CN107636133A

CN107636133A - The method of lubricating internal combustion engines

Info

Publication number: CN107636133A
Application number: CN201680026469.XA
Authority: CN
Inventors: A·梅修; R·I·威尔比
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2015-03-09
Filing date: 2016-03-07
Publication date: 2018-01-26
Also published as: US20210087493A1; US20220145204A1; SG11201707219VA; WO2016144880A1; BR112017019385A2; EP3268456A1; US20180044610A1

Abstract

Disclosed technology provides a kind of method for lubricating compression ignition engine of the maximum laden mass more than 2700kg, including supplies lubricating composition to engine, and lubricating composition includes：Oil with lubricant viscosity, with 10 to 40 metal than 300TBN or higher alkaline earth metal sulfonate detersive, alkaline earth metal sulfonate detersive with 3 to 9 metal than the TBN with 81 to 180mgKOH/g, wherein sulfonate detergent provides sulfonate matrix of the total amount for the 1 weight % to 3 weight % of lubricating composition, 0.1 to 1.2 weight % antioxidant, wherein at least 20 weight % antioxidant is phenol antioxidant, to supply boration compound existing for 25ppm to the amount of 300ppm boron, lubricating composition has 0.5 weight % to not more than 1.5 weight % sulfated ash content, lubricating composition has 6.5 to 15mgKOH/g TBN.

Description

Method for lubricating an internal combustion engine

Technical Field

The disclosed technology provides a method of lubricating a compression ignition internal combustion engine having a maximum loaded mass in excess of 2700kg, comprising supplying to the engine a lubricating composition comprising: an oil of lubricating viscosity, an alkaline earth metal sulphonate detergent of 300TBN or higher having a metal ratio of 10 to 40, an alkaline earth metal sulphonate detergent having a metal ratio of 3 to 9 and a TBN of 81 to 180mg KOH/g, wherein the sulphonate detergent provides a total of 1 to 3 wt% of the sulphonate base, 0.1 to 1.2 wt% of the antioxidant, wherein at least 20 wt% of the antioxidant is a phenolic antioxidant, the borated compound is present in an amount to provide 25ppm to 300ppm boron, the lubricating composition has a sulphated ash content of 0.5 wt% to no more than 1.5 wt%, and the TBN of the lubricating composition is 6.5 to 15mg KOH/g.

Background

Phenolic based detergents are known. These include phenolates based on phenolic monomers linked to a sulphur bridge or an alkylene bridge, such as a methylene linkage derived from formaldehyde. The phenolic monomers themselves are typically substituted with aliphatic hydrocarbon groups to provide a measure of oil solubility. The hydrocarbyl group may be an alkyl group, and historically dodecylphenol (or propylene tetramer-substituted phenol) has been widely used. Early mention of alkaline sulfurized polyvalent metal phenates is made in U.S. Pat. No. 2,680,96, Walker et al, 6 months and 1 day 1954; see also us 3,372,116, Meinhardt, 3.6.1968.

Alkyl phenol based detergents are known to provide deposit control, antioxidant and auxiliary wear reducing benefits. Recently, however, certain alkylphenols and products made therefrom have received increased attention due to their association with potentially endocrine disruptive materials. In particular, alkylphenol detergents based on C12 alkylphenol oligomers may contain residual monomeric C12 alkylphenols.

U.S. patent 7,943,796(Campbell et al, 2.2010, 4) discloses overbased salts of oligomeric alkylhydroxyaromatic compounds in which the alkyl group of the alkylhydroxyaromatic compound is derived from an olefin mixture comprising propylene oligomers having an initial boiling point of at least about 195 ℃ and a final boiling point of no more than about 325 ℃, as measured by ASTM D86. Also disclosed are lubricating oil compositions containing at least (a) a major amount of an oil of lubricating viscosity and (b) an overbased salt of an oligoalkylhydroxyaromatic compound.

U.S. Pat. No. 7,435,709(Stonebaker et al, 3.1.2007) discloses a lubricating oil composition exhibiting a reduced endocrine disrupting response comprising a major amount of an oil of lubricating viscosity, and a detergent comprising an unsulfided alkali or alkaline earth metal salt of the reaction product of (1) and (2), wherein (1) an olefin having at least 10 carbon atoms, wherein greater than 80 mole% of the olefin is a linear C20-C30n- α olefin, wherein less than 10 mole% of the olefin is a linear olefin having less than 20 carbon atoms, wherein less than 5 mole% of the olefin is a branched alkene having 18 or fewer carbon atoms, and (2) a hydroxyaromatic compound.

U.S. patent 8,183,192(Sinquinn et al, 8/4/2011) discloses overbased salts of oligomeric alkylhydroxyaromatic compounds for lubricating oil compositions, wherein the alkyl group of the alkylhydroxyaromatic compound is derived from an olefin mixture comprising propylene oligomers having an initial boiling point of at least about 195 ℃ and a final boiling point of greater than 325 ℃ up to about 400 ℃ as measured by ASTM D86. Also disclosed are propylene oligomers having an initial boiling point of at least about 195 ℃, and a final boiling point of greater than 325 ℃ to about 400 ℃, as measured by ASTM D86, wherein the propylene oligomers contain a carbon atom distribution comprising at least about 50 weight percent of C14 to C20 carbon atoms.

