EP2379686B1 - A lubricating oil additive composition and method of making the same - Google Patents

A lubricating oil additive composition and method of making the same Download PDF

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Publication number
EP2379686B1
EP2379686B1 EP09835596.9A EP09835596A EP2379686B1 EP 2379686 B1 EP2379686 B1 EP 2379686B1 EP 09835596 A EP09835596 A EP 09835596A EP 2379686 B1 EP2379686 B1 EP 2379686B1
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EP
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Prior art keywords
lubricating oil
mixtures
succinimide
post
anhydride
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EP09835596.9A
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German (de)
English (en)
French (fr)
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EP2379686A2 (en
EP2379686A4 (en
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William R. Ruhe, Jr.
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Chevron Oronite Co LLC
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Chevron Oronite Co LLC
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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
    • 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
    • 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2207/028—Overbased 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/142—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings polycarboxylic
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C10N2030/041—Soot induced viscosity control
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/70—Soluble oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/06—Chemical after-treatment of the constituents of the lubricating composition by epoxydes or oxyalkylation reactions

Definitions

  • the present invention is directed to an improved dispersant additive composition that is used in engine oils; and it is also directed to the process of making the same.
  • European Published Patent Application No. 0438848 discloses a lubricating oil containing a dispersant prepared by (i) reacting at least one polyamine with at least one acyclic hydrocarbyl substituted succinic acylating agent in which such acyclic hydrocarbyl substituent contains an average of at least 40 carbon atoms, such reaction being conducted using proportions such that the acylating agent is reacted with the polyamine in a mole ratio of from 1.05 to 2.85 moles per mole of polyamine, and (ii) reacting the product so formed with (a) at least one aliphatic vicinal dicarboxylic acid acylating agent containing 4 to 30 carbon atoms in the molecule and in which the two carboxyl groups are separated from each other by two aliphatic carbon atoms, or (b) an anhydride, acid halide, or ester of at least one such dicarboxylic acid acylating agent, or (c) a combination of (a) and (b), using
  • aromatic polybasic carboxylic acid phthalic acid, terephthalic acid, trimesic acid, trimellitic acid pyromellitic acid, etc.
  • alkenyl-succinic acid, or its anhydride having alkenyl group jointed of molecular weight about 300
  • U.S. Patent No. 3,692,681 discloses terephthalic acid dispersed in a hydrocarbon medium containing highly hindered acylated alkylene polyamines.
  • U.S. Patent No. 4,747,964 discloses additive compositions that may be either (1) the products obtained by reacting alkenylsuccinimides with aromatic dianhydrides, or (2) the products obtained by reacting alkenylsuccinimides with an anhydride or a dianhydride of mono- or polycarboxylic aliphatic, alicyclic or aromatic acid of low molecular weight, the obtained product being then reacted with at least one organic compound having several hydroxyl and/or amine groups.
  • These dispersing additive compositions may be added to lubricating oils in a proportion, for example, from 0.1 to 20% by weight.
  • Clark et al. U.S. Patent No. 6,255,258 discloses oil-soluble dispersant obtainable by reacting the reaction product of a polyamine and a long-chain hydrocarbyl-substituted dicarboxylic acid, anhydride or ester thereof with a polyanhydride, characterized in that the dispersant restricts the viscosity increase in an oil to below 8 Pa.s in the Haake rheology test defined herein at 2% w/w active matter and a shear rate of 0.26 s.sup.-1 Pa.s, and lubricating oil and fuel compositions and additive concentrates containing such a dispersant.
  • U.S. Patent No. 5,241,003 discloses succinimides, succinic esters, and succinic ester-amides are formed by (A) reacting (i) at least one substantially aliphatic polymer of at least one lower olefin, and (ii) an acidic reactant or a mixture of two or more acidic reactants represented by the general formula wherein R and R' are independently --OH, --O-lower alkyl, a halogen atom, or taken together are a single oxygen atom; and (B) reacting an acylating agent with at least one alcohol (preferably a polyhydric alcohol) or amine (preferably a polyamine having at least one primary amino group).
