WO1990007564A1 - Compositions lubrifiantes a base d'huile ou de carburant contenant des aminocarbamates de poly(oxypropylene) alkylphenyles de type ''a roue a aiguille'' a chaine sensiblement droite. - Google Patents

Compositions lubrifiantes a base d'huile ou de carburant contenant des aminocarbamates de poly(oxypropylene) alkylphenyles de type ''a roue a aiguille'' a chaine sensiblement droite. Download PDF

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Publication number
WO1990007564A1
WO1990007564A1 PCT/US1988/004710 US8804710W WO9007564A1 WO 1990007564 A1 WO1990007564 A1 WO 1990007564A1 US 8804710 W US8804710 W US 8804710W WO 9007564 A1 WO9007564 A1 WO 9007564A1
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WO
WIPO (PCT)
Prior art keywords
oxypropylene
aminocarbamate
carbon atoms
alkylphenyl poly
poly
Prior art date
Application number
PCT/US1988/004710
Other languages
English (en)
Inventor
Thomas F. Buckley, Iii
Original Assignee
Chevron Research Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chevron Research Company filed Critical Chevron Research Company
Priority to EP19890903547 priority Critical patent/EP0419488A4/en
Priority to AU32868/89A priority patent/AU633481B2/en
Priority to BR888807893A priority patent/BR8807893A/pt
Priority to JP89503274A priority patent/JPH03504376A/ja
Priority to PCT/US1988/004710 priority patent/WO1990007564A1/fr
Publication of WO1990007564A1 publication Critical patent/WO1990007564A1/fr
Priority to FI904247A priority patent/FI93441C/fi
Priority to KR90701956A priority patent/KR0120110B1/ko

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    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
    • 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
    • C08G65/2603—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 oxygen
    • C08G65/2606—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 oxygen containing hydroxyl groups
    • C08G65/2612—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 oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl 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
    • C10L1/18—Organic compounds containing oxygen
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • C10M133/18—Amides; Imides of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • hydrocarbon fuels These substances when used in internal combustion engines tend to form deposits on and around constricted areas of the engine contacted by the fuel.
  • Typical areas commonly and sometimes seriously burdened by the formation of deposits include carburetor ports, the throttle body and venturies, engine intake valves, etc.
  • Deposits adversely affect the operation of the vehicle. For example, deposits on the carburetor throttle body and venturies increase the fuel to air ratio of the gas mixture to the combustion chamber thereby increasing the amount of unburned hydrocarbon and carbon monoxide discharged from the chamber. The high fuel-air ratio also reduces the gas mileage obtainable from the vehicle.
  • detergent-type gasoline additives currently available which, to varying degrees, perform these functions. Three factors complicate the use of such detergent-type gasoline additives. First, with regard to automobile engines that require the use of nonleaded gasolines (to prevent disablement of catalytic converters used to reduce emissions), it has been found difficult to provide gasoline of high enough octane to prevent knocking and the
  • ORI degree of octane requirement increase
  • 3,144,311; 3,146,203; and 4,247,301 disclose lead-containing fuel compositions having reduced ORI properties.
  • the ORI problem is compounded by the fact that the most common method for increasing the octane rating of unleaded gasoline is to increase its aromatic content. This,
  • a third complicating factor relates to the lubricating oil compatibility of the fuel additive.
  • Fuel additives due to their higher boiling point over gasoline itself, tend to accumulate on surfaces in the combustion chamber of the engine. This accumulation of the additive eventually finds its way into the lubricating oil in the crankcase of the engine via a "blow-by" process and/or via cylinder
  • hydrocarbyl poly(oxypropylene) aminocarbamates are substantially more expensive than the hydrocarbyl poly(oxypropylene) aminocarbamates. This is because butylene oxide is much more expensive than propylene oxide. Currently, the price for butylene oxide (BO) is more than four times the price of propylene oxide (PO) on a pound for pound basis. However, because heretofore no known hydrocarbyl poly(oxypropylene) aminocarbamate was found to be sufficiently lubricating oil compatible and non-waxy, it was necessary to employ the more expensive hydrocarbyl poly(oxybutylene) aminocarbamates which are sufficiently lubricating oil compatible. Accordingly, it would be particularly advantageous to develop hydrocarbyl
  • poly(oxypropylene) aminocarbamates which are compatible in lubricating oil compositions and are non-waxy at -40oC.
  • the instant invention is directed to lubricating oil
  • compositions and fuel compositions containing a novel class of hydrocarbyl poly(oxypropylene) aminocarbamates are also liquids which do not fo.rm a wax at -40oC in a 50 weight percent solution with toluene.
  • U.S. Patent No. 4,160,648 discloses an intake system deposit control additive for fuels which is a hydrocarbyl poly(oxyalkylene) aminocarbamate wherein the hydrocarbyl is from 1 to 30 carbon atoms including alkyl or
  • alkylphenyl groups include tetrapropenylphenyl, olelyl and a mixture of C 16 , C 18 and C 20 alkyl groups.
  • U.S. Patent No. 4,288,612 discloses deposit control additives for gasoline engines which are hydrocarbyl poly(oxyalkylene) aminocarbamates wherein the hydrocarbyl group contains from 1 to about 30 carbon atoms including alkylphenyl groups wherein the alkyl group is straight or branched chain of from 1 to about 24 carbon atoms.
  • U.S. Patent No. 4,568,358 discloses diesel fuel compositions containing an additive such as a hydrocarbyl poly( oxyalkylene)
  • hydrocarbyl groups such as alkyl groups of 1 to 30 carbon atoms; aryl groups of 6 to 30 carbon atoms, alkaryl groups of 7 to 30 carbon atoms, etc.
  • U.S. Patent No. 4,332,595 discloses hydrocarbyl
  • poly(oxyalkylene) polyamines wherein the hydrocarbyl group is a hydrocarbyl radical of 8 to 18 carbon atoms derived from linear primary alcohols.
  • U.S. Patent Nos. 4,233,168 and 4,329,240 among others disclose lubricating oil compositions containing a
  • compositions containing C 1 to C 30 hydrocarbyl poly(oxyalkylene) aminocarbamates which include poly(oxypropylene) polymers none of these references disclose the unique hydrocarbyl group of this invention nor do any of these references suggest that use of this unique hydrocarbyl group would overcome the art recognized problem of lubricating oil incompatibility arising from using the prior art hydrocarbyl poly(oxypropylene) aminocarbamates, and especially the problem of low temperature wax
  • the present invention provides a liquid alkylphenyl poly(oxypropylene) aminocarbamate which does not form a wax when cooled to -40oC in a 50 weight percent solution with toluene, said aminocarbamate having at least one basic nitrogen and an average molecular weight of about 600 to 6,000 and wherein the alkyl group of said
  • alkylphenyl poly(oxypropylene) aminocarbamate is a
  • the instant invention is directed toward a fuel composition containing a novel class of hydrocarbyl poly(oxypropylene) aminocarbamates which as a fuel additive controls combustion chamber deposits thus minimizing ORI and in lubricating oil is compatible with the lubricating oil composition.
  • the instant invention is directed toward a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to about 5,000 parts per million of the alkylphenyl poly(oxypropylene) aminocarbamate of the present invention.
  • the instant invention is directed to a fuel concentrate comprising an inert stable oleophilic organic solvent boiling in the range of 150o to 400oF and from 5 to 50 weight percent of an alkylphenyl poly(oxypropylene) aminocarbamate of this invention.