U.S. patent 8,207,380(Campbell et al, 10/30/2008) discloses an alkylated hydroxyaromatic compound prepared by reacting at least one hydroxyaromatic compound with a branched olefinic oligomer having from about 20 to about 80 carbon atoms in the presence of an acid catalyst. When the effects of pubertal development and thyroid function in intact adolescent female rats are quantified, the alkylated hydroxyaromatic compound is determined to be substantially free of endocrine disruptive chemicals.

U.S. patent 8,198,225(Harrison et al, 6.2009-4) discloses sulfurized metal alkyl phenate compositions having low alkylphenol content. The sulfurized metal alkyl phenate composition may be prepared by reacting a phenol compound of formula (I) disclosed herein with an aldehyde to form a phenolic resin of formula (II) disclosed herein, and then by simultaneously reacting the phenolic resin with a metal base and a first sulfurizing agent. The overbased sulfurized metal alkylphenate compositions and sulfurized metal alkylphenate compositions disclosed therein are useful as detergents in formulating lubricating oil compositions. The lubricating oil compositions disclosed therein have reduced amounts of free phenolic compounds and salts thereof.

U.S. patent application 2011/0124539(Sinquinn et al, 2011, 26/2011) discloses an overbased sulfide salt of at least one alkylated hydroxyaromatic compound, wherein an alkyl substituent of the hydroxyaromatic compound is a residue having at least one isomerized olefin having from about 15 to about 99 weight percent branching, the overbased sulfide salt of at least one alkylated hydroxyaromatic compound is prepared by a process comprising (a) alkylating at least one hydroxyaromatic compound with at least one isomerized olefin having from about 15 to about 99 weight percent branching obtained by isomerizing at least one n- α -olefin having from about 10 to about 40 carbon atoms, (b) neutralizing and sulfiding the alkylated hydroxyaromatic compound in any order to provide at least one neutralized, sulfided alkylated hydroxyaromatic compound, and (c) overbasing the at least one neutralized, sulfided alkylated hydroxyaromatic compound

International publication WO 2013/059173a1(Cook et al, 25.4.2013) discloses a bridged dimeric or oligomeric phenolic compound comprising: at least one monomeric unit (a) of phenol or an alkyl-substituted phenol wherein the alkyl group contains 1 to 8 carbon atoms, or mixtures thereof; at least one monomeric unit (b) of an aliphatic hydrocarbyl-substituted phenol, wherein the aliphatic hydrocarbyl group contains at least about 25 carbon atoms, or mixtures thereof; and at least one sulfur-or carbon-containing bridging group; or a salt of the oligomeric material; wherein the average number of carbon atoms in the alkyl group and the aliphatic hydrocarbon group is 10 to 100.

International application No. WO US15/010802 entitled "method of lubricating an internal combustion engine" (inventor Galic Raguz, Mary and Loop, John G), filed on 9.1.2015, discloses a method of lubricating a compression ignition engine having a maximum loading mass in excess of 2700kg, comprising supplying to the engine a lubricating composition comprising: an oil of lubricating viscosity, an alkaline earth metal sulphonate detergent of 300TBN or higher having a metal ratio of 10 to 40, 0.1 to 4 wt% of a borated polyisobutylene succinimide dispersant, wherein the number average molecular weight of the polyisobutylene from which the borated polyisobutylene succinimide is derived is 550 to 1150, and 0.1 to 6 wt% of a polyisobutylene succinimide, wherein the number average molecular weight of the polyisobutylene from which the polyisobutylene succinimide is derived is 1550 to 2500, 0 to 0.2 wt% of a phenolic detergent, wherein the total amount of soap supplied by the alkaline earth metal sulphonate (typically calcium sulphonate) is 0.4 to 1 wt% of the lubricating composition, wherein the sulphated ash content of the lubricating composition is not more than 1.5 wt%.

International application No. WO US15/010793 entitled "method of lubricating an internal combustion engine" (inventor Galic Raguz, Mary and Loop, John G), filed on 9.1.2015, discloses a method of lubricating a compression ignition engine having a maximum loading mass in excess of 2700kg, comprising supplying to the engine a lubricating composition comprising: an oil of lubricating viscosity, 1.5 to 10 wt% of an ashless dispersant, an alkaline earth metal sulphonate detergent of 300TBN or more having a metal ratio of 10 to 40, an alkaline earth metal sulphonate detergent of 80TBN or less having a metal ratio of 1 to 5, wherein the lubricating composition contains 0 to 0.2 wt% of a phenol-based detergent, the ratio of the higher alkaline earth metal sulphonate detergent to the lower alkaline earth metal sulphonate detergent is 80:20 to 20:80, the total amount of soap supplied by the calcium sulphonate detergent is 0.4 to 1.5 wt% of the lubricating composition, and the sulphated ash content of the lubricating composition is no more than 1.5 wt%.

Disclosure of Invention

Lubricating compositions useful in diesel engines that can operate under harsh conditions and loads while reducing the effects of soot and soot related wear, as well as cleanliness and deposits. For example, the lubricating composition may have at least one of improved deposit control, improved wear control (i.e., reduced wear), or copper or lead Pb corrosion control.

The disclosed technology allows an internal combustion engine (typically a compression ignition engine) to have at least one of reduced soot, reduced deposit formation, reduced wear, and improved cleanliness.

As used herein, unless otherwise specified, the amount of additive present in the lubricating compositions disclosed herein is referenced on an oil-free basis, i.e., the amount of active material.