  • A reacting (i) at least one substantially aliphatic polymer of at least one lower olefin, and (ii) an acidic reactant or a mixture of two or more acidic reactants represented by the general formula wherein R and R' are independently --OH, --O-lower alkyl, a
  • alkenyl or alkyl succinimide additives which are the reaction product of a high molecular weight alkenyl- or alkyl-substituted succinic anhydride and a polyalkylene polyamine having an average of greater than 4 nitrogen atoms per mole, wherein the reaction product is post-treated with a cyclic carbonate, are compatible with fluorocarbon engine seals and, for concentration levels at which fluorocarbon seal compatibility is achieved, possess improved dispersancy and/or detergency properties when employed in lubricating oils and fuels,
  • a succinimide composition is prepared by reacting a mixture of an alkenyl or alkylsuccinic acid derivative, an unsaturated acidic reagent copolymer, and a polyamine under reactive conditions; then treating the reaction product with either a cyclic carbonate or a linear mono- or polycarbonate or boron compound under reactive conditions.
  • a polysuccinimide composition is prepared by reacting a mixture of a copolymer of a first unsaturated acidic reagent and a 1,1-disubstituted olefin; a copolymer of a second unsaturated acidic reagent and a 1-olefin, and a polyamine under reactive conditions; then treating the reaction product with either a cyclic carbonate or a linear mono- or polycarbonate or boron compound under reactive conditions.
  • a succinimide composition is prepared by reacting a mixture of an alkenyl or alkylsuccinic acid derivative, an unsaturated acidic reagent copolymer, and a polyamine under reactive conditions; then treating the reaction product with either a cyclic carbonate or a linear mono- or polycarbonate or boron compound under reactive conditions.
  • the present invention is directed to a lubricating oil additive composition prepared by the process which comprises the stops of:
  • the present invention is also directed to a lubricating oil composition
  • a lubricating oil composition comprising a major amount of an oil of lubricating viscosity and a minor amount of a lubricating oil additive composition prepared by the process which comprises the steps of:
  • the present invention is also directed to a method of making a lubricating oil additive composition which comprises the steps of:
  • the present invention relates to multi-functional lubricating oil additives which are useful as dispersants in an internal combustion engine.
  • One embodiment of the present invention is a post-treated oil-soluble lubricating oil additive composition.
  • the composition is prepared by the process which comprises the steps of (A) reacting a polyalkenyl succinic acid or a polyalkenyl succinic anhydride with at least one polyalkylene polyamine, having at least three nitrogen atoms, thereby producing a succinimide or succinamide or mixtures thereof; (B) reacting the product of step (A) with a first post-treating agent, thereby producing an initial post-treated succinimide or succinamide or mixtures thereof; and (C) reacting the product of step (B) with a second post-treating agent thereby producing a final post-treated succinimide or succinamide or mixtures thereof, wherein at least one basic nitrogen remains in the final post-treated succinimide or succinamide or mixtures thereof.
  • the composition is prepared by the process which comprises the steps of (A) reacting a polyalkenyl succinic acid or a polyalkenyl succinic anhydride with at least one polyalkylene polyamine, having at least three nitrogen atoms, thereby producing a succinimide or succinamide or mixtures thereof; (B) reacting the product of step (A) with a phthalic anhydride or naphthalic anhydride post-treating agent or mixtures thereof, thereby producing an initial post-treated succinimide or succinamide or mixtures thereof; and (C) reacting the product of step (B) with a cyclic carbonate thereby producing a final post-treated succinimide or succinamide or mixtures thereof, wherein at least one basic nitrogen remains in the final post-treated succinimide or succinamide or mixtures thereof.
  • the polyalkenyl succinic acid or polyalkenyl succinic anhydride is the reaction product of a polyalkenyl reactant and an unsaturated acidic reagent.
  • the polyalkenyl succinic acid or anhydride is formed either by the chlorination reaction process or the thermal reaction process.
  • the polyalkenyl reactant is a polyalkene that can be a polymer of a single type of olefin or it can be a copolymer of two or more types of olefins.
  • the principal sources of the polyalkenyl radical include olefin polymers, particularly polymers made from mono-olefins having from 2 to 30 carbon atoms. Especially useful are the polymers of 1-mono-olefins such as ethylene, propene, 1-butene, and isobutene. Polymers of isobutene are preferred.
  • polyalkenyl in addition to the pure polyalkenyl substituents described above, it is intended that the term "polyalkenyl” as used in this specification and in the claims, include those materials which are substantially polyalkenyl.
  • substantially polyalkenyl means that the polyalkenyl group contains no non-hydrocarbyl substituents or non-carbon atoms which significantly affect the polyalkenyl properties of such polyalkenyl substituents relative to their uses in this invention.
