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
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
  • C08G65/2633—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen the other compounds containing amide groups
• • 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
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular 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, 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)
  • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and 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
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
• • 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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
  • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
• • 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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1857—Aldehydes; Ketones
• • 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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • 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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
• • 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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
• • 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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• • 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
  • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
• • 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
  • C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
• • 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)

Definitions

• the present invention relates to the use of multiple amide polyether alcohol compounds as additives in fuel compositions and the use of these compounds to decrease intake valve deposits, control octane requirement increases and reduce octane requirment.
• the present invention further relates to multiple amide polyether alcohol compounds.
• the accumulation of deposits on the intake valves of internal combustion engines presents a variety of problems .
• the accumulation of such deposits is characterized by overall poor driveability including hard starting, stalls, and stumbles during acceleration and rough engine idle.
• additives which can be added to hydrocarbon fuels to prevent or reduce deposit formation, or remove or modify formed deposits, in the combustion chamber and on adjacent surfaces such as intake valves, ports, and spark plugs, which in turn causes a decrease in octane requirement.
• the present invention is directed to the use of multiple amide polyether alcohol compounds as additives in fuel compositions comprising a major amount of a mixture of hydrocarbons in the gasoline boiling range and a minor amount of one or more multiple amide polyether alcohol compounds of Formula I :
• R, and R 2 are each independently selected from the group consisting of hydrocarbyl of 2 to 100 carbon atoms and substituted hydrocarbyl of 2 to 100 carbon atoms;
• R 3 and R 4 are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms, substituted hydrocarbyl of 1 to 100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms;
• R 5 is selected from the group consisting of alkylene of 2 to 20 carbon atoms and alkylene of 2 to 20 carbon atoms having at least one methylene group replaced by at least one oxygen atom or at least one acylated nitrogen atom; and
• x and y are each from 1 to 50.
• the invention is also directed to the use of multiple amide polyether alcohol compounds for decreasing intake valve deposits, controlling octane requirement increases and reducing octane requirement.
• the present invention is further directed to multiple amide polyether alcohol compounds. Description Of The Preferred Embodiments Compounds
• the compounds of the present invention are a new class of additives useful for hydrocarbon fuels, e.g., fuels in the gasoline boiling range and for preventing deposits in engines, while also decomposing during combustion to environmentally acceptable products.
• the compounds are also proposed for controlling octane requirement increases and reducing octane requirement.
• the compounds produce very little residue and are miscible with carriers and other detergents.
• Non-limiting illustrative embodiments of the compounds useful as additives in the instant invention include those of Formula I :
• R, and R 2 are each independently selected from the group consisting of hydrocarbyl of 2 to 100 carbon atoms and substituted hydrocarbyl of 2 to 100 carbon atoms; x is from 1 to 50; and y is from 1 to 50.
• R, and/or R 2 are hydrocarbyl of a relatively high number of carbon atoms, i.e., greater than about 50 carbon atoms, each will be represented by polymeric hydrocarbyls derived from polyisobutylene, polybutene, polypropylene or poly-alphaolefin.
• hydrocarbyl represents a radical formed by the removal of one or more hydrogen atoms from a carbon atom of a hydrocarbon (not necessarily the same carbon atom) .
• Useful hydrocarbyls are aliphatic, aromatic, acyclic or cyclic.
• the hydrocarbyls are aryl, alkyl, alkenyl or cycloalkyl and are straight-chain or branched-chain.
• hydrocarbyls include methyl, ethyl, butyl, pentyl, ethylpentyl, hexenyl, ethylhexyl, dimethylhexyl , octamethylene, octenylene, cyclooctylene, methylcycl ⁇ octylene, dimethylcyclooctyl, isooctyl, dodecyl, hexadecenyl , octyl, eicosyl, hexacosyl, triacontyl and phenylethyl .
• the hydrocarbyls utilized may also be substituted.
• substituted hydrocarbyl refers to any "hydrocarbyls" which contain a functional group such as carbonyl, carboxyl, nitro, amino, hydroxy (e.g. hydroxyethyl ) , oxy, cyano, sulfonyl, and sulfoxyl.
• a functional group such as carbonyl, carboxyl, nitro, amino, hydroxy (e.g. hydroxyethyl ) , oxy, cyano, sulfonyl, and sulfoxyl.
• the majority of the atoms, other than hydrogen, in substituted hydrocarbyls are carbon, with the heteroatoms (i.e., oxygen, nitrogen, sulfur) representing only a minority, 33% or less, of the total non-hydrogen atoms present.
• R, and Rs are each selected from hydrocarbyl of 2 to 50 carbon atoms and substituted hydrocarbyl of 2 to 50 carbon atoms. More preferably, R, and R 2 are each selected from hydrocarbyl of 2 to 20 carbon atoms and substituted hydrocarbyl of 2 to 20 carbon atoms. Particularily preferred compounds are those in which R, and Rj are each independently selected from hydrocarbyl selected from the group consisting of alkyl of 2 to 20 carbon atoms, more preferably alkyl of 2 to 4 carbon atoms, especially alkyl of 4 carbon atoms.
• Particularly preferred compounds of Formula I are those in which R, and R ⁇ are hydrocarbyl (geminal or vicinal) of the formula:
• R ⁇ , R 7 and R 8 are each independently selected from hydrogen, hydrocarbyl, as defined hereinbefore, of 1 to 98 carbon atoms and substituted hydrocarbyl, as defined hereinbefore, of 1 to 98 carbon atoms.
• Preferred R ⁇ , R- and R 8 groups are those independently selected from hydrogen, hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to 18 carbon atoms.
