WO1987001722A1 - Diesel lubricants and methods - Google Patents

Diesel lubricants and methods Download PDF

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Publication number
WO1987001722A1
WO1987001722A1 PCT/US1986/001890 US8601890W WO8701722A1 WO 1987001722 A1 WO1987001722 A1 WO 1987001722A1 US 8601890 W US8601890 W US 8601890W WO 8701722 A1 WO8701722 A1 WO 8701722A1
Authority
WO
WIPO (PCT)
Prior art keywords
lubricant
group
acid
succinic
groups
Prior art date
Application number
PCT/US1986/001890
Other languages
English (en)
French (fr)
Inventor
David E. Ripple
Jack Lee Karn
Daniel M. Vargo
Original Assignee
The Lubrizol Corporation
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 The Lubrizol Corporation filed Critical The Lubrizol Corporation
Priority to AT86905651T priority Critical patent/ATE99355T1/de
Priority to BR8606979A priority patent/BR8606979A/pt
Priority to DE3689473T priority patent/DE3689473T2/de
Publication of WO1987001722A1 publication Critical patent/WO1987001722A1/en
Priority to FI872181A priority patent/FI872181A0/fi
Priority to NO872068A priority patent/NO872068L/no
Priority to DK253787A priority patent/DK253787D0/da

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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
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    • 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
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    • 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
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • 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
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    • 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
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    • 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
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus 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
    • 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
    • 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
    • C10M2223/042—Metal salts thereof
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • 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
    • 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
    • C10N2010/02—Groups 1 or 11
    • 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
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B2275/00—Other engines, components or details, not provided for in other groups of this subclass
    • F02B2275/14—Direct injection into combustion chamber

