EP1469060A1 - Composition polymerique pour les additifs pour lubrifiants - Google Patents

Composition polymerique pour les additifs pour lubrifiants Download PDF

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Publication number
EP1469060A1
EP1469060A1 EP04251893A EP04251893A EP1469060A1 EP 1469060 A1 EP1469060 A1 EP 1469060A1 EP 04251893 A EP04251893 A EP 04251893A EP 04251893 A EP04251893 A EP 04251893A EP 1469060 A1 EP1469060 A1 EP 1469060A1
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EP
European Patent Office
Prior art keywords
composition
polyisobutylene
alkene
substituent
mixtures
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.)
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Application number
EP04251893A
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German (de)
English (en)
Inventor
Renee A. Eveland
Jeffry G. Dietz
Douglas M. Barr
R. Ian Wilby
John K. Pudelski
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Lubrizol Corp
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Lubrizol Corp
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Publication of EP1469060A1 publication Critical patent/EP1469060A1/fr
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    • 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
    • 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
    • C10M2215/28—Amides; Imides
    • 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
    • C10N2020/02—Viscosity; Viscosity index
    • 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

Definitions

  • the present invention relates to an additive composition
  • an additive composition comprising in combination an acylating agent substituted with a polymer of an alkene with 6 to 40 carbon atoms; and an acylating agent substituted with polyisobutylene.
  • the invention may be used in lubricating compositions especially for use in internal combustion engines.
  • dispersants in lubricating oils to disperse soot and decrease the accumulation of sludge.
  • Known dispersants include nitrogen containing derivatives of polyisobutylene-substituted succinic acid and derivatives of polydecene. Neither polyisobutylene-substituted succinic acid nor polydecene derivatives exhibit both good low temperature and high temperature viscometrics.
  • Polyisobutylene-substituted succinic acid based dispersants provide good dispersant properties at high temperature. However, at low temperature, polyisobutylene succinic acid dispersants have poor viscometrics, causing lubricating oils to thicken. To compensate for the poor low temperature viscometrics, viscosity modifiers are added to lubricating oils. The presence of the viscosity modifiers can lead to the potential for soot deposits and the accumulation of sludge.
  • Polydecene-based dispersants are known for good low temperature viscometric properties, specifically kinematic viscosity and dynamic viscosity. However, at high temperature polydecene-based dispersants are less effective than polyisobutylene-substituted succinic acid based dispersants. Furthermore, polydecene is less attractive as a commercial product due to relatively high costs associated with its production.
  • GB Patent 1,439,567 discloses liquid organic compositions with detergent properties by reacting a polymer of a straight chain 1-olefin having at least 10 carbons, with maleic anhydride to form the corresponding polyalkenyl succinic anhydride.
  • the polyalkenyl succinic anhydride is then reacted with an alkylene polyamine to form the corresponding polyalkenyl succinimide.
  • compositions containing hydrocarbyl substituted carboxylic acylating agents made by reacting, (A) one or more alpha-beta olefinically unsaturated carboxylic acid reagents containing 2 to 20 carbon atoms, exclusive of the carboxyl-based groups with (B) one or more high molecular weight olefin polymers of more than 30 carbon atoms selected from the group consisting of (i) interpolymers of C 2-8 mono-1-olefins with C 12 -C 30 mono-olefins, (ii) mixtures of (a) homopolymers and/or interpolymers of C 2-8 mono-1-olefins with (b) homopolymers and/or interpolymers of C 12 -C 30 mono-olefins, and (iii) chlorinated or brominated analogs of (i) or (ii).
  • This invention includes the acylated amine and/or
  • PCT publication 99/46354 discloses the reaction products of maleic anhydride and oligoalkenes obtained through oligomerisation of linear C 8 - to C 12 -1-alkenes.
  • the linear C 8 - to C 12 -1-alkenes contain vinylidene double bond fractions above 30% and have a number average molecular weight from 1000 to 20,000.
  • compositions with dispersancy properties including good high and low temperature viscometrics, capable of improving seal compatability, capable of reducing the amount of volatile oils of lubricating viscosity used and capable of decreasing the accumulation of sludge and/or soot deposits.