  • a polyalkenyl substituent may contain one or more ether, oxo, nitro, thia, carbohydrocarbyloxy, or other non-hydrocarbyl groups as long as these groups do not significantly affect the polyalkenyl characteristics of the substituent.
  • polyalkenyl substituent of the polyalkenyl succinic compound should be substantially saturated, i.e., at least about 95% of the total number of carbon-to-carbon covalent linkages should be saturated linkages.
  • An excessive proportion of unsaturated linkages render the molecule susceptible to oxidation, deterioration, and polymerization and results in products unsuitable for use in hydrocarbon oils in many appl ications.
  • the size of the polyalkenyl substituent of the succinic compound appears to determine the effectiveness of the additives of this invention in lubricating oils.
  • Olefin polymers i.e., polyalkenes
  • the olefin polymer has a molecular weight of 500 to 5000 are preferred. More preferred, the olefin polymer has a molecular weight of from 700 to 3000. In a preferred embodiment, the olefin polymer has a molecular weight of about 1000. In another preferred embodiment, the olefin has a molecular weigh of about 2300.
  • the most common sources of these polyalkenes are the polyolefins such as polyethylene, polypropylene, polyisobutene, etc. A particularly preferred polyolefin is polyisobutene having a molecular weight from 900 to 2500.
  • unsaturated acidic reagent refers to maleic or fumaric reactants of the general formula: wherein X and X' are the same or different, provided that at least one of X and X' is a group that is capable of reacting to esterify alcohols, form amides, or amine salts with ammonia or amines, form metal salts with reactive metals or basically reacting metal compounds and otherwise function as acylating agents.
  • X and/or X' is --OH, --O-hydrocarbyl, --OM+ where M+ represents one equivalent of a metal, ammonium or amine cation, --NH 2 , --Cl, --Br, and taken together X and X' can be --O-- so as to form an anhydride.
  • X and X' are such that both carboxylic functions can enter into acylation reactions.
  • Maleic anhydride is a preferred unsaturated acidic reactant.
  • Suitable unsaturated acidic reactants include electron-deficient olefins such as monophenyl maleic anhydride; monomethyl, dimethyl, monochloro, monobromo, monofluoro, dichloro and difluoro maleic anhydride, N-phenyl maleimide and other substituted maleimides; isomaleimides; fumaric acid, maleic acid, alkyl hydrogen maleates and fumarates, dialkyl fumarates and maleates, fumaronilic acids and maleanic acids; and maleonitrile, and fumaronitrile.
  • electron-deficient olefins such as monophenyl maleic anhydride; monomethyl, dimethyl, monochloro, monobromo, monofluoro, dichloro and difluoro maleic anhydride, N-phenyl maleimide and other substituted maleimides; isomaleimides; fumaric acid, maleic acid, alkyl hydrogen maleates and fumarates, dialkyl fumarates
  • polyalkenyl succinic acids and anhydrides can be prepared by two different types of reactions or processes.
  • the first type of reaction or process involves either pre-reacting the polyalkene with a halogen, e.g., chlorine, and reacting the halogenated polyalkene with maleic acid or anhydride, or contacting the polyalkene and maleic anhydride or acid in the presence of a halogen, e.g., chlorine.
  • a halogen e.g., chlorine
  • This type of reaction or process is known in the art as the "chlorination" reaction and is described in U.S. Pat. No. 3,172,892, issued Mar. 9, 1965 to LeSuer et al. .
  • the second type of reaction or process which may be used to prepare polyalkenyl succinic anhydrides or acids involves simply contacting the hydrocarbon and the maleic anhydride or acid (in the absence of halogen) at an elevated temperature.
  • This type of reaction or process is known in the art as the thermal reaction.
  • the terms "thermal process” and "thermal reaction” include processes such as that disclosed in U.S. Pat. No. 3,361,673, issued Jan. 2, 1968 to Stuart et al. .
  • U.S. Pat. No. 3,912,764, issued Oct. 14, 1975 to Palmer involves a combination of the thermal and chlorination processes, as by reacting a substantial portion of the hydrocarbon and maleic anhydride or acid by the thermal process and then completing the reaction via a chlorination reaction.
  • an amine is reacted with the polyalkenyl succinic acid or anhydride described herein.
