JP2005516110A - Lubricating oil composition with improved friction properties - Google Patents

Abstract

The present invention relates to friction reducers for use in lubricating oil compositions comprising a particular group of amorphous polymers, such as aromatic compounds, esters, narrow mixtures of base oils, and / or amorphous olefin copolymers. These compositions can provide the benefit of a substantial reduction in coefficient of friction and improved fuel economy when mixed into a lubricating oil without detrimental effects such as instability, undesirably high viscosity and deposits. Is possible. In one aspect of the invention, pentaerythritol ester and optionally triol ester are added to the lubricating oil composition to provide reduced friction and improved fuel economy. In the second aspect of the present invention, similar results are obtained by adding a hydrocarbyl aromatic compound to a lubricating oil composition containing one or more Group II base oils and Group III base oils. In a third aspect, the present invention relates to a lubricating oil composition comprising an amorphous olefin copolymer and one or more of a Group II base oil and a Group III base oil. In one embodiment, the third aspect also includes one or more of hydrocarbyl aromatic compounds and polyol esters as part of the composition. In a fourth embodiment, a moderate concentration of hydrocarbyl aromatic is used in a lubricating oil composition comprising a paraffinic base oil and preferably a boronated polyisobutenyl succinimide ashless dispersant.

Description

  The present invention relates to lubricating oil compositions suitable for use in internal combustion engines.

  Lubricating oils for internal combustion engines contain additives that enhance the performance of the lubricating oil, in addition to at least one base oil. Various additives such as detergents, dispersants, friction reducers, viscosity index improvers, antioxidants, corrosion inhibitors, antiwear agents, pour point depressants, seal compatible additives and antifoam agents are lubricant compositions. Used in things.

  It is critical to maintain a lubricious film thickness on the metal surface that is sufficiently thick to maintain low friction at various operating temperatures and reduce wear of metal parts. It is also important to maintain cleanliness over the entire range of operating conditions while minimizing wear while maintaining good overall lubricating oil performance under the most severe operating conditions. Conventional lubricant and engine oil technologies include alcohols, hydrocarbyl diols, hydrocarbyl triols, alkane diols or triols, fatty acids amides such as esters, fatty acid esters, hydroxy esters, oleamides, hydroxyalkyl hydrocarbyl amides, bis (2-hydroxyethyl) oleamides. Bis-hydroxyalkyl hydrocarbyl amides, bis-hydroxyalkyl hydrocarbyl amines, bis-hydroxyalkyl hydrocarbyl amines such as bis (2-hydroxyethyl) oleylamine, borides above, acylates above, phosphorus-based compositions such as trioleyl phosphite, Inorganic containing molybdenum dithiocarbamate, molybdenum phosphorodithioate, molybdenum complexes of amine and / or alcohol moieties Traditionally friction reducing agent can be selected from one or more classes of Ribuden compound and / or friction reducing compounds exemplified by molybdenum compounds such as organic molybdenum compounds rely on extremes. Friction reducing agents often comprise a mixture of two or more of the above component classes. Some of the above prior art friction reducing compositions have been found to have serious and often undesirable side effects. Accordingly, it would be desirable to have several components and / or several systems with improved fuel economy that can be selected from a blend of high quality fuel economy improved lubricants.

US Pat. No. 4,956,122 US Pat. No. 4,827,064 US Pat. No. 4,827,073 U.S. Pat. No. 4,149,178 US Pat. No. 3,382,291 US Pat. No. 3,742,082 US Pat. No. 3,769,363 US Pat. No. 3,876,720 US Pat. No. 4,239,930 US Pat. No. 4,367,352 U.S. Pat. No. 4,413,156 U.S. Pat. No. 4,434,408 U.S. Pat. No. 4,910,355 US Pat. No. 4,956,122 US Pat. No. 5,068,487 US Pat. No. 4,218,330 US Pat. No. 5,055,626 European Patent Application No. 168534 US Pat. No. 4,658,072 US Pat. No. 5,075,269 US Pat. No. 2,817,693 U.S. Pat. No. 4,975,177 US Pat. No. 4,921,594 U.S. Pat. No. 4,897,178 British Patent 1,429,494 British Patent 1,350,257 British Patent No. 1,440,230 British Patent 1,390,359 European Patent Application No. 464546 European Patent Application No. 464547 US Pat. No. 4,594,172 U.S. Pat. No. 4,943,672 US Pat. No. 6,080,301 US Pat. No. 6,090,989 US Pat. No. 6,165,949 US Pat. No. 4,941,984 US Pat. No. 2,443,264 US Pat. No. 2,471,115 US Pat. No. 2,526,497 US Pat. No. 2,591,577 US Pat. No. 3,770,854 US Pat. No. 4,501,678 US Pat. No. 4,758,362 US Pat. No. 5,693,598 US Pat. No. 5,034,141 US Pat. No. 5,034,142 U.S. Pat. No. 4.798,684 US Pat. No. 5,084,197 US Pat. No. 3,595,791 US Pat. No. 6,034,039 US Pat. No. 3,172,892 US Pat. No. 3,215,707 US Pat. No. 3,219,666 US Pat. No. 3,316,177 US Pat. No. 3,341,542 US Pat. No. 3,444,170 US Pat. No. 3,454,607 US Pat. No. 3,541,012 US Pat. No. 3,630,904 US Pat. No. 3,632,511 US Pat. No. 3,787,374 U.S. Pat. No. 4,234,435 US Patent 3,036,003 US Pat. No. 3,200,107 US Pat. No. 3,254,025 US Pat. No. 3,275,554 US Pat. No. 3,438,757 US Pat. No. 3,454,555 US Pat. No. 3,565,804 US Pat. No. 3,413,347 US Pat. No. 3,697,574 US Pat. No. 3,725,277 US Pat. No. 3,725,480 US Pat. No. 3,762,882 US Pat. No. 4,454,059 US Pat. No. 3,329,658 US Pat. No. 3,449,250 US Pat. No. 3,519,565 US Pat. No. 3,666,730 US Pat. No. 3,687,849 US Pat. No. 3,702,300 US Pat. No. 4,100,082 US Pat. No. 5,705,458 European Patent Application No. 471071 US Pat. No. 3,087,936 US Pat. No. 3,172,892 US Pat. No. 3,219,666 US Pat. No. 3,272,746 U.S. Pat. No. 3,322,670 US Pat. No. 3,652,616 US Pat. No. 3,948,800 Canadian Patent No. 1,094,044 US Pat. No. 4,426,305 US Pat. No. 4,767,551 US Pat. No. 3,697,574 US Pat. No. 3,703,536 US Pat. No. 3,704,308 US Pat. No. 3,751,365 US Pat. No. 3,756,953 US Pat. No. 3,798,165 US Pat. No. 3,803,039 US Pat. No. 3,275,554 US Pat. No. 3,438,757 US Pat. No. 3,565,804 US Pat. No. 3,755,433 US Pat. No. 3,822,209 US Pat. No. 5,084,197 US Pat. No. 1,815,022 US Pat. No. 2,015,748 US Pat. No. 2,191,498 US Pat. No. 2,387,501 US Pat. No. 2,655,479 US Pat. No. 2,666,746 US Pat. No. 2,721,877 US Pat. No. 2,721,878 US Pat. No. 3,250,715 US Pat. No. 2,719,125 US Pat. No. 2,719,126 US Pat. No. 3,087,932 Olah GA (eds.) “Friedel-Crafts and Related Reactions”, New York, Interscience Publishers, 1963 publication Olah GA (eds.) "Friedel-Crafts and Related Reactions," Volume 2, Part, Chapters 14, 17 and 18, New York, Interscience Publishers ( Interscience Publishers), 1964 “Klamann in Lubricants and Related Products”, Verlag Chemie (Deerfield Beach, FL), Deerfield Beach, Florida, ISBN0-89573-177-0. "Lubricant Additives" by MW Ranney, Noyes Data Corporation (Parkridge, NJ), Parkridge, NJ, 1973 API publication 1509; www. API. org "Synthetic Lubricants" by Gunderson and Hart, Reinhold Publ. Corp., New York, 1962 ACS Petroleum Chemistry Preprints 1053-1058, Epen et al., “Poly n-Alkylbenzene Compounds: A Class of Hydrogen Liquid Compounds” and Wide Liquid Range Fluids), Philadelphia (Phila.), 1984. Dresser, H. “Synthetic Lubricants and High Performance Fluids”, Chapter 5 (RL Shubkin, Ed.), Marcel Decker, NY (Marcel Dekker), 1993 Book titled “Lubricant Additives” by C.V. Smallheer and R.K. Smith, Lezius-Hiles Co., Cleveland, Ohio, 1967 Year

  The present invention relates to friction reducers for use in lubricating oil compositions comprising a particular group of amorphous polymers, such as aromatic compounds, esters, narrow mixtures of base oils, and / or amorphous olefin copolymers. These compositions can provide the benefit of a substantial reduction in coefficient of friction and improved fuel economy when mixed into a lubricating oil without detrimental effects such as instability, undesirably high viscosity and deposits. Is possible.

