EP0562062B1 - Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissage - Google Patents

Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissage Download PDF

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Publication number
EP0562062B1
EP0562062B1 EP92918231A EP92918231A EP0562062B1 EP 0562062 B1 EP0562062 B1 EP 0562062B1 EP 92918231 A EP92918231 A EP 92918231A EP 92918231 A EP92918231 A EP 92918231A EP 0562062 B1 EP0562062 B1 EP 0562062B1
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Prior art keywords
borated
aromatic polyol
succinimide
catechol
composition
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EP92918231A
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German (de)
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EP0562062A1 (fr
EP0562062A4 (fr
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Anatoli Onopchenko
Edward T. Sabourin
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Chevron USA Inc
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Chevron Chemical Co LLC
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    • 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
    • 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
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    • 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
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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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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
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    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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Definitions

  • This invention relates to a discovery that a borated aromatic polyol having at least one aromatic ring and at least two hydroxyl groups and wherein at least two of the hydroxyl groups are on adjacent carbon atoms on the aromatic ring can serve to inhibit fluorocarbon engine seal deterioration in the presence of basic nitrogen.
  • the most important automotive lubricating formulations are based on using dispersants as additives.
  • One of the most effective dispersants in use today is based on succinic anhydride with a long polyisobutylene alkyl chain in the alpha position, i.e.: where R is a polyisobutylene.
  • TEPA tetraethylenepentamine
  • TETA triethylenetetramine
  • TBN Total Base Number
  • Anderson solves his fluorocarbon polymer seal compatibility problem by directly borating his hydroxylated polyamine based succinimides. Anderson fails to teach or suggest any solution to the fluorocarbon seal compatibility problem when using unhydroxylated polyamine based succinimides. In fact, Anderson teaches that boration of the unhydroxylated succinimides failed to solve the problem (Col. 3, lines 3 to 5). What is desired and needed is a separate additive to use with other lube oil additives containing basic nitrogen which will serve to inhibit the deterioration of engine seals of the fluorocarbon polymer type.
  • a borated aromatic polyol in a lubricating composition containing a minor proportion of a basic nitrogen compound, for the purpose of improving the compatibility of said lubricating oil towards fluorocarbon polymer engine seals, said borated aromatic polyol being obtainable by borating an aromatic polyol having the formula: where R"' is selected from the group consisting of H; OH; or an alkyl group having from 1 to 8 carbon atoms.
  • the borated aromatic polyol is used at an effective amount to improve the compatibility of the lubricating oil towards fluorocarbon engine seals.
  • a lubricant composition comprising a major proportion of a lubricating oil; a minor proportion of at least one basic nitrogen compound and a minor but effective compatibilizing amount of a borated aromatic polyol as an additive to passavate fluorocarbon polymer seals, said aromatic polyol being obtainable by borating an aromatic polyol having the formula: wherein R"' is selected from the group consisting of H; OH; or an alkyl group having from 1 to 8 carbon atoms.
  • R"' is selected from the group consisting of H; OH; or an alkyl group having from 1 to 8 carbon atoms.
  • the basic nitrogen content of the lubricating oil is provided through the use of an oil soluble alkyl or alkenyl mono- or bis-succinimide.
  • the borated aromatic polyol such as borated catechol, is believed to complex with the basic nitrogen.
  • the borated alkyl catechols of Liston are those where the alkyl group has from 10 to 30 carbon atoms (Col. 2, lines 22 et seq.).
  • additives may also be present in the lubricating oil in order to obtain a proper balance of properties such as dispersancy, corrosion, wear and oxidation inhibition which are critical for the proper operation of an internal combustion engine.
  • a method for improving the compatibility of a lubricating oil containing basic nitrogen to fluorocarbon seals in engines which comprises adding to said lubricating oil a compatibilizing amount of the borated aromatic polyols of this invention.
  • the Figure is a graphic representation of the change in dispersion units of a reference oil containing a alkylcatechol borate versus the number of carbon atoms inthe alkyl group of the alkylcatechol borate.
