BR112016002634B1 - method for lubricating a swivel end lever follower valve slack regulator - Google Patents

Abstract

METHOD FOR LUBRICATING A ROTARY END LEVER VALVE TRAIN LEVER REGULATOR The invention provides a method for lubricating a rotary end follower lever train slack regulator for a car compression ignition internal combustion engine of passenger having a reference mass not exceeding 2610 kg comprising providing the internal combustion engine with a lubricating composition comprising a lubricating viscosity oil 0.01% by weight to 3% by weight of a dispersing viscosity modifier, and 0.01% by weight at 3% by weight of an anti-wear agent containing zinc-free sulfur, where the lubricant composition has a sulfur content of less than 5000 ppm, a phosphorus content of 1000 ppm or less, and a sulfated ash content (typically 3000 to 12,000 ppm).

Description

FIELD OF THE INVENTION

[0001] The invention provides a method for lubricating a rotary end follower lever train slack regulator of a passenger car compression ignition internal combustion engine having a reference mass not exceeding 2610 kg comprising providing the an internal combustion engine a lubricating composition comprising a lubricating viscosity oil 0.01% by weight to 3% by weight of a dispersing viscosity modifier, and 0.01% by weight to 3% by weight of an anti-wear agent containing free sulfur zinc, where the lubricant composition has a sulfur content of less than 5000 ppm, a phosphorus content of 1000 ppm or less, and a sulfated ash content of 12,000 ppm or less, or 10,000 ppm or less.

BACKGROUND OF THE INVENTION

[0002] The internal combustion engine valve train is known to vary in both design and type of fuel. For example, the type of fuel can be gasoline or diesel; and the valve train can have general types of configuration such as a direct drive cam and cargo box, a rotating end lever follower, a push rod or a rocker. Valve train types are described in "Valve Train Components, Technology Failure Diagnosis", published by Schaeffler (see www.schaeffler- Aftermarket.com, serial number 94410002202266/0/0/1/2010 / PDF-GB) . When considering valve train designs from a tribiological point of view as it interacts with a lubricant, the specific type of valve train, to slide into the rolling ratio between contact and metallurgy can affect the lubrication regime differently, meaning that metallurgy engine pressure, contact pressure, contact speed, surface finish, slip-to-bearing contact (or slip-to-roll ratio) all affect the way in which lubricant additives interact and contribute to reducing wear, corrosion, or fatigue of the components of the motor.

[0003] For example, differences in engine design allow for different types of valve train designs. Valve train designs are selected by original equipment manufacturer (OEM) depending on the design requirements for their engines and while there is no "best" design for an engine, the OEM considers design factors including valve train design in combination with other factors such as different fuel types and engine size.

[0004] Heavy duty diesel engines are not noted to be limited to all motor vehicles with a "technically permissible maximum payload mass" per 3,500 kg, equipped with compression ignition engines or positive ignition natural gas (NG) or LPG engines. In contrast, the European Union indicates that for new light duty vehicles (passenger cars and light commercial vehicles) included within the scope of the test section ACEA "C" it has a "technically permissible maximum load mass" not exceeding 2610 kg. (Is my change correct?)

[0005] There is a distinct difference between passenger car, and heavy duty diesel engines. The difference in size from up to 3,500 kg to no more than 2610 kg means that engines of both types will experience significantly different operating conditions such as load, oil temperatures, function cycle and engine speeds. Heavy duty diesel engines are designed to maximize torque to transport payloads at maximum fuel economy while passenger car diesel is designed to commute people and accelerate at maximum fuel economy. The engineered purpose of the carrier versus communion engine results in different hardware designs and resulting stresses transmitted to the engineered lubricant to protect and lubricate the engine. Another distinct design difference is the revolution in operation per minute (RPM) that each engine operates when transporting versus switching. A heavy-duty diesel engine such as a typical 12-13 liter truck engine would not typically exceed 2200 rpm while a passenger car engine can go up to 4500 rpm. The difference in rpm between a heavy-duty diesel engine and a passenger car means that because of more extreme operating conditions a passenger car lubricant will be exposed to higher operating temperatures, higher shear, increased oxidation and deposit.

[0006] For many years engine design focused on heavy duty diesel and gasoline engines that have a valve train comprising a direct acting meat and cargo box, or a swing arm. The brief state-of-the-art references below emphasize the effects realized to improve engine lubrication design to improve soot handling for heavy duty diesel engines such as Mack T-10 or T-ll, or to minimize wear or sludge formation in gasoline engines such as those required for GF-3 approval or Sequence IIIF approval, or Peugeot TU3M engine. Effects have been made to reduce deposit formation on the meat valve train and cargo box of TDi Volskwagen engines.

[0007] US 2013/0143781 (Barton et al., Published on May 20, 2013) describes a method of lubricating an internal combustion engine and a lubricating composition comprising a lubricating viscosity oil and 0.1% in 70% by weight of a copolymer comprising units derived from monomers of (i) an otolefin and (ii) an ethylenically unsaturated carboxylic acid or its derivatives, esterified and amidated with an alcohol and an aromatic amine, respectively, wherein the copolymer is obtained by a process comprising: (1) reacting monomers (i) an α-olefin and (ii) an ethylenically unsaturated carboxylic acid or derivatives thereof to form a copolymer; (2) reaction of the product from step (1) with an aromatic amine; and (3) reacting the copolymer from step (2) with an alcohol to form a copolymer which is esterified and amidated.

[0008] US 2013/0143780 (Gieselman et al, published on May 20, 2013) discloses a lubricating composition comprising a lubricating viscosity oil and a compound comprising the reaction product of a polyolefin, an unsaturated aromatic acylating agent ethylenically (or carboxylic reagent), and an amine. In one embodiment the amine is an acyclic polyamine, the polyolefin is a polybutene, and the lubricant composition has a sulfated ash content of 0.3% by weight to 1.2% by weight of the lubricant composition. The lubricating composition is disclosed for use in an internal combustion engine that has a steel or aluminum surface (usually a steel surface).

[0009] US 2012/0184473 (Boffa et al., Published on December 20, 2012) discloses a lubricating oil composition comprising: i) a major amount of a base oil, ii) at least one soluble molybdenum compound in oil and iii) a zinc dialkyldithiophosphate compound, in which the molybdenum content derived from the molybdenum compound is at least 10 ppm Molybdenum based on the total weight of the lubricating oil composition and the phosphorus content derived from the dialkyldithiophosphate compound zinc content is about 200 ppm to 500 ppm, based on the total weight of the lubricating oil composition. The method of lubricating the engine of an engine, comprising the step of operating the engine with the lubricating oil composition, is also disclosed.

[0010] US 2012/0046206 (Gieselman et al., Published February 23, 2012) discloses a lubricating composition comprising a lubricating viscosity oil, a dispersant and an amine functionalized additive, wherein the amine functionalized additive is derived from an amine having at least 3 or 4 aromatic groups, wherein the amine functionalized additive is a product obtained obtained / which will be obtained by reaction of the amine having at least 3 aromatic groups with a functionalized carboxylic polymer. The lubricants are used in a Mack T 11 test, and further exemplify the use of sulfuric olefin antioxidants in an unspecified amount.

[0011] US 2009/0325831 (Mathur et al., Published June 30, 2008) discloses a lubricating composition comprising: a major amount of a lubricating viscosity oil; and a minor amount of a concentrated additive comprising a copolymer comprising modification of the viscosity index of the reaction product of an ethylene-olefin copolymer and a polyamine, wherein the polyamine comprises at least two primary amine functional groups or secondary. The lubricating composition is described as useful for a method of lubricating a car engine.

[0012] US 2009/0305923 (Visger et al., Published December 10, 2009) discloses a lubricant of a composition comprising a major amount of a lubricating viscosity oil and a minor amount of an esterified, nitrogen-functionalized interpolymer composition , derived from monomers comprising (i) at least one monomer selected from (a) aromatic vinyl monomers, and (ii) at least one α, β-unsaturated acylating agent; wherein a portion of said agent-derived unit acylation is esterified and wherein a portion of said agent-derived unit acylation is condensed with at least one aromatic amine containing at least one NH group capable of condensing with the unit derived from acylating agent monomer, the amine being selected from the group consisting of 4-aminodiphenylamine, 4-phenylazoaniline, 2-aminobenzimidazole, and 3-nitroaniline. The lubricant is described as useful for reducing soot-induced viscosity increase in heavy-duty diesel engines and exemplified in the Mack T-11 test.

