EP0531000A1 - Ölzusatzkonzentrate und Schmieröle mit erhöhten Leistungsfähigkeiten - Google Patents

Ölzusatzkonzentrate und Schmieröle mit erhöhten Leistungsfähigkeiten Download PDF

Info

Publication number
EP0531000A1
EP0531000A1 EP92307448A EP92307448A EP0531000A1 EP 0531000 A1 EP0531000 A1 EP 0531000A1 EP 92307448 A EP92307448 A EP 92307448A EP 92307448 A EP92307448 A EP 92307448A EP 0531000 A1 EP0531000 A1 EP 0531000A1
Authority
EP
European Patent Office
Prior art keywords
parts
mixture
oil
acid
soluble
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92307448A
Other languages
English (en)
French (fr)
Other versions
EP0531000B1 (de
Inventor
Andrew George Papay
Rolfe John Hartley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Afton Chemical Corp
Original Assignee
Afton Chemical Corp
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 Afton Chemical Corp filed Critical Afton Chemical Corp
Publication of EP0531000A1 publication Critical patent/EP0531000A1/de
Application granted granted Critical
Publication of EP0531000B1 publication Critical patent/EP0531000B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/95—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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/58—Heterocyclic compounds
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/02—Sulfurised compounds
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/08—Ammonium or amine salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/16—Reaction products obtained by Mannich reactions
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M165/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/044—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms having cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/30—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • 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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • 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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M2219/083—Dibenzyl sulfide
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2221/041—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving sulfurisation of macromolecular compounds, e.g. polyolefins
    • 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
    • C10M2223/043—Ammonium or amine 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
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • 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
    • C10N2040/02—Bearings
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
    • 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
    • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
    • 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
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • 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
    • C10N2040/255—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
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to additive concentrates and oleaginous compositions (i.e., lubricating oils and functional fluids) having enhanced performance properties.
  • additive concentrates containing, inter alia, sulfur-containing antiwear and/or extreme pressure additives, phosphorus-containing antiwear and/or extreme pressure additives, and other additive components have been proposed and used.
  • other additive components include acidic components such as carboxylic acids, hydrocarbyl phosphoric acids, and hydrocarbyl thiophosphoric acids; basic components such as amines; and ashless dispersants such as boronated succinimides.
  • the finished lubricating oil composition and additive concentrate from which it is made must be formulated to meet the American Petroleum Institute GL-5 requirements. This involves passing a battery of standard tests.
  • the provision of clean gears in the L-60 test is an important consideration in the marketplace. So far as is known, only a very limited number of lubricant additive packages have received GL-5 approval. Thus there is a need for additional automotive gear oil packages which give good performance in the GL-5 qualification tests, and especially for packages capable of satisfying the GL-5 requirements.
  • Still another need is for an ashless or low-ash lubricant additive package affording high dispersancy and high wear resistance to lubricants, such as crankcase lubricants, gear lubricants, manual and automatic transmission fluids, oil-based hydraulic fluids, wet brake fluids, and similar lubricants and functional fluids.
  • lubricants such as crankcase lubricants, gear lubricants, manual and automatic transmission fluids, oil-based hydraulic fluids, wet brake fluids, and similar lubricants and functional fluids.
  • an additive concentrate which comprises a minor proportion of diluent oil and a major proportion of additive components, said additive components comprising:
  • component a) refers collectively to the above components a-1), a-2), a-3) and a-4).
  • components a) and b) of such compositions makes it possible to achieve performance levels (reduction in sludge formation and/or deposition and reduction in wear in gears and/or other relatively moveable metal surfaces in contact with each other) normally achieved, if at all, by higher concentrations of component b).
  • components a) and b) should be proportioned such that the mass ratio (wt:wt) of sulfur in component b) to phosphorus in component a) is in the range of 8:1 to 30:1, more preferably in the range of 10:1 to 20:1, and most preferably in the range of 14:1 to 20:1.
  • the finished lubricating oils of this invention will usually contain at least about 0.5 wt % of sulfur as component b) and preferably will contain an amount of component b) to provide a sulfur content in the finished lubricant in the range of 1 to 3 wt %, and more preferably in the range of 1.5 to 3 wt %, of the total weight of the composition.
  • the foregoing additive concentrates further comprise one or more of the following additive components:
  • lubricant compositions which comprise a major proportion of at least one oil of lubricating viscosity and a minor amount of the various additive combinations referred to hereinabove.
  • compositions of this invention are ashless compositions (i.e., they contain no metal-containing additive components) or are low-ash compositions (i.e., base oil containing an additive concentrate or a combination of additives pursuant to this invention at a total concentration of 10% by weight will contain no more than 100 parts by weight, and more preferably no more than 50 parts by weight, of added metal per million parts by weight of the total composition.
  • Component a) -- i.e., a-1), a-2), a-3) or a-4) -- is one indispensable additive ingredient of the compositions of this invention.
  • oil-soluble additive compositions are formed by heating concurrently or any sequence at least one ashless dispersant which contains basic niaogen and/or at least one hydroxyl group with (i) at least one inorganic phosphorus acid or anhydride or at least one partial or total sulfur analog thereof, or any combination of the foregoing, and (ii) at least one boron compound, such that a liquid composition is formed.
  • the ashless dispersant which is heated concurrently or in any sequence with components (i) and (ii) is preferably a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group.
  • any suitable ashless dispersant formed in the customary manner can be heated with one or more boron compounds to cause boronation to occur and the resultant product mixture can then be heated with one or more inorganic phosphorus compounds such that a liquid phosphorus- and boron-containing composition [component a-1)] is formed.
  • a preformed ashless dispersant can be heated with one or more inorganic phosphorus compounds and thereafter the product mixture can be heated with one or more boron compounds so that a liquid phosphorus- and boron-containing composition is formed.
  • the preferred way of forming component a-1) is to heat a preformed ashless dispersant with a combination of one or more inorganic phosphorus compounds and one or more boron compounds to form a liquid phosphorus- and boron-containing composition.
  • the preformed ashless dispersant is concurrently heated with one or more inorganic phosphorus compounds and one or more boron compounds.
  • the resulting liquid product composition when subjected to chemical analysis reveals the presence of both phosphorus and boron.
  • component a-1 Rather than utilizing a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group, it is possible to produce component a-1) by:
  • oil-soluble additive compositions are formed by heating (i) at least one boron-free oil-soluble ashless dispersant containing basic nitrogen and/or at least one hydroxyl group, with (ii) at least one inorganic phosphorus acid such that a liquid boron-free phosphorus-containing composition is formed.
  • the ashless dispersant which is used in the process is preferably a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group.
  • any suitable boron-free ashless dispersant formed in the customary manner can be heated with one or more inorganic phosphorus acids to cause phosphorylation to occur.
  • the resulting liquid product composition when subjected to chemical analysis reveals the presence of phosphorus.
  • component a-2 Rather than utilizing a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group, it is possible to produce component a-2) by:
  • oil-soluble additive compositions are formed by heating concurrently or any sequence at least one ashless dispersant which contains basic nitrogen and/or at least one hydroxyl group with (i) at least one water-hydrolyzable organic compound of phosphorus -- preferably a water-hydrolyzable ester of an acid of phosphorus -- and water, and (ii) at least one boron compound, such that a liquid phosphorus- and boron-containing composition is formed, and from which water has been removed.
  • the ashless dispersant which is heated concurrently or in any sequence with components (i) and (ii) is preferably a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group.
  • any suitable ashless dispersant formed in the customary manner can be heated with one or more boron compounds to cause boronation to occur and the resultant product mixture can then be heated with water and one or more water-hydrolyzable organic phosphorus compounds such that a liquid phosphorus- and boron-containing composition [component a-3)] is formed.
  • a preformed ashless dispersant can be heated with water and one or more water-hydrolyzable organic phosphorus compounds and thereafter the product mixture can be heated with one or more boron compounds so that a liquid phosphorus- and boron-containing composition is formed.
  • the preferred way of forming component a-3) is to heat a preformed ashless dispersant with a combination of water, one or more water-hydrolyzable organic phosphorus compounds and one or more boron compounds to form a liquid phosphorus- and boron-containing composition.
  • the preformed ashless dispersant is concurrently heated with water, one or more water-hydrolyzable organic phosphorus compounds and one or more boron compounds.
  • the resulting liquid product composition when subjected to chemical analysis reveals the presence of both phosphorus and boron.
  • water is removed at least during or after the heating with (i) and (ii) (if conducted concurrently) or at least during or after the heating with (i) (if conducted sequentially).
  • Such heating is conducted under conditions such that partial or total hydrolysis of the water-hydrolyzable organic phosphorus compound occurs.
  • component a-3 Rather than utilizing a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group, it is possible to produce component a-3) by:
  • oil-soluble boron-free additive compositions are formed by heating (i) at least one boron-free oil-soluble ashless dispersant which contains basic nitrogen and/or at least one hydroxyl group, with (ii) at least one water-hydrolyzable organic phosphorus compound and water such that a liquid boron-free phosphorus-containing composition is formed.
  • the ashless dispersant which is used in the process is preferably a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group.
  • any suitable boron-free ashless dispersant formed in the customary manner can be heated with water and one or more water-hydrolyzable organic phosphorus compounds to cause phosphorylation to occur.
  • the resulting liquid product composition when subjected to chemical analysis reveals the presence of phosphorus.
  • component a-4 Rather than utilizing a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group, it is possible to produce component a-4) by:
  • Various methods can be used for removing water from component a-3) or a-4) during or after its formation.
  • the preferred method involves applying a suitable vacuum to the reaction system while heating the water-containing mixture to a suitably elevated temperature. In this way the water is readily stripped off.
  • a suitable vacuum to the reaction system while heating the water-containing mixture to a suitably elevated temperature. In this way the water is readily stripped off.
  • a phosphorus ester made from a lower alcohol such as methanol, ethanol, propanol, 2-propanol, butanol, or isobutyl alcohol
  • both lower alcohol liberated in the process and water can be stripped off from the product mixture during or on completion of the heating operation.
  • an ashless dispersant used in forming component a) is not a liquid but rather is in whole or in part in the solid state of aggregation at room temperature (e.g., 25°C)
  • a suitable solvent or diluent polar or non-polar, as may be required to dissolve the dispersant
  • phosphorylation and/or boronation as the case may be
  • component a including such solvent or diluent, is in the liquid state of aggregation at room temperature (e.g., 25°C), even though at a lower temperature the dispersant may revert in whole or in part to the solid state.
  • room temperature e.g. 25°C
  • component a-1 must be oil-soluble within the meaning of such term as set forth hereinafter.
  • component a in any instance wherein macro (i.e., non-dispersible) solids are formed or remain in the liquid composition after it has been formed, such solids should be removed, and can be readily removed, by any of a variety of conventional separation techniques such as filtration, centrifugation, or decantation.
  • macro i.e., non-dispersible
  • component a) is in whole or in part a micellar structure containing phosphorus- and/or boron-containing species or moieties.
  • this invention is not limited to, and should not be construed as being limited to, any specific structural configurations with respect to component a).
  • component a) is a liquid that is oil soluble and that if subjected to analysis reveals the presence of phosphorus and, in the case of a-1) and 1-3), boron.
  • component a) should possess dispersant properties.
  • Component a) may contain chemical species and/or moieties besides the phosphorus- and boron-containing species or moieties of a-1) or a-3) or the phosphorus-containing species and/or moieties of a-2) or a-4), such as, for example, nitrogen- and/or oxygen- and/or sulfur-containing species or moieties over and above the basic nitrogen and/or hydroxyl group(s) forming an essential part of the initial ashless dispersant itself.
  • organic phosphorus-containing compounds may be used along with inorganic phosphorus compounds in making component a-1) or a-2) and that inorganic phosphorus-containing compounds may be used along with water and one or more water-hydrolyzable organic phosphorus compounds in making component a-3) or a-4).
  • the inorganic phosphorus compound or compounds can be formed in situ, as, for example, by heating a mixture of phosphorus and sulfur to form a phosphorus sulfide, or by treating one or more organic phosphorus compounds to convert the same in whole or in part into one or more inorganic phosphorus compounds.
  • the water-hydrolyzable organic phosphorus compound or compounds can also be formed in situ, as, for example, by heating a mixture of one or more alcohols or phenols with one or more phosphorus halides (e.g., PCl3, POCl3, PSCl3, RPCl2, ROPCl2, RSPCl2, RPOCl2, ROPOCl2, RSPOCl2, RPSCl2, ROPSCl2, RSPSCl2, R2PCl, (RO)2PCl, (RS)2PCl, (RO)(RS)PCl, R2POCl, (RO)2POCl, (RS)2POCl, (RO)(RS)POCl, R2PSCl, (RO)2PSCl, (RS)2PSCl, where each R is, independently a hydrocarbyl group) and introducing water into the system in order to hydrolyze the water-hydrolyzable phosphorus ester so formed.
  • phosphorus halides e.g., PCl3,
  • the term "phosphorylated” means that the ashless dispersant has been heated with one or more inorganic phosphorus compounds [components a-1) and a-2)] or with one or more water-hydrolyzable organic phosphorus compounds and water [components a-3) and a-4)] such that the resultant product, on analysis, reveals the presence of phosphorus.
  • the term “boronated” means that the ashless dispersant has been heated with one or more boron compounds such that the resultant product, on analysis, reveals the presence of boron.
  • the terms "phosphorylated” and “boronated” are not to be construed as requiring that the resultant composition contain chemically bound phosphorus or boron.
  • ashless dispersants can be utilized in forming component a) of the compositions of this invention. These include the following types:
  • reaction products of (i) an acylating agent such as a monocarboxylic acid, or a dicarboxylic or other polycarboxylic acid, or a derivative thereof, with (ii) one or more compounds which contain amine groups and/or hydroxyl groups, such that the acylated reaction product contains basic nitrogen and/or at least one hydroxyl group.
  • an acylating agent such as a monocarboxylic acid, or a dicarboxylic or other polycarboxylic acid, or a derivative thereof
  • one or more compounds which contain amine groups and/or hydroxyl groups such that the acylated reaction product contains basic nitrogen and/or at least one hydroxyl group.
  • Patents 3,163,603; 3,184,474; 3,215,707; 3,219,666; 3,271,310; 3,272,746; 3,281,357; 3,306,908; 3,311,558; 3,316,177; 3,340,281; 3,341,542; 3,346,493; 3,381,022; 3,399,141; 3,415,750, 3,433,744; 3,444,170; 3,448,048; 3,448,049; 3,451,933; 3,454,607; 3,467,668; 3,522,179; 3,541,012; 3,542,678; 3,574,101; 3,576,743; 3,630,904; 3,632,510; 3,632,511; 3,697,428; 3,725,441; 3,868,330; 3,948,800; 4,234,435; and Re 26,433.
  • component a there are a number of sub-categories of carboxylic ashless dispersants.
  • One such sub-category which constitutes a preferred type for use in the formation of component a) is composed of the polyamine succinamides and more preferably the polyamine succinimides in which the succinic group contains a hydrocarbyl substituent containing at least 30 carbon atoms.
  • the polyamine used in forming such compounds contains at least one primary amino group capable of forming an imide group on reaction with a hydrocarbon-substituted succinic acid or acid derivative thereof such an anhydride, lower alkyl ester, acid halide, or acid-ester. Representative examples of such dispersants are given in U.S. Pat. Nos.
  • the alkenyl succinimides may be formed by conventional methods such as by heating an alkenyl succinic anhydride, acid, acid-ester, acid halide, or lower alkyl ester with a polyamine containing at least one primary amino group.
  • the alkenyl succinic anhydride may be made readily by heating a mixture of olefin and maleic anhydride to 180°-220°C.
  • the olefin is preferably a polymer or copolymer of a lower monoolefin such as ethylene, propylene, 1-butene, and isobutene.
  • the more preferred source of alkenyl group is from polyisobutene haring a number average molecular weight of up to 100,000 or higher.
  • the alkenyl group is a polyisobutenyl group having a number average molecular weight (determined using the method described in detail hereinafter) of 500-5,000, and preferably 700-2,500, more preferably 700-1,400, and especially 800-1,300.
  • the isobutene used in making the polyisobutene is usually (but not necessarily) a mixture of isobutene and other C4 isomers such as 1-butene.
  • the acylating agent formed from maleic anhydride and "polyisobutene” made from such mixtures of isobutene and other C4 isomers such as 1-butene can be termed a "polybutenyl succinic anhydride” and a succinimide made therewith can be termed a “polybutenyl succinimide”.
  • polyisobutenyl is used to denote the alkenyl moiety whether made from a highly pure isobutene or a more impure mixture of isobutene and other C4 isomers such as 1-butene.
  • Polyamines which may be employed in forming the ashless dispersant include any that have at least one primary amino group which can react to form an imide group.
  • a few representative examples include branched-chain alkanes containing two or more primary amino groups such as tetraamino-neopentane polyaminoalkanols such as 2-(2-aminoethylamino)-ethanol and 2-[2-(2-aminoethylamino)-ethylamino]-ethanol; heterocyclic compounds containing two or more amino groups at least one of which is a primary amino group such as 1-( ⁇ -aminoethyl)-2-imidazolidone, 2-(2-aminoethylamino)-5-nitropyridine, 3-amino-N-ethylpiperidine, 2-(2-aminoethyl)-pyridine, 5-aminoindole, 3-amino-5-mercapto- 1,2,4-triazole, and 4-(amino
  • the most preferred amines are the ethylene polyamines which can be depicted by the formula H2N(CH2CH2NH) n H wherein n is an integer from one to ten. These include: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, including mixtures thereof in which case n is the average value of the mixture.
  • the ethylene polyamines which have a primary amine group at each end can form mono-alkenylsuccinimides and bis-alkenylsuccinimides.
  • ethylene polyamine mixtures usually contain minor amounts of branched species and cyclic species such as N-aminoethyl piperazine, N,N′-bis(aminoethyl)piperazine, N,N′-bis(piperazinyl)ethane, and like compounds.
  • the preferred commercial mixtures have approximate overall compositions falling in the range corresponding to diethylene triamine to pentaethylene hexamine, mixtures generally corresponding in overall makeup to tetraethylene pentamine being most preferred.