  • the aromatic polyol for use in the invention is a single ring aromatic having from 2 to 3 hydroxyl groups and wherein two of the hydroxyl groups are on adjacent carbon atoms on the aromatic ring.
  • aromatic polyols used in the invention are those having the formula: where R'" is selected from the group consisting of H; OH; or an alkyl group having from 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms.
  • catechol borates While all catechol borates, as the data later show, can be expected to compatibilize the oil with the fluorocarbon polymer seals, catechol borates without any alkyl groups, or those carrying a short chain alkyl group of 1-8 carbons, were unexpectedly found by the dispersancy blotter spot test, to be discussed later, to be effective in enhancing the overall dispersancy, while alkylcatechol borates carrying long alkyl groups surprisingly showed a loss in the overall dispersancy.
  • mixtures of aromatic polyols as described above can be employed, the higher carbon number alkylated catechols tending to solubilize the lower molecular weight catechols in the lubricating oil.
  • catechol borate its solubility in the reference oil formulation at room temperature is limited, in spite of its excellent dispersancy characteristic. It has now been discovered that alkylcatechol borates having an alkyl group of ten carbon atoms or longer can be used effectively to enhance the solubility of catechol borate in a reference oil, and the overall loss in dispersancy of the higher alkylcatechol borates can be offset by the addition of the lower alkylcatechol borate or catechol borate which has a positive effect on the overall dispersancy. The most effective ratio to use for optimum results is a matter of simple experimentation.
  • aromatic polyols which can be used to prepare the borated aromatic polyols for use in this invention include, but are not limited to:
  • the aromatic polyols useful in preparing the additives of this invention are well known in the art and many are commercially available.
  • the alkyl catechols may be prepared, for example, as described in U.S.P. 4,629,578.
  • the aromatic polyols are borated by methods well known in the art, see for example U.S.P. 4,975,211 and U.S.P. 4,629,578.
  • the preferred boron compound to employ in the boration reaction is boric acid.
  • the borated compounds used in the working examples in this application were either prepared via published procedures in U.S.P. 4,975,211; and U.S.P. 4,629,578, or were purchased from commercial sources.
  • a boron compound with a labile hydrogen is necessary to borate the aromatic polyols of this invention.
  • a preferred boron source would have the formula: where Z can be hydrogen or an alkyl group having 1 to 20 carbon atoms, preferably 1 to 8.
  • Preferred is boric acid (B(OH) 3 ).
  • the simplest borated aromatic polyol to use in the compositions of this invention is catechol borate.
  • Catechol borate is a general term which has been used in the literature to describe any catechol-boric acid complex or reaction product.
  • the exact structure of the product, however, is dictated largely by stoichiometry (charge molar ratio of reactants). The extent of the reaction is most conveniently followed by the amount of water of reaction collected in a Dean-Stark trap using some appropriate organic azeotroping solvent such as toluene, o-xylene, m-xylene, p-xylene, xylene mixture, and etc.
  • All of catechol-boric acid structures are known from the literature and are shown in Table A below. For example, when the molar ratio of catechol to boric acid is 2:1, the major product was expected to have structure I.
  • the amount of the borated aromatic polyol to use in the compositions of this invention is that amount which is sufficient to improve the compatibility of the basic nitrogen containing additives in the lube oil base stock towards fluorocarbon engine seals.
  • the amount of borated aromatic polyol to add is at least the stoichiometric amount required to react or to passivate the basic nitrogen atoms present, although depending on the circumstances, the amount of boron added can be greater or less than the stoichiometric amount of available basic nitrogen. When less than the stoichiometric amount of boron was used, the full benefit of boron containing additives may not be reached, and the results may not be optimum.
  • the weight percent of said borated aromatic polyol is at least about 0.15 weight percent of the lube oil composition, more usually 0.5 to 5 weight percent although amounts to 10 weight percent or more can be used.
  • the borated aromatic polyols of this invention are useful in complexing with basic nitrogen in the lubricating oil so as to compatibilize the lubricating oil with the fluorocarbon seals.
  • compatibilize is meant that the basic nitrogen is passivated against attack on the fluorocarbon seals. Compatibility is measured by a pass rating on a VW Bench Test developed by Volkswagen and known in the industry as PV3334 bench test, carried out in accordance with the DIN 53504 procedure, which will be described in detail below using a standard reference elastomer AK6 from Parker-Pradifa GmbH of 2mm thickness (S2 specimen).