[0013] US 2008/182768 (Devlin et al., Published July 31, 2008) reveals better lubricant compositions for the biodiesel fuel engine. The biodiesel engine operates on a fuel containing from about 5 to about 100% by weight of biodiesel components and is lubricated with a lubricating oil composition that comprises a large amount of lubricating viscosity oil, and a lesser amount of hair. less a highly grafted multifunctional olefin copolymer, made by reacting an acylating agent with an olefin copolymer having a numerical average molecular weight greater than about 1,000, in the presence of a free radical initiator to provide an acylated olefin copolymer with a degree of grafting (DOG) of the acylating agent in the olefin of at least 0.5% by weight, and reacting the acylated olefin copolymer with an amine to provide the highly grafted multifunctional olefin copolymer in that the highly grafted multifunctional olefin copolymer is effective in reducing an increase in viscosity in the lubricating oil composition for the mechan ism of less than or equal to an increase in viscosity in a lubricating oil composition for an engine running on fuel without biodiesel components. The lubricant performs in the T-ll soot deposit test.

[0014] US 2007/01 1 1904 (Van Dam, published May 17, 2007) discloses a low sulfur and low phosphorus lubricating oil composition comprising: (a) a major amount of a viscosity oil lubricant; (b) one or more dispersants; (c) one or more antioxidants; and (d) one or more detergents; wherein the lubricating oil composition is di-alkyl diisophosphates essentially free of zinc and contains no more than 0.1 weight percent sulfur and provided that the lubricating oil composition does not contain alkylated and non-alkylated aromatic amines and tri-nuclear molybdenum compounds. The lubricant is evaluated in a Mack T-10 diesel engine cylinder shell wear test.

[0015] US 2006/0264342 (Shaw et al., Published 23 November 2006) describes a method of lubricating an internal combustion engine that has a meat and a rotary cam, the method comprising employing it as the lubricant for the mechanism of a lubricating composition comprising an oil base of lubricating viscosity, phosphorus in an amount of 50 to 900 ppm by weight, sulfur in an amount of 1500 to 3000 ppm by weight, boron in an amount between 0.0 at 100 ppm, the sulphated ash in an amount not exceeding 1.0% by mass, and a friction modifier in an amount from 0.0 to 0.1% by mass, the said amounts being based on mass of fully formulated lubricating oil composition. Preferred lubricating compositions also contain a viscosity-enhancing dispersant. Examples of viscosity-improving dispersants include amine reaction products, for example, polyamines, with a substituted monohydrocarbyl or dicarboxylic acid, wherein the hydrocarbyl substituent comprises a chain of sufficient length to impart a viscosity index improving properties for compounds. In general, the viscosity index-improving dispersant may be, for example, a polymer of a C4 to C24 unsaturated vinyl alcohol ester or a C3 to CIO unsaturated mono-carboxylic acid or a C4 to CIO dicarboxylic acid with an unsaturated monomer having 4 to 20 carbon atoms containing nitrogen; a polymer of a C2 to C20 olefin with a C3 to C3 unsaturated mono- or di-carboxylic acid neutralized with an amine, hydroxyamine or an alcohol; or an ethylene polymer with a C3-C20 olefin still reacting, either by grafting a C4 to C20 monomer containing unsaturated nitrogen into it or by grafting an unsaturated acid to the polymer structure and then reacting the carboxylic acid groups of the acid grafted with an amine, hydroxyamine or alcohol.

[0016] US 2003/0148895 (Robson et al., Published November 9, 2001) discloses a lubricating oil composition designed to reduce wear in the Peugeot TU3M gasoline wear test. This test is designed to investigate the wear of the meat and cargo box of an internal combustion engine. The disclosures in this document show that relatively high levels of boron (borate dispersant derivatives) and preferably increased with a significant amount of molybdenum (derived from, for example, a tri-nuclear molybdenum additive) are needed to reduce the wear of meat and box load to acceptable levels.

[0017] US 2006/0205614 (Artman et al., Published September 14, 2006) reveals a low sulfur content, the low phosphorus composition suitable for an internal combustion engine ignited compression lubricant, comprising: ( a) a lubricating viscosity oil; (b) a sulfurized olefin anti-wear agent substantially free of nitrogen, in an amount sufficient to provide a better anti-wear performance with the composition; (c) about 1 to about 10 weight percent of a nitrogen-containing dispersant; and (d) a detergent with excess base selected from the group consisting of salixarates, saligenins, salicylates, glyoxylates, and mixtures thereof; said composition containing less than about 0.1 weight percent phosphorus, less than about 0.4 weight percent sulfur, and having less than about 1.2% sulfated ash. The exemplified internal combustion engine is an API CH-4 Cummins Mil heavy-duty diesel engine.

[0018] US 8,420,583 (Boegner et al., Published May 22, 2003) discloses a lubricating oil composition comprising: a large amount of lubricating viscosity oil; and a smaller amount of at least one highly grafted multifunctional olefin copolymer, made by reacting an acylating agent with an olefin copolymer with a numerical average molecular weight greater than about 10,000 to about 50,000, in the presence of a primer. free radicals to provide an acylated olefin copolymer with a graft grade (DOG) of the acylating agent in the olefin from above about 1.5 to about 3.0 by weight. %, and reacting the acylated olefin copolymer with an amine to provide the highly grafted multifunctional olefin copolymer. Lubricating compositions are disclosed for internal combustion engines ignited by lubricating compression to reduce soot deposits.

[0019] US 8, 168,574 (Visger et al., Published on December 10, 2009) reveals a reduction in soot-induced increase in viscosity in heavy diesel engines. The lubricant composition disclosed therein comprises a lubricating viscosity oil and a composition functionalized with esterified nitrogen, an interpolymer derived from monomers comprising (i) at least one monomer selected from (a) aromatic vinyl monomers, and (ii) by least one α, β-unsaturated acylating agent; wherein a portion of said agent-derived unit acylation is esterified and wherein a portion of said agent-derived unit acylation is condensed with at least one aromatic amine containing at least one NH group capable of condensing with said agent acylation unit derived from the agent monomer, said amine being selected from the group consisting of 4-aminodiphenylamine, 4-phenylazoanilin, 2-aminobenzimidazole, and 3-nitroaniline.

[0020] US 8,093, 189 (Devlin et al., Published March 13, 2008) discloses a low SAP lubricating oil composition for heavy diesel engines, and particularly CJ-4, CI-4 PLUS or CI- 4 comprising a large amount of lubricating viscosity oil and a smaller amount of an amine-functionalized olefin copolymer dispersing viscosity index comprising the reaction product of an acylated olefin copolymer and a polyamine compound, characterized by the fact that the olefin copolymer dispersant viscosity index enhancer is present in an amount effective to inhibit filter clogging induced by the cooling fluid, as measured by the Cummins ISM EGR test, on the lubricating oil composition to be contaminated about 2 percent of the engine's coolant composed of a 50:50 mixture of water and pure (poly) ethylene glycol (total), compared to a modified form of the lubricating oil composition which contains, instead of a non-functionalized amine, the non-acylated form of the olefin copolymer dispersant, but is otherwise the same.

[0021] US 2006/025316 (Covitch et al., Published February 2, 2006) discloses a method for lubricating a heavy-duty diesel engine equipped with exhaust gas recirculation, comprising providing them with a composition comprising a lubricating viscosity oil and the reaction product of: (a) a polymer comprising carboxylic acid functionality or a reactive equivalent thereof, said polymer having a numerical average molecular weight greater than 5,000; and (b) an amine component comprising at least one aromatic amine containing at least one amino group capable of condensing with said carboxylic acid functionality to provide a pendant group and at least one additional group comprising at least one nitrogen atom , oxygen, or a sulfur atom, wherein said aromatic amine is selected from the group consisting of (i) a substituted nitro aniline (such as 3-nitroaniline), (ii) amines comprising two aromatic radicals linked by a group -C (O) NR-, a -C (O) O- group, a -O- group, a -NN- group, or a -SO2- group, where R is hydrogen or hydrocarbyl, one of the said aromatic units which support said condensable amino group, (iii) an aminoquinoline, (iv) an aminobenzimidazole, (v) an N, N-dialkylphenylenediamine group, and (vi) a substituted benzylamine ring.

[0022] US 2004/038836 (Devlin et al., Published February 26, 2004) discloses a lubricant suitable for use in a diesel engine, comprising: a lubricating oil with a viscosity suitable for use in a diesel engine; at least one polymer of functionalized olefins; and a dialkyl zinc dithiophosphate (ZDDP) in which ZDDP is made from a mixture of primary alcohols or a mixture of primary and secondary alcohols, where the lubricant has a high friction film value limit as measured using a High Frequency Reciprocating Equipment (HFRR) greater than or equal to 15.

[0023] US 2003/134754 (Kelley, published July 17, 2003) discloses a composition comprising: (a) a primary amount of an API Group I mineral oil base stock containing at least 300 ppm of sulfur, in Weight; (b) a molybdenum dithiocarbamate in an amount adequate to provide about 25 to about 600 ppm of molybdenum to the composition; (c) a succinimide dispersant based on a polyolefin-substituted succinic structure, wherein the polyolefin has a numerical average molecular weight of at least about 1300; (d) a zinc dialkylldithiophosphate derived from at least one secondary alcohol; and (e) at least one oxidation inhibitor selected from the group consisting of hindered phenols, alkylated aromatic amines, olefins and sulphides. The composition is known to be useful for engine lubricating oils formulated to meet the new specifications of ILSAC GF-3, using conventional high sulfur base oils and tested on Sequence IIIF gasoline engine.