Definitions

  • the present invention relates to diesel lubricants, and more particularly to diesel lubricants containing additives which are effective to minimize undesirable viscosity increases of the lubricant when the lubricant is used in diesel engines.
  • the invention also relates to methods of preparing basic alkali metal sulfonates, particularly basic potassium sulfonates, and a method of operating diesel engines which comprises lubricating said engines during operation with the diesel lubricants of the invention.
  • lubricating oils tend to deteriorate under conditions of use in present day internal combustion engines resulting in the formation of sludge, lacquer, carbonaceous materials and resinous materials which tend to adhere to the various engine parts, in particular, the engine rings, grooves and skirts.
  • diesel engines operated at low- speed and high-torque such as under prolonged idle and stop-and-go conditions have experienced extensive and undesirable thickening of the lubricant.
  • the undesirable thickening of the oil is caused by the high levels of insolubles (soot) .
  • One class of compounds which has been suggested for use in lubricating oils, particularly diesel oils are the normal and overbased sulfurized calcium alkyl phenolates such as described in U.S.
  • Another multi-purpose additive for lubricating oils having antioxidant, anti- thickening, anti-corrosion and detergent properties is described in U.S. Patent 3,897,352.
  • the additive described in this patent comprises a sulfurized. Group II metal nitrated alkyl phenolate.
  • the present invention relates to • a diesel lubricant containing certain specified types of carboxylic derivative compositions as dispersants and certain basic alkali metal salts.
  • This combination of specific dispersant and detergent is effective to minimize undesirable viscosity increases of diesel lubricants when used in diesel engines.
  • Lubricating oil formulations containing oil- soluble carboxylic acid derivatives and in particular, those obtained by the reaction of a carboxylic acid with an amino compound have been described previously such as in U.S. Patents 3,018,250; 3,024,195; 3,172,892; 3,216,936; 3,219,666; and 3,272,746.
  • Many of the above-identified patents also describe the use of such carboxylic acid derivatives in lubricating oils in combination with ash-containing detergents including basic metal salts of acidic organic materials such as sulfonic acids, carboxylic acids, etc.
  • the particular type of carboxylic acid derivative composition utilized in the diesel lubricant of the present invention are described generally in U.S. Patent 4,234,435.
  • This patent also describes lubricating compositions containing said carboxylic acid derivative compositions in combination with other additives such as fluidity modifiers, auxiliary detergents and dispersants of the ash-producing or ashless-type, oxidation inhibitors, etc.
  • a lubricating composition containing the carboxylic acid derivative, a basic calcium sulfonate, and other traditional additives is described in the '435 patent in Col. 52, lines 1-8.
  • the second critical component of the diesel lubricants of the present invention is at least one basic alkali metal salt of at least one acidic organic compound having a metal ratio of at least about 2.
  • Such compositions generally are referred to in the art as metallic or ash-detergents, and the use of such detergents in the lubricating oil formulations has been suggested in many prior art patents.
  • Canadian Patent 1,055,700 describes the use of basic alkali sulfonate dispersions in crankcase lubricants for both spark-ignited and compression-ignited internal combustion engines.
  • a lubricant In order to constitute an acceptable diesel lubricant, a lubricant must achieve two performance levels: Classification CC(Caterpillar 1-H) and Classification CD(Caterpillar 1-G) , with the 1-G level representing more severe, highly super-charged engine operation.
  • Classification CC(Caterpillar 1-H) and Classification CD(Caterpillar 1-G) There continues to be a need in the industry for compositions which can be added to diesel lubricants ' which will minimize, if not prevent; undesirable viscosity increase of the lubricant when used in diesel engines, and when formulated into diesel lubricants, the lubricants are capable of achieving Caterpillar 1-H and Caterpillar 1-G level performance without significantly adding to the cost of the diesel lubricant.
  • a diesel lubricant which comprises a major amount of an oil of lubricating viscosity and a minor amount, sufficient to minimize undesirable viscosity increases of the lubricant when used in diesel engines, of a composition
  • a composition comprising (A) at least one carboxylic derivative composition produced by reacting at least one substituted succinic acylating agent with at least one a ino compound containing at least one -NH- group wherein said acylating agent consists of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene characterized by an Mn value of at least about 1200 and an Mw/Mn ratio of at least about 1.5, and wherein said acylating agents are characterized by the presence within their structure of an average of at least about 1.3 succinic groups for each e-quivalent weight of substituent groups, and (B) at least one
  • the basic alkali metal salt (B) contained in the diesel lubricants of the invention is at least one sodium salt and more preferably, a sodium salt of a sulfoni ⁇ acid.
  • the invention also includes methods for preparing basic metal salts, particularly potassium salts, and methods for operating diesel engines which comprise lubricating said engines during operation with the diesel lubricants of the invention. Description of the Preferred Embodiments
  • the diesel lubricants of the present invention comprise a major amount of an oil of lubricating viscosity and a minor amount, sufficient to minimize undesirable viscosity increases of the lubricant when used in diesel engines, of a composition comprising a combination of (A) at least one carboxylic derivative composition as defined more fully below, and (B) at least one basic alkali metal salt of at least one acidic organic compound.
  • the oil of lubricating viscosity which is utilized in the preparation of the diesel lubricants of the invention may be based on natural oils, synthetic oils, or mixtures thereof.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffini ⁇ , naphthenic or mixed paraffinic- naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful.
  • animal oils and vegetable oils e.g., castor oil, lard oil
  • mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffini ⁇ , naphthenic or mixed paraffinic- naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful.
  • Synthetic lubricating oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.); poly(l-hexenes) , poly(l-octenes) , poly(l-decenes) , etc.
  • polymerized and interpolymerized olefins e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.
  • poly(l-hexenes) poly(l-octenes)
  • poly(l-decenes) etc.
  • alkylbenzenes e.g., dodecylbenzenes, tetra- decylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)- benzenes, etc.
  • polyphenyls e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils that can be used. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C3 fatty acid esters, or the C- ⁇ Oxo acid diester of tetraethylene glycol.
  • the oils prepared through polymerization of ethylene oxide or propylene oxide
  • esters of di ⁇ arboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, maloni ⁇ acid, alkyl malonic acids, alkenyl malonic acids, etc.
  • alcohols e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.
  • these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate
  • Esters useful as synthetic oils also include those made from C 5 to C j _ 2 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, tri ethylol propane, pentaerythritol, dipentaery- thritol, tripentaerythritol, etc.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butyl- phenyl)silicate, hexyl-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes, poly(methylphenyl)siloxanes, etc.).
  • synthetic lubricants e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4
  • Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.), polymeric tetrahydrofurans and the like.
  • Unrefined, refined and rerefined oils either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed herein- above can be used in the concentrates of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
  • Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
  • Component (A) which is utilized in the diesel lubricants of the present invention is at least one carboxylic derivative composition produced by reacting at least one substituted succinic acylating agent with at least one amino compound containing at least one -N-H- group wherein said acylating agent consists of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene characterized by an Mn value of at least about 1200 and an Mw/Mn ratio of at least about 1.5, and wherein said acylating • agents are characterized by the presence within their structure of an- average of at least about 1.3 succinic groups for each equivalent weight of substituent groups.
  • the substituted succinic acylating agent utilized the preparation of the carboxylic. derivative can be characterized by the presence within its structure of two groups or moieties.
  • the first group or moiety is referred to hereinafter, for convenience, as the "substituent group(s)" and is derived from a polyalkene.
  • the polyalkene from which the substituted groups are derived is characterized by an Mn (number average molecular weight) value of at least 1200 and more generally from about 1500 to about 5000, and an Mw/Mn value of at least about 1.5 and more generally from about 1.5 to about 6.
  • Mw represents the weight average molecular weight.
  • the number average molecular weight and the weight average molecular weight of the polybutenes can be measured by well known techniques of vapor phase osmometry (VPO) , membrane osmometry and gel permeation chromatography (GPC) . These techniques are well known to those skilled in the art and need not be described herein.
  • succinic group(s) The second group or moiety is referred to herein as the "succinic group(s)".
  • the succinic groups are those groups characterized by the structure
  • X and X 1 are the same or different provided at least one of X and X' is such that the substituted succinic acylating agent can function as carboxylic acylating agents. That is, at least one of X and X' must be such that the substituted acylating agent can form amides or amine salts with, and otherwise function as a conventional carboxylic acid acylating agents. Transesterification and transamidation reactions are considered, for purposes of this invention, as conventional acylating reactions.
  • X and/or X 1 is usually -OH, -O-hydrocarbyl, -0-M + where M + represents one equivalent of a metal, ammonium or amine cation, -NH 2 , -Cl, -Br, and together, X and X' can be -0- so as to form the anhydride.
  • M + represents one equivalent of a metal, ammonium or amine cation, -NH 2 , -Cl, -Br, and together, X and X' can be -0- so as to form the anhydride.
  • the specific identity of any X or X' group which is not one of the above is not critical so long as its presence does not prevent the remaining group from entering into acylation reactions.
  • X and 1 are each such that both carboxyl functions of the succinic group (i.e., both -C(0)X and -C(0)X' can enter into acylation reactions.
  • the substituted succinic acylating agents are characterized by the presence within their structure of 1.3 succinic groups (that is, groups corresponding to Formula I) for each equivalent weight of substituent groups.
  • the number of equivalent weight of substituent groups is deemed to be the number corresponding to the quotient obtained by dividing the Mn value of the polyalkene from which the substituent is derived into the total weight of the substituent groups present in the substituted succinic acylating agents.
  • substituted succinic acylating agents within this invention is that the substituent groups must have been derived from a polyalkene characterized by an Mw/Mn value of at least about 1.5.
  • Polyalkenes having the Mn and Mw values discussed above are known in the art and can be prepared according to conventional procedures. Several such polyalkenes, especially polybutenes, are commercially available.
  • the succinic groups will normally correspond to the formula
  • R and R' are each independently selected from the group consisting of -OH, -Cl, -O-lower alkyl, and when taken together, R and R' are -0-.
  • the succinic group is a succinic anhydride group. All the succinic groups in a particular succinic acylating agent need not be the same, but they can be the same. Preferably, the succinic groups will correspond to
  • substituted succinic acylating agents wherein the succinic groups are the same or different is within the ordinary skill of the art and can be accomplished through conventional procedures such as treating the substituted succinic acylating agents themselves (for example, hydrolyzing the anhydride to the free acid or converting the free acid to an acid chloride with thionyl chloride) and/or selecting the appropriate aleic or fumaric reactants.
  • the minimum number of succinic groups for each equivalent weight of substituent group is 1.3.
  • the maximum number generally will not exceed 6.
  • the minimum will be 1.4; usually 1.4 to about 6 succinic groups for each equivalent weight of substituent group.
  • a range based on this minimum is at least 1.5 to about 3.5, and more generally about 1.5 to about 2.5 succinic groups per equivalent weight of substituent groups.
  • substituted succinic acylating agents of this invention can be represented by the symbol R a j _(R 2 ) y wherein R- j _ represents one equivalent weight of substituent group, R 2 represents one succinic group corresponding to Formula (I) , Formula (II) , or Formula (III) , as discussed above, and y is a number equal to or greater than 1.3.
  • R- j _ and R represent more preferred substituent groups and succinic groups, respectively, as discussed elsewhere herein and by letting the value of y vary as discussed above.
  • a minimum Mw/Mn value of about 1.8 is preferred with a range of values of about 1.8 up to about 3.6 also being preferred.
  • a still more- preferred minimum value of Mw/Mn is about 2.0 with a preferred range of values of from about 2.0 to about 3.4 also being a preferred range.
  • An especially preferred minimum value of Mw/Mn is about 2.5 with a range of values of about 2.5 to about 3.2 also being especially preferred.
  • succinic acylating agents are intended to be understood as being both independent and dependent. They are intended to be independent in the sense that, for example, a preference for a minimum of 1.4 or 1.5 succinic groups per equivalent weight of substituent groups is not tied to a more preferred value of Mn or Mw/Mn. They are intended to be dependent in the sense that, for example, when a preference for a minimum of 1.4 or 1.5 succinic groups is combined with more preferred values of Mn and/or Mw/Mn, the combination of preferences does in fact describe still further more preferred embodiments of the invention.
  • the polyalkenes from which the substituent groups are derived are homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms; usually 2 to about 6 carbon atoms.
  • the interpolymers are those in which two or more olefin monomers are interpolymerized according to well-known conventional procedures to form polyalkenes having units within their structure derived from each of said two or more olefin monomers.
  • "interpolymer(s) " as used herein is inclusive of copolymers, terp ⁇ lymers, tetrapolymers, and the like.
  • the polyalkenes from which the substituent groups are derived are often conventionally referred to as "polyolefin(s) ".
  • - polymerizable internal olefin monomers (sometimes referred to in the literature as medial olefins) characterized by the presence within their structure of the group
  • polyalkenes can also be used to form the polyalkenes.
  • internal olefin monomers When internal olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which are_ interpolymers.
  • terminal olefins For purposes of this invention, when a particular polymerized olefin monomer can be classified as both a terminal olefin and an internal olefin, it will be deemed to be a terminal olefin.
  • pentadiene-1,3 i.e., piperylene
  • the polyalkenes from which the substituent groups of the succinic acylating agents are derived generally are hydrocarbon groups such as lower alkoxy, lower alkyl mercapto, hydroxy, mercapto, oxo, as keto and aldehydro groups, nitro, halo, cyano, carboalkoxy, (where alkoxy is usually lower alkoxy) , alkanoyloxy, and the like provided the non-hydrocarbon substituents do not substantially interfere with formation of the substituted succinic acid acylating agents of this invention. When present, such non-hydrocarbon groups normally will not contribute more than about 10% by weight of the total weight of the polyalkenes.
  • the polyalkene can contain such non-hydrocarbon substituent, it is apparent that the olefin monomers from which the polyalkenes are made can also contain such substituents. Normally, however, as a matter of practicality and expense, the olefin monomers and the polyalkenes will be free from non- hydrocarbon groups, except chloro groups which usually facilitate the formation of the substituted succinic acylating agents of this invention. (As used herein, the term "lower” when used with a chemical group such as in "lower alkyl” or “lower alkoxy” is intended to describe groups having up to 7 carbon atoms) .
  • the polyalkenes may include aromatic groups (especially phenyl groups and lower alkyl- and/or lower alkoxy-substituted phenyl groups such as para-(tert-butyl)phenyl) and cycloaliphatic groups such as * would be obtained from polymerizable cyclic olefins or cycloaliphatic substituted-polymerizable acyclic olefins, the polyalkenes usually will be free from such groups.
  • polyalkenes derived from interpolymers of both 1,3-dienes and styrenes such as butadiene-1,3 and styrene or para-(tert-butyl)styrene are exceptions to this generalization.
  • the olefin monomers from which the polyalkenes are prepared can contain aromatic and cycloaliphatic groups.