As used herein, the transitional term "comprising" which is synonymous with "including," containing, "or" characterized by.. is inclusive or open-ended and does not exclude additional unrecited elements or method steps. However, in each recitation of "including" herein, it is intended that the term also includes, as alternative embodiments, the phrases "consisting essentially of" and "consisting of," wherein "consists of" excludes any elements or steps not specified, "consisting essentially of" allows for the inclusion of additional unrecited elements or steps that do not materially affect the basic and novel and essential characteristics of the contemplated composition or method.

As used herein, the expression "compression ignition internal combustion engine" is intended to include internal combustion engines that are at least partially compression ignited. Accordingly, the disclosed technology is directed to methods of lubricating compression ignition internal combustion engines as well as spark-assisted compression ignition internal combustion engines.

As used herein, the term "soap" refers to the surfactant portion of a detergent and does not include metal bases, such as calcium carbonate. The soap term may also refer to a detergent base. For example, the sulfonate detergent, soap or matrix described herein may be a neutral salt of alkyl benzene sulfonic acid.

As used herein, all cited total base numbers are determined by ASTM method D2896-11.

The disclosed technology provides a method of lubricating a compression ignition internal combustion engine having a maximum loaded mass in excess of 2700kg, comprising supplying to the engine a lubricating composition comprising:

an oil of lubricating viscosity, which oil has,

an alkaline earth metal sulfonate detergent of 300TBN or higher having a metal ratio of 10 to 40,

an alkaline earth metal sulphonate detergent having a metal ratio of from 3 to 9 and a TBN of from 81 to 180mgKOH/g (measured according to ASTM D2896-11),

wherein the sulphonate detergent provides a sulphonate base in a total amount of 0.8 wt% to 3 wt%, or 0.9 wt% to 3 wt%, or 1 wt% to 3 wt% of the lubricating composition,

0.1 to 1.2 wt.% of an antioxidant, wherein at least 20 wt.% of the antioxidant may be phenolic antioxidants,

a borated compound present in an amount to provide 25ppm to 300ppm boron, which may be selected from

The boration of the ester-forming agent,

a borated dispersant, and

wherein,

the lubricating composition has a sulfated ash content of 0.4 wt% to 2 wt%, or 0.5 wt% to 1.8 wt%, or 0.5 wt% to no greater than 1.5 wt%, and

the lubricating composition has a TBN of 6.5 to 15mg KOH/g (as measured by ASTM D2896-11).

In one embodiment, the disclosed technology relates to a method of lubricating a compression ignition internal combustion engine having a maximum loaded mass in excess of 2700kg, comprising supplying to the engine a lubricating composition comprising:

an oil of lubricating viscosity, which oil has,

a borated ester present in an amount to provide 75ppm to 200ppm or 75ppm to 150ppm boron,

wherein,

an oil of lubricating viscosity, which oil has,

a borated dispersant present in an amount to provide 125ppm to 250ppm boron,

wherein,

In one embodiment, the lubricating composition comprises from 0 wt% to 0.2 wt%, or from 0 wt% to 0.1 wt% of the phenolic based detergent.

In various embodiments, the lubricating composition comprises 0.01 wt% to 0.2 wt%, or 0.05 wt% to 0.1 wt% of the phenolic based detergent.

Typically, the lubricating composition comprises 0 wt% of a phenolic based detergent.

The phenolic based detergent may be a phenate.

The phenolic based detergent may be selected from phenates and salicylates.

The phenolic based detergent may be selected from phenates, salicylates and salixarates.

The phenate may be a non-sulphur containing phenate, a sulphur containing phenate or a "hybrid" detergent formed with a mixed surfactant system, wherein the hybrid detergent is a mixed phenate-salicylate, sulphonate-phenate or sulphonate-phenate-salicylate.

In one embodiment, the lubricating composition comprises 0 wt% of a phenolic based detergent. In this embodiment, the lubricating composition comprises a detergent package of only sulphonate detergent.

Typically, the sulphonate detergent may be calcium sulphonate or magnesium sulphonate. Typically, the sulfonate may be a calcium sulfonate detergent.

The total amount of substrate supplied by the calcium sulfonate detergent may be 1.00 to 1.6 wt.%, 1.05 to 1.2 wt.%, or 1.05 to 1.1 wt.% of the lubricating composition.

The 300TBN or higher alkaline earth metal sulfonate detergents disclosed herein may have a metal ratio of 10 to 40, or 15 to 30, or 20 to 30, or 22 to 25. The calcium sulfonate detergent may have a metal ratio of, for example, 10 to 40, a TBN of 350 to 500 or 375 to 425, and a metal ratio of 20 to 25. For example, the alkaline earth metal sulfonate detergent may have a TBN of 375 to 425, a metal ratio of 20 to 30 or 22 to 25.

The alkaline earth metal sulphonate detergent of 300TBN or higher may be a calcium or magnesium sulphonate detergent, typically a calcium sulphonate detergent.

The alkaline earth metal sulphonate detergent has a metal ratio of from 3 to 9, a TBN of from 81 to 130mg KOH/g or from 82 to 100mg KOH/g. The metal ratio may be 4 to 8, or greater than 5 to 8, and the TBN may be 85 to 95mg KOH/g.

The alkaline earth metal sulphonate detergent may have a metal ratio of from 3 to 9 and is a calcium or magnesium sulphonate detergent, typically a calcium sulphonate detergent.