  • the instant invention is directed to a lubricating oil composition
  • a lubricating oil composition comprising an oil of lubricating viscosity and a dispersant effective amount of an alkylphenyl poly(oxypropylene) aminocarbamate of this invention.
  • the instant invention is directed to a lubricating oil concentrate comprising from about 90 to 50 weight percent of an oil of
  • the present invention also relates to the novel alkyl- phenol compounds which are employed to prepare the instant alkylphenyl poly(oxypropylene) aminocarbamates.
  • novel alkylphenol intermediate compounds are alkylphenois wherein the alkyl group is a substantially straight-chain alkyl group of from about 25 to 50 carbon atoms and is attached to the phenol ring at least 6 carbon atoms from the terminus of the longest chain of the alkyl group.
  • the alkyl group on the alkylphenol will contain from about 28 to 50 carbon atoms, and more
  • alkyl substituent is preferably derived from a
  • alkylphenyl poly(oxypropylene) aminocarbamates of the present invention consist of an amino moiety and an alkylphenyl poly(oxypropylene) polymer bonded through a carbamate linkage, i.e., -OC(O)N ⁇ .
  • alkylphenyl group employed in the instant invention in the alkylphenyl poly(oxypropylene) polymer is critical to achieving lubricating oil compatibility for the alkylphenyl poly(oxypropylene) aminocarbamates, while providing excellent low temperature properties.
  • pinwheel alkylphenyl group of this invention wherein the alkyl group is substantially straight-chain of from 25 to 50* carbon atoms results in an alkylphenyl
  • poly(oxypropylene) aminocarbamate which is lubricating oil compatible and non-waxy at low temperatures.
  • PO poly(oxypropylene) aminocarbamate
  • alpha olefin or “simple alpha olefin” as used herein refers generally to 1-olefins, wherein the double bond is at the terminal position of an alkyl chain. Alpha olefins are almost always mixtures of isomers and often also mixtures of compounds with a range of carbon numbers.
  • alpha olefins such as the C6, C8, C10, C12 and C14 alpha olefins
  • C 16-18 , or C 20-24 have increasing proportions of the double bond isomerized to an internal or vinylidene position; nonetheless these higher molecular weight cuts are also called alpha olefins herein.
  • alpha olefin oligomer(s) as used herein means olefin dimers, trimers, tetramers and pentamers prepared or derived from C 8 to C 20 alpha olefins.
  • AOO's have a pinwheel-type structure consisting of primarily internal disubstituted and trisubstituted olefins. The olefin double bond of these AOO's is
  • the alkyl substituent of the alkyphenyl moiety of the present alkylphenyl poly(oxpropylene) carbamates is a substantially straight-chain alkyl group having from about 25 to 50 carbon atoms.
  • straight-chain is meant to designate an alkyl group wherein greater than about 80 number percent of the individual carbon atoms in the alkyl substituent are either primary (CH 3 -) or secondary (-CH 2 -) carbon atoms. Preferably, greater than 85 number percent of the carbon atoms in the alkyl substituent are primary or secondary carbons.
  • the alkyl substituent in the alkylphenyl poly-(oxypropylene) aminocarbamates of the present invention is arranged in what will herein be designated as a "pinwheel” configuration. This configuration has been found to be critical to providing aminocarbamates having non-waxy low temperature characteristics. By “pinwheel” configuration is meant that the alkyl group is attached, for example to an aromatic ring, at a
  • a "pinwheel” alkyl phenol has an alkyl group comprising at least two tails of at least six carbon atoms in length, preferably at least 8 carbon atoms in length.
  • Preferred “pinwheel” compounds useful in this invention are those wherein the alkyl substituent has tails which are substantially straight-chain hydrocarbon radicals.
  • the alkylphenyl substituent of the aminocarbamate of this invention is derived from the corresponding alkylphenol.
  • alkylphenol is that prepared by alkylating phenol with one or more alpha olefin oligomers. Alkylation with alpha olefin oligomers, such as decene trimer or octene tetramer, provides alkylphenols having "pinwheel"
  • Such configurations can be represented by structure A as an example of decene trimer-derived
  • alkylphenol and structure B as an example of octene tetramer-derived alkylphenol, as shown below.
  • brackets are intended to denote the various manners of attachment of the alkyl group to the phenol.
  • alpha olefin oligomers used herein are prepared by methods well-known in the art.
  • One preferred method of preparing these oligomers is using BF 3 as the
  • alpha olefin oligomers are 75% or more di or
  • an alpha olefin trimer has a structure that can be represented by:
  • R n-2, and n is the carbon number of
  • Alpha olefin oligomers are substantially straight-chain with respect to the number of branched (i.e., tertiary or
  • Preferred alpha olefin oligomers are derived from C 8 to C 20 alpha olefins, more preferably, C 10 to C 16 alpha olefins.
  • Preferred AOO's are dimers, trimers, tetramers and pentamers.
  • the alkyl group of the instant carbamates is derived from alpha olefin oligomers selected from the group consisting of: C 8 tetramers, C 1 0 trimers, C 12 trimers, C 14 dimers and trimers, C 16 dimers and trimers, C 18 dimers and C 20 dimers.
  • the alkyl substituent of the present alkylphenyl poly(oxypropylene) aminocarbamates is arranged in a so-called “pinwheel” configuration.
  • This "pinwheel” configuration is readily distinguishable from alkyl groups wherein the hydrocarbon chains are attached at or near the terminus of the longest chain of the alkyl group, i.e., within 1 to 5 carbon atoms of a terminus.
  • aminocarbamates prepared from simple alpha olefins, (as compared to alpha olefin oligomers) as well as their
  • precursors including the phenols and the alkylphenyl poly(oxypropylene) alcohols, have alkyl groups in a
  • terminal configuration Compounds having an alkyl group in a terminal configuration are herein designated “terminal compounds", for example, C 20-24 terminal alkyl phenols and terminal alkyl carbamates. In terminal compounds such as terminal alkyl phenols, there is only 1 main chain emanating from near the attachment point of the alkyl group to the phenol. Terminal compounds include those prepared by reacting alpha olefins with phenol under typical acidic reaction conditions.
  • the Preferred Alkyphenyl Group The preferred alkylphenyl group of the alkylphenyl
  • poly(oxypropylene) aminocarbamate employed in this invention is derived from the corresponding alkylphenol of Formula I below:
  • R is a substantially straight-chain alkyl group of from about 25 to 50 carbon atoms and m is an integer from 1 to 2.
  • R is a substantially straight-chain alkyl group of from 28 to 50 carbon atoms. More preferably, R is a substantially straight-chain alkyl group of from 30 to 45 carbon atoms.
  • the alkylphenyl is a monoalkylphenyl
  • the alkylphenyl is a dialkylphenyl.
  • an alkylating catalyst at a temperature of from about 60oC to 200oC, and preferably 125oC to 180oC either neat or in an essentially inert solvent at atmospheric pressure.
  • a preferred alkylating catalyst is a sulfonic acid catalyst such as Amberlyst 15R available from Rohm and Haas, Philadelphia, Pennsylvania. Molar ratios of reactants can be employed. When molar ratios are employed, the reaction yields a mixture of dialkylphenol, monoalkylphenol and unreacted phenol.