  In one aspect of the invention, pentaerythritol ester and optionally triol ester are added to the lubricating oil composition to provide reduced friction and improved fuel economy. In a second embodiment of the present invention, similar results are obtained by adding a hydrocarbyl aromatic compound to a lubricating oil composition containing one or more of Group II base oil, Group I II base oil and wax isomerized base oil. It is done. In a third aspect, the present invention relates to a lubricating oil composition comprising an amorphous olefin copolymer and one or more of Group II base oil, Group III base oil and wax isomerized base oil. In one embodiment, the third aspect also includes one or more of hydrocarbyl aromatic compounds and polyol esters as part of the composition. In a fourth embodiment, a moderate concentration of hydrocarbyl aromatic is used in a lubricating oil composition comprising a paraffinic base oil and preferably a boronated polyisobutenyl succinimide ashless dispersant.

  Engine oil contains a base oil and various additives. These additives include detergents, dispersants, friction reducers, viscosity index improvers, antioxidants, corrosion inhibitors, antiwear agents, pour point depressants, seal compatible additives and antifoaming agents. . In order to be effective, these additives must be oil-soluble or oil-dispersible. Oil-soluble means that the compound is soluble in the base oil or lubricating oil composition under normal blending conditions.

  The present invention can provide the benefit of substantial reduction in coefficient of friction and improved fuel economy when mixed into a lubricant without harmful effects such as instability, undesirably high viscosity and deposits. Relates to a specific group of amorphous polymers such as aromatic compounds, esters, mixtures of base oils and / or amorphous olefin copolymers.

  In one aspect, the present invention has been found to provide an unexpectedly significant fuel economy improvement (friction reduction) benefit when formulated into a lubricating oil containing a hydrocarbyl aromatic composition. Relates to pentaerythritol ester. This enhancement of fuel efficiency improvement can be further improved by adding a specific ester to the above-mentioned pentaerythritol ester. In particular, this additional fuel economy improvement is seen in mixed triol ester and pentaerythritol ester systems in the presence of relatively low concentrations of hydrocarbyl aromatic compounds such as alkylated naphthalene. Useful concentrations of hydrocarbyl aromatic compounds range from about 1% or more. We believe that about 2% to about 45%, more preferably about 2% to about 30%, and even more preferably about 3% to about 15% of these hydrocarbyl aromatic compounds are often preferred. ing.

Desirable esters include pentaerythritol esters derived from monopentaerythritol polyols, dipentaerythritol polyols and polypentaerythritol polyols reacted with mixed hydrocarbyl acid (RCO ₂ H), wherein the effective -OH group is substantially Mention may be made of pentaerythritol esters whose amounts have been converted to esters. Acid moiety and esters of substituted hydrocarbyl radical, R comprises more than about _{C 6} ~ about _{C 16,} the preferred range is from about _{C 6} ~ about _{C 14,} alkyl, alkenyl, cycloalkyl, cycloalkenyl, linear, branched And related hydrocarbyl groups, and can optionally include S, N and / or O groups. Pentaerythritol esters having a substituted hydrocarbyl group and a mixed group of R are often preferred. For example, substituted hydrocarbyl radical, R is about 1: 4 to 4: may contain substantial amounts of hydrocarbyl moiety _{C 8} and _{C 10} in a ratio. In one embodiment, preferred pentaerythritol esters have R groups that include approximately about 55% C ₈ , about 40% C ₁₀ , and the remaining about 5% C ₆ and C ₁₂₊ moieties. For example, a useful type of pentaerythritol ester has a viscosity index of about 148, a pour point of about 3 ° C. and a kinematic viscosity of about 5.9 cSt at 100 ° C. Pentaerythritol esters can be used in lubricating oil compositions at a concentration of about 3% to about 30%, preferably about 4% to about 20%, more preferably about 5% to about 15%.

  Esters may include esters such as trimethylolpropane and trimethylolethane.

The hydrocarbyl aromatic compounds that can be used can be any hydrocarbyl molecule comprising at least about 5% by weight of a hydrocarbyl aromatic compound or hydrocarbyl aromatic compound derivative derived from an aromatic moiety such as a benzenoid moiety or a naphthenoid moiety. is there. These hydrocarbyl aromatic compounds include alkyl benzene, alkyl naphthalene, alkyl diphenyl oxide, alkyl naphthol, alkyl diphenyl sulfide, alkylated bis-phenol A and alkylated thiodiphenol. Aromatic compounds can be monoalkylated, dialkylated, multialkylated, and the like. Aromatic compounds can be monofunctionalized or polyfunctionalized. The hydrocarbyl group can also consist of a mixture of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl groups and other related hydrocarbyl groups. Hydrocarbyl group, it is possible in the range of from about _{C 6} ~ about _{C 60,} the range of from about _{C 8} ~ about _{C 40} is often preferred. Mixed groups of hydrocarbyl groups are preferred in many cases. The hydrocarbyl group can optionally include sulfur-containing substituents, oxygen-containing substituents, and / or nitrogen-containing substituents. Aromatic groups can also be derived from natural (petroleum) sources as long as at least about 5% of the molecule consists of the above types of aromatic moieties. A viscosity at 100 ° C. of about 3 cSt to about 50 cSt is preferred for the hydrocarbyl aromatic component, and a viscosity of about 3.4 cSt to about 20 cSt is more preferred for the hydrocarbyl aromatic component. In one embodiment, an alkyl naphthalene whose alkyl group consists primarily of 1-hexadecene is used. Other alkylates of aromatic compounds can be used advantageously. For example, naphthalene can be alkylated with olefins such as octene, decene, dodecene, tetradecene or higher olefins, and mixtures of similar olefins. Useful concentrations of hydrocarbyl aromatics in the lubricating oil composition are from about 2% to about 25%, preferably from about 4% to about 20%, more preferably from about 4% to about 15%, depending on the application. It is possible.

Alkylated aromatic compounds such as the hydrocarbyl aromatic compounds of the present invention may be prepared by well-known Friedel-Craft alkylation of aromatic compounds. See Non-Patent Document 1. For example, aromatic compounds such as benzene or naphthalene are alkylated with olefins, alkyl halides or alcohols in the presence of Friedel-Craft catalysts. See Non-Patent Document 2. Many homogeneous and heterogeneous solid catalysts are known to those skilled in the art. The choice of catalyst depends on the reactivity of the starting materials and the quality requirements of the product. For example, a strong acid such as AlCl ₃ , BF ₃ or HF may be used. In some cases, milder catalysts such as FeCl ₃ or SnCl ₄ are preferred. Other alkylation techniques use zeolites or solid superacids.

  Enhanced fuel economy is seen with a synergistic mixture of (a) a Group II paraffin oil blend containing a wax isomerized base oil or a Group III paraffin oil blend and (b) a hydrocarbyl aromatic compound. In particular, the above-mentioned groups comprising certain hydrotreated base oils in the presence of low concentrations of polyol-based esters (such as esters derived from trimethylolpropane and mixed hydrocarbyl acids) and hydrocarbyl aromatic compounds (such as alkylated naphthalene). The oil is surprisingly drastically improved in fuel efficiency (friction reduction) when compared directly to a lubricating oil containing a relatively high amount of about 40% high quality synthetic fluid derived from olefin oligomers such as 1-decene oligomers It has been found to provide benefits. For comparison, both groups of base oils have a viscosity of about 4 to about 50 cSt at 100 ° C. and a similar viscosity index of about 110 to about 150 or higher.

  In another embodiment of the present invention, certain amorphous olefin copolymers have a significant amount of Group II, particularly when formulated into a lubricating oil, including a wax isomerate oil, having a viscosity index of from about 110 to about 150 or greater. It has been found that when formulated in lubricating oils containing base oils or group III base oils, it provides unexpectedly significant fuel savings (friction reduction) benefits. Such olefin copolymers are not primarily crystalline. The copolymer used in the present invention has a molecular weight in the range of about 20,000 or more, preferably 60,000 or more, more preferably 100,000 or more, and even more preferably 150,000 or more. For example, in one embodiment, an amorphous ethylene-propylene copolymer that includes a significant to major amount of a propylene-derived copolymer has a molecular weight in the range of about 20,000 or greater. We have traditional esters at concentrations of about 1% to about 30% or more, preferably about 2% to about 25%, more preferably about 3% to about 20% in the final formulated lubricant. It is believed that the fuel saving benefits can be further enhanced when using the above amorphous olefin copolymer in the presence of a hydrocarbyl aromatic compound such as alkylnaphthalene.

  The use of these amorphous olefin copolymers in the present invention results in surprising low temperature pumping performance in lubricating oil compositions.

  In another embodiment of the present invention, significant fuel economy enhancement is achieved by the presence of at least a minute concentration of Group II or Group III hydrocracked base oil and / or hydrotreated base oil, preferably comprising wax isomerate oil. This is achieved with the use of moderate concentrations of hydrocarbyl aromatics below. These hydrocarbyl aromatic compounds are described above. Group II and Group III base oils and wax isomerized base oils are described below. The present inventors also believe that the present invention can greatly contribute to the enhancement of fuel economy, in which the presence of a specific ashless dispersant is observed.

