EP0663436B1 - Dispersants pour huile lubrifiante - Google Patents

Dispersants pour huile lubrifiante Download PDF

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Publication number
EP0663436B1
EP0663436B1 EP95300225A EP95300225A EP0663436B1 EP 0663436 B1 EP0663436 B1 EP 0663436B1 EP 95300225 A EP95300225 A EP 95300225A EP 95300225 A EP95300225 A EP 95300225A EP 0663436 B1 EP0663436 B1 EP 0663436B1
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EP
European Patent Office
Prior art keywords
oil
product
weight
inhibitor
composition according
Prior art date
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Expired - Lifetime
Application number
EP95300225A
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German (de)
English (en)
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EP0663436A1 (fr
Inventor
Susan M. Nicholson
Mark Rees
C. Thomas West
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Afton Chemical Ltd
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Afton Chemical Ltd
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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
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
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    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • 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
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    • C10M2207/287—Partial esters
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    • 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
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Definitions

  • This invention relates to new and highly useful dispersants for use as additives to natural and synthetic lubricating oils. More particularly this invention relates to novel dispersant compositions that have reduced reactivity toward fluoroelastomers coupled with effective dispersancy, especially for engine oils for either spark-ignition passenger car service or heavy duty diesel engine service.
  • a continuing problem in the art of lubrication is to provide lubricant compositions which satisfy the demands imposed upon them by the original equipment manufacturers.
  • One such requirement is that the lubricant satisfy one or more tests for fluoroelastomer degradation under specified laboratory test conditions.
  • the commercial reality is that if the lubricant is unable to pass the applicable test or tests, it is unlikely to meet acceptance in the marketplace.
  • Standard test methods for evaluating fluoroelastomer compatibility of lubricant compositions include the Volkswagen PV 3334 Seal Test and the CCMC Viton Seal Test (CEC L-39-T-87 Oil/Elastomer Compatibility Test).
  • This invention is deemed to fulfill the foregoing need in an effective and efficient manner.
  • the dispersant compositions of this invention are deemed to fulfill these requirements as they exhibit little antagonism toward fluoroelastomers and most if not all are capable of achieving passing results in one or more of the foregoing test procedures.
  • the dispersants make possible highly effective control of sludge, varnish and wear under various types of engine service.
  • an oil-soluble dispersant composition which comprises:
  • Another embodiment of this invention is a composition which comprises from 1 to 99 wt% of at least one oil of lubricating viscosity and from 99 to 1 wt% of a combination of the above components a) and b), proportioned as above.
  • Still another embodiment is an additive concentrate formulated for use as a crankcase lubricating oil additive (also known as a DI-pack) which comprises the above components a) and b), proportioned as above; c) at least one oil-soluble metal dihydrocarbyl dithiophosphate (preferably one or more zinc dialkyl dithiophosphate antiwear/extreme pressure agents); d) at least one alkali or alkaline earth metal-containing detergent (e.g., an alkali or alkaline earth metal sulfonate, carboxylate, salicylate, or sulfurized alkylphenate, or combination of two or more of such detergents); and e) one or more inhibitors selected from oxidation inhibitor(s), foam inhibitor(s), rust inhibitors), corrosion inhibitor(s) and friction inhibitor(s); wherein components a), b), c), d) and e) are proportioned in the additive concentrate such that blending a minor amount of the additive concentrate in a base oil (e.g., at a
  • a minor dispersing amount of a) plus b) in the finished lubricating oil is typically in the range of 2 to 5.5 wt% with the proviso that the level of nitrogen from b) in the finished lubricating oil does not exceed 0.042 wt%.
  • a minor wear-inhibiting amount of c) in the finished lubricating oil is typically in the range of 0.5 to 1.25 wt%, and when the wear inhibitor is in the form of a phosphorus-containing product, a minor wear-inhibiting amount is typically equivalent to a phosphorus content in the finished lubricating oil in the range of 0.04 to 0.12 wt% of phosphorus.
  • a minor detergent amount of d) in the finished lubricating oil is typically in the range of 0.5 to 3.5 wt%
  • a minor oxidation inhibiting amount of oxidation inhibitor in the finished lubricating oil is typically in the range of 0.2 to 3 wt%
  • a minor foam inhibiting amount of foam inhibitor in the finished lubricating oil is typically in the range of 0.0002 to 0.001 wt%
  • a minor rust inhibiting amount of rust inhibitor in the finished lubricating oil is typically in the range of 0.01 to 0.4 wt%
  • a minor corrosion inhibiting amount of corrosion inhibitor in the finished lubricating oil is typically in the range of 0.01 to 0.4 wt%
  • a minor friction inhibiting amount of friction inhibitor in the finished lubricating oil is typically in the range of 0.02 to 2 wt%.
  • the respective components a), b), c), and d), and each of the selected components of e) can be a single component or it can be a
  • a further embodiment provides a finished lubricating oil composition which comprises a major amount of at least one oil of lubricating viscosity; a minor dispersant amount of a) plus b) proportioned as above; a minor wear-inhibiting amount of c); a minor detergent amount of d); and at least one inhibitor of e), e.g., optionally, but preferably, a minor oxidation inhibiting amount of at least one oxidation inhibitor; optionally, but preferably, a minor foam inhibiting amount of foam inhibitor; optionally, a minor friction inhibiting amount of friction inhibitor; optionally, a minor rust inhibiting amount of rust inhibitor; and optionally, a minor corrosion inhibiting amount of corrosion inhibitor.
  • a minor lubricating oil composition which comprises a major amount of at least one oil of lubricating viscosity; a minor dispersant amount of a) plus b) proportioned as above; a minor wear-inhibiting amount of c); a minor detergent amount of d
  • the finished lubricating oil composition preferably additionally contains a minor viscosity improving amount of at least one viscosity index improver.
  • this invention provides lubricant compositions comprising oil of lubricating viscosity and one or more, and preferably all, of the following components: viscosity index improver, metal (most preferably zinc) dialkyl dithiophosphate, alkali or alkaline earth metal detergent (preferably sulfonate, sulfurized phenate and/or salicylate), antioxidant (preferably phenolic, aromatic amine, sulfurized olefin or copper-based), and antifoam agent (preferably silicone-based).