[0024] For a passenger diesel car engine designed with a rotary-end lever follower valve train with a slack regulator, few studies have been reported in an attempt to improve lubricant performance while reducing wear. As a result, Peugeot introduced a test method called DW10 Slack Regulator Test, performed in laboratory tests APL (Automobil-Prüftechnik Landau GmbH) for the engine having its design. A lubricant must obtain a wear rating of 7 or higher to pass the wear requirements of this test. The purpose of the present invention is to reduce wear on the diesel engine passenger car with a rotary end lever follower valve train with a slack adjuster and in a specific embodiment having a wear rating greater than 7, as measured in the DW10 Slack Test Adjuster.

SUMMARY OF THE INVENTION

[0025] As used here to reference the values of additives present in the lubricant composition disclosed here, they are quoted on an oil-free basis, that is, the amount of active agents, unless otherwise indicated.

[0026] As used herein, the transition term "comprises", which is synonymous with "including", "containing", or "characterized by", is inclusive or open and does not exclude additional steps or elements not recited. However, in each recitation of "comprising" used here, it is intended that the term also covers, as alternative modalities, the phrases "consisting essentially of" and "consisting of", where "consists of" excludes any element or unspecified pitch and "consisting essentially of" allows the inclusion of additional non-recited elements or steps that do not materially affect the basic and new characteristics of the method or composition under consideration.

[0027] The invention relates to a method of lubricating the slack-end valve train slack regulator of a compression-ignition internal combustion engine for passenger vehicles with a reference mass not exceeding 2610 kg comprising providing the internal combustion engine with a lubricating composition comprising a lubricating viscosity oil of 0.01% by weight to 3% by weight of a dispersing viscosity modifier, and 0.01% by weight to 3% by weight of a sulfur-containing zinc-free anti-wear agent, where the lubricant composition has a sulfur content of less than 5000 ppm, a phosphorus content of 1,000 ppm or less, and a sulfate ash content (typically 3000 to 12,000 ppm), or 10,000 ppm or less.

[0028] The passenger car reference mass not exceeding 2610 kg is a technical characteristic defined by the European Union, as specified in Euro 5 and 6 emission requirements. The same standard is applied by the professional association of the industry ACEA (Association of European Car Manufacturers) in such a way that it defines a light passenger car in Section C of the European oil ACEA Sequences for 2010. As such, the method of the present invention relates to the lubrication of a light combustion engine passenger car. internal compression ignition (a diesel engine), comprising a slack end follower lever train slack regulator.

[0029] The lubricating composition can have a sulfur content of 500 to 4000 ppm, or 1000 to 3000 ppm, a phosphorus content of 300 to 900 ppm, or 400 to 750 ppm and a sulfated ash content of 3000 and 7000 ppm .

[0030] The lubricant composition may comprise an anti-wear agent containing zinc-free sulfur comprising from 0.1 to 0.5% by weight of sulfuric olefin, and 0.1 to 0.5% by weight of an olefin copolymer. functionalized with an amine dispersing group, wherein the olefin copolymer is an ethylene-propylene copolymer.

[0031] The lubricant composition may comprise from 0.1% by weight to 0.4% by weight of anti-wear agent containing sulfur free of molybdenum dithiocarbamate zinc, and 0.1 to 0.5% by weight, of a olefin copolymer further functionalized with an amine dispersing group, wherein the olefin copolymer is an ethylene-propylene copolymer.

[0032] The lubricant composition disclosed herein may further comprise detergent with excess calcium sulfonate base present at 0.01 to 0.5% by weight, or 0.05 to 0.3% by weight of the lubricant composition (typically in that the detergent with excess of calcium sulfonate base has a TBN of 300 to 500 mg of KOH / g).

[0033] The slack regulator typically comprises a common ball and socket.

[0034] The slack regulator is usually a hydraulic slack regulator.

[0035] The slack regulator is typically a hydraulic slack regulator comprising a common ball and socket. In a mode of the slack regulator it does not have a chrome coating, a tin layer, a nitride coating, or a boride coating.

[0036] The invention further provides the method or use of a lubricating composition comprising: a lubricating viscosity oil 0.01% by weight to 3% by weight of a dispersing viscosity modifier, and 0.01% by weight at 3% by weight of an anti-wear agent containing zinc-free sulfur, where the lubricant composition has a sulfur content of less than 5,000 ppm, a phosphorus content of 1,000 ppm or less, and a sulfated ash content of typically 3,000 to 12,000 ppm, or 10,000 ppm or less, to reduce wear and tear on an internal combustion engine that comprises a rotary end lever follower valve slack regulator.

[0037] Wear reduction can be measured by the Peugeot DW10 Slack Regulation Test with a pass rate of 7 or higher.

DETAILED DESCRIPTION OF THE INVENTION

[0038] The present invention provides a method for lubricating an internal combustion engine and a use as described above.

Lubricating viscosity oils

[0039] The lubricating composition comprises a lubricating viscosity oil. Such oils include natural and synthetic oils, derived from hydrocracking, hydrogenation, and hydro-finish oil, refined, oils, or unrefined mixtures of these refined. A more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008 / 147704, paragraphs [0054] to [0056] (similar disclosure is provided in US Patent Application 2010/197536, see [0072] to [0073]). A more detailed description of natural and synthetic lubricating oils is described in paragraphs [0058] to [0059], respectively, of document W02008 / 147704 (similar disclosure is provided in Patent Application US2010 / 197536, paragraphs [0075] to [ 0076]). Synthetic oils can also be produced through Fischer-Tropsch reactions and can typically be Fischer-Tropsch hydroisomerized hydrocarbons or waxes. In one embodiment, oils can be prepared by a synthetic gas-liquid Fischer-Tropsch process, as well as other gas-to-liquid oils.

[0040] Lubricating viscosity oils can also be defined as specified in the April 2008 version of "Appendiz E - API Base Oil INterchangeability Guidelines for Passanger Car Engine Oils and Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock Categories". API guidelines are also summarized in U.S. Patent 7,285,516 (see column 11, row 64 through column 12, row 10).

[0041] In one embodiment the lubricating viscosity oil may be an API group I to IV of mineral oil, an ester or synthetic oil, or mixtures thereof. In one embodiment, the lubricating viscosity oil may be an API group II, Group III, mineral oil Group IV, an ester or synthetic oil, or mixtures thereof.

[0042] The amount of lubricating viscosity oil present is typically the balance remaining after subtracting 100% by weight from the sum of the amount of the additives of the present invention and other performance additives.

[0043] The lubricating composition can be in the form of a concentrate and / or a fully formulated lubricant. If the lubricant composition of the invention (comprising the additives described herein) is in the form of a concentrate that can be combined with the additional oil to form, in whole or in part, a finished lubricant), the ratio between these additives for oil of lubricating viscosity and / or for oil thinner includes the ranges from 1:99 to 99: 1 by weight, or 80:20 to 10:90 by weight. Typically, the lubricating composition of the present invention comprises at least 50% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight of an oil of lubricating viscosity.

Dispersing Viscosity Modifier

[0044] The lubricant composition of the invention contains a dispersing viscosity modifier. The dispersing viscosity modifier can be present in 0.05% by weight to 1.5% by weight, or 0.1% by weight at 1% by weight, or 0.1 to 0.5% by weight.

The dispersing viscosity modifier may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine; polymethacrylates functionalized with an amine, or the styrene-maleic anhydride copolymers with an amine. More detailed description of dispersant viscosity modifiers are disclosed in International Publication W02006 / 015,130 or 4,863,623 U.S Patents .; 6, 107,257; 6, 107,258; 6, 17,825; and US 7,790,661. In one embodiment, the dispersing viscosity modifier can include those described in U.S. Patent 4,863,623 (see column 2, row 15 to column 3, row 52) or International Publication W02006 / 015,130 (see page 2, paragraph [0008] and the preparatory examples are described in paragraphs [0065] to [0073]).

[0046] In a particular embodiment, the dispersant viscosity modifier comprises an olefin copolymer more functionalized with a dispersing amine group. Typically, the olefin copolymer is an ethylene-propylene copolymer.

[0047] The olefin copolymer has a numerical average molecular weight of 5,000 to 100,000, or 7,500 to 60,000, or 8,000 to 45,000.

The dispersing amine group can be prepared / derived from the reaction of the olefin copolymer (typically an ethylene-propylene copolymer) with an acylating agent (maleic anhydride, typically), and an aromatic amine having a primary amino group or secondary. Typically, the dispersing viscosity modifier can be an ethylene-propylene-acylated copolymer with maleic anhydride and reacted with an aromatic amine.