  • Methods for the production of polyalkylene polyamines are known and reported in the literature. See for example U.S. Pat. Nos. 4,827,037; and 4,983,736; and EP Pub. Nos. 412,611; 412,612; 412,613; 412,614; and 412,615, and references cited therein.
  • especially preferred ashless dispersants for use in the present invention are the products of reaction of a polyethylene polyamine, e.g., mixture known in the trade as "triethylene tetramine” or “tetraethylene pentamine", with a hydrocarbon-substituted carboxylic acid or anhydride (or other suitable acid derivative) made by reaction of a polyolefin, preferably polyisobutene, having a number average molecular weight of 500 to 5,000, preferably 700 to 2,500, more preferably 700 to 1,400 and especially 800 to 1,300, with an unsaturated polycarboxylic acid or anhydride, e.g., maleic anhydride, maleic acid, or fumaric acid, including mixtures of two or more such substances.
  • a polyethylene polyamine e.g., mixture known in the trade as "triethylene tetramine” or “tetraethylene pentamine
  • a hydrocarbon-substituted carboxylic acid or anhydride or other suitable acid derivative
  • uccinimide is meant to encompass the completed reaction product from reaction between the amine reactant(s) and the hydrocarbon-substituted carboxylic acid or anhydride (or like acid derivative) reactant(s), and is intended to encompass compounds wherein the product may have amide, amidine, and/or salt linkages in addition to the imide linkage of the type that results from the reaction of a primary amino group and an anhydride moiety.
  • Residual unsaturation in the alkenyl group of the alkenyl succinimide may be used as a reaction site, if desired.
  • the alkenyl substituent may be hydrogenated to form an alkyl substituent.
  • the olefinic bond(s) in the alkenyl substituent may be sulfurized, halogenated, or hydrohalogenated.
  • component a Another sub-category of carboxylic ashless dispersants which can be used in forming component a) includes alkenyl succinic acid esters and diesters of polyhydric alcohols containing 2-20 carbon atoms and 2-6 hydroxyl groups. Representative examples are described in U.S. Pat. Nos. 3,331,776; 3,381,022; and 3,522,179.
  • the alkenyl succinic portion of these esters corresponds to the alkenyl succinic portion of the succinimides described above including the same preferred and most preferred subgenus, e.g., alkenyl succinic acids and anhydrides, where the alkenyl group contains at least 30 carbon atoms and notably, polyisobutenyl succinic acids and anhydrides wherein the polyisobutenyl group has a number average molecular weight of 500 to 5,000, preferably 700 to 2,500, more preferably 700 to 1,400, and especially 800 to 1,300.
  • the alkenyl group can be hydrogenated or subjected to other reactions involving olefinic double bonds.
  • Alcohols useful in preparing the esters include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol, glycerol, sorbitol, 1,1,1-trimethylol ethane, 1,1,1-trimethylol propane, 1,1,1-trimethylol butane, pentaerythritol, and dipentaerythritol.
  • the succinic esters are readily made by merely heating a mixture of alkenyl succinic acid, anhydrides or lower alkyl (e.g., C1-C4) ester with the alcohol while distilling out water or lower alkanol. In the case of acid-esters less alcohol is used. In fact, acid-esters made from alkenyl succinic anhydrides do not evolve water.
  • Still another sub-category of carboxylic ashless dispersants useful in forming component a) comprises an alkenyl succinic ester-amide mixture. These may be made by heating the above-described alkenyl succinic acids, anhydrides or lower alkyl esters with an alcohol and an amine either sequentially or in a mixture. Alcohols and amines such as those described above are also useful in this embodiment.
  • linear and/or branched chain monohydric alcohols such as 1-butanol, 2-butanol, 2-methyl-1-propanol, pentanol, hexanol, octanol, decanol, lauryl alcohol, oleyl alcohol, eicosanol, or ethylene glycol monomethyl ether, can be used provided they are used with one or more polyamines.
  • amino alcohols can be used alone or with the alcohol and/or amine to form the ester-amide mixtures.
  • the amino alcohol can contain 2-20 carbon atoms, 1-6 hydroxy groups and 1-4 amine nitrogen atoms. Examples are ethanolamine, diethanolamine, N-ethanol-diethylene triamine, and trimethylol aminomethane.
  • alkenyl group of the succinic ester-amide can be hydrogenated or subjected to other reactions involving olefinic double bonds.
  • ester-amide mixtures are described in U.S. Pat. Nos. 3, 184,474; 3,576,743; 3,632,511; 3,804,763; 3,836,471; 3,862,981; 3,936,480; 3,948,800; 3,950,341; 3,957,854; 3,957,855; 3,991,098; 4,071,548; and 4,173,540.
  • Yet another sub-category of carboxylic ashless dispersants useful in forming component a) comprises the Mannich-based derivatives of hydroxyaryl succinimides.
  • Such compounds can be made by reacting a polyalkenyl succinic anhydride with an aminophenol to produce an N-(hydroxyaryl) hydrocarbyl succinimide which is then reacted with an alkylene diamine or polyalkylene polyamine and an aldehyde (e.g., formaldehyde), in a Mannich-base reaction. Details of such synthesis are set forth in U.S. Pat. No. 4,354,950.
  • the alkenyl succinic anhydride or like acylating agent is derived from a polyolefin, preferably a polyisobutene, having a number average molecular weight of 500 to 5,000, preferably 700 to 2,500, more preferably 700 to 1,400, and especially 800 to 1,200.
  • a polyolefin preferably a polyisobutene
  • residual unsaturation in the polyalkenyl substituent group can be used as a reaction site as for example, by hydrogenation or sulfurization.
  • hydrocarbyl polyamine dispersants are generally produced by reacting an aliphatic or alicyclic halide (or mixture thereof) containing an average of at least about 40 carbon atoms with one or more amines, preferably polyalkylene polyamines. Examples of such hydrocarbyl polyamine dispersants are described in U.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,671,511; 3,821,302; 3,394,576; and in European Patent Publication No. 382,405.
  • the hydrocarbyl-substituted polyamines are high molecular weight hydrocarbyl-N-substituted polyamines containing basic nitrogen in the molecule.
  • the hydrocarbyl group typically has a number average molecular weight in the range of 750-10,000, more usually in the range of 1,000-5,000.
  • the hydrocarbyl radical may be aliphatic or alicyclic and, except for adventitious amounts of aromatic components in petroleum mineral oils, will be free of aromatic unsaturation.
  • the hydrocarbyl groups will normally be branched-chain aliphatic, having 0-2 sites of unsaturation, and preferably from 0-1 site of ethylene unsaturation.
  • the hydrocarbyl groups are preferably derived from petroleum mineral oil, or polyolefins, either homo-polymers or higher-order polymers, or 1-olefins of from 2-6 carbon atoms. Ethylene is preferably copolymerized with a higher olefin to insure oil solubility.
  • Illustrative polymers include polypropylene, polyisobutylene, or poly-1-butene.
  • the polyolefin group will normally have at least one branch per six carbon atoms along the chain, preferably at least one branch per four carbon atoms along the chain.
  • These branched-chain hydrocarbons are readily prepared by the polymerization of olefins of from 3-6 carbon atoms and preferably from olefins of from 3-4 carbon atoms.
  • the composition is a mixture of materials having various structures and molecular weights. Therefore, in referring to molecular weight, number average molecular weights are intended. Furthermore, when speaking of a particular hydrocarbon group, it is intended that the group include the mixture that is normally contained within materials which are commercially available. For example, polyisobutylene is known to have a range of molecular weights and may include small amounts of very high molecular weight materials.
  • Particularly preferred hydrocarbyl-substituted amines or polyamines are prepared from polyisobutenyl chloride.
  • the polyamine employed to prepare the hydrocarbyl-substituted polyamine is preferably a polyamine having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms.
  • the polyamine is reacted with a hydrocarbyl halide (e.g., chloride) to produce the hydrocarbyl-substituted polyamine.
  • the polyamine preferably has a carbon-to-nitrogen ratio of from 1:1 to 10:1.
  • the amine portion of the hydrocarbyl-substituted amine may be substituted with substituents selected from (A) hydrogen, and (B) hydrocarbyl groups of from 1 to 10 carbon atoms.
  • the polyamine portion of the hydrocarbyl-substituted polyamine may be substituted with substituents selected from (A) hydrogen, (B) hydrocarbyl groups of from 1 to 10 carbon atoms, (C) acyl groups of from 2 to 10 carbon atoms, and (D) monoketo, monohydroxy, mononitro, monocyano, lower alkyl and lower alkoxy derivatives of (B) and (C).
  • At least one of the nitrogens in the hydrocarbyl-substituted amine or polyamine is a basic nitrogen atom, i.e., one titratable by a strong acid.
  • Hydrocarbyl as used in describing the substituents in the amine or polyamine used in forming the dispersants, denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof e.g., aralkyl.
  • the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particularly acetylenic unsaturation.
  • the hydrocarbyl substituted polyamines used in forming the dispersants are generally, but not necessarily, N-substituted polyamines.
  • hydrocarbyl groups and substituted hydrocarbyl groups which may be present in the amine portion of the dispersant include alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls such as propenyl, isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls, such as 2-hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl, 4-hydroxybutyl, etc., ketoalkyls, such as 2-ketopropyl, 6-ketooctyl, etc., alkoxy and lower alkenoxy alkyls, such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl, 2-(2-ethoxyethoxy)ethyl, 2-(2-(2-ethoxyethoxy)eth
  • Typical amines useful in preparing the hydrocarbyl-substituted amines include methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, di-n-propylamine, etc. Such amines are either commercially available or are prepared by art recognized procedures.
  • the polyamine component may also contain heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds, wherein the heterocyclic comprises one or more 5-6 membered rings containing oxygen and/or nitrogen.
  • heterocyclics may be saturated- or unsaturated and substituted with groups selected from the aforementioned (A), (B), (C), and (D).
  • the heterocyclis are exemplified by piperazines, such as 2-methylpiperazine, 1,2-bis(N-piperazinyl-ethane), and N,N′-bis(N-piperazinyl)piperazine, 2-methylimidazoline, 3-aminopiperidine, 2-aminopyridine, 2-( ⁇ -aminoethyl)-3-pyrroline, 3-aminopyrrolidine, N-(3-aminopropyl)morpholine, etc.
  • the piperazines are preferred.
  • Typical polyamines that can be used to form the hydrocarbyl polyamine dispersants include the following: ethylene diamine, 1,2-propylene diamine, 1,3-propylene diamine, diethylene triamine, triethylene tetramine, hexamethylene diamine, tetraethylene pentamine, methylaminopropylene diamine, N-( ⁇ -aminoethyl)piperazine, N,N′-di( ⁇ -aminoethyl)piperazine, N,N′-di( ⁇ -aminoethyl)imidazolidone-2, N-( ⁇ -cyanoethyl)ethane- 1,2-diamine, 1,3,6,9-tetraaminooctadecane, 1,3,6-triamino-9-oxadecane, N-methyl-1,2-propanediamine, and 2-(2-aminoethylamino)ethanol.
  • polyalkylene amines in which the alkylene groups differ in carbon content, such as for example bis(aminopropyl)ethylenediamine.
  • Such compounds are prepared by the reaction of acrylonitrile with an ethyleneamine, for example, an ethyleneamine having the formula H2H(CH2CH2NH) n H wherein n is an integer from 1 to 5, followed by hydrogenation of the resultant intermediate.
  • the product prepared from ethylene diamine and acrylonitrile has the formula H2N-(CH2)3NH(CH2)2NH(CH2)3NH2.
  • the polyamine used as a reactant in the production of the hydrocarbyl-substituted polyamine is not a single compound but a mixture in which one or several compounds predominate with the average composition indicated.
  • tetraethylene pentamine prepared by the polymerization of aziridine or the reaction of 1,2-dichloroethane and ammonia will have both lower and higher amine members, e.g., triethylene tetramine, substituted piperazines and pentaethylene hexamine, but the composition will be largely tetraethylene pentamine and the empirical formula of the total amine composition will closely approximate that of tetraethylene pentamine.
  • the preferred hydrocarbyl-substituted polyalkylene polyamines for use in this invention may be represented by the formula R1NH-(-R2-NH-) ⁇ -H wherein R1 is hydrocarbyl having an average molecular weight of from 750 to 10,000; R2 is alkylene of from 2 to 6 carbon atoms; and ⁇ is an integer of from 0 to 10.
  • R1 is hydrocarbyl having an average molecular weight of from 1,000 to 10,000.
  • R2 is alkylene of from 2 to 3 carbon atoms and ⁇ is preferably an integer of from 1 to 6.
  • Type C - Mannich polyamine dispersants .
  • This category of ashless dispersant which can be utilized in the formation of component a) is comprised of reaction products of an alkyl phenol, with one or more aliphatic aldehydes containing from 1 to 7 carbon atoms (especially formaldehyde and derivatives thereof), and polyamines (especially polyalkylene polyamines of the type described hereinabove).
  • the polyamine group of the Mannich polyamine dispersants is derived from polyamine compounds characterized by containing a group of the structure -NH- wherein the two remaining valances of the nitrogen are satisfied by hydrogen, amino, or organic radicals bonded to said nitrogen atom These compounds include aliphatic, aromatic, heterocyclic and carbocyclic polyamines.
  • the source of the oil-soluble hydrocarbyl group in the Mannich polyamine dispersant is a hydrocarbyl-substituted hydroxy aromatic compound comprising the reaction product of a hydroxy aromatic compound, according to well known procedures, with a hydrocarbyl donating agent or hydrocarbon source.
  • the hydrocarbyl substituent provides substantial oil solubility to the hydroxy aromatic compound and, preferably, is substantially aliphatic in character.
  • the hydrocarbyl substituent is derived from a polyolefin having at least about 40 carbon atoms.
  • the hydrocarbon source should be substantially free from pendant groups which render the hydrocarbyl group oil insoluble. Examples of acceptable substituent groups are hide, hydroxy, ether, carboxy, ester, amide, nitro and cyano. However, these substituent groups preferably comprise no more than about 10 weight percent of the hydrocarbon source.
  • the preferred hydrocarbon sources for preparation of the Mannich polyamine dispersants are those derived from substantially saturated petroleum fractions and olefin polymers, preferably polymers of mono-olefins having from 2 to 30 carbon atoms.
  • the hydrocarbon course can be derived, for example, from polymers of olefins such as ethylene, propene, 1-butene, isobutene, 1-octene, 1-methylcyclohexene, 2-butene and 3-pentene. Also useful are copolymers of such olefins with other polymerizable olefinic substances such as styrene.
  • these copolymers should contain at least 80 percent and preferably 95 percent, on a weight basis, of units derived from the aliphatic mono-olefins to preserve oil solubility.
  • the hydrocarbon source generally contains at least 40 and preferably at least 50 carbon atoms to provide substantial oil solubility to the dispersant.
  • the olefin polymers having a number average molecular weight between 600 and 5,000 are preferred for reasons of easy reactivity and low cost. However, polymers of higher molecular weight can also be used.
  • Especially suitable hydrocarbon sources are isobutylene polymers.
  • the Mannich polyamine dispersants are generally prepared by reacting a hydrocarbyl-substituted hydroxy aromatic compound with an aldehyde and a polyamine.
  • the aldehyde is typically an aliphatic aldehyde containing 1 to 7 carbon atoms, and in most cases is formaldehyde or a compound such as formalin or a polyformaldehyde from which formaldehyde is derived during the reaction.
  • the substituted hydroxy aromatic compound is contacted with from 0.1 to 10 moles of polyamine and 0.1 to 10 moles of aldehyde per mole of substituted hydroxy aromatic compound.
  • the reactants are mixed and heated to a temperature above about 80°C. to initiate the reaction.
  • the reaction is carried out at a temperature from 100° to 250°C.
  • the resulting Mannich product has a predominantly benzylamine linkage between the aromatic composed and the polyamine.
  • the reaction can be carried out in an inert diluent such as mineral oil, benzene, toluene, naphtha, ligroin, or other inert solvents to facilitate control of viscosity, temperature, and reaction rate.
  • polyamines are preferred for use in preparing the Mannich polyamine dispersants, and suitable polyamines include, but are not limited to, alkylene diamines and polyalkylene polyamines (and mixtures thereof) of the formula: wherein n is an integer from 1 to 10, R is a divalent hydrocarbyl group of from 1 to 18 carbon atoms, and each A is independently selected from the group consisting of hydrogen and monovalent aliphatic groups containing up to 10 carbon atoms which can be substituted with one or two hydroxyl groups. Most preferably, R is a lower alkylene group of from 2 to 6 carbon atoms and A is hydrogen.
  • Suitable polyamines for use in preparation of the Mannich polyamine dispersants include, but are not limited to, methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines and heptylene polyamines. The higher homologs of such amines and related aminoalkyl-substituted piperazines are also included.
  • polyamines include ethylene diamine, triethylene tetramine, tris(2-aminoethyl)amine, propylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, decamethylene diamine, di(heptamethylene) triamine, pentaethylene hexamine, di(trimethylene) triamine, 2-heptyl-3-(2-aminopropyl)imidazoline, 1,3-bis(2-aminoethyl)imidazoline, 1-(2-aminopropyl)piperazine, 1,4-bis(2-aminoethyl)piperazine and 2-methyl-1-(2-aminobutyl)piperazine. Higher homologs, obtained by condensing two or more of the above mentioned amines, are also useful as are the polyoxyalkylene polyamines.
  • the polyalkylene polyamines are especially useful in preparing the Mannich polyamine dispersants for reasons of cost and effectiveness.
  • Such polyamines are described in detail under the heading "Diamines and Higher Amines" in Kirk-Othmer, Encyclopedia of Chemical Technology , Second Edition, Vol. 7, pp. 22-39. They are prepared most conveniently by the reaction of an ethylene imine with a ring-opening reagent such as ammonia. These reactions result in the production of somewhat complex mixtures of polyalkylene polyamines which include cyclic condensation products such as piperazines. Because of their availability, these mixtures are particularly useful in preparing the Mannich polyamine dispersants. However, it will be appreciated that satisfactory dispersants can also be obtained by use of pure polyalkylene polyamines.
  • Alkylene diamines and polyalkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atom are also useful in preparing the Mannich polyamine dispersants. These materials are typically obtained by reaction of the corresponding polyamine with an epoxide such as ethylene oxide or propylene oxide.
  • Preferred hydroxyalkyl-substituted diamines and polyamines are those in which the hydroxyalkyl groups have less than about 10 carbon atoms.
  • Suitable hydroxyalkyl-substituted diamines and polyamines include, but are not limited to, N-(2-hydroxyethyl)ethylenediamine, N,N′-bis(2-hydroxyethyl)ethylenediamine, mono(hydroxypropyl)diethlenetriamine, (di(hydroxypropyl)tetraethylenepentamine and N-(3-hydroxybutyl)tetramethylenediamine. Higher homologs obtained by condensation of the above mentioned hydroxyalkyl-substituted diamines and polyamines through amine groups or through ether groups are also useful.
  • Any conventional formaldehyde yielding reagent is useful for the preparation of the Mannich polyamine dispersants.
  • formaldehyde yielding reagents are trioxane, paraformaldehyde, trioxymethylene, aqueous formalin and gaseous formaldehyde.
  • Other aldehydes which can be used include acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, hexanal, heptanal, and mixtures of two or more of these.
  • Mannich base dispersants for use in this invention are Mannich base ashless dispersants formed by condensing about one molar proportion of long chain hydrocarbon-substituted phenol with from 1 to 2.5 moles of formaldehyde and from 0.5 to 2 moles of polyalkylene polyamine.
  • Type D - Polymeric polyamine dispersants .
  • polymers containing basic amine groups and oil solubilizing groups for example, pendant alkyl groups having at least about 8 carbon atoms.
  • Such polymeric dispersants are herein referred to as polymeric polyamine dispersants.
  • Such materials include, but are not limited to, interpolymers of decyl methacrylate, vinyl decyl ether or a relatively high molecular weight olefin with aminoalkyl acrylates and aminoalkyl acrylamides.
  • Examples of polymeric polyamine dispersants are set forth in the following patents: U.S. Pat. Nos. 3,329,658; 3,449,250; 3,493,520; 3,519,565; 3,666,730; 3,687,849; 3,702,300.
  • Type E Post-treated basic nitrogen-containing and/or hydroxyl-containing ashless dispersants .
  • any of the ashless dispersants referred to above as types A-D can be subjected to post-treatment with one or more suitable reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, anhydrides of low molecular weight dibasic acids, nitriles, and epoxides.
  • suitable reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, anhydrides of low molecular weight dibasic acids, nitriles, and epoxides.