  • the present invention provides a composition comprising:
  • the invention further provides a composition comprising:
  • the invention further provides a method for preparing an acylating agent composition, comprising reacting a carboxylic acid reactant with a mixture of an alkene polymer of 6 to about 40 carbon atoms and a polyisobutylene, wherein the weight ratios of the alkene polymer and the polyisobutylene employed are about 25:75 to about 75:25.
  • the invention further provides a method for preparing an acylating agent composition, comprising reacting a carboxylic acid reactant with an alkene polymer of 6 to about 40 carbon atoms, and separately reacting a carboxylic acid reactant with a polyisobutylene, and subsequently combining the reaction products; wherein the weight ratios of the alkene polymer and the polyisobutylene employed are about 25:75 to about 75:25.
  • the invention further provides a method for preparing a dispersant composition, comprising mixing together:
  • the invention further provides a method for lubricating an internal combustion engine, comprising supplying thereto a lubricant comprising the composition as described herein.
  • the present invention further provides a composition capable of providing good high temperature and low temperature viscometrics. It can further lead to a decrease in sludge accumulation and soot deposits. It further provides compositions capable of decreasing the amount of viscosity modifier in lubricating oils. It further provides compositions capable of reducing the amount of volatile oils of lubricating viscosity used and capable of imparting improved seal compatability.
  • composition of the present invention comprises:
  • the weight percent ratio of alkene polymer to polyisobutylene ratio is 30:70 to 70:30, more preferably 35:65 to 65:35, more preferably 40:60 to 60:40 and most preferably 45:55 to 55:45.
  • the alkene comprises carbon atoms ranging from a lower value of carbon atoms of 6, 7, 8, 9 or 10; and an upper value of 40, 30, 20, 18, 16, 14 or 11 carbon atoms, or any combinations of lower and higher values, e.g., 6-40, 6-20, 6-11, 8-40, 8-20, or 8-11.
  • composition comprises:
  • the alkene polymer with 6 to 11 carbons atoms and the polyisobutylene are present in a weight ratio of 10:90 to 90:10, more preferably, 20:80 to 80:20, more preferably 25:75 to 75 to 25, even more preferably 30:70 to 70:30, even more preferably 35:65 to 65:35, even more preferably 40:60 to 60:40 and most preferably 45:55 to 55:45.
  • the polyalkene preferably contains a vinylidene double bond.
  • the fraction of polyalkene molecules containing the vinylidene double bond is at least 25%, more preferably at least 30%, even more preferably at least 45%, even more preferably at least 55% and most preferably at least 70%.
  • alkenes include monomers selected from the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-henicosene, 1-docosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-octacosene, 1-nonacosene and mixtures thereof.
  • a preferred alkene is 1-decene.
  • Polyisobutylene is derived from isobutylene. It preferably contains a vinylidene double bond. Preferably the fraction of polyisobutylene molecules containing a vinylidene double bond is at least 25%, more preferably at least 30%, even more preferably at least 45%, even more preferably at least 55% and most preferably at least 70%.
  • the number average molecular weight of the substituents (a) and (b) of the invention can be controlled using a variety of techniques such as reaction temperature, initiators, monomer concentration and type of chain transfer agent.
  • the number average molecular weight of the substituents of each (a) and (b) is preferably 350 to 25,000, more preferably 500 to 15,000, and most preferably 1,000 to 5,000.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include:
  • the acylating agents include monobasic or polybasic carboxylic acids or reactive equivalents thereof.
  • Reactive equivalents of carboxylic acids include anhydrides, esters, acylated nitrogen, acyl halide, nitriles, metal salts or mixtures thereof.
  • anhydrides, particularly of diacids are preferred.
  • Monobasic carboxylic acids include those represented by the formula: wherein R 1 is hydrogen or hydrocarbyl containing 1 to 20, preferably 1 to 10, more preferably 1 to 5 and most preferably 1 to 2 carbon atoms; and R 2 is hydrogen or alkyl with 1 to 6, preferably 1 to 4 and most preferably 1 to 2 carbon atoms.