  • dialkylphenol and monoalkylphenol can be used to prepare the additives used in the compositions of this invention whereas the unreacted phenol is preferably removed from the post reaction mixture via conventional techniques.
  • molar excess of phenol can be employed, i.e., 2 to 2.5 equivalents of phenol for each equivalent of olefin with unreacted phenol recycled.
  • inert solvents include benzene, toluene, chlorobenzene and 250 thinner which is a mixture of aromatics, paraffins and naphthenes.
  • the preferred alkylphenyl group is derived from a pinwheel phenol.
  • Pinwheel phenols may be prepared from alpha olefin oligomers.
  • Useful AOO derived alkylphenols have average molecular weights in the range of 480 to 790, and average alkyl carbon numbers ranging from 25 to 50, and preferably from 28 to 50. More preferred average alkyl carbon numbers are in the range of from 30 to 45.
  • Alternative methods of preparing the alkylphenol compounds used herein are also contemplated.
  • "Pinwheel" alkyl phenols can be synthesized by any number of methods.
  • Particularly preferred monoalkylphenols employed in this invention are either ortho-monoalkylphenols of Formula II below:
  • dialkylphenols employed in this invention are generally 2,4-dialkylphenols of Formula IV below:
  • alkylphenyl poly(oxypropylene) polymers which are utilized in preparing the carbamates of the present
  • alkylphenyl poly(oxypropylene) glycols are monohydroxy compounds, i.e., alcohols, often termed alkylphenyl "capped" poly( oxypropylene) glycols and are to be distinguished from the poly(oxypropylene) glycols (diols), which are not alkylphenyl terminated, i.e., not capped.
  • the alkylphenyl poly(oxypropylene) alcohols are produced by the addition of propylene oxide to the alkylphenol of Formula I, i.e.,
  • poly(oxypropylene) polymers will vary in chain length but their properties
  • Each poly- (oxypropylene) polymer contains at least 1 oxypropylene unit, preferably from 1 to about 100 oxypropylene units, more preferably from about 5 to about 50 oxypropylene units, and most preferably from about 10 to about 25 oxypropylene units.
  • Methods of production and properties of these polymers are disclosed in U.S. Patent Nos. 2,841,479 and 2,782,240, which are incorporated herein by reference, as well as Kirk-Othmer's "Encyclopedia of Chemical
  • the amine moiety of the alkylphenyl poly(oxypropylene) aminocarbamate employed in this invention is preferably derived from a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms.
  • the polyamine is preferably reacted with an alkylphenyl
  • chloroformate is itself derived from alkylphenyl
  • the polyamine encompassing diamines, provides the product alkylphenyl poly(oxypropylene) aminocarbamate with, on average, at least about one basic nitrogen atom per carbamate molecule, i.e., a nitrogen atom titratable by a strong acid.
  • the polyamine preferably has a
  • the polyamine may be substituted with substituents selected from (A) hydrogen, (B) hydrocarbyl groups of from 1 to about 10 carbon atoms, (C) acyr groups of from 2 to about 10 carbon atoms, and (D) monoketo, monohydroxy, mononitro, monocyano, lower alkyl and lower alkoxy derivatives of (B) and (C).
  • At least one of the substituents on one of the basic nitrogen atoms of the polyamine is hydrogen, e.g., at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen atom.
  • Hydrocarbyl denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl.
  • the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylene and acetylenic, particularly acetylenic unsaturation.
  • the substituted polyamines of the present invention are generally, but not necessarily, N-substituted polyamines.
  • hydro- carbyl groups and substituted hydrocarbyl groups include alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls such as propenyl, isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls, such as 2-hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl,
  • ketoalkyls such as 2-ketopropyl, 6-ketooctyl, etc.
  • alkoxy and lower alkenoxy alkyls such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl,2-(2ethoxyethoxy)ethyl, 2-(2-(2-ethoxyethoxy)ethoxy)ethyl, 3,6,9,12-tetraoxatetradecyl, 2-(2-ethoxyethoxy)hexyl, etc.
  • the acyl groups of the aforementioned (C) substituents are such as propionyl, acetyl, etc. The more preferred
  • substituents are hydrogen, C 1 -C 4 alkyls and C 1 -C 4
  • hydroxyalkyls In a substituted polyamine the substituents are found at any atom capable of receiving them.
  • the substituted. atoms e.g., substituted nitrogen atoms, are generally geometric- ally inequivalent, and consequently the substituted amines finding use in the present invention can be mixtures of mono- and polysubstituted polyamines with substituent groups situated at equivalent and/or inequivalent atoms.
  • the more preferred polyamine finding use within the scope of the present invention is a polyalkylene polyamine, including alkylene diamine, and including substituted polyamines, e.g., alkyl and hydroxyalkyl-substituted polyalkylene polyamine.
  • the alkylene group contains from 2 to 6 carbon atoms, there being preferably from 2 to 3 carbon atoms between the nitrogen atoms.
  • Such groups are exemplified by ethylene, 1,2-propylene,
  • 2,2-dimethyl-propylene trimethylene 1,3,2-hydroxypropylene, etc.
  • polyamines include ethylene diamine, diethylene triamine, di(trimethylene)triamine, dipropylene triamine, triethylene tetramine, tripropylene tetramine, tetraethylene pentamine, and pentaethylene hexamine.
  • Such amines encompass isomers such as branched-chain polyamines and the previously mentioned substituted polyamines,
  • polyalkylene polyamines including hydroxy- and hydrocarbyl-substituted polyamines.
  • polyalkylene polyamines those containing 2-12 amine nitrogen atoms and 2-24 carbon atoms are especially preferred, and the C 2 -C 3 alkylene polyamines are most preferred, in particular, the lower polyalkylene polyamines, e.g., ethylene diamine, diethylene triamine, propylene diamine, dipropylene triamine, etc.
  • the amine component of the alkylphenyl poly(oxypropylene) aminocarbamate also may be derived from heterocyclic
  • heterocycles may be saturated or unsaturated and substituted with groups selected from the aforementioned (A), (B)(, (C) and (D).
  • the heterocycles are exemplified by piperazines, such as 2-methylpiperazine,
  • N-(3aminopropyl)morpholine etc.
  • the piperazines are preferred.
  • Another class of suitable polyamines are diaminoethers represented by Formula VII
  • X 1 and X 2 are independently alkylene from 2 to about 5 carbon atoms and r is an integer from 1 to about 10.
  • Diamines of Formula VII are disclosed in U.S. Patent. No. 4,521,610, which is incorporated herein by reference for its teaching of such diamines. Typical polyamines that can be used to form the compounds of this invention by reaction with a
  • poly(oxyalkylene) chloroformate include the following:
  • N'-acetyl-N-methyl-N-(beta-aminoethyl)ethane-1,2-diamine N-acetonyl-1,2-propanediamine, N-(beta-nitroethyl)-1,3-propane diamine, 1,3-dimethyl-5(beta-amino ⁇ ethyl)hexahydrotriazine, N-(beta-aminoethyl)hexahydrotri-azine, 5-(beta-aminoethyl)-1,3,5-dioxazine,
  • the amine component of the alkylphenyl poly(oxypropylene) aminocarbamate may also be derived from an
  • amine-containing compound which is capable of reacting with an alkylphenyl poly(oxypropylene) alcohol to produce an alkylphenyl poly(oxypropylene) aminocarbamate having at least one basic nitrogen atom.