In one embodiment, both the sulfonate detergent having a metal ratio of 3 to 9 and the sulfonate detergent having a metal ratio of 10 to 40 are calcium sulfonate detergents.

The compression ignition internal combustion engine may be a heavy duty diesel engine. The loading mass (sometimes referred to as the vehicle total weight rating (GVWR)) may exceed 2700kg (or 6,000 meibs) 2900 kg, or exceed 3,00 kg, or exceed 3300 kg, or exceed 3,500kg, or exceed 3,700 kg, or exceed 3,900 kg (or 8,500 meibs). Generally, the upper limit of the loading mass or GVWR may be determined by the national government and may be 10,000kg, i.e., 9,000kg, or 8,000kg, i.e., 7,500 kg. The upper limit of the loading mass may be up to 40 kilo-kilograms, or up to 20 kilo-kilograms, or up to 6 kilo-kilograms, or up to 44,000 kilo-kilograms, or up to 40,000 kilo-kilograms. Typically, a loading mass in excess of 12 thousand may be used for off-road vehicles.

Heavy duty diesel engines are limited to all motor vehicles with "maximum technically allowed loading mass" in excess of 3,500kg, equipped with compression ignition engines or forced ignition Natural Gas (NG) or LPG engines. In contrast, the european union indicates that the "maximum loading mass technically allowed" does not exceed 2610 kg for new light vehicles (passenger cars and light commercial vehicles) contained within the scope of the ACEA test section "C".

There is a clear distinction between passenger cars and heavy duty diesel engines. The size difference from over 3,500kg to no more than 2610 kg means that the two types of engines will experience significantly different operating conditions, such as load, oil temperature, duty cycle and engine speed. Heavy duty diesel engines are intended to maximize torque to transport payload at maximum fuel economy, while passenger car diesel engines are designed for commuters and acceleration at maximum fuel economy. The design goals of engine transport and commute have led to different hardware designs and different stresses imposed on lubricants designed to protect and lubricate the engine. Another unique design difference is the operating cycle per minute (RPM) of each engine running at transport vs. A heavy duty diesel engine such as a typical 12-13 liter truck engine will not normally exceed 2200rpm, while a passenger car engine can reach 4500 rpm.

In one embodiment, the internal combustion engine may be a heavy duty diesel compression ignition (or spark assisted compression ignition) internal combustion engine.

In one embodiment, the lubricating composition is characterized by having (i) a sulfur content of 0.5 wt.% or less, (ii) a phosphorus content of 0.1 wt.% or less, and (iii) a sulfated ash content of 0.5 wt.% to 1.5 wt.% or less.

In one embodiment, the lubricating composition can be characterized as having at least one of (i) a sulfur content of 0.2 wt.% to 0.4 wt.% or less, (ii) a phosphorus content of 0.08 wt.% to 0.15 wt.%, and (iii) a sulfated ash content of 0.5 wt.% to 1.5 wt.% or less.

In one embodiment, the lubricating composition may be characterized as having a sulfated ash content of 0.9 wt% to 1.4 wt%, or 1.05 wt% to 1.2 wt%.

In one embodiment, the lubricating composition comprises an antioxidant, wherein the phenolic antioxidant comprises at least 40 wt% of the antioxidant, or at least 50 wt% of the antioxidant, typically from 45 wt% to 90 wt%, or from 55 wt% to 80 wt% of the antioxidant.

In one embodiment, the lubricating composition contains an aminic antioxidant, typically a diarylamine or an alkylated diarylamine, and includes phenyl- α -naphthylamine (PANA), an alkylated diphenylamine or an alkylated phenylnaphthylamine, or mixtures thereof.

When present, the aminic antioxidant comprises up to 60 wt.% of the antioxidant, or up to 50 wt.% of the antioxidant, typically from 5 wt.% to 55 wt.%, or from 10 to 45 wt.% of the antioxidant.

In one embodiment, the lubricating composition comprises a sulfurized olefin, such as sulfurized 4-butoxycarbonylcyclohexene or sulfurized α -olefin (e.g., C10-24, C14-20, C16-18 α -olefin) or sulfurized diisobutylene, or mixtures thereof, when present, the sulfurized olefin antioxidant constitutes up to 60 wt.% of the antioxidant, or up to 50 wt.% of the antioxidant, typically from 5 wt.% to 55 wt.%, or from 10 to 45 wt.% of the antioxidant.

In one embodiment, the antioxidant comprises a phenolic or aminic antioxidant or mixtures thereof, and wherein the antioxidant may be present at 0.1 wt% to 3 wt%, or 0.5 wt% to 2.75 wt%, or 1 wt% to 2.5 wt%.

The lubricating composition disclosed herein may be characterized by a Total Base Number (TBN) content of 7 to 14, or 7.5 to 12mg KOH/g or 8 to 10mg KOH/g.

In another embodiment, the disclosed technology provides for the use of the lubricating composition disclosed herein to provide at least one of reduced soot, reduced deposit formation, reduced wear and improved cleanliness in a compression ignition internal combustion engine (typically a diesel internal combustion engine).

Detailed Description

The disclosed technology provides a method for lubricating an internal combustion engine and the use as described above.

Oil of lubricating viscosity

The lubricating composition comprises an oil of lubricating viscosity. These oils include natural and synthetic oils, oils derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, and rerefined oils, and mixtures thereof.