  • Monobasic carboxylic acids and derivatives thereof include (meth)acrylic acid, cinnamic acid, crotonic acid, 3-phenylpropenoic acid, ⁇ , ⁇ -decenoic acid, glyoxylic acid and mixtures thereof.
  • (meth)acrylic is intended to encompass both acrylic and methacrylic.
  • Dibasic carboxylic acids and derivatives thereof include fumaric acid, maleic acid, mesaconic acid, itaconic acid, and citraconic acid.
  • the derivative of a dibasic carboxylic acid is maleic anhydride.
  • the carboxylic acid includes glyoxylic acid or an ester thereof, or the hemiacetals of any of them.
  • a preferred class of glyoxylic acid derivatives are glyoxylic acid esters.
  • suitable glyoxylic acid esters include methyl glyoxylate, ethyl glyoxylate, n-propyl glyoxylate, isopropyl glyoxylate, n-butyl glyoxylate, isobutyl glyoxylate, pentyl glyoxylate, hexyl glyoxylate, heptyl glyoxylate, octyl glyoxylate, nonyl glyoxylate, decyl glyoxylate, undecyl glyoxylate, dodecyl glyoxylate, tridecyl glyoxylate, tetradecyl glyoxylate, pentadecyl glyoxylate,
  • Preferred acylating agents are selected from the group consisting of maleic acid, maleic anhydride, (meth) acrylic acid, itaconic acid, fumaric acid, glyoxylic acid and mixtures thereof.
  • composition comprises the reaction product of:
  • compositions of the invention can be prepared using the following methods:
  • Amines suitable for reacting with the mixture (a) and (b) include monoamines and polyamines, preferably polyamines.
  • the polyamines may be linear or branched and are selected from the group consisting of alkylenepolyamine, cycloaliphatic polyamine, heterocyclic polyamines and mixtures thereof.
  • the alkylenepolyamines are selected from the group consisting of ethylenepolyamines, propylenepolyamines, butylenepolyamines and mixtures thereof.
  • propylenepolyamines include propylenediamine, dipropylenetriamine or mixtures thereof.
  • Ethylenepolyamines are preferred and specific compounds include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms and so-called "heavy amines" such as HPA-XTM from Union Carbide and E-100TM from Dow, and mixtures thereof.
  • the polyamines are ⁇ , ⁇ -diaminoalkanes.
  • Suitable ⁇ , ⁇ -diaminoalkanes include diaminopropanes, diaminobutanes or mixtures thereof.
  • Specific diaminoalkanes are selected from the group consisting of N-(2-aminoethyl)-1,3-propane diamine, 3,3'-diamine-N-methyldipropylamine, tris(2-amino-ethyl)amine, N,N-bis(3-aminopropyl)-1,3-propane diamine, N,N'-1,2-ethanediylbis-(1,3-propane diamine) and mixtures thereof.
  • polyamines include di-(trimethylene)triamine, piperazine, diaminocyclohexanes and mixtures thereof.
  • Alcohols suitable for reacting with the mixture (a) and (b) include monohydric and polyhydric alcohols.
  • Polyhydric alcohols are preferred with 2 to 10, preferably 2 to 6 hydroxy groups.
  • the alcohols can be aliphatic, cycloaliphatic, aromatic, or heterocyclic.
  • Suitable alcohols include dihydroxypropanes, dihydroxybutanes, dihydroxy-pentanes, glycerine, trihydroxypropanes, trihydroxybutanes, trihydroxypentanes and mixtures thereof.
  • the preferred alcohol is a polyol.
  • Suitable polyols include ethylene glycol, propylene glycol, butylene glycol, pentaerthyritol, mannitol, sorbitol, glycerol, erythritol, 2-hydroxymethyl-2-methyl-1,3-propanediol (trimethylolethane), 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (trimethylolpropane), 1,2,4-hexanetriol and mixtures thereof.
  • Aminoalcohols suitable for the invention contain 1 to 6 and preferably 1 to 3 hydroxy groups; and 1 to 8 and preferably 1 to 2 amine groups.