  For example, a preferred class of compositions comprising about 20% hydrocarbyl aromatics, about 40% Group II paraffin base oil, and about 3% by weight boronated polyisobutyl succinimide ashless dispersant may be particularly useful. Has been found. Useful ashless dispersants are described below.

Group II and / or Group III hydrotreated base oils or hydrocracked base oils, including wax isomerized oils, or synthetic base oils such as polyalphaolefin lubricating oils are combined with each component of the embodiments of the present invention. Preferred as a lubricating base oil when used. At least about 20% of the total composition should contain such a Group II base oil or Group III base oil containing wax isomerized oil, with at least about 30% being more preferred, and optionally at least about 50% being more Preferably, even more than about 80% is even more preferred in some cases. A gas-liquid (GTL) base oil can also be used preferentially in combination with the components of the present invention as part or all of the base oil used to formulate the final lubricating oil. Mixtures of all or part of these base oils can be used advantageously and may be preferred in many cases. We have found that the components of the present invention in combination with a lower amount of alternative fluids such as the hydrocarbyl aromatic compounds described above as exemplified by C ₁₂ , C ₁₄ , C ₁₆ and / or C ₁₈ alkylated naphthalene. Improvements and benefits are considered best when added to a lubricating system consisting primarily of Group II and / or Group III base oils, including wax isomerate. In some cases, hydrocarbyl aromatic products substantially comprising monoalkylated naphthalene may be preferred.

  Other components, including effective amounts of co-base oils and various performance additives, can be advantageously used in conjunction with the components of the present invention. These co-base oils are derived from polyalphaolefin oligomer low viscosity oil, polyalphaolefin oligomer medium viscosity oil and polyalphaolefin oligomer high viscosity oil, dibasic acid ester, polyol ester, gas-liquid (GTL) type technology. Other hydrocarbon oils such as prepared oils and supplemental hydrocarbyl aromatics. These co-base oils also contain small amounts of decene derived trimers and tetramers, as well as small amounts of Group I base oils. However, the above Group II base oils and / or Group III base oils containing wax isomerized oils are the main ones, and fluids comprising the elements of the above invention that require a substantial portion of such base oils Conditioned to constitute at least about 50% of the total base oil contained therein. Base oils, co-base oils and other performance additives are discussed in more detail below.

  The present invention relates to an effective amount of another lubricating oil component in a lubricating oil composition, such as, for example, polar and / or nonpolar lubricating base oils, as well as, for example, antioxidants, metal dispersants and non-metal dispersants, metal detergents Agents and non-metallic detergents, corrosion inhibitors and rust inhibitors, metal deactivators, anti-wear agents (metal and non-metallic, phosphorus and non-phosphorous, sulfur and non-sulfur), poles Pressure additive (metallic and non-metallic, phosphorous and nonphosphorous, sulfur and nonsulfur), anti-seizure agent, pour point depressant, wax modifier, viscosity modifier, seal conformant, friction It can be used in combination with performance additives such as, but not limited to, modifiers, lubricants, antifouling agents, dyes, antifoaming agents, demulsifiers and others. For a review of many commonly used additives, see Non-Patent Document 3, which also provides a good discussion of the many lubricating oil additives discussed below. Non-patent document 4 also describes.

[Base oil]
A wide range of lubricating oils are known in the art. Lubricating oils useful in the present invention are both natural and synthetic oils. Natural and synthetic oils (or mixtures thereof) can be used unrefined, refined, or rerefined (the latter also known as reclaimed or reprocessed oil). Unrefined oils are oils obtained directly from natural or synthetic sources and are used without further purification. These include shale oil obtained directly from retort operation, petroleum oil obtained directly from primary distillation and ester oil obtained directly from the esterification process. Refined oils are similar to those discussed for unrefined oils, except that the refined oil has undergone one or more refinement steps to improve at least one lubricating oil property. Those skilled in the art are familiar with many purification processes. These processes include solvent extraction, secondary distillation, acid extraction, base extraction, filtration and percolation. Rerefined oils are obtained by a process that is similar to refined oils but uses previously used oils.

  Groups I, II, III, IV and V are broad classifications of base stocks developed and defined by the American Petroleum Institute (Non-Patent Document 5) to provide guidance for lubricating base oils. It is. Group I base oils generally have a viscosity index between about 80 and 120 and contain greater than about 0.03% sulfur and / or less than about 90% saturation. Group II base oils generally have a viscosity index between about 80 and 120, and contain no more than about 0.03% sulfur and no less than about 90% saturation. Group III base oils generally have a viscosity index greater than about 120 and contain no more than about 0.03% sulfur and greater than about 90% saturation. Group IV includes polyalphaolefins (POA). Group V base oils include base oils not included in Groups I-IV. The following table summarizes the characteristics of each of these five groups.

  Natural oils include animal oils, vegetable oils (eg, castor oil and lard oil) and mineral oils. It is possible to use animal oils and vegetable oils having preferred thermal oxidative stability. Of the natural oils, mineral oil is preferred. Mineral oils vary widely with regard to crude oil sources, for example whether they are paraffinic, naphthenic or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful in the present invention. Natural oils also differ with respect to the methods used for production and refining, for example regarding the distillation range and whether they are straight-run, cracked, hydrogen refined, or solvent extracted.

Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils such as polymerized olefins and interpolymerized olefins such as polybutylene, polypropylene, propylene isobutylene copolymers, ethylene-olefin copolymers and ethylene-alpha olefin copolymers. Polyalphaolefin (PAO) base oil is a commonly used synthetic hydrocarbon oil. As an _example, it may be used _{C 8, C 10, C 12} , C 14 olefins or derived PAO mixtures thereof. See Patent Literature 1, Patent Literature 2, and Patent Literature 3. These patent documents are incorporated herein by reference in their entirety.

The number average molecular weight of PAO, which is a known material and is commercially available on a large scale commercially from ExxonMobil Chemical Company, Chevron-Phillips, BP-Amoco and others, is Although PAO can be made with viscosities up to about 100 cSt (100 ° C.), it typically varies from about 250 to about 3,000. PAOs are not limited to C ₂ to about C ₃₂ alpha olefins, but typically consist of relatively low molecular weight hydrogenated polymers or oligomers of alpha olefins containing them. C ₈ to about C ₁₆ alpha olefins such as 1-octene, 1-decene and 1-dodecene are preferred. Preferred polyalphaolefins are poly-1-octene, poly-1-decene and poly-1-dodecene and mixtures thereof and mixed olefin derived polyolefins. However, higher olefin dimers in the C ₁₄ -C ₁₈ range may be used to provide a low viscosity base oil with an acceptable low volatility. Depending on the viscosity grade and starting oligomers, the PAO may be primarily trimers and tetramers of starting olefins containing higher order small amounts of oligomers having a viscosity range of 1.5-12 cSt.

PAO fluids include, for example, Friedel containing complexes of aluminum trichloride, boron trifluoride or boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate. It may be conveniently prepared by the polymerization of alpha olefins in the presence of a polymerization catalyst such as a Kraft catalyst. For example, the method disclosed by Patent Document 4 or Patent Document 5 may be conveniently used herein. Other descriptions of PAO synthesis can be found in US Pat. C ₁₄ -C ₁₈ olefin dimers are described in US Pat. All of the aforementioned patent documents are incorporated herein by reference in their entirety.

  Other useful synthetic lubricating base oils may also be used, such as the synthetic lubricating base oils described in the original work of Non-Patent Document 6. This reference is incorporated herein by reference.

  In the alkylated aromatic base oil, the alkyl substituent is typically an alkyl group having about 8 to 25 carbon atoms, usually 10 to 18 carbon atoms. As many as three such substituents may be present. The tri-alkylbenzene may be produced by cyclization dimerization of 1-alkyne having 8 to 12 carbon atoms as described in Patent Document 17. Other alkylbenzenes are described in US Pat. Alkylbenzenes are used especially as lube base oils for low temperature applications (Arctic vehicle service and refrigeration oils) and in papermaking oils. Alkylbenzenes are linear alkylbenzenes (LAB) such as Vista Chem. Co., Huntsman Chemical Co., Chevron Chemical Co., and Nippon Oil Co. Are commercially available from manufacturers. Linear alkyl benzenes have a good low pour point and low temperature viscosity combined with good solvency for the additive and a VI value greater than 100. Other alkylated aromatic compounds that may be used when necessary are described, for example, in Non-Patent Document 8.