  • metal most preferably zinc dialkyl dithiophosphate
  • alkali or alkaline earth metal detergent preferably sulfonate, sulfurized phenate and/or salicylate
  • antioxidant preferably phenolic, aromatic amine, sulfurized olefin or copper-based
  • antifoam agent preferably silicone-based
  • Still another embodiment involves the use of components a) and b), proportioned as above, in minor amount in oil of lubricating viscosity to provide dispersancy and to minimize degradation of fluoroelastomers that are in contact with the oil either during additive qualification tests or during use under actual service conditions.
  • component a) thereof be a borated component, i.e., the product thereof is heated with a boron compound or other suitable boron source at a temperature high enough to form a product having a boron content in the range of up to about 1 wt%, excluding the weight of solvent and/or diluent, if any, that may be associated with said product.
  • the base oils used in forming the lubricant compositions of this invention can be natural or synthetic oils of lubricating viscosity, or suitable blends thereof.
  • the base oils can be hydrocarbon oils derived from petroleum (or tar sands, coal, shale, etc.).
  • the base oils can be or include 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; and the like. Mixtures of mineral, natural and/or synthetic oils in any suitable proportions are also useable.
  • natural oils of suitable viscosities such as rapeseed oil, etc.
  • 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;
  • the base oil is preferably a petroleum-derived mineral oil of the type and viscosity suitable for use in forming a passenger car engine oil, a heavy duty diesel engine oil, or a drivetrain lubricant.
  • AG dispersant is used to designate a product made by reacting aminoguanidine or a basic salt thereof with a hydrocarbyl-substituted succinic acid or anhydride in a mole ratio of from 0.4 to 1.3 moles of the aminoguanidine or basic salt thereof per mole of the succinic acid or anhydride compound.
  • borated AG dispersant is used to designate a product made in two stages, namely, (i) reacting aminoguanidine or a basic salt thereof with a hydrocarbyl-substituted succinic acid or anhydride in a mole ratio of from 0.4 to 1.3 moles of the aminoguanidine or basic salt thereof per mole of the succinic acid or anhydride compound; and (ii) borating the product so produced.
  • a suitably proportioned mixture of an aliphatic hydrocarbyl-substituted succinic acid derivative (acid, anhydride, lower alkyl ester, or acyl halide) and aminoguanidine or a basic salt thereof is heated, preferably under an inert atmosphere, at a temperature in the range of 80 to 200°C, and preferably in the range of 140 to 200°C, with temperatures in the range 160 to 170°C being most preferred.
  • the reaction can be conducted in the presence or absence of a solvent or reaction diluent.
  • alkenyl succinic acylating agents in which the alkenyl substituent is derived from a polyolefin of lower molecular weight (e.g., a GPC number average molecular weight of 1300), it is preferred to conduct the acylation reaction in the absence of a reaction diluent, and to add a diluent, such as a mineral oil to the reaction product after it has been produced.
  • a diluent such as a mineral oil
  • alkenyl succinic acylating agents in which the alkenyl substituent is derived from a polyolefin of somewhat higher molecular weight (e.g., a GPC number average molecular weight of 2100), it is desirable to conduct the reaction in a suitable diluent such as process oil or the like. Reaction times are typically in the range of from 1 to 4 hours. Suitable inert atmospheres include nitrogen, argon, krypton, neon, etc. As noted above, it is required pursuant to this invention, to employ a product made using from 0.4 to 1.3 moles of aminoguanidine or basic salt thereof per mole of the aliphatic hydrocarbyl-substituted succinic acid derivative.
  • AG dispersants are characterized by having an infrared peak in the region of 1590 cm -1 . Additionally, the spectrum may exhibit a peak in the region of 1690 cm -1 , but AG dispersants can be used that do not exhibit this latter peak. When made at mole ratios of about 1:1 or lower, a peak at 1725 cm -1 appears. The 1590 cm -1 peak is nearly absent in the Examples of U.S. Pat. No. 5,080,815.
  • the chemical structures of the products of this invention are unknown, but on the basis of their infrared spectra, they do not appear to have any significant content of triazole moieties, as is shown by the absence of the 1640 cm -1 IR peak present in the Examples of U.S. Pat. No. 5,080,815.
  • acylating agents have been extensively described and discussed in the literature, for example U.S. Pat. Nos. 3,215,707; 3,219,666; 3,231,587; 3,254,025; 3,282,955; 3,361,673; 3,401,118; 3,912,764; 4,110,349; 4,234,435; 4,908,145; 5,071,919; 5,080,815; and 5,137,978.
  • acylating agents of this type are manufactured in large quantities and are in widespread use in the manufacture of dispersants.
  • Preferred acylating agents for use in forming component a) are derived from a polyalkene having a number average molecular weight as determined by GPC in the range of 900 to 5000. Most preferably they have a number average molecular weight in the range of 1200 to 2500. While homopolymers and copolymers of a variety of 1-olefins can be used for preparing the acylating agents, commercial grades of polyisobutene are the preferred materials.
  • PIBSA 60% active polyisobutenyl succinic anhydride
  • AGB aminoguanidine bicarbonate
  • 600 g 600 g of a 100 neutral base oil.
  • the mole ratio of AGB to PIBSA is 1.2:1.
  • the mixture is heated at 170°C under a nitrogen sweep for 2 hours with stirring.
  • the product is filtered while hot and allowed to cool.
  • Example A-1 The procedure of Example A-1 is repeated using a chemically equivalent amount of PIBSA produced using a polyisobutylene having a number average molecular weight of about 1290 in lieu of the higher molecular weight PIBSA of Example A-1.
  • Example A-1 The procedure of Example A-1 is repeated except that the AGB:PIBSA mole ratio is 1.1:1.
  • Example A-3 is repeated except that the PIBSA of Example A-2 is employed.
  • Product formed as in Example A-3 is borated by heating 2290 g of the 44% active product so formed with 212.5 g of a superborated polyisobutenyl succinic ester-amide containing approximately 2.5% of boron at 160°C for 2 hours.
  • the resultant product is diluted with 154 g oil to give a product containing 0.2% boron.
  • Example A-5 is repeated, but using 2000 g of product formed as in Example A-4 and 185.6 g of the superborated ester-amide.
  • the boron content of the borated product is 0.2% on dilution with 134 g oil.
  • Example A-1 Product formed as in Example A-1 (2290 g) is borated by heating with 572.5 g of the superborated ester-amide and diluted with oil to give a product with 0.5% boron.
  • Example A-7 is repeated except that 2000 g of active product formed as in Example A-2 is used instead of the higher molecular weight product of Example A-1.
  • Example A-1 The procedure of Example A-1 is repeated seven times in the same manner except that the proportions of AGB and PIBSA are varied such that the respective AGB:PIBSA mole ratios are 0.4:1, 0.5:1. 0.6:1, 0.7:1, 0.8:1, 0.9:1 and 1:1.