  • polyalkene there is a general preference for aliphatic, hydrocarbon polyalkenes free from aromatic and cycloaliphatic groups (other than the diene-styrene interpolymer exception already noted) .
  • polyalkenes which are derived from the group consisting of homopolymers and interpolymers of terminal hydrocarbon olefins of 2 to about 16 carbon atoms.
  • interpolymers of terminal olefins are usually preferred, interpolymers optionally containing up to about 40% of polymer units derived from internal olefins of up to about 16 carbon atoms are also within a preferred group.
  • a more preferred class of polyalkenes are those selected from the group consisting of homopolymers and interpolymers of terminal olefins of 2 to about 6 carbon atoms, more preferably 2 to 4 carbon atoms.
  • another preferred class of polyalkenes are the latter more preferred polyalkenes optionally containing up to about 25% of polymer units derived from internal olefins of up to about 6 carbon atoms.
  • terminal and internal olefin monomers which can be used to prepare the polyalkenes according to conventional, well-known polymerization techniques include ethylene; propylene; butene-1; butene-2; isobutene; pentene-1; hexene-1; heptene-1; octene-1; nonene-1; decene-1; pentene-2; propylene-tetramer; diisobutylene; isobutylene trimer; butadiene-1,2; butadiene-1,3; pentadiene-1,2; penta- diene-1,3; pentadiene-1,4; isoprene; hexadiene-1,5; 2-chloro-butadiene-l,3; 2-methyl-heptene-l; 3-cy ⁇ lo- hexylbutene-1; 2-methyl-pentene-1; styrene; 2,4- dichloro styrene
  • hydrocarbon polymerizable monomers are preferred and of these hydrocarbon monomers, the terminal olefin monomers are particularly preferred.
  • polyalkenes include polypropylenes, polybutenes, ethylene-propylene copolymers, styrene-isobutene copolymers, isobutene- butadiene-1,3 copolymers, propene-isoprene copolymers, isobutene-chloroprene copolymers, isobutene-(para- methyl)styrene copolymers, copolymers of hexene-1 with hexadiene-1,3, copolymers of o ⁇ tene-1 with hexene-1, copolymers of heptene-1 with pentene-1, copolymers of 3-methyl-butene-1 with octene-1, copolymers of 3,3- dimethyl-pentene-1 with hex
  • interpolymers include copolymer of 95% (by weight) of isobutene with 5% (by weight) of styrene; terpoly er of 98% of isobutene with 1% of piperylene and -1% of chloroprene; terpolymer of.95% of isobutene with 2% of butene-1 and 3% of hexene-1; terpolymer of 60% of isobutene with 20% of pentene-1 and 20% of octene-1; copolymer of .80% of hexene-1 and 20% of heptene-1; terpolymer of 90% of isobutene with 2% of cy ⁇ lohexene and 8% of propylene; and copolymer of 80% of ethylene and 20% of propylene.
  • a preferred source of polyalkenes are the poly(isobutene)s obtained by polymerization of C 4 refinery stream having a butene content of about 35 to about 75% by weight and an isobutene content of about 30 to about 60% by weight in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (greater than about 80% of the total repeating units) of isobutene repeating units of the configuration
  • one or more of the above-de-scribed polyalkenes is reacted with one or more acidic reactants selected from the group consisting of maleic or fumaric reactants of the general formula
  • maleic and fumaric reactants will- be one or more compounds corresponding to the formula
  • the maleic or fumaric reactants will be maleic acid, fumaric acid, maleic anhydride, or a mixture of two or more of these.
  • the maleic reactants are usually preferred over the fumaric reactants because the former are more readily available and are, in general, more readily reacted with the polyalkenes (or derivatives thereof) to prepare the substituted succinic acylating agents of the present invention.
  • the especially preferred reactants are maleic acid, maleic anhydride, and mixtures of these. Due to availability and ease of reaction, maleic anhydride will usually be employed.
  • the one or more polyalkenes and one or more maleic or fumaric reactants can be reacted according to any of several known procedures in order to produce the substituted succinic acylating agents of the present invention.
  • the procedures are analogous to procedures used to prepare the high molecular weight succinic anhydrides and other equivalent - succinic acylating analogs thereof except that the polyalkenes (or polyolefins) of the prior art are replaced with the particular polyalkenes described above and the amount of maleic or fumaric reactant used must be such that there is at least 1.3 succinic groups for each equivalent weight of the substituent group in the final substituted succinic acylating agent produced.
  • maleic reactant is often used hereafter. When used, it should be understood that the term is generic to acidic reactants selected from maleic and fumaric reactants corresponding to Formulae (IV) and (V) above including a mixture of such reactants.
  • Chlorination is generally carried out at a temperature of about 75°C to about 125°C. If a diluent is used in the chlorination procedure, it should be one which is not itself readily subject to further chlorination. Poly- and perchlorinated and/or fluorinated alkanes and benzenes are examples of suitable diluents.
  • the second step in-the two-step chlorination procedure is to react the chlorinated polyalkene with the maleic reactant at a temperature usually within the range of about 100°C to about 200°C.
  • the mole ratio of chlorinated polyalkene to maleic reactant is usually about 1:1.
  • a mole of chlorinated polyalkene is that weight of chlorinated polyalkene corresponding to the Mn value of the unchlorinated polyalkene.
  • a stoichiometric excess of maleic reactant can be used, for example, a mole ratio of 1:2.
  • an equivalent weight of chlorinated polyalkene is the weight corresponding to the Mn value divided by the average number of chloro groups per molecule of chlorinated polyalkene while the equivalent weight of a maleic reactant is its molecular weight.
  • the ratio of chlorinated polyalkene to maleic reactant will normally be such as to provide about one equivalent of maleic reactant for each mole of chlorinated polyalkene up to about one equivalent of maleic reactant for each equivalent of chlorinated polyalkene with the understanding that it is normally desirable to provide an excess of maleic reactant; for example, an excess of about 5% to about 25% by weight. Unreacted excess maleic reactant may be stripped from the reaction . product, usually under vacuum, or reacted during a further stage of the' - process as explained below.
  • the resulting polyalkenyl-substituted succinic acylating agent is, optionally, again chlorinated if the desired number of succinic groups are not present in the product. If there is present, at the time of this subsequent chlorination, any excess maleic reactant from the second step, the excess will react as additional chlorine is introduced during the subsequent chlorination. Otherwise, additional maleic reactant is introduced during and/or subsequent to the additional chlorination step. This technique can be repeated until the total number of succinic groups per equivalent weight of substituent groups reaches the desired level.
  • Another procedure for preparing substituted succinic acid acylating agents of the invention utilizes a process described in U.S. Patent 3,912,764 and U.K. Patent 4,440,219, both of which are expressly incorporated herein by re erence for their teachings in regard to that process.
  • the polyalkene and the maleic reactant are first reacted by heating them together in a "direct alkylation" procedure.
  • chlorine is introduced into the reaction mixture to promote reaction of the remaining unreacted maleic reactants.
  • 0.3 to 2 or more moles of maleic anhydride are used in the reaction for each mole of olefin polymer; i.e., polyalkene.
  • the direct alkylation step is conducted at temperatures of 180°C to 250°C. During the chlorine-introducing- stage, a temperature-of 160°C to 225°C is employed. In utilizing this process to prepare the substituted succinic acylating agents of this invention, it would be necessary to use sufficient maleic reactant and chlorine to incorporate at least 1.3 succinic groups into the final product for each equivalent weight of polyalkene.
  • the one-step process involves preparing a mixture of the polyalkene and the maleic reactant containing the necessary amounts of both to provide the desired substituted succinic acylating agents of this invention. This means that there must be at least 1.3 moles of maleic reactant for each mole of polyalkene in order that there can be at least 1.3 succinic groups for each equivalent weight of substituent groups. Chlorine is then introduced into the mixture, usualy by passing chlorine gas through the mixture with agitation, while maintaining a temperature of at least about 140°C.
  • the polyalkene is sufficiently fluid at 140°C and above, there is no need to utilize an additional substantially inert, normally liquid solvent/diluent in the one-step process.
  • a solvent/diluent it is preferably one that resists chlorination.
  • the poly- and per-chlorinated and/or -fluorinated alkanes, cy ⁇ loalkanes, and benzenes can be used for this purpose.
  • Chlorine may be introduced continuously or intermittently during the one-step process.
  • the rate of introduction of the chlorine is not critical although, for maximum utilization of the chlorine, the rate * should be about the same as the rate of consumption of chlorine in the course of the reaction.
  • the introduction rate of chlorine exceeds the rate of consumption, chlorine is evolved from the reaction mixture. It is ' often advantageous to use a closed system, including superatmospheric pressure, in order to prevent loss of chlorine so as to maximize chlorine utilization.
  • the minimum temperature at which the reaction in the one-step process takes place at a reasonable rate is about 140°C.
  • the minimum temperature at which the process is normally carried out is in the neighborhood of 140°C.
  • the preferred temperature range is usually between about 160°C and about 220°C. Higher temperatures such as 250°C or even higher may be used but usually with litle advantage. In fact, temperatures in excess of 220°C are often disadvantageous with respect to preparing the particular acylated succinic compositions * of this invention because they tend to "crack" the polyalkenes (that is, reduce their molecular weight by thermal degradation) and/or decompose the maleic reactant. For this reason, maximum temperatures of about 200°C to about 210°C are normally not exceeded.
  • the upper limit of the useful temperature in the one-step process is determined primarily by the decomposition point of the components in the reaction mixture including the reactants and the desired products.
  • the decomposition point is that temperature at which there is sufficient decomposition of any reactant or product such as to interfere with the production of the desired products.
  • the molar ratio of maleic reactant to chlorine is such that there is at least about one mole of chlorine for each mole of maleic reactant to be incorporated into the product. Moreover, for practical reasons, a slight excess. usually in the neighborhood of about 5% to about 30% by weight of chlorine, is utilized in order to offset any loss of chlorine from the- reaction mixture. Larger amounts of excess chlorine may be used but do not appear to produce any beneficial results.
  • the molar ratio of polyalkene to maleic reactant is such that there is at least about 1.3 moles of maleic reactant for each mole of polyalkene. This is necessary in order that there can be at least 1.3 succinic groups per equivalent weight of substituent group in the product. Preferably, however, an excess of maleic reactant is used. Thus, ordinarily about a 5% to about 25% excess of maleic reactant will be used relative to that amount necessary to provide the desired number of succinic groups in the product.
  • a preferred process for preparing the substituted acylating compositions of this invention comprises heating and contacting at a temperature of. at least about 140°C up to the decomposition temperature
  • the substituted acylated compositions as produced by such a process are, likewise, part of this invention.
  • a direct alkylation reaction can precede the introduction of chlorine.
  • the original reaction mixture will contain the total amount of polyalkene and acidic reactant to be utilized.
  • the amount of chlorine used will normally be such as to provide about one mole of chlorine for each unreacted mole of (B) present at the time chlorine introduction is commenced.
  • the amount of chlorine introduced to complete reaction will be based on the unreacted 0.75 mole of (B) ; that is, at least about 0.75 mole of chlorine (or an excess as explained above) will then be introduced.
  • R and R' are as defined above, and
  • This process, as described, includes only the one-step process; that is. a process where all of both (A) and (B) are present in the initial reaction mixture.
  • the substituted acylated composition as produced by such a process are, likewise, part of this invention.
  • substituted succinic acylating agent(s) is used in describing the substituted succinic acylating agents regardless of the process by which they are produced. Obviously, as discussed in more detail hereinbefore, several processes are available for producing the substituted succinic acylating agents.
  • substituted acylating composition(s) is used to describe the reaction mixtures produced by the specific preferred processes described in detail herein. Thus, the identity_of particular substituted acylating compositions is dependent upon a particular process of manufacture. It is believed that the novel acylating agents used in . this invention can best be described and claimed in the alternative manner inherent in the use of this terminology as thus explained. This is particularly true because, while the products of this invention are clearly substituted succinic acylating agents as defined and discussed above, their structure cannot be represented by a single specific chemical formula. In fact, mixtures of products are inherently present.
  • reaction temperature is from about 160°C to about 220°C
  • polyalkenes wherein the polyalkene is a homopolymer or interpoly er of terminal olefins of 2 to about 16 carbon atoms, with the proviso that said interpolymers can optionally contain up to about 40% of the polymer units derived from internal olefins of up to about 16 carbon atoms, constitutes the preferred aspect of the process and compositions prepared by the process.
  • polyalkenes for use in the process and in preparing the compositions of the process are the homopolymers•- and interpolymers of terminal olefins of 2 to 6 carbon atoms with the proviso that said interpolymers can optionally contain up to about 25% of polymer units derived from internal olefins of up to about 6 carbon atoms.
  • Especially preferred polyalkenes are polybutenes, ethylene- propylene copolymers, polypropylenes with the polybutenes being particularly preferred.
  • the succinic group content of the substituted acylating compositions thus produced are preferably the same as that described in regard to the substituted succinic acylating agents.
  • the substituted acylating compositions characterized by the presence within their structure of an average of at least 1.4 succinic groups derived from (B) for each equivalent weight of the substituent groups derived from (A) are preferred with those containing at least 1.4 up to about 3.5 succinic groups derived from (B) for each equivalent weight of substituent groups derived from (A) being still more preferred.
  • substituted acylating compositions characterized by the presence within their structure of at least 1.5 succinic groups derived from (B) for each equivalent weight of substituent group derived from (A) are still further preferred, while those containing at least 1.5 succinic groups derived from (B) for each equivalent weight of substituent group derived from (A) being especially preferred.
  • An especially preferred process for preparing the substituted acylating compositions comprises heating at a temperature of about 160°C to about 220°C a mixture comprising:
  • R and R' are each -OH or when taken together, R and R 1 are -0-, and
  • (C) Chlorine wherein the mole ratio of (A) : (B) is such that there is at least 1.5 moles of (B) for each mole of (A) and the number of moles of (A) is the quotient of the total weight of (A) divided by the value of Mn, and the amount of chlorine employed is such as to provide at least about one mole of chlorine for each mole of (B) to be reacted with (A) , said acylating compositions being characterized by the presence within their structure of an average of at least 1.5 groups derived from (B) for each equivalent weight of the substituent groups derived from (A) .
  • substituted acylating compositions produced by such a process constitute a preferred class of such compositions.
  • acylating reagent(s) is often used hereafter to refer, collectively, to both the substituted succinic acylating agent and to the substituted acylating compositions used in this invention.
  • the acylating reagents of this invention are intermediates in processes for preparing the carboxylic derivative compositions (A) comprising reacting one or more acylating reagents with an amino compound characterized by the presence within its structure of at least one group.
  • the amino compound characterized by the presence within its structure of at least one -NH- group can be a monoamine or polyamine compound.
  • hydrazine and substituted hydrazines containing up to three substituents are included as amino compounds suitable for preparing carboxylic derivative compositions. Mixtures of two or more amino compounds can be used in the reaction with one or more acylating reagents of this invention.
  • the amino compound contains at least one primary amino group (i.e., -NH 2 ) and more preferably the amine is a polyamine, especially a polyamine containing at least two -NH- groups, either or both of which are primary or secondary amines.
  • the polyamines not only result in - carboxylic acid derivative compositions derived from- monoamines, but these preferred polyamines result in carboxylic derivative compositions which exhibit more pronounced V.I. improving properties.
  • the amines can be aliphatic, cyclo ⁇ aliphatic, aromatic, .