  • the oil soluble alkenyl or alkyl mono- or bis-succinimides which are employed in this invention are generally known as lubricating oil detergents and are described in U.S. Pat Nos. 2,992,708, 3,018,291, 3,024,237, 3,100,673, 3,219,666, 3,172,892 and 3,272,746.
  • the alkenyl succinimides are the reaction product of a polyolefin polymer-substituted succinic anhydride with an amine, preferably a polyalkylene polyamine.
  • the polyolefin polymer-substituted succinic anhydrides are obtained by reaction of a polyolefin polymer or a derivative thereof with maleic anhydride.
  • the succinic anhydride thus obtained is reacted with the amine compound.
  • the preparation of the alkenyl succinimides has been described many times in the art. See, for example, U.S. Pat. Nos. 3,390,082, 3,219,666 and 3,172,892.
  • Reduction of the alkenyl substituted succinic anhydride yields the corresponding alkyl derivative.
  • a product comprising predominantly mono- or bis-succinimide can be prepared by controlling the molar ratios of the reactants.
  • a predominantly mono-succinimide product will be prepared.
  • two moles of the succinic anhydride are reacted per mole of polyamine, a bis-succinimide will be prepared.
  • alkenyl succinimide is a mono- or a bis-succinimide prepared from a polyisobutene-substituted succinic anhydride of a polyalkylene polyamine.
  • the polyisobutene (from which the polyisobutene-substituted succinic anhydride is prepared) is obtained by polymerizing isobutene and can vary widely in its composition.
  • the average number of carbon atoms can range from 30 or less to 250 or more, with a resulting number average molecular weight of about 400 or less to 3,000 or more.
  • the average number of carbon atoms per polyisobutene molecule will range from about 50 to about 100 with the polyisobutene having a number average molecular weight of about 600 to about 1,500.
  • the average number of carbon atoms per polyisobutene molecule ranges from about 60 to about 90, and the number average molecular weight ranges from about 800 to 1,300.
  • the polyisobutene is reacted with maleic anhydride according to well-known procedures to yield the polyisobutene-substituted succinic anhydride. See, for example, U.S. Pat. Nos. 4,388,471 and 4,450,281.
  • each alkylene radical of the polyalkylene polyamine usually has up to about 8 carbon atoms.
  • the number of alkylene radicals can range up to about 8.
  • the alkylene radical is exemplified by ethylene, propylene, butylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, etc.
  • the number of amino groups generally, but not necessarily, is one greater than the number of alkylene radicals present in the amine, i.e., if a polyalkylene polyamine contains 3 alkylene radicals, it will usually contain 4 amino radicals.
  • the number of amino radicals can range up to about 9.
  • the alkylene radical contains from about 2 to about 4 carbon atoms and all amine groups are primary or secondary. In this case, the number of amine groups exceeds the number of alkylene groups by 1.
  • the polyalkylene polyamine contains from 3 to 5 amine groups.
  • polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, di-(trimethylene)triamine, tri(hexamethylene)tetramine, etc.
  • amines suitable for preparing the alkenyl succinimide useful in this invention include the cyclic amines such as piperazine, morpholine and dipiperazines.
  • alkenyl succinimides used in the compositions of this invention have the following formula: wherein:
  • the alkenyl succinimide is present in the lubricating oil compositions useful in this invention in an amount sufficient to impart the desired dispersant properties to the lubricating oil to prevent the deposit of contaminants formed in the oil during operation of the engine.
  • the weight percent succinimide is from 1 to 20 weight percent of the finished lubricating oil, usually from 2 to 15 weight percent and preferably from 1 to 10 weight percent of the total composition.
  • the complex may be formed by reacting the borated alkyl catechol and the succinimide together neat at a temperature above the melting point of the mixture of reactants and below the decomposition temperature, or in a diluent in which both reactants are soluble.
  • the reactants may be combined in the proper ratio in the absence of a solvent to form a homogeneous product which may be added to the oil or the reactants may be combined in the proper ratio in a solvent such as toluene or chloroform, the solvent stripped off, and the complex thus formed may be added to the oil.
  • the complex may be prepared in a lubricating oil as a concentrate containing from about 20 to 90% by weight of the complex, which concentrate may be added in appropriate amounts to the lubricating oil in which it is to be used or the complex may be prepared directly in the lubricating oil in which it is to be used.
  • the diluent is preferably inert to the reactants and products formed and is used in an amount sufficient to ensure solubility of the reactants and to enable the mixture to be efficiently stirred.