• R ⁇ and ? may be taken together to form a divalent linking hydrocarbyl group of 3 to 12 carbon atoms.
• R ⁇ , R ? and/or R 8 are substituted hydrocarbyl, they are preferably oxy- substituted hydrocarbyl.
• R, and R 2 are each selected from hydrocarbyl and substituted hydrocarbyl as represented by Formula II above wherein each R 8 is hydrogen and each R ⁇ is independently selected from hydrogen, alkyl of 1 to 18 carbon atoms and oxy-substituted hydrocarbyl of 1 to 18 carbon atoms, particularly those compounds wherein each R 8 is hydrogen and each R ⁇ is independently hydrogen or alkyl of 1 to 2 carbon atoms, especially those compounds wherein each R 8 is hydrogen and each R j is alkyl of 2 carbon atoms .
• R ⁇ is preferably an alkoxy-substituted alkylene of 1 to 18 carbon atoms or an aryloxy-sub ⁇ tituted alkylene of 1 to 18 carbon atoms.
• Particularly preferred alkoxy-substituted alkylene groups include ethylhexyleneoxymethylene , isopropoxymethylene, butoxymethylene and mixtures thereof.
• Particularly preferred aryl-substituted alkylene groups include nonylphenoxymethylene, phenoxymethylene and mixtures thereof.
• each x is from 1 to 50, preferably from 1 to 40, and even more preferably from 1 to 26.
• x will not have a fixed value but will instead be represented by a range of different values.
• x is considered to be a (number) average of the various values of x that are found in a given composition, which number has been rounded to the nearest integer.
• each R can be alkyl of four carbon atoms.
• the R,'s can differ and for instance, independently be alkyl from two to four carbon atoms.
• the R, ' s may be present in blocks, i.e., all x groups in which R, is alkyl of three carbon atoms will be adjacent, followed by all x groups in which R, is alkyl of two carbon atoms, followed by all x groups in which R, is alkyl of four carbon atoms.
• the R, ' s differ, they may also be present in any random distribution.
• each y is also from 1 to 50, preferably from 1 to 40, and even more preferably from 1 to 26.
• y will not have a fixed value but will instead be represented by a range of different values.
• y is considered to be a (number) average of the various values of y that are found in a given composition, which number has been rounded to the nearest integer.
• each R 2 can be alkyl of four carbon atoms.
• the R 2 's can differ and for instance, independently be alkyl from two to four carbon atoms.
• the R 2 's may be present in blocks, i.e., all y groups in which R j is alkyl of three carbon atoms will be adjacent, followed by all y groups in which R 2 is alkyl of two carbon atoms, followed by all y groups in which R 2 is alkyl of four carbon atoms.
• R, and R 2 will be the same and x and y will have the same value.
• R 3 and R 4 of Formula I are each independently selected from the group consisting of hydrocarbyl, as defined hereinbefore, of 1 to 100 carbon atoms, substituted hydrocarbyl, as defined hereinbefore, of 1 to 100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms.
• R 3 and/or R 4 are hydrocarbyl or substituted hydrocarbyl, each will preferably be independently selected from hydrocarbyl or substituted hydrocarbyl of 1 to 50 carbon atoms, more preferably of 1 to 20 carbon atoms and most preferably of 1 to 10 carbon atoms.
• R 3 and/or R 4 are hydrocarbyl of a relatively high number of carbon atoms, i.e., greater than about 50 carbon atoms, each will be represented by polymeric hydrocarbyls derived from polyisobutylene, polybutene, polypropylene or poly-alphaolefin.
• R 3 and R 4 are each independently selected from hydrocarbyl of 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms and more preferably 1 to 10 carbon atoms.
• Particularly preferred compounds are those in which when R 3 and R 4 are hydrocarbyl, they are selected from alkyl of 1 to 20 carbon atoms, preferably alkyl of 1 to 10 carbon atoms.
• R 3 and/or R 4 can also be polyoxyalkylene alcohol of 2 to 200 carbon atoms.
• R 3 and/or R 4 are polyoxyalkylene alcohol, they are preferably polyoxyalkylene alcohol of Formula IV: wherein each R, is independently selected from the group consisting of hydrocarbyl, as defined hereinbefore, of 2 to 100 carbon atoms and substituted hydrocarbyl, as defined hereinbefore, of 2 to 100 carbon atoms and z is from 1 to 50.
• each R is hydrocarbyl of a relatively high number of carbon atoms, i.e., greater than about 50 carbon atoms, each will be represented by polymeric hydrocarbyls derived from polyisobutylene, polybutene, polypropylene or poly-alphaolefin.
• each R is independently selected from hydrocarbyl of 2 to 50 carbon atoms and substituted hydrocarbyl of 2 to 50 carbon atoms. More preferably, each R, is independently selected from hydrocarbyl of 2 to 20 carbon atoms and substituted hydrocarbyl of 2 to 20 carbon atoms.
• Preferred compounds are those in which each R, is hydrocarbyl selected from the group consisting of alkyl of 2 to 20 carbon atoms, more preferably alkyl of 2 to 4 carbon atoms, especially alkyl of 4 carbon atoms .
• Particularly preferred compounds of Formula I are those in which when R 3 and/or R 4 are polyoxyalkylene alcohol of Formula IV, the R, of the polyoxyalkylene alcohol is hydrocarbyl (geminal or vicinal) of formula:
• R 10 , R u and R 12 are each independently selected from hydrogen, hydrocarbyl, as defined hereinbefore, of 1 to 98 carbon atoms or substituted hydrocarbyl, as defined hereinbefore, of 1 to 98 carbon atoms.