  • heterocy ⁇ lic including aliphatic-substituted cycloaliphatic, aliphatic- substituted aromatic, aliphatic-substituted hetero ⁇ cy ⁇ lic, cycloaliphatic-substituted aliphatic, cy ⁇ lo- aliphatic-substituted heterocyclic, aromatic-substi ⁇ tuted aliphatic, aromatic-substituted cycloaliphatic, aromatic-substituted heterocyclic, heterocyclic-substi- tuted aliphatic, heterocycli ⁇ -substituted alicycli ⁇ , and heterocy ⁇ lic-substituted aromatic amines and may be saturated or unsaturated.
  • the amines may also contain non-hydrocarbon substituents or groups as long as these groups do not significantly interfere with the reaction of the amines with the acylating reagents of this invention.
  • non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl mercapto, nitro, interrupting groups such as -o- and -S- (e.g., as in such groups as -CH 2 CH 2 -X- CH 2 CH - where X is -O- or -S-) .
  • the amines ordinarily contain less than about 40 carbon atoms in total and usually not more than about 20 carbon atoms in total.
  • Aliphatic monoamines include mono-aliphatic and di-aliphatic substituted amines wherein the aliphatic groups can be saturated or unsaturated and straight or branched chain. Thus, they are primary or secondary aliphatic amines. Such amines include, for example, mono- and di-alkyl-substituted amines, mono- and di-alkenyl-substituted amines, and amines having one N-alkenyl substituent and one N-alkyl substituent and the like. The total number of carbon atoms in these aliphatic monoamines will, as mentioned before, normally will not exceed about 40 and usually not exceed about 20 carbon atoms.
  • Such monoamines include ethylamine, diethylamine, n-butylamine, di-n-butylammine, allylamine, isobutyl- a ine, cocoamine, stearylamine, laurylamine, methyl- lauryla ine, oleylamine, N-methyl-octylamine, dode ⁇ yl- amine, octadecylamine, and the like.
  • Examples of cy ⁇ loaliphatic-substituted aliphatic amines, aromatic- substituted aliphatic amines, and hetero ⁇ yclic-substi- tuted aliphatic amines include 2-( ⁇ y ⁇ lohexyl)-ethyl- amine, benzylamine, phenethylamine, and 3-(furylpropyl) amine.
  • Cycloaliphatic monoamines are those monoamines wherein there is one cycloaliphatic substituent attached directly to the amino nitrogen through a carbon atom in the cyclic ring structure.
  • Examples of cycloaliphatic monoamines include cy ⁇ lohexylamines, cyclopentylamines, cyclohexenylamines, cyclopentyl ⁇ amines, N-ethyl-cyclohexylamine, dicyclohexylamines, and the like.
  • Examples - of aliphatic-substituted, aromatic-substituted, and heterocyclic-substituted • cycloaliphatic monoamines- include propyl-substituted cyclohexylamines, phenyl-substituted cyclopentylamines, and pyranyl-substituted cyclohexylamine.
  • Aromatic amines include those monoamines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen.
  • the aromatic ring will usually be a ononuclear aromatic ring (i.e., one derived from benzene) but can include fused aromatic rings, especially those derived from naphthalene.
  • aromatic monoamines include aniline, di(para-methylphenyl) amine, naphthylamine, N-(n-butyl)aniline, and the like.
  • Examples of aliphatic-substituted, cycloaliphatic-substituted, and heterocyclic-substituted aromatic monoamines are para-ethoxyaniline, para-dodecylaniline, cyclohexyl- substituted naphthylamine, and thienyl-substituted aniline.
  • Polyamines are aliphatic, cycloaliphatic and aromatic polyamines analogous to the above-described monoamines except for the presence within their structure of another amino nitrogen.
  • the other amino nitrogen can be a primary, secondary or tertiary amino nitrogen.
  • polyamines examples include N-amino- propyl-cyclohexylamines, N,N'-di-n-butyl-para-phenylene diamine, bis-(para-aminophenyl)methane, 1,4-diamino- cyclohexane, and the like.
  • Heterocyci ⁇ mono- and polyamines can also be used in making the carboxylic derivative compositions of this invention.
  • the terminology "heterocyclic mono- and polyamine(s) " is intended to describe those heterocyclic amines containing at least one primary or secondary amino group and- at least one nitrogen as a heteroatom " in the heterocyclic ring.
  • the hetero-N atom in the ring can be a tertiary -amino nitrogen; that is, one that does not have hydrogen attached directly to the ring nitrogen.
  • Heterocyclic amines can be saturated or unsaturated and can contain various substituents such as nitro, alkoxy, alkyl mercapto, alkyl, alkenyl, aryl, alkaryl, or aralkyl substituents. Generally, the total number of carbon atoms in the substituents will not exceed about 20. Heterocyclic amines can contain hetero atoms other than nitrogen, especially oxygen and sulfur. Obviously they can contain more than one nitrogen hetero atom. The five- and six-membered heterocyclic rings are preferred.
  • heterocyclics are aziridines, azetidines, azolidines, tetra- and di-hydro pyridines, pyrroles, indoles, piperidines, imidazoles, di- and tetrahydroimidazoles, piperazines, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkyl- morpholines, N-aminoalkylthiomorpholines, N-aminoalkyl- piperazines, N,N'-di-aminoalkylpiperazines, azepines, azocines, azonines, anovanes and tetra-, di- and perhydro derivatives of each of the above and mixtures of two or more of these heterocyclic amines.
  • Preferred heterocyclic amines are the saturated 5- and 6-membered heterocyclic amines containing only nitrogen, oxygen and/or sulfur in the hetero ring, especially the piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the like.
  • Piperidine, aminoalkyl- substituted piperidines, piperazine, aminoalkyl- substituted morpholines, pyrrolidine, and aminoalkyl- substituted pyrrolidines are • especially preferred.
  • the a inoalkyl.-substituents are .substituted on a nitrogen atom forming part of the hetero ring.
  • Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine, and N,N'-di-aminoethylpiperazine.
  • Hydroxyamines both mono- and polyamines are also useful as (a) provided they contain at least one primary or secondary amino group.
  • Hydroxy-substituted amines having only tertiary amino nitrogen such as in tri-hydroxyethyl amine are thus excluded as (a) (but can be used as (b) as disclosed hereafter) .
  • the hydroxy-substituted amines contamplated are those having hydroxy substituents bonded directly to a carbon atom other than a carbonyl carbon atom; that is, they have hydroxy groups capable of functioning as alcohols.
  • hydroxy-substituted amines in ⁇ lude ethanolamine, di-(3-hydroxypropy1)-amine, 3-hydroxybutyl-amine, 4-hydroxybutyl-amine, diethanol- amine, di-(2-hydroxypropy1)-amine, N-(hydroxypropyl)- propy1amine, N-(2-hydroxyethyl)-cyclohexylamine, 3-hy- droxycyclopentylamine, para-hydroxyaniline, N-hydroxy- ethyl piperazine, and the like.
  • Hydrazine and substituted-hydrazine can also be used. At least one of the nitrogens in the hydrazine must contain a hydrogen directly bonded thereto. Preferably there are at least two hydrogens bonded directly to hydrazine nitrogen and, more preferably, both hydrogens are on the same nitrogen.
  • the substituents which may be present on the hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and the like. Usually, the substituents are alkyl, especially lower alkyl, phenyl, and substituted phenyl such as lower alkoxy substituted phenyl or lower alkyl substituted phenyl.
  • substituted hydrazines are methylhydrazine, N,N-dimethyl-hydrazine, N,N'-dimethylhydrazine, phenylhydrazine, N-phenyl-N'- ethylhydrazine, N-(para-toly1)-N'-(n-butyl) -hydrazine, N-(para-nitrophenyl)-hydrazine, N-(para-nitrophenyl)- N-methyl-hydrazine, N,N*-di(para-chlorophenol)-hydra ⁇ zine, N-phenyl-N'-cy ⁇ lohexylhydrazine, and the like.
  • the high molecular weight hydrocarbyl amines both mono-amines and polyamines, which can be used as (a) are generally prepared by reacting a chlorinated polyolefin having a molecular weight of at least about 400 with ammonia or amine.
  • a chlorinated polyolefin having a molecular weight of at least about 400 with ammonia or amine.
  • Such amines are known in the art and described, for example, in U.S. Patents 3,275,554 and 3,438,757, both of which are expressly incorporated herein by reference for their disclosure in regard to how to prepare these amines. All that is required for use of these amines is that they possess at least one primary or- secondary amino group.
  • branched polyalkylene polyamines are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogen-bonded aminoalkylene
  • these polyamines contain at least three primary amino groups and at least one tertiary amino group.
  • Suitable amines also include polyoxyalkylene polyamines, e.g., polyoxyalkylene diamines and polyoxyalkylene triamines, having average molecular weights ranging from about 200 to 4000 and preferably from about 400 to 2000.
  • polyoxyalkylene polyamines may be characterized by the formulae
  • m has a value of about 3 to 70 and preferably about 10 to 35.
  • the alkylene groups may be straight or branched chains and contain from 1 to 7 carbon atoms and usually from 1 to 4 carbon atoms.
  • the various alkylene groups present within Formulae (VI) and (VII) may be the same or different.
  • the preferred polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 2000.
  • the polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc. under- the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403, etc.”.
  • the most preferred amines are the alkylene polyamines, including the polyalkylene polyamines, as described in more detail hereafter.
  • the alkylene polyamines include those conforming to the formula
  • n is - from 1 to about 10; each R 3 is independently a hydrogen atom, a hydrocarbyl group or-a hydroxy-substituted hydrocarbyl group having up . to about 30 atoms, with the proviso that at least one R J group is a hydrogen atom and u is an alkylene group of about 2 to about 10 carbon atoms. Preferably u is ethylene or propylene. Especially preferred are the alkylene polyamines where each R 3 is hydrogen with the ethylene polyamines and mixtures of ethylene polyamines being the most preferred. Usually n will have an average value of from about 2 to about 7.
  • alkylene polyamines include methylene polyamine, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines, heptylene polyamines, etc.
  • the higher homologs of such amines and related amino alkyl-substituted piperazines are also included.
  • Alkylene polyamines useful in preparing the carboxylic derivative compositions include ethylene diamine, triethylene tetramine, propylene diamine, trimethylene diamine, hexamethylene diamine, deca ⁇ methylene diamine, ' hexamethylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene)triamine, N-(2-amino- ethyl)piperazine, l,4-bis(2,aminoethyl)piperazine, and the like. Higher homologs as are obtained by condensing two or more of the above-illustrated alkylene amines are useful as (a) as are mixtures of two or more of any of the afore-described polyamines.
  • Ethylene polyamines such as those mentioned above, are especially useful for reasons of cost and effectiveness.
  • Such polyamines are described in detail under the heading "Diamines and Higher Amines” in The Encyclopedia of Chemical Technology, Second Edition, Kirk and Oth er, Volume 7, pages 27-39, Inters ⁇ ience Publishers, Division of John Wiley and Sons, 1965, which is hereby incorporated by reference for the disclosure of useful polyamines.
  • Such compounds are prepared most conveniently by the reaction of an alkylene chloride with ammonia or by reaction of an ethylene imine with a ring-opening reagent such as ammonia, etc.
  • polyamine bottoms can be characterized as having less than two, usually less than one percent (by weight) material boiling below about 200°C.
  • ethylene polyamine bottoms which are readily available and found to be quite useful, the bottoms contain less than about two percent (by weight) total diethylene triamine (DETA) or triethylene tetramine (TETA) .
  • DETA diethylene triamine
  • TETA triethylene tetramine
  • alkylene polyamine bottoms can be reacted solely with the acylating agent, in which case the amino reactant consists essentially of alkylene polyamine bottoms, or they can--be used with other amines and polyamines, or alcohols or mixtures thereof. —In these latter cases at least one amino reactant comprises alkylene polyamine bottoms.
  • Hydroxylalkyl alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms are also useful in preparing derivatives of the afore-described olefini ' c carboxylic acids.
  • Preferred- hydroxylalkyl-substituted alkylene polyamines are those in which the hydroxyalkyl group is a lower hydroxyalkyl group, i.e., having less than eight carbon atoms.
  • hydroxyalkyl-substituted polyamines examples include N-(2-hydroxyethyl)ethylene diamine,N,N-bis(2- hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl) piperazine, monohydroxypropyl-substituted diethylene triamine, dihydroxypropyl-substituted tetraethylene pentamine, . N-(2-hydroxybutyl)tetramethylene diamine, etc.
  • Higher homologs as are obtained by condensation of the above-illustrated hydroxy alkylene polyamines through amino radicals or through hydroxy radicals are likewise useful as (a) . Condensation through amino radicals results in a higher amine accompanied -by removal of ammonia and condensation through the hydroxy radicals results in products containing ether linkages accompanied by removal of water.
  • the carboxylic derivative compositions (A) produced from the acylating reagents and the amino compounds described hereinbefore produce a ⁇ ylated amines which include amine salts, amides, i ides and imidazolines as well as mixtures thereof.
  • a ⁇ ylated amines which include amine salts, amides, i ides and imidazolines as well as mixtures thereof.
  • carboxylic acid derivatives from the acylating reagents and the amino compounds
  • one or more acylating reagents and one or more amino compounds are heated, optionally in the presence - of a normally liquid, substantially inert organic liquid .
  • acylating reagent and the amino compound are reacted in amounts sufficient to provide from about one-half equivalent to about 2 moles of amino compound per equivalent of acylating reagent.
  • an equivalent of amino compound is that amount of the amino compound corresponding to the total weight of amino compound divided by the total number of nitrogens present.
  • octylamine has an equivalent weight equal to its molecular weight
  • ethylene diamine has an equivalent weight equal to one-half its molecular weight
  • aminoethylpiperazine has an equivalent weight equal to one-third its molecular weight.
  • the numbers of equivalents of acylating reagent depends on the number of carboxylic functions (e.g., -C(0)X, -C(0)X', -C(0)R, and -C(0)R', wherein X, X', R and R 1 are as defined above) present in the acylating reagent.
  • carboxylic functions e.g., -C(0)X, -C(0)X', -C(0)R, and -C(0)R', wherein X, X', R and R 1 are as defined above.
  • acylating reagent for each succinic group in the acylating reagents or-,— from another viewpoint, two equivalents for each group in the acylating reagents derived from (B) ; i.e., the maleic reactant from which ⁇ the acylating reagent is prepared.
  • Conventional techniques are readily available for determining the number of carboxyl functions (e.g., acid number, saponification number) and, thus, the number of equivalents of acylating reagent available to react with amine.
  • acylating reagents can be used in the same manner as the high molecular weight acylating agents of the prior art in preparing acylated amines suitable for use as component (A) in the diesel lubricants of this invention.
  • U.S. Patents 3,172,892; 3,219,666; 3,272,746; and 4,234,435 are expressly incorporated herein by reference for their disclosure with respect to the procedures applicable to reacting the acylating reagents with the amino compounds as described above.
  • the acylating reagents the latter can be substituted for the high molecular weight carboxylic acid acylating agents disclosed * in these patents on an equivalent basis. That is, where one equivalent of the high molecular weight carboxylic acylating agent disclosed in these incorporated patents is utilized, one equivalent of the acylating reagent of this invention can be used.
  • acylating reagents of this invention should be reacted with amino compounds which contain sufficient polyfunctional reactant, (e.g., polyamine) so that at least about 25% of the total number of carboxyl groups (from the succinic groups or from the groups derived from the malei ⁇ reactant) are ' reacted with a polyfunctional reactant.
  • polyfunctional reactant e.g., polyamine
  • Another optional aspect of this invention involves the post-treatment of the carboxylic derivative compositions (A) .
  • the process for post- treating the carboxylic acid derivative compositions is again analogous to the post-treating processes used with respect to similar derivatives of the high molecular weight carboxylic acid acylating agents of the prior art. Accordingly, the same reaction conditions, ratio of reactants and the like can be used.
  • Acylated nitrogen compositions prepared by reacting the acylating reagents with an amino compound as described above are post-treated by contacting the acylated nitrogen compositions thus formed (e.g., the carboxylic derivative compositions) with one or more post-treating reagents selected from the group consisting of boron ' oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, carbon disulfide, sulfur, sulfur chlorides, alkenyl cyanides, carboxylic acid acylating agents, aldehydes, ketones, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocar
  • patents also describe post- treating processes and post-treating reagents applicable to the carboxylic derivative compositions (A): U.S. Patents 3,200,107; 3,254,025; 3,256,185; 3,282,955; 3,284,410; 3,366,569; 3,403,102; 3,428,561; 3,502,677; 3,639,242; 3,708,522; 3,865,813; 3,865,740; 3,954;639.
  • the reaction mixture is held at 200-224°C for 6.33 hours, stripped at 210°C under vacuum and filtered.
  • the filtrate is the desired polyisobutene-substituted ._ succinic acylating agent having a saponification equivalent number of 94 as determined by ASTM procedure D-94.
  • the reaction mixture is heated at 201-.236°C with nitrogen blowing for 2 hours and stripped under vacuum at 203°C.
  • the reaction mixture is filtered to yield the filtrate as the desired polyisobutene-substituted succinic acylating agent having a saponification equivalent number of 92 as determined by ASTM procedure D-94.