Unrefined oils are those obtained directly from a natural or synthetic source, usually without (or with a small amount of) further purification treatment.

Refined oils are similar to unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like.

Rerefined oils are also known as reclaimed or post-treated oils and are obtained by processes similar to those used to obtain refined oils and often are further processed by techniques for removing spent additives and oil breakdown products.

Natural oils useful in making the lubricants of the present invention include animal oils, vegetable oils (e.g., castor oil), mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.

Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers); poly (1-hexene), poly (1-octene), poly (1-decene), and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) -benzene); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof or mixtures thereof.

Other synthetic lubricating oils include polyol esters (e.g., polyol esters)3970) Diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphionic acid) or polymeric tetrahydrofurans. The synthetic oil may be prepared by a Fischer-Tropsch reactionAnd may typically be a hydroisomerized fischer-tropsch hydrocarbon or wax. In one embodiment, the oil may be prepared by a Fischer-Tropsch gas-liquid synthesis process, as well as other gas-liquid oils.

Oils of lubricating viscosity may also be defined as set forth in the American Petroleum Institute (API) basic oil interchange guidelines.five base oil groups are set forth as group I (sulfur content >0.03 wt%, and/or <90 wt% saturates, viscosity index 80-120), group II (sulfur content ≦ 0.03 wt%, > 90 wt% saturates, viscosity index 80-120), group III (sulfur content ≦ 0.03 wt%, > 90 wt% saturates, viscosity index ≧ 120), group IV (all poly α olefins (PAOs)), and group V (all others not included in groups I, II, III or IV).

The oil of lubricating viscosity may also be an API group II plus base oil, which term refers to a group II base oil having a viscosity index of greater than or equal to 110 and less than 120, as described in SAE publication "Design Practice: Passenger Car Automatic Transmission", fourth edition, AE-29, 2012, pages 12-9 and column 1, line 57 of US8,216,448.

The oil of lubricating viscosity may also be an API group III base oil, which term refers to a group III base oil having a viscosity index greater than or equal to 130. Group III + is known in the art and is described in "Lubereport", 26.2.2014, an article entitled "SK Sees GroupIII Shortfall" published by Nancy DeMarco. This article is available from http:// www.aselube.com/media/11910/sk _ ses _ group _ iii _ shortfall.

The oil of lubricating viscosity may be an API group IV oil or mixtures thereof, i.e., a poly α olefin, a poly α olefin may be prepared by a metallocene-catalyzed process or a non-metallocene process.

Oils of lubricating viscosity include API group I, group II, group III, group IV, group V oils or mixtures thereof.

The oil of lubricating viscosity may comprise an API group I, group II, group III, group IV oil or mixtures thereof.

The oil of lubricating viscosity may comprise an API group I, group II, group III oil or mixtures thereof.

The oil of lubricating viscosity may comprise an API group I, group II oil or mixtures thereof.

The oil of lubricating viscosity may comprise an API group I oil.

The oil of lubricating viscosity may comprise an API group II oil.

The amount of oil of lubricating viscosity present may generally be the balance remaining after subtracting the sum of the amounts of the above additives and other performance additives from 100 wt.%.

The lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the disclosed technology is in the form of a concentrate (which may be combined with additional oil to form a whole or partial finished lubricant), the ratio of the components of the disclosed technology to the oil of lubricating viscosity and/or to the diluent oil comprises from 1:99 to 99:1 by weight, or from 80:20 to 10:90 by weight.

In one embodiment, the lubricating composition is not an aqueous composition.

The kinematic viscosity of the lubricating composition at 100 ℃ may be from 2cSt to 20cSt (or mm), measured according to ASTM D445-14²In s). At ambient temperature (5-30 ℃). The lubricating composition may be liquid, i.e. not a gel or semi-solid.

Antioxidant agent

The lubricating composition comprises an antioxidant as described herein. Typically, the antioxidant comprises a phenolic or aminic antioxidant or a mixture thereof. The antioxidant comprises a diarylamine, an alkylated diarylamine, a hindered phenol, or a mixture thereof.

The diarylamine or alkylated diarylamine may be phenyl- α -naphthylamine (PANA), alkylated diphenylamine or alkylated phenylnaphthylamine, or mixtures thereof.

Hindered phenol antioxidants typically contain a secondary and/or tertiary butyl group as a sterically hindering group. The phenolic group may be further substituted with a hydrocarbyl group (typically a linear or branched alkyl group) and/or a bridging group attached to a second aromatic group. Examples of suitable hindered phenol 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-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and may include, for example, Irganox from Ciba^TML-135. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistries is found in U.S. patent 6,559,105.

In one embodiment, the antioxidant comprises a mixture of sulfurized olefin, phenolic, and aminic antioxidants.

For example, the antioxidant mixture may be:

the phenolic antioxidant comprises at least 40 wt%, or at least 50 wt%, of the antioxidant, typically from 45 wt% to 90 wt%, or from 55 wt% to 80 wt%, of the antioxidant;

the aminic antioxidant comprises up to 60 wt.%, or up to 50 wt.%, of the antioxidant, typically from 5 wt.% to 55 wt.%, or from 10 to 45 wt.%, of the antioxidant; and

the sulfurized olefin antioxidant comprises up to 60 wt%, or up to 50 wt%, of the antioxidant, typically from 5 wt% to 55 wt%, or from 10 to 45 wt%, of the antioxidant.