• Preferred R 10 , R u and R 12 groups . are those independently selected from hydrogen, hydrocarbyl of 1 to 18 carbon atoms or substituted hydrocarbyl of 1 to 18 carbon atoms.
• R 10 and R ⁇ or alternatively R 10 and R u , may be taken together to form a divalent linking hydrocarbyl group of 3 to 12 carbon atoms.
• R I0 , R ⁇ and/or R 12 are substituted hydrocarbyl, the are preferably oxy- substituted hydrocarbyl.
• the most preferred compounds of Formula I are those in which the Ro of the polyoxyalkylene alcohol is hydrocarbyl or substituted hydrocarbyl as represented by Formula V above wherein each R I2 is hydrogen and each R 10 is independently selected from hydrogen, alkyl of 1 to 18 carbon atoms and oxy- substituted hydrocarbyl of 1 to 18 carbon atoms, particularly those compounds where each R 12 is hydrogen and each R I0 is independently selected from hydrogen or alkyl of 1 to 2 carbon atoms, especially those compounds where each R 12 is hydrogen and each R 10 is alkyl of two carbon atoms .
• R l0 is preferably an alkoxy-substituted alkylene of 1 to 18 carbon atoms or an aryloxy-substituted alkylene of 1 to 18 carbon atoms.
• Particularly preferred alkoxy-substituted alkylene groups include ethylhexyleneoxymethylene , isopropoxymethylene, butoxymethylene and mixtures thereof.
• Particularly preferred aryl-substituted alkylene groups include nonylphenoxymethylene, phenoxymethylene and mixtures thereof.
• z is from 1 to 50, preferably from 1 to 40, and even more preferably from 1 to 26.
• z will not have a fixed value but will instead be represented by a range of different values.
• z is considered to be a (number) average of the various values of z that are found in a given composition, which number has been rounded to the nearest integer.
• each R can be alkyl of four carbon atoms.
• the R o 's can differ and for instance, independently be alkyl from two to four carbon atoms.
• the Ro's may be present in blocks, i.e., all z groups in which R, is alkyl of three carbon atoms will be adjacent, followed by all z groups in which Ro is alkyl of two carbon atoms, followed by all z groups in which R, is alkyl of four carbon atoms.
• the Ro's may also be present in any random distribution.
• R 3 and R 4 may differ or R 3 and R 4 can be the same. In the most preferred embodiments, R 3 and R 4 will be the same. In one preferred embodiment, R 3 and R 4 are selected from hydrocarbyl of 1 to 100 carbon atoms. When R 3 and R 4 are hydrocarbyl, preferably the sum of the values of x and y will not exceed 40, even more preferably, the sum of the values of x and y will not exceed 26. In the preferred embodiment when R 3 and R 4 are hydrocarbyl, x will preferably be from 1 to 13 and y will preferably be from 1 to 13. In an alternative preferred embodiment, R 3 and R 4 will be polyoxyalkylene alcohol of Formula
• R 3 and R 4 are polyoxyalkylene alcohol of Formula IV, preferably the sum of the values of x, y and both z' ⁇ (the z for R 3 and _R 4 ) will not exceed 40, even more preferably, the sum of the values of x, y and both z's will not exceed 26.
• x will preferably be from 1 to 13
• y will preferably be from 1 to 13
• each z will preferably be from 1 to 13.
• R 5 is selected from the group consisting of alkylene of 2 to 20 carbon atoms and alkylene of 2 to 20 carbon atoms having at least methylene group replaced by at least one oxygen atom or at least one acylated nitrogen atom.
• Rj is alkylene of 2 to 20 carbon atoms
• the alkylene may be in any form, including straight chained alkylenes or branched chained alkylenes.
• R 5 can be ethylene (-CH 2 -CH 2 -) , propylene ( ⁇ CH 2 -CH 2 -CH 2 -) or butylene (-CH 2 -
• R 5 is alkylene
• I CH 3 will be alkylene of 2 to 10 carbon atoms, even more preferably alkylene of 2 to 4 carbon atoms. s can also be alkylene of 2 to 20 carbon atoms in which at least one methylene group is replaced by at least one oxygen atom or at least one acylated nitrogen atom.
• R 5 has at least one methylene group replaced by at least one oxygen atom, R 5 will preferably be oxyalkylene having from 2 to 10 carbon atoms and from 1 to 4 oxygen atoms.
• ⁇ is oxyalkylene it will preferably be oxyalkylene of Formula VII:
• R 5 is a nitrogen-containing alkylene of 2 to 20 carbon atoms
• the nitrogen-containing alkylene will preferably be of Formula VIII:
• R 13 is alkyl of 1 to 18 carbon atoms, preferably alkyl of 1 to 8 carbon atoms and most preferably alkyl of 1 carbon atom.
• the present invention is also directed to compounds of Formula I wherein R,, R 2 , R 3 , R 4 , x and y are as defined hereinbefore .
• the compounds of Formula I have a weight average molecular weight of at least 600.
• the weight average molecular weight is from about 800 to about 4000, even more preferably from about 800 to about 2000.
• Typical compounds represented by Formula I include those listed by structure, along with the initiator used to make each, in Table 1.
• x is from 1 to 26 and y is from 1 to 26.
• the compounds of Formula I are illustratively prepared by alkoxylation, i.e., reacting an initiator selected from dia ide ⁇ , triamides, polya ides, amidoalcohols and polyamidoalcohols with one or more epoxides in the presence of a potassium compound.