  • Temperatures for preparing the complex may be in the range of from 25°C to 200°C and preferably 25°C to 100°C depending on whether the complex is prepared neat or in a diluent, i.e., lower temperatures may be used when a solvent is used.
  • complexes of this invention may also be used in combination with other additive systems in conventional amounts for their known purpose.
  • the base composition described above will be formulated with supplementary additives to provide the necessary stability, detergency, dispersancy, anti-wear and anti-corrosion properties.
  • the lubricating oils to which the complexes prepared by reacting the borated alkyl catechols and succinimides may contain an alkali or alkaline earth metal phenate, and Group II metal salt dihydrocarbyl dithiophosphate.
  • succinimides act as excellent dispersants
  • additional succinimide may be added to the lubricating oil compositions, above the amounts added in the form of the complex with the borated alkyl catechols.
  • the amount of succinimides can range up to about 20% by weight of the total lubricating oil compositions.
  • the alkali or alkaline earth metal hydrocarbyl sulfonates may be either petroleum sulfonate, synthetically alkylated aromatic sulfonates, or aliphatic sulfonates such as those derived from polyisobutylene.
  • One of the more important functions of the sulfonates is to act as a detergent and dispersant.
  • the sulfonates are well known in the art. These hydrocarbyl group must have a sufficient number of carbon atoms to render the sulfonate molecule oil soluble.
  • the hydrocarbyl portion has at least 20 carbon atoms and may be aromatic or aliphatic, but is usually alkylaromatic. Most preferred for use are calcium, magnesium or barium sulfonates which are aromatic in character.
  • Certain sulfonates are typically prepared by sulfonating a petroleum fraction having aromatic groups, usually mono- or dialkylbenzene groups, and then forming the metal salt of the sulfonic acid material.
  • Other feedstocks used for preparing these sulfonates include synthetically alkylated benzenes and aliphatic hydrocarbons prepared by polymerizing a mono- or diolefin, for example, a polyisobutenyl group prepared by polymerizing isobutene.
  • the metallic salts are formed directly or by metathesis using well-known procedures.
  • the sulfonates may be neutral or overbased having base numbers up to about 44 or more. Carbon dioxide and calcium hydroxide or oxide are the most commonly used material to produce the basic or overbased sulfonates. Mixtures of neutral and overbased sulfonates may be used.
  • the sulfonates are ordinarily used so as to provide from 0.3% to 10% by weight of the total composition. Preferably, the neutral sulfonates are present from 0.4% to 5% by weight of the total composition and the overbased sulfonates are present from 0.3% to 33% by weight of the total composition.
  • the phenates for use in this invention are those conventional products which are the alkali or alkaline earth metal salts of alkylated phenols.
  • One of the functions of the phenates is to act as a detergent and dispersant. Among other things, it prevents the deposit of contaminants formed during high temperature operation of the engine.
  • the phenols may be mono- or polyalkylated.
  • the alkyl portion of the alkyl phenate is present to lend oil solubility to the phenate.
  • the alkyl portion can be obtained from naturally occurring or synthetic sources.
  • Naturally occurring sources include petroleum hydrocarbons such as white oil and wax. Being derived from petroleum, the hydrocarbon moiety is a mixture of different hydrocarbyl groups, the specific composition of which depends upon the particular oil stock which was used as a starting material.
  • Suitable synthetic sources include various commercially available alkenes and alkane derivatives which, when reacted with the phenol, yield an alkylphenol.
  • Suitable radicals obtained include butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl, triacontyl, and the like.
  • Other suitable synthetic sources of the alkyl radical include olefin polymers such as polypropylene, polybutylene, polyisobutylene and the like.
  • the alkyl group can be straight-chained or branch-chained, saturated or unsaturated (if unsaturated, preferably containing not more than 2 and generally not more than 1 site of olefinic unsaturation).
  • the alkyl radicals will generally contain from 4 to 30 carbon atoms. Generally when the phenol is monoalkyl-substituted, the alkyl radical should contain at least 8 carbon atoms.
  • the phenate may be sulfurized if desired. It may be either neutral or overbased and if overbased will have a base number of up to 200 to 300 or more. Mixtures of neutral and overbased phenates may be used.
  • the phenates are ordinarily present in the oil to provide from 0.2% to 27% by weight of the total composition.
  • the neutral phenates are present from 0.2% to 9% by weight of the total composition and the overbased phenates are present from 0.2 to 13% by weight of the total composition.
  • the overbased phenates are present from 0.2% to 5% by weight of the total composition.
  • Preferred metals are calcium, magnesium, strontium or barium.