Alternatively, the antioxidant mixture may be:

the phenolic antioxidant comprises at least 40 wt.% of the antioxidant, or at least 50 wt.% of the antioxidant, typically from 45 wt.% to 90 wt.%, or from 55 wt.% to 80 wt.% of the antioxidant;

the aminic antioxidant comprises up to 60 wt.% of the antioxidant, or up to 50 wt.% of the antioxidant, typically from 5 wt.% to 55 wt.%, or from 10 to 45 wt.% of the antioxidant and

the sulfurized olefin antioxidant comprises up to 60 wt.% of the antioxidant, or up to 50 wt.% of the antioxidant, typically from 5 wt.% to 55 wt.%, or from 10 to 45 wt.% of the antioxidant.

Sulfonate detergent

As defined herein, the sulfonate detergents of the disclosed technology may be overbased for detergents having a TBN of at least 300, and neutral to slightly overbased for TBN of 81 to 130 mgKOH/g.

Overbased materials, also known as overbased or superbased salts, are generally single phase, homogeneous newtonian systems characterized by a metal content that is present based on the stoichiometric neutralization of the metal and the particular acidic organic compound reacted with the metal. Overbased materials are prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, preferably carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert organic solvent for the acidic organic material (mineral oil, naphtha, toluene, xylene, etc.), a stoichiometric excess of a metal base, and a promoter such as calcium chloride, acetic acid, phenol, or an alcohol. The acidic organic material typically has a sufficient number of carbon atoms to provide solubility in oil. The amount of "excess" metal (stoichiometry) is usually expressed as a metal ratio. The term "metal ratio" is the ratio of the total equivalents of metal to the equivalents of acidic organic compound. The metal ratio of the neutral metal salt is 1. A salt having 3.5 times the metal present in the normal salt has a metal excess of 3.5 equivalents or a ratio of 4.5.

"soap content", metal ratio and TBN are known to the person skilled in the art and are explained in the standard textbook entitled "Chemistry and technology of Lubricants", third edition, edited by RM Mortier and ST Orszulik, copyright 2010, pages 219 to 220, subheading 7.2.5.Detergent Classification.

The lubricating compositions disclosed herein typically comprise at least one calcium sulfonate detergent as described herein.

In various embodiments, the lubricating composition comprises at least one or at least two other sulfonate detergents. Sulfonate detergents of the disclosed technology are known to those skilled in the art.

In another embodiment, the lubricating composition further comprises another sulphonate detergent, typically a magnesium, sodium or zinc overbased sulphonate. Typically, any additional sulphonate detergent may be a magnesium or sodium sulphonate detergent, with magnesium sulphonate being more typical.

In one embodiment, the lubricating composition comprises an alkaline earth metal sulphonate detergent of 300TBN or higher having a metal ratio of 10 to 40 and an alkaline earth metal sulphonate detergent of 82 to 100TBN or lower having a metal ratio of 3 to 9.

In one embodiment, the lubricating composition comprises an alkaline earth metal sulphonate detergent of 300TBN or more, comprising a magnesium sulphonate detergent having a metal ratio of 10 to 40, and an alkaline earth metal sulphonate detergent of 80TBN or less, comprising a calcium sulphonate detergent having a metal ratio of 1 to 5.

In one embodiment, the lubricating composition comprises an alkaline earth metal sulphonate detergent of 300TBN or more, a mixture comprising a calcium sulphonate detergent having a metal ratio of 10 to 40 and a magnesium sulphonate detergent having a metal ratio of 10 to 40, and an alkaline earth metal sulphonate detergent of 80TBN or less, comprising a calcium sulphonate detergent having a metal ratio of 1 to 5.

Alkaline earth metal sulphonate detergents of 300TBN or higher and alkaline earth metal sulphonate detergents of 80TBN or lower may be prepared from the same or different hydrocarbyl-substituted sulphonic acids. Typically the hydrocarbyl-substituted sulphonic acid is an alkyl-substituted sulphonic acid.

The sulfonate salts may be prepared from mono-or di-hydrocarbyl substituted benzene (or toluene, naphthalene, indenyl, indanyl or dicyclopentadienyl) sulfonic acids, wherein the hydrocarbyl group may contain from 6 to 40 or from 8 to 35 or from 9 to 30 carbon atoms.

The hydrocarbyl group may be derived from polypropylene or a linear or branched alkyl group containing at least 10 carbon atoms. Examples of suitable alkyl groups include branched and/or linear decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl or mixtures thereof.

In one embodiment, the hydrocarbyl-substituted sulfonic acid may include polypropene benzene sulfonic acid and C₁₆-C₂₄Alkyl benzene sulfonic acid, or mixtures thereof.

In one embodiment, the 300TBN sulfonate detergent may be a predominantly linear alkylbenzene sulfonate detergent having a metal ratio of from 10 to 40, as described in paragraphs [0026] to [0037] of U.S. patent application 2005065045 (issued as US7,407,919). The predominantly linear alkylbenzene sulfonate detergent may be particularly helpful in improving fuel economy.

Typically, the metal ratio of the 300TBN or higher alkaline earth metal sulfonate detergent is from 12 to 30, or from 12 to 22, or from 16 to 20, or from 10 to 20, or from 20 to 30, or from 22 to 25mg KOH/G. In one embodiment, the 300TBN metal ratio may be from 16 to 20, and in another embodiment from 22 to 25.