• the compounds of Formula I are prepared utilizing initiators represented by the general formula:
• R 14 and R 15 are each independently selected from the group consisting of hydrogen and hydroxyalkyls of 2 to 100 carbon atoms
• R 16 and R, 7 are selected from the group consisting of hydrogen, hydrocarbyl, as defined hereinbefore, of 1 to 100 carbon atoms, substituted hydrocarbyl, as defined hereinbefore, of 1 to 100 carbon atoms and hydroxyalkyls of 2 to 100 carbon atoms
• R I8 is selected from the group consisting of alkylene of 2 to 20 carbon atoms and alkylene of 2 to 20 carbon atoms having at least one methylene group replaced with at least one oxygen or at least one acylated nitrogen atom (note that R 18 is defined the same as B ⁇ above).
• R 14 and R 15 are each independently selected from the group consisting of hydrogen and hydroxyalkyls of 2 to 50 carbon atoms. Even more preferably, R 14 and R 15 are each independently selected from the group consisting of hydrogen and hydroxyalkyls of 2 to 20 carbon atoms.
• R I6 and R I7 are each independently selected from the group consisting of hydrogen, hydrocarbyl of 1 to 50 carbon atoms, substituted hydrocarbyl of 1 to 50 carbon atoms and hydroxyalkyls of 2 to 50 carbon atoms.
• R, 6 and R 17 are each independently selected from the group consisting of hydrogen, hydrocarbyl of 1 to 20 carbon atoms, substituted hydrocarbyl of 1 to 20 carbon atoms and hydroxyalkyls of 2 to 20 carbon atoms .
• Non-limiting examples of initiators which are employed include diamides such as N,N'-ethylenebisstearamide, N,N'- bisacetamide and Diacetamide of JEFFAMINE® EDR-148; triamides such as Diethylenetriamine amide or diethylene triacetamide; polyamides such as triethylenetetramine amide and tetraethylenepentamine amide; and diamidoalcohols such as JEFFAMINE® EDR-148 gamma butyrolactone adduct; with diamidoalcohols being the most preferred.
• diamides such as N,N'-ethylenebisstearamide, N,N'- bisacetamide and Diacetamide of JEFFAMINE® EDR-148
• triamides such as Diethylenetriamine amide or diethylene triacetamide
• polyamides such as triethylenetetramine amide and tetraethylenepentamine amide
• diamidoalcohols such as JEFFAMINE® EDR-
• Select initiators are also available commercially, including, but not limited to, N,N'-ethylenebisstearamide (Kemanide® W-45, obtained from Witco Chemical Corporation), N,N'-ethylenebisstearamide (Kemanide® W- 40, obtained from Witco Chemical Corporation), N,N'- ethylenebisstearamide (Kemanide® W-39, obtained from Witco Chemical Corporation) and N,N'-ethylenebisoleamide (Kemanide® W- 20, obtained from Witco Chemical Corporation).
• the initiators may also be prepared by any of the methods known and described in the art.
• diamides can be formed by reacting a diamine with a carboxylic acid, ester or lactones (such as gamma-butyrolactone) .
• the one or more epoxides employed in the reaction with the initiators to prepare the compounds of Formula I contain from 2 to 100 carbon atoms, preferably from 2 to 50 carbon atoms, more preferably from 2 to 20 carbon atoms, most preferably from 2 to 4 carbon atoms.
• the epoxides may be internal epoxides such as 2,3 epoxides of the formula:
• R ⁇ R 7 , R 10 and R ⁇ are as defined hereinbefore or terminal epoxides such as 1,2 epoxides of the formula:
• R 6 , R g , R 10 and R 12 are as defined hereinbefore.
• Formulas X and XII correspond to geminal and vicinal hydrocarbyls for R, and R 2 while Formulas XI and XIII correspond to geminal and vicinal hydrocarbyls for Ro
• any one of R ⁇ and R 7 , R 10 and R ⁇ , R 6 and R 8 or R 10 and R 12 may be taken together to form a cycloalkylene epoxide or a vinylidene epoxide by forming a divalent linking hydrocarbyl group of 3 to 12 carbon atoms.
• suitable compounds of Formulas X, XI, XII and XIII will include compounds such as nonylphenyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, butyl glycidyl ether, alkyl C 12 -C 13 glycidyl ether, alkyl C 8 -C 10 glycidyl ether, 2- ethylhexyl glycidyl ether and isopropyl glycidyl ether.
• the terminal epoxides represented by Formulas XII and XIII are utilized. Ideally these terminal epoxides are 1 , 2-epoxyalkanes .
• Suitable 1,2- epoxyalkanes include 1 , 2-epoxyethane, 1 , 2-epoxypropane, 1,2- epoxybutane, 1 , 2-epoxydecane, 1, 2-epoxydodecane, 1,2- epoxyhexadecane, 1 , 2-epoxyoctadecane and mixtures thereof.
• the one or more epoxides and initiator are contacted at a ratio from about 7 : 1 to about 55:1 moles of epoxide per mole of initiator. Preferably, they are contacted at a molar ratio from about 10:1 to about 30:1, with the most preferred molar ratio being about 20:1.
• the reaction is carried out in the presence of potassium compounds which act as alkoxylation catalysts.
• Such catalysts are conventional and include potassium methoxide, potassium ethoxide, potassium hydroxide, potassium hydride and potassium-t-butoxide.
• the preferred catalysts are potassium hydroxide and potassium-t-butoxide.
• the catalysts are used in a base stable solvent such as alcohol, ether or hydrocarbons.