  • the aminoalcohols of the invention can be selected from the group consisting of ethanolamine, isopropanolamine, diethanolamine, triethanolamine, diethylethanolamine, dimethylethanolamine, dibutylethanolamine, 3-amino-1,2-propanediol; serinol; 2-amino-2-methyl-1,3-propanediol; tris(hydroxymethyl)-aminomethane; 1-amino-1-deoxy-D-sorbitol; diethanol amine; diisopropanolamine; N-methyl-N,N-diethanol amine; triethanolamine; N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene-diamine, 2-amino-2-methyl-1-propanol, 2-dimethylamino-methyl-1-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propan
  • composition of the present invention can be added to an oil of lubricating viscosity.
  • oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined and re-refined oils, and mixtures thereof.
  • Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
  • Purification techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like.
  • Re-refined oils are also known as reclaimed or reprocessed oils, and are obtained by processes similar to those used to obtain refined oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
  • Natural oils useful in making the inventive lubricants include animal oils, vegetable oils (e.g., castor oil, lard oil), mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
  • animal oils e.g., castor oil, lard oil
  • mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
  • Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerised and interpolymerised olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(1-hexenes), poly(1-octenes), poly(1-decenes), and mixtures thereof; alkyl-benzenes (e.g.
  • dodecylbenzenes dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); alkylated diphenyl ethers and alkylated diphenyl sulphides and the derivatives, analogs and homologs thereof and mixtures thereof.
  • Polyalphaolefins are typically hydrogenated when used as lubricating oils.
  • synthetic lubricating oils include but are not limited to liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), and polymeric tetrahydrofurans.
  • Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes.
  • Oils of lubricating viscosity can also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
  • the five base oil groups are as follows: Group I (sulphur content >0.03 wt %, and/or ⁇ 90 wt % saturates, viscosity index 80-120); Group II (sulphur content ⁇ 0.03 wt %, and ⁇ 90 wt % saturates, viscosity index 80-120); Group III (sulphur content ⁇ 0.03 wt %, and ⁇ 90 wt % saturates, viscosity index ⁇ 120); Group IV (all polyalphaolefins (PAOs)); and Group V (all others not included in Groups I, II, III, or IV).
  • the oil of lubricating viscosity is selected from an API Group II, Group III, Group IV, Group V oil and mixtures thereof.
  • the oil of lubricating viscosity is typically present at 30 to 99.9, preferably 55 to 99, and more preferably 65 to 96 and most preferably 73 to 95 weight percent of the lubricating oil composition.
  • compositions of the invention can be present in an oil of lubricating viscosity in amounts of 0.1 to 30, preferably 0.5 to 20, more preferably 1 to 15, and most preferably 5 to 12 weight percent of the lubricating oil composition.
  • the present invention is in the form of a concentrate (which can be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of each of the above-mentioned dispersant, as well as other components, to diluent oil is typically in the range of 99:1 to 10:90 by weight.
  • the lubricating composition can include additives selected from the group consisting of antioxidants, metal deactivators, detergents, antiwear agents, dispersants, antiscuffing agents, extreme pressure agents, foam inhibitors, demulsifiers, viscosity modifiers, pour point depressants and mixtures thereof.
  • the total combined amount of the optional additives present can be 0 to 40, preferably 0.5 to 25, more preferably 3 to 20 and most preferably 5 to 15 weight percent of the lubricating oil composition.
  • Antioxidants include hindered phenols represented by the formula: wherein R 3 and R 4 are independently branched or linear alkyl groups containing about 1 to 24, preferably 4 to 18, and most preferably 4 to 12 carbon atoms. R 3 and R 4 can be either straight or branched chain; branched is preferred. Preferably the phenol is butyl substituted containing two t-butyl groups. When the t-butyl groups occupy the 2,6-positions, the phenol is sterically hindered.
  • Q is hydrogen or hydrocarbyl. Examples of suitable hydrocarbyl groups include 2-ethylhexyl, n-butyl, dodecyl or mixtures thereof.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are either straight or branched chain and contain 4 to 18, preferably 4 to 12 carbon atoms.