  • the sulfurized alkaline earth metal alkyl phenates are preferred. These salts are obtained by a variety of processes such as treating the neutralization product of an alkaline earth metal base and an alkylphenol with sulfur. Conveniently the sulfur, in elemental form, is added to the neutralization product and reacted at elevated temperatures to produce the sulfurized alkaline earth metal alkyl phenate.
  • a basic sulfurized alkaline earth metal alkyl phenate is obtained. See, for example, the process of Walker et al., U.S. Pat. No. 2,680,096. Additional basicity can be obtained by adding carbon dioxide to the basic sulfurized alkaline earth metal alkyl phenate. The excess alkaline earth metal base can be added subsequent to the sulfurization step but is conveniently added at the same time as the alkaline earth metal base is added to neutralize the phenol.
  • Carbon dioxide and calcium hydroxide or oxide are the most commonly used materials to produce the basic or "overbased” phenates.
  • a process wherein basic sulfurized alkaline earth metal alkylphenates are produced by adding carbon dioxide is shown in Hanneman, U.S. Pat. No. 3,178,368.
  • the Group II metal salts of dihydrocarbyl dithiophosphoric acids exhibit wear, antioxidant and thermal stability properties.
  • Group II metal salts of phosphorodithioic acids have been described previously. See, for example, U.S. Pat. No. 3,390,080, columns 6 and 7, wherein these compounds and their preparation are described generally.
  • the Group II metal salts of the dihydrocarbyl dithiophosphoric acids useful in the lubricating oil composition of this invention contain from about 4 to about 12 carbon atoms in each of the hydrocarbyl radicals and may be the same or different and may be aromatic, alkyl or cycloalkyl.
  • Preferred hydrocarbyl groups are alkyl groups containing from 4 to 8 carbon atoms and are represented by butyl, isobutyl, sec-butyl, hexyl, isohexyl, octyl, 2-ethylhexyl and the like.
  • the metals suitable for forming these salts include barium, calcium, strontium, zinc and cadmium, of which zinc is preferred.
  • the Group II metal salt of a dihydrocarbyl dithiophosphoric acid has the following formula: wherein:
  • the dithiophosphoric salt is present in the lubricating oil compositions of this invention in an amount effective to inhibit wear and oxidation of the lubricating oil.
  • the amount ranges from about 0.1 to about 4 percent by weight of the total composition, preferably the salt is present in an amount ranging from about 0.2 to about 2.5 percent by weight of the total lubricating oil composition.
  • the final lubricating oil composition will ordinarily contain 0.025 to 0.25% by weight phosphorus and preferably 0.05 to 0.15% by weight.
  • the finished lubricating oil may be single or multigrade.
  • Multigrade lubricating oils are prepared by adding viscosity index (VI) improvers.
  • Typical viscosity index improvers are polyalkyl methacrylates, ethylene-propylene copolymers, styrene-diene copolymers and the like.
  • So-called decorated VI improvers having both viscosity index and dispersant properties are also suitable for use in the formulations of this invention.
  • the lubricating oil used in the compositions of this invention may be a mineral oil or a synthetic oil of lubricating viscosity, preferably suitable for use in the crankcase of an internal combustion engine.
  • Crankcase lubricating oils ordinarily have a viscosity of about 1300 cSt at 0°F. (-18°C.) to 22.7 cSt at 210°F. (99°C.).
  • the lubricating oils may be derived from synthetic or natural sources.
  • Mineral oil for use as the base oil in this invention includes paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions. Synthetic oils include both hydrocarbon synthetic oils and synthetic esters.
  • Useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C 6-12 alpha olefins such as 1-decene trimer, tetramer, and higher oligomers. Likewise, alkyl benzenes of proper viscosity, such as didodecyl benzene, can be used.
  • Useful synthetic esters include the esters of both monocarboxylic acid and polycarboxylic acids as well as monohydroxy alkanols and polyols.
  • Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate and the like.
  • Complex esters prepared from mixtures of mono and dicarboxylic acid and mono and dihydroxy alkanols can also be used.
  • Blends of hydrocarbon oils with synthetic oils are also useful. For example, blends of 10 to 25 weight percent hydrogenated 1-decene trimer with 75 to 90 weight percent 33 cSt at 100°F. (38°C.) mineral oil gives an excellent lubricating oil base.
  • additives which may be present in the formulation include rust inhibitors, foam inhibitors, corrosion inhibitors, metal deactivators, pour point depressants, antioxidants, and a variety of other well-known additives.
  • the candidate additives were tested for their compatibility in a bench test (PV3334) by suspending a fluorocarbon coupon (AK6) in an oil solution heated at 150°C for 96 hours (4 days) followed by measuring a change in the physical properties of the specimen, particularly the tensile strength (TS), and the percent elongation to break (EL) in accordance with DIN53504 procedure, and observing whether any cracks had developed at 120% elongation (CR).