• the catalysts are employed in a wide variety of concentrations .
• the potassium compounds will be used in an amount from about 0.02% to about 5.0% of the total weight of the mixture, preferably from about 0.1% to about 2.0% of the total weight of the mixture, and most preferably about 0.2% of the total weight of the mixture.
• the reaction is conveniently carried out in a conventional autoclave reactor equipped with heating and cooling means.
• the process is practiced batchwise, continuously or semicontinuously .
• the manner in which the alkoxylation reaction is conducted is not critical to the invention.
• the initiator and potassium compound are mixed and heated under vacuum for a period of at least 30 minutes.
• the one or more epoxides are then added to the resulting mixture, the reactor sealed and pressurized with nitrogen, and the mixture stirred while the temperature is gradually increased.
• the temperature for alkoxylation is from about 80°C to about 180°C, preferably from about 100°C to about 150°C, and even more preferably from about 120°C to about 140°C.
• the alkoxylation reaction time is generally from about 2 to about 20 hours, although longer or shorter times are employed.
• the product of Formula I is normally liquid and is recovered by conventional techniques such as filtration and distillation.
• the product is used in its crude state or is purified, if desired, by conventional techniques such as aqueous extraction, solid absorption and/or vacuum distillation to remove any remaining impurities .
• the compounds of Formula I are prepared by reacting a carboxylic ester as described hereinbefore with a diaminoalcohol or diamine.
• other catalyst chemistry such as the use of acidic catalysts, can be employed to achieve the compounds of Formula I .
• Fuel Compositions The compounds of Formula I are useful as additives in fuel compositions which are burned or combusted in internal combustion engines.
• the fuel compositions of the present invention comprise a major amount of a mixture of hydrocarbons in the gasoline boiling range and a minor amount of one or more of the compounds of Formula I.
• the term "minor amount” means less than about 10% by weight of the total fuel composition, preferably less than about 1% by weight of the total fuel composition and more preferably less than about 0.1% by weight of the total fuel composition.
• Suitable liquid hydrocarbon fuels of the gasoline boiling range are mixtures of hydrocarbons having a boiling range of from about 25°C to about 232°C, and comprise mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons.
• Preferred are gasoline mixtures having a saturated hydrocarbon content ranging from about 40% to about 80% by volume, an olefinic hydrocarbon content from 0% to about 30% by volume and an aromatic hydrocarbon content from about 10% to about 60% by volume.
• the base fuel is derived from straight run gasoline, polymer gasoline, natural gasoline, dimer and trimerized olefins, synthetically produced aromatic hydrocarbon mixtures, or from catalytically cracked or thermally cracked petroleum stocks, and mixtures of these.
• the hydrocarbon composition and octane level of the base fuel are not critical.
• the octane level, (R+M)/2, will generally be above about 85.
• Any conventional motor fuel base can be employed in the practice of the present invention.
• hydrocarbons in the gasoline can be replaced by up to a substantial amount of conventional alcohols or ethers, conventionally known for use in fuels.
• the base fuels are desirably substantially free of water since water could impede a smooth combustion.
• the hydrocarbon fuel mixtures to which the invention is applied are substantially lead-free, but may contain minor amounts of blending agents such as methanol, ethanol, ethyl tertiary butyl ether, methyl tertiary butyl ether, and the like, at from about 0.1% by volume to about 15% by volume of the base fuel, although larger amounts may be utilized.
• blending agents such as methanol, ethanol, ethyl tertiary butyl ether, methyl tertiary butyl ether, and the like, at from about 0.1% by volume to about 15% by volume of the base fuel, although larger amounts may be utilized.
• the fuels can also contain conventional additives including antioxidants such as phenolics, e.g., 2,6-di-tert- butylphenol or phenylenediamine ⁇ , e.g., N,N'-di-sec-butyl-p- phenylenediamine, dyes, metal deactivators , dehazers such as polyester-type ethoxylated alkylphenol-formaldehyde resins.
• antioxidants such as phenolics, e.g., 2,6-di-tert- butylphenol or phenylenediamine ⁇ , e.g., N,N'-di-sec-butyl-p- phenylenediamine
• dyes e.g., N,N'-di-sec-butyl-p- phenylenediamine
• metal deactivators e.g., N,N'-di-sec-butyl-p- phenylenediamine
• Corrosion inhibitors such as a polyhydric alcohol ester of a succinic acid derivative having on at least one of its alpha- carbon atoms an unsubstituted or substituted aliphatic hydrocarbon group having from 20 to 500 carbon atoms, for example, pentaerythritol diester of polyisobutylene-substituted succinic acid, the polyisobutylene group having an average molecular weight of about 950, in an amount from about 1 ppm by weight to about 1000 ppm by weight, may also be present.
• the fuels can also contain antiknock compounds such as methyl cyclopentadienylmanganese tricarbonyl and orthoazidophenol as well as co-antiknock compounds such as benzoyl acetone.
• An effective amount of one or more compounds of Formula I are introduced into the combustion zone of the engine in a variety of ways to prevent build-up of deposits, or to accomplish the reduction of intake valve deposits or the modification of existing deposits that are related to octane requirement.
• a preferred method is to add a minor amount of one or more compounds of Formula I to the fuel .
• one or more compounds of Formula I are added directly to the fuel or are blended with one or more carriers and/or one or more additional detergents to form an additive concentrate which can be added at a later date to the fuel.
• each compound of Formula I is added in an amount up to about 1000 ppm by weight, especially from about 1 ppm by weight to about 600 ppm by weight based on the total weight of the fuel composition.