In one embodiment, the lubricating composition comprises a calcium sulphonate detergent having a metal ratio of 10 to 40 and a calcium sulphonate detergent having a metal ratio of 3 to 9.

In one embodiment, the lubricating composition comprises a calcium sulphonate detergent having a metal ratio of 10 to 40, a calcium sulphonate detergent having a metal ratio of 3 to 9 and a magnesium sulphonate detergent having a metal ratio of 12 to 40.

The TBN of the magnesium sulfonate detergent can be 300-500 or 350-425mg KOH/g; the metal ratio is 12 to 40 or 14 to 25. The magnesium sulfonates may have the same or different hydrocarbyl-substituted sulfonic acids and are as defined above for the calcium sulfonate detergents.

Other sulfonate (typically magnesium sulfonate) detergents, if present, may be present in an amount of 0.01 wt% to 0.5 wt% or 0.2 wt% to 0.3 wt%. Typically, the lubricating composition consists of only two (or three) detergents, i.e. two calcium sulfonate detergents, and optionally a magnesium sulfonate detergent, which may or may not be present in different embodiments.

Borated compounds

The borated compound may be present in an amount to supply 25ppm to 300ppm boron, and the borated compound may be selected from a borate ester, a borated dispersant, or a mixture thereof.

In one embodiment, the boron-containing compound may be a borate ester represented by the formula:

wherein each R may independently be an organic group, and any two adjacent R groups may together form a cyclic group, or

Wherein the boron-containing compound may be a borate ester represented by the formula:

wherein: r, R¹，R²，R³And R⁴Independently a hydrocarbyl group having 1 to 12 carbon atoms; and R is⁵And R⁶Independently an alkylene group having 1 to 6 carbon atoms, in one embodiment 2 to 4 carbon atoms, wherein each R may independently be an organic group, and any two adjacent R groups may together form a cyclic group.

wherein R is¹，R²，R³，R⁴，R⁵，R⁶，R⁷And R⁸Independently hydrogen or a hydrocarbyl group. Typically, each hydrocarbyl group may contain 1 to 12 or 1 to 4 carbon atoms.

In one embodiment, the borate ester comprises at least one alkyl group having from 10 to about 32 carbon atoms, the alkyl group having a branch at the β or higher, the borate ester being present in an amount to provide from 1 to 1000ppm by weight boron to the lubricant composition.

The alkyl group may be branched at position β the alkyl group may have a general formula represented by-CH₂-CH(R¹)(R²) Structure of (a) wherein R¹May be an alkyl group having 7 to 18 carbon atoms, R²May be of a ratio R¹Alkyl groups of fewer carbon atoms.

In one embodiment, the alkyl group has a structure represented by CH₂CH(R¹)(R²) Structure of (a) wherein R¹May be an alkyl group having 7 to 18 carbon atoms, R²May be of a ratio R¹Alkyl with two fewer carbon atoms.

The alkyl group may be derived from a Guerbet (Guerbet) alcohol. The alkyl group may be 2-propylheptyl, 2-butyloctyl, 2-hexyldecyl or 2-octyldodecyl.

In one embodiment, the boronic ester may be represented by one or more of the following formulae:

(RO)₃B，

(RO)₂B-O-B(OR)₂，

or

Wherein each R may independently be an alkyl group having 10 to 32 carbon atoms and has a branching at β or higher.

The borate ester may comprise a trialkyl borate. The borate ester may be a material represented by the following structure:

the borate ester may be present at 75ppm to 120ppm or 80ppm to 110ppm of the lubricating composition.

In one embodiment, the borated compound may be a borated dispersant. Typically, the borated dispersant may be a borated succinimide. A borated succinimide, or mixtures thereof.

Borated succinimides may be known to those skilled in the art and may be prepared by reacting a borating agent, such as boric acid, with a polyisobutylene succinimide. Typically, the polyisobutylene from which the polyisobutylene succinimide is derived has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500.

The borated polyisobutylene succinimide may have a carbonyl to nitrogen ratio of 1:1 to 1:5, or 1:1 to 1:4, or 1:1.3 to 3: or 1:1.5 to 1:2, or 1:1.4 to 1: 0.6.

The borated dispersant may be present at 125ppm to 250ppm or 150ppm to 200ppm of the lubricating composition.

Non-borated dispersants

The lubricating composition may also contain a non-borated dispersant.

When present, the non-borated dispersant may be present at 1 wt% to 8 wt%, or 2.5 wt% to 7 wt%, or 3 wt% to 6 wt% of the lubricating composition.

The non-borated dispersant may typically be a succinimide dispersant.

The non-borated succinimide dispersant may be derived from a polyisobutylene succinimide, wherein the polyisobutylene from which the polyisobutylene succinimide is derived has a number average molecular weight of 350 to 5000, or 750 to 3000 or 1550 to 2500.

The non-borated dispersants of polyisobutylene succinimide may be derived from aliphatic polyamines or mixtures thereof.

The aliphatic polyamine can be an aliphatic polyamine, such as an ethylene polyamine, a propylene polyamine, a butylene polyamine, or mixtures thereof. In one embodiment, the aliphatic polyamine may be an ethylene polyamine. In one embodiment, the aliphatic polyamine may be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine bottoms, and mixtures thereof.