  • Such post-treated ashless dispersants can be used in forming component a) of the compositions of this invention provided that the post-treated dispersant contains residual basic nitrogen and/or one or more residual hydroxyl groups.
  • the phosphorylated or the phosphorylated and boronated dispersant can be subjected to post-treatment with such reagents.
  • the post-treatment can be conducted in between the phosphorylation and boronation or conversely, between the boronation and the phosphorylation. Examples of post-treatment procedures and post-treated ashless dispersants are set forth in the following U.S. Patents: U.S. Pat. Nos.
  • Mannich-based derivatives of hydroxyaryl succinimides that have been post-treated with C5-C9 lactones such as ⁇ -caprolactone and optionally with other post-treating agents as described for example in U.S. Pat. No. 4,971,711 can also be utilized in forming component a) for use in the practice of this invention, provided that such post-treated Mannich-based derivatives of hydroxyaryl succinimides contain basic nitrogen, and/or at least one hydroxyl group. See also U.S. Pat. Nos.
  • One preferred category of post-treated ashless dispersants is comprised of basic nitrogen-containing and/or hydroxyl group-containing ashless dispersants which have been heated with (1) a phosphorus compound such that they contain phosphorus, or (2) a boron compound such that they contain boron, all with the proviso that such post-treated products contain residual basic nitrogen and/or one or more residual hydroxyl groups.
  • a phosphorus compound such that they contain phosphorus
  • a boron compound such that they contain boron
  • the boron-containing post-treated ashless dispersants of the prior art type can be converted into a material suitable for use as component a-1) or a-3) simply by conducting a phosphorylation in the manner described herein. If desired, additional boron can also be incorporated into a prior art type post-treated boron-containing ashless dispersant by conducting a boronation in the manner described herein either before, during or after the phosphorylation.
  • the ashless dispersant(s) used in forming component a) can be any mixture containing any two or more ashless dispersants containing basic nitrogen and/or at least one hydroxyl group.
  • ashless dispersants which contain little, if any, halogen atoms such as chlorine atoms.
  • additive concentrates which, when dissolved in a halogen-free base oil, at a concentration of 10% by weight, yield an oleaginous composition in which the total halogen content, if any, is 100 ppm or less.
  • Typical procedures for producing component a-1) phosphorylated and boronated ashless dispersants involve concurrently or sequentially heating one or more ashless dispersants of the types described above with at least one inorganic phosphorus compound and at least one boron compound under conditions yielding a liquid phosphorus- and boron-containing composition.
  • inorganic phosphorus compounds which are useful in forming such products include phosphorous acid (H3PO3, sometimes depicted as H2(HPO3), and sometimes called ortho-phosphorous acid or phosphonic acid), phosphoric acid (H3PO4, sometimes called orthophosphoric acid), hypophosphoric acid (H4P2O6), metaphosphoric acid (HPO3), pyrophosphoric acid (H4P2O7), hypophosphorous acid (H3PO2, sometimes called phosphinic acid), pyrophosphorous acid (H4P2O5, sometimes called pyrophosphonic acid), phosphinous acid (H3PO), tripolyphosphoric acid (H5P3O10), tetrapolyphosphoric acid (H6P4O13), trimetaphosphoric acid (H3P3O9), phosphorus trioxide, phosphorus tetraoxide, and phosphorus pentoxide.
  • Partial or total sulfur analogs such as phosphorotetrathioic acid (H3PS4), phosphoromonothioic acid (H3PO3S), phosphorodithioic acid (H3PO2S2), phosphorotrithioic acid (H3POS3), phosphorus sesquisulfide, phosphorus heptasulfide, and phosphorus pentasulfide (P2S5, sometimes referred to as P4S10) can also be used in forming products suitable for use as component a-1) in the practice of this invention.
  • the inorganic phosphorus halide compounds such as PCl3, PBr3, POCl3, PSCl3, etc.
  • the preferred phosphorus reagent is phosphorous acid, (H3PO3).
  • the form or composition of the inorganic compound(s) as charged into the mixture to be heated or being heated may be altered in situ.
  • the action of heat and/or water can transform certain inorganic phosphorus compounds into other inorganic phosphorus compounds or species. Any such in situ transformations that may occur are within the purview of this invention provided that the liquid phosphorylated ashless dispersant reveals on analysis the presence therein of phosphorus (as well as boron).
  • Suitable compounds of boron useful in forming the phosphorylated and boronated ashless dispersants for use as component a-1) include, for example, boron acids, boron oxides, boron esters, and amine or ammonium salts of boron acids.
  • Illustrative compounds include boric acid (sometimes referred to as orthoboric acid), boronic acid, tetraboric acid, metaboric acid, pyroboric acid, esters of such acids, such as mono-, di-, and tri-organic esters with alcohols or polyols having up to 20 or more carbon atoms (e.g., methanol, ethanol, 2-propanol, propanol, butanols, pentanols, hexanols, ethylene glycol, propylene glycol, trimethylol propane, diethanol amine, etc.), boron oxides such as boric oxide and boron oxide hydrate, and ammonium salts such as ammonium borate, ammonium pyroborate, etc.
  • boric acid sometimes referred to as orthoboric acid
  • boronic acid such as tetraboric acid, metaboric acid, pyroboric acid
  • esters of such acids such as mono-, di-, and
  • boron halides such as boron trifluoride, and boron trichloride
  • Amine borane addition compounds and hydrocarbyl boranes can also be used, although they tend to be relatively expensive.
  • the preferred boron reagent is boric acid, H3BO3.
  • auxiliary nitrogen compounds are long chain primary, secondary and tertiary alkyl amines containing from 12 to 24 carbon atoms, including their hydroxyalkyl and aminoalkyl derivatives.
  • the long chain alkyl group may optionally contain one or more ether groups. Examples of suitable compounds are oleyl amine, N-oleyltrimethylene diamine, N-tallow diethanolamine, N,N-dimethyl oleylamine, and myristyloxapropyl amine.
  • benzotriazole including lower (C1-C4) alkyl-substituted benzotriazoles, which function to protect copper surfaces.
  • the concurrent heating step or the combination of sequential heating steps is conducted at temperatures sufficient to produce a final liquid composition which contains both phosphorus and boron.
  • the heating can be carried out in the absence of a solvent by heating a mixture of the ashless dispersant and one or more suitable inorganic phosphorus compounds, or one or more suitable boron compounds, or, preferably, a combination of one or more suitable inorganic phosphorus compounds and one or more suitable boron compounds.
  • the temperatures used will vary somewhat depending upon the nature of the ashless dispersant and the inorganic phosphorus and/or boron reagent being utilized. Generally speaking however, the temperature will usually fall within the range of 40 to 200°C.
  • the duration of the heating is likewise susceptible to variation, but ordinarily will fall in the range of 1 to 3 hours.
  • it is important to thoroughly agitate the components to insure intimate contact therebetween.
  • the phosphorous acid may be utilized in the form of an aqueous solution thereby introducing water into the system to facilitate dissolution of the boric acid.
  • Water (and when using boron esters, alcohol) formed in the process and any added water is preferably removed from the heated mixture by vacuum distillation at temperatures of from 100 to 140°C.
  • the heating step or steps will be conducted in a diluent oil or other inert liquid medium such as light mineral oils, etc.
  • the amount of phosphorus compound employed in the heating process ranges from 0.001 mole to 0.999 mole per mole of basic nitrogen and free hydroxyl in the mixture being heated, up to one half of which may be contributed by an auxiliary nitrogen compound.
  • the amount of boron compound employed ranges from 0.001 mole to 1 mole per mole of basic nitrogen and/or hydroxyl in the mixture which is in excess of the molar amount of inorganic phosphorus compound.
  • the last-to-be-used reagent(s) -- inorganic phosphorus compound(s) or boron compound(s), as the case may be -- can be used in an amount equivalent to (or even in excess of) the amount of basic nitrogen and/or hydroxyl groups in the dispersant being heated with such last-to-be-used reagent(s).
  • the amount of added water is not particularly critical as it is removed by distillation during the course of, or at the end of, the heating step. Amounts of up to 1% by weight of the mixture being heated are preferred. When used, the amount of diluent usually ranges from 10 to 50% by weight of the mixture being subjected to heating.
  • the phosphorylated and boronated dispersants utilized as component a-1) in the compositions of this invention when in their undiluted state should have on a weight basis a phosphorus content of at least 100 parts per million (ppm) (preferably at least 500 ppm and more preferably at least 1,000 ppm) and a boron content of at least 100 ppm (preferably at least 500 ppm and more preferably at least 1,000 ppm).
  • component a-1 in part by use of one or more organic phosphorus compounds such as one or more organic phosphates (e.g., trihydrocarbyl phosphates, dihydrocarbyl monoacid phosphates, monohydrocarbyl diacid phosphates, or mixtures thereof), phosphites (e.g., trihydrocarbyl phosphites, dihydrocarbyl hydrogen phosphites, hydrocarbyl diacid phosphites, or mixtures thereof), phosphonates (e.g., hydrocarbyl phosphonic acids, mono- and/or dihydrocarbyl esters of phosphonic acids, or mixtures thereof), phosphonites (e.g., hydrocarbyl phosphinic acids, mono- and/or dihydrocarbyl esters of phosphinic acids, or mixtures thereof), etc., or the partial or total sulfur analogs thereof, and in part by use of one or more inorganic phosphorus compounds,
  • component a-1 when in the undiluted state preferably contains at least 3,000 ppm (more preferably at least 5,000 ppm and most preferably at least 7,000 ppm) of phosphorus and at least 1,500 ppm (more preferably at least 2,500 ppm and most preferably at least 3,500 ppm) of boron.
  • a mixture is formed from 260 parts of a commercial succinimide ashless dispersant (HiTEC® 644 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl Canada Limited), 100 parts of a 100 Solvent Neutral refined mineral oil diluent, 8 parts of phosphorous acid, 3.5 parts of tolutriazole, 8 parts of boric acid, and 3.0 parts of water.
  • the mixture is heated at 100°C for two hours until all of the solid materials are dissolved.
  • a vacuum of 40 mm Hg is gradually drawn on the product to remove the water while the temperature is slowly raised to 100°C.
  • a clear solution or composition is obtained which is soluble in oil and suitable for use as component a-1).
  • Example 2 The procedure of Example 1 is repeated except that the succinimide ashless dispersant used is derived from polybutene having a number average molecular weight of 1,100.
  • the average number of succinic groups per alkenyl group in the succinimide is approximately 1.2.
  • Example 1 The procedure of Example 1 is repeated except that the succinimide ashless dispersant used is derived from polybutene having a number average molecular weight of 2,100.
  • Example 1 The procedure of Example 1 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a Mannich polyamine dispersant (AMOCO® 9250 dispersant; Amoco Corporation).
  • AMOCO® 9250 dispersant as supplied by the manufacturer is believed to be a boronated dispersant and in such case, another material suitable for use as component a-1) can be formed by eliminating the boric acid and water from the procedure used in this example and thereby conducting phosphorylation on an already boronated dispersant.
  • Example 1 The procedure of Example 1 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a commercial ashless dispersant of the pentaerythritol succinic ester type (Lubrizol® 936 dispersant; The Lubrizol Corporation).
  • the initial dispersant as supplied by the manufacturer is believed to be a boronated dispersant.
  • the dispersant can, if desired, be subjected just to phosphorylation to thereby form still another product suitable for use as component a-1).
  • Example 1 The procedure of Example 1 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional hour at 100°C to provide a clear, oil-soluble composition suitable for use as component a-1).
  • Example 2 The procedure of Example 1 is repeated except that the P2S5 is replaced by 7 parts of phosphorus pentoxide (P2O5).
  • a mixture of 11,904 parts of a commercial boronated succinimide (HiTEC® 648 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl Canada Limited) and 96 parts of phosphorous acid is heated to 100-110°C for 2 hours to form a homogeneous liquid composition suitable for use as component a-1) in the practice of this invention.
  • 100 Solvent Neutral mineral oil can be added to form an 80% solution of the additive in the oil.
  • a mixture of 260 parts of a commercial succinimide (HiTEC® 644 dispersant), and 8 parts of phosphorous acid is heated to 100°C for 2 hours.
  • To this product is added 8 parts of orthoboric acid and 4 parts of water, and the resultant mixture is heated at 100°C for another 2 hours.
  • Water present in the reaction mixture is removed by applying a vacuum of 40 mm of Hg and gradually raising the temperature to 110°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-1).
  • a mixture of 260 parts of a commercial succinimide (HiTEC® 644 dispersant), 8 parts of orthoboric acid and 4 parts of water is heated to 100°C for 2 hours. Then 8 parts of phosphorous acid is added to the reaction mixture and the temperature of the mixture is held at 100°C for another 2 hours. Water present in the reaction mixture is removed by applying a vacuum of 40 mm of Hg and gradually raising the temperature to 110°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-1).
  • a mixture of 260 parts of a commercial succinic pentaerythritol ester ashless dispersant (Lubrizol® 936 dispersant), and 8 parts of phosphorous acid is heated to 100°C for 2 hours.
  • a commercial succinic pentaerythritol ester ashless dispersant Librizol® 936 dispersant
  • 8 parts of phosphorous acid is heated to 100°C for 2 hours.
  • 8 parts of orthoboric acid and 4 parts of water is heated at 100°C for another 2 hours.
  • Water present in the reaction mixture is removed by applying a vacuum of 40 mm of Hg and gradually raising the temperature to 110°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-1).
  • a mixture of 260 parts of a commercial succinic pentaerythritol ester ashless dispersant (Lubrizol® 936 dispersant), 8 parts of orthoboric acid and 4 parts of water is heated to 100°C for 2 hours. Then 8 parts of phosphorous acid is added to the reaction mixture and the temperature of the mixture is held at 100°C for another 2 hours. Water present in the reaction mixture is removed by applying a vacuum of 40 mm of Hg and gradually raising the temperature to 110°C. The resultant homogeneous liquid composition is suitable for use as component a-1).
  • a mixture of 260 parts of a commercial Mannich polyamine dispersant (AMOCO® 9250 dispersant), and 8 parts of phosphorous acid is heated to 100°C for 2 hours.
  • To this product are added 8 parts of orthoboric acid and 4 parts of water, and the resultant mixture is heated at 100°C for another 2 hours.
  • Water present in the reaction mixture is removed by applying a vacuum of 40 mm of Hg and gradually raising the temperature to 110°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-1).
  • a mixture of 260 parts of a commercial Mannich polyamine dispersant (AMOCO® 9250 dispersant), 8 parts of orthoboric acid and 4 parts of water is heated to 100°C for 2 hours. Then 8 parts of phosphorous acid is added to the reaction mixture and the temperature of the mixture is held at 100°C for another 2 hours. Water present in the reaction mixture is removed by applying a vacuum of 40 mm of Hg and gradually raising the temperature to 110°C. The resultant homogeneous liquid composition is suitable for use as component a-1).
  • Example 16 The procedure of Example 16 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 16 The procedure of Example 16 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional hour at 100°C to provide a clear, oil-soluble composition suitable for use as component a-1).
  • Example 18 The procedure of Example 18 is repeated except that the P2S5 is replaced by 7 parts of phosphorus pentoxide (P2O5).
  • Example 20 The procedure of Example 20 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 20 The procedure of Example 20 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional hour at 100°C to provide a clear, oil-soluble composition suitable for use as component a-1).
  • Example 20 The procedure of Example 20 is repeated except that the P2S5 is replaced by 7 parts of phosphorus pentoxide (P2O5).
  • Example 24 The procedure of Example 24 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 24 The procedure of Example 24 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional hour at 100°C to provide a clear, oil-soluble composition suitable for use as component a-1).
  • Example 24 The procedure of Example 24 is repeated except that the P2S5 is replaced by 7 parts of phosphorus pentoxide (P2O5).
  • Example 28 The procedure of Example 28 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 28 The procedure of Example 28 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional hour at 100°C to provide a clear, oil-soluble composition suitable for use as component a-1).
  • Example 28 The procedure of Example 28 is repeated except that the P2S5 is replaced by 7 parts of phosphorus pentoxide (P2O5).
  • Example 32 The procedure of Example 32 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 32 The procedure of Example 32 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional hour at 100°C to provide a clear, oil-soluble composition suitable for use as component a-1).
  • Example 32 The procedure of Example 32 is repeated except that the P2S5 is replaced by 7 parts of phosphorus pentoxide (P2O5).
  • Example 36 The procedure of Example 36 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 36 The procedure of Example 36 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional hour at 100°C to provide a clear, oil-soluble composition suitable for use as component a-1).
  • Example 36 The procedure of Example 36 is repeated except that the P2S5 is replaced by 7 parts of phosphorus pentoxide (P2O5).
  • Example 40 The procedure of Example 40 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 40 The procedure of Example 40 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional hour at 100°C to provide a clear, oil-soluble composition suitable for use as component a-1).
  • Example 40 The procedure of Example 40 is repeated except that the P2S5 is replaced by 7 parts of phosphorus pentoxide (P2O5).
  • Example 44 The procedure of Example 44 is repeated except that the tolutriazole is omitted from the reaction mixture.
  • Typical procedures for producing component a-2) phosphorylated ashless dispersants involve heating one or more ashless dispersants of the types described above with at least one inorganic phosphorus acid under conditions yielding a liquid phosphorus-containing composition.
  • inorganic phosphorus acids which are useful in forming such products include phosphorous acid (H3PO3, sometimes depicted as H2(HPO3), and sometimes called ortho-phosphorous acid), phosphoric acid (H3PO4, sometimes called orthophosphoric acid), hypophosphoric acid (H4P2O6), metaphosphoric acid (HPO3), pyrophosphoric acid (H4P2O7), hypophosphorous acid (H3PO2, sometimes called phosphinic acid), pyrophosphorous acid (H4P2O5, sometimes called pyrophosphonic acid), phosphinous acid (H3PO), tripolyphosphoric acid (H5P3O10), tetrapolyphosphoric acid (H6P4O13), trimetaphosphoric acid (H3P3
  • Partial or total sulfur analogs such as phosphorotetrathioic acid (H3PS4), phosphoromonothioic acid (H3PO3S), phosphorodithioic acid (H3PO2S2), phosphorotrithioic acid (H3POS3), can also be used in forming products suitable for use as component a-2).
  • the preferred phosphorus reagent is phosphorous acid, (H3PO3).
  • the form or composition of the inorganic acid(s) as charged into the mixture to be heated or being heated may be altered in situ.
  • the action of heat and/or water can transform certain inorganic phosphorus compounds into other inorganic phosphorus compounds or species. Any such in situ transformations that may occur are within the purview of this invention provided that the liquid phosphorylated ashless dispersant reveals on analysis the presence therein of phosphorus.
  • auxiliary nitrogen compounds are long chain primary, secondary and tertiary alkyl amines containing from 12 to 24 carbon atoms, including their hydroxyalkyl and aminoalkyl derivatives.
  • the long chain alkyl group may optionally contain one or more ether groups. Examples of suitable compounds are oleyl amine, N-oleyltrimethylene diamine, N-tallow diethanolamine, N,N-dimethyl oleylamine, and myristyloxapropyl amine.
  • benzotriazole including lower (C1-C4) alkyl-substituted benzotriazoles, which function to protect copper surfaces.
  • the heating step is conducted at temperatures sufficient to produce a liquid composition which contains phosphorus.
  • the heating can be carried out in the absence of a solvent by heating a mixture of the ashless dispersant and one or more suitable inorganic phosphorus compounds.
  • the temperatures used will vary somewhat depending upon the nature of the ashless dispersant and the inorganic phosphorus reagent being utilized. Generally speaking however, the temperature will usually fall within the range of 40 to 200°C.
  • the duration of the heating is likewise susceptible to variation, but ordinarily will fall in the range of 1 to 3 hours.