  • the phenol is butyl substituted.
  • R 11 and R 12 are independently hydrogen or hydrocarbyl; preferably R 11 and R 12 are arylalkyl or alkyl groups.
  • the alkyl groups can be linear or branched, linear being preferred.
  • R 11 and R 12 are preferably in the para position.
  • the arylalkyl or alkyl groups typically contain 1 to 15, preferably 1 to 10, and more preferably 1 to 5 carbon atoms.
  • the bridging group Y includes -CH 2 - (methylene bridge) or -CH 2 OCH 2 - (ether bridge).
  • Examples of methylene-bridged sterically hindered phenols include 4,4'-methylene-bis-(6-tert-butyl o-cresol), 4,4 -methylene-bis-(2-tert-amyl-o-cresol), 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), 4,4-methylene-bis-(2,6-di-tertbutyl-phenol) and mixtures thereof.
  • the antioxidant is a hindered ester-substituted phenol represented by the formula: wherein R 13 , R 14 and R 15 are straight or branched alkyl group containing 2 to 22, preferably 2 to 18, more preferably 4 to 8 carbon atoms. Specific examples include of alkyl groups include 2-ethylhexyl or n-butyl ester, dodecyl and mixtures thereof.
  • alkylated diphenylamines that can be represented by the following formula: wherein R 16 and R 17 are independently hydrogen or hydrocarbyl, preferably arylalkyl or alkyl groups.
  • the arylalkyl groups contain 5 to 20, preferably 6 to 10 carbons atoms.
  • the alkyl groups can be linear or branched, preferably linear; the alkyl group contains 1 to 24, preferably 2 to 18 and most preferably 4 to 12 carbon atoms; and z is independently 0, 1, 2, or 3, provided that at least one aromatic ring contains a hydrocarbyl group.
  • Preferred alkylated diphenylamines include bis-nonylated diphenylamine and bis-octylated diphenylamine and mixtures thereof.
  • Metal deactivators can be used to neutralise the catalytic effect of metal for promoting oxidation in lubricating oil.
  • metal deactivators include derivatives of benzotriazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, 2-alkyl-dithiobenzothiazoles, 2-(N,N-dialkyldithiocarbamoyl)benzothiazoles, 2,5-bis(alkyl-dithio)-1,3,4-thiadiazoles, 2,5-bis(N,N-dialkyldithiocarbamoyl)-1,3,4-thiadiazoles, 2-alkyldithio-5-mercapto thiadiazoles and mixtures thereof.
  • the metal deactivator is a hydrocarbyl substituted benzotriazole compound.
  • the benzotriazole compounds can include hydrocarbyl substitutions in at least one of the following ring positions 1- or 2- or 4- or 5- or 6- or 7-.
  • the hydrocarbyl groups contain about 1 to about 30, preferably about 1 to about 15, more preferably about 1 to about 7 carbon atoms, most preferably the metal deactivator is 5-methylbenzotriazole, which may be used alone or in combination.
  • Detergents include neutral or overbased, carbonated or non-carbonated Newtonian or non-Newtonian, basic salts of alkali, alkaline earth and transition metals with one or more hydrocarbyl sulphonic acid, carboxylic acid, phosphorus acid, mono- and/or di- thiophosphorus acid, alkyl phenol, sulphur coupled alkyl phenol compounds, salixarates, saligenins or mixtures thereof.
  • Commonly used metals are sodium, potassium, calcium, magnesium, lithium or mixtures thereof. Most commonly used metals include sodium, magnesium, calcium and mixtures thereof.
  • Overbased detergents are disclosed for instance in US Patent 3,629,109.
  • Dispersants are often known as ashless-type dispersants because, prior to mixing in a lubricating oil composition, they do not contain ash-forming metals; and they do not normally contribute any ash forming metals when added to a lubricant.
  • Ashless type dispersants are characterised by a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimide with number average molecular weight in the range 350 to 5000, preferably 500 to 3000.