  • the amine is a polyalkylene polyamine, which contains at least two primary amines. More preferred the polyalkylene polyamine compound has at least 3 nitrogen atoms.
  • the polyalkylene polyamine is diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylene pentamine (TEPA), pentaethylenehexamine (PEHA),, heavy polyamine (HPA), or mixtures thereof. Higher molecular weight polyethyleneamines may also be employed.
  • the polyalkylene polyamines may contain branched, cyclic structures or mixtures thereof.
  • the polyalkylene polyamine may be a polyether amine that contains both primary and secondary amines.
  • Both initial and final post-treating agents require a primary or secondary nitrogen site with which to react. After both post-treatment steps, it is preferred that some of the nitrogen atoms are basic nitrogens.
  • the succinimide is post-treated with at a first post-treating agent, thereby producing an initial post-treated succinimide or succinamide or mixtures thereof.
  • the initial post-treated succinimide or succinamide or mixtures thereof is subsequently reacted with a second post-treating agent.
  • the initial post-treated succinimide is prepared by reacting a succinimide with an aromatic carboxylic acid anhydride.
  • the aromatic carboxylic acid anhydrides may be substituted (i.e., methyl, nitro-, hydroxyl groups depending from the aromatic ring).
  • Typical aromatic anhydrides include trimellitic anhydride, phthalic anhydride and naphthalic anhydride.
  • the aromatic anhydride is phthalic anhydride or naphthalic anhydride.
  • the final post-treated succinimide is prepared by reacting the initial post-treated succinimide with second post-treating agent, which preferably is a cyclic carbonate.
  • Typical cyclic carbonates for use in this invention include the following: 1,3-dioxolan-2-one (ethylene carbonate); 4-methyl-1,3-dioxolan-2-one (propylene carbonate); 4-ethyl-1,3-dioxolan-2-one (butylene carbonate); 4-hydroxymethyl-1,3-dioxolan-2-one; 4,5-dimethyl-1,3-dioxolan-2-one; 4-ethyl-1,3-dioxolan-2-one; 4,4-dimethyl-1,3-dioxolan-2-one; 4-methyl-5-ethyl-1,3-dioxolan-2-one; 4,5-diethyl-1,3-dioxolan-2-one; 4,4-diethyl-1,3-dioxolan-2-one; 1,3-dioxan-2-one; 4,4-dimethyl-1,3-dioxan-2-one; 5,5-
  • Suitable cyclic carbonates may be prepared from sacchrides such as sorbitol, glucose, fructose, galactose and the like and from vicinal diols prepared from C 1 -C 30 olefins by methods known in the art.
  • cyclic carbonates are commercially available such as 1,3-dioxolan-2-one or 4-methyl-1,3-dioxolan-2-one.
  • Cyclic carbonates may be readily prepared by known reactions. For example, reaction of phosgene with a suitable alpha alkane diol or an alkan-1,3-diol yields a carbonate for use within the scope of this invention as for instance in U.S. Pat. No. 4,115,206 .
  • the cyclic carbonates useful for this invention may be prepared by transesterification of a suitable alpha alkane diol or an alkan-1,3-diol with, e.g., diethyl carbonate under transesterification conditions. See, for instance, U.S. Pat. Nos. 4,384,115 and 4,423,205 their teaching of the preparation of cyclic carbonates.
  • Typical linear mono-carbonates include diethyl carbonate, dimethyl carbonate, dipropyl carbonate and the like.
  • Typical linear poly-carbonates include poly(propylene carbonate) and the like.
  • Typical aromatic carboxylic anhydrides include 2,3 - pyrazinedicarboxylic anhydride; 2,3 - pydridinedicarboxylic anhydride; 3,4 - pyridinedicarboxylic anhydride; diphenic anhydride; isatoic anhydride; phenyl succinic anhydride; 1- naphthalene acetic anhydride; 1, 2, 4 - benzene tricarboxylic anhydride and the like.
  • Typical aromaticcarboxylic acids include the acids of the aforementioned anhydrides.
  • Typical aromatic carboxylic acid esters include dimethyl phthalate, diethyl phthalate, dimethylhexyl phthalate, mono methylhexyl phthalate, mono ethyl phthalate, and mono methyl phthalate.
  • the second post-treating agent is a cyclic carbonate or a linear monocarbonate.
  • the first post-treating agent is an aromatic carboxylic acid, acid anhydride or ester.