  • the phosphorous acid may be utilized in the form of an aqueous solution. Water formed in the process and any added water is preferably removed from the heated mixture by vacuum distillation at temperatures of from 100 to 140°C. The heating may be conducted in more than one stage if desired. Preferably the heating step or steps will be conducted in a diluent oil or other inert liquid medium such as light mineral oils, and the like.
  • the amount of inorganic phosphorus acid employed in the heating process preferably ranges from 0.001 mole to 0.999 mole per mole of basic nitrogen and free hydroxyl in the mixture being heated, up to one half of which may be contributed by an auxiliary nitrogen compound. It is possible however to use the inorganic phosphorus acid(s) in excess of the amount of basic nitrogen and/or hydroxyl groups in the dispersant being heated.
  • the amount of diluent usually ranges from 10 to 50% by weight of the mixture being subjected to heating. Water can be added to the mixture, before and/or during the heating, if desired.
  • the phosphorylated dispersants utilized as component a-2) in the compositions of this invention when in their undiluted state will have on a weight basis a phosphorus content of at least 5,000 parts per million (ppm) (preferably at least 6,000 ppm and more preferably at least 7,000 ppm).
  • organic phosphorus compounds such as one or more organic phosphates (e.g., trihydrocarbyl phosphates, dihydrocarbyl monoacid phosphates, monohydrocarbyl diacid phosphates, or mixtures thereof), phosphites (e.g., trihydrocarbyl phosphites, dihydrocarbyl hydrogen phosphites, hydrocarbyl diacid phosphites, or mixtures thereof), phosphonates (e.g., hydrocarbyl phosphonic acids, mono- and/or dihydrocarbyl esters of phosphonic acids, or mixtures thereof), phosphonites (e.g., hydrocarbyl phosphinic acids, mono- and/or dihydrocarbyl esters of phosphinic acids, or mixtures thereof), etc., or the partial or total sulfur analogs thereof, and in part by use of one or more inorganic phosphorus acids,
  • organic phosphates e.g., trihydr
  • a mixture is formed from 260 parts of a polyisobutenyl succinimide ashless dispersant (derived from polybutene having a number average molecular weight of 950 and a mixture of a polyethylene polyamines having an average overall composition approximating that of tetraethylene pentamine), 100 parts of a 100 Solvent Neutral refined mineral oil diluent, 8 parts of solid phosphorous acid, and 3.5 parts of tolutriazole.
  • the mixture is heated at 110°C for two hours.
  • a vacuum of 40 mm Hg is gradually drawn on the product to remove traces of water while the temperature is maintained at 110°C.
  • a clear solution or composition is obtained which is soluble in oil and suitable for use as component a-2).
  • Example 51 The procedure of Example 51 is repeated except that the succinimide ashless dispersant used is derived from polybutene having a number average molecular weight of 1,150.
  • the average number of succinic groups per alkenyl group in the succinimide is approximately 1.2.
  • Example 51 The procedure of Example 51 is repeated except that the succinimide ashless dispersant used is derived from polybutene having a number average molecular weight of 2,100.
  • Example 51 The procedure of Example 51 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a boron-free Mannich polyamine dispersant made from tetraethylene pentamine, polyisobutenyl phenol (made from polyisobutene having a number average molecular weight of about 1710 and formalin) having a nitrogen content of 1.1%.
  • a boron-free Mannich polyamine dispersant made from tetraethylene pentamine, polyisobutenyl phenol (made from polyisobutene having a number average molecular weight of about 1710 and formalin) having a nitrogen content of 1.1%.
  • Example 51 The procedure of Example 51 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of an ashless dispersant of the pentaerythritol succinic ester type.
  • Example 51 The procedure of Example 51 is repeated except that 9.6 parts of orthophosphoric acid is used in place of the phosphorous acid, and the mixture is heated for three hours at 110°C to provide a clear, oil-soluble composition suitable for use as component a-2).
  • Example 51 The procedure of Example 51 is repeated except that the phosphorous acid is replaced by 6.4 parts of hypophosphorous acid.
  • a polyisobutenyl succinimide (derived from polyisobutene having a number average molecular weight of 950 and a mixture of polyethylene polyamines having an overall average composition approximating that of tetraethylene pentamine) warmed to 28°C are added 54.31 parts of phosphorous acid, 20.27 parts of tolutriazole and 23.91 parts of water. This mixture is heated at 110°C for 1.5 hours. Then the reflux condenser is replaced by a distillation column and water is removed under vacuum for 2.25 hours at 110°C to form a homogeneous liquid composition suitable for use as component a-2).
  • a mixture of 7300 parts of a polyisobutenyl succinimide (derived from polybutene having a number average molecular weight of about 1,300 and a mixture of polyethylene polyamines having an average overall composition approximating that of tetraethylene pentamine), and 2500 parts of 100 Solvent Neutral mineral oil is heated to 90-100°C. To this mixture is added 200 parts of phosphorous acid and the resultant mixture is heated at 90-100°C for 2 hours. The resultant homogeneous liquid composition is suitable for use as component a-2).
  • a mixture of 58,415.5 parts of a polyisobutenyl succinimide (derived from polyisobutene having a number average molecular weight of 1300 and a mixture of polyethylene polyamines having an overall average composition approximating that of tetraethylene pentamine), and 12,661.6 parts of 100 Solvent Neutral mineral oil is heated to 80°C. To this mixture is added 1942.28 parts of phosphorous acid and the resultant mixture is heated at 110°C for 2 hours. The resultant homogeneous liquid composition is suitable for use as component a-2).
  • Example 61 The procedure of Example 61 is repeated using 45,600 parts of the ashless dispersant, 8983.2 parts of the mineral oil diluent, and 2416.8 parts of the phosphorous acid.
  • a mixture of 14,400 parts of a polyisobutenyl succinimide (derived from polyisobutene having a number average molecular weight of 950 and a mixture of polyethylene polyamines having an overall average composition approximating that of tetraethylene pentamine), and 3121.2 parts of 100 Solvent Neutral mineral oil is heated to 80°C. To this mixture is added 478.8 parts of phosphorous acid and the resultant mixture is heated at 110°C for 2 hours. The resultant homogeneous liquid composition contains about 1.04% of phosphorus and is suitable for use as component a-2).
  • a mixture of 7300 parts of ashless dispersant as used in Example 60, 2500 parts of 100 Solvent Neutral mineral oil, and 200 parts of phosphorous acid is formed at room temperature and heated to 110°C for two hours.
  • the resultant homogeneous liquid composition is suitable for use as component a-2).
  • a mixture of 4680 parts of phosphorylated dispersant formed as in Example 64 and 2340 parts of a commercial boronated succinimide ashless dispersant (HiTEC® 648 dispersant) is formed.
  • the resultant homogeneous liquid composition is suitable for use in the practice of this invention.
  • a portion of the resultant mixture can be heated to 110°C for two hours, and this resultant homogeneous liquid composition is also suitable for use as component a-2).
  • Example 66 The procedure of Example 66 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 67 The procedure of Example 67 is repeated except that the phosphorous acid is replaced by 11.1 parts of phosphoromonothioic acid (H3PO3S).
  • Example 69 The procedure of Example 69 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 70 The procedure of Example 70 is repeated except that the phosphorous acid is replaced by 13.7 parts of phosphoramidic acid, (HO)2PONH2.
  • Example 72 The procedure of Example 72 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 73 The procedure of Example 73 is repeated except that the phosphorous acid is replaced by 9.6 parts of orthophosphoric acid.
  • Example 75 The procedure of Example 75 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 76 The procedure of Example 76 is repeated except that 11 parts of phosphoric acid is used in place of the phosphorous acid to provide a clear, oil-soluble composition suitable for use as component a-2).
  • Example 77 The procedure of Example 77 is repeated except that 10 parts of an equimolar mixture of phosphoric acid and phosphorous acid is used.
  • Example 79 The procedure of Example 79 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 80 The procedure of Example 80 is repeated except that 15.8 parts of phosphorotetrathioic acid (H3PS4) is used in place of the phosphorous acid.
  • H3PS4 phosphorotetrathioic acid
  • Example 82 The procedure of Example 82 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 83 The procedure of Example 83 is repeated except that 6.4 parts of hypophosphorous acid (H3PO2) is used in place of the phosphorous acid.
  • H3PO2 hypophosphorous acid
  • Example 85 The procedure of Example 85 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 86 The procedure of Example 86 is repeated except that 9.6 parts of orthophosphoric acid is used instead of the phosphorous acid.
  • the resultant mixture is heated at 100-105°C for two hours. Then the temperature is gradually raised to 115°C with the application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes and until 120°C/40 mm Hg has been reached. A flow of dry nitrogen is then applied to the system and the product mixture is allowed to cool.
  • the product mixture is suitable for use as component a-2).
  • Example 88 The procedure of Example 88 is repeated except that the tolutriazole is omitted from the reaction mixture.
  • Example 63 The procedure of Example 63 is repeated except that 763.2 parts of phosphorous acid (H3PO3) and 2,836.8 parts of 100 Solvent Neutral mineral oil are used. The phosphorus content of the final product is about 1.66%.
  • Example 63 The procedure of Example 63 is repeated except that the proportions of the reaction components are 14,400 parts of the succinimide, 3409.2 parts of the mineral oil, and 190.8 parts of phosphorous acid (H3PO3). This product contains approximately 0.40% of phosphorus.
  • Example 61 The procedure of Example 61 is repeated except that the proportions of the reaction components are 45,600 parts of the succinimide, 10,795.8 parts of the process oil, and 604.2 parts of phosphorous acid (H3PO3). This product contains approximately 0.41 % of phosphorus.
  • Typical procedures for producing component a-3) phosphorylated and boronated ashless dispersants involve concurrently or sequentially heating one or more ashless dispersants of the types described above with (i) water and at least one water-hydrolyzable organic phosphorus compound and (ii) at least one boron compound under conditions yielding a liquid phosphorus- and boron-containing composition.
  • halophosphine halides e.g., hydrocarbyl phosphorus tetrahalides, dihydrocarbyl phosphorus trihalides, and trihydrocarbyl phosphorus dihalides
  • halophosphines monohalophosphines and dihalophosphines
  • water-hydrolyzable is meant that the organic phosphorus compound when boiled at atmospheric pressure for a period of 5 hours with either (a) distilled water, or (a) water adjusted to at least one pH between 1 and 7 by use of H2SO4, or (c) water adjusted to at least one pH between 7 and 13 with KOH, is hydrolyzed to the extent of at least 50 mole %.
  • hydrolysis of certain types of organophosphorus compounds results in concomitant oxidation, and compounds which undergo both hydrolysis and oxidation under the foregoing conditions are usable in forming the phosphorylated dispersants for use in this invention.
  • sulfur-containing organophosphorus compounds undergo loss of sulfur under hydrolysis conditions.
  • the preferred water-hydrolyzable organic phosphorus compounds are the water-hydrolyzable phosphate esters, and the water-hydrolyzable phosphite esters, especially the dihydrocarbyl hydrogen phosphites.
  • Suitable compounds of boron useful in forming the phosphorylated and boronated ashless dispersants for use as component a-3) include, for example, boron acids, boron oxides, boron esters, and amine or ammonium salts of boron acids.
  • Illustrative compounds include boric acid (sometimes referred to as orthoboric acid), boronic acid, tetraboric acid, metaboric acid, pyroboric acid, esters of such acids, such as mono-, di-, and tri-organic esters with alcohols or polyols having up to 20 or more carbon atoms (e.g., methanol, ethanol, 2-propanol, propanol, butanols, pentanols, hexanols, ethylene glycol, propylene glycol, trimethylol propane, diethanol amine, etc.), boron oxides such as boric oxide and boron oxide hydrate, and ammonium salts such as ammonium borate, ammonium pyroborate, etc.
  • boric acid sometimes referred to as orthoboric acid
  • boronic acid such as tetraboric acid, metaboric acid, pyroboric acid
  • esters of such acids such as mono-, di-, and
  • boron halides such as boron trifluoride, boron trichloride, and the like, are undesirable as they tend to introduce halogen atoms into the boronated dispersant, a feature which is detrimental from the environmental, toxicological and conservational standpoints.
  • Amine borane addition compounds and hydrocarbyl boranes can also be used, although they tend to be relatively expensive.
  • the preferred boron reagent is boric acid, H3BO3.
  • auxiliary nitrogen compounds are long chain primary, secondary and tertiary alkyl amines containing from 12 to 24 carbon atoms, including their hydroxyalkyl and aminoalkyl derivatives.
  • the long chain alkyl group may optionally contain one or more ether groups. Examples of suitable compounds are oleyl amine, N-oleyltrimethylene diamine, N-tallow diethanolamine, N,N-dimethyl oleylamine, and myristyloxapropyl amine.
  • benzotriazole including lower (C1-C4) alkyl-substituted benzotriazoles, which function to protect copper surfaces.
  • the concurrent heating step or the combination of sequential heating steps is conducted at temperatures sufficient to produce a final liquid composition which contains both phosphorus and boron.
  • the heating can be carried out in the absence of a solvent by heating a mixture of the ashless dispersant, water and one or more suitable organic phosphorus compounds, or one or more suitable boron compounds, or, preferably, a combination of water, one or more suitable organic phosphorus compounds and one or more suitable boron compounds.
  • the temperatures used will vary somewhat depending upon the nature of the ashless dispersant and the organic phosphorus and/or boron reagent being utilized. Generally speaking however, the temperature will usually fall within the range of 40 to 200°C.
  • the duration of the heating is likewise susceptible to variation, but ordinarily will fall in the range of 1 to 3 hours.
  • it is important to thoroughly agitate the components to insure intimate contact therebetween.
  • it is preferable to add water with the boric acid to facilitate initial dissolution of the boric acid.
  • Water and relatively volatile alcohols formed in the hydrolysis process and the added water are preferably removed from the heated mixture by vacuum distillation at temperatures of from 100 to 140°C.
  • the heating step or steps will be conducted in a diluent oil or other inert liquid medium such as light mineral oils, and the like.
  • the amount of phosphorus compound employed in the heating process ranges from 0.001 mole to 0.999 mole per mole of basic nitrogen and free hydroxyl in the mixture being heated, up to one half of which may be contributed by an auxiliary nitrogen compound.
  • the amount of boron compound employed ranges from 0.001 mole to 1 mole per mole of basic nitrogen and/or hydroxyl in the mixture which is in excess of the molar amount of inorganic phosphorus compound.
  • the last-to-be-used reagent(s) -- water and organic phosphorus compound(s) or boron compound(s), as the case may be -- can be used in an amount equivalent to (or even in excess of) the amount of basic nitrogen and/or hydroxyl groups in the dispersant being heated with such last-to-be-used reagent(s).
  • the ashless dispersant with one or more water-hydrolyzable organic phosphorus compounds in the presence of water.
  • the water can be added before and/or during the heating step, and before, after, or at the same time one or more phosphorus compounds are introduced into the vessel in which the heating is taking place or is to take place. It is also possible to heat the ashless dispersant with the organic phosphorus compound and then subsequently heat the resultant composition with water, although this procedure is less preferred.
  • the amount of added water is not particularly critical as long as a sufficient amount is present to effect hydrolysis of the water-hydrolyzable organic phosphorus compound.
  • Water present in the system can be removed by distillation (preferably at reduced pressure) during the course of, and preferably is removed at the end of, the heating step. Amounts of water up to 15% by weight of the mixture being heated are preferred, and amounts of water of up to 5% by weight are particularly preferred. When used, the amount of diluent usually ranges from 10 to 50% by weight of the mixture being subjected to heating.
  • the hydrolysis of the water-hydrolyzable organic phosphorus compound(s) employed in the phosphorylation operation can be effected in any of a variety of ways.
  • the dispersant to be phosphorylated, one or more water-hydrolyzable organic phosphorus compounds, and water may be mixed together and heated either in an open system at atmospheric pressure or in a closed system at superatmospheric pressure. If conducted with an open system, the temperature may be kept below the boiling point of water and the mixture subjected to stirring of sufficient intensity to cause and maintain intimate contact among the components within the hydrolysis reaction mixture.
  • the system When conducting the hydrolysis in a closed system, the system may be kept at one or more selected autogenous pressures by suitable adjustment and regulation of the temperature. And, still higher pressures may be imposed upon the system, as for example by injecting high pressure steam into a sealed autoclave containing the hydrolysis reaction mixture.
  • the water itself may be charged to the system in any suitable form, such as in the form of liquid water, steam, or even ice. Similarly, the water may be introduced in the form of hydrated solids so that the water is released by the application of heat during the course of the hydrolysis operation. Injection of wet steam into a well-agitated hydrolysis system is one preferred way of conducting the operation.
  • the hydrolysis operation should be conducted under any given set or sequence of hydrolysis conditions for a period of time long enough that at least 10%, preferably at least 50%, and most preferably at least 75%, of the organic phosphorus compound(s) present in the hydrolysis mixture has been hydrolyzed.
  • the nature of the hydrolysis products can be expected to vary in relation to the type of phosphorus compound(s) used and the severity of the hydrolysis conditions imposed upon the hydrolysis system.
  • inorganic and organic hydrolysis products can be formed in the system, and these in turn can be expected to be taken up by the ashless dispersant(s) present in the system substantially as they are formed.
  • the phosphorylation may be conducted apart from the boronation, or it may be conducted concurrently with the boronation.
  • any of the foregoing hydrolysis procedures can be utilized, the principal difference being that one or more boron compounds are used in combination with one or more water-hydrolyzable organic phosphorus compounds.
  • small amounts of one or more acids e.g., sulfuric acid, phosphoric acid, phosphorous acid, etc.
  • bases e.g., NaOH, KOH, ammonium hydroxide, etc.
  • the phosphorylated and boronated dispersants utilized as component a-3) in the compositions of this invention when in their undiluted state should have on a weight basis a phosphorus content of at least 100 parts per million (ppm) (preferably at least 500 ppm and more preferably at least 1000 ppm) and a boron content of at least 100 ppm (preferably at least 500 ppm and more preferably at least 1000 ppm).
  • ppm parts per million
  • boron content of at least 100 ppm preferably at least 500 ppm and more preferably at least 1000 ppm
  • component a-3) in part by use of one or more inorganic phosphorus compounds such as phosphorous acid (H3PO3, sometimes depicted as H2(HPO3), and sometimes called ortho-phosphorous acid or phosphonic acid), phosphoric acid (H3PO4, sometimes called orthophosphoric acid), hypophosphorous acid (H3PO2, sometimes called phosphinic acid), hypophosphoric acid (H4P2O6), metaphosphoric acid (HPO3), pyrophosphoric acid (H4P2O7), pyrophosphorous acid (H4P2O5, sometimes called pyrophosphonic acid), phosphinous acid (H3PO), tripolyphosphoric acid (H5P3O10), tetrapolyphosphoric acid (H6P4O13), trimetaphosphoric acid (H3P3O9), phosphorus trioxide, phosphorus tetraoxide, phosphorus pentoxide, and/or partial or total sulfur analogs of the foregoing such as phosphorotetrathio
  • component a-3 when in the undiluted state preferably contains at least 3000 ppm (more preferably at least 5000 ppm and most preferably at least 7000 ppm) of phosphorus and at least 1500 ppm (more preferably at least 2500 ppm and most preferably at least 3500 ppm) of boron.
  • a mixture is formed from 260 parts of a commercial succinimide ashless dispersant (HiTEC® 644 dispersant), 100 parts of a 100 Solvent Neutral refined mineral oil diluent, 26 parts of dibutyl hydrogen phosphite, 3.5 parts of tolutriazole, 10 parts of boric acid, and 8 parts of water.
  • the mixture is heated at 100°C for two hours until all of the solid materials are dissolved.
  • a vacuum of 40 mm Hg is gradually drawn on the product to remove the water and butanol while the temperature is slowly raised to 100°C.
