then vacuum stripped. The resulting non-quaternized polyisobutylene monosuccinimide detergent is cooled and collected.
  • a quaternized polyisobutylene succinimide detergent is prepared by reacting, in a jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to subline addition pipe, nitrogen line and thermocouple/temperature controller system, 100 pbw polyisobutylene succinic anhydride (which is itself prepared from 1000 number average molecular weight high vinylidene polyisobutylene and maleic anhydride reaction in a 1 : 1.2 molar ratio) 10.9 pbw dimethyl a- minopropylamine, where the anhydride is preheated to about 80°C, the amine is added to the system over about 8 hours, where the reaction mixture temperature is kept below 120°C.
  • 100 pbw polyisobutylene succinic anhydride which is itself prepared from 1000 number average molecular weight high vinylidene polyisobutylene and maleic anhydride reaction in a 1 : 1.2 molar ratio
  • Example B additive performs about as well as the quaternized polyisobutylene succinimide detergent of Example F and much better than the non-quaternized polyisobutylene succinimide detergent of Example E. All of the examples perform better than the base fuel alone, however the additives of Examples B and F perform significantly better that the base fuel.
  • the DW-10 screen test uses the Coordinating European Council's (CEC) F-98-08 testing protocol, which utilizes a Peugeot DW-10 engine. This is a light duty direct injection, common rail engine test that measures engine power loss, which relates to fuel detergent additive efficiency. Lower power loss values indicate better detergent performance.
  • the test engine is representative of new engines coming into the market.
  • Each composition uses the same base fuel and contains 71 ppm, on an actives basis, of the additive being evaluated. The results obtained are as follows:
  • Example B and D additives performs about as well as the quatemized polyisobutylene succinimide detergent of Example F and much better than the non-quaternized polyisobutylene succinimide detergent of Example E. All of the examples perform better than the base fuel alone, however the additives of Examples B, D and F perform significantly better that the base fuel.
  • Examples B, D and F were tested for viscosity at their original actives levels, about 85% actives for Example B and D, and about 75% actives for Example F.
  • Examples B and D were also tested for viscosity at 75% actives, all on a weight basis, to allow for a better comparison to Example F.
  • the reduced actives samples are prepared by mixing the example additive with an appropriate amount of 2-ethylhexanol. The viscosities of these blends were then determined using ASTM D445. The results obtained are presented below: Table 3 - Viscometric Data
  • a quaternized polyester amide salt detergent is prepared by reacting, in a jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to subline addition pipe, nitrogen line and thermocouple/temperature controller system, 3501 grams of the non-quaternized polyester amide of Example A, 80.4 grams of acetic acid, 24.5 grams of water, and 141.3 ml of propylene oxide, where the reaction is carried out at about 75°C and the propylene oxide is fed in to the reaction vessel over about 4 hours with moderate stirring. The reaction mixture is then held at temperature for about 3 hours.
  • TAN 0 mg KOH/gram
  • TBN 27.76 mg KOH/gram
  • kinematic viscosity at 100°C 327.4 cSt (as measured by ASTM D445)
  • an acetate peak by IR at 1575 cm "1 , and is 1.42% nitrogen.
  • Example H- Quaternized Polyester Amide Salt Detergent (inventive example) [0117]
  • a quaternized polyester amide salt detergent is prepared by reacting, in a jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to subline addition pipe, nitrogen line and thermocouple/temperature controller system, 3401 grams of the non-quaternized polyester amide of Example C, 107.3 grams of acetic acid, 32.0 grams of water, and 1875.1 ml of propylene oxide, where the reaction is carried out at about 75°C and the propylene oxide is fed in to the reaction vessel over about 3.5 hours with moderate stirring. The reaction mixture is then held at temperature for about 3 hours.
  • TAN 0 mg KOH/gram
  • TBN 26.4 mg KOH/gram
  • kinematic viscosity at 100°C 201.3 cSt (as measured by ASTM D445)
  • an acetate peak by IR 1574 cm "1 , and is 1.33% nitrogen.
  • each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements. As used herein, the expression "consisting essentially of permits the inclusion of substances that do not materially affect the basic and novel characteristics of the composition under consideration.

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Abstract

La présente invention a pour objet des sels d'ammonium quaternaire de polyester, comprenant des sels d'amine, d'amide, et d'ester, leurs procédés de fabrication, et leur utilisation en tant qu'additifs, y compris leur utilisation dans des carburants, tels qu'un carburant diesel et des mazouts. La présente invention concerne en particulier l'utilisation de sels d'ammonium quaternaire de polyester en tant que détergents dans des carburants et leurs procédés de fabrication.
EP11791398.8A 2010-11-24 2011-11-21 Sels d'ammonium quaternaire de polyester Withdrawn EP2643384A1 (fr)

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US41676710P 2010-11-24 2010-11-24
PCT/US2011/061620 WO2012071313A1 (fr) 2010-11-24 2011-11-21 Sels d'ammonium quaternaire de polyester

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CN (1) CN103328537B (fr)
AU (1) AU2011332104B2 (fr)
BR (1) BR112013012792A2 (fr)
CA (1) CA2818753A1 (fr)
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BR112017015959B1 (pt) 2015-01-30 2022-11-08 The Lubrizol Corporation Composição para limpeza de sistemas de distribuição de combustível, sistemas de admissão de ar e câmaras de combustão, método para remover pelo menos um de depósitos de válvula de admissão de ar, depósitos de injetor de combustível, e depósitos de câmara de combustão interna, e, uso da composição
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JP7083310B2 (ja) 2015-12-03 2022-06-10 中国石油化工股▲ふん▼有限公司 アミン系ポリマー、その製造方法、およびその用途
TW201840635A (zh) * 2017-01-26 2018-11-16 美商盧伯利索先進材料有限公司 具有改良化學及熱安定性之含有一或二個四級胺錨定基的聚合分散劑
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KR102568029B1 (ko) 2023-01-06 2023-08-22 최승연 소음순 성형용 디자인 툴 및 이를 이용한 소음순 성형방법

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US20130239468A1 (en) 2013-09-19
CN103328537B (zh) 2015-05-27
CA2818753A1 (fr) 2012-05-31
SG190372A1 (en) 2013-06-28
AU2011332104A1 (en) 2013-06-13
BR112013012792A2 (pt) 2016-09-13
WO2012071313A1 (fr) 2012-05-31
KR20130117820A (ko) 2013-10-28
CN103328537A (zh) 2013-09-25

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