  Other useful lubricating base oils include hydroisomerized wax base oils (eg, gas oil, slack wax, fuel hydrocracking furnace bottom oil, etc.), wax isomerized groups including hydroisomerized Fischer-Tropsch wax. Oils, gas-liquid (GTL) base oils, as well as other wax isomerized hydroisomerized base oils, or mixtures thereof. Fischer-Tropsch wax, a high boiling residue of Fischer-Tropsch synthesis, is a highly paraffinic hydrocarbon with a very low sulfur content. The hydroprocessing used for the production of such base oils is either an amorphous hydrocracking such as a special lube hydrocracking (LHCD) catalyst or a crystalline hydrocracking / hydroisomerization catalyst, preferably a zeolite catalyst. / Hydrogen isomerization catalyst may be used. For example, one useful catalyst is ZSM-48 described in US Pat. The disclosure of this patent document is incorporated herein by reference in its entirety. Processes for producing hydrocracking / hydroisomerization distillate and hydrocracking / hydroisomerization wax are described, for example, in US Pat. Each of the aforementioned patent documents is incorporated herein by reference in its entirety. Particularly preferred processes are described in US Pat. These patent documents are also incorporated herein by reference. A process using a Fischer-Tropsch wax raw material is described in Patent Document 31 and Patent Document 32. The disclosures of these patent documents are incorporated herein by reference in their entirety. Gas-liquid (GTL) base oils, Fischer-Tropsch wax derived base oils and other wax-derived hydroisomerization (wax isomerization) base oils are advantageously used in the present invention and have a kinematic viscosity of about 4.0 cSt at 100 ° C. and As illustrated by GTL4 having a viscosity index of about 141, it has a useful kinematic viscosity at 100 ° C. of about 3 cSt to about 50 cSt, preferably about 3 cSt to about 30 cSt, more preferably about 3.5 cSt to about 25 cSt. sell. These gas-liquid (GTL) base oils, Fischer-Tropsch wax derived base oils and other wax-derived hydroisomerized base oils may have advantageous pour points of about −20 ° C. or less, and under certain conditions It may have an advantageous pour point of -25 ° C or less, with a useful pour point being about -30 ° C to about -40 ° C or less. Useful compositions of gas-liquid (GTL) base oils, Fischer-Tropsch wax-derived base oils and wax-derived hydroisomerized base oils are listed, for example, in US Pat. Incorporated herein by reference.

  Gas-liquid (GTL) base oils, Fischer-Tropsch wax derived base oils have beneficial kinematic viscosity advantages over conventional Group II base oils and Group III base oils, and the advantages are consistent with the present invention. It can be used very advantageously. Gas-liquid (GTL) base oils can have significantly higher kinematic viscosities up to about 20-50 cSt at 100 ° C, compared to commercial group II base oils at 100 ° C. The kinematic viscosity can be up to about 15 cSt, and the commercial group III base oil can have a kinematic viscosity at 100 ° C. up to about 10 cSt. The higher kinematic viscosity range of gas-liquid (GTL) base oils compared to the more limited kinematic viscosity range of Group II and Group III base oils is an additional factor in the formulation of lubricating oil compositions in combination with the present invention. It is possible to provide beneficial benefits. In combination with the low sulfur content of suitable olefin oligomer base oils and / or alkyl aromatic base oils and in combination with the present invention, gas-liquid (GTL) base oils and other wax-derived hydroisomerized base oils are exceptional. The low sulfur content can provide additional benefits in lubricating oil compositions where a very low overall sulfur content can beneficially affect lubricating oil performance.

Alkylene oxide polymers and interpolymers and their derivatives containing modified terminal hydroxyl groups obtained, for example, by esterification or etherification are useful synthetic lubricating oils. By way of example, these oils are ethylene oxide or propylene oxide, alkyl ethers and aryl ethers of these polyoxyalkylene polymers (eg, methyl-polyisopropylene glycol ether having an average molecular weight of about 1000, molecular weight of about 500-1000. diphenyl ether of polyethylene glycol having, and about 1000-1500 diethyl ether of polypropylene glycol having a molecular weight of), or their mono- and polycarboxylic esters (e.g., acid esters, mixed C _{3 to 8} fatty acid ester or tetra it may be obtained by polymerization of C ₁₃ oxo acid diester) of ethylene glycol.

  Esters constitute a useful base oil. Additive solubility and seal compatibility characteristics may be ensured by the use of esters such as dibasic acid and monoalkanol esters and monocarboxylic acid polyol esters. Examples of the former type of ester include phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl Examples include esters of dicarboxylic acids such as malonic acid and alkenylmalonic acid, and various alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, and 2-ethylhexyl alcohol. Specific examples of these types of esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl Examples thereof include phthalate and dieicosil sebacate.

Particularly useful synthetic esters are one or more polyhydric alcohols, preferably hindered polyols (neopentyl polyols such as neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol, Methylolpropane, pentaerythritol and dipentaerythritol) and alkanoic acids containing at least about 4 carbon atoms (preferably caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behen C ₅ -C ₃₀ acids such as saturated straight chain fatty acids containing acid, or the corresponding branched chain fatty acids or esters obtained by reaction of an unsaturated fatty acid or any mixture of these materials), such as oleic acid.

  Suitable synthetic ester components include esters of trimethylolpropane, trimethylolbutane, trimethylolethane, pentaerythritol and / or dipentaerythritol and one or more monocarboxylic acids containing from about 5 to about 10 carbon atoms. . These esters, such as “Mobil” P-41 and P-51 esters (ExxonMobil Chemical Company), are widely available commercially.

  Silicon-based oils are another class of useful synthetic lubricants. These oils include polyalkyl-, polyaryl-, polyalkoxy-, and polyaryloxy-siloxane oils and silicate oils. Examples of suitable silicon-based oils include tetraethyl silicate, tetraisopropyl silicate, tetra- (2-ethylhexyl) silicate, tetra- (4-methyl-hexyl) silicate, tetra- (pt-butylphenyl) silicate, hexyl- (4-Methyl-2-pentoxy) disiloxane, poly (methyl) siloxane and poly- (methyl-2-methylphenyl) siloxane.

  Another class of synthetic lubricants are esters of phosphorus-containing acids. These include, for example, tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid. Another class of oil includes polymeric tetrahydrofuran and the like.

  In addition to the unique additive action of the hydrocarbyl aromatic compounds and high molecular weight olefin oligomers of the present invention, we have used them in combination with the ingredients of the present invention to provide the superior performance characteristics documented above. Highly refined low sulfur group II base oil / low sulfur group III base oil instead of or in addition to group IV base oil and group V base oil It is contemplated that hydrotreated oils, HDP, etc.) and wax isomerized base oils may be used.

  The types and amounts of performance additives used in combination with the present invention in the lubricating oil composition are not limited by the examples given herein by way of illustration.

[Antiwear and EP additives]
Internal combustion engine lubricants require the presence of antiwear and / or extreme pressure (EP) additives to provide adequate antiwear protection for the internal combustion engine. The specifications for engine oil have increasingly shown a trend for improving the antiwear properties of the oil. Antiwear and EP additives play this role by reducing the friction and wear of metal parts.

While there are many different types of antiwear agents, over the decades, the main antiwear agent for crankcase oils of internal combustion engines has been a metal alkylthio whose primary metal component is zinc or zinc dialkyldithiophosphate (ZDDP). Phosphate, more particularly metal dialkyldithiophosphate. ZDDP compounds generally have the formula: Zn [Sn (S) (OR ¹ ) (OR ² )] ₂ , where R ¹ and R ² are C ₁ -C ₁₈ alkyl groups, preferably C ₂ -C _12. A compound of an alkyl group). These alkyl groups may be linear or branched. ZDDP is typically used in an amount of about 0.4-1.4% by weight of the total lubricating oil composition. However, a greater or lesser amount can be advantageously used in many cases.

  However, it has been found that these additive phosphorous has a detrimental effect on the catalyst in the catalytic converter and also on the automotive oxygen sensor. One way to minimize this effect is to use a phosphorus-free antiwear agent in place of some or all of the ZDDP.

Various non-phosphorous additives are also used as antiwear agents. Sulfurized olefins are useful as antiwear and EP additives. Sulfur-containing olefins are prepared by sulfiding various organic materials including aliphatic, arylaliphatic or cycloaliphatic olefinic hydrocarbons containing about 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms. Is possible. The olefinic compound contains at least one non-aromatic double bond. These compounds have the formula:
R ³ R ⁴ C = CR ⁵ R ⁶
Defined by
In the formula, each of R ^{3 to} R ⁶ is independently hydrogen or a hydrocarbon group. Preferred hydrocarbon groups are alkyl groups or alkenyl groups. Any two of R ^{3 to} R ⁶ may be linked to form a cyclic ring. Additional information regarding the preparation of sulfurized olefins and sulfurized olefins can be found in US Pat. This patent document is incorporated herein by reference in its entirety.

The use of polysulfides of thiophosphoric acid and thiophosphoric acid esters as lubricating oil additives is disclosed in US Pat. The addition of phosphorothionyl disulfide as an antiwear, antioxidant and EP additive is disclosed in US Pat. As an antiwear agent in lubricating oils of alkylthiocarbamoyl compounds (eg, bis (dibutyl) thiocarbamoyl) in combination with molybdenum compounds (eg, oxymolybdenum diisopropyl phosphorodithioate sulfide) and phosphorus esters (eg, dibutyl hydrogen phosphite) The use of is disclosed in US Pat. U.S. Patent No. 6,057,031 discloses the use of carbamate additives to provide improved antiwear and extreme pressure properties. The use of thiocarbamate as an antiwear agent is disclosed in US Pat. Mori - Sulfur alkyl dithiocarbamate trimer complex (R = C ₈ ~C ₁₂ alkyl) thio carbamate / molybdenum complexes also useful antiwear agents and the like. Each of the aforementioned patent documents is incorporated herein by reference in its entirety.