[0049] The formation of a dispersing viscosity modifier is well known in the art. The dispersant viscosity modifier can include, for example, those described in US Patent 7,790,661 US column 2, line 48 to column 10, line 38.

[0050] In one embodiment, the dispersant viscosity modifier can be prepared by grafting an olefinic carboxylic acid acylating agent to a polymer of 15 to 80 mole percent ethylene, 20 to 85 mole percent C3-10 ot-monoolefin, and from 0 to 15 mole percent of unconjugated diene or triene, said polymer having an average molecular weight ranging between 5,000 and 500,000, and still reacting said grafted polymer with an amine (typically an amine aromatic).

[0051] In another embodiment, the dispersant viscosity modifier can be a reaction product of: (a) a polymer comprising carboxylic acid functionality or a reactive equivalent thereof, said polymer having a numerical average molecular weight greater than 5,000; and (b) an amine component comprising at least one aromatic amine containing at least one amino group capable of condensing with said carboxylic acid functionality to provide a pendant group and at least one additional group comprising at least one nitrogen atom , oxygen, or a sulfur atom, wherein said aromatic amine is selected from the group consisting of (i) a substituted nitroaniline, (ii) an amine comprising two aromatic moieties linked by a -C (O) group NR-, a -C (O) O- group, a -O- group, a -N = N- group, or a -SO2 group, where R is hydrogen or hydrocarbyl, one of the said aromatic units bearing the said condensable amino group, (iii) an amino quin line, (iv) an aminobenzimidazole, (v) an N, N-dialkylphenylenediamine group, (VI), an aminodiphenylamine (also N, N-phenyldiamine), and (vii) an substituted benzylamine ring.

bem como vários anéis aromáticos condensados ou não-ligados. Nestes e estruturas relacionadas, Rv, Rvi, e Rvii pode ser independentemente, entre outros grupos aqui revelados, grupos alquila -H, -C1-18, grupos nitro, -NH-Ar, - N =N-Ar, -NH-CO-Ar, -OOC-Ar, -OOC-alquila C1-18, -COO-alquila C1-18, -OH, grupos -O- (CH2CH2-O) nCi-i8 alquila, e -0- (CH2CH2θ)nAr (em que n é 0 a 10) .[0052] The aromatic amine of the dispersing viscosity modifier can also include those that can be represented by the general structure NH2-Ar or T-NH-Ar, where T can be alkyl or aromatic, Ar represents an aromatic group, including nitrogen containing or amino substituted with aromatic groups and Ar groups including any of the following structures:

as well as several condensed or unbound aromatic rings. In these and related structures, Rv, Rvi, and Rvii can be independently, among other groups disclosed herein, alkyl groups -H, -C1-18, nitro groups, -NH-Ar, - N = N-Ar, -NH-CO -Ar, -OOC-Ar, -OOC-C1-18 alkyl, -COO-C1-18 alkyl, -OH, groups -O- (CH2CH2-O) nCi-i8 alkyl, and -0- (CH2CH2θ) nAr ( where n is 0 to 10).

[0053] Aromatic amines include those amines that a carbon atom of the aromatic ring structure is directly linked to amino nitrogen. The amines can be monoamines or polyamines. The aromatic ring will typically be a mononuclear aromatic ring (i.e., a benzene derivative), but can include fused aromatic rings, especially naphthalene derivatives. Examples of aromatic amines include aniline, N-alkylanilines such as N-methylaniline and N-butylaniline, di- (para-methylphenyl) amine, 4-aminodiphenylamine, N, N-dimethylphenylenediamine, naphthylamine, 4- (4-nitrophenylazo) aniline (Disperse Orange 3), sulfamethazine, 4-phenoxyaniline, 3-nitro aniline, 4-aminoacetanilide (N- (4-aminophenyl) acetamide)), 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl-amino salicylate ), N- (4-amino-phenyl) -benzamide, various benzylamines such as 2,5-dimethoxybenzylamine, 4-phenylazoaniline, and substituted versions thereof. Other examples include para-ethoxyaniline, para-dodecylaniline, substituted naphthylamine-cyclohexyl, and aniline substituted by thienyl. Examples of other suitable aromatic amines include amino substituted compounds and aromatic amines in which the amine nitrogen is a part of an aromatic ring, such as 3-aminoquinoline, 5-aminoquinoline, and 8-aminoquinoline. Also included are aromatic amines such as 2-aminobenzimidazole, which contains a secondary amino group attached directly to the aromatic ring and a primary amino group attached to the imidazole ring. Other amines include N- (4-anilinophenyl) -3-aminobutanamide or 3-amino propyl imidazole. However, other amines include 2,5-dimethoxybenzylamine.

e variações isoméricas, onde Rviii e Rix são, independentemente, grupos alquila ou alcoxi tais como metila, metoxi, ou etoxi. Em um exemplo, Rviii e Rix são ambos -OCH3 e o material é conhecido como azul rápido RR [CAS # 6268-05-9].[0054] Additional aromatic amines and related compounds are disclosed in US Patent 6,107,257,257 and 6,107,258; some of them include aminocarbazoles, benzoimidazoles, aminoindoles, aminopyrroles, amino-indazolinones, amino-perimidines, mercaptotriazoles, aminophenothiazines, aminopyridines, amino-pyrazines, aminopyrimines, pyridines, pyrimidines, pyrazines, amines, thiazines, amines and thiazides Other suitable amines include 3-amino-N- (4-anilinophenyl) butanamide-N-isopropyl, and N- (4-anilinophenyl) - 3 - {(3-aminopropyl) - (cocoalkyl) amino} butanamide. Other aromatic amines that can be used include various aromatic amine dye intermediates containing multiple aromatic rings linked by, for example, amide structures. Examples include materials of general structure:

and isomeric variations, where Rviii and Rix are, independently, alkyl or alkoxy groups such as methyl, methoxy, or ethoxy. In one example, Rviii and Rix are both -OCH3 and the material is known as fast blue RR [CAS # 6268-05-9].

[0055] In another example, Rix is -OCH3 and Rviii represents a -CH3 group, and the material is known as Fast Violet B [99-21 -8]. When both Rviii and Rix are ethoxy, the material is Fast Blue BB [120-00-3]. U.S. Patent 5,744,429 discloses other aromatic amine compounds, particularly aminoalkylphenothiazines. N-substituted aromatic acid compounds of amide, such as those disclosed in U.S. Patent Application 2003/0030033 A1, can also be used for the purposes of the present invention. Suitable aromatic amines include those in which amine nitrogen is a substituent on an aromatic carboxy compound, that is, nitrogen is not sp2 hybridized within an aromatic ring.

[0056] The aromatic amine can also comprise an amine formed by the reaction of an aldehyde with 4-aminodiphenylamine. The resulting amine can be described as an amine-coupled alkylene group having at least 4 aromatic groups, at least one -NH2 functional group, and at least 2 secondary or tertiary amino groups. The aldehyde can be aliphatic, alicyclic or aromatic. The aliphatic aldehyde can be linear or branched. Examples of a suitable aromatic aldehyde include benzaldehyde or o-vanillin. Examples of an aliphatic aldehyde include formaldehyde (or a reactive equivalent, such as formalin or paraformaldehyde), ethanal or propanal. Typically, the aldehyde can be formaldehyde or benzaldehyde. Alternatively, this aromatic amine can also be prepared by the methodology described in Berichte der Deutschen Chemischen Gesellschaft (1910), 43, 728-39.

em que cada variável R1 pode ser hidrogênio ou um grupo C1-5 alquila (tipicamente de hidrogênio); R2 pode ser hidrogênio ou um grupo C1-5 alquila (tipicamente de hidrogênio); U pode ser um hidrocarboneto de grupo alifático, aliciclico ou aromático, com a condição de que quando U é um grupo alifático, o grupo alifático pode ser linear ou ramificado contendo grupo alquileno de 1 a 5, oula2 átomos de carbono; e W pode ser de 0 a 9 ou de 0 a 3 ou 0 a 1 (tipicamente 0) .[0057] The aromatic amine formed by coupling an aldehyde and 4-aminodiphenylamine is described in European Patent Application EP 2 401 348 A and can also be represented by the formula:

where each variable R1 can be hydrogen or a C1-5 alkyl group (typically hydrogen); R2 can be hydrogen or a C1-5 alkyl group (typically hydrogen); U can be an aliphatic, alicyclic or aromatic hydrocarbon, with the proviso that when U is an aliphatic group, the aliphatic group can be linear or branched containing 1 to 5 alkylene group, or 2 carbon atoms; and W can be 0 to 9 or 0 to 3 or 0 to 1 (typically 0).

[0058] In one embodiment it includes the aromatic amine of 4-aminodiphenylamine, the aldehyde (typically formaldehyde) coupled to 4-aminodiphenylamine, nitro-aniline (3-nitro-aniline), Disperse Orange 3- (DO3), or mixtures thereof. Anti-wear agent containing zinc-free sulfur

[0059] The lubricant composition of the invention contains an anti-wear agent containing zinc-free sulfur. The anti-wear agent containing zinc-free sulfur can be present in 0.01% by weight to 1.5% by weight, 0.05% by weight at 1% by weight, or 0.1 to 0.5% by weight of lubricating composition.