  • a substituted aminoisocyanate such as (R) 2 NCH 2 CH 2 NCO, wherein R is, for example, a hydrocarbyl group, reacts with the alcohol to produce the aminocarbamate additive finding use within the. scope of the present invention.
  • Typical aminoisocyanates that may be used to form the fuel additive compounds of this invention by reaction with a hydrocarbylpoly(oxyalkylene) alcohol include the following: N,N-(di-methyl)aminoisocyanatoethane, generally, N,N-(dihydrocarbyl)aminoisocyanatoalkane, more generally, N-(perhydrocarbyl)-isocyanatopol-olyalkylene polyamine,
  • the amine used as a reactant in. the production of the carbamate of the present invention is not a single compound but a mixture in which one or several compounds, predominate with the average composition indicated.
  • tetraethylene pentamine prepared by the polymerization of aziridine or the reaction of dichloroethylene and ammonia will have both lower and higher amine members, e.g., triethylene tetramine, substituted piperazines and pentaethylene hexamine, but the composition will be mainly tetraethylene pentamine and the empirical formula of the total amine composition will closely approximate that of tetraethylene pentamine.
  • poly(oxypropylene) component and the preferred polyamine component, the preferred alkylphenyl poly(oxypropylene) aminocarbamate additive of the present invention is obtained by linking these components together through a carbamate linkage i.e..
  • ether oxygen may be regarded as the terminal hydroxyl oxygen of the alkylphenyl poly(oxypropylene) alcohol component, and the carbonyl group -C(O)- is preferably provided by the coupling agent, e.g., phosgene.
  • the alkylphenyl poly(oxypropylene) aminocarbamate employed in the present invention has at least one basic nitrogen atom per molecule.
  • a "basic nitrogen atom” is one that is titratable by a strong acid, e.g., a primary, secondary. or tertiary amino nitrogen, as distinguished from, for example, an amido nitrogen, i.e.,
  • the basic nitrogen is in a primary or secondary amino group.
  • aminocarbamate has an average molecular weight of from about 600 to 6,000; preferably an average molecular weight of from 800 to 3,000; and most preferably an average molecular weight of from 1,000 to 2,500.
  • alkylphenyl poly(oxypropylene) aminocarbamate A preferred class of alkylphenyl poly(oxypropylene) aminocarbamate can be described by the following general formula:
  • R is a substantially straight-chain alkyl group of from about 25 to 50 carbon atoms; R 1 is alkylene of 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 600 to 6,000; and p is an integer from 1 to about 6; and wherein said compound does not form a wax when cooled to -40oC in a 50 weight percent solution with toluene.
  • R is attached to the phenyl ring at least 6 carbon atoms from the terminus of the longest chain of said alkyl group R.
  • Hydrophilic-Lipophilic Balance It is important that the relatively hydrophilic propylene oxide polymeric back-bone be balanced by the hydrophobic alkyl carbons of the alkyl phenol.
  • the aminocarbamates of this invention must achieve a good hydrophilic-lipophilic balance (HLB) in order to have sufficient hydrocarbon solubility in oil and therefore to not perform
  • the ratio of the number of carbon atoms in the alkyl group needs to be about twice the number of propylene oxide units.
  • the alkyl chain attached to the phenoxy radical should have approximately 2n carbon atoms; preferably, between 2n-4 and 2n+4 carbon atoms; most preferably between 2n and 2n+4 carbon atoms.
  • the additives employed in this invention can be most conveniently prepared by first reacting the appropriate alkylphenyl poly(oxypropylene) alcohol with phosgene to produce an alkylphenyl poly(oxypropylene) chloroformate. The chloroformate is then reacted with the polyamine to produce the desired alkylphenyl poly(oxypropylene)
  • aminocarbamate Preparation of aminocarbamates are disclosed in U.S.
  • the reaction may be carried out a temperatures from -10o to 100oC, preferably in the range of 0o to 50oC.
  • the reaction will usually be complete within 1/4 to 5 hours. Times of reaction will usually be in the range of from 2 to 4 hours.
  • a solvent may be used in the chloroformylation reaction. Suitable solvents include benzene, toluene, etc.
  • the reaction of the resultant chloroformate with the amine may be carried out neat or preferably in solution.
  • Temperatures of from -10o to 200oC may be utilized, the desired product may be obtained by water wash and
  • the mole ratio of polyamine to polyether chloroformate will generally be in the range from about 2 to 20 moles of polyamine per mole of chloroformate, and more usually 5 to 15 moles of polyamine per mole of chloroformate. Since suppression of polysubstitution of the polyamino is usually desired, large molar excesses of the polyamine will be used. Additionally, the preferred adduct is the monocarbamate compound, as opposed to the bis(carbamate) or disubstituted aminoether.
  • the reaction or reactions may be conducted with or without the presence of a reaction solvent.
  • a reaction solvent is generally employed whenever necessary to reduce the viscosity of the reaction product. These solvents should be stable and inert to the reactants and reaction product. Depending on the temperature of the reaction, the
  • the reaction time may vary from less than 1 minute to 3 hours.
  • the reaction mixture may be subjected to extraction with a hydrocarbon-water or
  • hydro-carbon-alcohol-water medium to free the product from any low-molecular-weight amine salts which have formed and any unreacted diamine.
  • the product may then be isolated by evaporation of the solvent. Further purification may be effected by column chromatography on silica gel.
  • the reaction may be carried out in the medium in which it will ultimately find use, e.g.,
  • the final mixture may be in a form to be used directly for blending in fuels.
  • An alternative process for preparing the alkylphenyl poly(oxypropylene) aminocarbamates employed in this invention involves the use of an arylcarbonate intermediate. That is to say, the alkylphenyl poly(oxypropylene) alcohol is reacted with an aryl chloroformate to form an arylcarbonate which is then reacted with the polyamine to form the aminocarbamate employed in this invention.
  • aryl chloroformates include phenyl chloroformate, p-nitrophenyl chloroformate, 2,4-dinitrophenyl chloroformate, p-chlorophenyl chloroformate, 2,4-dichlorophenyl chloroformate, and
  • aryl carbonate intermediate allows for conversion to amino-carbamates containing close to the theoretical basic nitrogen while employing less excess of polyamine, i.e., molar ratios of generally from 1:1 to about 5:1 of
  • arylcarbonate intermediate are disclosed in U.S. Serial Nos. 586,533 and 689,616, which are incorporated herein by reference.
  • the aminocarbamates of this invention are mixtures of many individual compounds.
  • the alkyl group will typically have a variety of carbon numbers since the starting olefins are not generally pure compounds and, for any given carbon number in the alkyl group, there are many structural isomers.
  • mono- and dialkyl phenols are generally obtained.
  • the number of propylene oxide units is an average number and different molecules will have a somewhat different number of PO units.
  • fully formulated lubricating oils containing a dispersant are also included within the scope of this invention.
  • the alkenyl succinimide is present to act as a dispersant and prevent formation of deposits formed during operation of the engine.
  • the alkenyl succinimides are well-known in the art.
  • the alkenyl succinimides are the reaction product of a polyolefin polymer-substituted succinic anhydride with an amine, preferably a polyalkylene polyamine.
  • the polyolefin polymersubstituted succinic anhydrides are obtained by reaction of a polyolefin polymer or a derivative thereof with maleic anhydride.
  • the succinic anhydride thus obtained is reacted with the amine compound.