  • Succinimide dispersants and their preparation are disclosed, for instance, in US Patent 4,234,435.
  • the lubricant may additionally contain an antiwear agent.
  • antiwear agents include metal thiophosphates, especially zinc dialkyldithiophosphates; phosphoric acid esters or salt thereof; phosphites; and phosphorus-containing carboxylic esters, ethers, and amides.
  • the lubricant may also contain an antiscuffing agent.
  • Antiscuffing agents that decrease adhesive wear are often sulphur containing compounds.
  • the sulphur containing compounds include organic sulphides and polysulphides, such as benzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl tetrasulphide, di-tertiary butyl polysulphide, sulphurised sperm oil, sulphurised methyl ester of oleic acid, sulphurised alkylphenol, sulphurised dipentene, sulphurised terpene, sulphurised Diels-Alder adducts, alkyl sulphenyl N'N-dialkyl dithiocarbamates, the reaction product of polyamines with polybasic acid esters, chlorobutyl esters of 2,3-dibromo-propoxyisobutyric acid, acetoxymethyl
  • EP agents include compounds selected from the group consisting of chlorinated wax, organic sulphides and polysulphides, such as benzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl tetrasulphide, sulphurised sperm oil, sulphurised methyl ester of oleic acid, sulphurised alkylphenol, sulphurised dipentene, sulphurised terpene, and sulphurised Diels-Alder adducts; phosphosulphurised hydrocarbons, such as the reaction product of phosphorus sulphide with turpentine or methyl oleate, phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g.
  • Foam inhibitors are known and include organic silicones such as polyacetates, dimethyl silicone, polysiloxanes, polyacrylates or mixtures thereof.
  • foam inhibitors include polyethylacrylate, poly-2-ethylhexylacrylate, polyvinylacetate and mixtures thereof.
  • Demulsifiers are known and include derivatives of propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkyl amines, amino alcohols, diamines or polyamines reacted sequentially with ethylene oxide or substituted ethylene oxides or mixtures thereof.
  • demulsifiers include polyethylene glycols, poly(ethyleneoxides), poly(propylene oxides), (ethylene oxide-propylene oxide) polymers and mixtures thereof.
  • Pour point depressants include esters of maleic anhydride-styrene copolymers, polymethacrylates; polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkylfumarates, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers, alkyl phenol formaldehyde condensation resins, alkyl vinyl ethers and mixtures thereof.
  • Viscosity modifiers include copolymers of styrene-butadiene rubbers, ethylene-propylene polymers, polyisobutenes, hydrogenated styreneisoprene polymers, hydrogenated radical isoprene polymers, polymethacrylate acid esters, polyacrylate acid esters, polyalkyl styrenes, alkenyl aryl conjugated diene copolymers, polyolefins, polyalkylmethacrylates, esters of maleic anhydride-styrene copolymers or mixtures thereof.
  • compositions of the present invention are useful as additives in greases, gear oils, industrial fluids, hydraulic fluids, transmission fluids, turbine oils, circulating oils, and engine oils. They are particularly useful in lubricants for internal combustion engines, such as diesel fuelled engines or gasoline fuelled engines. Such engines can be lubricated by supplying thereto a lubricating oil composition comprising the components as described above.
  • lubricating oil compositions of the invention in internal combustion engines will typically exhibit at least one improved property selected from the group consisting of good high temperature viscometrics, low temperature viscometrics, decrease in sludge accumulation, decrease in soot deposits, improved seal compatability, reduced amount of volatile oils of lubricating viscosity and a decrease in amount of viscosity modifier required, and improved seal compatability.
  • Improved seal compatibility can be revealed by improved tensile strength, improved elongation strength and decreased hardness.
  • Mixtures of polydecene (obtained from BP Amoco) with number average molecular weight of 1656 and high vinylidene polyisobutylene with number average molecular weight of 1510 are reacted with maleic anhydride.
  • the mixtures of high vinylidene polydecene and high vinylidene polyisobutylene contain approximately 1600g of sample with weight ratios of polydecene: polyisobutylene of 1600:0, 1200:400, 800:800, 400:1200 and 0:1600 and are reacted with approximately 213.9g of maleic anhydride.