[0060] The anti-wear agent containing zinc-free sulfur can be selected from the group consisting of a sulfurized olefin, a molybdenum compound, an amine salt of a compound containing (thio) phosphorus, a thiadiazole, and mixtures thereof.

[0061] In one embodiment, the anti-wear agent containing zinc-free sulfur may be a molybdenum compound. The molybdenum compound can be an antioxidant or an anti-wear agent. The molybdenum compound can be selected from the group consisting of molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof. Typically, the molybdenum compound can be molybdenum dithiocarbamate, or molybdenum dithiophosphate.

[0062] The molybdenum compound can provide the lubrication composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 ppm to 750 ppm and 5 400 ppm, or 20 ppm to 350 ppm molybdenum. Examples of molybdenum dithiocarbamates, which can be used as an antioxidant, include commercial materials sold under the trade names, such as VANLUBE 822 ™ and Molyvan ™ A by RT Vanderbilt Co., Ltd., and Adeka Sakura-Lube ™ S- 100, S-165, S- 600 and 525, or mixtures thereof.

[0063] In another embodiment, the anti-wear agent containing zinc-free sulfur may be a sulfurized olefin. The olefin can be a sulfur polysulfide.

[0064] In one embodiment, the sulfurized olefin includes dihydrocarbyl polysulfides; sulfurized olefins; esters of sulfur fatty acids from both natural and synthetic origins; trithiones; sulfurized thienyl derivatives; sulfurized terpenes; sulfurized C2-C8 mono-olefin oligomers; and sulfurized Diels-Alder adducts such as those disclosed in U.S. Patent Number Re 27,331. Specific examples include sulfurized polyisobutylene, sulfurized isobutylene, sulfurized diisobutylene, sulfurized triisobutylene, polysulfide diphenyl polysulfide, dibenzyl polysulfide, dinonyl polysulfide, and mixtures of di-tert-butyl polysulfide such as di-tert-butyl mixtures di-butyl di-tert-tetrasulfide butyl-trisulfide and tert-butyl-pentasulfide, among others. Combinations of such categories of sulfur-containing anti-wear and / or extreme pressure agents can also be used, such as a combination of sulfurized isobutylene and di-tert-butyltrisulfide, a combination of sulfurized isobutylene and dinonyl trisulfide, a combination of long oils sulfurized and dibenzyl polysulfide.

[0065] In another embodiment, at least 50% by weight of the polysulfide molecules are a mixture of tri- or tetra-sulfides. In other embodiments, at least 55% by weight, or at least 60% by weight of the polysulfide molecules are a mixture of tri- or tetra-sulfides.

[0066] The polysulfide includes an organic polysulfide sulfated from oils, fatty acids or esters (such as ester containing sulfuric olefin), olefins or polyolefins.

[0067] Oils that can be sulfurized include natural or synthetic oils, such as mineral oils, lard oil, carboxylate esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (eg myristyl oleate and oleate) of oleyl), and unsaturated synthetic esters or glycerides.

[0068] Fatty acids include those that contain 8 to 30, or 12 to 24 carbon atoms. Examples of fatty acids include oleic, linoleic, linolenic, and long oil. Sulfur fatty acid esters prepared from mixed unsaturated fatty acid esters, such as are obtained from animal fats and vegetable oils, including long oil, flaxseed oil, soybean oil, rapeseed oil and fish oil.

[0069] The olefin polysulfide includes derivatives from a wide range of alkenes. Alkenes typically have one or more double bonds. The olefins in one embodiment contain 3 to 30 carbon atoms. In other embodiments, olefins contain 3 to 16, or 3 to 9 carbon atoms. In one embodiment, the sulfurized olefin includes an olefin from propylene, isobutylene, pentene, or mixtures thereof.

[0070] In another polysulfide o comprises a polyolefin derived from polymerization by known techniques, an olefin, as described above.

[0071] In yet another embodiment includes dibutyl tetrasulfide polysulfide, sulfuric oleyl acid methyl ester, sulfuric alkylphenol, sulfuric dipentene, sulfurized dicyclopentadiene, sulfurized terpene, and sulfurized Diels-Alder adducts.

[0072] In another embodiment the sulfur olefin may be an olefin containing sulfur ester. The sulfur ester-containing olefin may include a sulfuric 4-cyclohexene carbobutoxy.

[0073] In yet another embodiment of an anti-wear agent containing zinc-free sulfur can be a thiadiazole compound. Examples of a thiadiazole include 2,5-dimercapto-1,3,4-thiadiazole, or its oligomers, a hydrocarbyl substituted with 2,5-dimercapto-1, 3,4-thiadiazole, a hydrocarbylthio substituted with 2,5-dimercapto 1,3,4-thiadiazole, or its oligomers. The 2,5-dimercapto-1,3,4-thiadiazole-substituted hydrocarbyl oligomers typically form by forming a sulfur-sulfur bond between 2,5-dimercapto-1,3,4-thiadiazole units to form oligomers of two or more of said thiadiazole units. These thiadiazole compounds can also be used in the treatment of dispersing powders, as mentioned below, in the formation of a dimercaptothiadiazole derivative of a polyisobutylene succinimide.

[0074] Examples of a suitable thiadiazole compound include at least one of a dimercaptothiadiazole, 2,5-dimercapto- [1,3,4] -thiadiazole, 3,5-dimercapto- [1,2,4] - thiadiazole, 3,4-dimercapto- [1,2,5] -thiadiazole, or 4-5- dimercapto- [1,2,3] -thiadiazole. Typically readily available materials, such as 2,5-dimercapto-1, 3,4-thiadiazole or a substituted 2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbylthio substituted with 2,5-dimercapto-1, 3,4-thiadiazole are commonly used.

em que R3 e R4 podem ser, independentemente, hidrogênio ou um hidrocarboneto, tipicamente contendo de 4 a 40, ou de 6 a 30, oudeβalδ, ouδalδ átomos de carbono, com a condição de que pelo menos um é um grupo hidrocarboneto; e R5, R6, R7 e R8 pode ser, independentemente, hidrogênio ou um grupo hidrocarbila, com a condição de que pelo menos um é um grupo hidrocarbila.[0075] In one embodiment the anti-wear agent containing zinc-free sulfur can be an amine salt of a (uncle) compound containing phosphorus. The amine salt of a phosphorus-containing (uncle) compound can be an amine salt of a phosphate hydrocarbon ester (i.e., an amine salt of a phosphoric acid hydrocarbon ester). The amine salt of a phosphate hydrocarbon ester can be derived from an amine salt of a phosphate. The amine salt of the phosphate ester can hydrocarbon represented by the formula:

wherein R3 and R4 may independently be hydrogen or a hydrocarbon, typically containing 4 to 40, or 6 to 30, oudeβalδ, ouδalδ carbon atoms, with the proviso that at least one is a hydrocarbon group; and R5, R6, R7 and R8 may independently be hydrogen or a hydrocarbyl group, with the proviso that at least one is a hydrocarbyl group.

[0076] The hydrocarbon groups of R3 and / or R4 can be linear, branched, or cyclic.

The amine salt of a hydrocarbon phosphate ester can be prepared as described in U.S. Patent 6,468,946. Column 10, lines 15 to 63 describes phosphoric acid esters formed by reacting phosphorus compounds, followed by reaction with an amine to form an amine salt of a hydrocarbon phosphate ester. Column 10, line 64, up to column 12, line 23, describes preparative examples of reactions between phosphorus pentoxide with an alcohol (with 4 to 13 carbon atoms), followed by a reaction with an amine (usually Primene® -R 81) to form an amine salt of a hydrocarbon phosphate ester.

[0078] The amine salt of a compound containing (thio) phosphorus may also be a compound described in European patent applications EP 2 318 493 A and 2 023 113 A. Disclosed in both EP applications is a free amine salt sulfur content of a phosphorus compound obtained / obtainable by a process which comprises: the reaction of an amine with either (i) a hydroxy-substituted phosphoric acid diester, or (ii) a phosphorylated di- or tri-ester phosphoric acid, and represented by Formula (1) and (la) in both publications.

The lubricating composition may comprise from 0.01% by weight to 1.5% by weight of sulfurized olefins, 0.05% by weight to 1.5% by weight, of an olefin copolymer still functionalized with a group dispersing amine.

[0080] The lubricant composition may further comprise a compound containing molybdenum selected from the group consisting essentially of molybdenum dithiocarbamate, and molybdenum dithiophosphate (typically molybdenum dithiocarbamate) present in an amount ranging from 0.01 to 0.75 % by weight, or 0.05% by weight at 0.5% by weight, or 0.1% by weight at 0.4% by weight.