  • a clear solution or composition is obtained which is soluble in oil and suitable for use as component a-3).
  • Example 97 The procedure of Example 97 is repeated except that the succinimide ashless dispersant used is derived from polybutene having a number average molecular weight of 1,100.
  • the average number of succinic groups per alkenyl group in the succinimide is approximately 1.2.
  • Example 97 The procedure of Example 97 is repeated except that the succinimide ashless dispersant used is derived from polybutene having a number average molecular weight of 2,100.
  • Example 97 The procedure of Example 97 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a Mannich polyamine dispersant (AMOCO® 9250 dispersant).
  • AMOCO® 9250 dispersant as supplied by the manufacturer is believed to be a boronated dispersant and in such case, another material suitable for use as component a-3) can be formed by eliminating the boric acid from the procedure used in this example and thereby conducting phosphorylation on an already boronated dispersant.
  • Example 97 The procedure of Example 97 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a commercial ashless dispersant of the pentaerythritol succinic ester type (Lubrizol® 936 dispersant).
  • the initial dispersant as supplied by the manufacturer is believed to be a boronated dispersant.
  • the dispersant can, if desired, be subjected just to phosphorylation to thereby form still another product suitable for use as component a-3).
  • Example 97 The procedure of Example 97 is repeated except that 16 parts of trimethyl phosphite is used in place of the dibutyl hydrogen phosphite, to provide a clear, oil-soluble composition suitable for use as component a-3).
  • Example 97 The procedure of Example 97 is repeated except that the dibutyl hydrogen phosphite is replaced by 16.3 parts of O-ethyl-O,O- 1,2-ethanediyl phosphite.
  • a mixture of 12,000 parts of a commercial boronated succinimide (HiTEC® 648 dispersant), 90 parts of water, and 584 parts of triphenylmethane phosphonyl dichloride is heated to 100-110°C for 6 hours while sweeping the reaction mixture with nitrogen.
  • a vacuum of 40 mm Hg is then gradually applied to remove water and thereby form a homogeneous liquid composition suitable for use as component a-3).
  • 100 Solvent Neutral mineral oil can be added to form an 80% solution of the additive in the oil.
  • a mixture of 260 parts of a commercial succinimide (HiTEC® 644 dispersant), 3 parts of water, 13 parts of tributyl phosphate, and 4 parts of phosphorous acid is heated to 100°C for 2 hours.
  • To this product is added 8 parts of orthoboric acid and 4 parts of water, and the resultant mixture is heated at 100°C for another 2 hours.
  • a vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 110°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-3).
  • a mixture of 260 parts of a commercial succinimide (HiTEC® 644 dispersant), 8 parts of orthoboric acid and 4 parts of water is heated to 100°C for 2 hours. Then 16 parts of diethyl hydrogen phosphite and 6 parts of aqueous ammonium hydroxide (3N) are added to the reaction mixture and the temperature of the mixture is held at 100°C for another 2 hours. A vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 110°C. The resultant homogeneous liquid composition is suitable for use as component a-3 ).
  • a mixture of 260 parts of a commercial succinic pentaerythritol ester ashless dispersant (Lubrizol® 936 dispersant), 6 parts of water, and 16 parts of methyl dichlorophosphate is heated to 100°C for 2 hours.
  • a commercial succinic pentaerythritol ester ashless dispersant Librizol® 936 dispersant
  • 8 parts of orthoboric acid and 4 parts of water is heated at 100°C for another 2 hours.
  • the mixture is then swept with nitrogen for one hour at 100°C.
  • a vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 110°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-3).
  • a mixture of 260 parts of a commercial succinic pentaerythritol ester ashless dispersant (Lubrizol® 936 dispersant), 8 parts of orthoboric acid and 6 parts of water is heated to 100°C for 2 hours. Then 19 parts of methyl bis(phenyl) phosphate, 5 parts of phosphoric acid, and 0.4 part of additional water are added to the reaction mixture and the temperature of the mixture is held at 100°C for another 2 hours. A vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 130°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-3).
  • a mixture of 260 parts of a commercial Mannich polyamine dispersant (AMOCO® 9250 dispersant), 8 parts of water, and 35 parts of dibenzyl methyl phosphate is heated to 100°C for 2 hours.
  • a vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 130°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-3).
  • a mixture of 260 parts of a commercial Mannich polyamine dispersant (AMOCO® 9250 dispersant), 8 parts of orthoboric acid and 4 parts of water is heated to 100°C for 2 hours. Then 9 parts of monophenyl phosphate, 4 parts of phosphorous acid, and an additional 3 parts of water are added to the reaction mixture and the temperature of the mixture is held at 100°C for another 2 hours. A vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 130°C. The resultant homogeneous liquid composition is suitable for use as component a-3).
  • Example 112 The procedure of Example 112 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 112 The procedure of Example 112 is repeated except that 9 parts of an equimolar mixture of dibutyl hydrogen phosphite and monobutyl dihydrogen phosphite is used in place of the dibutyl chlorophosphate to provide a clear, oil-soluble composition suitable for use as component a-3).
  • Example 112 The procedure of Example 112 is repeated except that the dibutyl chlorophosphate is replaced by 11 parts of mono-2-naphthyl orthophosphate.
  • Example 116 The procedure of Example 116 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 116 The procedure of Example 116 is repeated except that 15 parts of trimethyl phosphite is used in place of the phenyl dimethyl phosphate to provide a clear, oil-soluble composition suitable for use as component a-3).
  • Example 116 The procedure of Example 116 is repeated except that the phenyl dimethyl phosphate is replaced by 36 parts of 4-dimethyl-aminophenyl phosphorus tetrachloride and the heated mixture in (c) is swept with nitrogen during the three-hour period.
  • Example 120 The procedure of Example 120 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 120 The procedure of Example 120 is repeated except that 26 parts of dibutyl hydrogen phosphite is used in place of the bis(2-ethylhexyl) hydrogen phosphite to provide a clear, oil-soluble composition suitable for use as component a-3).
  • Example 120 The procedure of Example 120 is repeated except that the bis(2-ethylhexyl) hydrogen phosphite is replaced by 15 parts of trimethyl phosphite.
  • Example 124 The procedure of Example 124 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 124 The procedure of Example 124 is repeated except that 8 parts of ethyl dichlorophosphate and 4 parts of phosphorous acid are used in place of the dibutyl chlorophosphate to provide a clear, oil-soluble composition suitable for use as component a-3).
  • Example 124 The procedure of Example 124 is repeated except that the dibutyl chlorophosphate is replaced by 10 parts of dibutyl hydrogen phosphite and 5 parts of phosphoric acid.
  • Example 128 The procedure of Example 128 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 128 The procedure of Example 128 is repeated except that 20 parts of diethyl chlorophosphate is used in place of the diethyl hydrogen phosphite to provide a clear, oil-soluble composition suitable for use as component a-3).
  • Example 128 The procedure of Example 128 is repeated except that the diethyl hydrogen phosphite is replaced by 12 parts of ethyl dibutyl phosphate and 4 parts of phosphorous acid.
  • Example 132 The procedure of Example 132 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 132 The procedure of Example 132 is repeated except that 23 parts of butyl dichloro phosphate is used in place of the ethyl dichloro phosphate to provide a clear, oil-soluble composition suitable for use as component a-3).
  • Example 132 The procedure of Example 132 is repeated except that the ethyl dichloro phosphate is replaced by 30 parts of monobutyl-mono-2-ethylhexyl hydrogen phosphite.
  • Example 136 The procedure of Example 136 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 136 The procedure of Example 136 is repeated except that 14 parts of dibenzyl phosphate is used in place of the monobenzyl phosphate to provide a clear, oil-soluble composition suitable for use as component a-3).
  • Example 136 The procedure of Example 136 is repeated except that the monobenzyl phosphate is replaced by 17 parts of monophenyl dibenzyl phosphate.
  • Example 140 The procedure of Example 140 is repeated except that the tolutriazole is omitted from the reaction mixture.
  • Example 128 The procedure of Example 128 is repeated except that the diethyl hydrogen phosphite is replaced by 10 parts of dimethyl hydrogen phosphite.
  • Example 128 The procedure of Example 128 is repeated except that the diethyl hydrogen phosphite is replaced by 5 parts of dimethyl hydrogen phosphite and 4 parts of phosphorous acid.
  • Typical procedures for producing component a-4) phosphorylated ashless dispersants involve heating one or more ashless dispersants of the types described above with at least one water-hydrolyzable organic phosphorus compound and water under conditions yielding a liquid phosphorus-containing composition.
  • the water-hydrolyzable organic phosphorus compounds used and the conditions under which they are used are the same as described above in connection with production of component a-3), except of course no boron compound is employed in the process.
  • the phosphorylated dispersants utilized as component a-4) in the compositions of this invention when in their undiluted state will have on a weight basis a phosphorus content of at least 5,000 parts per million (ppm) (preferably at least 6,000 ppm and more preferably at least 7,000 ppm).
  • a mixture is formed from 260 parts of a polyisobutenyl succinimide ashless dispersant (derived from polybutene having a number average molecular weight of about 950 and a mixture of a polyethylene polyamines having an average overall composition approximating that of tetraethylene pentamine), 100 parts of a 100 Solvent Neutral refined mineral oil diluent, 26 parts of dibutyl hydrogen phosphite, 3.5 parts of tolutriazole and 8 parts of water.
  • the mixture is heated at 110°C for two hours.
  • a vacuum of 40 mm Hg is gradually drawn on the product to remove water and butanol while the temperature is maintained at 110°C.
  • a clear solution or composition is obtained which is soluble in oil and suitable for use as component a-4).
  • Example 149 The procedure of Example 149 is repeated except that the succinimide ashless dispersant used is derived from polybutene having a number average molecular weight of 1,100.
  • the average number of succinic groups per alkenyl group in the succinimide is approximately 1.2.
  • Example 149 The procedure of Example 149 is repeated except that the succinimide ashless dispersant used is derived from polybutene having a number average molecular weight of 2,100.
  • Example 149 The procedure of Example 149 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a boron-free Mannich polyamine dispersant made from tetraethylene pentamine, polyisobutenyl phenol (made from polyisobutene having a number average molecular weight of about 1710 and formalin) having a nitrogen content of 1.1%.
  • a boron-free Mannich polyamine dispersant made from tetraethylene pentamine, polyisobutenyl phenol (made from polyisobutene having a number average molecular weight of about 1710 and formalin) having a nitrogen content of 1.1%.
  • Example 149 The procedure of Example 149 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of an ashless dispersant of the pentaerythritol succinic ester type.
  • Example 149 The procedure of Example 149 is repeated except that 16 parts of trimethyl phosphite is used in place of the dibutyl hydrogen phosphite to provide a clear, oil-soluble composition suitable for use as component a-4).
  • Example 149 The procedure of Example 149 is repeated except that the dibutyl hydrogen phosphite is replaced by 16.3 parts of O-ethyl-O,O-1,2-ethanediyl phosphite.
  • a mixture of 12,000 parts of a commercial boron-free succinimide (HiTEC® 644 dispersant), 90 parts of water, and 584 parts of triphenylmethane phosphonyl dichloride is heated to 100-110°C for 6 hours while sweeping the reaction mixture with nitrogen.
  • a vacuum of 40 mm Hg is then gradually applied to remove water and thereby form a homogeneous liquid composition suitable for use as component a-4).
  • Solvent Neutral mineral oil can be added to form an 80% solution of the additive in the oil.
  • a mixture of 260 parts of a commercial succinimide (HiTEC® 644 dispersant), 3 parts of water, 13 parts of tributyl phosphate, and 4 parts of phosphorous acid is heated to 100°C for 2 hours. Then a vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 110°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-4).
  • a mixture of 260 parts of polyisobutenyl succinimide (derived from polybutene having a number average molecular weight of about 1,100 and a mixture of polyethylene polyamines having an average overall composition approximating that of tetraethylene pentamine), 4 parts of water, 16 parts of diethyl hydrogen phosphite and 6 parts of aqueous ammonium hydroxide (3N) is heated at 100°C for 2 hours. A vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 110°C. The resultant homogeneous liquid composition is suitable for use as component a-4).
  • a mixture of 260 parts of a polyisobutenylsuccinic pentaerythritol ester ashless dispersant, 6 parts of water, and 16 parts of methyl dichlorophosphate is heated to 100°C for 2 hours. The mixture is then swept with nitrogen for one hour at 100°C. A vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 110°C. The resultant homogeneous liquid composition is suitable for use as component a-4).
  • a mixture of 260 parts of a succinic pentaerythritol ester ashless dispersant, 6.5 parts of water, 19 parts of methyl bis(phenyl) phosphate, and 5 parts of phosphoric acid is heated at a temperature 100°C for 2 hours.
  • a vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 130°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-4).
  • a mixture of 260 parts of a Mannich polyamine dispersant, 8 parts of water, and 35 parts of dibenzyl methyl phosphate is heated to 100°C for 2 hours.
  • a vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 130°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-4).
  • a mixture of 260 parts of a Mannich polyamine dispersant, 9 parts of monophenyl phosphate, 4 parts of phosphorous acid, and 7 parts of water is heated to 100°C for 2 hours.
  • a vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 130°C.
  • the resultant homogeneous liquid composition is suitable for use as component a-4).
  • a mixture of 46.8 parts of phosphorylated dispersant formed as in Example 158 and 23.4 parts of a commercial boronated succinimide ashless dispersant (HiTEC® 648 dispersant) is formed.
  • the resultant homogeneous liquid composition is suitable for use in the practice of this invention.
  • a portion of the resultant mixture can be heated to 110°C for two hours, and this resultant homogeneous liquid composition is also suitable for use as component a-4) in the practice of this invention.
  • Example 165 The procedure of Example 165 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 165 The procedure of Example 165 is repeated except that 9 parts of an equimolar mixture of dibutyl hydrogen phosphite and monobutyl dihydrogen phosphite is used in place of the dibutyl chlorophosphate to provide a clear, oil-soluble composition suitable for use as component a-4).
  • Example 165 The procedure of Example 165 is repeated except that the dibutyl chlorophosphate is replaced by 11 parts of mono-2-naphthyl orthophosphate.
  • Example 169 The procedure of Example 169 is repeated except that 15 parts of trimethyl phosphite is used in place of the phenyl dimethyl phosphate to provide a clear, oil-soluble composition suitable for use as component a-4).
  • Example 169 The procedure of Example 169 is repeated except that the phenyl dimethyl phosphate is replaced by 36 parts of 4-dimethyl-aminophenyl phosphorus tetrachloride and the heated mixture in (c) is swept with nitrogen during the three-hour period.
  • Example 172 The procedure of Example 172 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 172 The procedure of Example 172 is repeated except that 26 parts of dibutyl hydrogen phosphite is used in place of the bis(2-ethylhexyl) hydrogen phosphite to provide a clear, oil-soluble composition suitable for use as component a-4).
  • Example 172 The procedure of Example 172 is repeated except that the bis(2-ethylhexyl) hydrogen phosphite is replaced by 15 parts of trimethyl phosphite.
  • Example 176 The procedure of Example 176 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 176 The procedure of Example 176 is repeated except that 8 parts of ethyl dichlorophosphate and 4 parts of phosphorous acid are used in place of the dibutyl chlorophosphate to provide a clear, oil-soluble composition suitable for use as component a-4).
  • Example 176 The procedure of Example 176 is repeated except that the dibutyl chlorophosphate is replaced by 10 parts of dibutyl hydrogen phosphite and 5 parts of phosphoric acid.
  • Example 180 The procedure of Example 180 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 180 The procedure of Example 180 is repeated except that 20 parts of diethyl chlorophosphate is used in place of the diethyl hydrogen phosphite to provide a clear, oil-soluble composition suitable for use as component a-4).
  • Example 180 The procedure of Example 180 is repeated except that the diethyl hydrogen phosphite is replaced by 12 parts of ethyl dibutyl phosphate and 4 parts of phosphorous acid.
  • Example 184 The procedure of Example 184 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 184 The procedure of Example 184 is repeated except that 23 parts of butyl dichloro phosphate is used in place of the ethyl dichloro phosphate to provide a clear, oil-soluble composition suitable for use as component a-4).
  • Example 184 The procedure of Example 184 is repeated except that the ethyl dichloro phosphate is replaced by 30 parts of monobutyl-mono-2-ethylhexyl hydrogen phosphite.
  • Example 188 The procedure of Example 188 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).
  • Example 188 The procedure of Example 188 is repeated except that 14 parts of dibenzyl phosphate is used in place of the monobenzyl phosphate to provide a clear, oil-soluble composition suitable for use as component a-4).
  • Example 188 The procedure of Example 188 is repeated except that the monobenzyl phosphate is replaced by 17 parts of monophenyl dibenzyl phosphate.
  • Example 192 The procedure of Example 192 is repeated except that the tolutriazole is omitted from the reaction mixture.
  • Example 196 The procedure of Example 196 is repeated except that the dibutyl hydrogen phosphite is replaced by 10 parts of dimethyl hydrogen phosphite.
  • Example 196 The procedure of Example 196 is repeated except that the dibutyl hydrogen phosphite is replaced by 5 parts of dimethyl hydrogen phosphite and 4 parts of phosphorous acid.
  • a particularly preferred embodiment of this invention involves using as component a-1) and a-3) a phosphorylated and boronated alkenyl succinimide of a polyethylene polyamine or mixture of polyethylene polyamines, wherein the succinimide is formed from (i) an alkenyl succinic acylating agent having a succination ratio (i.e., the ratio of the average number of chemically bound succinic groups per alkenyl group in the molecular structure of the succinic acylating agent) in the range of 1 to 1.3, the alkenyl group being derived from a polyolefin (most preferably a polyisobutene) having a number average molecular weight in the range of 600 to 1,300 (more preferably in the range of 700 to 1,250 and most preferably in the range of 800 to 1,200).
  • a succination ratio i.e., the ratio of the average number of chemically bound succinic groups per alkenyl group in the molecular structure of the
  • Another particularly preferred embodiment of this invention involves using as component a-2) and a-4) a phosphorylated alkenyl succinimide of a polyethylene polyamine or mixture of polyethylene polyamines, wherein the succinimide is formed from (i) an alkenyl succinic acylating agent having a succination ratio (i.e., the ratio of the average number of chemically bound succinic groups per alkenyl group in the molecular structure of the succinic acylating agent) in the range of 1 to 1.3, the alkenyl group being derived from a polyolefin (most preferably a polyisobutene) having a number average molecular weight in the range of 600 to 1,300 (more preferably in the range of 700 to 1,205 and most preferably in the range of 800 to 1,200).
  • a succination ratio i.e., the ratio of the average number of chemically bound succinic groups per alkenyl group in the molecular structure of the succinic acy
  • a variety of oil-soluble metal-free sulfur-containing antiwear and/or extreme pressure additives can be used as the other indispensable component in the practice of this invention, provided they have the requisite minimum sulfur content of at least 20 wt %. Examples are included within the categories of dihydrocarbyl polysulfides; sulfurized olefins; trithiones; sulfurized thienyl derivatives; sulfurized terpenes; sulfurized oligomers of C2-C8 monoolefins; xanthates; hydrocarbyl trithiocarbonates; and sulfurized Diels-Alder adducts such as those disclosed in U.S. reissue patent Re 27,331.
  • sulfurized polyisobutene of M ⁇ n 1,100 sulfurized isobutylene, sulfurized diisobutylene, sulfurized triisobutylene, dicyclohexyl polysulfide, diphenyl polysulfide, dibenzyl polysulfide, dinonyl polysulfide, and mixtures of di-tert-butyl polysulfide such as mixtures of di-tert-butyl trisulfide, di-tert-butyl tetrasulfide and di-tert-butyl pentasulfide, among others.