  • the reaction mixture is cooled to 170°C.
  • 105 parts (1.48 moles) of gaseous chlorine is added beneath the surface in 8 hours.
  • the reaction mixture is heated at 190°C with nitrogen blowing for 2 hours and then stripped under vacuum at 190°C.
  • the reaction mixture is filtered to yield the filtrate as the desired polyisobutene-substituted succinic acylating agent.
  • a mixture of 800 parts of a polyisobutene falling within the scope of the claims of the present invention and having an Mn of about 2000, 646 parts of mineral oil and 87 parts of maleic anhydride is heated to 179°C in 2.3 hours. At 176-180°C, 100 parts of gaseous chlorine is added beneath the surface over a 19-hour period. The reaction mixture is stripped by blowing with nitrogen for 0.5 hour at 180°C. The residue -is an oil-containing solution of the desired polyisobutene-substituted succinic acylating agent.
  • a mixture is prepared by the addition of 10.2 parts (0.25 equivalent) of a commercial mixture of ethylene polyamines having from about 3 to about 10 nitrogen atoms per molecule to 113 parts of mineral oil and 161 parts (0.25 equivalent) of the substituted succinic acylating agent prepared in Example A-l at 138°C.
  • the reaction mixture is heated to 150°C in 2 hours and stripped by blowing with nitrogen.
  • the reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.
  • a mixture is prepared by the addition of 57 parts (1.38 equivalents) of a commercial mixture of ethylene polyamines • having from about 3 to 10 nitrogen atoms per molecule to 1067 parts of mineral oil and 893 parts (1.38 equivalents) of the substituted succinic acylating agent prepared in Example A-2 at 140-145°C.
  • the reaction mixture is heated to 155°C in 3 hours and stripped by blowing with nitrogen.
  • the reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.
  • a mixture is prepared by the addition of 18.2 parts (0.433 equivalent) of a commercial mixture of ethylene polyamines having from about 3 to 10 nitrogen atoms per molecule to 392 parts of mineral oil and 348 parts (0.52 equivalent) of the substituted succinic acylating agent prepared in Example A-2 at 140°C.
  • the reaction mixture is heated to 150°C in 1.8 hours and stripped by blowing with nitrogen.
  • the reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.
  • a mixture is prepared by the addition of 5500 parts of the oil solution of the substituted succinic acylating agent prepared in Example A-7 to 3000 parts of mineral oil and 236 parts of a commercial mixture of ethylene polyamines having an average of about 3-10 nitrogen atoms per molecule at 150°C over a one-hour period.
  • the reaction mixture is heated at 155-165°C for two hours, then stripped by blowing with nitrogen at 165°C for one hour.
  • the reaction mixture is filtered to yield the filtrate as an oil solution of the desired nitrogen-containing product.
  • Examples A-14 through A-27 are prepared by following the general procedure set forth in Example A-10.
  • a mixture is prepared by the addition of 31 parts of carbon disulfide over a period of 1.66 hours to 853 parts of the oil solution of the product prepared in Example A-14 at 113-145°C.
  • the reaction mixture is held at 145-152°C for 3.5 hours, then filtered to yield an oil solution of the desired product.
  • a mixture of 62 parts of boric acid and 2720 parts of the oil solution of the product prepared in Example A-10 is heated at 150°C under nitrogen for 6 hours.
  • the reaction mixture is filtered to yield the filtrate as an oil solution of the desired boron- containing product.
  • An oleyl ester of boric acid is prepared by heating an equimolar mixture of oleyl alcohol and boric acid in toluene at the reflux temperature while water is removed azeotropically. The reaction mixture is then heated to 150°C under vacuum and the residue is the ester having a boron content of 3.2% and a saponification number of 62. A mixture of 344 parts of the heater and 2720 parts of the oil solution of the product prepared in Example A-10 is heated at 150°C for 6 hours and then filtered. The filtrate is an oil solution of the desired boron-containing product.
  • a mixture of 3420 parts of the oil-containing solution of the product prepared in Example A-12 and 53 parts of acrylonitrile is heated at reflux temperature from 125-145°C for 1.25 hours, at 145°C for 3 hours and then stripped at 125°C under vacuum. The residue is an oil solution of the desired product.
  • a mixture is prepared by the addition of 44 parts of ethylene oxide over a period of one hour to 1460 parts of the oil solution of the product prepared in Example A-ll at 150°C.
  • the reaction mixture is held at 150°C for one hour, then filtered to yield the filtrate as an oil solution of the desired product.
  • a mixture of 1160 parts of the oil solution of the product of Example A-10 and 73 parts of terephthalic acid is heated —at 150-160°C and filtered.
  • the filtrate is an oil solution of the desired product.
  • a decyl ester of phosphoric acid is prepared by adding one mole of phosphorus pentaoxide to three moles of decyl alcohol at -a temperature within the range of 32-55°C and then heating the mixture at 60-63°C until the reaction is complete.
  • the product is a mixture of the decyl esters of phosphoric acid having a phosphorus content of 9.9% and an acid number of 250 (phenolphthalein indicator) .
  • a mixture of 1750 parts of the oil solution of the product prepared in Example A-10 and 112 parts of the above decyl ester is heated at 145-150°C for one hour. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.
  • a mixture of 2920 parts of the oil solution of the product prepared in Example A-ll and 69 parts of thiourea is heated to 80°C and held at 80°C for 2 hours.
  • the reaction mixture is then heated at 150-155°C for 4 hours, the last of which the mixture is blown with nitrogen.
  • the reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.
  • a mixture of 1160 parts of the oil solution of the product prepared in Example A-10 and 67 parts of sulfur monochloride is heated for one hour at 150°C under nitrogen.
  • the mixture is filtered to yield an oil solution of the desired sulfur-containing product.
  • a mixture is prepared by the addition of 11.5 parts of formic acid to 1000 parts of the oil solution of the product prepared in Example A-ll at 60°C.
  • the reaction mixture is heated at 60-100°C for 2 hours, 92-100°C for 1.75 hours and then filtered to yield an oil solution of the desired product.
  • Component (B) of the diesel lubricants of this invention is at least one basic alkali metal salt of at least one acidic organic compound.
  • This component is among those art-recognized---metal-containing composi ⁇ tions variously refered to by such names as “basic”, “superbased” and “overbased” salts or complexes. The method for their preparation is commonly referred to-as “overbasing”.
  • metal ratio is often used to define the quantity of metal in these salts or complexes relative to the quantity of organic anion, and is defined as the - ratio of the number of equivalents thereof which would be present in a normal salt based upon the usual stoichiometry of the compounds involved.
  • the alkali metals present in the basic alkali metal salts include principally lithium, sodium and potassium, with sodium and potassium being preferred.
  • the most useful acidic organic compounds are sulfur acids, carboxylic acids, organic phosphorus acids and phenols.
  • the sulfur acids include sulfoni ⁇ , sulfamic thiosulfonic, sulfini ⁇ sulfeni ⁇ , partial ester sulfuric, sulfurous and thiosulfuric acids.
  • the sulfur acid is a sulfonic acid.
  • the sulfonic acids are preferred as component (B) in the diesel lubricants of the invention. They include those represented by the formulae
  • R ⁇ is an aliphatic or aliphatic-substituted cycloaliphatic hydrocarbon or essentially hydrocarbon radical free from acetyleni ⁇ unsaturation and containing up to about 60 carbon atoms.
  • R 1 is aliphatic, it usually contains at least about 15_ carbon atoms; when it is an aliphatic-substituted cycloaliphatic radical, the aliphatic substituents usually contain a total of at least about 12 carbon atoms.
  • R 1 examples are alkyl, alkenyl and alkoxyalkyl radicals, and aliphatic-substituted cycloaliphatic radicals wherein the aliphatic substituents are alkyl, alkenyl, alkoxy, alkoxyalkyl, carboxyalkyl and the like.
  • the cycloaliphatic nucleus is derived from a cycloalkane or a cy ⁇ loalkene such as cyclopentane, cyclohexane, cyclohexene or cyclopentene.
  • r are cetylcy ⁇ lohexyl, laurylcyclohexyl, cetyloxyethyl, octadecenyl, and radicals derived from petroleum, saturated and " unsaturated paraffin wax, and olefin polymers including polymerized monoolefins and diolefins containing about 2-8 carbon atoms per olefinic monomer unit.
  • R 1 can also contain other substituents such as phenyl, cycloalkyl, hydroxy, mercapto, halo, nitro, amino, nitroso, lower alkoxy, lower alkylmercapto, carboxy, carbalkoxy, oxo or thio. or interrupting groups such as -NH-, -0- or -S-, as long as the essentially hydrocarbon character thereof is not destroyed. .
  • R 2 is generally a hydrocarbon or essentially hydrocarbon radical free from acetylenic unsaturation and containing from about 4 to about 60 aliphatic carbon atoms, preferably an aliphatic hydrocarbon radical such as alkyl or alkenyl. It may also, however, contain substituents or interrupting groups such as those enumerated above provided the essentially hydrocarbon character thereof is retained. In general, any non-carbon atoms present m R x or R do not account for more than 10% of the total weight thereof.
  • T is a cyclic nucleus which may be derived from, an aromatic hydrocarbon... such as benzene, naphthalene, anthracene or biphenyl, or from a heterocycllic compound such as pyridine, indole or isoindole.
  • an aromatic hydrocarbon nucleus especially a benzene or naphthalene nucleus.
  • the subscript x is at least 1 and is generally 1-3.
  • the subscripts r and y have an average value of about 1-4 per molecule and are generally also 1.
  • sulfonic acids useful in preparing the salts (B) . It is to be understood that such examples serve also to illustrate the salts of such sulfonic acids useful as component (B) . In other words, for every sulfonic acid enumerating, it is intended that the corresponding basic alkali metal salts thereof are also understood to be illustrated.
  • Such sulfonic acids include- mahogany sulfonic acids, bright stock sulfonic acids, petrolatum sulfonic acids, mono- and polywax-substituted naphthalene sulfonic acids, cetyl- chlorobenzene sulfonic acids, cetylphenol sulfonic acids, cetylphenol disulfide sulfonic acids, cetoxy- capryl benzene sulfonic acids, dicetyl thianthrene sulfonic acids, dilauryl beta-naphthol sulfonic acids, dicapryl nitronaphthalene sulfonic acids, saturated paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, t
  • Alkyl-substituted benzene sulfonic acids wherein the alkyl group contains at least 8 carbon atoms including dodecyl benzene "bottoms" sulfonic acids are particularly useful.
  • the latter are acids derived from benzene which has been alkylated with propylene tetramers or isobutene trimers to introduce 1, 2, 3, or more branched-chain C 12 substituents on the benzene ring.
  • Dodecyl benzene bottoms principally mixtures of mono- and di-dode ⁇ yl benzenes, are available as by-products from the manufacture of household detergents.
  • Suitable carboxylic acids include aliphatic, cycloaliphatic ..and aromatic mono- and polybasic carboxylic acids free from acetylenic unsaturation, including naphthenicr acids, alkyl- or alkenyl- substituted cyclopentanoic acids, alkyl- or alkenyl- substituted cyclohexanoic acids, and alkyl- or alkenyl-substituted aromatic carboxylic acids.
  • the aliphatic acids generally contain from about 8 to about 50, and preferably from about 12 to about 25 carbon atoms.
  • the cycloaliphatic and aliphatic carboxylic acids are preferred, and they can be saturated or unsaturated.
  • Specific examples include 2-ethylhexanoic acid, linoleni ⁇ acid, propylene tetramer-substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capri ⁇ acid, palmitoleic acid, linoleic acid, lauri ⁇ acid, oleic acid, ricinoleic acid, undecyclic acid, dioctylcyclopentanecarboxyli ⁇ acid, myristic acid, dilauryldecahydronaphthalene-carboxylic acid, stearyl-o ⁇ tahydroindenecarboxylic acid, palmitic acid, alkyl- and alkenylsuccinic acids, acids formed by oxidation of petrolatum or of hydrocarbon waxes, and commercially available mixtures - of two or more carboxylic acids such as tall oil acids, rosin acids, and the like.
  • the pentavalent phosphorus acids useful in the preparation of component (B) may be represented by the formula
  • each of R 3 and R 4 is hydrogen or a hydrocarbon or essentially hydrocarbon group preferably having from -about 4 to about 25 carbon atoms, at least one of R 3 and R 4 being hydrocarbon or essentially hydrocarbon; each of X 1 , X 2 , X 3 and X 4 is oxygen or sulfur; and each of a and b is 0 or 1.
  • the phosphorus acid may be an organophosphori ⁇ , phosphonic or phosphinic acid, or a thio analog of any of these.
  • the • phosphorus acids may be those of the formula
  • R 3 is a phenyl group or (preferably) an alkyl group having up to 18 carbon atoms
  • R 4 is hydrogen or a similar phenyl or alkyl group. Mixtures of such phosphorus acids are often preferred because of their ease of preparation.
  • Component (B) may also be prepared from phenols; that is, compounds containing a hydroxy group bound directly to an aromatic ring.
  • phenol as used herein includes compounds having more than one hydroxy group bound to an aromatic ring, such as catechol, resorcinol and hydroquinone. It also includes alkylphenols such as the cresols and ethylphenols, and alkenylphenols.
  • phenols containing at least one alkyl substituent containing about 3-100 and especially about 6-50 carbon atoms such as heptylphenol, octylphenol, dodecyl- phenol, tetrapropene-alkylated phenol, octadecylphenol and polybutenylphenols.
  • Phenols containing more than one alkyl substituent may also be used-, but the monoalkylphenols are preferred because of - -their availability and ease of production.
  • condensation products of the above-described phenols with at least one lower aldehyde or ketone are also useful, the term "lower" denoting aldehydes and ketones containing not more than 7 carbon atoms.
  • Suitable aldehydes include formaldehyde, a ⁇ etaldehyde, propionaldehyde, the butyraldehydes, the valeraldehydes and benzaldehyde.
  • aldehyde-yielding reagents such as paraformaldehyde, trioxane, methylol. Methyl Formcel and paraldehyde. Formaldehyde and the formaldehyde-yielding reagents are especially preferred.
  • the equivalent weight of the acidic organic compound is its molecular weight divided by the number of acidic groups (i.e., sulfonic acid, carboxy or acidic hydroxy groups) present per molecule.
  • the alkali metal salts (B) are basic alkali metal salts having metal ratios of at least about 2 and more generally from about 4 to about 40, preferably from about 6 to about 30 and especially from about 8 to about 25.
  • the basic salts (B) are oil-soluble dispersions prepared by contacting for a period of time sufficient to form a stable dispersion, at a temperature between the solidification temperature of the reaction mixture and its decomposition temperature:
  • (B-l) at least one acidic gaseous material selected from the group consisting of carbon dioxide, hydrogen sulfide and sulfur dioxide, with
  • (B-2-c) at least one lower aliphatic alcohol, alkyl phenol, or sulfurized alkyl phenol
  • (B-2-d) at least one oil-soluble carboxylic acid or functional derivative thereof.
  • component (B-2-d) is optional.
  • a satisfactory basic sulfonic acid salt can be prepared with or without the carboxylic acid in the mixture (B-2) .
  • Reagent (B-l) is at least one acidic gaseous material which may be carbon dioxide, hydrogen sulfide or sulfur dioxide; mixtures of these gases are also useful. Carbon dioxide is preferred.
  • reagent (B-2) generally is a mixture containing at least four components of which component (B-2-a) is at least one oil-soluble sulfonic acid as previously defined, or a derivative thereof susceptible to overbasing. Mixtures of sulfonic acids and/or their derivatives may also be used.
  • Sulfonic acid derivatives susceptible to overbasing include their metal salts, especially the alkaline earth, zinc and lead salts; ammonium salts and amine salts- (e.g., the ethylamine, butyla ine and ethylene polyamine salts) ; and esters such as the ethyl, butyl and glycerol esters.
  • Component (B-2-b) is at least one alkali metal or a basic compound thereof.
  • basic alkali metal compounds are the hydroxides, alkoxides (typically those in which the alkoxy group contains up to 10 and preferably up to 7 carbon atoms) , hydrides and amides.
  • -useful basic alkali metal compounds include sodium hydrox-ide, potassium hydroxide, lithium hydroxide, sodium propoxide, lithium methoxide, potassium ethoxide, sodium butoxide, lithium hydride, sodium hydride, potassium hydride, lithium amide, sodium amide and potassium amide.
  • component (B-2-b) for the purpose of this invention is equal to its molecular weight, since the alkali metals are monovalent.
  • Component (B-2-c) may be at least one lower aliphatic alcohol, preferably a monohydric or dihydric alcohol.
  • Illustrative alcohols are methanol, ethanol, 1-propanol, 1-hexanol, isopropanol, isobutanol, 2-pentanol, 2,2-dimethyl-l-propanol, ethylene glycol, 1-3-propanediol and 1,5-pentanediol.
  • the alcohol also may be a glycol ether such as Methyl Cellosolve.
  • the preferred alcohols are methanol, ethanol and propanol, with methanol being especially preferred.
  • Component (B-2-c) also may be at least one alkyl phenol or sulfurized alkyl phenol.
  • the sulfurized alkyl phenols are preferred, especially when.
  • (B-2-b) is potassium or one of its basic compounds such as potassium hydroxide.
  • phenol includes compounds having more than one hydroxy group bound to an aromatic ring, and the aromatic ring may be a benzyl or naphthyl ring.
  • alkyl phenol includes mono- and di-alkylated phenols in which each alkyl substituent contains from about 6 to about 100 carbon atoms, preferably about 6 to about 50 carbon atoms.
  • Illustrative alkyl phenols include heptyl- phenols, octylphenols, decylphenols, dodecylphenols, polypropylene (M.W. of about 150) -substituted phenols, polyisobutene (M.W. of about 1200) -substituted phenols, cyclohexyl phenols.