[0081] The lubricant composition may comprise from 0.01% by weight to 0.75% by weight of molybdenum dithiocarbamate, from 0.05% by weight to 1.5% by weight, of an olefin copolymer still functionalized with a dispersing amine group, wherein the olefin copolymer is an ethylene-propylene copolymer.

[0082] The lubricant composition may comprise from 0.01% by weight to 1.5% by weight of sulfurized olefins, 0.01% by weight to 0.75% by weight of molybdenum dithiocarbamate, 0.05% by weight 1.5% by weight of an olefin copolymer still functionalized with a dispersing amine group, wherein the olefin copolymer is an ethylene-propylene copolymer. Other performance additives

[0083] A lubricating composition can be prepared by adding the product of the process described here to an oil of lubricating viscosity, optionally in the presence of other performance additives (as described here below).

[0084] The lubricating composition of the invention optionally comprises other performance additives. The other performance additives include at least one of the metal deactivators, viscosity modifying agents, detergents, friction modifiers, anti-wear agents, corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam, demulsifiers, spill point depressants, sealing swelling agents and mixtures thereof. Typically, the fully formulated lubricating oil will contain one or more of these performance additives.

[0085] In one embodiment, the invention provides a lubricating composition that further comprises a detergent with excess of base containing metal. The metal of the metal-containing detergent can be zinc, sodium, calcium, barium or magnesium. Typically, the metal of the metal-containing detergent can be sodium, calcium or magnesium.

[0086] The detergent with excess of base containing metal can be selected from the group consisting of non-sulfur-containing phenates, sulfur-containing phenates, sulfonates, salixarates, salicylates, and mixtures thereof, or borate equivalents thereof. The detergent with excess base can be borated with a bleaching agent, such as boric acid.

[0087] The metal based excess detergent may also include "hybrid" detergents formed with mixed surfactant systems, including phenate and / or sulfonate components, eg phenate / salicylates, sulfonate / phenates, sulfonate / salicylates, sulfonates / phenates / salicylates, as described; for example, in U.S. Patents 6,429,178; 6429,179; 6,153,565; and 6,281,179. When, for example, a hybrid sulfonate detergent / phenate is employed, the hybrid detergent would be considered equivalent to different amounts of phenate and sulfonate detergents by introducing similar amounts of phenate and sulfonate soaps, respectively.

[0088] Typically, a detergent with excess base containing metal can be zinc, sodium, calcium or magnesium salt of a phenate, sulfate-containing phenate, sulfonate, salixarate or salicylate. Excess base salixarates, phenates and salicylates typically have a total base number of 180 to 450 TBN. Sulfonates with excess base usually have a total base number of 250 to 600, or 300 to 500. Detergents with excess base are known in the art. In one embodiment, the detergent may be a predominantly linear alkylbenzene sulfonate detergent that has a metal ratio of at least 8, as described in paragraphs [0026] to [0037] of US Patent Application 2005065045 (and granted as US 7,407,919). The predominantly linear alkylbenzene sulfonate detergent can be particularly useful to assist in improving fuel economy.

[0089] Typically, the detergent with excess of base containing metal can be a detergent with excess of base of calcium or magnesium.

[0090] Detergents with excess base are known in the art. Excess base materials, otherwise referred to as excess base or super base salts, are generally single-phase, homogeneous Newtonian systems characterized by a metal content in which they would be present for neutralization according to the stoichiometry of the metal and the particular acidic organic compound, reacted with the metal. Excess base materials are prepared by reacting an acidic material (typically an inorganic acid or a lower carboxylic acid, preferably carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for said organic acid material, a stoichiometric excess of a base metal, and a promoter, such as calcium chloride, acetic acid, alcohol or phenol. The acidic organic material normally has a sufficient number of carbon atoms to provide a certain degree of oil solubility. The amount of "excess" of metal (stoichiometrically) is usually expressed in terms of the proportion of metals. The term "metal ratio" is the ratio of the total metal equivalents to the acidic organic compound equivalents. A neutral metal salt has a metal ratio of one. A salt that has 3.5 times more metal as present in a normal salt, will have excess metal of 3.5 equivalents, or a ratio of 4.5. The term "metal ratio is also explained in the standard textbook entitled" Chemistry and Technology of Lubricants ", third edition, edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, page 219, subheading 7.25.

[0091] In another embodiment, the lubricating composition further comprises a super sulfated calcium sulfonate detergent and a calcium phenate detergent with excess of base in an amount such that the sulfated ash content is 1000 ppm or less (such as 100 ppm at 1000 ppm, or 300 ppm at 900 ppm).

[0092] The lubricating composition, in another embodiment, comprises an antioxidant, wherein the antioxidant comprises a phenolic antioxidant or an amino acid or mixtures thereof. Antioxidants include diaryl amines, alkylated diaryl amines, hindered phenols, or mixtures thereof. When present the antioxidant is present in 0.1% by weight to 3% by weight, or 0.5% by weight to 2.75% by weight, or 1% by weight to 2.5% by weight of the lubricating composition.

[0093] The alkylated diaryl amine or diaryl amine can be a phenyl-a-naphthylamine (PANA), an alkylated diphenylamine, or an alkylated phenyl amphylamine, or mixtures thereof. Alkylated diphenylamine may include di-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, di-octyl diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof. In one embodiment of diphenylamine it may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof. In another embodiment, the alkylated diphenylamine may include nonyl diphenylamine, or dinonyl diphenylamine. Alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnaphthylamine.

[0094] The hindered phenol antioxidant often contains a secondary butyl and / or a tertiary butyl group as a stereochemically preventing group. The phenol group can be further substituted with a hydrocarbyl group (typically straight or branched alkyls) and / or a linking group that binds to a second aromatic group. Examples of suitable impaired phenolic antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2 , 6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butyl-phenol. In one embodiment, the prevented phenol antioxidant may be an ester and may include, for example, Ciba's Irganox ™ G-135. A more detailed description of the chemistry of the ester containing appropriate hindered antioxidant is found in US Patent 6,559, 105.

[0095] The lubricating composition may, in another embodiment, include a dispersant, or mixtures thereof. The dispersant can be a succinimide dispersant, a Mannich dispersing agent, a succinamide dispersant, a polyolefin succinic acid ester, amide, ester or amide, or mixtures thereof. In one embodiment, the dispersing agent can be present as a single dispersant. In one embodiment, the dispersing agent can be present as a mixture of two or three different dispersants, at least one of which can be a succinimide dispersant.

[0096] The succinimide dispersant can be derived from an aliphatic polyamine, or mixtures thereof. The aliphatic polyamine can be aliphatic polyamine such as an ethylene polyamine, a propylene polyamine, a butylene polyamine, or mixtures thereof. In an aliphatic polyamine modality it can be ethylene polyamine. In one embodiment, the aliphatic polyamine can be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, distillation polyamine, and mixtures thereof.

[0097] In one embodiment, the dispersing agent may be a succinic acid ester, amide or polyolefin ester-amide. For example, a polyolefin succinic acid ester can be a polyisobutylene succinic acid ester of pentaerythritol, or mixtures thereof. A polyolefin succinic acid-amide ester can be a polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and a polyamine, as described above.

[0098] The dispersant may be a long-chain alkenyl group of N-substituted succinimide. An example of an N-substituted long-chain alkenyl succinimide is the polyisobutylene succinimide. Typically, the polyisobutylene from which polyisobutylene succinic anhydride is derived has a numerical average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500. Succinimide dispersants and their preparation are disclosed, for example in US Patents 3, 172,892, 3,219,666, 3,316,177, 3340281, 3351552, 3381022, 3433744, 3444170, 3467668, 3501405, 3542680, 3576743, 3,632.51 1, 4,234,435, Re 26,433, and 6, 165235, 7238650 and order EP 0 355 895 A.

[0099] Dispersing agents can also be post-treated by conventional methods by reacting with any of a variety of agents. These include boron compounds (such as boric acid), urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, such as terephthalic acid, hydrocarbon-substituted anhydrides, maleic anhydride, nitriles, epoxides, and compounds phosphorus. In one embodiment, the post-treated dispersant is borated. In one embodiment, the post-treated dispersant is reacted with dimercaptothiadiazoles. In one embodiment, the post-treated dispersant is reacted with phosphoric or phosphorous acid. In one embodiment, the post-treated dispersant is reacted with terephthalic acid and boric acid (as described in US Patent Application US2009 / 0054278.

[0100] When present, the dispersing agent can be present at 0.01% by weight to 20% by weight, or 0.1% by weight at 15% by weight, or 0.1% by weight at 10% by weight , or 1% by weight to 6% by weight, or 1 to 3% by weight of the lubricating composition.