  • the preparation of the alkenyl succinimides has been described many times in the art. See, for example, U.S. Patent Nos. 3,390,082;
  • alkenyl substituted succinic anhydride yields the corresponding alkyl derivative.
  • the alkyl succinimides are intended to be included within the scope of the term "alkenyl succinimide".
  • a product comprising predominantly mono or bis-succinimide can be prepared by controlling the molar ratios of the reactants. Thus, for example, if one mole of amine is reacted with one mole of the alkenyl or alkyl substituted succinic anhydride, a predominantly mono-succinimide product will be prepared. If two moles of the succinic anhydride are reacted per mole of polyamine, a bis-succinimide will be prepared. Particularly good results are obtained with the lubricating oil compositions of this invention when the alkenyl
  • succinimide is a polyisobutene-substituted succinic anhydride of a polyalkylene polyamine.
  • the polyisobutene from which the polyisobutene-substituted succinic anhydride is obtained by polymerizing isobutene can vary widely in its compositions.
  • the average number of carbon atoms can range from 30 or less to 250 or more, with a resulting number average molecular weight of about 400 or less to 3,000 or more.
  • the average number of carbon atoms per polyisobutene molecule will range from about 50 to about 100 with the polyisobutenes having a number average molecular weight of about 600 to about 1,500.
  • the average number of carbon atoms per polyisobutene molecule ranges from about 60 to about 90, and the number average molecular weight ranges from about 800 to 1,300.
  • the polyisobutene is reacted with maleic anhydride according to well-known procedures to yield the
  • each alkylene radical of the polyalkylene polyamine usually has up to about 8 carbon atoms.
  • the number of alkylene radicals can range up to about 8.
  • the alkylene radical is exemplified by ethylene, propylene, butylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, etc.
  • the number of amino groups generally, but not necessarily, is one greater than the number of alkylene radicals present in the amine, i.e., if a polyalkylene polyamine contains 3 alkylene radicals, it will usually contain 4 amino radicals.
  • the number of amino radicals can range up to about 9.
  • the alkylene radical contains from about 2 to about 4 carbon atoms and all amine groups are primary or secondary. In this case, the number of amine groups exceeds the number of alkylene groups by 1.
  • the number of amine groups exceeds the number of alkylene groups by 1.
  • polyalkylene polyamine contains from 3 to 5 amine groups. Specific examples of the polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, tripropylenetetramine,
  • alkenyl succinimides used in the compositions of this invention have the following formula:
  • R 1 represents an alkenyl group, preferably a substantially saturated hydrocarbon prepared by polymerizing aliphatic monoolefins.
  • R 1 is prepared from isobutene and has an average number of carbon atoms and a number average molecular weight as described above;
  • the "Alkylene" radical represents a substantially
  • hydrocarbyl group containing up to about 8 carbon atoms and preferably containing from about 2-4 carbon atoms as described hereinabove; c.
  • A represents a hydrocarbyl group, an amine-substituted hydrocarbyl group, or hydrogen.
  • the hydrocarbyl group and the amine-substituted hydrocarbyl groups are
  • A represents hydrogen; d. n represents an integer of from about 1 to 10, and
  • alkenyl succinimide preferably from about 3-5.
  • alkenyl succinimide is the modified succinmides which are disclosed in U.S. Patent No. 4,612,132 which is incorporated herein by reference.
  • the alkenyl succinimide is present in the lubricating oil compositions of the invention in an amount effective to act as a dispersant and prevent the deposit of contaminants formed in the oil during operation of the engine.
  • the amount of alkenyl succinimide can range from about 1 percent to about 20 percent weight of the total lubricating oil composition.
  • the amount of alkenyl succinimide present in the lubricating oil composition of the invention ranges from about 1 to about 10 percent by weight of the total composition.
  • the alkali or alkaline earth metal hydrocarbyl sulfonates may be either petroleum sulfonate, synthetically alkylated aromatic sulfonates, or aliphatic sulfonates such as those derived from polyisobutylene.
  • One of the more important functions of the sulfonates is to act as a detergent and dispersant. These sulfonates are well-known in the art.
  • the hydrocarbyl group must have a sufficient number of carbon atoms to render the sulfonate molecule oil soluble.
  • the hydrocarbyl portion has at least 20 carbon atoms and may be aromatic or aliphatic, but is usually alkylaromatic. Most preferred for use are calcium,
  • Certain sulfonates are typically prepared by sulfonating a petroleum fraction having aromatic groups, usually mono- or dialkylbenzene groups, and then forming the metal salt of the sulfonic acid material.
  • Other feedstocks used for preparing these sulfonates include synthetically alkylated benzenes and aliphatic hydrocarbons prepared by polymerizing a mono or diolefin, for example, a polyisobutenyl group prepared by polymerizing isobutene.
  • the metallic salts are formed directly or by metathesis using well-known
  • the sulfonates may be neutral or overbased having base numbers up to about 400 or more. Carbon dioxide and calcium hydroxide or oxide are the most commonly used material to produce the basic or overbased sulfonates. Mixtures of neutral and overbased sulfonates may be used.
  • the sulfonates are ordinarily used so as to provide from 0.3% to 10% by weight of the total composition. Preferably, the neutral sulfonates are present from 0.4% to 5% by weight of the total composition and the overbased sulfonates are present from 0.3% to 3% by weight of the total composition.
  • the phenates for use in this invention are those
  • the phenates are to act as a detergent and dispersant. Among other things, it prevents the deposition of contaminants formed during high temperature operation of the engine.
  • the phenols may be mono or polyalkylated.
  • the alkyl portion of the alkyl phenate is present to lend oil solubility to the phenate.
  • the alkyl portion can be obtained from naturally occurring or synthetic sources.
  • Naturally occurring sources include petroleum hydrocarbons such as white oil and wax. Being derived from petroleum, the hydrocarbon moiety is a mixture of different hydrocarbyl groups, the specific composition of which depends upon the particular oil stock which was used as a starting material.
  • Suitable synthetic sources include various commercially available alkenes and alkane derivatives which, when reacted with the phenol, yield an alkylphenol. Suitable radicals obtained include butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl, tricontyl, and the like.
  • Other suitable synthetic sources of the alkyl radical include olefin polymers such as polypropylene, polybutylene,
  • alkyl group can be straight-chained or branch-chained, saturated or unsaturated (if unsaturated, preferably
  • the alkyl radicals will generally contain from 4 to 30 carbon atoms. Generally when the phenol is monoalkyl-substituted, the alkyl radical should contain at least 8 carbon atoms.
  • the phenate may be sulfurized if desired. It may be either neutral or
  • overbased and if overbased will have a base number of up to 200 to 300 or more.
  • Mixtures of neutral and overbased phenates may be used.
  • the phenates are ordinarily present in the oil to provide from 0.2% to 27% by weight of the total composition.
  • the neutral phenates are present from 0.2% to 9% by weight of the total composition and the overbased
  • phenates are present from 0.2 to 13% by weight of the total composition. Most preferably, the overbased phenates are present from 0.2% to 5% by weight of the total composition.
  • Preferred metals are calcium, magnesium, strontium or barium.
  • the sulfurized alkaline earth metal alkyl phenates are preferred. These salts are obtained by a variety of
  • the Group II metal salts of the dihydrocarbyl dithiophosphoric acids useful in the lubricating oil composition of this invention contain from about 4 to about 12 carbon atoms in each of the hydrocarbyl radicals and may be the same or different and may be aromatic, alkyl or cycloalkyl.