• the amount will be from about 50 ppm by weight to about 400 ppm by weight, and even more preferably from about 75 ppm by weight to about 250 ppm by weight based on the total weight of the fuel composition.
• the carrier when utilized, will have a weight average molecular weight from about 500 to about 5000.
• Suitable carriers include hydrocarbon based materials such as polyisobutylenes (PIB's), polypropylenes (PP's) and polyalphaolefins (PAO' ⁇ ); polyether based materials such as polybutylene oxides (poly BO' ⁇ ), polypropylene oxides (poly PO's), polyhexadecene oxides (poly HO's) and mixtures thereof (i.e., both (poly BO) + (poly PO) and (poly-BO-PO) ) ; and mineral oils such as Exxon Naphthenic 900 sus and high viscosity index (HVI) oils.
• the carrier is preferably selected from PIB's, poly BO's, and poly PO's, with poly BO's being the most preferred.
• the carrier concentration in the final fuel composition is up to about 1000 ppm by weight. When a carrier is present, the preferred concentration is from about 50 ppm by weight to about 400 ppm by weight, based on the total weight of the fuel composition.
• the fuel compositions of the present invention may also contain one or more additional detergents .
• additional detergents When additional detergents are utilized, the fuel compo ⁇ ition will comprise a mixture of a major amount of hydrocarbons in the gasoline boiling range as described hereinbefore, a minor amount of one or more compounds of Formula I as described hereinbefore and a minor amount of an additional detergent such as polyalkylenyl amines, Mannich amines, polyalkenyl succinimides , poly(oxyalkylene) carbamate ⁇ , poly(alkenyl )-N-substituted carbamate ⁇ and mixtures thereof.
• a carrier as described hereinbefore may also be included.
• the term "minor amount” means less than about 10% by weight of the total fuel composition, preferably less than about 1% by weight of the total fuel composition and more preferably less than about 0.1% by weight of the total fuel composition.
• the polyalkylenyl amine detergents utilized comprise at least one monovalent hydrocarbon group having at least 50 carbon atoms and at least one monovalent hydrocarbon group having at most five carbon atoms bound directly to separate nitrogen atoms of a diamine.
• Preferred polyalkylenyl amines are polyisobutenyl amines. Polyisobutenyl amines are known in the art and representative examples are di ⁇ closed in various U.S. Patents including U.S. Patent No. 3,753,670, U.S.
• polyisobutenyl amines for use in the present fuel composition include N-polyisobutenyl-N' ,N'-dimethyl-l, 3- dia inopropane (PIB-DAP) and OGA-472 (a polyisobutenyl ethylene diamine available commercially from Oronite) .
• PIB-DAP N-polyisobutenyl-N' ,N'-dimethyl-l, 3- dia inopropane
• OGA-472 a polyisobutenyl ethylene diamine available commercially from Oronite
• the Mannich amine detergents utilized comprise a condensation product of a high molecular weight alkyl- substituted hydroxyaromatic compound, an amine which contains an amino group having at least one active hydrogen atom (preferably a polyamine), and an aldehyde.
• a high molecular weight alkyl- substituted hydroxyaromatic compound preferably a polyamine
• an aldehyde preferably a polyamine
• Such Mannich amines are known in the art and are disclosed in U.S. Patent No. 4,231,759, incorporated herein by reference.
• the Mannich amine is an alkyl substituted Mannich amine.
• the polyalkenyl ⁇ uccinimide detergents comprise the reaction product of a dibasic acid anhydride with either a polyoxyalkylene diamine, a hydrocarbyl polyamine or mixtures of both. Typically the succinimide is sub ⁇ tituted with the polyalkenyl group but the polyalkenyl group may be found on the polyoxyalkylene diamine or the hydrocarbyl polyamine.
• Polyalkenyl succinimides are also known in the art and representative examples are disclosed in various U.S. Patents including U.S. Patent No. 4,810,261, U.S. Patent No. 4,852,993, U.S. Patent No. 4,968,321, U.S. Patent No.4, 985, 047 , U.S. Patent No. 5,061,291 and U.S. Patent No. 5,147,414, each incorporated herein by reference.
• the poly(oxyalkylene) carbamate detergents comprise an amine moiety and a poly(oxyalkylene) moiety linked together through a carbamate linkage, i.e.,
• poly(oxyalkylene) carbamates are known in the art and representative examples are disclosed in various U.S. Patents including, U.S. Patent No. 4,191,537, U.S. Patent No. 4,160,648, U.S. Patent No. 4,236,020, U.S. Patent No. 4,270,930, U.S. Patent No. 4,288,612 and U.S. Patent No. 4,881,945, each incorporated herein by reference.
• Particularly preferred poly(oxyalkylene) carbamate ⁇ for use in the present fuel composition include OGA-480 (a poly(oxyalkylene) carbamate which is available commercially from Oronite).
• poly( alkenyl )-N-sub ⁇ tituted carbamate detergents utilized are of the formula:
• R 1 is a hydrocarbyl or sub ⁇ tituted hydrocarbyl group
• Poly(alkenyl )-N-substituted carbamates are known in the art and are disclosed in U.S. Patent No. 4,936,868, incorporated herein by reference.
• the one or more additional detergents are added directly to the hydrocarbons, blended with one or more carriers, blended with one or more compounds of Formula I, or blended with one or more compounds of Formula I and one or more carriers before being added to the hydrocarbons .
• the concentration of the one or more additional detergents in the final fuel composition is generally up to about 1000 ppm by weight for each additional detergent.