  Glycerol esters may be used as antiwear agents. For example, monooleate, dioleate and trioleate, monopalmitate and monomyristate may be used.

  ZDDP is combined with other compositions that provide anti-wear properties. Patent Document 45 discloses that a combination of a thiodixanthogen compound (for example, octylthiodixanthogen) and a metal thiophosphate (for example, ZDDP) can improve the antiwear property. Patent Document 46 discloses that the use of metal alkoxyalkyl xanthates (eg, nickel ethoxyethyl xanthate) and dixanthogens (eg, diethoxyethyl dixanthogen) in combination with ZDDP improves anti-wear properties. Yes. Each of the aforementioned patent documents is incorporated herein by reference in its entirety.

  Preferred antiwear agents include zinc dithiophosphate and / or phosphorus and sulfur compounds such as sulfur, nitrogen, boron, molybdenum phosphorodithioate, molybdenum dithiocarbamates, and heterocyclic compounds such as dimercaptothiadiazole, mercaptobenzothiadiazole And various organomolybdenum derivatives including triazine, and alicyclic compounds, amines, alcohols, esters, diols, triols, fatty acid amines, and the like can also be used. Such additives may be used in an amount of about 0.01 to 6% by weight, preferably about 0.01 to 4% by weight.

[Viscosity index improver]
Viscosity index improvers (also known as VI improvers, viscosity modifiers and viscosity improvers) provide lubricating oils with high and low temperature operation suitability. These additives impart shear stability at high temperatures and acceptable viscosity at low temperatures.

  Suitable viscosity index improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both viscosity index improvers and dispersants. Typical molecular weights of these polymers are between about 10,000 and 1,000,000, more typically about 20,000 to 500,000, and still more typically about 50,000 to 200,000, Between 000.

  Examples of suitable viscosity index improvers are methacrylates, butadienes, olefins or alkylated styrene polymers and copolymers. Polyisobutylene is a commonly used viscosity index improver. Another suitable viscosity index improver is polymethacrylate (eg, copolymers of alkyl methacrylates of various chain lengths), some of which also function as pour point depressants. Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene and polyacrylates (eg, copolymers of acrylates of various chain lengths). Specific examples include styrene-isoprene polymers or styrene-butadiene polymers having a molecular weight of 50,000 to 200,000.

  The viscosity index improver may be used in an amount of about 0.01 to 8% by weight, preferably about 0.01 to 4% by weight.

[Antioxidant]
Antioxidants delay the oxidative degradation of the base oil in use. Such degradation can lead to deposits on the metal surface, the presence of sludge or increased viscosity of the lubricating oil. Those skilled in the art are aware of various antioxidants that are useful in lubricating oil compositions. For example, see Non-Patent Document 3 and Patent Document 47 and Patent Document 48 listed above. Each of these references is incorporated herein by reference in its entirety.

Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of specific phenolic compounds. Typical phenolic antioxidant compounds are hindered phenolic compounds, which are compounds containing sterically blocked hydroxyl groups, which include dihydroxyaryls in which the hydroxyl groups are in the o-position or p-position relative to each other. Derivatives of compounds are mentioned. Typical phenolic antioxidants include hindered phenols substituted with C ₆ + alkyl groups and alkylene-linked derivatives of these hindered phenols. Examples of this type of phenolic material include 2-t-butyl-4-heptylphenol, 2-t-butyl-4-octylphenol, 2-t-butyl-4-dodecylphenol, 2,6-di-t -Butyl-4-heptylphenol, 2,6-di-tert-butyl-4-dodecylphenol, 2-methyl-6-tert-butyl-4-heptylphenol and 2-methyl-6-tert-butyl-4- Dodecylphenol is mentioned. Other useful hindered monophenolic antioxidants include, for example, hindered 2,6-di-alkyl-phenolic propionic acid ester derivatives. Bis-phenolic antioxidants can also be advantageously used in combination with the present invention. Examples of ortho-linked phenols include 2,2′-bis (6-tert-butyl-4-heptylphenol), 2,2′-bis (6-tert-butyl-4-octylphenol) and 2,2′- Bis (6-t-butyl-4-dodecylphenol) is mentioned. Para-linked bisphenols include, for example, 4,4′-bis (2,6-di-t-butylphenol) and 4,4′-methylene-bis (2,6-di-t-butylphenol).

Non-phenolic antioxidants that may be used include aromatic amine antioxidants, which may be used either alone or in combination with phenol. Typical examples of non-phenolic antioxidants include the formula: R ⁸ R ⁹ R ¹⁰ N [wherein R ⁸ is an aliphatic group, aromatic group or substituted aromatic group, and R ⁹ is aromatic. R ¹⁰ is H, alkyl, aryl or R ¹¹ S (O) _x R ¹² (where R ¹¹ is an alkylene, alkenylene or aralkylene group, and R ¹² is a higher group, or a substituted aromatic group, Alkyl group or alkenyl, aryl or alkaryl group, and x is 0, 1 or 2)], and alkylated aromatic amines and non-alkylated aromatic amines. The aliphatic group R ⁸ may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms. An aliphatic group is a saturated aliphatic group. Preferably, both R ⁸ and R ⁹ are aromatic groups or substituted aromatic groups, and the aromatic group may be a condensed ring aromatic group such as naphthyl. The aromatic groups R ⁸ and R ⁹ may be linked together with other groups such as S.

  Typical aromatic amine antioxidants have an alkyl substituent of at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl and decyl. Generally, aliphatic groups do not contain more than about 14 carbon atoms. General types of amine-based antioxidants useful in the present compositions include diphenylamine, phenylnaphthylamine, phenothiazine, imidodibenzyl and diphenylphenylenediamine. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used. Specific examples of aromatic amine antioxidants useful in the present invention include p, p'-dioctyldiphenylamine, t-octylphenyl-alpha-naphthylamine, phenyl-alphanaphthylamine and p-octylphenyl-alpha-naphthylamine. It is done.

  Sulfurized alkylphenols and their alkali metal or alkaline earth metal salts are also useful antioxidants. Low sulfur peroxide decomposers are useful as antioxidants.

  Another class of antioxidants used in lubricating oil compositions are oil-soluble copper compounds. Any suitable oil-soluble copper compound may be blended into the lubricating oil. Examples of suitable copper antioxidants include copper dihydrocarbyl thiophosphate or copper dihydrocarbyl dithiophosphate and a carboxylic acid copper salt (natural or synthetic). Other suitable copper salts include copper dithiocarbamate, sulfonate, phenate and acetylacetonate. Basic, neutral or acidic copper (I) and / or copper (II) salts derived from alkenyl succinic acids or acid anhydrides are known to be particularly useful.

  Preferred antioxidants include hindered phenols, arylamines, low sulfur peroxide decomposers and other related components. These antioxidants may be used individually by type or in combination with each other. Such additives may be used in an amount of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

[Cleaning agent]
Detergents are commonly used in lubricating oil compositions. A typical detergent is an anionic material comprising a long chain lipophilic portion of the molecule and a smaller anionic or oleophobic portion of the molecule. The anionic portion of the detergent is typically derived from an organic acid such as sulfaic acid, carboxylic acid, phosphoric acid, phenol or mixtures thereof. The counter ion is typically an alkaline earth metal or alkali metal.

  A salt containing a substantially stoichiometric amount of metal is expressed as a neutral salt and has a total base number of 0 to 8 (TBN as measured by ASTM D2896). Many compositions contain a large amount of a metal base achieved by reaction of an excess of a metal compound (eg, metal hydroxide or metal oxide) with an acid gas (such as carbon dioxide) and are overbased. Yes. Useful detergents can be neutral, can be lightly overbased, or can be very overbased.

  Desirably, at least some of the detergent is overbased. Overbased detergents will help neutralize acidic impurities introduced by the combustion process and become trapped in the oil. Typically, the overbased material has a metal ion to anion moiety ratio of the detergent of about 1.05: 1 to 50: 1 on an equivalent basis. More preferably, the ratio is from about 4: 1 to about 25: 1. The resulting detergent is an overbased detergent typically having a TBN of about 150 or more, often about 250 to 450 or more. Preferably, the overbasing cation is sodium, calcium or magnesium. Mixtures of different TBN detergents can be used in the present invention.

  Preferred detergents include the alkali metal salts or alkaline earth metal salts of sulfates, phenates, carboxylates, phosphates and salicylates.