  • Preferred hydrocarbyl groups are alkyl groups containing from 4 to 8 carbon atoms and are represented by butyl, isobutyl, sec. -butyl, hexyl, isohexyl, octyl,
  • the metals suitable for forming these salts include barium, calcium, strontium, zinc and cadmium, of which zinc is preferred.
  • the Group II metal salt of a dihydrocarbyl dithiophosphoric acid has the following formula:
  • R 2 and R 3 each independently represent hydrocarbyl
  • M 1 represents a Group II metal cation as described
  • the dithiophosphoric salt is present in the lubricating oil compositions of this invention in an amount effective to inhibit wear and oxidation of the lubricating oil.
  • the amount ranges from about 0.1 to about 4 percent by weight of the total composition.
  • the salt is present in an amount ranging from about 0.2 to about 2.5 percent by weight of the total lubricating oil composition.
  • the final lubricating oil composition will ordinarily contain 0.025 to 0.25% by weight phosphorus and preferably 0.05 to 0.15% by weight.
  • Viscosity index (VI) improvers are either non-dispersant or dispersant VI improvers.
  • Non-dispersant VI improvers are typically hydrocarbyl polymers including copolymers and terpolymers. Typically hydrocarbyl copolymers are
  • Dispersant VI improvers can be prepared by functionalizing non-dispersant VI improvers.
  • non-dispersant hydrocarbyl copolymer and terpolymer VI improvers can be functionalized to produce aminated oxidized VI improvers having dispersant properties and a number average molecular weight of from 1,500 to 20,000.
  • dispersant VI improvers are disclosed in U.S. Patents Nos. 3,864,268; 3,769,216; 3,326,804 and 3,316,177 which are incorporated herein by reference for their teaching of such dispersant VI improvers.
  • Other dispersant VI improvers include amine-grafted acrylic polymers and copolymers wherein one monomer contains at least one amino group. Typical compositions are described in British Patent No. 1,488,382; and U.S. Patents Nos.
  • Non-dispersant and dispersant VI improvers are generally employed at from 5 to 20 percent by weight in the
  • alkylphenyl poly(oxypropylene) aminocarbamates of this invention will generally be employed in a hydrocarbon distillate fuel.
  • concentration of this additive necessary in order to achieve the desired detergency and dispersancy varies depending upon the type of fuel employed, the presence of other detergents, dispersants and other additives, etc. Generally, however, from 30 to 5,000 weight parts per million (ppm), and preferably 100 to 500 ppm and more preferably 200 to 300 ppm of alkylphenyl
  • poly(oxypropylene) aminocarbamate per part of base fuel is needed to achieve the best results.
  • a less amount of alkylphenyl poly(oxypropylene) aminocarbamate may be used.
  • concentrations for example 30 to 70 ppm may be preferred.
  • Higher concentrations, i.e., 2,000 to 5,000 ppm may result in a clean-up effect on combustion chamber deposits.
  • the deposit control additive may also be formulated as a concentrate, using an inert stable oleophilic organic solvent boiling in the range of about 150 to 400oF.
  • an aliphatic or an aromatic hydrocarbon solvent is used, such as benzene, toluene, xylene or higher-boiling aromatics or aromatic thinners.
  • Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol and the like, in combination with hydrocarbon solvents, are also suitable for use with the
  • the amount of the additive will be ordinarily at least 5 percent by weight and generally not exceed 50 percent by weight, preferably from 10 to 30 weight percent.
  • a demulsifier to the gasoline or diesel fuel composition.
  • demulsifiers are generally added at from 1 to 15 ppm in the fuel composition. Suitable demulsifiers include for instance L-1562 , a high molecular weight glycol capped phenol available from Petrolite Corp., Tretolite Division, St. Louis, Missouri, and OLOA 2503Z , available from Chevron Chemical Company, San Francisco, California.
  • antiknock agents e.g., methylcyclopentadienyl manganese tricarbonyl, tetramethyl or tetraethyl lead, or other dispersants or detergents such as various substituted succinimides, amines, etc.
  • lead scavengers such as aryl halides, e.g., dichlorobenzene or alkyl halides, e.g., ethylene dibromide.
  • antioxidants, metal deactivators and demulsifiers may be present.
  • other well-known additives can be employed such as pour point depressants, flow improvers, cetane improvers, etc.
  • the alkylphenyl poly(oxypropylene) aminocarbamates of this invention are useful as dispersant additives when employed in lubricating oils.
  • the additive When employed in this manner, the additive is usually present in from 0.2 to 10 percent by weight to the total composition, preferably at about 0.5 to 8 percent by weight and more preferably at about 1 to 6 percent by weight.
  • the lubricating oil used with the additive compositions of this invention may be mineral oil or synthetic oils of lubricating viscosity and preferably suitable for use in the crankcase of an internal combustion engine. Crankcase lubricating oils ordinarily have a viscosity of about 1300 CSt 0oF to 22.7 CSt at 210oF (99oC).
  • the lubricating oils may be derived from synthetic or natural sources.
  • Mineral oil for use as the base oil in this invention includes paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions.
  • Synthetic oils include both hydrocarbon synthetic oils and synthetic esters.
  • Useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C 6 to C 12 alpha olefins such as 1-decene trimer. Likewise, alkyl benzenes of proper viscosity such as didodecyl benzene, can be used.
  • Useful synthetic esters include the esters of both monocarboxylic acid and polycarboxylic acids as well as monohydroxy alkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate and the like. Complex esters prepared from mixtures of mono and dicarboxylic acid and mono and dihydroxy alkanols can also be used. Blends of hydrocarbon oils with synthetic oils are also useful. For example, blends of 10 to 25 weight percent hydrogenated 1-decene trimer with 75 to 90 weight percent 150 SUS (100oF) mineral oil gives an excellent lubricating oil base.
  • Additive concentrates are also included within the scope of this invention.
  • the concentrates of this invention usually include from about 90 to 50 weight percent of an oil of lubricating viscosity and from about 10 to 50 weight percent of the additive of this invention.
  • the concen- trates contain sufficient diluent to make them easy to handle during shipping and storage.
  • Suitable diluents for the concentrates include any inert diluent, preferably an oil of lubricating viscosity, so that the concentrate may be readily mixed with lubricating oils to prepare lubricating oil compositions.
  • Suitable lubricating oils which can be used as diluents typically have viscosities in the range from about 35 to about 500 Saybolt Universal Seconds ( SUS ) at 100oF (38oC), although an oil of lubricating viscosity may be used.
  • Other additives which may be present in the formulation include rust inhibitors, foam inhibitors, corrosion
  • This example shows alpha-olefin oligomers useful in this invention.
  • Into a dry 500-ml, three-necked round bottom flask, equipped with a heating mantle, a mechanical stirrer, and a condenser were charged 200 grams of C 14 alpha olefin (Chevron Chemical Co., San Francisco) and 10 grams of an experimental alumina-supported fluorosulfonic acid catalyst (DOW XUS 40036.07), available from Dow Chemical Company.
  • This product was converted to polyoxypropylene alcohol without further purification.
  • This phenol was a nonviscous liquid at room temperature and became a thick oil at lower temperature. No waxing was observed.
  • the C 16 -derived olefin oligomer of Example C was used to alkylate phenol in a manner similar to that described in Example 1A.