  • the reactants are heated to 203°C over 3 1/2 hours and held at this temperature for twenty-four hours.
  • the product of the reaction is then heated to 210°C for one hour under vacuum at 0.67 kPa (5mm Hg) to remove volatiles.
  • the dispersant is dissolved in a 5W-30 lubricating oil prepared containing 68.9 weight percent of YubaseTM 3050 API Group 3 base oil, 5 mm 2 s -1 (cSt) at 100°C and 31.1 weight percent of PAO-6 Group 4 base oil, 6 mm 2 s -1 (cSt) at 100°C.
  • Reference examples 1 and 2 contain 100wt % of polyisobutylene succinimide and 100wt % of polydecene succinimide respectively.
  • Examples 1 to 3 contain polyisobutylene succinimide: polydecene succinimide weight percent ratios of 25:75, 50:50 and 75:25 respectively.
  • lubricating oil composition contains a 50:50 mixture of the polyisobutylene: polydecene dispersant.
  • Reference examples R5 to R8 contain 7 to 10 wt% of a polyisobutylene dispersant in 5W-30 grade lubricating oil compositions containing 56 weight percent of API Group 4, PAO-4 base oil, 4 mm 2 s -1 (cSt) at 100°C, 30 weight percent of API Group 4, PAO-6 base oil, 6 mm 2 s -1 (cSt) at 100°C and 13.6 weight percent of PL 3970 API Group 5 base oil, 4.5 mm 2 s -1 (cSt) at 100°C.
  • seal properties such as tensile strength, elongation and hardness are improved when compositions containing a weight percent ratio of polydecene to polyisobutylene 25:75 to 75:25 are used.
  • dispersants of the invention provide improved seal properties compared with conventional dispersants.
  • a dispersant sample is dissolved in Exxon 100N diluent oil at six concentrations between 0.125 wt% and 0.004 wt% and mixed with a sludge sample. The resulting mixture is allowed to stand for 24 hours. The amount of sludge remaining in solution at the lowest concentration of dispersant is measured.
  • the sludge ratio is calculated by dividing the amount of sludge by the weight percent of the dispersant used. The higher the sludge ratio indicates a lower concentration of dispersant is better able to keep the sludge in solution.
  • the results obtained for examples 1 to 3 and comparative examples 1 and 2 are: Example Mixture Sludge Ratio Wt % Polydecene Wt % Polyisobutylene R3 0 100 225 4 25 75 225 5 50 50 175 6 75 25 125 R4 100 0 63
  • compositions with weight percent ratios of polydecene to polyisobutylene between 25:75 and 75:25 have good dispersancy properties. Furthermore, better results are obtained when the polydecene to polyisobutylene is between 25:75 and 50:50.
  • the KV100 (kinematic viscosity) value is determined by measuring the time for 40g of oil to flow under gravity through a calibrated glass capillary viscometer.