  • the first post-treating agent i.e., phthalic anhydride, or 1,8-naphthalic anhydride
  • the first post-treating agent is added to a reactor containing the succinimide and heated, thereby producing an initial post-treated succinimide.
  • the initial post-treated succinimide is reacted further with a second post-treating agent, such as ethylene-carbonate.
  • a succinimide is prepared by a process comprising charging the polyalkenyl succinic acid or polyalkenyl succinic anhydride in a reactor, optionally under a nitrogen purge, and heating at a temperature of from 80°C to 170°C.
  • a diluent oil may be charged under a nitrogen purge in the same reactor.
  • An amine compound is charged, optionally under a nitrogen purge, to the reactor. This mixture is heated under a nitrogen purge to a temperature in range from 130°C to 200°C.
  • a vacuum is applied to the mixture for 0.5 to 2.0 hours to remove any water formed in the reaction.
  • the succinimide can also be made using a process comprising simultaneously charging all the reactants - the polyalkenyl succinic acid or polyalkenyl succinic anhydride and the amine compound at the desired ratios into the reactor.
  • One or more of the reactants can be charged at an elevated temperature to facilitate mixing and reaction.
  • a static mixer can be used to facilitate mixing of the reactants as they are being charged to the reactor.
  • the reaction is carried out for 0.5 to 2 hours at a temperature from 130°C to 200°C.
  • a vacuum is applied to the reaction mixture during the reaction period to remove any water formed in the reaction.
  • An initial post-treated succinimide is prepared by a process comprising charging the succinimide in a reactor, optionally under a nitrogen purge, and heating at a temperature of from 80°C to 170°C.
  • a diluent oil may be charged under a nitrogen purge in the same reactor.
  • An aromatic carboxylic acid anhydride is charged, optionally under a nitrogen purge, to the reactor. This mixture is heated under a nitrogen purge to a temperature in range from 130°C to 200°C.
  • a vacuum is applied to the mixture for 0.5 to 2.0 hours to remove any water formed in the reaction.
  • An initial post-treated succinimide is formed.
  • a final post-treated succinimide is prepared by a process comprising charging the initial post-treated succinimide in a reactor, optionally under a nitrogen purge, and heating at a temperature of from 80°C to 200°C.
  • a diluent oil may be charged under a nitrogen purge in the same reactor.
  • a cyclic carbonate is charged, optionally under a nitrogen purge, to the reactor, thereby producing a final post-treated succinimide.
  • the final post-treated succinimide described above is generally added to a base oil that is sufficient to lubricate moving parts, for example internal combustion engines, gears, and transmissions.
  • the lubricating oil composition of the present invention comprises a major amount of oil of lubricating viscosity and a minor amount of the lubricating oil additive composition.
  • the base oil employed may be any of a wide variety of oils of lubricating viscosity.
  • the base oil of lubricating viscosity used in such compositions may be mineral oils or synthetic oils.
  • the base oils may be derived from synthetic or natural sources.
  • Mineral oils for use as the base oil in this invention include, for example, paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions.
  • Synthetic oils include, for example, both hydrocarbon synthetic oils and synthetic esters and mixtures thereof having the desired viscosity.
  • Hydrocarbon synthetic oils may include, for example, oils prepared from the polymerization of ethylene, polyalphaolefin or PAO oils, or oils prepared from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gases such as in a Fisher-Tropsch process.
  • Useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C 6 to C 12 alpha olefins such as 1-decene trimer.
  • alkyl benzenes of proper viscosity such as didodecyl benzene, can be used.
  • Useful synthetic esters include the esters of monocarboxylic acids and polycarboxylic acids, as well as mono-hydroxy alkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate, and the like. Complex esters prepared from mixtures of mono and dicarboxylic acids and mono and dihydroxy alkanols can also be used. Blends of mineral oils with synthetic oils are also useful.
  • the base oil can be a refined paraffin type base oil, a refined naphthenic base oil, or a synthetic hydrocarbon or non-hydrocarbon oil of lubricating viscosity.
  • the base oil can also be a mixture of mineral and synthetic oils.