• the preferred concentration for each additional detergent is from about 50 ppm by weight to about 400 ppm by weight, based on the total weight of the fuel composition, even more preferably from about 75 ppm by weight to about 250 ppm by weight, based on the total weight of the fuel composition.
• the invention further provides a proces ⁇ for decrea ⁇ ing intake valve deposits in engines utilizing the multiple amide polyether alcohols of the present invention.
• the process comprises supplying to and combusting or burning in an internal combustion engine a fuel composition comprising a major amount of hydrocarbons in the gasoline boiling range and a minor amount of one or more compounds of Formula I as described hereinbefore.
• the invention further provides a process for controlling octane requirement increase ⁇ in engines utilizing the multiple amide polyether alcohols of the present invention.
• the proces ⁇ compri ⁇ e ⁇ supplying to and combusting or burning in an internal combustion engine a fuel composition comprising a major amount of hydrocarbons in the gasoline boiling range and a minor amount of one or more compounds of Formula I as described hereinbefore.
• Octane requirement is the maximum octane number of a gasoline that presents trace knock in a given engine within the engine's normal operating range.
• An increase in octane requirement is generally experienced during mileage accumulation on a new engine. The increase is typically attributed to an increase in engine deposits.
• the test protocol for octane requirement increase control must establish the stable octane requirement of the base gasoline relative to a clean engine.
• Base gasoline is typically the te ⁇ t gasoline without additives or special treatment; however, it may be gasoline containing additives for a specific compari ⁇ on.
• Octane requirement increa ⁇ e control testing consists of operating an engine a ⁇ embled with clean combu ⁇ tion chambers and induction ⁇ y ⁇ tem component ⁇ on a test gasoline to octane stabilization, measuring the octane requirement at regular intervals.
• the octane requirement increase control is the difference between the stabilized octane requirement of the engine operated on test gasoline and that of the stabilized octane requirement of the engine on base gasoline.
• the invention still further provides a process for reducing octane requirement in engines utilizing the multiple amide polyether alcohols of the present invention.
• the process comprises supplying to and combusting or burning in an internal combustion engine a fuel composition comprising a major amount of hydrocarbons in the gasoline boiling range and a minor amount of one or more compounds of Formula I as described hereinbefore.
• Octane requirement reduction is the reduction of the octane requirement of an engine by the action of a particular gasoline, usually measured as a decrease from a stabilized octane requirement condition.
• Octane requirement reduction is a performance feature that demonstrates a reduction from the established octane requirement of a base gasoline in a given engine.
• Octane requirement reduction testing consists of operating an engine, which has achieved ⁇ table octane requirement using base gasoline, on a test gasoline for approximately 100 to 250 hours.
• Octane mea ⁇ urement ⁇ are made daily and octane requirement reduction i ⁇ a reduction of octane requirement from that of base gasoline .
• Several octane requirement reduction tests may be conducted in a series for fuel to fuel comparison, or test fuel to base fuel comparison, by re ⁇ tabilizing on base fuel between octane requirement reduction tests.
• the contribution of specific depo ⁇ its is determined by removing deposits of interest and remeasuring octane requirement immediately after the engine is warmed to operating temperature.
• the octane requirement contribution of the deposit is the difference in ratings before and after deposit removal.
• the multiple amide polyether alcohols used in the following examples were prepared by reacting an initiator with one or more epoxides in the presence of a potassium compound to produce compounds of Formula I having a weight average molecular weight from about 600 to about 4000.
• the weight average molecular weight (MW) was measured by gel permeation chromatography (GPC). Rotary evaporation under reduced pressure typically was conducted at a temperature from room temperature to 120°C.
• GPC gel permeation chromatography
• the Initiator from Step 1 (80 g) was mixed with potas ⁇ ium hydroxide (1.7 g in 1.78 water) and then ⁇ ubjected to rotary evaporation under reduced pre ⁇ ure at 80°C to remove water and form pota ⁇ ium salt.
• the mixture was then charged along with 1,2-epoxybutane (320 g, 4.4 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system.
• the autoclave reactor was sealed, purged of air with nitrogen and then pres ⁇ urized to 50 p ⁇ i with nitrogen at room temperature.
• the mixture wa ⁇ then heated to a temperature of 135°C-140°C for 6 hour ⁇ .
• Example 2 The initiator of Step 1 of Example 1 (JEFFAMINE® 148-gamma butyrolactone adduct, 95 g) was mixed with potassium hydroxide (1.7 g in 1.7 g water) and then subjected to rotary evaporation under reduced pressure to remove water and form potassium salt. The mixture was then charged along with 1,2-epoxybutane (505 g, 7.01 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor wa ⁇ sealed, purged of air with nitrogen and then pre ⁇ urized to 50 psi with nitrogen at room temperature. The mixture was then heated to a temperature of 137°C-140°C for 5 hours.
• 1,2-epoxybutane 505 g, 7.01 moles
• the autoclave reactor wa ⁇ ⁇ ealed, purged of air with nitrogen and pressurized with nitrogen to 50 psi at room temperature. The mixture was heated to 200°C for 6 hours. The autoclave reactor was then cooled to room temperature and excess gas was vented. The product was then subjected to rotary evaporation under reduced pressure to remove unreacted ethyl acetate. A light yellow solid (N,N' ⁇ ethylene bis-acetamide) showing 100% yield and purity by NMR analysis was obtained.
• the initiator of Step 1 (56 g, 0.25 mole), toluene (150 g) and potassium-t-butoxide (2.3 g) was subjected to rotary evaporation under reduced pressure at 80°C.