  • Combinations of such categories of sulfur-containing antiwear and/or extreme pressure agents can also be used, such as a combination of sulfurized isobutylene and di-tert-butyl trisulfide, a combination of sulfurized isobutylene and dinonyl trisulfide, a combination of sulfurized triisobutylene and dibenzyl polysulfide.
  • the preferred sulfur-containing antiwear and/or extreme pressure agents are the oil-soluble active sulfur-containing antiwear and/or extreme pressure agents.
  • these are substances which possess a linkage of two or more sulfur atoms (e.g., -S-S-, -S-S-S-, -S-S-S-S-, -S-S-S-S-S-, etc.).
  • a sulfur-containing material is an active sulfur-containing material
  • the dried coupon is then rubbed with a paper towel moistened with acetone to remove any surface flakes formed by copper corrosion.
  • the coupon is then air-dried and weighed to the nearest 0.1 mg.
  • the difference in weight between the initial copper coupon and the coupon after the test represents the extent to which the copper was corroded under the test conditions. Therefore the larger the weight difference, the greater the copper corrosion, and thus the more active the sulfur compound.
  • the sulfur-containing agent is considered "active". Oil-soluble sulfur-containing antiwear and/or extreme pressure agents yielding a weight loss of above 50 mg in the above test are more preferred.
  • oil-soluble sulfur-containing antiwear and/or extreme pressure agents and more preferably oil-soluble active sulfur-containing antiwear and/or extreme pressure agents, that yield less than 25 ppm, and more preferably less than 10 ppm, and most preferably no detectable amounts, of vapor space H2S when heated in the concentrated state for one week at 65°C.
  • HiTEC® 309 and 312 sulfurized isobutylene additives are especially desirable in this respect.
  • the most preferred oil-soluble metal-free sulfur-containing antiwear and/or extreme pressure agents from the cost-effectiveness standpoint are the sulfurized olefins containing at least 30% by weight of sulfur, the dihydrocarbyl polysulfides containing at least 25% by weight of sulfur, and mixtures of such sulfurized olefins and polysulfides.
  • di-tert-alkyl polysulfides having a sulfur content of at least 35% by weight are particularly desirable.
  • Sulfurized isobutylene having a sulfur content of at least 40% and as much as 50% by weight or more and a chlorine content of less than 1% by weight is the most especially preferred material.
  • This optional but preferred component is composed of one or more oil-soluble amine salts of one or more partial esters of one or more phosphoric acids and/or thiophosphoric acids.
  • Such compounds may be collectively represented by the formulas or mixtures thereof.
  • each of R1, R2, R3, R4, R5, R6,and R7 is, independently, a hydrocarbyl group and each of X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, and X12 is, independently, an oxygen atom or a sulfur atom.
  • the amine salts are formed with one or more partially esterified monothiophosphoric acids.
  • These are compounds of Formulas (I), (II), and (III) above wherein only one of X1, X2, X3, and X4, only one of X5, X6, X7, and X8, and only one of X9, X10, X11, and X12 is a sulfur atom.
  • the amine salts are formed with one or more partially esterified phosphoric acids.
  • These are compounds of Formulas (I), (II), and (III) above wherein all of X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, and X12 are oxygen atoms.
  • Another preferred sub-category of amine salts are those formed with one or more partially esterified dithiophosphoric acids. These are compounds of Formulas (I), (II), and (III) above wherein two of X1, X2, X3, and X4, two of X5, X6, X7, and X8, and two of X9, X10, X11, and X12 are sulfur atoms.
  • amine salts of Formulas (I), (II), and (III) above wherein three or four of X1, X2, X3, and X4, three or four of X5, X6, X7, and X8, and three or four of X9, X10, X11, and X12 are sulfur atoms.
  • oil-soluble amine salts are useful as components in the compositions of this invention, it is most preferred to include at least one oil-soluble amine salt of a dihydrocarbyl monothiophosphoric acid (one sulfur atom per molecule), either alone or in combination with at least one oil-soluble amine salt of a dihydrocarbyl phosphoric acid (no sulfur atom in the molecule).
  • Use can be made of the octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, cyclohexylamine, phenylamine, mesitylamine, oleylamine, cocoamine, soyamine, C12 ⁇ 14 tertiary alkyl primary amine, C22 ⁇ 24 tertiary alkyl primary amine, and phenethylamine salts or adducts of the above and similar partially esterified acids of monothiophosphoric acid, including mixtures of any such compounds.
  • the preferred amine salts are salts of aliphatic amines, especially the saturated or olefinically unsaturated aliphatic primary amines, such as n-octylamine, 2-ethylhexylamine, tert-octylamine, n-decylamine, the C10, C12, C14 and C16 tertiary alkyl primary amines (either singly or in any combinations thereof, such as a mixture of the C12 and C14 tertiary alkyl primary amines), n-undecylamine, lauryl amine, hexadecylamine, heptadecylamine, octadecylamine, the C22 and C24 tertiary alkyl primary amines (either singly or in combination), decenylamine, dodecenylamine, palmitoleylamine, oleylamine, linoleyl
  • Secondary hydrocarbyl amines and tertiary hydrocarbyl amines can also be used either alone or in combination with each other or in combination with primary amines.
  • any combination of primary, secondary and/or tertiary amines, whether monoamine or polyamine, can be used in forming the salts or adducts.
  • Use of primary amines is preferred.
  • Especially preferred amines are alkyl monoamines and alkenyl monoamines having from 8 to 24 carbon atoms in the molecule.
  • Amine salts of partially esterified monothiophosphoric acids are usually made by reacting a mono- and/or dihydrocarbyl phosphite with sulfur or an arrive sulfur-containing compound such as are referred to above under the caption "Sulfur-Containing Antiwear and/or Extreme Pressure Agents" and one or more primary or secondary amines. Such reactions tend to be highly exothermic reactions which can become uncontrollable, if not conducted properly.
  • One preferred method of forming these amine salts involves a process which comprises (i) introducing, at a rate such that the temperature does not exceed about 60°C, one or more dihydrocarbyl hydrogen phosphites, such as a dialkyl hydrogen phosphite, into an excess quantity of one or more active sulfur-containing materials, such as sulfurized branched-chain olefin (e.g., isobutylene, diisobutylene, triisobutylene, etc.), while agitating the mixture so formed, (ii) introducing into this mixture, at a rate such that the temperature does not exceed about 60°C, one or more aliphatic primary or secondary amines, preferably one or more aliphatic primary monoamines having in the range of 8 to 24 carbon atoms per molecule while agitating the mixture so formed, and (iii) maintaining the temperature of the resultant agitated reaction mixture at between 55 and 60°C until reaction is substantially complete.
  • This group of optional but preferred compounds is composed of O,O-dihydrocarbyl-S-hydrocarbyl thiothionophosphates (also known as O,O-dihydrocarbyl-S-hydrocarbyl phosphorothiothionates) which can be represented by the general formula: wherein each of R1, R2, and R3 is independently a hydrocarbyl group, especially where R3 is an alicyclic hydrocarbyl group.
  • Particularly preferred are the O,O-dialkyl-S-hydrocarbyl phosphorothiothionates wherein R3 is an alicyclic group an R1 and R2 are alkyl groups each having up to 18 carbon atoms and most preferably up to 12 carbon atoms.
  • Exemplary compounds suitable for use in the compositions of this invention include such compounds as trioctylphosphorothiothionate, tridecylphosphorothiothionate, trilaurylphosphorothiothionate, O,O-diethyl bicyclo(2.2.1)-hepten-2-yl phosphorothiothionate, O,O-diethyl 7,7-dimethyl-bicyclo(2.2.1)-5-hepten-2-yl phosphorothiothionate, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with cis-endomethylene-tetrahydrophthalic acid dimethyl ester, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with cis-endomethylene-tetrahydrophthalic acid dibutyl ester, the product formed by reaction of dithiophosphoric acid-O,O-dibutyl ester with cis-endomethylene
  • Another component which can be and preferably is used in the compositions of this invention is one or more amine salts of one or more long chain carboxylic acids.
  • the acids can be monocarboxylic acids or polycarboxylic acids. Generally speaking, these acids contain from 8 to 50 carbon atoms in the molecule and thus the salts are oil-soluble.
  • a variety of amines can be used in forming such salts, including primary, secondary and tertiary amines, and the amines can be monoamines, or polyamines. Further, the amines may be cyclic or acyclic aliphatic amines, aromatic amines, heterocyclic amines, or amines containing various mixtures of acyclic and cyclic groups.
  • Preferred amine salts include the alkyl amine salts of alkanoic acid and the alkyl amines salts of alkanedioic acids.
  • the amine salts are formed by classical chemical reactions, namely, the reaction of an amine or mixture of amines, with the appropriate acid or mixture of acids. Accordingly, further discussion concerning methods for the preparation of such materials would be redundant.
  • lauryl ammonium laurate i.e., the lauryl amine salt of lauric acid
  • stearyl ammonium laurate i.e., the lauryl amine salt of lauric acid
  • stearyl ammonium laurate cyclohexyl ammonium laurate
  • octyl ammonium laurate pyridine laurate
  • aniline laurate lauryl ammonium stearate
  • stearyl ammonium stearate cyclohexyl ammonium stearate, octylammonium stearate
  • pyridine stearate aniline stearate
  • lauryl ammonium octanoate stearyl ammonium octanoate
  • cyclohexyl ammonium octanoate octyl ammonium octanoate
  • aniline octanoate nonyl am
  • the primary amine salts are the primary amine salts of long chain monocarboxylic acids in which the amine thereof is a monoalkyl monoamine, RNH2; the secondary amine salts of long chain monocarboxylic acids in which the amine thereof is a dialkyl monoamine, R2NH; the tertiary amine salts of long chain monocarboxylic acids in which the amine thereof is a trialkyl monoamine, R3N; the bis primary amine salts of long chain dicarboxylic acids in which the amine thereof is a monoalkyl monoamine, RNH2; the bis secondary amine salts of long chain dicarboxylic acids in which the amine thereof is a dialkyl monoamine, R2NH; the bis tertiary amine salts of long chain dicarboxylic acids in which the amine thereof is a trialkyl monoamine, R3N; and mixtures thereof.
  • R is an alkyl group which contains up to 30 or more carbon
  • Typical additives which may be employed as demulsifiers include alkyl benzene sulfonates, polyethylene oxides, polypropylene oxides, block copolymers of ethylene oxide and propylene oxide, and salts and esters or oil soluble acids.
  • One type of copper corrosion inhibitor additives is comprised of thiazoles, triazoles and thiadiazoles.
  • examples of such compounds include benzotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles, 2-mercapto-5-hydrocarbyldithio-1,3,4- thiadiazoles, 2,5-bis(hydrocarbylthio)-1,3,4-thiadiazoles, and 2,5-(bis)hydrocarbyldithio)-1,3,4-thiadiazoles.
  • the preferred compounds are the 1,3,4-thiadiazoles, especially the 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles and the 2,5-bis(hydrocarbylthio)- 1,3,4-thiadiazoles, a number of which are available as articles of commerce.
  • Such compounds are generally synthesized from hydrazine and carbon disulfide by known procedures. See for example U.S. Pat. Nos. 2,749,311; 2,760,933; 2,765,289; 2,850,453; 2,910,439; 3,663,561; 3,862,798; 3,840,549; and 4,097,387.
  • Suitable inhibitors of copper corrosion include ether amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; and imidazolines. Materials of these types are well known to those skilled in the art and a number of such materials are available as articles of commerce.
  • the boron-containing additive components are preferably oil-soluble additive components, but effective use can be made of boron-containing components which are sufficiently finely divided as to form stable dispersions in the base oil.
  • boron-containing components include the finely-divided inorganic orthoborate salts such as lithium borate, sodium borate, potassium borate, magnesium borate, calcium borate, ammonium borate and the like.
  • the oil-soluble boron-containing components include boronated ashless dispersants (often referred to as borated ashless dispersants) and esters of acids of boron.
  • borated ashless dispersants examples include boronated ashless dispersants and descriptions of methods by which they can be prepared are well-documented in the literature. See for example the disclosures of U.S. Pat. Nos. 3,087,936; 3,254,025; 3,281,428; 3,282,955; 3,533,945; 3,539,633; 3,658,836; 3,697,574; 3,703,536; 3,704,308; 4,025,445; and 4,857,214.
  • the oleaginous fluids and additive concentrates of this invention can and preferably will contain additional components in order to partake of the properties which can be conferred to the overall composition by such additional components.
  • additional components will, to a large extent, be governed by the particular use to which the ultimate oleaginous composition (lubricant or functional fluid) is to be subjected.
  • Supplemental metal-free phosphorus-containing antiwear and/or extreme pressure agents can be used in the compositions of this invention.
  • Such compounds are for the most part partially or fully esterified acids of phosphorus, and include for example phosphates, phosphites, phosphonates, phosphonites, and their various sulfur analogs.
  • Examples include monohydrocarbyl phosphites; monohydrocarbyl phosphates; monohydrocarbyl mono-, di-, tri-, and tetrathiophosphites; monohydrocarbyl mono-, di-, tri-, and tetrathiophosphates; dihydrocarbyl phosphites; dihydrocarbyl phosphates; dihydrocarbyl mono-, di-, tri-, and tetrathiophosphites; dihydrocarbyl mono-, di-, tri-, and tetrathiophosphates; trihydrocarbyl phosphites; trihydrocarbylphosphates; trihydrocarbyl mono-, di-, tri-, and tetrathiophosphites; trihydrocarbyl mono-, di-, tri-, and tetrathiophosphates; trihydrocarbyl phosphites; trihydrocarbylphosphates; trihydro
  • a few specific specific examples of such compounds are tricresyl phosphate, tributyl phosphite, triphenyl phosphite, tri-(2-ethylhexyl) phosphate, dihexyl thiophosphite, diisooctyl butylphosphonate, tricyclohexyl phosphate, cresyl diphenyl phosphate, tris(2-butoxyethyl) phosphite, diisopropyl dithiophosphate, tris(tridecyl)tetrathiophosphate, tris(2-chloroethyl) phosphate, and like compounds.
  • ashless dispersants can be utilized in the compositions of this invention. These include carboxylic ashless dispersants, polymeric polyamine dispersants, and post-treated dispersants of these types. All such materials which have been described hereinabove.
  • Most oleaginous compositions will contain a conventional quantity of one or more antioxidants in order to protect the composition from premature degradation in the presence of air, especially at elevated temperatures.
  • Typical antioxidants include hindered phenolic antioxidants, secondary aromatic amine antioxidants, sulfurized phenolic antioxidants, oil-soluble copper compounds, and phosphorus-containing antioxidants.
  • Illustrative sterically hindered phenolic antioxidants include orthoalkylated phenolic compounds such as 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2- tert-butylphenol, 2,6-diisopropylphenol, 2-methyl-6- tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4-(N,N-dimethylaminomethyl)- 2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 2-methyl- 6-styrylphenol, 2,6-di-styryl-4-nonylphenol, and their analogs and homologs. Mixtures of two or more such mononuclear phenolic compounds are also suitable.
  • methylene-bridged alkylphenols are also useful.
  • Illustrative methylene bridged compounds include 4,4′-methylenebis(6-tert-butyl-o-cresol), 4,4′-methylenebis(2-tert-amyl-o-cresol), 2,2′-methylene-bis(4-methyl-6-tert-butylphenol), 4,4′-methylene-bis(2,6-di-tert-butylphenol), and similar compounds.
  • aromatic secondary monoamines are preferred, aromatic secondary polyamines are also suitable.
  • Illustrative aromatic secondary monoamines include diphenylamine, alkyl diphenylamines containing 1 or 2 alkyl substituents each having up to about 16 carbon atoms, phenyl- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, alkyl- or aralkyl-substituted phenyl- ⁇ -naphthylamine containing one or two alkyl or aralkyl groups each having up to about 16 carbon atoms, alkyl- or aralkyl-substituted phenyl- ⁇ naphthylamine containing one or two alkyl or aralkyl groups each having up to about 16 carbon atoms, and similar compounds.
  • a preferred type of aromatic amine antioxidant is an alkylated diphenylamine of the general formula wherein R1 is an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms) and R2 is a hydrogen atom or an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms). Most preferably, R1 and R2 are the same.
  • Naugalube 438L a material which is understood to be predominately a 4,4′-di-nonyldiphenylamine (i.e., bis(4-nonylphenyl)amine) wherein the nonyl groups are branched.
  • antioxidants for inclusion in the compositions of this invention is comprised to one or more liquid, partially sulfurized phenolic compounds such as are prepared by reacting sulfur monochloride with a liquid mixture of phenols -- at least about 50 weight percent of which mixture of phenols is composed of one or more reactive, hindered phenols -- in proportions to provide from 0.3 to 0.7 gram atoms of sulfur monochloride per mole of reactive, hindered phenol so as to produce a liquid product.
  • Typical phenol mixtures useful in making such liquid product compositions include a mixture containing by weight about 75% of 2,6-di-tert-butylphenol, about 10% of 2-tert-butylphenol, about 13% of 2,4,6-tri-tert-butylphenol, and about 2% of 2,4-di-tert-butylphenol.
  • the reaction is exothermic and thus is preferably kept within the range of 15°C to 70°C, most preferably between 40°C to 60°C.
  • One suitable mixture is comprised of a combination of (i) an oil-soluble mixture of at least three different sterically-hindered tertiary butylated monohydric phenols which is in the liquid state at 25°C, (ii) an oil-soluble mixture of at least three different sterically-hindered tertiary butylated methylene-bridged polyphenols, and (iii) at least one bis(4-alkylphenyl)amine wherein the alkyl group is a branched alkyl group having 8 to 12 carbon atoms, the proportions of (i), (ii) and (iii) on a weight basis falling in the range of 3.5 to 5.0 parts of component (i) and 0.9 to 1.2 parts of component (ii) per part by weight of component (iii).
  • compositions of this invention may also contain a suitable quantity of a rust inhibitor.
  • a rust inhibitor This may be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous metal surfaces.
  • Such materials include include oil-soluble monocarboxylic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, cerotic acid, etc., and oil-soluble polycarboxylic acids including dimer and trimer acids, such as are produced from tall oil fatty acids, oleic acid, or linoleic acid.
  • oil-soluble monocarboxylic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, cerotic acid, etc.
  • alkenylsuccinic acids in which the alkenyl group contains 10 or more carbon atoms such as, for example, tetrapropenylsuccinic acid, tetradecenylsuccinic acid, and hexadecenylsuccinic acid; long-chain ⁇ , ⁇ -icarboxylic acids in the molecular weight range of 600 to 3000; and other similar materials.
  • Products of this type are currently available from various commercial sources, such as, for example, the dimer and trimer acids sold under the HYSTRENE trademark by the Humco Chemical Division of Witco Chemical Corporation and under the EMPOL trademark by Emery Chemicals.
  • acidic corrosion inhibitors are the half esters of alkenyl succinic acids having 8 to 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols.
  • the corresponding half amides of such alkenyl succinic acids are also useful.
  • some or all of the carboxylic groups of these carboxylic acid type corrosion inhibitors may be neutralized by excess amine present in the compositions.
  • Other suitable corrosion inhibitors include ether amines; acid phosphates; amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; and imidazolines. Materials of these types are well known to those skilled in the art and a number of such materials are available as articles of commerce.
  • R1, R2, R5, R6 and R7 is, independently, a hydrogen atom or a hydrocarbyl group containing 1 to 30 carbon atoms
  • each of R3 and R4 is, independently, a hydrogen atom, a hydrocarbyl group containing 1 to 30 carbon atoms, or an acyl group containing from 1 to 30 carbon atoms.
  • the groups R1, R2, R3, R4, R5, R6 and R7, when in the form of hydrocarbyl groups can be, for example, alkyl, cycloalkyl or aromatic containing groups.
  • R1 and R5 are the same or different straight-chain or branched-chain hydrocarbon radicals containing 1-20 carbon atoms. Most preferably, R1 and R5 are saturated hydrocarbon radicals containing 3-6 carbon atoms.
  • R2, either R3 or R4, R6 and R7, when in the form of hydrocarbyl groups, are preferably the same or different straight-chain or branched-chain saturated hydrocarbon radicals.
  • a dialkyl ester of an aminosuccinic acid is used in which R1 and R5 are the same or different alkyl groups containing 3-6 carbon atoms, R2 is a hydrogen atom, and either R3 or R4 is an alkyl group containing 15-20 carbon atoms or an acyl group which is derived from a saturated or unsaturated carboxylic acid containing 2-10 carbon atoms.