  • Lubricating oil concentrates are also envisioned. These concentrates usually include from 90 wt% to 10 wt%, preferably from 90 wt% to 50 wt%, of an oil of lubricating viscosity and from 10 wt% to 90 wt% of the final post-treated succinimide described herein. Typically, the concentrates contain sufficient diluent to make them easy to handle during shipping and storage. Suitable diluents for the concentrates include any inert diluent, preferably an oil of lubricating viscosity, so that the concentrate may be readily mixed with lubricating oils to prepare lubricating oil compositions.
  • Suitable lubricating oils that may be used as diluents typically have viscosity in the range from 35 to 500 Saybolt Universal Seconds (SUS) at 100 degrees F (38 degrees C), although any oil of lubricating viscosity may be used.
  • SUS Saybolt Universal Seconds
  • the following additive components are examples of some of the components that may be favorably employed in the lubricating oil composition.
  • the final post-treated succinmide of the present invention is added to an oil of lubricating viscosity thereby producing a lubricating oil composition.
  • the final post-treated succinimide, added to an oil of lubricating viscosity, is used in an internal combustion engine, thereby improving dispersancy of soot, sludge and the like.
  • a 1 L reactor was charged with 549.94 g of 1000 MW PIBSA (available from Chevron Oronite, LLC) and 263 g of Chevron RLOP 100N base oil.
  • a distillation head fitted with a condenser and 250 mL round bottom flask was attached to the 1 L reactor.
  • the system was placed under a nitrogen atmosphere and the mixture was heated to 160°C.
  • Diethylenetriamine (41.80 g; available from Sigma-Aldrich) was then added to the mixture over a 30 minute period.
  • the mixture was heated at 160°C for an additional 90 minutes.
  • a vacuum was then applied at ⁇ 0 mm Hg for 30 minutes.
  • the product had the following properties:
  • Phthalic Anhydride Post-Treated Mono-succinimide Derived from 1000 MW PIBSA and DETA (Phthalic Anhydride:PIBSA Charge Mole Ratio of 0.80:1)
  • Example 1 The product of Example 1 was heated to 160°C in the apparatus as described in Example 1 under a nitrogen atmosphere. Phthalic anhydride (53.25 g; available from Sigma-Aldrich) was added over the course of 15 minutes. The reaction mixture was heated at 160°C for an additional 90 minutes. A vacuum was then applied at ⁇ 0 mm Hg for 30 minutes.
  • the product had the following properties:
  • Phthalic Anhydride Post-Treated Mono-succinimide Derived from 1000 MW PIBSA and HPA (Phthalic Anhydride:PIBSA Charge Mole Ratio of 0.80:1)
  • Phthalic Anhydride Post-Treated Mono-succinimide Derived from 2300 MW PIBSA and HPA (Phthalic Anhydride:PIBSA Charge Mole Ratio of 0.80:1)
  • Example 6 A 1 L reactor was charged with 890.44 g of Example 6 and was heated to 160°C under a nitrogen atmosphere. Phthalic anhydride (25.97 g) was added. The reaction mixture was heated at 160°C for an additional 90 minutes. A vacuum was then applied at 10 mm Hg for 30 minutes.
  • the product had the following properties:
  • a 2 L reactor was charged with 1000.9 g of 2300 MW PIBSA (available from Chevron Oronite, LLC). The system was placed under a nitrogen atmosphere and the mixture was heated to 160°C. Heavy polyamine (52.24 g) was then added to the mixture over a 20 minute period. The mixture was heated at 160°C for an additional 60 minutes. Vacuum was then applied ( ⁇ 20 mm Hg (absolute)) for 30 minutes.
  • the product had the following properties:
  • Phthalic Anhydride Post-Treated Mono-succinimide Derived from 2300 MW PIBSA and HPA (Phthalic Anhydride:PIBSA Charge Mole Ratio of 0.60:1)
  • the mono-succinimides and post-treated mono-succinimides from Examples 1-10 were reacted in the soot thickening bench test.
  • 98.0 g of the test sample was weighed and placed into a 250 mL beaker.