  • Examples A-9 to A-15 are repeated, but using product formed as in Example A-2 in place of the product formed as in Example A-1.
  • Example A-1 is repeated except that 1.0 mole of AGB is reacted with 0.8 mole of PIBSA. Boration to a boron level of 0.2% is carried out at a suitable temperature between 145 and 165°C using boric acid. Water is stripped off at approximately 155°C and 40 mm Hg on completion of the boration.
  • This oil-soluble ashless dispersant is obtained by reacting (i) an acyclic hydrocarbyl succinic acylating agent and (ii) an alkylene polyamine having an average of about 3 to about 6 nitrogen atoms (and preferably an average of about 4 to about 5 nitrogen atoms) per molecule in a mole ratio of about 1.6 to 2 (and preferably about 1.8 to 2) moles of (i) per mole of (ii) to form a succinimide and heating the succinimide so formed concurrently or in any sequence and at a temperature in the range of about 150 to about 180°C with (iii) at least one dicarboxylic acylating agent having less than 20 carbon atoms in the molecule, and (iv) at least one boron material to form a product having (1) a total base number in the range of about 33 to about 45 milligrams of KOH per gram of said product (excluding the weight of any solvent and/or diluent that may be associated
  • Aliphatic hydrocarbyl-substituted succinic acid derivatives (acid, anhydride, lower alkyl ester, or acyl halide), such as alkenyl succinic anhydrides, that are used as reactant (i) above are of the same general types as used in forming component a). Thus for further details one should refer to the description given hereinabove. It is to be understood and appreciated however that the acylating agents used in forming components a) and b) need not be identical to each other.
  • the number average molecular weights of polyolefins used in forming these respective succinic acylating agents can be the same, or they can differ from each other whereby the number average molecular weight of either one of the polyolefins can be higher than that of the other.
  • the succinic acylating agents used in forming components a) and b) can (and preferably are) both anhydrides, although it is possible to use different kinds of functionalized succinic acylating agents in forming these respective components (e.g., using an anhydride for forming one of the components, and a free acid for forming the other).
  • Alkylene polyamines having an average of from about 3 to about 6 nitrogen atoms per molecule used as reactants (ii) in forming component b) are generally referred to in the art as dialkylene triamines, trialkylene tetramines, tetraalkylene pentamines and pentaalkylene hexamines.
  • the alkylene groups of these materials can have from 2 to 4 or more carbon atoms each.
  • Preferred for use are the polyethylene polyamines, i.e., the polyalkylene polyamines in which the alkylene groups are ethylene (i.e., dimethylene) groups.
  • the alkylene polyamines used in the synthesis of component b) can be substantially pure compounds of the specified structure (e.g., substantially pure tetraethylene pentamine of the formula: H 2 N-C 2 H 4 -NH-C 2 H 4 -NH-C 2 H 4 -NH-C 2 H 4 -NH 2 ) or they can be technical grade materials such as are available on the open market from a number of suppliers. These technical grade products are often referred to for example as diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine even though they typically comprise linear, branched and cyclic species.
  • the dicarboxylic acylating agent having less than 20 carbon atoms in the molecule used as reactant (iii) in post-treating the succinimide is preferably selected from (a) acyclic dicarboxylic acids having up to 6 carbon atoms in the molecule and wherein the carboxyl groups are attached to adjacent carbon atoms, (b) anhydrides of the said dicarboxylic acids, (c) acyl halides of the said dicarboxylic acids, and (d) acyclic mono- and/or dihydrocarbyl esters of the said dicarboxylic acids having no more than 7 carbon atoms per hydrocarbyl group.
  • acylating agents include maleic acid, maleic anhydride, ⁇ -ethylmaleic acid, malic acid, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, succinic acid, succinic anhydride, ⁇ -methylsuccinicacid, acid, ⁇ , ⁇ -dimethylsuccinic acid, ⁇ , ⁇ -dimethylsuccinic acid, ⁇ -ethylsuccinic acid, thiomalic acid, tartaric acid, the monoalkyl esters of the foregoing acids wherein the alkyl group has from 1 to 7 carbon atoms, the dialkyl esters of the foregoing acids wherein each alkyl group has from 1 to 7 carbon atoms, the monoalkenyl esters of the foregoing acids wherein the alkenyl group has from 2 to 7 carbon atoms, the dialkenyl esters of the foregoing acids wherein each alkenyl group has
  • Reactant (iv) is a boron-containing material of the same general type as can be used in borating component a) in accordance with preferred embodiment thereof.
  • temperature and other boration conditions used can be the same or similar to those applicable for use in forming a borated version of component a).
  • the borating agents and boration conditions used in forming component b) and in forming a borated version of component a) need not be identical to each other.
  • the borating agents can both be the same boron acid, boron ester, boron halide, boron oxide, ammonium borate, organoborane, or superborated ashless dispersant, or conversely, the borating agent used in forming one of the components can differ from that used in borating the other.
  • the times, temperatures and proportions of ingredients used in the respective borations can be the same or different from each other -- one component can be borated to a higher level than the other.
  • polyisobutenylsuccinic anhydride formed from polyisobutylene having a GPC number average molecular weight of about 1300 and tetraethylene pentamine (TEPA) in a mole ratio of 1.8:1 are reacted at 165-170°C for 4 hours.
  • PIBSA polyisobutenylsuccinic anhydride
  • TEPA tetraethylene pentamine
  • MA maleic anhydride
  • boric acid is added to the second stage reaction mixture at a temperature of 150-155°C in an amount corresponding to 4.0 moles per mole of TEPA initially employed.
  • the mixture is heated at 150°C for one hour and then water formed in the third stage reaction is removed by applying a vacuum of 40 mm for one hour.
  • the resulting succinimide is both acylated and boronated and has a nitrogen content of 1.74%, and a boron content of 1.20%.
  • Example B-1 The procedure of Example B-1 is repeated except that the amount of boric acid is reduced to 3.0 moles per mole of TEPA initially used.
  • Example B-1 Repetition of Example B-1 wherein the amount of boric acid is still further reduced to 2.0 moles per mole of TEPA initially used yields a concentrate (diluted as in Example B-1) having a boron content of 0.62%.
  • Example B-1 is repeated but using 3.25 moles of boric acid per mole of TEPA initially used.
  • the product concentrate (diluted as in Example B-1) contains 0.88% boron.