  • aminosuccinic acid derivatives is a dialkylester of an aminosuccinic acid of the above formula wherein R1 and R5 are isobutyl, R2 is a hydrogen atom, R3 is octadecyl and/or octadecenyl and R4 is 3-carboxy-1-oxo-2-propenyl.
  • R6 and R7 are most preferably hydrogen atoms.
  • Suitable antifoam agents include silicones and organic polymers such as acrylate polymers. Various antifoam agents are described in Foam Control Agents by H.T. Kerner (Noyes Data Corporation, 1976, pages 125-176). Mixtures of silicone-type antifoam agents such as the liquid dialkyl silicone polymers with various other substances are also effective. Typical of such mixtures are silicones mixed with an acrylate polymer, silicones mixed with one or more amines, and silicones mixed with one or more amine carboxylates.
  • Friction modifiers F) Friction modifiers .
  • These materials include such substances as the alkyl phosphonates as disclosed in U.S. Pat. No. 4,356,097, aliphatic hydrocarbyl-substituted succinimides derived from ammonia or alkyl monoamines as disclosed in European Patent Publication No. 20037, dimer acid esters as disclosed in U.S. Pat. 4,105,571, and oleamide.
  • Such additives when used are generally present in amounts of 0.1 to 3 weight percent.
  • Glycerol oleates are another example of fuel economy additives and these are usually present in very small amounts, such as 0.05 to 1 weight percent based on the weight of the formulated oil.
  • Suitable friction modifiers include aliphatic amines or ethoxylated aliphatic amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic esters, aliphatic carboxylic ester-amides, aliphatic phosphates, aliphatic thiophosphonates, aliphatic thiophosphates, etc., wherein the aliphatic group usually contains above about eight carbon atoms so as to render the compound suitably oil soluble.
  • a desirable friction modifier additive combination which may be used in the practice of this invention is described in European Patent Publication No. 389,237. This combination involves use of a long chain succinimide derivative and a long chain amide.
  • Additives may be introduced into the compositions of this invention in order to improve the seal performance (elastomer compatibility) of the compositions.
  • Known materials of this type include dialkyl diesters such as dioctyl sebacate, aromatic hydrocarbons of suitable viscosity such as Panasol AN-3N, products such as Lubrizol 730, polyol esters such as Emery 2935, 2936, and 2939 esters from the Emery Group of Henkel Corp. and Hatcol 2352, 2962, 2925, 2938, 2939, 2970, 3178, and 4322 polyol esters from Hatco Corp.
  • diesters include the adipates, azelates, and sebacates of C8-C13 alkanols (or mixtures thereof), and the phthalates of C4-C13 alkanols (or mixtures thereof). Mixtures of two or more different types of diesters (e.g., dialkyl adipates and dialkyl azelates, etc.) can also be used.
  • Such materials include the n-octyl, 2-ethylhexyl, isodecyl, and tridecyl diesters of adipic acid, azelaic acid, and sebacic acid, and the n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl diesters of phthalic acid.
  • the lubricant compositions can contain one or more viscosity index improvers (polymeric materials which are often supplied in the form of a solution in a solvent or carrier fluid).
  • viscosity index improvers polymeric materials which are often supplied in the form of a solution in a solvent or carrier fluid.
  • Dispersant viscosity index improvers which combine the activity of dispersants and viscosity index improvers, suitable for use in the compositions of this invention are described, for example, in U.S. Pat. Nos. 3,702,300; 4,068,056; 4,068,058; 4,089,794; 4,137,185; 4,146,489; 4,149,984; 4,160,739; and 4,519,929.
  • pour point depressants Another useful type of additive which can be included in compositions of this invention is one or more pour point depressants.
  • pour point depressants in oil-base compositions to improve the low temperature properties of the compositions is well known to the art. See, for example, the books Lubricant Additives by C. V. Smalheer and R. Kennedy Smith (Lezius-Hiles Co. Publishers, Cleveland, Ohio, 1967); Gear and Transmission Lubricants by C. T. Boner (Reinhold Publishing Corp., New York, 1964); and Lubricant Additives by M. W. Ranney (Noyes Data Corporation, New Jersey, 1973).
  • polymethacrylates polymethacrylates
  • polyacrylates condensation products of haloparaffin waxes and aromatic compounds
  • vinyl carboxylate polymers are also useful as pour point depressants.
  • terpolymers made by polymerizing a dialkyl fumarate, vinyl ester of a fatty acid and a vinyl alkyl ether. Techniques for preparing such polymers and their uses are disclosed in U.S. Pat. No. 3,250,715.
  • the free amines which can be employed in the compositions of this invention can be any of the amines referred to above in connection with the amine salts of partial esters of phosphoric acid or thiophosphoric acids or in connection with the amine salts of carboxylic acids, provided that the amines are oil-soluble.
  • the preferred type is composed of alkyl primary monoamines, and alkenyl primary monoamines, especially those containing from 6 to 24 carbon atoms.
  • amines examples include hexylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, eicosylamine, docosylamine, tetracosylamine, oleylamine, cocoamine, soyamine, C12 ⁇ 14 tertiary alkyl primary amine, and C22 ⁇ 24 tertiary alkyl primary amine.
  • the free amine used in the compositions will correspond to the amine used in forming either the amine salt of the phosphorus acid or the amine salt of the carboxylic acid, or both.
  • free amine refers to the form of the amine as it is charged into the blender or mixing vessel in which the additive concentrate or the lubricating oil or functional fluid composition is being formed. Some or all of the free amine may complex with or react with other components being used in the product being formed, such as acidic additive components. Thus the term “free amine” does not signify or imply that the amine must remain free -- all or part of it may remain uncomplexed and unreacted, but this is not a requirement.
  • the additive combinations of this invention can be incorporated in a wide variety of lubricants and functional fluids in effective amounts to provide suitable active ingredient concentrations.
  • the base oils not only can be hydrocarbon oils of lubricating viscosity derived from petroleum (or tar sands, coal, shale, etc.), but also can be natural oils of suitable viscosities such as rapeseed oil, etc., and synthetic oils such as hydrogenated polyolefin oils; poly- ⁇ -olefins (e.g., hydrogenated or unhydrogenated ⁇ -olefin oligomers such as hydrogenated poly-1-decene); alkyl esters of dicarboxylic acids; complex esters of dicarboxylic acid, polyglycol and alcohol; alkyl esters of carbonic or phosphoric acids; polysilicones; fluorohydrocarbon oils; and mixtures of mineral, natural and/or synthetic oils in any proportion, etc.
  • base oil for this disclosure includes all the foregoing.
  • the additive combinations of this invention can thus be used in lubricating oil and functional fluid compositions, such as automotive crankcase lubricating oils, automatic transmission fluids, gear oils, hydraulic oils, cutting oils, etc., in which the base oil of lubricating viscosity is a mineral oil, a synthetic oil, a natural oil such as a vegetable oil, or a mixture thereof, e.g., a mixture of a mineral oil and a synthetic oil.
  • the base oil of lubricating viscosity is a mineral oil, a synthetic oil, a natural oil such as a vegetable oil, or a mixture thereof, e.g., a mixture of a mineral oil and a synthetic oil.
  • Suitable mineral oils include those of appropriate viscosity refined from crude oil of any source including Gulf Coast, Midcontinent, Pennsylvania, California, Alaska, Middle East, North Sea, etc. Standard refinery operations may be used in processing the mineral oil.
  • general types of petroleum oils useful in the compositions of this invention are solvent neutrals, bright stocks, cylinder stocks, residual oils, hydrocracked base stocks, paraffin oils including pale oils, and solvent extracted naphthenic oils. Such oils and blends of them are produced by a number of conventional techniques which are widely known by those skilled in the art.
  • the base oil can consist essentially of or comprise a portion of one or more synthetic oils.
  • suitable synthetic oils are homo- and inter-polymers of C2-C12 olefins, carboxylic acid esters of both monoalcohols and polyols, polyethers, silicones, polyglycols, silicates, alkylated aromatics, carbonates, thiocarbonates, orthoformates, phosphates and phosphites, borates and halogenated hydrocarbons.
  • oils are homo- and interpolymers of C2-C12 monoolefinic hydrocarbons, alkylated benzenes (e.g., dodecyl benzenes, didodecyl benzenes, tetradecyl benzenes, dinonyl benzenes, di-(2-ethylhexyl)benzenes, wax-alkylated naphthalenes); and polyphenyls (e.g., biphenyls, terphenyls).
  • alkylated benzenes e.g., dodecyl benzenes, didodecyl benzenes, tetradecyl benzenes, dinonyl benzenes, di-(2-ethylhexyl)benzenes, wax-alkylated naphthalenes
  • polyphenyls e.g., biphenyls,
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of synthetic oils. These are exemplified by the oils prepared through polymerization of alkylene oxides such as ethylene oxide or propylene oxide, and the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500) or mono- and poly-carboxylic esters thereof, for example, the acetic acid ester, mixed C3-C6 fatty acid esters, or the C13 Oxo acid diester of tetraethylene glycol.
  • alkylene oxides such as ethylene oxide or propylene oxide
  • Another suitable class of synthetic oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer
  • alcohols e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol.
  • esters include dibutyl adipate, di(2-ethylhexyl) adipate, didodecyl adipate, di(tridecyl) adipate, di(2-ethylhexyl) sebacate, dilauryl sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, di(eicosyl) sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • esters which may be used include those made from C3-C18 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol and dipentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another class of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, poly(methyl)siloxanes, and poly(methylphenyl)siloxanes.
  • synthetic lubricants e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, poly(methyl)siloxanes, and poly(methylphenyl)siloxanes.
  • Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, triphenyl phosphite, and diethyl ester of decane phosphonic acid.
  • liquid esters of phosphorus-containing acids e.g., tricresyl phosphate, trioctyl phosphate, triphenyl phosphite, and diethyl ester of decane phosphonic acid.
  • Also useful as base oils or as components of base oils are hydrogenated or unhydrogenated liquid oligomers of C6-C16 ⁇ -olefins, such as hydrogenated or unhydrogenated oligomers formed from 1-decene.
  • Methods for the production of such liquid oligomeric 1-alkene hydrocarbons are known and reported in the literature. See for example U. S. Pat. Nos. 3,749,560; 3,763,244; 3,780,128; 4,172,855; 4,218,330; 4,902,846; 4,906,798; 4,910,355; 4,911,758; 4,935,570; 4,950,822; 4,956,513; and 4,981,578.
  • hydrogenated 1-alkene oligomers of this type are available as articles of commerce, e.g., under the trade designations ETHYLFLO 162, ETHYLFLO 164, ETHYLFLO 166, ETHYLFLO 168, ETHYLFLO 170, ETHYLFLO 174, and ETHYLFLO 180 poly- ⁇ -olefin oils (Ethyl Corporation; Ethyl Canada Limited; Ethyl S.A.). Blends of such materials can also be used in order to adjust the viscometrics of the given base oil. Suitable 1-alkene oligomers are also available from other suppliers. As is well known, hydrogenated oligomers of this type contain little, if any, residual ethylenic unsaturation.
  • Preferred oligomers are formed by use of a Friedel-Crafts catalyst (especially boron trifluoride promoted with water or a C1 ⁇ 20 alkanol) followed by catalgic hydrogenation of the oligomer so formed using procedures such as are described in the foregoing U.S. patents.
  • a Friedel-Crafts catalyst especially boron trifluoride promoted with water or a C1 ⁇ 20 alkanol
  • catalyst systems which can be used to form oligomers of 1-alkene hydrocarbons, which, on hydrogenation, provide suitable oleaginous liquids include Ziegler catalysts such as ethyl aluminum sesquichloride with titanium tetrachloride, aluminum alkyl catalysts, chromium oxide catalysts on silica or alumina supports and a system in which a boron trifluoride catalyst oligomerization is followed by treatment with an organic peroxide.
  • Ziegler catalysts such as ethyl aluminum sesquichloride with titanium tetrachloride, aluminum alkyl catalysts, chromium oxide catalysts on silica or alumina supports and a system in which a boron trifluoride catalyst oligomerization is followed by treatment with an organic peroxide.
  • Typical natural oils that may be used as base oils or as components of the base oils include castor oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, soybean oil, sunflower oil, safflower oil, hemp oil, linseed oil, tung oil, oiticica oil, jojoba oil, and meadowfoam oil. Such oils may be partially or fully hydrogenated, if desired.
  • the base oils used in the compositions of this invention may be composed of (i) one or more mineral oils, (ii) one or more synthetic oils, (iii) one or more natural oils, or (iv) a blend of (i) and (ii), or (i) and (iii), or (ii) and (iii), or (i), (ii) and (iii) does not mean that these various types of oils are necessarily equivalents of each other.
  • Certain types of base oils may be used in certain compositions for the specific properties they possess such as high temperature stability, non-flammability or lack of corrosivity towards specific metals (e.g., silver or cadmium). In other compositions, other types of base oils may be preferred for reasons of availability or low cost.
  • the skilled artisan will recognize that while the various types of base oils discussed above may be used in the compositions of this invention, they are not necessarily functional equivalents of each other in every instance.
  • the components of the additive compositions of this invention are employed in the oleaginous liquids (e.g., lubricating oils and functional fluids) in minor amounts sufficient to improve the performance characteristics and properties of the base oil or fluid.
  • the amount employed is most preferably the amount sufficient to render the pH (determined as described hereinafter) of the finished additive concentrate as formed within the range of 4 to 9.
  • the amounts of the other components will vary in accordance with such factors as the viscosity characteristics of the base oil or fluid employed, the viscosity characteristics desired in the finished product, the service conditions for which the finished product is intended, and the performance characteristics desired in the finished product.
  • concentrations (weight percent) of the components (active ingredients) in the base oils or fluids are illustrative:
  • component a-2 when using component a-2) or a-4), the following concentrations (weight percent) of the components (active ingredients) in the base oils or fluids are illustrative:
  • the individual components can be separately blended into the base oil or fluid or can be blended therein in various subcombinations, if desired. Moreover, such components can be blended in the form of separate solutions in a diluent. Except for viscosity index improvers and/or pour point depressants (which in many instances are blended apart from other components), it is preferable to blend the other selected components into the base oil by use of an additive concentrate of this invention, as this simplifies the blending operations, reduces the likelihood of blending errors, and takes advantage of the compatibility and solubility characteristics afforded by the overall concentrate.
  • the additive concentrates of this invention will contain the individual components in amounts proportioned to yield finished oil or fluid blends consistent with the concentrations tabulated above.
  • the additive concentrate will contain one or more diluents such as light mineral oils, to facilitate handling and blending of the concentrate.
  • concentrates containing up to 50% by weight of one or more diluents or solvents can be used.
  • the oleaginous liquids provided by this invention can be used in a variety of applications.
  • they can be employed as crankcase lubricants, gear oils, hydraulic fluids, manual transmission fluids, automatic transmission fluids, cutting and machining fluids, brake fluids, shock absorber fluids, heat transfer fluids, quenching oils, and transformer oils.
  • the compositions are particularly suitable for use as automotive and industrial gear oils.
  • the formulation or blending operations are relatively simple and involve mixing together in a suitable container or vessel, using a dry, inert atmosphere where necessary or desirable, appropriate proportions of the selected ingredients.
  • Those skilled in the art are cognizant of and familiar with the procedures suitable for formulating and blending additive concentrates and lubricant compositions.
  • the order of addition of components to the blending tank or vessel is not critical provided of course, that the components being blended at any given time are not incompatible or excessively reactive with each other. Agitation such as with mechanical stirring equipment is desirable to facilitate the blending operation.
  • the additive ingredients When forming the lubricant compositions of this invention, it is usually desirable to introduce the additive ingredients into the base oil with stirring and application of mildly elevated temperatures, as this facilitates the dissolution of the components in the oil and achievement of product uniformity.
  • reaction vessel To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite, and 1.75 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 38.3 parts of sulfurized isobutylene, 14.3 parts of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphite, 0.1 part of tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6 parts of dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8 parts of dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite, and 1.75 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 38.3 parts of sulfurized isobutylene, 14.3 parts of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphite, 0.1 part of tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6 parts of dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8 parts of dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite, and 1.75 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 38.3 parts of sulfurized isobutylene, 14.3 parts of di-tert-nonyl polysulfrde, 5.7 parts of dibutyl hydrogen phosphite, 0.1 part of tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6 parts of dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8 parts of dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite, and 1.75 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 38.3 parts of sulfurized isobutylene, 14.3 parts of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphite, 0.1 part of tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6 parts of dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8 parts of dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • compositions of this invention were illustrated in several standard L-37 and L-42 tests.
  • the composition was prepared by blending together the following components in which the proportions are by weight:
  • the phosphorylated ashless dispersant was formed from a polyisobutenyl succinimide, viz., HiTEC® 646 additive (Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl Canada Ltd.).
  • Example 51 Phosphorylation was accomplished in the manner of Example 51 using 2.7 parts by weight of HiTEC® 646 additive, 0.3 parts by weight of solid phosphorous acid (H3PO3), and 1 part by weight of process oil diluent.
  • the slfurized isobutylene was HiTEC® 309 sulfurized isobutylene additive; (Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl Canada Ltd.).
  • This oil blend had kinematic viscosity at of 153.98 cSt at 40°C, and 16.63 cSt at 100°C.
  • the procedure used in determining pH of preferred additive concentrates of this invention involves diluting the sample of the composition in a mixture of methanol and toluene and then assaying "non-aqueous" pH with a conventional pH probe as used in aqueous systems.
  • Copper corrosion ratings for the purposes of this invention are conducted using the standard ASTM D-130 procedure modified to the extent that the additive concentrate to be tested is first stored in an oven for 120 hours at 65°C. Then the concentrate is blended into the test oil to the selected test concentration and the test is conducted at 121°C.
  • oil-soluble is used in the sense that the component in question has sufficient solubility in the selected base oil in order to dissolve therein at ordinary temperatures to a concentration at least equivalent to the minimum concentration specified herein for use of such component.
  • solubility of such component in the selected base oil will be in excess of such minimum concentration, although there is no requirement that the component be soluble in the base oil in all proportions.
  • certain useful additives do not completely dissolve in base oils but rather are used in the form of stable suspensions or dispersions. Additives of this type can be employed in the compositions of this invention, provided they do not significantly interfere with the performance or usefulness of the composition in which they are employed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP92307448A 1991-08-21 1992-08-14 Ölzusatzkonzentrate und Schmieröle mit erhöhten Leistungsfähigkeiten Expired - Lifetime EP0531000B1 (de)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US74795691A 1991-08-21 1991-08-21
US74793991A 1991-08-21 1991-08-21
US74794291A 1991-08-21 1991-08-21
US74801991A 1991-08-21 1991-08-21
US748019 1991-08-21
US747942 1991-08-21
US747956 1991-08-21
US747939 1991-08-21