[0101] In one embodiment, the friction modifier can be selected from the group consisting of derivatives of long chain fatty acids from amines, esters of long chain fatty acids, or derivatives of long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; alkyl fatty tartrates; alkyl fatty tartrimides; alkyl fatty tartramides; fatty glycolates; and fatty glycolamides. The friction modifier can be present at 0% by weight to 6% by weight, or 0.01% by weight at 4% by weight, or 0.05% by weight at 2% by weight, or 0.1% by weight at 2% by weight of the lubricating composition.

[0102] As used herein, the term "fatty alkyl" or "fatty" in relation to friction modifiers means a carbon chain with 10 to 22 carbon atoms, typically a linear carbon chain.

[0103] Examples of suitable friction modifiers include derivatives of long chain amine fatty acids, fatty acid esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene polyamines; amine salts of alkylphosphoric acids; alkyl fatty tartrates; alkyl fatty tartrimides; alkyl fatty tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, boron-based fatty epoxides; glycerol esters; boron-based glycerol esters; fatty amines; alkoxylated fatty amines; borate alkoxylated fatty amines; hydroxyls and polyhydroxy fatty amines, including tertiary hydroxy fatty amines; hydroxyalkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; ethoxylated fatty alcohols; condensation products of carboxylic acids and polyalkylene polyamines; or reaction products of fatty carboxylic acids with guanidine, aminoguanidine, urea, thiourea or and their salts.

[0104] Friction modifiers can also cover materials such as fatty sulfur compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or a polyol monoester soybean oil and an aliphatic carboxylic acid.

[0105] In another embodiment, the friction modifier may be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester may be a monoester and in another embodiment, the long-chain fatty acid ester may be a triglyceride.

[0106] The lubricant composition optionally also includes at least one anti-wear agent. Examples of suitable anti-wear agents include titanium compounds, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, metal dihydrocarbildithiophosphates (such as zinc dialhyldithiophosphates), phosphites (such as dibutyl phosphite phthalate), phosphonates , thiocarbamate containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-linked thio-carbamates, and bis (S-alkyldithiocarbamyl) disulfides. The anti-wear agent may, in one embodiment, include a tartrate, or tartrimide as disclosed in International Publication WO 2006/044411 or in Canadian patent CA 1 183 125. The tartrate or tartrimide may contain alkyl ester groups, where the sum of carbon atoms in the alkyl groups it is at least 8. The anti-wear agent may, in one embodiment, include a citrate as disclosed in US Patent Application 20050198894.

[0107] Another class of additives includes oil-soluble titanium compounds as described in US 7,727,943 and US2006 / 0014651. Oil-soluble titanium compounds can function as anti-wear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions. In one embodiment, the titanium compound is a soluble oil of titanium (IV) alkoxide. Titanium alkoxide is formed from a monohydric alcohol, a polyol or mixtures thereof. Monohydric alkoxides can have 2 to 16, or 3 to 10 carbon atoms. In one embodiment, titanium alkoxide is titanium (IV) isopropoxide. In one embodiment, titanium alkoxide is titanium (IV) 2-ethylhexoxide. In one embodiment, the titanium compound comprises alkoxide from a 1,2-diol vicinal or polyol. In one embodiment, the 1,2-diol vicinal comprises a glycerol mono-ester fatty acid, often the fatty acid is oleic acid.

[0108] In one embodiment, the oil-soluble titanium compound is a titanium carboxylate. In an additional embodiment the titanium (IV) carboxylate is titanium neodecanoate.

[0109] The lubricating composition may, in one embodiment, also include an anti-wear agent containing phosphorus. Typically, the phosphorus-containing anti-wear agent may be a dialkyldithiophosphate of zinc salts, phosphite, phosphate, phosphonate, and ammonium phosphate, or mixtures thereof. Zinc dialkyldithiophosphates are known in the art. The anti-wear agent may be present at 0 wt% to 3 wt%, or 0.1 wt% to 1.5 wt%, or 0.5 wt% to 0.9 wt% of the lubricating composition.

[0110] Extreme pressure (EP) agents that are soluble in oil include EP agents containing sulfur and chloro-sulfur, dimercaptothiadiazole derivatives or CS2 derivatives of dispersants (usually succinimide dispersants), derivatives of dormant hydrocarbon EP agents and EP phosphorus agents . Examples of such EP agents include chlorinated wax; defines such as sulfur (sulfur isobutylene), a hydrocarbyl substituted with 2,5-dimercapto-1,3,4-thiadiazole, or its oligomers, sulfides and organic polysulfides, such as dibenzyl disulfide, bis- (chlorobenzyl) disulfide, tetrasulfide dibutyl, sulfuric methyl ester of oleic acid, sulfurylphenols, sulfuric dipentenes, sulfuric terpenes, and sulfuric Diels-Alder adducts; phosphosulfurized hydrocarbons, such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphoric esters such as phosphite dihydrocarbons and trihydrocarbons, for example, dibutyl, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl, tridecyl phosphite, distearyl phosphite and substituted phenol polypropylene phosphite; metallic thiocarbamates, such as zinc and barium dioctyldiocarbamate heptyl-phenol diacid; alkyl amine salts and dialkylphosphoric acids or derivatives, including, for example, the amine salt of a product of the reaction of a dialkyl-dithiophosphoric acid with propylene oxide and subsequently followed by an additional reaction with P2O5; and mixtures thereof (as described in US 3, 197,405).

[0111] Foam inhibitors that may be useful in the compositions of the present invention include polysiloxanes, ethyl acrylate and 2-ethylhexyl copolymers and vinyl acetate optionally; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and ethylene oxide (propylene oxide), polymers.

[0112] Spill point depressants that may be useful in the compositions of the invention include polyalphaolefin esters, maleic-styrene anhydride copolymers, poly (meth) acrylates, polyacrylates or polyacrylamides.

[0113] Demulsifiers include trialkyl phosphates, and various ethylene glycol polymers and copolymers, ethylene oxide, propylene oxide, or mixtures thereof.

[0114] Metal deactivators include derivatives of benzotriazoles (typically tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles. Metal deactivators can also be described as corrosion inhibitors.

[0115] Sealing swelling agents include sulphene derivatives Exxon necton-37 ™ (FN 1380) and Exxon Mineral Seal Oil ™ (FN 3200).

Industrial Application

[0116] The internal combustion engine can be a 4-stroke engine. The internal combustion engine may or may not have a recirculation of the exhaust gas system. The internal combustion engine can be equipped with an emission control system and a turbocharger. Examples of the emission control system include particulate filters (DPF), or systems that employ selective catalytic reduction (SCR).

[0117] The sulfur content of the lubricating composition may be 1% by weight or less, or 0.8% by weight or less, or 0.5% by weight or less, or 0.3% by weight or less. In one embodiment, the sulfur content can be in the range of 0.001% by weight to 0.5% by weight, or 0.01% by weight to 0.3% by weight. The phosphorus content can be 0.2% by weight or less, or 0.12% by weight or less, or 0.1% by weight or less, or 0.085% by weight or less, or 0.08% by weight. weight or less, or even 0.06% by weight or less, 0.055% by weight or less, or 0.05% by weight or less. In one embodiment, the phosphorus content can be from 0.04% by weight to 0.12% by weight. In one embodiment, the phosphorus content can be from 100 ppm to 1000 ppm, or 200 ppm to 600 ppm. The total sulfated ash content can be from 0.3% by weight to 1.2% by weight, or 0.5% by weight to 1.1% by weight of the lubricating composition. In one embodiment, the sulfated ash content can be from 0.5% by weight to 1.1% by weight of the lubricating composition.

[0118] In one embodiment the lubricant composition can be characterized as having at least one of (i) a sulfur content of 0.5% by weight or less, (ii) a phosphorus content of 0.12% by weight or less, and (iii) a sulfated ash content of 0.5% by weight to 1.1% by weight of the lubricating composition.

[0119] The lubricating composition can have an SAE viscosity degree of XW-Y, where X can be 0, 5, 10, or 15; and Y can be 20, 30, or 40.

[0120] The following examples provide illustrations of the invention. These examples are non-exhaustive and are not intended to limit the scope of the invention.

EXAMPLES

[0121] Example 1 (EX1): is the 0W-30 lubrication composition comprising at least 74% by weight of an API Group III / Group IV base oil mixture, molybdenum dithiocarbamate in an amount to provide about of 300 ppm molybdenum, 0.33% by weight in a dispersing viscosity modifier prepared by reaction of ethylene-propylene copolymer, with maleic anhydride and reacting with 3-nitroaniline and dimethylaminopropylamine (DMAPA). The lubricating composition also contains a succinimide polyisobutylene, 2.1% by weight of a mixture of aminic and phenolic antioxidants, 0.65% by weight of zinc dialguyldithiophosphate, 0.1% by weight of superbasified calcium sulfonate, 1% by weight of calcium phenate with excess base, and 0.6% by weight of a viscosity modifier. The lubricating composition has a sulfur content of less than 0.3% by weight, a phosphorus content of about 600 ppm, and a sulfated ash content of 0.55% by weight.