  • the test sample contained 8 wt. % based on 50% actives of the test dispersant, 50 millimoles of an overbased phenate detergent, 18 millimoles of a zinc dithiophosphate wear inhibitor and 7.3 wt. % of a VI improver, in 85% 150N oil, 15% 600N oil.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP09835596.9A 2008-12-22 2009-12-15 A lubricating oil additive composition and method of making the same Active EP2379686B1 (en)

Applications Claiming Priority (2)

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US12/341,410 US20100160192A1 (en) 2008-12-22 2008-12-22 lubricating oil additive composition and method of making the same
PCT/US2009/068101 WO2010075103A2 (en) 2008-12-22 2009-12-15 A lubricating oil additive composition and method of making the same

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EP2379686A4 EP2379686A4 (en) 2012-06-20
EP2379686B1 true EP2379686B1 (en) 2013-07-31

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12018225B2 (en) 2020-07-23 2024-06-25 Chevron Oronite Company Llc Succinimide dispersants post-treated with heteroaromatic glycidyl ethers that exhibit good soot handling performance

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120180382A1 (en) * 2011-01-19 2012-07-19 Afton Chemical Corporation Fuel Additives and Gasoline Containing the Additives
US8927469B2 (en) * 2011-08-11 2015-01-06 Afton Chemical Corporation Lubricant compositions containing a functionalized dispersant
WO2014007379A1 (ja) * 2012-07-05 2014-01-09 Ｊｘ日鉱日石エネルギー株式会社 コハク酸イミド化合物、潤滑油添加剤及び潤滑油組成物
JP5876779B2 (ja) * 2012-07-05 2016-03-02 Ｊｘ日鉱日石エネルギー株式会社 コハク酸イミド化合物、潤滑油添加剤及び潤滑油組成物
JP5952660B2 (ja) * 2012-07-05 2016-07-13 Ｊｘエネルギー株式会社 コハク酸イミド化合物、潤滑油添加剤及び潤滑油組成物
CN103075628A (zh) * 2013-01-05 2013-05-01 清华大学 润滑剂、摩擦副及控制摩擦副之间摩擦系数的方法
US9068135B1 (en) * 2014-02-26 2015-06-30 Afton Chemical Corporation Lubricating oil composition and additive therefor having improved piston deposit control and emulsion stability
US9574158B2 (en) * 2014-05-30 2017-02-21 Afton Chemical Corporation Lubricating oil composition and additive therefor having improved wear properties
US20160032213A1 (en) 2014-07-31 2016-02-04 Chevron U.S.A. Inc. Sae 15w-30 lubricating oil composition having improved oxidative stability
US10179886B2 (en) * 2016-05-17 2019-01-15 Afton Chemical Corporation Synergistic dispersants
US20180016515A1 (en) 2016-07-14 2018-01-18 Afton Chemical Corporation Dispersant Viscosity Index Improver-Containing Lubricant Compositions and Methods of Use Thereof
CA3061706A1 (en) * 2017-05-19 2018-11-22 Chevron Oronite Company Llc Dispersants, method of making, and using same
US10822569B2 (en) 2018-02-15 2020-11-03 Afton Chemical Corporation Grafted polymer with soot handling properties
US10851324B2 (en) 2018-02-27 2020-12-01 Afton Chemical Corporation Grafted polymer with soot handling properties
JP7150455B2 (ja) 2018-03-30 2022-10-11 出光興産株式会社 潤滑油用分散剤及びその製造方法、並びに潤滑油組成物
US10899989B2 (en) 2018-10-15 2021-01-26 Afton Chemical Corporation Amino acid grafted polymer with soot handling properties
US11046908B2 (en) * 2019-01-11 2021-06-29 Afton Chemical Corporation Oxazoline modified dispersants
US11008527B2 (en) * 2019-01-18 2021-05-18 Afton Chemical Corporation Engine oils for soot handling and friction reduction
CN111676080A (zh) * 2020-06-23 2020-09-18 新乡市瑞丰新材料股份有限公司 一种新型高效烟炱分散剂的制备方法
JP2023535415A (ja) * 2020-07-23 2023-08-17 シェブロン・オロナイト・カンパニー・エルエルシー 良好な煤処理性能を示す芳香族グリシジルエーテルで後処理されたスクシンイミド分散剤

Family Cites Families (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3100673A (en) * 1963-08-13 Dyeings and prints possessing fastness
US2992708A (en) * 1954-01-14 1961-07-18 Lyon George Albert Air circulating wheel structure
DE1248643B (de) * 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Verfahren zur Herstellung von öllöslichen aeylierten Aminen
NL124842C (zh) * 1959-08-24
NL255194A (zh) * 1959-08-24
NL255193A (zh) * 1959-08-24
US3287271A (en) * 1965-01-21 1966-11-22 Chevron Res Combined detergent-corrosion inhibitors