  Sulfonates may be prepared from sulfonic acids typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons. Examples of hydrocarbons include those obtained by alkylation of benzene, toluene, xylene, naphthalene, biphenyl and their halogenated derivatives (eg, chlorobenzene, chlorotoluene and chloronaphthalene). The alkylating agent typically has about 3 to 70 carbon atoms. The alkaryl sulfonate typically contains from about 9 to about 80 or more carbon atoms, more typically from about 16 to 60 carbon atoms.

  Non-Patent Document 3 cited above discloses many of the overbased metal salts of various sulfonic acids that are useful as detergents and dispersants in lubricating oils. Non-Patent Document 9 similarly discloses many of the overbased sulfonates useful as dispersants / detergents.

Alkaline earth metal phenates are another useful class of detergents. These detergents are the reaction of alkaline earth metal hydroxides or oxides (eg CaO, Ca (OH) ₂ , BaO, Ba (OH) ₂ , MgO, MG (OH) ₂ ) with alkylphenols or sulfurized alkylphenols. It is possible to manufacture by. Useful alkyl groups include straight or branched _C 1 _{-C 30} alkyl groups, preferably _C 4 _{-C 20} alkyl group. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol and 1-ethyldecylphenol. It should be noted that the starting alkylphenol may contain more than one alkyl substituent, each independently linear or branched. When using non-sulfurized alkylphenols, the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and a sulfiding agent (including sulfur halides such as elemental sulfur and sulfur dichloride) and then reacting the sulfurized phenol with an alkaline earth metal base.

  Metal salts of carboxylic acids are also useful as detergents. These carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid to remove free water from the reaction product. These compounds may be overbased to provide the desired TBN level. Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids. Useful salicylic acids include long chain alkyl salicylates. One useful family of compositions is of the following formula:

In the formula, R is a hydrogen atom or an alkyl group having 1 to about 30 carbon atoms, n is an integer of 1 to 4, and M is an alkaline earth metal. Preferred R groups are at least C ₁₁ , preferably C ₁₃ or higher alkyl chains. R may be optionally substituted with a substituent that does not interfere with the function of the detergent. M is preferably calcium, magnesium or barium. More preferably, M is calcium.

  Hydrocarbyl substituted salicylic acid may be prepared from phenol by a Kolbe reaction. For additional information regarding the synthesis of these compounds, see US Pat. This patent document is incorporated herein by reference in its entirety. The metal salt of hydrocarbyl substituted salicylic acid may be prepared by metathesis of the metal salt in a polar solvent such as water or alcohol.

  Alkaline earth metal phosphates are also useful as detergents.

  The detergent may be a simple detergent or a detergent known as a hybrid or hybrid detergent. The latter detergent can provide the properties of two detergents without the need to blend separate materials. For example, see US Pat. Preferred detergents include calcium phenate, calcium sulfonate, calcium salicylate, magnesium phenate, magnesium sulfonate, magnesium salicylate and other related ingredients including boronated detergents. The total detergent concentration is typically about 0.01 to about 6.0% by weight, preferably about 0.1 to 0.4% by weight.

[Dispersant]
Oil-insoluble oxidation byproducts are produced during engine operation. The dispersant helps keep these by-products in solution, thus reducing by-product deposits on the metal surface. The dispersant may be ashless or ash forming in nature. Preferably, the dispersant is ashless. So-called ashless dispersants are organic materials that produce virtually no ash upon combustion. For example, non-metal containing dispersants or boronated metal free dispersants are considered ashless. In contrast, the metal-containing detergents discussed above produce ash when burned.

  Suitable dispersants typically comprise polar groups attached to relatively high molecular weight hydrocarbon chains. The polar group typically contains at least one element of nitrogen, oxygen or phosphorus. A typical hydrocarbon chain contains 50 to 400 carbon atoms.

  Many dispersants can be chemically characterized as phenates, sulfonates, sulfurized phenates, salicylates, naphthenates, stearates, carbamates, thiocarbamates, phosphorus derivatives. A particularly useful class of dispersants are long-chain substituted alkenyl succinic acid compounds, typically alkenyl succinic acid derivatives typically prepared by reaction of substituted succinic anhydrides with polyhydroxy or polyamino compounds. The long chain group constituting the lipophilic part of the molecule that imparts solubility in oil is usually a polyisobutylene group. Many examples of this type of dispersant are well known commercially and in the literature. Representative US patents describing such dispersants are US Pat. Other types of dispersants are described in US Pat. A further description of dispersants can be found, for example, in US Pat. All of the aforementioned patent documents are incorporated herein by reference in their entirety.

  Hydrocarbyl-substituted succinic compounds are a popular dispersant. Especially succinimides, succinates or succinate amines prepared by reaction of hydrocarbon-substituted succinic compounds having preferably at least 50 carbon atoms in the hydrocarbon substituent with at least one equivalent of an alkyleneamine are Useful.

  Succinimide is formed by a condensation reaction between an alkenyl succinic anhydride and an amine. The molar ratio can vary depending on the polyamine. For example, the molar ratio of alkenyl succinic anhydride to TEPA can vary from about 1: 1 to about 5: 1. Typical examples are shown in Patent Documents 85 to 92. These patent documents are incorporated herein by reference in their entirety.

  Succinic esters are formed by the condensation reaction between alkenyl succinic anhydrides and alcohols or polyols. The molar ratio can vary depending on the alcohol or polyol used. For example, condensation products of alkenyl succinic anhydride and pentaerythritol are useful dispersants.

  Succinic ester amides are formed by a condensation reaction between alkenyl succinic anhydrides and alkanolamines. For example, suitable alkanolamines include polyalkenyl polyamines such as ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines and polyethylene polyamines. An example is propoxylated hexamethylenediamine. A typical example is shown in Patent Document 93. This patent document is incorporated herein by reference.

  The molecular weight of the alkenyl succinic anhydride used in the previous paragraph typically ranges between 800 and 2,500. The above products can be post-reacted with various reagents such as carboxylic acids such as sulfur, oxygen, formaldehyde, oleic acid and borate esters or boron compounds such as highly boronated dispersants. The dispersant can be boronated at about 0.1 to about 5 moles of boron per mole of dispersant reaction product.

  Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde and amines. See Patent Document 94. This patent document is incorporated herein by reference. Processing aids and catalysts such as oleic acid and sulfonic acid can also be part of the reaction mixture. The molecular weight of the alkylphenol is in the range of 800 to 2,500. Typical examples are shown in Patent Documents 95 to 101. These patent documents are incorporated herein by reference in their entirety.

Typical high molecular weight fatty acid modified Mannich condensation products useful in the present invention can be prepared from high molecular weight alkyl-substituted hydroxyaromatic compounds or HN (R) ₂ group-containing reactants.

Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol, polybutylphenol and other polyalkylphenols. These polyalkylphenols are high molecular weight polypropylene, polybutylene or other compounds in the presence of an alkylation catalyst such as BF ₃ to provide an alkyl substituent having an average molecular weight of 600 to 100,000 on the benzene ring of the phenol. It can be obtained by alkylation of phenol with a polyalkylene compound.

An example of a HN (R) ₂ group-containing reactant is an alkylene polyamine, primarily a polyethylene polyamine. Other representative organic compounds containing at least one HN (R) ₂ group suitable for use in the preparation of Mannich condensation products are well known and include monoamino and diamino alkanes and substituted analogs thereof. For example, ethylamine and diethanolamine, aromatic diamines such as phenylenediamine, diaminonaphthalene, heterocyclic amines such as morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine and piperidine, melamine and substituted analogs thereof.

Examples of alkylene polyamide reactants include ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, nonaethylenedecaamine and decaethylene. Undekaamin and the aforementioned _{equations: H 2 N- (Z-NH-} ) n H (Z in the previous formula is a bivalent ethylene, n represents 1 to 10) nitrogen content corresponding to alkylene polyamines of And a mixture of such amines. Propylene diamine and corresponding propylene polyamines such as di-, tri-, tetra-, pentapropylene tri-, tetra-, penta- and hexaamine are also suitable reactants. Alkylene polyamines are usually obtained by reaction of ammonia with dihaloalkanes such as dichloroalkanes. Thus, alkylene polyamines obtained from the reaction of 2-11 moles of ammonia with 1-10 moles of dichloroalkane having 2-6 carbon atoms and chlorine on different carbons are suitable alkylene polyamine reactants.

  Aldehyde reactants useful in the preparation of high molecular weight products useful in the present invention include aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol (b-hydroxybutyraldehyde). Formaldehyde reactants or formaldehyde-producing reactants are preferred.

  Hydrocarbyl-substituted amine ashless dispersant additives are well known to those skilled in the art. For example, see Patent Documents 102-107. These patent documents are incorporated herein by reference in their entirety.

  Preferred dispersants include boronated succinimides and non-boronated succinimides, including those derived from monosuccinimides, bissuccinimides and / or mixtures of monosuccinimides and bissuccinimides. Here, the hydrocarbyl succinimide is a hydrocarbylene group such as polyisobutylene having a Mn of about 500 to about 5000, preferably about 1000 to 3000, more preferably about 1000 to 2000, and even more preferably about 1000 to 1600. Or derived from a mixture of such hydrocarbylene groups. Other preferred dispersants include succinic esters and amides, alkylphenol-polyamine linked Mannich adducts, their capping derivatives and other related compounds. Such additives may be used in an amount of about 0.1 to 20% by weight, preferably about 0.1 to 8% by weight.