  • a passing test criteria included the following: no evidence of crack development; a tensile strength change of less than 20% (gain or loss); and an elongation change of less than 25% (gain or loss). Obviously, an ideal case would show no cracks and 0% change in TS and EL. This test procedure will be referred to above and later simply as the "VW Bench Test.”
  • the baseline formulation used for testing a fluorocarbon coupon contained a dispersant (6% by weight), i.e., either a mono- or bis-succinimide; an overbased calcium hydrocarbyl sulfonate (30 mmol/kg); an overbased calcium phenate (20 mmol/kg); mixed primary and secondary zinc dialkyl dithiophosphates (22.5 mmol/kg) ; and ethylene-propylene copolymer viscosity index improver (13% by weight) in 150N Exxon base oil. When borated additives were tested, these were added in appropriate percentages as top treats on top of the baseline formulation above.
  • Examples 1-4 are base runs and show that the presence of mono- or bis-succinimides alone in the formulation without borated aromatic polyols, lack compatibility of the oil to the fluorocarbon elastomers, i.e., no pass of the VW Bench Test.
  • borated t-butyl catechol results in passivation of the basic nitrogen (Ex 13) using bis-succinimides but fails using the mono-succinimides (Ex 14).
  • Examples 27 and 28 in Table 2 below show that increasing the concentration of the borated t-butyl catechol to 2% results in a "PASS" with the mono-succinimide.
  • Examples 15-19 show that using only 1 weight percent of several different alkylated borated catechols within the scope of the invention is insufficient to passivate the fluorocarbon elastomers. Examples in Table 2 below show that increasing the concentrations of such catechols results in a PASS.
  • Examples 5, 46 and 47 show that the aromatic polyol can be a single (Ex 5) or condensed ring (Ex 47) aromatic as long as two hydroxy groups are present on adjacent aromatic ring carbon atoms (Compare Examples 5 and 46, which were successful, to Example 45 which was unsuccessful due to the hydroxy groups being on non-adjacent aromatic ring carbon atoms). The presence of an additional hydroxy group on the ring (pyrogallol) is acceptable (See Example 46).
  • the fully synthetic base oil was used in a formulation containing a mixture of dispersants (7.3%), an overbased calcium sulfonate (0.7%), highly overbased calcium phenate (3.4%), mixed zincs (2%), and polyol ester (8.3%) in a commercial synthetic PAO base fluid (as above) (68%) and polyisoprene VI improver (10.3%), blended to a 5W40 specification.
  • the borated additives were added as "top treats" on top of the reference formulation in the percentages given in the examples summarized in Table 5 below.
  • the reference oil formulation contained 3.5% dispersant, 50 mmol/kg calcium as hydrocarbyl sulfonates, 17 mmol/kg zinc dialkyl dithiophosphate, and 6.8% viscosity index improver in Chevron 100N base oil.
  • the oxidation test employed herein measures the resistance of the test sample to oxidation using pure oxygen with a Dornte-type oxygen absorption apparatus [R. W. Dornte, "Oxidation of White Oils," Industrial and Engineering Chemistry, 28 p. 26 (1936)].
  • the conditions are: an atmosphere of pure oxygen exposed to the test oil, an oil temperature of 340° F.
  • catechol borate and short chain alkyl catechol borates (1-8 carbons in the alkyl chain) were found to have unexpectedly superior dispersancy properties compared to long-chain alkyl catechol borates.
  • the dispersancy properties are measured by the "dispersancy spot test" ("Test").
  • Example 4 of U.S. Patent 4,199,462 Column 7, lines 13 et seq.
  • the Test set forth in Example 4 of the '462 Patent has been modified for the seventh series of runs to be discussed below.
  • the purpose of the seventh series of runs was to compare the dispersive properties of (1) catechol borate (2) butyl catechol borate and (3) a long-chain (average C 22 ) alkyl catechol borate with the reference SAE30 oil containing the sludge.
  • Catechol borate showed a gain of about 50 units over the reference value of 396.
  • t-Butyl catechol borate showed a gain of about 18 units while the long chain alkyl catechol borate showed a loss of about 25 units.
  • the attached Figure is a plot of these data with the carbon number of the alkyl group on the x-axis and a loss or gain in dispersancy on the y-axis.
  • alkylcatechol borates with alkyl groups below 10 carbon i.e., 8 or 9, should not only provide passing results in the VW Bench Test, but also offer no loss in the overall dispersancy, a quite unexpected result.
  • catechol borate has the advantages set forth above, it and the lower alkyl catechol borates have low solubility in base oils.
  • catechol borate was soluble only to the extent of about 0.3 weight percent or less.
  • alkyl-catechol borates containing a long alkyl group can effectively be employed to enhance the solubility of the less soluble catechol borate in the formulated base oil.
  • catechol borate was soluble only to the extent of about ⁇ 0.3%, but this value was exceeded by adding an alkylcatechol containing a long (avg C22) alkyl group.