• the resulting mixture was then charged along with 1,2-epoxybutane (344 g, 4.8 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system.
• the autoclave reactor was sealed, purged of air with nitrogen and then pres ⁇ urized to 50 p ⁇ i with nitrogen at room temperature.
• the mixture wa ⁇ then heated to a temperature of 134°C-142°C for 10 hour ⁇ .
• Step 1 of Example 3 Ethylenediamine diacetamide, 67 g) , potas ⁇ ium-t-butoxide (3.1 g) and toluene (50 g) were mixed and subjected to rotary evaporation under reduced pressure to remove water and form potassium salt.
• the mixture was then charged along with 1,2-epoxybutane (533 g, 7.4 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system.
• the autoclave reactor was sealed, purged of air with nitrogen and pressurized with nitrogen to 50 psi at room temperature.
• the mixture was then heated to 125°C-129°C for 7 hours.
• Step 2-Butoxylation of Initiator The initiator of Step 1 (diethylene triacetamide, 82 g, 0.35 mole), potas ⁇ ium hydroxide (2.4 g in 2.0 g water) and toluene (10 g) were mixed and ⁇ ubjected to rotary evaporation under reduced pressure to remove water and form potassium salt. The mixture was then charged along with 1,2-epoxybutane (514 g, 7.1 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged of air with nitrogen and then pressurized to 50 psi with nitrogen at room temperature.
• Step 1- Preparation of Initiator JEFFAMINE® EDR-148 (obtained from Texaco Chemical Company, 148 g, 1.0 mole) and ethyl acetate (264 g, 3.0 moles) were charged into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system.
• the autoclave reactor was sealed, purged of air with nitrogen and pressurized with nitrogen to 50 psi at room temperature. The mixture was heated to 200°C for six hours.
• the resulting product was ⁇ ubjected to rotary evaporation under reduced pre ⁇ sure to remove unreacted ethyl acetate.
• a mixture of the Initiator of Step 1, (Diacetamide of JEFFAMINE® EDR-148, 73.5 g, 0.375 mole), pota ⁇ ium hydroxide (2.4 g in 2.0 g water) and toluene (10 g) wa ⁇ subjected to rotary evaporation under reduced pressure to remove water and form pota ⁇ ium salt.
• the resulting mixture was charged along with 1,2-epoxybutane (527 g, 7.3 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system.
• the autoclave reactor was sealed, purged of air with nitrogen and pressurized with nitrogen to 50 psi at room temperature.
• the base fuel utilized comprised either premium unleaded gasoline (PU) (90+ octane, [R+M/2]) and/or regular unleaded gasoline (RU) (85-88 octane, [R+M/2]).
• PU premium unleaded gasoline
• RU regular unleaded gasoline
• Those skilled in the art will recognize that fuels containing heavy catalytically cracked stock ⁇ , such as most regular fuels, are typically more difficult to additize in order to control deposits and effectuate octane requirement reduction and octane requirement increase control.
• the multiple amide polyether alcohol compounds utilized were prepared as indicated by Example number and were used at the concentration indicated in ppm by weight. The tests employed are described below and the results of the various test ⁇ are ⁇ et forth in the table ⁇ below.
• Intake Valve Deposit Test ⁇ Engine ⁇ from vehicles were installed in dynamometer cells in such a way as to simulate road operation using a cycle of idle, low speed and high speed components while carefully controlling specific operating parameters. Fuels with and without the compounds of Formula I were tested in a variety of engines having port fuel injection including a 3.3 L Dodge to determine the effectiveness of the instant compounds in reducing intake valve deposits ("L" refers to liter). Carbureted 0.359 L Hyundai generator engines were also utilized to determine the effectiveness of the instant compounds in reducing intake valve deposits . Before each test, the engine was inspected, the induction system components were cleaned and new intake valves were weighed and installed. The oil was changed and new oil and fuel filters, gaskets and spark plug ⁇ were installed.
• the tests were run in cycles consisting of idle, 35 mph and 65 mph for a period of 100 hours unless indicated otherwise.
• the tests were run in cycles consisting of a no load idle mode for one minute followed by a three minute mode with a load at 2200 rpm's for a period of 40 hour ⁇ unle ⁇ s indicated otherwise.
• the intake valves were removed and weighed.
• Intake valve deposit results from Honda generator engines and 3.3 L Dodge engines obtained using the multiple amide polyether alcohols of the present invention are included in the tables below. All test ⁇ of the compound ⁇ of the pre ⁇ ent invention were carried out with additive concentration ⁇ (the amount of Compound Example # used) of 200 parts per million (ppm) non-volatile matter (nv ) except where otherwise indicated. Base fuel results which have 0 ppm additive are also included for comparision purposes. The base fuel are indicated by the absence of a Compound Example # (indicated in the Compound Example # column by " —").

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Combustion & Propulsion (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Polyethers (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=8166361

Family Applications (1)

Country Status (6)

Family Cites Families (5)

• 1996
  • 1996-10-11 WO PCT/EP1996/004430 patent/WO1998016598A1/en not_active Application Discontinuation
  • 1996-10-11 CA CA002268116A patent/CA2268116A1/en not_active Abandoned
  • 1996-10-11 JP JP51793298A patent/JP2001505595A/ja active Pending
  • 1996-10-11 KR KR1019990703177A patent/KR20000049097A/ko not_active Application Discontinuation
  • 1996-10-11 AU AU72907/96A patent/AU7290796A/en not_active Abandoned
  • 1996-10-11 EP EP96934643A patent/EP0932655A1/de not_active Withdrawn

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events