  • Example B-1 The procedure of Example B-1 is repeated except that the reaction with boric acid is conducted before the reaction with maleic anhydride and the amount of boric acid used corresponds to 3.0 moles per mole of TEPA used in the first stage reaction.
  • the final product (diluted as in Example B-1) contains 0.9% boron.
  • Example 5 is repeated except that the maleic anhydride and the boric acid are concurrently reacted with the succinimide formed in the first stage reaction.
  • One such product on dilution with 100 solvent neutral mineral oil contained 1.66% nitrogen and 0.87% boron.
  • polyisobutenylsuccinic anhydride formed from polyisobutylene with a GPC number average molecular weight of about 1300 and tetraethylene pentamine (TEPA) in a mole ratio of 1.8:1 are reacted at 165-170°C for 4 hours and then mineral oil added.
  • PIBSA polyisobutenylsuccinic anhydride
  • TEPA tetraethylene pentamine
  • MA maleic anhydride
  • boric acid (BA) is added to the second stage reaction product in an amount equivalent to 3.0 moles per mole of TEPA used in the first stage and the resultant mixture is heated at 150-155°C for 2-1/2 hours.
  • the additive concentrate has a nitrogen content of 1.8% and a boron content of 0.9%.
  • Example B-7 The procedure of Example B-7 is repeated except that in the first stage the PIBSA and TEPA are reacted in a molar ratio of 1.7:1.
  • the MA is used in amount equivalent to a mole ratio of 0.4:1 relative to the TEPA used in the first stage.
  • the boric acid (3.0 moles per mole of TEPA used in the first stage reaction) is added in an oil slurry.
  • the product on dilution has a nitrogen content of 1.95% and a boron content of 0.64%.
  • polyisobutenylsuccinic anhydride having a GPC number average molecular weight of about 1200 and TEPA are reacted in a mole ratio of 1.8:1.
  • maleic anhydride is added to the first stage reaction product in an amount equivalent to 0.35 mole per mole of TEPA used in the first stage and the resultant mixture is heated at 165-170°C for 1-1/2 hours after which mineral oil is added.
  • boric acid is added to the second stage reaction product in an amount equivalent to 0.4 mole per mole of TEPA used in the first stage and the resultant mixture is heated at 150 to 155°C for 3 hours.
  • the product has a nitrogen content of 1.85% and a boron content of 0.15%.
  • Metal hydrocarbyl dithiophosphates are usually prepared by reacting phosphorus pentasulfide with one or more alcohols or phenolic compounds or diols to produce a hydrocarbyl dithiophosphoric acid which is then neutralized with one or more metal-containing bases.
  • a monohydric alcohol or phenol is used in this reaction, the final product is a zinc dihydrocarbyl dithiophosphate.
  • a suitable diol e.g., 2,4-pentanediol
  • the final product is a zinc salt of a cyclic hydrocarbyl dithiophosphoric acid. See, for example, U.S. Pat. No. 3,089,850.
  • These cyclic derivatives function in essentially the same way as the dihydrocarbyl analogs.
  • Suitable oil-soluble metal dihydrocarbyl dithiophosphates include molybdenum dihydrocarbyl dithiophosphates, nickel dihydrocarbyl dithiophosphates, copper dihydrocarbyl dithiophosphates, cadmium dihydrocarbyl dithiophosphates, cobalt dihydrocarbyl dithiophosphates, and similar materials.
  • the hydrocarbyl groups include cyclic and acyclic groups, both saturated and unsaturated, such as alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, cycloalkylalkyl, aralkyl, and the like.
  • the hydrocarbyl groups may contain elements other than carbon and hydrogen provided such other elements do not detract from the predominantly hydrocarbonaceous character of the hydrocarbyl group.
  • the hydrocarbyl groups may contain ether oxygen atoms, thioether sulfur atoms, secondary or tertiary amino nitrogen atoms, and/or inert functional groups such as esterified carboxylic groups, keto groups, thioketo groups, and the like.
  • the preferred materials are the oil-soluble zinc dihydrocarbyl dithiophosphates, especially the oil-soluble zinc dialkyl dithiophosphates, and most especially oil-soluble zinc dialkyl dithiophosphates in which the alkyl groups are a mixture of primary and secondary alkyl groups.
  • Such primary and secondary alkyl group mixtures can be formed by forming a mixture of two or more zinc dialkyldithiophosphates that results in a mixture or combination of zinc dialkyl dithiophosphates having the desired types and proportions of primary and secondary alkyl groups.
  • the primary and secondary alkyl group mixtures can be formed by reacting phosphorus pentasulfide with a mixture or combination of primary and secondary alcohols that yields a zinc dialkyl dithiophosphate product having the desired types and proportions of primary and secondary alkyl groups.
  • the phosphorodithioic acids from which the metal salts are formed can be prepared by the reaction of about 4 moles of one or more alcohols (cyclic or acyclic) or one or more phenols or mixture of one or more alcohols and one or more phenols (or about 2 moles of one or more diols) per mole of phosphorus pentasulfide, and the reaction may be carried out within a temperature range of from about 50 to about 200°C. The reaction generally is completed in about 1 to 10 hours. Hydrogen sulfide is liberated during the reaction.
  • the alcohols used in forming the phosphorodithioic acids by the above method are preferably primary alcohols, or secondary alcohols. Mixtures thereof are also suitable.
  • the primary alcohols include propanol, butanol, isobutyl alcohol, pentanol, 2-ethyl-1-hexanol, isooctyl alcohol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, octadecanol, eicosanol, and the like.
  • the primary alcohols may contain various substituent groups such as halogen atoms, nitro groups, etc., which do not interfere with the desired reaction.
  • suitable secondary alcohols are included 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 4-methyl-2-pentanol, 5-methyl-2-hexanol, and the like.
  • mixtures of various alcohols such as mixtures of 2-propanol with one or more higher molecular weight primary alcohols, especially primary alcohols having from 4 to about 13 carbon atoms in the molecule.
  • Such mixtures preferably contain at least 10 mole percent of 2-propanol, and usually will contain from about 20 to about 90 mole percent of 2-propanol.
  • the alcohol comprises about 30 to 50 mole percent of 2-propanol, about 30 to 50 mole percent isobutyl alcohol and about 10 to 30 mole percent of 2-ethyl-1-hexanol.
  • alcohols include 2-propanol/butanol; 2-propanol/2-butanol; 2-propanol/2-ethyl-1-hexanol; butanol/2-ethyl-l-hexanol; isobutyl alcohol/2-ethyl-1-hexanol; and 2-propanol/tridecanol.