[Pour point depressant]
Conventional pour point depressants (also known as lubricating oil flow improvers) may be added to the compositions of the present invention if desired. These pour point depressants may be added to the lubricating oil composition of the present invention to lower the minimum temperature at which the fluid can flow or can flow. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers and dialkyl fumarate, fatty acid vinyl esters and allyl vinyl ether terpolymers. Is mentioned. U.S. Pat. Nos. 5,077,086 and 6,028,116 describe the preparation of useful pour point depressants and / or pour point depressants. Each of these references is incorporated herein by reference in its entirety. Such additives may be used in an amount of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

[Corrosion inhibitor]
Corrosion inhibitors are used to reduce the deterioration of metal parts in contact with the lubricating oil composition. Suitable corrosion inhibitors include thiadiazole. For example, see Patent Documents 117 to 119. These patent documents are incorporated herein by reference in their entirety. Such additives may be used in an amount of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

[Seal compatible additive]
The seal compatibilizer helps to swell the rubber elastic seal by causing a chemical reaction in the fluid or a physical change in the elastomer. Suitable seal compatibilizers for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (eg, butylbenzyl phthalate) and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.01 to 3% by weight, preferably about 0.01 to 2% by weight.

[Defoaming agent]
Antifoaming agents can be advantageously added to the lubricating oil composition. These agents delay the formation of stable foam. Silicones and organic polymers are typical antifoaming agents. For example, polysiloxanes such as silicone oil or polydimethylsiloxane provide antifoam properties. Antifoaming agents are commercially available and may be used in small amounts as usual in addition to other additives such as demulsifiers. The amount of these additives combined is usually less than 1% and often less than 0.1%.

[Rust inhibitor and rust inhibitor]
An anti-rust additive (or corrosion inhibitor) is an additive that protects a lubricated metal surface against chemical erosion by water or other foreign matter. A variety of these antirust additives are commercially available. Such a rust inhibitor is described in Non-Patent Document 3 described above.

  One type of rust inhibitor additive is a polar compound that preferentially wets the metal surface and thus protects the metal surface with an oil film. Another type of anti-rust additive absorbs water by introducing an anti-rust additive into the water-in-oil emulsion so that only the oil touches the metal surface. Yet another type of anti-rust additive is chemically bonded to the metal resulting in a non-reactive surface. Examples of suitable additives include zinc dithiophosphate, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

[Friction modifier]
Friction modifiers are any material that can change the coefficient of friction of any lubricant or fluid containing such materials. Friction modifiers, also known as friction reducers or lubricants or oil agents, and such other agents that change the coefficient of friction of lubricating base oils, formulated lubricating oil compositions or functional fluids, if necessary For example, it may be used effectively in combination with the base oil or lubricating oil composition of the present invention. Friction modifiers that reduce the coefficient of friction are particularly advantageous when combined with the base oil and lubricating oil compositions of the present invention. The friction modifier may include a metal-containing compound or material and an ashless compound or material, or a mixture thereof. The metal-containing friction modifier may include a metal salt or a metal-ligand complex. Here, the metal may include an alkali metal, an alkaline earth metal, or a transition group metal. Such metal-containing friction modifiers may also have low ash properties. Transition metals can include Mo, Sb, Sn, Fe, Cu, Zn, and others. Ligand includes alcohol, polyol, glycerol, partial ester glycerol, thiol, carboxylate, carbamate, thiocarbamate, dithiocarbamate, phosphate, thiophosphate, dithiophosphate, amide, imide, amine, thiazole, thiadiazole, dithiazole, diazole , Hydrocarbyl derivatives of triazole, and other polar molecular functional groups containing effective amounts of O, N, S or P individually or in combination. In particular, for example, Mo-containing dithiocarbamate [Mo (DTC)], Mo-dithiophosphate [Mo (DTP)], Mo-amine [Mo (Am)], Mo-alcolate, Mo-alcohol-amide, etc. The compounds can be particularly effective.

  Ashless friction modifiers may also include lubricating oil materials containing an effective amount of polar groups, such as hydroxyl group-containing hydrocarbyl base oils, glycerides, partial glycerides and glyceride derivatives. The polar groups in the friction modifier may include hydrocarbyl groups that contain effective amounts of O, N, S, or P individually or in combination. Other friction modifiers that may be particularly effective include, for example, fatty acid salts (both ash-containing and ashless derivatives), fatty alcohols, fatty acid amides, fatty acid esters, hydroxyl-containing carboxylates, and comparable synthetic long chains. Examples include hydrocarbyl acid, alcohol, amide, ester and hydroxycarboxylate. In some cases, fatty organic acids, fatty amines and sulfurized fatty acids may be used as suitable friction modifiers.

  Useful concentrations of friction modifiers may range from about 0.01 wt% to 10-15 wt% or more, with a preferred range often being about 0.1 wt% to 5 wt%. The concentration of molybdenum-containing material is often described in terms of Mo metal concentration. Advantageous concentrations of Mo may range from about 10 ppm to 3000 ppm or more, often the preferred range is about 20 ppm to 2000 ppm, and in some cases the more preferred range is about 30 to 1000 ppm. All types of friction modifiers may be used alone or in a mixture with the material of the present invention. In many cases, a mixture of two or more friction modifiers or a mixture of a friction modifier and another surface active material is also desirable.

[Typical additive amount]
When the lubricating oil composition contains one or more additives discussed above, the additives are blended into the composition in an amount sufficient for the additive to perform its intended function. Typical amounts of such additives useful in the present invention are shown in Table 2 below.

  Note that many of the additives are shipped from the manufacturer and used in the formulation with a certain amount of base oil solvent. Accordingly, the weights in the table below and other amounts listed in this patent indicate the amount of active ingredient (ie, the non-solvent or non-diluent part of the ingredient). The weight percentages shown below are based on the total weight of the lubricating oil composition.

  Unless otherwise stated, the kinematic viscosity at 40 ° C. or 100 ° C. is determined according to ASTM test method D445, the viscosity index is determined by ASTM test method D2270, the pour point is determined by ASTM test method D97, TBN Is determined by ASTM test method D2896.

  The hydrocarbyl aromatic compound in the following examples is an alkylated naphthalene (primarily monoalkylated) having a kinematic viscosity of about 4.6 cSt at 100 ° C. Mainly monoalkylated naphthalene is prepared by alkylation of naphthalene with an olefin consisting primarily of 1-hexadecene.

  In the examples, the ingredients listed below are used in the lubricating oil composition.

  All examples presented herein illustrate the invention but do not limit the compositions relating to the invention.

  In order to determine the effect of compositional changes on fuel economy of the test lubricant, a series of industrial approval sequences VIB fuel economy engine tests (ASTM Research Report D02-1469) were conducted. Fuel economy improvement (FEI) limits for various SAE viscosity grades are shown in ASTM D4485. Referring to Table 4, Comparative Example 3.1 shows a standard engine test formulation and establishes a reference FEI value to be used in comparison with the FEI values of the examples of the present invention. The% difference in FEI (positive or negative) between the comparative example 3.1 and the standard D4485 limit is first calculated. Similarly, the% difference (positive or negative) on FEI between the various candidate oils and the standard D4485 limit is then calculated. The% predominance of the candidate FEI value over the FEI value of Comparative Example 3.1 is then calculated. The percent advantage values for each of the candidate oils are summarized in Table 4 below.

  It has been surprisingly found that the addition of about 8-9 to about 15% of the above-described pentaerythritol ester (PE ester) has resulted in a significant and surprising fuel economy enhancement. The addition of 9.4% of these PE esters to SAE 10W-30 automotive engine oil showed a surprising 44% fuel economy enhancement. The addition of 12% of this PE ester to SAE 10W-30 automotive engine oil showed a surprising 65% fuel economy enhancement. The addition of 15% of this PE ester to SAE 10W-30 automotive engine oil showed a surprising 77% fuel economy enhancement. It can be seen that such increasing concentrations of PE ester resulted in greater fuel economy. Each of these test oils contained a hydrocarbyl aromatic base oil. It is possible that the presence of such hydrocarbyl aromatics may have contributed to the favorable results obtained.

  Addition of about 8% or more of the above-described pentaerythritol ester (PE ester), optionally in combination with the addition of 2% trimethylolpropane ester, is even more significantly and more surprisingly at least 25% in sequence VIB engine testing. Surprisingly it has been found that it has improved fuel economy. It is contemplated that these test oils contain hydrocarbyl aromatic compounds, and the presence of such hydrocarbyl aromatic compounds may have contributed to the favorable results obtained.