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Abstract

On a découvert que certains polyols aromatiques boratés tels que du borate de pyrocatéchine peuvent servir d'additifs efficaces pour l'huile de graissage afin que cette dernière soit compatible avec les joints d'étanchéité constitués d'un polymère au fluorocarbone, lorsque ladite huile de graissage contient de l'azote basique.

Claims (18)

  1. Utilisation d'un polyol aromatique boraté dans une composition lubrifiante contenant une moindre proportion d'un composé contenant de l'azote basique, en vue d'améliorer la compatibilité de cette huile lubrifiante vis-à-vis de joints en polymère fluorocarboné de moteurs, ce polyol aromatique boraté pouvant être obtenu par boratation d'un polyol aromatique répondant à la formule :
    Figure 00590001
    dans laquelle R"' est choisi dans le groupe consistant en H ; OH ; ou un groupe alkyle ayant 1 à 8 atomes de carbone.
  2. Utilisation suivant la revendication 1, dans laquelle le composé contenant de l'azote basique est un succinimide.
  3. Utilisation suivant la revendication 2, dans laquelle le succinimide comprend le produit de réaction d'un acide ou anhydride succinimique à substituant polybutène en C8 à C500 et d'une alkylènepolyamine.
  4. Utilisation suivant la revendication 3, dans laquelle la quantité de polyol aromatique boraté est au moins égale à la quantité stoechiométrique relative à l'azote basique présent dans la composition.
  5. Utilisation suivant la revendication 4, dans laquelle le polyol aromatique boraté est le catéchol boraté.
  6. Utilisation suivant la revendication 4, dans laquelle le polyol aromatique boraté est le pyrogallol boraté.
  7. Utilisation suivant la revendication 4, dans laquelle le polyol aromatique boraté est le tertio-butyl-catéchol boraté.
  8. Utilisation suivant la revendication 4, dans laquelle le pourcentage en poids du succinimide va de 1 à 20 % en poids de la composition.
  9. Utilisation suivant la revendication 1, comprenant en outre une quantité suffisante d'un catéchol boraté à groupe alkyle à longue chaíne, dont le groupe alkyle a au moins 10 atomes de carbone, pour faciliter la solubilisation de ce polyol aromatique boraté.
  10. Composition lubrifiante comprenant une proportion dominante d'une huile lubrifiante ; une proportion moindre d'au moins un composé contenant de l'azote basique et une quantité compatibilisante moindre mais efficace d'un polyol aromatique boraté comme additif pour passiver des joints en polymère fluorocarboné, ce polyol aromatique pouvant être obtenu par boratation d'un polyol aromatique répondant à la formule :
    Figure 00600001
    dans laquelle R"' est choisi dans le groupe consistant en H ; OH ; ou un groupe alkyle ayant 1 à 8 atomes de carbone.
  11. Composition suivant la revendication 10, dans laquelle le composé contenant de l'azote basique est un succinimide.
  12. Composition suivant la revendication 11, dans laquelle le succinimide comprend le produit de réaction d'un acide ou anhydride succinimique à substituant polybutène en C8 à C500 et d'une alkylènepolyamine.
  13. Composition suivant la revendication 12, dans laquelle la quantité de polyol aromatique boraté est au moins la quantité stoechiométrique relative à l'azote basique présente dans la composition.
  14. Composition suivant la revendication 13, dans laquelle le polyol aromatique boraté est le catéchol boraté.
  15. Composition suivant la revendication 13, dans laquelle le polyol aromatique boraté est le pyrogallol boraté.
  16. Composition suivant la revendication 13, dans laquelle le polyol aromatique boraté est le tertio-butyl-catéchol boraté.
  17. Composition suivant la revendication 13, dans laquelle le pourcentage en poids du succinimide va de 1 à 20 % en poids de la composition.
  18. Composition suivant la revendication 10, qui contient en outre une quantité suffisante d'un catéchol boraté portant un groupe alkyle à longue chaíne, dont le groupe alkyle a au moins 10 atomes de carbone, pour faciliter la solubilisation de ce polyol aromatique boraté.
EP92918231A 1991-10-08 1992-08-25 Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissage Expired - Lifetime EP0562062B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US772821 1985-09-05
US77282191A 1991-10-08 1991-10-08
PCT/US1992/007141 WO1993007242A1 (fr) 1991-10-08 1992-08-25 Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissage

Publications (3)

Publication Number Publication Date
EP0562062A1 EP0562062A1 (fr) 1993-09-29
EP0562062A4 EP0562062A4 (fr) 1994-04-27
EP0562062B1 true EP0562062B1 (fr) 1998-01-07

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Application Number Title Priority Date Filing Date
EP92918231A Expired - Lifetime EP0562062B1 (fr) 1991-10-08 1992-08-25 Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissage

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Country Link
EP (1) EP0562062B1 (fr)
JP (1) JP3231322B2 (fr)
CA (1) CA2097828C (fr)
DE (1) DE69223942T2 (fr)
SG (1) SG48193A1 (fr)
WO (1) WO1993007242A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
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US20120149618A1 (en) * 2010-12-14 2012-06-14 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
US8933001B2 (en) 2010-03-31 2015-01-13 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
DE102020117671A1 (de) 2020-07-03 2021-10-21 Fuchs Petrolub Se Polyharnstoff-Schmierfette enthaltend Carbonate und deren Verwendung
DE102020008047A1 (de) 2020-07-03 2022-01-05 Fuchs Petrolub Se Polyharnstoff-Schmierfette enthaltend Carbonate und deren Verwendung