  • Cycloaliphatic alcohols suitable for use in the production of the phosphorodithioic acids include cyclopentanol, cyclohexanol, methylcyclohexanol, cyclooctanol, borneol and the like.
  • such alcohols are used in combination with one or more primary alkanols such as butanol, isobutyl alcohol, or the like.
  • Illustrative phenols which can be employed in forming the phosphorodithioic acids include phenol, o-cresol, m-cresol, p-cresol, 4-ethylphenol, 2,4-xylenol, and the like. It is desirable to employ phenolic compounds in combination with primary alkanols such propanol, butanol, hexanol, or the like.
  • alcohols which can be employed include benzyl alcohol, cyclohexenol, and their ring-alkylated analogs.
  • the preparation of the zinc salts of the dihydrocarbyl dithiophosphoric acids or the cyclic hydrocarbyl dithiophosphoric acids is usually effected by reacting the acid product with a suitable zinc compound such as zinc oxide, zinc carbonate, zinc hydroxide, zinc alkoxide, or other appropriate zinc salt. Simply mixing and heating such reactants is normally sufficient to cause the reaction to occur and the resulting product is usually of sufficient purity for use.
  • the salts are formed in the presence of a diluent such as an alcohol, water or a light mineral oil.
  • Neutral salts are prepared by reacting one equivalent of the zinc oxide or hydroxide with one equivalent of the acid.
  • Basic zinc salts are prepared by adding an excess (i.e., more than one equivalent) of the zinc oxide or hydroxide with one equivalent of the dihydrocarbyl phosphorodithioic acid or cyclic hydrocarbyl phosphorodithioic acid.
  • incorporation of certain ingredients such as small amounts of zinc acetate or acetic acid in conjunction with the zinc reactant will facilitate the reaction and provide an improved product.
  • certain ingredients such as small amounts of zinc acetate or acetic acid
  • use of up to about 5% of zinc acetate in combination with the required amount of zinc oxide tends to facilitate the formation of zinc dihydrocarbyl dithiophosphates.
  • the preferred zinc salts of dialkyl dithiophosphoric acids generally contain alkyl groups having at least three carbon atoms each, and preferably the alkyl groups contain up to 10 carbon atoms although as noted above, even higher molecular weight alkyl groups are entirely feasible.
  • a few illustrative zinc dialkyl dithiophosphates include zinc diisopropyl dithiophosphate, zinc dibutyl dithiophosphate, zinc diisobutyl dithiophosphate, zinc di-sec-butyl dithiophosphate, the zinc dipentyl dithiophosphates, the zinc dihexyl dithiophosphates, the zinc diheptyl dithiophosphates, the zinc dioctyl dithiophosphates, the zinc dinonyl dithiophosphates, the zinc didecyl dithiophosphates, and the higher homologs thereof.
  • zinc salts of dithiophosphoric acids formed from mixtures of isopropyl alcohol and secondary butyl alcohol; isopropyl alcohol, isobutyl alcohol, and 2-ethylhexyl alcohol; isopropyl alcohol, butyl alcohol, and pentyl alcohol; isobutyl alcohol and octyl alcohol; and the like.
  • the metal dihydrocarbyldithiophosphates may be products that have been post-treated with such compounds as carboxylic acids or epoxides.
  • the metal-containing detergents which can be employed are oil-soluble or oil-dispersible basic salts of alkali or alkaline earth metals with one or more of the following acidic substances (or mixtures thereof): (1) sulfonic acids, (2) carboxylic acids, (3) salicylic acids, (4) alkylphenols, (5) sulfurized alkylphenols, (6) organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage.
  • Such organic phosphorus acids include those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride.
  • a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride.
  • the most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium.
  • the salts can be low-base materials or overbased materials or combinations thereof.
  • component d) is an overbased metal detergent with a total base number (TBN) of at least 200, and more preferably in the range of 250 to 500.
  • TBN is determined in accordance with ASTM D-2896-88.
  • a particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60° to 200°C.
  • the inhibitors which can be used in the practice of this invention include one or more oxidation inhibitors, foam inhibitors, rust inhibitors, corrosion inhibitors and friction inhibitors.
  • Oxidation inhibitors suitable for use in the compositions of this invention include hindered phenolic antioxidants, secondary aromatic amine antioxidants, sulfurized phenolic antioxidants, sulfurized olefin antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants, and the like. Mixtures of two or more of these respective types of antioxidants can be used.
  • aromatic secondary monoamines are preferred, aromatic secondary polyamines are also suitable.
  • Illustrative aromatic secondary monoamines include diphenylamine, ring-alkylated diphenylamines containing 1 or more alkyl ring-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 wherein one or both rings are substituted by an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, and more preferably 8 or 9 carbon atoms.
  • alkyl group preferably a branched alkyl group
  • One such preferred compound is available commercially as Naugalube 438L, a material which is understood to be predominately a 4,4'-dinonyldiphenylamine wherein the nonyl groups are branched.
  • oxidation inhibitor for inclusion in the compositions of this invention is one or more oil-soluble sulfurized phenolic compounds.
  • Oil-soluble sulfurized linear alpha-olefins are also highly satisfactory oxidation inhibitors.
  • Suitable foam inhibitors are described in Foam Control Agents by H. T. Kerner (Noyes Data Corporation, 1976, pages 125-176).
  • Typical foam inhibitors include silicones and organic polymers such as acrylate polymers. 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. Other such mixtures include combinations of a dimethyl silicone oil with (i) a partial fatty acid ester of a polyhydric alcohol (U.S. Pat. No.
  • Rust inhibitors that can be used may be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous metal surfaces.
  • Such materials 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, linoleic acid, or the like.
  • 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.
  • oil-soluble polycarboxylic acids including dimer and trimer acids, such as
  • alkenylsuccinic acids in which the alkenyl group contains 10 or more carbon atoms such as, for example, tetrapropenylsuccinic acid, tetradecenylsuccinic acid, hexadecenylsuccinic acid, and the like; long-chain ⁇ , ⁇ -dicarboxylic 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, dimer and trimer acids.
  • Another useful type of 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.
  • alkenyl succinic acids are also useful.
  • suitable corrosion inhibitors include ether amines; acid phosphates; amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; imidazolines; and the like.
  • thiazoles examples include benzotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole, 2-mercaptobenzothiazole, 2,5-dimercapto1,3,4-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-dithiadiazoles and the 2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazoles, a number of which are available as articles of commerce.