  • the resulting pinwheel alkyl phenol had an average alkyl carbon content of 34 carbon atoms.
  • the reaction mixture was heated to about 140oC for about 8 hours with stirring under a nitrogen atmosphere.
  • the reaction mixture was stripped by heating under vacuum and the product was filtered hot over
  • alkylphenol with a hydroxyl number of 110 and with 56% para-alkylphenol content. This alkylphenol had
  • Example 2A The procedure of Example 2A was used except 966 gm C 20 -C 28 alpha olefins and 211.5 gm of phenol were used.
  • the procedure of Example 2A was used except 966 gm C 20 -C 28 alpha olefins and 211.5 gm of phenol were used.
  • resulting alkyl phenol had approximately 6% dialkyl phenol and an average alkyl carbon number of 24. This product was a wax at room temperature.
  • Example 2B was realkylated using an additional 10% C 20 -C 24 alpha Chevron olefin (per conditions described in Example 1C). This reaction thus afforded an alkylphenol composed of approximately 16% dialkyl phenol species. The average alkyl carbon number was 26. This product was a wax at room temperature. Comparative Example 3
  • Example 2A To a dried 12-liter 3-necked flask under a nitrogen atmosphere was added 3.5 liter of toluene and 2020.5 grams (4.61 moles) of a C 20 to C 28 terminal alkylphenol prepared in a manner similar to Example 2A. The system was warmed to approximately 60oC and 60 grams (1.54 moles) of metallic potassium cut into small pieces was slowly added with vigorous stirring. The temperature of the reaction system was allowed to increase during this addition and reached approximately 100oC. After 2-1/2 hours, all of the metallic potassium was dissolved. The reaction system was then allowed to cool to 60oC. Afterwards, 4552 grams (78.37 moles) of propylene oxide was added to the system by an addition funnel at an addition rate slow enough to avoid flooding of the vapor condensing system.
  • the system was then gently refluxed for 72 hours at which point the temperature increased to 110oC and was held there for an additional 3 hours.
  • the system was then cooled to 60oC and the reaction quenched by the addition of 0.54 liter of 3N HCl solution.
  • the system was then dried by azeotropic distillation.
  • Example 5A The entire chloroformate/toluene solution of Example 5A was diluted with 4 liters of dry toluene. In a separate flask, 2565 grams (42.7 moles) ethylene diamine (EDA) was also diluted with 4 liters of dry toluene. At room temperature
  • This product was a waxy paste at room temperature and did not pass the wax test as described in Example 45.
  • n-butanol for the C 20 to C 28 alkylphenol.
  • the n-butyl poly(oxypropylene) alcohol was then treated with phosgene in the manner of Example 5A to yield the n-butyl poly(oxypropylene) chloroformate which was reacted with 1093 grams (18.2 moles) of ethylene diamine in the manner of Example 6 to yield the title compound as a light yellow liquid having an alkalinity value of 22.5 and 0.56 weight percent basic nitrogen.
  • This product was a liquid at room temperature and passed the wax test of Example 45.
  • hydrocarbyl poly(oxyalkylene) alcohols were prepared by employing different hydrocarbyl groups including those of Examples 2A and 3; by employing different poly(oxyalkylene) groups of different chain lengths. Examples 9 through 17 found below in Table I summarizes the different hydrocarbyl poly(oxyalkylene) alcohols so prepared.
  • hydrocarbyl poly(oxyalkylene) aminocarbamates were prepared by employing different hydrocarbyl groups including those of Examples 2 and 3 and by employing poly(oxyalkylene) groups of different chain lengths. Examples 18 through 28 are found in Table II, which summarizes the different hydrocarbyl poly(oxyalkylene) aminocarbamates so prepared.
  • Example 2C The alkyl phenol of Example 2C was converted to a 14 PO polymer (as determined by Nmr) in a manner similar to that described in Example 4, but using 14 moles of PO per mole of phenol. This product was a waxy paste at room temperature.
  • Example 1A was slowly added potassium metal (5.4 gr) in small pieces with vigorous mechanical stirring. The pot temperature increased to approximately 100oC during the addition, and after 2-1/2 hours, all of the potassium was dissolved. After cooling to 60oC, 585 mis of propylene oxide (486 grams, 8.36 moles) was added in such a way as to avoid flooding of the vapor condensing system. The reaction solution was gently refluxed for 72 hours at which point the temperature rose to 110oC and was held at temperature for an additional 3 hours. After cooling to 60oC, the reaction was quenched with 60 ml of 3N HCl (a slight excess) and dried by azeotropic distillation. The crude product was then diluted with hexane (3 liter), extracted three times with slightly basic brine.
  • the pinwheel alkyl phenol of example 1A (C 14 -derived) was converted to the poly(oxypropylene) alcohol by reaction with 16 mole equivalents of propylene oxide in a manner similar to that described in Example 32.
  • Example 29 Preparation of the Terminal Low Dialkyl C 20-24 Carbamate EDA Without further purification, the terminal alkylphenol alcohol of Example 29 was converted to the chloroformate as described in Example 5A, except that a 20 weight percent solution of phosgene in toluene was employed rather than condensed phosgene liquid (for handling convenience and safety). After reaction, the chloroformate was then
  • Example 5A poly(oxypropylene) alcohol containing 13 PO units using a procedure similar to that described in Example 4. This alcohol was converted to the corresponding chloroformate, as in Example 5A using a phosgene/toluene solution. The chloroformate was degassed and used without further
  • Example 31 The poly(oxypropylene) alcohol of Example 31 was converted to the corresponding chloroformate as in Example 5A and reached with EDA to afford the desired ethylene diamine carbamate in a manner similar to that of Example 6
  • Example 38 By increasing the dialkyl content to a higher level (Example 38) performance is restored to base case values. None of these examples, however, represents a total solution to the overall problem which additionally requires these additives to be nonwaxy at low temperatures, thus passing the test of Example 45.
  • Example 5B The chloroformate/toluene solution of Example 5B was diluted to 2 liters with dry toluene. In a separate flask,
  • the pinwheel alcohols 33 and 34 were reacted in a manner similar to Examples 5 and 7 to give a C 14 -derived DETA pinwheel carbamate having 16 oxypropylene units and an average alkyl carbon number of 34 (Example 40) and a
  • the lubricating oil composition was formulated to contain: 6 percent by weight of a monopolyisobutenyl succinimide; 20 millimoles per kilogram of a highly overbased sulfurized calcium phenate; 30 millimoles per kilogram of a highly overbased sulfurized calcium hydrocarbyl sulfonate; 22.5 millimoles per kilogram of a zinc dithiophosphate; 13 weight percent of a commercial non-dispersant viscosity index improver; 5 parts per million of a foam inhibitor in 150N Exxon base oil to give a 10 W 40 formulated oil.
  • the oil solubility of the additive was determined as
  • Formulated oils containing alkylphenyl poly(oxypropylene) aminocarbamate were tested in a Sequence V-D test method as well as formulated oils containing comparative hydrocarbyl poly(oxyalkylene) aminocarbamates. This procedure utilizes a Ford 2.3-liter, four-cylinder Pinto engine. The test method simulates a type of severe field test service
  • Examples 18 through 22 represent prior art hydrocarbyl poly(oxyalkylene) aminocarbamates.
  • This Table establishes that the alkylphenyl poly(oxypropylene) aminocarbamates of this invention (Examples 39-41) were less detrimental, i.e. gave decreased crankcase deposits, as measured by average varnish in the Sequence V-D results.