  • condensation products of the above-described phenols with at least one lower aldehyde or ketone are also useful, the term "lower" denoting aldehydes and ketones containing not more than 7 carbon atoms.
  • Suitable aldehydes include formaldehyde, acetaldehyde, propionaldehyde, the butyraldehydes, the valeraldehydes and benzaldehyde.
  • aldehyde-yielding reagents such as paraformaldehyde, trioxane, methylol. Methyl Formcel and paraldehyde. Formaldehyde and the formaldehyde-yielding reagents are especially preferred.
  • the sulfurized alkylphenols include phenol sulfides, disulfides or polysulfides.
  • the sulfurized phenols can be derived from any " suitable alkylphenol by technique known to those skilled in the art, and many sulfurized phenols are commercially available.
  • the sulfurized alkylphenols may be prepared by reacting an alkylphenol with elemental sulfur and/or a sulfur monohalide (e.g., sulfur monochloride) . This- reaction may be conducted in the presence of excess base to result in the salts of the mixture of sulfides, disulfides or polysulfides that may be produced depending upon the reaction conditions. It is the resulting product of this reaction which is used in the preparation of component (B-2) in the present invention.
  • U.S. Patents 2,971,940 and 4,309,293 disclose various sulfurized phenols which are illustrative of component (B-2-c) .
  • Benzene (217 parts) is added to phenol (324 parts, 3.45 moles) at 38°C and the mixture is heated to 47°C.
  • Boron trifluoride (8.8 parts, 0.13 mole) is blown into the mixture over a one-half hour period at 38-52°C.
  • Polyisobutene (1000 parts, 1.0 mole) derived from the polymerization of C4 monomers predominating in isobutylene is added to the mixture at 52-58°C over a 3.5 hour period. The mixture is held at 52°C for 1 additional hour.
  • a 26% solution of aqueous ammonia (15 parts) is added and the mixture is heated to 70°C over a 2-hour period.
  • a reactor equipped with a stirrer, condenser, thermometer and subsurface addition tube is charged with 1000 parts of the reaction product of Example 1.
  • the temperature is adjusted to 48-49° and 319 parts sulfur dichloride is added while the temperature is kept below 60°.
  • the batch is then heated to 88-93° while nitrogen blowing until the acid number (using bromphenol blue indicator) is less than 4.0. 400 parts diluent oil is then added, and the mixture is mixed thoroughly.
  • Example 3 1000 parts of the reaction product of Example 1 is reacted with 175 parts of sulfur dichloride. The reaction product is diluted with 400 parts diluent oil.
  • Example 3 1000 parts of the reaction product of Example 1 is reacted with 319 parts of sulfur dichloride. Diluent oil (788 parts) is added to the reaction product, and the materials are mixed thoroughly.
  • Example 4 1000 parts of the reaction product of Example 2 are reacted with 44 parts of sulfur dichloride to produce the sulfurized phenol.
  • the equivalent weight of component (B-2-c) is its molecular weight divided by the number of hydroxy groups per molecule.
  • Component (B-2-d) is at least one oil-soluble carboxylic acid as previously described, or functional derivative thereof.
  • suitable carboxylic acids are those of the formula R ⁇ (COOH) n , wherein n is an integer from 1 to 6 and is preferably 1 or 2 and R5 is a saturated or substantially saturated aliphatic radical (preferably a hydrocarbon radical) having at least 8 aliphatic carbon atoms. Depending upon the value of n, R 5 will be a monovalent to hexavalent radical.
  • R5 may contain non-hydrocarbon substituents provided they do not alter substantially its hydrocarbon character. Such substituents are preferably present in amounts of not more than about 20% by weight. Exemplary substituents include the non- hydrocarbon substituents enumerated hereinabove with reference' to component (B-2-a) .
  • R ⁇ may also contain olefinic unsaturation up to a maximum of about 5% and preferably not more than 2% olefinic linkages based upon the total number of carbon-to-carbon covalent linkages present. The number of carbon atoms in R ⁇ is usually about 8-700 depending upon the source of R 5 .
  • a preferred series of carboxylic acids and derivatives is prepared by reacting an olefin polymer or halogenated olefin polymer with an alpha,beta-unsaturated acid or its anhydride such as acrylic, methacrylic, maleic or fumaric acid or maleic anhydride to form the corresponding substituted acid or derivative thereof.
  • the R 5 groups in these products have a number average molecular weight from about 150 to about 10,000 and usually from about 700 to about 5000, as determined, for example, by gel permeation chromatography.
  • the monocarboxylic acids useful as component (B-2-d) have the formula R 5 COOH.
  • examples of such acids are caprylic, capric, palmitic, stearic, isostearic, linoleic and behenic acids.
  • a particularly preferred group of monocarboxylic acids is prepared by the reaction of a halogenated olefin polymer, such as a chlorinated polybutene, with acrylic acid or methacrylic acid.
  • Suitable dicarboxylic acids include the substituted succinic acids having the formula
  • R ⁇ is the same as R ⁇ as defined above.
  • R 6 may be an olefin polymer-derived group formed by polymerization of such monomers as ethylene, propylene, 1-buterie, isobutene, 1-pentene, 2-pentene, 1-hexene and 3-hexene.
  • R 6 may also be derived from a high molecular weight substantially saturated petroleum fraction.
  • the hydrocarbon-substituted succinic acids and their derivatives constitute the most preferred class of carboxylic acids for use as component (B-2-d) .
  • Functional derivatives of the above-discussed acids useful as component (B-2-d) include the anhydrides, esters, amides, imides, a idines and metal or ammonium salts.
  • the reaction products of olefin polymer-substituted succinic acids and mono- " or polyamines, particularly polyalkylene polyamines, having up to . about 10 amino nitrogens are especially suitable. These reaction products generally comprise mixtures of one or more of amides, imides and amidines.
  • the reaction products of polyethylene amines containing up to about 10 nitrogen atoms and polybutene-substituted succinic anhydride wherein the polybutene radical comprises .principally isobutene units are particularly useful.
  • the half-amide, half-metal salt and half-ester, half-metal salt derivatives of such substituted succinic acids are also useful.
  • This class of alcohols includes ethylene glycol, glycerol, sorbitol, pentaerythritol, poly ⁇ ethylene glycol, diethanolamine, triethanolamine, N,N'-di(hydroxyethyl) ethylene diamine and the like.
  • the reaction product may comprise products resulting from the reaction of the acid group with both the hydroxy and * amino functions.
  • this reaction mixture can include half-esters, half-amides, esters, amides, and imides.
  • the ratios of equivalents of the constituents of reagent (B-2) may vary widely.
  • the ratio of component (B-2-b) to (B-2-a) is at least about 4:1 and usually not more than about 40:1, preferably between 6:1 ' and 30:1 and most preferably between 8:1 and 25:1. While this ratio may sometimes exceed 40:1, such' an excess normally will serve no useful purpose.
  • the ratio of equivalents of component (B-2-c) to component (B-2-a) is between about 1:20 and 80:1, and preferably between about 2:1 and 50:1.
  • component . (B-2-c) is an alkyl phenol or sulfurized alkyl phenol
  • the inclusion of the carboxylic acid (B-2-d) is optional.
  • the ratio of equivalents of component (B-2-d) to component (B-2-a) generally is from about 1:1 to about 1:20 and preferably from about 1:2 to about 1:10.
  • Reagents (B-l) and (B-2) are generally contacted until there is no further reaction between the two or until the reaction substantially ceases.
  • useful dispersions can be prepared- when contact between reagents (B-l) and (B-2) is maintained for a period of time sufficient for about 70% of reagent (B-l) , relative to the amount required if the reaction were permitted to proceed to its completion or "end point", to react.
  • the point at which the reaction is completed or substantially ceases may be ascertained by any of a number of conventional methods.
  • One such method is measurement of the amount of gas (reagent (B-l)) entering and leaving the mixture; the reaction may be considered substantially complete when the amount leaving is about 90-100% of the amount entering.
  • the reaction temperature is not critical. Generally, it will be between the solidification temperature of the reaction mixture and its decomposition temperature (i.e., the lowest decomposition temperature of any component thereof) . Usually, the temperature will be from about 25° to about 200°C and preferably from about 50° to about 150°C.
  • Reagents (B-l) and (B-2) are conveniently contacted at the reflux temperature of the mixture. This temperature will obviously depend upon the boiling points of the various components; thus, when methanol is used as component (B-2-c) , the contact temperature will be at or below the reflux temperature of methanol.
  • reagent (B-2-c) is an alkyl phenol or a sulfurized alkyl phenol
  • the temperature of the reaction must be at or above the water-diluent azeotrope temperature so that the water formed in the reaction can be removed.
  • the diluent in such cases generally will be a volatile organic liquid such as aliphatic and aromatic hydrocarbons. Examples of such diluents include heptane, decane, toluene, xylene, etc.
  • the reaction is ordinarily conducted at atmospheric pressure, although superatmospheric pressure often expedites the reaction and promotes optimum utilization of reagent (B-l) .
  • the process can also be carried out at reduced pressure but, for obvious practical reasons, this is rarely done.
  • the reaction is usually conducted in the presence of a substantially inert, normally liquid organic diluent, which functions as both the dispersing and reaction medium.
  • This diluent will comprise at least about 10% of the total weight of the reaction mixture. Ordinarily it will not exceed about 80% by weight, and it is preferably about 30-70% thereof.
  • diluents which are soluble in lubricating oil.
  • the diluent usually itself comprises a low viscosity lubricating oil.
  • organic diluents can be employed either alone or in combination with lubricating oil.
  • Preferred diluents for this purpose include the aromatic hydrocarbons such as benzene, toluene and xylene; halogenated derivatives thereof such as chlorobenzene; lower boiling petroleum distillates such as petroleum ether and various naphthas; normally liquid aliphatic and cycloaliphatic hydrocarbons such as hexane, heptane, hexene, cyclohexene, cyclopentane, cyclohexane and ethylcyclohexane, and their halogenated derivatives.
  • Dialkyl ketones such as dipropyl ketone and ethyl butyl ketone, and the alkyl aryl ketones such as acetophenone, are likewise useful, as are ethers such as n-propyl ether, n-butyl ether, n-butyl methyl ether and isoa yl ether.
  • the weight ratio of oil to the other diluent is generally from about 1:20 to about 20:1. It is usually desirable for a mineral lubricating oil to comprise at least about 50% by -weight of the diluent, especially if the product is to be used as a lubricant additive.
  • the total amount of diluent present is not particularly critical since it is inactive. However, the diluent will ordinarily comprise about 10-80% and preferably about 30-70% by weight of the reaction mixture.
  • any solids in the mixture are preferably removed by filtration or other . conventional means.
  • readily removable diluents, the alcoholic promoters, and water formed during the reaction can be removed by conventional techniques such as distillation. It is usually desirable to remove substantially all water from the reaction mixture since the presence of water may lead to difficulties in filtration and to the formation of undesirable emulsions in fuels and lubricants. Any such water present is readily removed by heating at atmospheric or reduced pressure or by azeotropic distillation.
  • the potassium salt is prepared using carbon dioxide and the sulfurized alkylphenols as component (B-2-c) .
  • the use of the sulfurized phenols results in basic salts of higher metal ratios and the formation of more uniform and stable salts.
  • the reaction generally is conducted in an aromatic diluent such as xylene, and water is removed as a xylene-water azeotrope during the reaction.
  • component (B) The chemical structure of component (B) is not known with certainty.
  • the basic salts or complexes may be solutions or, more likely, stable dispersions. Alternatively, they may be regarded as "polymeric salts" formed by the reaction of the acidic material, the oil-soluble acid being overbased, and the metal compound. In view of the above, these compositions are most conveniently defined by reference to the method by which they are formed.
  • the methanol and other volatile materials are stripped from the carbonated mixture by blowing nitrogen through it at 2 cfh. while the temperature is slowly increased to 150°C over 90 minutes. After stripping is completed, the remaining mixture is held at 155-165°C for about 30 minutes and filtered to yield an oil solution of the desired basic sodium sulfonate having a metal ratio.of about 7.75.- This solution contains 12.5% oil.
  • Example B-2 Following the- procedure of Example B-l, a solution of 780 parts (1 equivalent) of an alkylated benzenesulfonic acid and 119 parts of the polybutenyl succinic anhydride in 442 parts of mineral oil is mixed with 800 parts (20 equivalents) of sodium hydroxide and 704 parts (22 equivalents) of methanol. The mixture is blown with carbon dioxide at 7 cfh. for 11 minutes as the temperature slowly increases to 97°C. The rate of carbon dioxide flow is reduced to 6 cfh. and the temperature decreases slowly to 88°C over about 40 minutes. The rate of carbon dioxide flow is reduced to 5 cfh. for about 35 minutes and the temperature slowly decreases to 73°C.
  • the volatile materials are stripped by blowing nitrogen through the carbonated mixture at 2 cfh. for 105 minutes as the temperature is slowly increased to 160°C. After stripping is completed, the mixture is held at 160°C for an additional 45 minutes and then filtered to yield an oil solution of the desired basic sodium sulfonate having a metal ratio of about 19.75. This solution contains 18.7% oil.
  • Example B-l Following the procedure of Example B-l, a solution of 3120 parts (4 equivalents) of an alkylated benzenesulfonic acid and 284 parts of the polybutenyl succinic anhydride in 704 parts of mineral oil is mixed with 1280 parts (32 equivalents) of sodium hydroxide and 2560 parts (80 equivalents) of methanol. The mixture is blown with carbon dioxide at 10 cfh. for 65 minutes as the temperature increases to 90°C and then slowly decreases to 70°C. The volatile material is stripped by blowing nitrogen at 2 cfh. for 2 hours as the temperature is slowly increased to 160°C. After stripping is completed, the mixture is held at 160°C for 0.5 hour, and then filtered to yield an oil solution of the desired basic sodium sulfonate having a metal ratio of about 7.75. This solution contains 12.35% oil content.
  • Example B-l a solution of 3200 parts (4 equivalents) of an alkylated benzenesulfonic acid and 284 parts of the polybutenyl succinic anhydride in 623 parts of mineral oil is mixed with 1280 parts (32 equivalents) of sodium hydroxide and 2560 parts (80 equivalents) of methanol.
  • the mixture is blown with carbon dioxide at 10 cfh. for about 77 minutes. During this time the temperature increases to 92°C and then gradually drops to 73°C.
  • the volatile materials are stripped by blowing with nitrogen gas at 2 cfh. for about 2 hours as the temperature of the reaction mixture is slowly increased to 160°C.
  • the final traces of volatile material are vacuum stripped and the residue is held at 170°C and then filtered to yield a clear oil solution of the desired sodium salt, having a metal ratio of about 7.72.
  • This solution has an oil content of 11%.
  • Example B-5 Following the procedure of Example B-l, a solution of 780 parts (1 equivalent) of an alkylated benzenesulfonic acid and 86 parts of the polybutenyl succinic anhydride ih 254 parts of mineral oil is mixed with 480 parts (12 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. The reaction mixture is blown with carbon dioxide at 6 cfh. for about 45 minutes. During this time the temperature increases to 95°C and then gradually decreases to 74°C. The volatile material is stripped by blowing with nitrogen gas at 2 cfh. for about one hour as the temperature is increased to 160°C. After stripping is complete the mixture is 1 held at 160°C for 0.5 hour and then filtered to yield an oil solution of the desired sodium salt, having a metal ratio of 11.8. The oil content of this solution is * 14.7%.
  • Example B-6 Following the procedure of Example B-l, a solution of 3120 parts (4 equivalents) of an alkylated benzenesulfonic acid and 344 parts of the polybutenyl succinic anhydride in 1016 parts of mineral oil is mixed with 1920 parts (48 equivalents) of sodium hydroxide and 2560 parts (80 equivalents) of methanol. The mixture is blown with carbon dioxide at 10 cfh. for about 2 hours. During this time the temperature increases to 96°C and then gradually drops to 74°C. The volatile materials are stripped by blowing with nitrogen gas at 2 cfh. for about"2 hours as the temperature is increased from 74° to 160°C by external heating. The stripped mixture is heated for an additional hour at 160°C and filtered. The filtrate is vacuum stripped to remove a small amount of water, and again filtered to give a solution of the desired sodium salt, having a metal ratio of about 11.8. The oil content of this solution is 14.7%.
  • Example B-7 Following the procedure of Example B-l, a solution of 2800 parts (3.5 equivalents) 'of an alkylated benzenesulfonic acid and 302 parts of the polybutenyl succinic anhydride in 818 parts of mineral oil is mixed with 1680 parts (42 equivalents) of sodium hydroxide and 2240 parts (70 equivalents) of methanol. The mixture is blown with carbon dioxide- for about 90 minutes at 10 cfh. During this period, the temperature increases to 96°C and then slowly drops to 76°C. The volatile materials are stripped by blowing with nitrogen at 2 cfh. as the temperature is slowly increased from 76°C to 165°C by external heating. Water is removed by vacuum stripping. Upon filtration, an oil solution of the desired basic sodium salt is obtained. It has a metal ratio of about 10.8 and the oil content is 13.6%.