  • Examples 4-6 and comparative examples R3-R4 demonstrate the high temperature viscometrics for compositions of the invention with a dispersant treat rate held at 9wt %. The results obtained are: Example Mixture Wt % Polydecene Wt% Polyisobutylene KV100°C R3 0 100 13.10 4 25 75 12.73 5 50 50 12.01 6 75 25 11.69 R4 100 0 11.01

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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)
EP04251893A 2003-04-04 2004-03-30 Composition polymerique pour les additifs pour lubrifiants Withdrawn EP1469060A1 (fr)

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US407742 1995-03-21
US10/407,742 US20040198613A1 (en) 2003-04-04 2003-04-04 Polymer composition for lubricant additives

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009135876A1 (fr) * 2008-05-07 2009-11-12 Basf Se COPOLYMÈRES BISÉQUENCÉS α-OLÉFINE/ISOBUTÈNE
WO2010031984A1 (fr) * 2008-09-22 2010-03-25 Arkema France Polyolefine issue de ressources renouvelables et son procede de fabrication
EP3894526A1 (fr) * 2018-12-10 2021-10-20 The Lubrizol Corporation Compositions lubrifiantes comprenant un mélange d'additifs dispersants

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10604719B2 (en) * 2018-02-22 2020-03-31 Chevron Japan Ltd. Lubricating oils for automatic transmissions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4489194A (en) * 1982-08-09 1984-12-18 The Lubrizol Corporation Carboxylic acylating agents substituted with olefin polymers of high/low molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
US4693838A (en) * 1985-10-29 1987-09-15 Exxon Chemical Patents Inc. Multifunctional viscosity index improver
EP0778333A2 (fr) * 1995-11-09 1997-06-11 The Lubrizol Corporation Compositions comprenant des composés carboxyliques, leur dérivés, et des lubrifiants, des fuels et des concentrés les contenant
WO2001000688A1 (fr) * 1999-06-24 2001-01-04 The Lubrizol Corporation Produits dispersants prepares a partir de polymeres d'olefine a polydispersite elevee
US20030018198A1 (en) * 1999-12-27 2003-01-23 Hiroaki Koshima Succinimide compounds and use thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4566983A (en) * 1982-08-09 1986-01-28 The Lubrizol Corporation Combination of carboxylic acylating agents substituted with olefin polymers of high and low molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
US4596663A (en) * 1982-08-09 1986-06-24 The Lubrizol Corporation Carboxylic acylating agents substituted with olefin polymers of high molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
CA1262721A (fr) * 1985-07-11 1989-11-07 Jacob Emert Additifs-dispersants solubles dans l'huile, utiles dans des compositions oleagineuses
US5670081A (en) * 1993-12-08 1997-09-23 The Lubrizol Corporation Salt compositions and functional fluids using same
US6077909A (en) * 1997-02-13 2000-06-20 The Lubrizol Corporation Low chlorine content compositions for use in lubricants and fuels
US5912213A (en) * 1997-06-05 1999-06-15 The Lubrizol Corporation Substituted carboxylic acylating agent compositions and derivatives thereof for use in lubricants and fuels
EP0933416A1 (fr) * 1998-01-30 1999-08-04 Chevron Chemical S.A. Utilisation de poly alpha oléfines (PAO) de 1-docecène ou 1-tetradecène pour améliorer la stabilité thermique d'huile de moteur dans un moteur à combustion interne

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4489194A (en) * 1982-08-09 1984-12-18 The Lubrizol Corporation Carboxylic acylating agents substituted with olefin polymers of high/low molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
US4693838A (en) * 1985-10-29 1987-09-15 Exxon Chemical Patents Inc. Multifunctional viscosity index improver
EP0778333A2 (fr) * 1995-11-09 1997-06-11 The Lubrizol Corporation Compositions comprenant des composés carboxyliques, leur dérivés, et des lubrifiants, des fuels et des concentrés les contenant
WO2001000688A1 (fr) * 1999-06-24 2001-01-04 The Lubrizol Corporation Produits dispersants prepares a partir de polymeres d'olefine a polydispersite elevee
US20030018198A1 (en) * 1999-12-27 2003-01-23 Hiroaki Koshima Succinimide compounds and use thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009135876A1 (fr) * 2008-05-07 2009-11-12 Basf Se COPOLYMÈRES BISÉQUENCÉS α-OLÉFINE/ISOBUTÈNE
US8357829B2 (en) 2008-05-07 2013-01-22 Basf Se α-olefin/isobutene diblock copolymers
CN102015798B (zh) * 2008-05-07 2014-03-05 巴斯夫欧洲公司 α-烯烃/异丁烯二嵌段共聚物
WO2010031984A1 (fr) * 2008-09-22 2010-03-25 Arkema France Polyolefine issue de ressources renouvelables et son procede de fabrication
FR2936249A1 (fr) * 2008-09-22 2010-03-26 Arkema France Polyolefine issue de ressources renouvelables et son procede de fabrication
EP3894526A1 (fr) * 2018-12-10 2021-10-20 The Lubrizol Corporation Compositions lubrifiantes comprenant un mélange d'additifs dispersants

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