  • Such products 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.
  • Other suitable corrosion inhibitors include ether amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; imidazolines; and the like.
  • Friction inhibitors which can be used 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, oleamide, sulfurized linear olefins, and the like.
  • Glycerol oleates such as glycerol monooleate, glycerol dioleate and pentaerythritol monooleate are further examples of suitable friction inhibitors which can be used to control friction and improve fuel economy.
  • 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.
  • Still other suitable additives can be included if desired.
  • a 10W-40 finished lubricant of this invention is formed from the following components: Component Percentage a) 3.17 b) 1.09 c) 1.06 d) 2.67 e) 1.40 Base oil, VI Improver, Diluent Oils Balance to 100% Component a) is formed as in Example A-5 and component b) as in Example B-4.
  • Component c) is a mixture of zinc dialkyldithiophosphates of which 50% are C 3 and C 6 secondary alkyl groups and 50% are C 3 , C 4 and C 8 primary and secondary alkyl groups.
  • Component d) is a mixture of 1.32% overbased calcium sulfonate, 0.7% low-base calcium sulfonate, and 0.65% sulfurized alkylphenate.
  • Component e) is a mixture of 0.8% tertiary butylated phenolic antioxidant, 0.2% aromatic amine antioxidant, 0.4% sulfurized olefin oxidation inhibitor, and less than 0.001% of silicone type foam inhibitor.
  • Commercial materials used in forming this component mixture include HITEC® 611, 1656, 4733, 7169, and 7304 additives (Ethyl Petroleum Additives, Ltd.; Ethyl Petroleum Additives, Inc.); OLOA 216C additive (Chevron Chemical Company); and Naugalube 438L additive (Uniroyal Chemical Company).
  • the viscosity index improver is of the OCP type (Paratone 8000; Exxon Chemical Company).
  • the finished lubricant has a total base number (TBN) of 10 mg of KOH per gram using the ASTM D2896 procedure, a zinc content of 0.12%, a phosphorus content of 0.11% a calcium content of 0.35% and a boron content of 0.02%.
  • TBN total base number
  • a 10W-40 lubricant of this invention is formed from the following components: Component Percentage a) 3.11 b) 1.10 c) 0.94 d) 2.36 e) 1.50 Base oil, VI Improver, Diluent Oils Balance to 100% Component a) is formed as in Example A-37 and component b) as in Example B-4.
  • Component c) is a mixture of C 3 and C 6 zinc dialkyldithiophosphates.
  • Component d) is a mixture of 1.18% overbased calcium sulfonate, 0.85% low-base calcium sulfonate, and 0.33% sulfurized alkylphenate.
  • Component e) is a mixture of 1.0% tertiary butylated phenolic antioxidant, 0.5% aromatic amine antioxidant, and less than 0.001% of silicone type foam inhibitor.
  • a finished lubricant of this invention is produced from the same components as in Example I but using the following proportions: Component Percentage a) 2.97 b) 1.37 c) 1.06 d) 2.67 e) 1.40 Base oil, VI Improver, Diluent Oils Balance to 100%
  • a lubricating oil composition of this invention is produced using components a) and b) as in Example II, a 400 TBN overbased magnesium alkylbenzene sulfonate as component d), and components c) and e) as in Example I in the proportions given in the following table: Component Percentage a) 3.11 b) 1.10 c) 1.06 d) 2.28 e) 1.40 Base oil, VI Improver, Diluent Oils Balance to 100%
  • compositions of this invention is illustrated by the results of the MWM KD 12E engine test which measures performance of heavy duty diesel engine lubricants under controlled conditions. Performance is expressed in terms of a numerical scale in which the higher the numerical value, the better the performance. In two such tests a lubricant of this invention and a comparable lubricant not of this invention were used. Both contained in addition to dispersant, a mixture of primary and secondary alkyl zinc dialkyl dithiophosphates, a mixture of high-base and low-base calcium sulfonates and a calcium sulfurized alkyl phenate in substantially the same relative proportions.
  • the principal difference between these two lubricants is that the dispersant of the lubricant not of this invention consisted solely of a higher dosage level of component a). Both lubricants were formulated to 10W-40 specification grade and had a TBN of 10 mg of KOH per gram and an ash level of 1.42%. The lubricant of this invention gave a rating of 80.6 as compared to a rating of 70.9 for the lubricant not of this invention.
  • Example II In tests conducted in similar fashion using the Volkswagen Intercooled (PV 1431) Test, a typical composition of this invention formed as in Example II was found to give significantly better piston cleanliness than a comparable lubricant composition not of this invention. In both cases the diesel engine was operated on a diesel fuel with a sulfur content of 0.3%.
  • oil-soluble means that the product under discussion can be dissolved or stably dispersed in a 100 Solvent Neutral mineral oil to a concentration of at least 1% by weight at 25°C.

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Claims (20)

  1. Composition de dispersant, soluble dans l'huile, qui comprend :
    a) un produit, soluble dans l'huile, formé en faisant réagir de l'aminoguanidine avec un agent d'acylation alkyl- ou alcénylsuccinique à chaíne longue en un rapport molaire de 0,4 à 1,3 mole d'aminoguanidine et/ou d'un de ses sels basiques par mole dudit agent d'acylation ; et
    b) un produit, soluble dans l'huile, formé en faisant réagir (i) un agent d'acylation hydrocarbylsuccinique acyclique et (ii) une alkylènepolyamine ayant un nombre moyen de 3 à 6 atomes d'azote par molécule en un rapport molaire de 1,6 à 2 moles de constituant (i) par mole de constituant (ii) pour former un succinimide et en chauffant le succinimide ainsi formé conjointement ou suivant n'importe quelle séquence et à une température comprise dans l'intervalle de 150 à 180°C avec (iii) au moins un agent d'acylation dicarboxylique ayant moins de 20 atomes de carbone dans la molécule, et (iv) au moins un composé de bore pour former un produit ayant (1) un indice de basicité total compris dans l'intervalle de 33 à 45 mg de KOH par gramme dudit produit en excluant le poids du solvant ou diluant, s'il en existe un quelconque, qui peut être associé audit produit, et (2) une teneur en bore comprise dans l'intervalle de 1,0 à 1,4 % en poids en excluant le poids de tout solvant et/ou diluant qui peut être associé audit produit ;
    dans laquelle les constituants a) et b) sont présents en des proportions telles que, pour chaque quantité de 0,7 à 1,8 partie en poids d'azote du constituant a), il existe 0,3 à 1,5 partie en poids d'azote du constituant b).