  • Example B-8 Following the procedure of Example B-l, a solution of 780 parts (1 equivalent) of an alkylated benzenesulfonic acid and 103 parts of the polybutenyl succinic anhydride in 350 parts of mineral oil is mixed with 640 parts (16 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. This mixture is blown with carbon dioxide for about one hour at 6 cfh. During this period, the temperature increases to 95°C and then gradually decreases to 75°C. The volatile material is stripped by blowing with nitrogen. During stripping, the temperature initially drops to 70°C over 30 minutes and then slowly rises to 78°C over 15 minutes. The mixture is then heated to 155°C over 80 minutes. The stripped, mixture is heated for . an additional 30 minutes at 155-160°C and filtered. The filtrate is an oil solution of the desired basic sodium sulfonate, having a metal ratio of about 15.2. It has an oil content of 17.1%.
  • Example B-9 Following the procedure of Example B-l, a solution of. 2400 parts (3 equivalents) of an alkylated benzenesulfonic acid and 308 parts- of the polybutenyl succinic anhydride in 991 parts of mineral oil .is mixed with 1920 parts (48 equivalents) of sodium hydroxide and 1920 parts (60 equivalents) of methanol. This mixture is blown with carbon dioxide at 10 cfh. for 110 minutes, during which time the temperature rises to 98°C and then slowly decreases to 76°C over about 95 minutes. The methanol and water are stripped by blowing with nitrogen at 2 cfh. as the temperature of the mixture slowly increases to 165°C. The last traces of volatile material are vacuum stripped and the residue is filtered to yield an oil solution of the desired sodium salt having a metal ratio of 15.1. The solution has an oil content of 16.1%.
  • Example B-10 Following the procedure of Example B-l, a solution of 780 parts (1 equivalent) of an alkylated benzenesulfonic acid and 119 parts of the polybutenyl succinic anhydride in 442 parts of mineral oil is mixed well with 800 parts (20 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. This mixture is blown with carbon dioxide for about 55 minutes at 8 cfh. During this period, the temperature of the mixture increases to 95°C and then slowly decreases to 67°C. The methanol and water are stripped by blowing with nitrogen at 2 cfh. for about 40 minutes while the temperature is slowly increased to 160°C. After stripping, the temperature of the mixture is maintained at 160-16-5°C for about 30 minutes. The product is then filtered to give a solution of the corresponding sodium sulfonate having a metal ratio of about 16.8. This solution contains 18.7% oil.
  • Example B-ll Following the procedure of Example B-l, 836 parts (1 equivalent) of a sodium petroleum sulfonate (sodium "Petronate”) in an oil solution containing 48% oil and 63 parts of the polybutenyl succinic anhydride is heated to 60°C and treated with 280 parts (7 equivalents) of sodium hydroxide and 320 parts (10 equivalents) of methanol. The reaction mixture is blown with carbon dioxide at 4 cfh. for about 45 minutes. During this time, the temperature increases to 85°C and then slowly decreases to 74°C. The volatile material is stripped by blowing with nitrogen at 2 cfh. while the temperature is gradually increased to 160°C.
  • sodium petroleum sulfonate sodium "Petronate”
  • Example B-12 Following the procedure of Example B-ll, 1256 parts (1.5 equivalents)- of the sodium petroleum sulfonate in an oil solution containing 48% oil and 95 parts of polybutenyl succinic anhydride is heated to 60°C and treated with 420 parts (10.5 equivalents) of sodium hydroxide and 960 parts (30 equivalents) of methanol. The mixture is blown with carbon dioxide at 4 cfh. for 60 minutes. During this time, the temperature is increased to 90°C and then slowly decreases to 70°C.
  • the volatile materials are stripped by blowing with nitrogen and slowly increasing the temperature to 160°C. After stripping, the reaction mixture is allowed to stand at 160°C for 30 minutes and then is filtered to yield an-oil solution of sodium sulfonate having a metal ratio of about 8.0. The oil content of the solution is 22.2%.
  • Example B-13 A mixture of 584 parts (0.75 mole) of a commercial dialkyl aromatic sulfonic acid, 144 parts (0.37 mole) of a sulfurized tetrapropenyl phenol prepared as in Example 3, 93 parts of a polybutenyl succinic anhydride as used in Example B-l, 500 parts of xylene and 549 parts of oil is prepared and heated with stirring to 70°C whereupon 97 parts of potassium hydroxide are added. The mixture is heated to 145°C while azeotroping water and xylene. Additional potassium hydroxide (368 parts) is added over 10 minutes and heating is continued at about 145-150°C whereupon the mixture is blown with carbon dioxide at 1.5 cfh. for about 110 minutes.
  • the volatile materials are stripped by blowing with nitrogen and slowly increasing the temperature to about 160°C. After stripping, the reaction mixture is filtered to yield an oil solution of the desired potassium sulfonate having a metal ratio of about 10. Additional oil is added to the reaction product to provide an oil content of the final solution of 39%.
  • Example B-14 A mixture of 705 parts (0.75 mole) of a commercially available mixture of straight and branched chain alkyl aromatic sulfonic acid, 98 parts (0.37 mole) of a tetrapropenyl phenol prepared as in Example 1, 97 parts of a polybutenyl succinic anhydride as used in Example B-l, 750 parts of xylene, and 133 parts of oil is prepared and heated with stirring to about 50°C whereupon 65 parts of sodium hydroxide dissolved in 100 parts of water are added. The mixture is heated to about 145°C while removing an azeotrope of water and xylene. After cooling the reaction mixture overnight, 279 parts of sodium hydroxide are added.
  • the mixture is heated to 145°C and blown with carbon dioxide at about 2 cfh. for 1.5 hours.
  • An azeotrope of water and xylene is removed.
  • a second increment of 179 parts of sodium hydroxide is added as the mixture is stirred and heated to 145°C whereupon the mixture is blown with carbon dioxide at a rate of 2 cfh. for about 2 hours.
  • Additional oil 133 parts is added to the mixture after 20 minutes.
  • a xylene:water azeotrope is removed and the residue is stripped to 170°C at 50 mm. Hg.
  • the reaction mixture is filtered through a filter aid and the filtrate is the desired product containing 17.01% sodium and 1.27% sulfur.
  • Example B-15 A mixture of 386 parts (0.75 mole) of a commercially available primary branched chain monoalkyl aromatic sulfonic acid, 58 parts (0.15 mole) of a sulfurized tetrapropenyl phenol prepared as in Example 3, 926 grams of oil and 700 grams of xylene is prepared, heated to a temperature of 70°C whereupon 97 parts of potassium hydroxide are added over a period of 15 minutes. The mixture is heated to 145°C while removing water. An additional 368 parts of potassium hydroxide are added over 10 minutes, and the stirred mixture is heated to 145°C whereupon the mixture is blown with carbon dioxide at 1.5 cfh. for about 2 hours. The mixture is stripped to 150°C and finally at 150°C at 50 mm. Hg. The residue is filtered, and the filtrate is the desired-product.
  • the diesel lubricants of the present invention containing components (A) and (B) as described above may be further characterized as containing at least about 0.8 sulfate ash and more generally at least about 1% sulfate ash.
  • the amounts of components (A) and (B) included in the diesel lubricants of the present invention may vary over a wide range as can be determined by - one skilled in the art. Generally, however, the diesel lubricants of the present invention will contain from about 1.0 to about 10% by weight of component (A) and from about 0.05 to about 5% and more generally up to about 1% by weight of component (B) ..
  • the diesel lubricants of the present invention also contain (C) . at least one oil-soluble neutral or basic alkaline earth metal salt of at least one acidic organic compound.
  • Such salt compounds generally are referred to as ash- containing detergents.
  • the acidic organic compound may be at least one sulfur acid, carboxylic acid, phosphorus acid, or phenol, or mixtures thereof.
  • Calcium, magnesium and barium are the preferred alkaline earth metals. Salts containing a mixture of ions of two or more of these alkaline earth metals can' be used.
  • the salts which are useful as component (C) can be neutral or basic.
  • the neutral salts contain an amount of alkaline earth metal which is just sufficient to neutralize the acidic groups present in the salt anion, and the basic salts contain an excess of the alkaline earth metal cation.
  • the commonly employed methods for preparing the basic salts comprises heating a mineral oil solution of the acid with a stoichiometric excess of a metal neutralizing agent, e.g., a metal oxide, hydroxide, carbonate, bicarbonate, sulfide, etc., at temperatures above about 50°C.
  • a metal neutralizing agent e.g., a metal oxide, hydroxide, carbonate, bicarbonate, sulfide, etc.
  • various promoters may be used in the neutralizing process to aid in the incorporation o -the large excess of metal.
  • These promoters are presently known and include such compounds as the phenolic substances, e.g., phenol, naphthol, alkylphenol, thiophenol, sulfurized alkyl ⁇ phenol and the various condensation products of formaldehyde with a phenolic substance, e.g., alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve carbitol, ethylene, glycol, stearyl alcohol, and cyclohexyl alcohol; amines such as aniline, phenylene- diamine, phenothiazine, phenyl-beta-naphthylamine, and dodecyl amine, etc.
  • phenolic substances e.g., phenol, naphthol, alkylphenol, thiophenol, sulfurized alkyl ⁇ phenol and the various condensation products of formaldehyde with a phenolic substance
  • alcohols such as methanol, 2-propanol,
  • a particularly effective process for preparing the basic salts comprises mixing the acid with an excess of the basic alkaline earth metal in the presence of the phenolic promoter and a small amount of water and carbonating the mixture at an elevated temperature, e.g., 60°C to about 200°C.
  • the acidic organic compound from which the salt of component (C) is derived may be at least one sulfur acid, carboxylic acid, phosphorus acid, or phenol or mixtures thereof.
  • Such acidic organic compounds previously have been described above with respect to the preparation of the alkali metal salts (component (B) ) , and all of the acidic organic compounds described above can be utilized in the preparation of the alkaline earth metal salts useful as component (C) by techniques known in the art.
  • component (C) included in the diesel lubricants of the present invention also may be varied over a wide range, and useful amounts can be readily determined by one skilled in the art.
  • Component (C) functions as an auxiliary or supplemental detergent.
  • the amount of component (C) contained in a diesel lubricant of -the invention may vary from about 0% to about 5% or more.
  • a mixture of 906 parts of an oil solution of an alkyl phenyl sulfonic acid (having an average molecular weight of 450, vapor phase osmometry), 564 parts mineral oil, 600 parts toluene, 98.7 parts magnesium oxide and 120 parts water is blown with carbon dioxide at a temperature of 78-85°C for 7 hours at a rate of about 3 cubic feet of carbon dioxide per hour.
  • the reaction mixture is constantly agitated throughout the carbonation. After carbonation, the reaction mixture is stripped to 165°/20 tor and the residue filtered.
  • the filtrate is an oil solution of the desired overbased magnesium sulfonate having a metal ratio of about 3.
  • a polyisobutenyl succinic anhydride is prepared by reacting a chlorinated pol (isobutene) (having an average chlorine content of 4.3% and an average of 82 carbon atoms) with maleic anhydride at about 200°C.
  • the resulting polyisobutenyl succinic anhydride has a saponification number of 90.
  • the mixture is heated to 115°C and 125 parts of water is added drop-wise over a period of one hour.
  • the mixture is then allowed to reflux at 150°C until all the barium oxide is reacted. Stripping and filtration provides a filtrate having a barium content of 4.71%.
  • a basic calcium sulfonate having a metal ratio of about 15 is prepared by carbonation, in increments, of a mixture of calcium hydroxide, a neutral sodium petroleum sulfonate, calcium chloride, methanol and an alkyl phenol.
  • a mixture of 323 parts of mineral oil, 4.8 parts of water, 0.74 parts of calcium chloride, 79 parts of lime, and 128 parts of methyl alcohol is prepared, and warmed to a temperature of about 50°C.
  • the mixture then is blown with carbon dioxide at a temperature of about 50°C at the rate of about 5.4 pounds per hour for about 2.5 hours.
  • 102 additional parts of oil are added and the mixture is stripped of volatile materials at a temperature of about 150-155°C at 55 mm. pressure.
  • the residue is filtered and the filtrate is the desired oil solution of the overbased calcium sulfonate having calcium content of about 3.7% and a metal ratio of about 1.7.
  • the present invention also contemplates the use of other additives in the diesel lubricant compositions of the present invention.
  • additives include such conventional additive types as anti-oxidants, extreme pressure agents, corrosion- inhibiting agents, pour point depressants, color stabilizing agents, anti-foam " agents, and other such additive materials known generally to those skilled in the art of formulating diesel lubricants.
  • chlorinated aliphatic hydrocarbons such as chlorinated wax
  • organic sulfides and polysulf-ides such as benzyl disulfide, bis(chlorobenzyl)disulfide, dibutyl tetra- sulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene
  • phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate
  • phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite, dipentyl phenyl phosphi
  • Zinc dialkylphosphoro- dithioates are a well known example.
  • pour point depressants are a particularly useful type of additive often -included in the lubricating oils described herein. -
  • the use ⁇ f such pour point depressants in oil-based compositions to improve low temperature properties of oil-based compositions is well known in the art. See, for example, page 8 of "Lubricant Additives" by C.V. Smalheer and R. Kennedy Smith (Lezius-Hiles Co. publishers, Cleveland, Ohio, 1967) .
  • pour point depressants examples include polymethacrylates; polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkylfumarates, vinyl esters of fatty acids and alkyl vinyl ethers.
  • Pour point depressants useful for the purposes of this invention techniques for their preparation and their uses are described in U.S. Patents 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 which are hereby incorporated by reference for their relevant disclosures.
  • Anti-foam agents are used to reduce or prevent the formation of stable foam.
  • Typical anti-foam agents include silicones or organic polymers. Additional anti-foam compositions are described in "Foam Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976) , pages 125-162.
  • Zinc salt of mixed isobutyl- and primary amyl-phosphoro- dithioic acid .39 .39 .39 .39
  • Zinc salt of mixed isooctyl phosphorodithioic acid 1.04 1.04 1.04 1.04
  • the diesel lubricants of the present invention are useful in the operation of diesel engines, and when the diesel lubricants of the present invention are so utilized, the diesel engines can be operated for longer periods of time without undergoing undesirable viscosity increases. Furthermore, the diesel lubricants of the present invention are capable of passing the Caterpillar l-G-2 and the Caterpillar l-H-2 test procedures.
  • the test operation consists of an initial break-in-period (after major rebuild only) a test oil flush, and 150 hours of steady state operation at 1200 rpm and 1080 ft/lb. of torque.
  • No oil changes or additions are made, although eight 4 oz. oil samples are taken periodically from the oil pan drain valve during the test for analysis. Sixteen ounces of oil are taken at the oil pan drain valve before each 4 oz. sample is taken to purge the drain line. This purge sample is then returned to the engine after sampling. No make-up oil is added to the engine to replace the 4 oz. samples.
  • the kinematic viscosity at 210°F is measured at 100 and 150 hours into the test, and the "viscosity slope" is calculated.
  • the "viscosity slope” is defined as the difference between the 100 and 150-hour viscosity divided by 50. It is desirable that the viscosity slope should be as small a number as possible, reflecting a minimum viscosity increase as the test progresses.
  • the kinematic viscosity at 210°F can be measured by two procedures. In both procedures, the sample is passed through a No. 200 sieve before it is loaded into the Cannon reverse flow viscometer. In the ASTM D-445 method, the viscometer is chosen to result in flow times equal to or greater than 200 seconds. In the method described in the Mack: T-7 specification, a Cannon 300 viscometer is used for all viscosity determinations. Flow times for the latter procedure are typically 50-100 seconds for fully formulated 15W-40 diesel lubricants.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
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PCT/US1986/001890 1985-09-19 1986-09-12 Diesel lubricants and methods WO1987001722A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AT86905651T ATE99355T1 (de) 1985-09-19 1986-09-12 Verwendung von kombinationen aus bestimmten additiven in dieselschmiermittel.
BR8606979A BR8606979A (pt) 1985-09-19 1986-09-12 Lubrificante diesel,metodo para operar diesel e metodo para preparar um sal de metal alcalino basico
DE3689473T DE3689473T2 (de) 1985-09-19 1986-09-12 Verwendung von Kombinationen aus bestimmten Additiven in Dieselschmiermittel.
FI872181A FI872181A0 (fi) 1985-09-19 1987-05-18 Dieselmotorsmoerjmedel och foerfaranden.
NO872068A NO872068L (no) 1985-09-19 1987-05-18 Diesel smoeremidler.
DK253787A DK253787D0 (da) 1985-09-19 1987-05-19 Smoeremidler til dieselmotorer og fremgangsmaade tilat drive en dieselmotor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US77797585A 1985-09-19 1985-09-19
US777,975 1985-09-19