As shown by Examples 3.2, 3.3 and 3.4 in Table 4, fuel economy enhancements of up to 78% are seen in these combinations. This benefit is from about 0% to about 20% hydrocarbyl aromatics, from about 20% to about 60% Group II paraffinic base oil and from about 0.5% to about 5% pure boronated polyisobutyl. The maximum can be reached by the use of a tenylsuccinimide ashless dispersant (active material 0.33% to 3.3% by weight). Here, polyisobutenyl monosuccinimide and polyisobutenyl bissuccinimide are prepared by reaction of polyisobutenyl succinic anhydride having an _Mn of approximately 1300 with respect to the PIB group and an amine. Preferred amounts are about 4% to about 15% hydrocarbyl aromatic, about 30% to about 50% Group II paraffinic base oil and about as received by weight corresponding to the HFRR test of the dispersant of FIG. It may be 1% to about 4% boronated polyisobutenyl succinimide ashless dispersant. Pure boronated polyisobutenyl succinimide ashless dispersant is approximately 2/3 active ingredient and provides about 2% active ingredient when added to the oil blend.

  Those skilled in the art will readily recognize that these findings may be extended to any paraffinic base oil. The inventors have realized that this discovery can also use Group III base oils, preferably gas-liquid (GTL) base oils or Fischer-Tropsch base oils. Thus, as a non-limiting illustrative sample, we have about 70% by weight Group III base oil, about 8-9% by weight pentaerythritol derived ester and about 5-6% by weight hydrocarbyl aromatic compound. We have also noticed that the mixture, the rest of which is a performance additive package, achieves the same surprising fuel savings.

  To determine the effect of compositional changes on fuel economy of the test lubricant, a series of industrial approval sequence VIB fuel economy engines tests are conducted. Referring to Table 5, Comparative Example 4.1 is used as a standard engine test formulation to establish a baseline FEI value used in subsequent calculations as described above.

  Significant FEI enhancement when a relatively high concentration of Group II / III paraffin base oil is included in the lubricating oil composition in the presence of both hydrocarbyl aromatics and polyol esters such as those derived from trimethylolpropane Surprisingly found in the sequence VIB engine test is a surprising finding. By using about 44% of these paraffinic base oils, about 2% of trimethylolpropane ester and about 5% of alkylated naphthalene as a hydrocarbyl aromatic compound, a 30% increase in fuel economy is observed. By using about 44% of these paraffinic base oils, about 2% of trimethylolpropane ester and about 5.5% of alkylated naphthalene as a hydrocarbyl aromatic compound, a 26% fuel economy enhancement is seen. This benefit can be maximized by using about 3% to 30% hydrocarbyl aromatic, about 40% to about 90% paraffinic base oil and about 1% to about 20% trimethylolpropane ester. Preferred amounts are about 4% to about 20% hydrocarbyl aromatic, about 40% or more paraffinic base oil and about 2% to about 10% by weight trimethylolpropane ester. These engine tests clearly demonstrate the benefits of these fuel saving formulations.

  In the presence of about 1% to about 10% or more of any traditional polyol ester and / or hydrocarbyl aromatic compounds such as alkylnaphthalene and / or other co-base oils in the final blended lubricating oil, We believe that the benefits of fuel economy can be further enhanced when using the above group II / III paraffin base stocks.

  Those skilled in the art will readily recognize that these findings may be extended to any paraffinic base oil. The inventors have realized that this discovery can also use Group III base oils, preferably gas-liquid (GTL) base oils or Fischer-Tropsch base oils. Thus, as a non-limiting illustrative sample, we have about 40% by weight Group III base oil, about 30-35% PAO, about 2% by weight trimethylolpropane and about 4-6% by weight. We have also noticed that the mixture of hydrocarbyl aromatics, with the remainder being the performance additive package, achieves the same surprising fuel savings.

  Certain amorphous olefin copolymers, when formulated in lubricating oils, are particularly formulated in lubricating oils containing significant amounts of Group II or Group III base oils having a viscosity index of from about 110 to about 150 or greater. At times, it has been found to provide unexpected and significant fuel savings (friction reduction) benefits. To determine the effect of compositional changes on fuel economy of the test lubricant, a series of industrial approval sequence VIB fuel economy engines tests are conducted. Comparative Example 5.1 is used as a standard engine test formulation to establish a reference FEI value used in subsequent calculations as described above.

  Addition of 5% amorphous olefin copolymer to blended oil blended with polyalphaolefin base oil derived from mixed group II / III and decene olefins has surprisingly improved fuel economy in sequence VIB engine testing A 26% to 38% enhancement is a surprising finding. These results indicate that the unexpected fuel economy of such formulations comprising about 1% to about 20%, preferably about 2% to about 15%, most preferably about 3% to about 10% of an amorphous olefin copolymer. It clearly shows the benefits of improvement.

  In the presence of about 1% to about 10% or more of any traditional polyol ester and / or hydrocarbyl aromatic compounds such as alkylnaphthalene and / or other co-base oils in the final blended lubricating oil, It has been found that the fuel saving benefits can be further enhanced when using the above amorphous olefin copolymer.

  Those skilled in the art will readily recognize that these findings may be extended to any paraffinic base oil. The inventors have realized that this discovery can also use Group III base oils, preferably gas-liquid (GTL) base oils or Fischer-Tropsch base oils. Thus, as a non-limiting illustrative sample, we have about 30% by weight Group III base oil, about 40% by weight PAO, about 2% by weight trimethylolpropane and about 4-10% by weight. It has also been observed that blends of hydrocarbyl aromatics with the remainder being performance additive packages achieve the same surprising fuel efficiency improvements.

  The sequence VIB engine test is preferably a medium concentration hydrocarbyl aroma in the presence of at least a small concentration of a Group II base oil or Group III base oil or hydrocracked and / or hydrotreated base oil containing wax isomerized oil. This indicates that the use of a group compound can achieve a significant improvement in fuel efficiency. The presence of specific ashless dispersants can also contribute significantly to the observed fuel savings. To determine the effect of compositional changes on fuel economy of the test lubricant, a series of industrial approval sequence VIB fuel economy engines tests are conducted. Comparative Example 6.1 is used as a standard engine test formulation to establish a baseline FEI value used in subsequent calculations as described above.

  Enhanced fuel economy can be achieved by the use of certain paraffinic base oils in the presence of moderate concentrations of hydrocarbyl aromatics, preferably in the presence of certain boronated polyisobutenyl succinimide ashless dispersants. Is a surprising discovery. As shown by Table 6.2, Examples 6.2, 6.3, and 6.4, fuel economy enhancements of up to 77% are seen in these combinations. This benefit is from about 0% to about 20% hydrocarbyl aromatics, from about 20% to about 60% Group II paraffinic base oil, and from about 0.5% to about 5% by weight as received. The maximum can be reached by the use of polyisobutenyl succinimide ashless dispersant. Preferred amounts are about 4% to about 15% hydrocarbyl aromatic, about 30% to about 50% Group II paraffinic base oil and about as received by weight corresponding to the HFRR test of the dispersant of FIG. It may be 1% to about 4% boronated polyisobutenyl succinimide ashless dispersant. The results of the sequence VIB fuel saving engine test clearly show the unexpected benefits that can be obtained by using the components of the present invention.

  Those skilled in the art will readily recognize that these findings may be extended to any paraffinic base oil. The inventors have realized that this discovery can also use Group III base oils, preferably gas-liquid (GTL) base oils or Fischer-Tropsch base oils. Thus, as a non-limiting illustrative sample, we have about 30% by weight Group III base oil, about 30-40% PAO, about 2% by weight trimethylolpropane and about 5-40% by weight. We have also noticed that the mixture of hydrocarbyl aromatics, with the remainder being the performance additive package, achieves the same surprising fuel savings.

  All US patents, non-US patents and applications and non-patent literature cited herein are hereby incorporated by reference in their entirety.

FIG. 6 is a plot of coefficient of friction as a function of temperature for various compositions.

Claims (6)

Based on the total lubricating oil composition,
(A) at least 20% by weight of one or more base oils selected from the group consisting of Group II base oils, Group III base oils and wax isomerized oils;
(B) with at least 4% by weight of a hydrocarbyl aromatic compound,
A lubricating oil composition comprising a mixture. The lubricating oil composition according to claim 1, hydrocarbyl group, characterized in that it comprises a boron hydrocarbyl succinimide having a M _n of 1,000 to 5,000.   The lubricating oil according to claim 2, wherein the boronated hydrocarbyl succinimide is a boronated polyisobutenyl succinimide and is provided in an active species of 0.3 to 3.3 wt%. Composition. (A) at least 40% of one or more base oils selected from the group consisting of Group II base oils, Group III base oils and wax isomerized oils;
4. Lubrication according to claim 3, comprising (b) at least 20% hydrocarbyl aromatic compound, and (c) 2% by weight active boronated polyisobutenyl succinimide. Oil composition.   The lubricating oil composition according to claim 3, wherein the one or more base oils comprise 20 to 60 wt%.   6. The boronated hydrocarbyl succinimide comprises boronated polyisobutenyl monosuccinimide and boronated polyisobutenyl bissuccinimide according to any one of claims 3-5. Lubricating oil composition.

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