Publications (2)

Publication Number Publication Date
EP0531000A1 true EP0531000A1 (de) 1993-03-10
EP0531000B1 EP0531000B1 (de) 1997-02-05

Family

ID=27505642

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92307448A Expired - Lifetime EP0531000B1 (de) 1991-08-21 1992-08-14 Ölzusatzkonzentrate und Schmieröle mit erhöhten Leistungsfähigkeiten

Country Status (5)

Country Link
EP (1) EP0531000B1 (de)
JP (1) JPH05263090A (de)
AU (1) AU657150B2 (de)
CA (1) CA2076140C (de)
DE (1) DE69217299D1 (de)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5468403A (en) * 1993-12-22 1995-11-21 Exxon Chemical Patents Inc. Phosphorus- and mono- or di-sulfide-containing additives for lubrication oils
GB2301113A (en) * 1995-05-22 1996-11-27 Ethyl Petroleum Additives Ltd Extreme pressure gear lubricant
EP0807676A2 (de) 1996-05-17 1997-11-19 Ethyl Petroleum Additives Limited Brennstoffzusätze und -zusammensetzungen
US5763372A (en) * 1996-12-13 1998-06-09 Ethyl Corporation Clean gear boron-free gear additive and method for producing same
EP1142983A1 (de) * 2000-04-03 2001-10-10 Idemitsu Kosan Company Limited Schmiermittelzusatz
WO2003076557A1 (en) * 2002-03-04 2003-09-18 The Lubrizol Corporation Lubricating compositions with good thermal stability and demulsibility properties
US6797678B2 (en) 2000-04-03 2004-09-28 Idemitsu Kosan Co., Ltd. Lubricant additive
US6844300B2 (en) 2001-02-20 2005-01-18 Ethyl Corporation Low phosphorus clean gear formulations
US7531486B2 (en) 2005-03-31 2009-05-12 Exxonmobil Chemical Patents Inc. Additive system for lubricant
US7648948B2 (en) 2005-04-08 2010-01-19 Exxonmobil Chemical Patents Inc. Additive system for lubricants
US7803332B2 (en) 2005-05-31 2010-09-28 Exxonmobil Chemical Patents Inc. Reactor temperature control
US8034754B2 (en) 2005-03-31 2011-10-11 The Lubrizol Corporation Fluids for enhanced gear protection
US8389449B2 (en) 2003-04-25 2013-03-05 Chevron Oronite Company Llc Gear oil having low copper corrosion properties
US20140162918A1 (en) * 2011-05-06 2014-06-12 Petrochina Company Limited Industrial gear lubricating oil composition used for resisting micro-pitting
WO2016137880A1 (en) * 2015-02-26 2016-09-01 Dow Global Technologies Llc Enhanced extreme pressure lubricant formulations
WO2016137882A1 (en) * 2015-02-26 2016-09-01 Dow Global Technologies Llc Lubricant formulations with enhanced anti-wear and extreme pressure performance
CN107502433A (zh) * 2017-09-13 2017-12-22 华北电力大学（保定） 一种开式齿轮油
US20180119051A1 (en) * 2015-03-30 2018-05-03 Idemitsu Kosan Co., Ltd. Lubricant composition

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6884855B2 (en) * 2003-01-30 2005-04-26 Chevron Oronite Company Llc Sulfurized polyisobutylene based wear and oxidation inhibitors
JP4734117B2 (ja) * 2003-10-09 2011-07-27 出光興産株式会社 潤滑油添加剤及び潤滑油組成物
US20050101494A1 (en) 2003-11-10 2005-05-12 Iyer Ramnath N. Lubricant compositions for power transmitting fluids

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4058468A (en) * 1976-06-07 1977-11-15 Ethyl Corporation Lubricant composition
EP0359522A1 (de) * 1988-09-16 1990-03-21 Ethyl Petroleum Additives, Inc. Öllösliche phosphorhaltige Verschleissschutzadditive für Schmieröle
EP0384639A1 (de) * 1989-02-21 1990-08-29 Ethyl Petroleum Additives, Inc. Vorbehandelte automatische Kraftübertragungsflüssigkeiten und ihre Herstellung
EP0428393A1 (de) * 1989-11-13 1991-05-22 Ethyl Petroleum Additives, Inc. Getriebeöle und Zusätze dafür
EP0430624A1 (de) * 1989-11-27 1991-06-05 Ethyl Petroleum Additives, Inc. Getriebeöle und Zusätze dafür
EP0459656A1 (de) * 1990-05-17 1991-12-04 Ethyl Petroleum Additives, Inc. Schmiermittelzusammensetzungen
EP0399764B1 (de) * 1989-05-22 1992-03-25 Ethyl Petroleum Additives Limited Schmiermittel-Zusammensetzungen
EP0492934A1 (de) * 1990-12-21 1992-07-01 Ethyl Petroleum Additives, Inc. Schmierölzusammensetzungen, Konzentrate und ihre Verwendung

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4058468A (en) * 1976-06-07 1977-11-15 Ethyl Corporation Lubricant composition
EP0359522A1 (de) * 1988-09-16 1990-03-21 Ethyl Petroleum Additives, Inc. Öllösliche phosphorhaltige Verschleissschutzadditive für Schmieröle
EP0384639A1 (de) * 1989-02-21 1990-08-29 Ethyl Petroleum Additives, Inc. Vorbehandelte automatische Kraftübertragungsflüssigkeiten und ihre Herstellung
EP0399764B1 (de) * 1989-05-22 1992-03-25 Ethyl Petroleum Additives Limited Schmiermittel-Zusammensetzungen
EP0428393A1 (de) * 1989-11-13 1991-05-22 Ethyl Petroleum Additives, Inc. Getriebeöle und Zusätze dafür
EP0430624A1 (de) * 1989-11-27 1991-06-05 Ethyl Petroleum Additives, Inc. Getriebeöle und Zusätze dafür
EP0459656A1 (de) * 1990-05-17 1991-12-04 Ethyl Petroleum Additives, Inc. Schmiermittelzusammensetzungen
EP0492934A1 (de) * 1990-12-21 1992-07-01 Ethyl Petroleum Additives, Inc. Schmierölzusammensetzungen, Konzentrate und ihre Verwendung

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5468403A (en) * 1993-12-22 1995-11-21 Exxon Chemical Patents Inc. Phosphorus- and mono- or di-sulfide-containing additives for lubrication oils
US5527478A (en) * 1993-12-22 1996-06-18 Exxon Chemical Patents Inc. Phosphorus-and mono- or di-sulfide-containing additives for lubrication oils
GB2301113A (en) * 1995-05-22 1996-11-27 Ethyl Petroleum Additives Ltd Extreme pressure gear lubricant
EP0744456A2 (de) * 1995-05-22 1996-11-27 Ethyl Petroleum Additives Limited Schmiermittelzusammensetzungen
EP0744456A3 (de) * 1995-05-22 1996-12-11 Ethyl Petroleum Additives Limited Schmiermittelzusammensetzungen
EP0807676A2 (de) 1996-05-17 1997-11-19 Ethyl Petroleum Additives Limited Brennstoffzusätze und -zusammensetzungen
US5763372A (en) * 1996-12-13 1998-06-09 Ethyl Corporation Clean gear boron-free gear additive and method for producing same
EP0848052A2 (de) * 1996-12-13 1998-06-17 Ethyl Corporation Borfreie Zusatzzusammensetzung, Verfahrenzu ihrer Herstellung und Verwendung zum Schmieren von Kraftfahrzeug-Wechselgetrieben.
EP0848052A3 (de) * 1996-12-13 1998-06-24 Ethyl Corporation Borfreie Zusatzzusammensetzung, Verfahrenzu ihrer Herstellung und Verwendung zum Schmieren von Kraftfahrzeug-Wechselgetrieben.
AU725264B2 (en) * 1996-12-13 2000-10-12 Ethyl Corporation Clean gear boron-free gear additive and method for producing same
CN1075109C (zh) * 1996-12-13 2001-11-21 乙基公司 清净齿轮的无硼齿轮润滑油添加剂和其生产方法
EP1142983A1 (de) * 2000-04-03 2001-10-10 Idemitsu Kosan Company Limited Schmiermittelzusatz
US6352962B1 (en) 2000-04-03 2002-03-05 Idemitsu Kosan Co., Ltd. Lubricant additive comprising reaction product of phosphate or phosphite and boronated dispersant
US6797678B2 (en) 2000-04-03 2004-09-28 Idemitsu Kosan Co., Ltd. Lubricant additive
US6844300B2 (en) 2001-02-20 2005-01-18 Ethyl Corporation Low phosphorus clean gear formulations
WO2003076557A1 (en) * 2002-03-04 2003-09-18 The Lubrizol Corporation Lubricating compositions with good thermal stability and demulsibility properties
EP1490460A1 (de) 2002-03-04 2004-12-29 The Lubrizol Corporation Schmiermittelzusammensetzung mit guter thermischer stabilität und entemulgierbarkeitseigenschaften
US8536102B2 (en) 2003-04-25 2013-09-17 Chevron Oronite Company Llc Gear oil having low copper corrosion properties
US8389449B2 (en) 2003-04-25 2013-03-05 Chevron Oronite Company Llc Gear oil having low copper corrosion properties
US7531486B2 (en) 2005-03-31 2009-05-12 Exxonmobil Chemical Patents Inc. Additive system for lubricant
US8034754B2 (en) 2005-03-31 2011-10-11 The Lubrizol Corporation Fluids for enhanced gear protection
US7648948B2 (en) 2005-04-08 2010-01-19 Exxonmobil Chemical Patents Inc. Additive system for lubricants
US7902132B2 (en) 2005-04-08 2011-03-08 The Lubrizol Corporation Additive system for lubricants
US7803332B2 (en) 2005-05-31 2010-09-28 Exxonmobil Chemical Patents Inc. Reactor temperature control
US20140162918A1 (en) * 2011-05-06 2014-06-12 Petrochina Company Limited Industrial gear lubricating oil composition used for resisting micro-pitting
US9347016B2 (en) * 2011-05-06 2016-05-24 Petrochina Company Limited Industrial gear lubricating oil composition used for resisting micro-pitting
WO2016137880A1 (en) * 2015-02-26 2016-09-01 Dow Global Technologies Llc Enhanced extreme pressure lubricant formulations
WO2016137882A1 (en) * 2015-02-26 2016-09-01 Dow Global Technologies Llc Lubricant formulations with enhanced anti-wear and extreme pressure performance
US10428293B2 (en) 2015-02-26 2019-10-01 Dow Global Technologies Llc Enhanced extreme pressure lubricant formulations
US20180119051A1 (en) * 2015-03-30 2018-05-03 Idemitsu Kosan Co., Ltd. Lubricant composition
US11124732B2 (en) * 2015-03-30 2021-09-21 Idemitsu Kosan Co., Ltd. Lubricant composition
CN107502433A (zh) * 2017-09-13 2017-12-22 华北电力大学（保定） 一种开式齿轮油
CN107502433B (zh) * 2017-09-13 2021-01-26 华北电力大学（保定） 一种开式齿轮油

Also Published As

Publication number Publication date
AU657150B2 (en) 1995-03-02
JPH05263090A (ja) 1993-10-12
EP0531000B1 (de) 1997-02-05
CA2076140C (en) 2002-02-26
CA2076140A1 (en) 1993-02-22
DE69217299D1 (de) 1997-03-20
AU2111492A (en) 1993-02-25

Similar Documents

Publication Publication Date Title
EP0531000B1 (de) Ölzusatzkonzentrate und Schmieröle mit erhöhten Leistungsfähigkeiten
US5328619A (en) Oil additive concentrates and lubricants of enhanced performance capabilities
AU657563B2 (en) Oil additive concentrates and lubricants of enhanced performance capabilities
US5652201A (en) Lubricating oil compositions and concentrates and the use thereof
US5358652A (en) Inhibiting hydrolytic degradation of hydrolyzable oleaginous fluids
US5464549A (en) Oil soluble dispersants suitable for use in fuels and lubricants
US5358650A (en) Gear oil compositions
EP0537338B1 (de) Thermisch stabile Zusammensetzungen und diese enthaltende Schmiermitteln und funktionelle Flüssigkeiten
US5700764A (en) Lubricant compositions
EP0493928A1 (de) Schmierölzusammensetzungen, Konzentrate und ihre Verwendung
AU655785B2 (en) Lubricating oil compositions and concentrations and the use thereof
CA2009487C (en) Hydroxyalkane phosphonic acids and derivatives thereof and lubricants containing same
CA2009488C (en) Lubricants containing salts of hydroxyalkane phosphonic acids
AU657528B2 (en) Lubricating oil compositions and concentrates and the use thereof
AU646516B2 (en) Lubricating oil compositions and concentrations and the use thereof

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT

17P Request for examination filed

Effective date: 19930611

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ETHYL PETROLEUM ADDITIVES, INC.

17Q First examination report despatched

Effective date: 19950404

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19970205

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19970205

REF Corresponds to:

Ref document number: 69217299

Country of ref document: DE

Date of ref document: 19970320

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970506

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000720

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20000809

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010814

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010831

BERE Be: lapsed

Owner name: ETHYL PETROLEUM ADDITIVES INC.

Effective date: 20010831

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010814

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

Ref country code: FR

Ref legal event code: CA

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070817

Year of fee payment: 16

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20090430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080901