US3272746A (en) * 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3374174A (en) * 1966-04-12 1968-03-19 Lubrizol Corp Composition
US3692681A (en) * 1968-08-02 1972-09-19 Chevron Res Dispersion of terephthalic acid in detergent containing hydrocarbon oil medium
US3912764A (en) * 1972-09-29 1975-10-14 Cooper Edwin Inc Preparation of alkenyl succinic anhydrides
JPS51130409A (en) * 1975-05-08 1976-11-12 Karonaito Kagaku Kk Lubricating oil composition
US4115206A (en) * 1977-07-21 1978-09-19 Phillips Petroleum Company Separation of phenol-, cyclohexanone-, and cyclohexylbenzene-containing mixtures employing an organic carbonate
US4384115A (en) * 1981-12-14 1983-05-17 The Dow Chemical Company Process for preparing tetrahydro-1,3-oxazin-2-ones
US4423205A (en) * 1982-05-24 1983-12-27 Ethyl Corporation Cationic polymerization of cyclic carbonates
US4612132A (en) * 1984-07-20 1986-09-16 Chevron Research Company Modified succinimides
US4747850A (en) * 1984-07-20 1988-05-31 Chevron Research Company Modified succinimides in fuel composition
FR2586255B1 (fr) * 1985-08-14 1988-04-08 Inst Francais Du Petrole Compositions ameliorees d'additifs dispersants pour huiles lubrifiantes et leur preparation
US5241003A (en) * 1990-05-17 1993-08-31 Ethyl Petroleum Additives, Inc. Ashless dispersants formed from substituted acylating agents and their production and use
US5356552A (en) * 1993-03-09 1994-10-18 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Chlorine-free lubricating oils having modified high molecular weight succinimides
US5334321A (en) * 1993-03-09 1994-08-02 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Modified high molecular weight succinimides
US5716912A (en) * 1996-04-09 1998-02-10 Chevron Chemical Company Polyalkylene succinimides and post-treated derivatives thereof
US5821205A (en) * 1995-12-01 1998-10-13 Chevron Chemical Company Polyalkylene succinimides and post-treated derivatives thereof
US5753597A (en) * 1996-08-20 1998-05-19 Chevron Chemical Company Polymeric dispersants
US5894676A (en) * 1997-04-02 1999-04-20 Digiovanni; Robert Brick laying template
US6255258B1 (en) * 1998-11-04 2001-07-03 Infineum Usa L.P. Dispersant additive
US6214775B1 (en) * 1999-10-13 2001-04-10 Chevron Chemical Company Llc Haze-free post-treated succinimides
US6451920B1 (en) * 1999-11-09 2002-09-17 Chevron Chemical Company Llc Process for making polyalkylene/maleic anhydride copolymer
US6855674B2 (en) * 2000-12-22 2005-02-15 Infineum International Ltd. Hydroxy aromatic Mannich base condensation products and the use thereof as soot dispersants in lubricating oil compositions
US20030224948A1 (en) * 2002-02-14 2003-12-04 Dam Willem Van Lubricating oil additive comprising EC-treated succinimide, borated dispersant and corrosion inhibitor
JP4571776B2 (ja) * 2002-11-05 2010-10-27 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物
CA2496100A1 (en) * 2004-03-10 2005-09-10 Afton Chemical Corporation Power transmission fluids with enhanced extreme pressure characteristics
US20060030498A1 (en) * 2004-08-05 2006-02-09 Hartley Rolfe J Lubricating oil additive concentrates
US8455568B2 (en) * 2008-04-25 2013-06-04 Chevron Oronite Company Llc Lubricating oil additive composition and method of making the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12018225B2 (en) 2020-07-23 2024-06-25 Chevron Oronite Company Llc Succinimide dispersants post-treated with heteroaromatic glycidyl ethers that exhibit good soot handling performance

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EP2379686A2 (en) 2011-10-26
SG172329A1 (en) 2011-07-28
JP5558486B2 (ja) 2014-07-23
CA2747730A1 (en) 2010-07-01
CA2747730C (en) 2016-08-02
WO2010075103A2 (en) 2010-07-01
CN102264879A (zh) 2011-11-30
US20100160192A1 (en) 2010-06-24
EP2379686A4 (en) 2012-06-20
JP2012513495A (ja) 2012-06-14
WO2010075103A3 (en) 2010-10-21

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