Publications (1)

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WO1987001722A1 true WO1987001722A1 (en) 1987-03-26

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ID=25111887

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1986/001890 WO1987001722A1 (en) 1985-09-19 1986-09-12 Diesel lubricants and methods

Country Status (11)

Country Link
EP (1) EP0240516B1 (es)
JP (1) JPS63501018A (es)
AU (1) AU591710B2 (es)
BR (1) BR8606979A (es)
CA (1) CA1284145C (es)
DE (1) DE3689473T2 (es)
ES (1) ES2001974A6 (es)
FI (1) FI872181A0 (es)
MX (1) MX169871B (es)
WO (1) WO1987001722A1 (es)
ZA (1) ZA867071B (es)

Cited By (23)

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EP0337602A2 (en) * 1988-02-29 1989-10-18 Exxon Chemical Patents Inc. Polyanhydride modified adducts or reaction products and oleaginous compositions containing same
FR2631969A1 (fr) * 1988-05-27 1989-12-01 Lubrizol Corp Compositions d'huiles lubrifiantes
FR2632655A1 (fr) * 1988-06-13 1989-12-15 Lubrizol Corp Compositions d'huile lubrifiante et concentres
FR2634781A1 (fr) * 1988-08-01 1990-02-02 Lubrizol Corp Compositions d'huile lubrifiante et concentres
US4904401A (en) * 1988-06-13 1990-02-27 The Lubrizol Corporation Lubricating oil compositions
FR2636071A1 (fr) * 1988-09-08 1990-03-09 Lubrizol Corp Compositions d'huiles lubrifiantes
EP0389573A1 (en) * 1988-08-01 1990-10-03 Lubrizol Corp LUBRICATING OIL COMPOSITIONS AND CONCENTRATES.
WO1990015124A1 (en) * 1989-06-01 1990-12-13 The Lubrizol Corporation Lubricating oil compositions and concentrates
WO1991013133A2 (en) * 1990-02-23 1991-09-05 The Lubrizol Corporation High temperature functional fluids
US5230817A (en) * 1988-02-29 1993-07-27 Exxon Chemical Patents Inc. Polyanhydride modified adducts or reactants and oleaginous compositions containing same
US5256325A (en) * 1988-02-29 1993-10-26 Exxon Chemical Patents Inc. Polyanhydride modified adducts or reactants and oleaginous compositions containing same
WO1993023505A1 (en) * 1992-05-15 1993-11-25 The Lubrizol Corporation Lubricating compositions and concentrates
WO1993023504A1 (en) * 1992-05-15 1993-11-25 The Lubrizol Corporation Lubricating compositions and concentrates
WO1993024599A1 (en) * 1992-05-29 1993-12-09 The Lubrizol Corporation Diesel lubricants and methods
WO1995034619A1 (en) * 1994-06-16 1995-12-21 Exxon Chemical Limited Lubricating oils containing alkali metal additives
US5562864A (en) * 1991-04-19 1996-10-08 The Lubrizol Corporation Lubricating compositions and concentrates
US5614480A (en) * 1991-04-19 1997-03-25 The Lubrizol Corporation Lubricating compositions and concentrates
US6235688B1 (en) 1996-05-14 2001-05-22 Chevron Chemical Company Llc Detergent containing lithium metal having improved dispersancy and deposit control
WO2001044419A1 (en) * 1999-12-15 2001-06-21 The Lubrizol Corporation LUBRICANTS CONTAINING A BIMETALLIC DETERGENT SYSTEM AND A METHOD OF REDUCING NOx EMISSIONS EMPLOYING SAME
US6727208B2 (en) 2000-12-13 2004-04-27 The Lubrizol Corporation Lubricants containing a bimetallic detergent system and a method of reducing NOx emissions employing same
US7217683B1 (en) 2001-09-05 2007-05-15 Blanski Rusty L Lubrication via nanoscopic polyhedral oligomeric silsesquioxanes
WO2014047180A1 (en) 2012-09-21 2014-03-27 Exxonmobil Research And Engineering Company Lubricant and fuel dispersants and methods of preparation thereof
WO2014047184A1 (en) 2012-09-21 2014-03-27 Exxonmobil Research And Engineering Company Lubricant and fuel dispersants and methods of preparation thereof

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GB2023169A (en) * 1978-06-14 1979-12-28 Lubrizol Corp Concentrates lubricant composotions and mathods for improving fuel economy of internal combustion engines
GB2062672A (en) * 1979-11-07 1981-05-28 Lubrizol Corp Additive compositions comprising sulphurized alkyl phenol and high molecular weight dispersant
GB2116583A (en) * 1982-03-12 1983-09-28 Lubrizol Corp Lubricant and fuel additives containing aminophenols

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GB2023169A (en) * 1978-06-14 1979-12-28 Lubrizol Corp Concentrates lubricant composotions and mathods for improving fuel economy of internal combustion engines
GB2062672A (en) * 1979-11-07 1981-05-28 Lubrizol Corp Additive compositions comprising sulphurized alkyl phenol and high molecular weight dispersant
GB2116583A (en) * 1982-03-12 1983-09-28 Lubrizol Corp Lubricant and fuel additives containing aminophenols

Cited By (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0337602A2 (en) * 1988-02-29 1989-10-18 Exxon Chemical Patents Inc. Polyanhydride modified adducts or reaction products and oleaginous compositions containing same
US5385687A (en) * 1988-02-29 1995-01-31 Exxon Chemical Patents Inc. Polyanhydride modified adducts or reactants and oleaginous compositions containing same
US5256325A (en) * 1988-02-29 1993-10-26 Exxon Chemical Patents Inc. Polyanhydride modified adducts or reactants and oleaginous compositions containing same
US5230817A (en) * 1988-02-29 1993-07-27 Exxon Chemical Patents Inc. Polyanhydride modified adducts or reactants and oleaginous compositions containing same
EP0537865A3 (en) * 1988-02-29 1993-06-23 Exxon Chemical Patents Inc. Polyanhydride modified dispersants
EP0537865A2 (en) * 1988-02-29 1993-04-21 Exxon Chemical Patents Inc. Polyanhydride modified dispersants
EP0337602A3 (en) * 1988-02-29 1990-11-22 Exxon Chemical Patents Inc. Polyanhydride modified adducts or reaction products and oleaginous compositions containing same
FR2631969A1 (fr) * 1988-05-27 1989-12-01 Lubrizol Corp Compositions d'huiles lubrifiantes
EP0394377A4 (en) * 1988-05-27 1991-10-02 The Lubrizol Corporation Lubricating oil compositions
BE1001976A3 (fr) * 1988-05-27 1990-05-02 Lubrizol Coporation Composition d'huiles lubrifiantes.
EP0394377A1 (en) * 1988-05-27 1990-10-31 Lubrizol Corp LUBRICATING OIL COMPOSITIONS.
EP0379566A1 (en) * 1988-06-13 1990-08-01 Lubrizol Corp LUBRICATING OIL COMPOSITIONS.
BE1001978A3 (fr) * 1988-06-13 1990-05-02 Lubrizol Corp Compositions et concentres d'huiles lubrifiantes.
US4904401A (en) * 1988-06-13 1990-02-27 The Lubrizol Corporation Lubricating oil compositions
EP0375769A1 (en) * 1988-06-13 1990-07-04 Lubrizol Corp COMPOSITIONS AND CONCENTRATES OF LUBRICATING OILS.
EP0375769A4 (en) * 1988-06-13 1991-10-02 The Lubrizol Corporation Lubricating oil compositions and concentrates
FR2632655A1 (fr) * 1988-06-13 1989-12-15 Lubrizol Corp Compositions d'huile lubrifiante et concentres
US4981602A (en) * 1988-06-13 1991-01-01 The Lubrizol Corporation Lubricating oil compositions and concentrates
EP0379566A4 (en) * 1988-06-13 1990-12-27 The Lubrizol Corporation Lubricating oil compositions
EP0382806A4 (en) * 1988-08-01 1990-12-27 The Lubrizol Corporation Lubricating oil compositions and concentrates
EP0389573B1 (en) * 1988-08-01 1995-01-11 The Lubrizol Corporation Lubricating oil compositions and concentrates
FR2634781A1 (fr) * 1988-08-01 1990-02-02 Lubrizol Corp Compositions d'huile lubrifiante et concentres
EP0382806A1 (en) * 1988-08-01 1990-08-22 Lubrizol Corp LUBRICATING OIL COMPOSITIONS AND CONCENTRATES.
BE1001979A3 (fr) * 1988-08-01 1990-05-02 Lubrizol Corp Concentres et compositions d'huiles lubrifiantes.
EP0389573A1 (en) * 1988-08-01 1990-10-03 Lubrizol Corp LUBRICATING OIL COMPOSITIONS AND CONCENTRATES.
BE1002106A5 (fr) * 1988-09-08 1990-07-03 Lubrizol Corp Composition d'huiles lubrifiantes.
FR2636071A1 (fr) * 1988-09-08 1990-03-09 Lubrizol Corp Compositions d'huiles lubrifiantes
WO1990015124A1 (en) * 1989-06-01 1990-12-13 The Lubrizol Corporation Lubricating oil compositions and concentrates
WO1991013133A3 (en) * 1990-02-23 1991-11-14 Lubrizol Corp High temperature functional fluids
WO1991013133A2 (en) * 1990-02-23 1991-09-05 The Lubrizol Corporation High temperature functional fluids
US5366648A (en) * 1990-02-23 1994-11-22 The Lubrizol Corporation Functional fluids useful at high temperatures
US5614480A (en) * 1991-04-19 1997-03-25 The Lubrizol Corporation Lubricating compositions and concentrates
US5562864A (en) * 1991-04-19 1996-10-08 The Lubrizol Corporation Lubricating compositions and concentrates
WO1993023504A1 (en) * 1992-05-15 1993-11-25 The Lubrizol Corporation Lubricating compositions and concentrates
WO1993023505A1 (en) * 1992-05-15 1993-11-25 The Lubrizol Corporation Lubricating compositions and concentrates
WO1993024599A1 (en) * 1992-05-29 1993-12-09 The Lubrizol Corporation Diesel lubricants and methods
WO1995034619A1 (en) * 1994-06-16 1995-12-21 Exxon Chemical Limited Lubricating oils containing alkali metal additives
AU692888B2 (en) * 1994-06-16 1998-06-18 Exxon Chemical Limited Lubricating oils containing alkali metal additives
US6235688B1 (en) 1996-05-14 2001-05-22 Chevron Chemical Company Llc Detergent containing lithium metal having improved dispersancy and deposit control
WO2001044419A1 (en) * 1999-12-15 2001-06-21 The Lubrizol Corporation LUBRICANTS CONTAINING A BIMETALLIC DETERGENT SYSTEM AND A METHOD OF REDUCING NOx EMISSIONS EMPLOYING SAME
US6727208B2 (en) 2000-12-13 2004-04-27 The Lubrizol Corporation Lubricants containing a bimetallic detergent system and a method of reducing NOx emissions employing same
US7217683B1 (en) 2001-09-05 2007-05-15 Blanski Rusty L Lubrication via nanoscopic polyhedral oligomeric silsesquioxanes
WO2014047180A1 (en) 2012-09-21 2014-03-27 Exxonmobil Research And Engineering Company Lubricant and fuel dispersants and methods of preparation thereof
WO2014047184A1 (en) 2012-09-21 2014-03-27 Exxonmobil Research And Engineering Company Lubricant and fuel dispersants and methods of preparation thereof
US9315761B2 (en) 2012-09-21 2016-04-19 Exxonmobil Chemical Patents Inc. Lubricant and fuel dispersants and methods of preparation thereof
US10017708B2 (en) 2012-09-21 2018-07-10 Exxonmobil Chemical Patents Inc. Lubricant and fuel dispersants and methods of preparation thereof

Also Published As

Publication number Publication date
CA1284145C (en) 1991-05-14
EP0240516B1 (en) 1993-12-29
DE3689473D1 (de) 1994-02-10
FI872181A (fi) 1987-05-18
AU591710B2 (en) 1989-12-14
AU6338286A (en) 1987-04-07
JPS63501018A (ja) 1988-04-14
ES2001974A6 (es) 1988-07-01
FI872181A0 (fi) 1987-05-18
MX169871B (es) 1993-07-29
ZA867071B (en) 1987-05-27
DE3689473T2 (de) 1994-06-16
EP0240516A1 (en) 1987-10-14
BR8606979A (pt) 1987-11-03

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