Families Citing this family (11)

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US5569644A (en) * 1995-05-18 1996-10-29 The Lubrizol Corporation Additive combinations for lubricants and functional fluids
US5962380A (en) * 1995-06-06 1999-10-05 Chevron Chemical Company Llc Fluorocarbon elastomer compatibility improving agent having wear inhibition effect
FR2762848B1 (fr) * 1997-05-05 2000-02-04 Chevron Res & Tech Utilisation de composes borates pour ameliorer la compatibilite d'huiles lubrifiantes avec des elastomeres fluorocarbones
US6010986A (en) * 1998-07-31 2000-01-04 The Lubrizol Corporation Alcohol borate esters to improve bearing corrosion in engine oils
US20040171501A1 (en) * 2003-02-27 2004-09-02 Leeuwen Jeroen Van Method for improving elastomer compatibility
US8901050B2 (en) 2010-03-31 2014-12-02 Chevron Oronite Company Llc Method for improving copper corrosion performance
US8993496B2 (en) 2010-03-31 2015-03-31 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
US9150811B2 (en) 2010-03-31 2015-10-06 Cherron Oronite Company LLC Method for improving copper corrosion performance
US9388362B2 (en) * 2012-10-30 2016-07-12 Chevron Oronite Company Llc Friction modifiers and a method of making the same
WO2016138227A1 (fr) * 2015-02-26 2016-09-01 The Lubrizol Corporation Détergents aromatiques et compositions lubrifiantes de ceux-ci
CN111718778B (zh) * 2020-06-23 2022-04-19 长沙众城石油化工有限责任公司 一种复合钙基润滑脂及其制备方法

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US2795548A (en) * 1954-06-29 1957-06-11 California Research Corp Lubricant compositions
US4482464A (en) * 1983-02-14 1984-11-13 Texaco Inc. Hydrocarbyl-substituted mono- and bis-succinimide having polyamine chain linked hydroxyacyl radicals and mineral oil compositions containing same
US4629577A (en) * 1985-06-17 1986-12-16 Chevron Research Company Method for improving fuel economy of internal combustion engines
CA1237959A (fr) * 1983-09-29 1988-06-14 Andrew G. Papay Procede de boration
US4629578A (en) * 1985-06-17 1986-12-16 Chevron Research Company Succinimide complexes of borated alkyl catechols and lubricating oil compositions containing same
US4713190A (en) * 1985-10-23 1987-12-15 Chevron Research Company Modified carboxylic amide dispersants
US5061390A (en) * 1989-07-05 1991-10-29 Chevron Research And Technology Company Diethylamine complexes of borated alkyl catechols and lubricating oil compositions containing the same
ATE126263T1 (de) * 1989-09-15 1995-08-15 Chevron Usa Inc Alkylaminkomplexe borierter alkylkatecholen und diese komplexe enthaltende schmierölzusammensetzungen.

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8933001B2 (en) 2010-03-31 2015-01-13 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
US20120149618A1 (en) * 2010-12-14 2012-06-14 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
US8716202B2 (en) * 2010-12-14 2014-05-06 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
DE102020117671A1 (de) 2020-07-03 2021-10-21 Fuchs Petrolub Se Polyharnstoff-Schmierfette enthaltend Carbonate und deren Verwendung
DE102020008047A1 (de) 2020-07-03 2022-01-05 Fuchs Petrolub Se Polyharnstoff-Schmierfette enthaltend Carbonate und deren Verwendung
WO2022002317A1 (fr) 2020-07-03 2022-01-06 Fuchs Petrolub Se Graisses lubrifiantes à base de polyurée contenant des carbonates, et leur utilisation
DE102020117671B4 (de) 2020-07-03 2022-06-09 Fuchs Petrolub Se Schmierstellen aufweisend eine Polyharnstoff-Schmierfett-Zusammensetzung und eine Dichtung umfassend ein Dichtmaterial aus fluorierten Elastomeren und die Verwendung der Polyharnstoff-Schmierfett-Zusammensetzung für eine Schmierstelle umfassend eine derartige Dichtung

Also Published As

Publication number Publication date
EP0562062A1 (fr) 1993-09-29
DE69223942T2 (de) 1998-06-18
SG48193A1 (en) 1998-04-17
JPH06505526A (ja) 1994-06-23
EP0562062A4 (fr) 1994-04-27
CA2097828A1 (fr) 1993-04-09
DE69223942D1 (de) 1998-02-12
CA2097828C (fr) 2003-07-08
JP3231322B2 (ja) 2001-11-19
WO1993007242A1 (fr) 1993-04-15

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