  2. Composition suivant la revendication 1, dans laquelle le rapport molaire dans le produit a) est compris dans l'intervalle de 0,8 à 1,3 mole d'aminoguanidine et/ou d'un de ses sels basiques par mole dudit agent d'acylation ; dans laquelle l'alkylènepolyamine de b) a un nombre moyen de 4 ou 5 atomes d'azote par molécule ; dans laquelle ledit rapport molaire du constituant (i) par mole du constituant (ii) dans b) va de 1,8 à 2 moles de constituant (i) par mole de constituant (ii) ; et dans laquelle, pour chaque quantité de 0,8 à 1,7 partie en poids d'azote de a), il existe 0,4 à 1,4 partie en poids d'azote de b).
  3. Composition suivant la revendication 2, dans laquelle le constituant a) est boraté de telle sorte qu'il ait une teneur en bore allant jusqu'à environ 1 % en poids, en excluant le poids du solvant et/ou diluant, s'il en existe un quelconque, associé audit produit.
  4. Composition qui comprend 1 à 99 % en poids d'au moins une huile de viscosité propre à la lubrification et 99 à 1 % en poids d'une composition suivant la revendication 1.
  5. Composition qui comprend 1 à 99 % en poids d'au moins une huile de viscosité propre à la lubrification et 99 à 1 % en poids d'une composition suivant la revendication 3.
  6. Concentré d'additif qui comprend :
    a) un produit, soluble dans l'huile, formé en faisant réagir de l'aminoguanidine avec un agent d'acylation alkyl- ou alcénylsuccinique à chaíne longue en un rapport molaire de 0,4 à 1,3 mole d'aminoguanidine et/ou d'un de ses sels basiques par mole dudit agent d'acylation ;
    b) un produit, soluble dans l'huile, formé en faisant réagir (i) un agent d'acylation hydrocarbylsuccinique acyclique et (ii) une alkylènepolyamine ayant un nombre moyen de 3 à 6 atomes d'azote par molécule en un rapport molaire de 1,6 à 2 moles de constituant (i) par mole de constituant (ii) pour former un succinimide et en chauffant le succinimide ainsi formé conjointement ou suivant n'importe quelle séquence et à une température comprise dans l'intervalle de 150 à 180°C avec (iii) au moins un agent d'acylation dicarboxylique ayant moins de 20 atomes de carbone dans la molécule, et (iv) au moins un composé de bore pour former un produit ayant (1) un indice de basicité total compris dans l'intervalle de 33 à 45 mg de KOH par gramme dudit produit en excluant le poids du solvant ou diluant, s'il en existe un quelconque, qui peut être associé audit produit, et (2) une teneur en bore comprise dans l'intervalle de 1,0 à 1,4 % en poids en excluant le poids de tout solvant et/ou diluant qui peut être associé audit produit ;
    c) au moins un dihydrocarbyldithiophosphate métallique, soluble dans l'huile ;
    d) au moins un détergent contenant un métal alcalin ou alcalino-terreux ; et
    e) un ou plusieurs inhibiteurs choisis entre au moins un inhibiteur d'oxydation, au moins un inhibiteur de moussage, au moins un inhibiteur de formation de rouille, au moins un inhibiteur de corrosion et au moins un inhibiteur de frottement ;
    lesdits constituants a) et b) étant présents en des proportions telles que, pour chaque quantité de 0,7 à 1,8 partie en poids d'azote de a), il existe 0,3 à 1,5 partie en poids d'azote de b), et les constituants a), b), c), d) et e) étant présents dans le concentré d'additif en des proportions telles que le mélange d'une petite proportion du concentré d'additif avec une huile de base donne une formulation d'huile qui contient une quantité dispersante de a) plus b) en les proportions précitées, une quantité inhibitrice d'usure de c), une quantité détergente de d) et une quantité inhibitrice de chacun des inhibiteurs choisis.
  7. Composition suivant la revendication 6, dans laquelle le dihydrocarbyldithiophosphate métallique consiste en au moins un agent anti-usure/extrême pression du type dialkyldithiophosphate de zinc.
  8. Composition suivant la revendication 7, dans laquelle les groupes alkyle du dialkyldithiophosphate de zinc consistent en un mélange de groupes alkyle primaires et de groupes alkyle secondaires.
  9. Composition suivant la revendication 6, dans laquelle le constituant a) est boraté de telle sorte qu'il ait une teneur en bore allant jusqu'à environ 1 % en poids, en excluant le poids du solvant et/ou diluant, s'il en existe un quelconque, associé audit produit.
  10. Composition suivant la revendication 9, dans laquelle le dihydrocarbyldithiophosphate métallique consiste en au moins un agent anti-usure/extrême pression du type dialkyldithiophosphate de zinc.
  11. Composition suivant la revendication 10, dans laquelle les groupes alkyle de ce dialkyldithiophosphate de zinc consistent en un mélange de groupes alkyle primaires et groupes alkyle secondaires.
  12. Composition d'huile lubrifiante qui comprend une quantité dominante d'au moins une huile de viscosité propre à la lubrification et
    a) une petite quantité dispersante d'un produit, soluble dans l'huile, formé en faisant réagir de l'aminoguanidine avec un agent d'acylation alkyl- ou alcénylsuccinique à chaíne longue en un rapport molaire de 0,4 à 1,3 mole d'aminoguanidine et/ou d'un de ses sels basiques par mole dudit agent d'acylation ;
    b) une petite quantité dispersante d'un produit, soluble dans l'huile, formé en faisant réagir (i) un agent d'acylation hydrocarbylsuccinique acyclique et (ii) une alkylènepolyamine ayant un nombre moyen de 3 à 6 atomes d'azote par molécule en un rapport molaire de 1,6 à 2 moles de constituant (i) par mole de constituant (ii) pour former un succinimide et en chauffant le succinimide ainsi formé conjointement ou suivant n'importe quelle séquence et à une température comprise dans l'intervalle de 150 à 180°C avec (iii) au moins un agent d'acylation dicarboxylique ayant moins de 20 atomes de carbone dans la molécule, et (iv) au moins un composé de bore pour former un produit ayant (1) un indice de basicité total compris dans l'intervalle de 33 à 45 milligrammes de KOH par gramme dudit produit en excluant le poids du solvant ou diluant, s'il en existe un quelconque, qui peut être associé audit produit, et (2) une teneur en bore comprise dans l'intervalle de 1,0 à 1,4 % en poids en excluant le poids de tout solvant et/ou diluant qui peut être associé audit produit ;
    c) une petite quantité inhibitrice d'usure d'au moins un dihydrocarbyldithiophosphate métallique soluble dans l'huile ;
    d) une petite quantité détergente d'au moins un détergent contenant un métal alcalin ou alcalino-terreux ; et
    e) une petite quantité inhibitrice d'un ou plusieurs inhibiteurs choisis entre au moins un inhibiteur d'oxydation, au moins un inhibiteur de moussage, au moins un inhibiteur de formation de rouille, au moins un inhibiteur de corrosion et au moins un inhibiteur de frottement ;
    lesdits constituants (a) et b) étant présents en des proportions telles que, pour chaque quantité de 0,7 à 1,8 partie en poids d'azote de a), il existe 0,3 à 1,5 partie en poids d'azote de b), sous réserve que ladite composition d'huile lubrifiante ne contienne pas plus de 0,042 % en poids d'azote provenant de b).