  • the table also establishes that the additives of this invention possess lubricating oil compatibility. This is particularly surprising in view of the fact that prior art hydrocarbyl poly(oxypropylene) aminocarbamates are not lubricating oil compatible, i.e.. Examples 18, 19 and 20.
  • the thermal oxidative stability of fuel additives can be measured by thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • the TGA procedure employed Du Pont 951 TGA instrumentation coupled with a microcomputer for data analysis. Samples of the fuel additives, approximately 25 milligrams, were heated isothermally at 200oC under air flowing at 100 cubic centimeters per minute. The weight of the sample was monitored as a function of time. Incremental weight loss is considered to be a first order process.
  • Kinetic data i.e., rate
  • test additive (30 gr) is dissolved in an equivalent weight of reagent grade toluene, cooled to -40oC, and held at that temperature for four weeks. The sample solution is then inspected for visual clarity ("brightness"). If any sedimented solids appear or the sample is hazy, the sample has failed the test. A sample which passes this test is one described as "clear and bright", a well-known
  • Nmr spectroscopy provides a method for measuring the
  • Cr(III)-tris-acetylacetonate i.e., Cr(III) (AcAc) 3 .
  • the ether protons of interest lie in the region between 3.2 and 4.0 ppm.
  • mass of methylene and methine protons which include the separated multiplets observed for the first and the last epoxide units assembled in these
  • Analytical methods for determining the general nature of the alkylphenyl substituent of the aminocarbamates can be accompushed in the following manner: A sample of an alkylphenyl poly(oxyalkylene) aminocarbamate identified by Infrared and Nmr spectroscopy) is hydrolyzed using strong base to afford the corresponding
  • the tropylium ions generated from simple alpha olefins will typically contain from 1-3 carbon atoms more than those accounted for by the aromatic ring itself.
  • the same ionized species generated from the pinwheel alkyl phenols employed in the invention will contain many more carbon atoms due to fragmentation at the benzylic positions. It is important to recognize that such tropylium ion species are readily formed from alkyl phenols, and high energy impact ionization may be too severe a technique for all cases. As a result, under forcing conditions, more detailed information concerning the structure of the alkyl portion may be lost. In these cases, it is possible to examine "low energy" impact ionization which may be useful for observing these tropylium ions. In any event, tropylium ions are noted for their relative stability and more often than not appear as the base ion peak (peak of highest relative intensity). See: Silverstein, Bassler, and Morril,
  • integrated H spectra indicate the relative balance of aryl to aliphatic hydrogens which can be used to approximate the average hydrocarbon content of the phenol. This information may also be obtained by using integrated 13 C Nmr spectra of these products. Thus, the number of aromatic carbons can be used as an internal standard for gauging the average number of saturated carbons in the phenol. Typically, the 1H and 13 C Nmr results are averaged and are in good agreement with the chemical determination. It is assumed that the average alkyl hydrocarbon content of the phenols does not change during the reaction to make the alcohols, chloroformates and carbamates.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On décrit des aminocarbamates liquides de poly(oxypropylène) alkylphényles qui ne se transforment pas en cire lorsque refroidies à -40°C, se trouvant dans une solution de 50 % en poids avec du toluène, lesdits aminocarbamates ayant au moins un azote de base et un poids moléculaire moyen compris entre environ 600 et 6000, et dont le groupe alkyle est formé d'une chaîne sensiblement droite comprenant entre 25 et 50 atomes de carbone. On décrit également des compositions et des concentrés de carburant de même que des compositions et des concentrés d'huile de lubrification contenant lesdits aminocarbamates de poly(oxypropylène) alkylphényles.
PCT/US1988/004710 1988-12-30 1988-12-30 Compositions lubrifiantes a base d'huile ou de carburant contenant des aminocarbamates de poly(oxypropylene) alkylphenyles de type ''a roue a aiguille'' a chaine sensiblement droite. WO1990007564A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP19890903547 EP0419488A4 (en) 1988-12-30 1988-12-30 Lubricating oil compositions and fuel compositions containing substantially straight chain pinwheel alkylphenyl poly(oxypropylene) aminocarbamates
AU32868/89A AU633481B2 (en) 1988-12-30 1988-12-30 Lubricating oil compositions and fuel compositions containing substantially straight chain pinwheel alkylphenyl poly(oxypropylene) aminocarbamates
BR888807893A BR8807893A (pt) 1988-12-30 1988-12-30 Poli(oxipropileno)aminocarbamato alquilfenilico liquido,composto,composicao e concentrado de combustivel e de oleo lubrificante,e alquilfenol
JP89503274A JPH03504376A (ja) 1988-12-30 1988-12-30 実質上直鎖のピンホイールアルキルフェニルポリ（オキシプロピレン）アミノカルバメートを含有する、潤滑油組成物及び燃料組成物
PCT/US1988/004710 WO1990007564A1 (fr) 1988-12-30 1988-12-30 Compositions lubrifiantes a base d'huile ou de carburant contenant des aminocarbamates de poly(oxypropylene) alkylphenyles de type ''a roue a aiguille'' a chaine sensiblement droite.
FI904247A FI93441C (fi) 1988-12-30 1990-08-28 Alkyylifenyylipoly(oksipropyleeni)aminokarbamaatteja ja niitä sisältäviä voiteluöljy- ja polttoainekoostumuksia
KR90701956A KR0120110B1 (en) 1988-12-30 1990-08-31 Lubrication oil compositions and fuel compositions containing substantially straight chain pinwheel alkylphenyl poly(oxypropylene)aminocarbamates

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1988/004710 WO1990007564A1 (fr) 1988-12-30 1988-12-30 Compositions lubrifiantes a base d'huile ou de carburant contenant des aminocarbamates de poly(oxypropylene) alkylphenyles de type ''a roue a aiguille'' a chaine sensiblement droite.

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US5366517A (en) * 1992-12-18 1994-11-22 Chevron Research And Technology Company Fuel additive compositions containing poly(oxyalkylene) hydroxyaromatic ethers and poly(oxyalkylene) amines
US5366519A (en) * 1992-12-18 1994-11-22 Chevron Research And Technology Company Fuel additive compositions containing poly(oxyalkylene) hydroxyaromatic esters and poly(oxyalkylene) amines
EP0752415A1 (fr) * 1995-07-06 1997-01-08 Chevron Chemical Company Amides aromatiques de poly(oxyalkylène) carbamates et composition de combustible les contenant
WO2023089354A1 (fr) 2021-11-16 2023-05-25 Hediger Richard Procédé de production d'un additif pour carburant

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US6841616B2 (en) * 2003-03-28 2005-01-11 Arkema Inc. Polymerization of halogen-containing monomers using siloxane surfactant

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EP0752415A1 (fr) * 1995-07-06 1997-01-08 Chevron Chemical Company Amides aromatiques de poly(oxyalkylène) carbamates et composition de combustible les contenant
WO2023089354A1 (fr) 2021-11-16 2023-05-25 Hediger Richard Procédé de production d'un additif pour carburant

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EP0419488A1 (fr) 1991-04-03
BR8807893A (pt) 1990-12-11
KR910700324A (ko) 1991-03-14
JPH03504376A (ja) 1991-09-26
EP0419488A4 (en) 1994-11-23
KR0120110B1 (en) 1997-10-22

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