[0122] Example 2 (EX2): is a 0W-30 lubricant composition comprising at least 74% by weight of an API Group III / Group IV mixture of base oil, 0.3% by weight of a sulphured olefin, 0.33% by weight of a viscosity dispersant modifier prepared by reaction of ethylene-propylene copolymer, with maleic anhydride and reacting with 3-nitroaniline and dimethylaminopropylamine (DMAPA). The lubricating composition also contains a polyisobutylene succinimide, 2.1% by weight of a mixture of aminic and phenolic antioxidants, 0.65% by weight of zinc dialguyldithiophosphate, 0.1% by weight of superbasified calcium sulfonate, 1% by weight. weight of calcium with excess of phenate base, and 0.6% by weight of a viscosity modifier. The lubricating composition has a sulfur content of less than 0.3% by weight, a phosphorus content of about 600 ppm, and a sulfated ash content of 0.55% by weight.

[0123] Comparative Example 1 (EC1): it is similar to EX1 except that the lubricant does not contain a molybdenum dithiocarbamate, a dispersing viscosity modifier, or a sulfurized a-olefin. The lubricating composition has a sulfur content of less than 0.3% by weight, a phosphorus content of about 600 ppm, and a sulfated ash content of 0.55% by weight.

[0124] Comparative Example 2 (EC2): it is similar to EX1 except that it contains a molybdenum dithiocarbamate present in an amount sufficient to provide 500 ppm of molybdenum, and without dispersing viscosity modifier, or sulfurized olefin. The lubricating composition has a sulfur content of less than 0.3% by weight, a phosphorus content of about 600 ppm, and a sulfated ash content of 0.55% by weight.

[0125] Comparative Example 3 (CE3): it is similar to EX2 except that it contains 0.2% by weight of sulfuric olefin and does not contain a molybdenum dithiocarbamate, or a dispersing viscosity modifier. The lubricating composition has a sulfur content of less than 0.3% by weight, a phosphorus content of about 600 ppm, and a sulfated ash content of 0.55% by weight.

[0126] Comparative Example 4 (CE4): it is similar to EX1, except that it does not contain molybdenum dithiocarbamate. The lubricating composition has a sulfur content of less than 0.3% by weight, a phosphorus content of about 600 ppm, and a sulfated ash content of 0.55% by weight.

[0127] Examples of lubricants EX1, EX2, and CE1 to CE4 are evaluated by the DW10 engine test protocol performed by APL in 2011-2013. The results obtained for the tests are shown in the table below. Typically better results are obtained for samples with a rating of seven or more, and the test specifies a minimum pass rating of 7.

[0128] The results obtained from the DW10 clearance regulator test indicate that a lubricant composition defined by the present invention passes the test, and lubricant compositions outside the scope of the claimed invention fail the test.

[0129] It is known that some of the materials described above can interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. The products thus formed, including the products formed above employing the lubricating composition of the present invention in their intended use, may not be susceptible to easy description. However, all of these modifications and reaction products are included within the scope of the present invention; the present invention encompasses the lubricating composition prepared by mixing the components described above.

[0130] Each of the documents mentioned above is incorporated by reference. Except in the examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying quantities of materials, reaction conditions, molecular weight, number of carbon atoms, and the like, are to be understood as modified by the word "about ". Unless otherwise indicated, each chemical or composition referred to herein must be interpreted as being a commercial grade material that may contain isomers, by-products, derivatives, and other such materials that are normally understood to be present in the commercial type. However, the amount of each chemical component is shown exclusive of any solvent oil or diluent, which can usually be present in commercial material, unless otherwise indicated. It is to be understood that the quantity, range and upper and lower limits of the relationship established in this document can be combined independently. Likewise, the ranges and quantities for each element of the present invention can be used in conjunction with ranges of quantities or any of the other elements.

[0131] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its common sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and which has a predominantly hydrocarbon character. Examples of hydrocarbyl groups include: hydrocarbons, including aliphatic, alicyclic, aromatic substituents; substituted hydrocarbon substituents, i.e. groups containing non-hydrocarbon substituents which, in the context of this invention, do not alter the predominantly hydrocarbon character of the substituent; and heteroatom substituents, that is, the substituents, which similarly have a predominantly hydrocarbon character but contain different carbon in a ring or chain. A more detailed definition of the term "hydrocarbyl substituent" or "hydrocarbyl group" is described in paragraphs [0118] to [0119] of International Publication W02008147704, or a similar definition in paragraphs [0137] to [0141] of the published application US 2010- 0197536.

[0132] As used herein, the total number of basic detergent (TBN) can be measured according to ASTM D2896.

[0133] Although the invention has been explained in relation to its preferred modalities, it is to be understood that several modifications of the same will be evident to those skilled in the art after reading the specification. Consequently, it is to be understood that the invention disclosed herein is intended to cover such changes that fall within the scope of the appended claims.

Claims (17)

1. Method for lubricating a rotary end follower valve slack regulator of a passenger car compression ignition internal combustion engine having a reference mass not exceeding 2610 kg characterized by the fact that it comprises providing to the internal combustion engine a lubricating composition comprising a lubricating viscosity oil, from 0.01% by weight to 3% by weight of a dispersing viscosity modifier, and 0.01% by weight to 3% by weight of an agent anti-wear containing zinc-free sulfur, where the lubricant composition has a sulfur content of less than 5000 ppm, a phosphorus content of 1000 ppm or less, and a sulfated ash content of 3000 to 12,000 ppm. 2. Method according to claim 1, characterized by the fact that the lubricating composition has a sulfur content of 500 to 4000 ppm, or 1000 to 3000 ppm, a phosphorus content of 300 to 900 ppm, or 400 to 750 ppm, and a sulfated ash content of 3000 to 7000 ppm. Method according to either of claims 1 and 2, characterized in that the dispersant viscosity modifier is an ethylene-propylene copolymer still functionalized with a dispersing amine group. 4. Method according to claim 3, characterized in that the olefin copolymer has a numerical average molecular weight of 5000 to 100,000 or 7500 to 60,000 or 8000 to 45,000. Method according to either of claims 3 and 4, characterized in that the dispersing amine group is derived from the reaction of the olefin copolymer with an acylating agent and an aromatic amine having a primary or secondary amino group. Method according to any one of claims 1 to 5, characterized in that the dispersing viscosity modifier is present at 0.05% by weight to 1.5% by weight, or 0.1% by weight at 1% by weight, or 0.1 to 0.5% by weight. Method according to any one of claims 1 to 6, characterized in that the anti-wear agent containing zinc-free sulfur is selected from the group consisting of a sulfurized olefin, molybdenum dithiocarbamate, molybdenum dithiophosphate, an amine salt of a compound containing (uncle) phosphorus, a thiadiazole, and mixtures thereof. 8. Method according to claim 7, characterized in that the sulfurized olefin is an ester-containing sulfuric olefin. 9. Method according to claim 8, characterized by the fact that the sulfur olefin is a sulfur 4-carbobutoxy cyclohexene. Method according to any one of claims 1 to 9, characterized in that the anti-wear agent containing zinc-free sulfur is present at 0.01% by weight to 1.5% by weight, 0.05% by weight weight at 1% by weight, or 0.1% at 0.5% by weight. Method according to any one of claims 1 to 10, characterized in that the lubricating composition comprises anti-wear agent containing zinc-free sulfur comprising 0.01% by weight to 1.5% by weight of sulfuric olefin, and 0.05% by weight to 1.5% by weight, an olefin copolymer still functionalized with a dispersing amine group, wherein the olefin copolymer is an ethylene-propylene copolymer. Method according to any one of claims 1 to 11, characterized in that the lubricating composition comprises an anti-wear agent containing zinc-free sulfur comprising 0.1 to 0.5% by weight of sulfuric olefin, and 0, 1 to 0.5% by weight of an olefin copolymer still functionalized with a dispersing amine group, wherein the olefin copolymer is an ethylene-propylene copolymer. 13. Method according to any one of claims 1 to 12, characterized in that the lubricating composition further comprises an antioxidant, wherein the antioxidant comprises a phenolic antioxidant or an aminic or mixtures thereof, and in which the antioxidant is present to 0.1% by weight to 3% by weight, or 0.5% by weight to 2.75% by weight, or 1% by weight to 2.5% by weight. Method according to any one of claims 1 to 13, characterized in that the lubricating composition further comprises a detergent with an excess of calcium sulfonate base and a detergent with an excess of calcium phenate base in an amount of so the sulfur ash content is 1000 ppm or less. 15. Method according to claim 14, characterized by the fact that the detergent with excess calcium sulfonate base is present at 0.01 to 0.5% by weight, or 0.05 to 0.3% in weight of the lubricating composition. 16. Method according to any one of claims 1 to 15, characterized in that the clearance regulator comprises a ball and socket joint. 17. Method according to any one of claims 1 to 16, characterized in that the play regulator is a hydraulic play regulator.