  13. Composition suivant la revendication 12, comprenant en outre une quantité, améliorant l'indice de viscosité, d'un agent améliorant l'indice de viscosité.
  14. Composition suivant la revendication 12, dans laquelle le dihydrocarbyldithiophosphate métallique consiste en au moins un agent anti-usure/extrême pression du type dialkyldithiophosphate de zinc.
  15. Composition suivant la revendication 14, dans laquelle les groupes alkyle de ce dialkyldithiophosphate de zinc consistent en un mélange de groupes alkyle primaires et de groupes alkyle secondaires.
  16. Composition suivant la revendication 12, qui comprend en outre une quantité, améliorant l'indice de viscosité, d'un agent améliorant l'indice de viscosité, et dans laquelle le dihydrocarbyldithiophosphate métallique consiste en au moins un agent anti-usure/extrême pression du type dialkyldithiophosphate de zinc.
  17. Composition suivant la revendication 12, dans laquelle le constituant e) comprend une petite quantité, inhibant l'oxydation, d'au moins un inhibiteur d'oxydation; une petite quantité, inhibant le moussage, d'un inhibiteur de moussage ; et une petite quantité, inhibant le frottement, d'un inhibiteur de frottement.
  18. Composition suivant la revendication 12, dans laquelle le constituant a) est boraté de telle sorte qu'il ait une teneur en bore allant jusqu'à environ 1 % en poids, en excluant le poids du solvant et/ou diluant, s'il en existe un quelconque, associé audit produit.
  19. Composition suivant la revendication 18, qui comprend en outre une quantité, améliorant l'indice de viscosité, d'un agent améliorant l'indice de viscosité, et dans laquelle le dihydrocarbyldithiophosphate métallique consiste en au moins un agent anti-usure/extrême pression du type dialkyldithiophosphate de zinc.
  20. Composition suivant la revendication 19, dans laquelle les groupes alkyle du dialkyldithiophosphate de zinc consistent en un mélange de groupes alkyle primaires et de groupes alkyle secondaires ; et dans laquelle le constituant e) comprend une petite quantité, inhibant l'oxydation, d'au moins un inhibiteur d'oxydation, une petite quantité, inhibant le moussage, d'un inhibiteur de moussage, et une petite quantité, inhibant le frottement, d'un inhibiteur de frottement.
EP95300225A 1994-01-14 1995-01-13 Dispersants pour huile lubrifiante Expired - Lifetime EP0663436B1 (fr)

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US183043 1994-01-14

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EP0663436B1 true EP0663436B1 (fr) 2000-09-06

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US5454962A (en) * 1993-06-25 1995-10-03 Ethyl Petroleum Additives, Inc. Fluoroelastomer-friendly crankcase and drivetrain lubricants and their use
GB2307685B (en) * 1995-12-01 1999-07-07 Ethyl Petroleum Additives Ltd Seal compatible diesel dispersants
JP4028614B2 (ja) * 1997-02-03 2007-12-26 東燃ゼネラル石油株式会社 潤滑油組成物
JP3599231B2 (ja) * 1999-06-04 2004-12-08 出光興産株式会社 トラクションドライブ用流体
US20080171677A1 (en) * 2006-04-13 2008-07-17 Buck William H Low SAP engine lubricant additive and composition containing non-corrosive sulfur and organic borates
WO2008120599A1 (fr) 2007-03-30 2008-10-09 Idemitsu Kosan Co., Ltd. Composition lubrifiante
US8623105B2 (en) 2008-05-13 2014-01-07 Afton Chemical Corporation Fuel additives to maintain optimum injector performance
US20100037514A1 (en) * 2008-05-13 2010-02-18 Afton Chemical Corporation Fuel additives to maintain optimum injector performance
US8529643B2 (en) 2008-05-13 2013-09-10 Afton Chemical Corporation Fuel additives for treating internal deposits of fuel injectors
US20100107482A1 (en) * 2008-11-06 2010-05-06 Bennett Joshua J Conductivity-improving additives for fuel
US9663743B2 (en) 2009-06-10 2017-05-30 Afton Chemical Corporation Lubricating method and composition for reducing engine deposits
GB2480612A (en) * 2010-05-24 2011-11-30 Afton Chemical Ltd Oxidation stabilized fuels having enhanced corrosion resistance

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GB998869A (en) * 1962-05-07 1965-07-21 Monsanto Co Imido compounds, their production and use
GB1121681A (en) * 1965-08-31 1968-07-31 Lubrizol Corp Compositions containing substituted succinic acid derivatives
US4908145A (en) * 1987-09-30 1990-03-13 Amoco Corporation Engine seal compatible dispersants for lubricating oils
DE69021872T3 (de) * 1990-06-06 2003-02-13 Ethyl Petroleum Additives Ltd., Bracknell Modifizierte Lösungsmittelzusammensetzungen.
CA2065945A1 (fr) * 1991-05-29 1992-11-30 David L. Wooton compositions et concentres oleagineux lubrifiants et utilisation connexe
US5454962A (en) * 1993-06-25 1995-10-03 Ethyl Petroleum Additives, Inc. Fluoroelastomer-friendly crankcase and drivetrain lubricants and their use

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DE69518673T2 (de) 2001-05-23
AU1015995A (en) 1995-07-27
JPH07252492A (ja) 1995-10-03
CA2140168A1 (fr) 1995-07-15
JP3920363B2 (ja) 2007-05-30
DE69518673D1 (de) 2000-10-12
CA2140168C (fr) 2004-06-01

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