Non-borated polyisobutylene succinimide dispersants and their preparation are disclosed in, for example, U.S. Pat. nos. 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433 and 6,165,235, 7,238,650 and EP patent application 0355895A.

In one embodiment, the non-borated polyisobutylene succinimide may be present at 2.5 wt% to 6 wt% or 3 wt% to 5 wt% of the lubricating composition.

The non-borated polyisobutylene succinimide may have a carbonyl to nitrogen ratio of 1:1 to 1:5, or 1:1 to 1:4, or 1:1.3 to 3: or 1:1.5 to 1:2, or 1:1.4 to 1: 0.6.

In one embodiment, the non-borated dispersant may include an amine-functionalized additive, which may be derived from an amine having at least 3 or 4 aromatic groups.

As used herein, the term "aromatic radical" is used in the general sense of the term and is known to be defined by H ü ckel theory as having 4n +2 pi electrons per ring system accordingly, one aromatic radical may have 6 or 10 or 14 pi electrons accordingly, a benzene ring has 6 pi electrons, a naphthylene ring has 10 pi electrons, an acridine group has 14 pi electrons an example of an amine having at least 3 or 4 aromatic radicals may be represented by formula (1):

wherein each of the variables is independently selected from the group consisting of,

R¹may be hydrogen or C_1-5Alkyl (typically hydrogen);

R²may be hydrogen or C_1-5Alkyl (typically hydrogen);

u may be an aliphatic, cycloaliphatic or aromatic group, provided that when U may be an aliphatic group, the aliphatic group may be a linear or branched alkylene group containing 1 to 5 or 1 to 2 carbon atoms; and w may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).

Examples of amines having at least 3 or 4 aromatic groups may be represented by formula (1 a):

R¹may be hydrogen or C_1-5Alkyl (typically hydrogen);

R²may be hydrogen or C_1-5Alkyl (typically hydrogen);

Alternatively, the compound of formula (1a) may also be represented by the following formula:

wherein each variable U, R¹And R²As above, w may be 0 to 9 or 0 to 3 or 0 to 1 (typically 0).

Examples of the amine having at least 3 or 4 aromatic groups may be represented by any of the following formulae (2) and/or (3):

in one embodiment, the amine having at least 3 or 4 aromatic groups may comprise a mixture of compounds represented by the above formula. It will be appreciated by those skilled in the art that compounds of formulae (2) and (3) may also be reacted with the aldehydes described below to form acridine derivatives. Acridine derivatives that can be formed include compounds represented by the following formulas (2a) or (3a) to (3 c). In addition to these compounds representing these formulas, one skilled in the art will also appreciate that other acridine structures may be possible in which aldehydes are reacted with other benzyl groups bridged with > NH groups. Examples of the acridine structure include those represented by the formula (2a), (3a) or (3b) or (3 c):

any or all of the N-bridged aromatic rings can be further condensed and possibly aromatized. Another of many possible structures includes formula (3 b):

further condensation reactions may also occur with any of the above formulas (2), (2a) (3) or (3a) to (3c) resulting in the formation of one or more acridine moieties per molecule.

Examples of amines having at least 3 or 4 aromatic groups may be bis [ p- (p-aminoanilino) phenyl ] -methane, 2- (7-amino-acridin-2-ylmethyl) -N-4- {4- [4- (4-amino-phenylamino) -benzyl ] -phenyl } -benzene-1, 4-diamine, N-4- {4- [4- (4-amino-phenylamino) -benzyl ] -phenyl } -2- [4- (4-amino-phenylamino) -cyclohexa-1, 5-dienylmethyl ] -benzene-1, 4-diamine, N- [4- (7-amino-acridin-2-ylmethyl) -phenyl ] -benzene-1, 4-diamine or mixtures thereof.

In one embodiment, the amine having at least 3 or 4 aromatic groups can be bis [ p- (p-aminophenyl) phenyl ] methane, 2- (7-amino-acridin-2-ylmethyl) -N-4- {4- [4- (4-amino-phenylamino) -benzyl ] -phenyl } -benzene-1, 4-diamine, or a mixture thereof.

Amines having at least 3 or 4 aromatic groups can be prepared by a process comprising reacting an aldehyde with an amine, typically 4 aminodiphenylamine. The resulting amines can be described as having at least 3 or 4 aromatic groups, at least one-NH₂An alkylene-coupled amine having a functional group and at least 2 secondary or tertiary amino groups.

The aldehyde may be aliphatic, alicyclic or aromatic. The aliphatic aldehydes may be linear or branched. Examples of suitable aromatic aldehydes include benzaldehyde or o-vanillin. Examples of aliphatic aldehydes include formaldehyde (or reactive equivalents thereof such as formalin or paraformaldehyde), acetaldehyde or propionaldehyde. Typically, the aldehyde may be formaldehyde or benzaldehyde.

Alternatively, amines having at least 3 or 4 aromatic groups can also be prepared by the process described in Berichte der Deutschen Chemischen Gesellschaft (1910), 43,728-39.

In one embodiment, the amine having at least 3 or 4 aromatic groups may be obtained/obtainable by a process comprising reacting isatoic anhydride or an alkyl-substituted isatoic anhydride with an aromatic amine having at least two aromatic groups and a reactive primary or secondary amino group. The resulting material can be described as an anthranilic acid derivative.

In one embodiment, the anthranilic acid derivative may be prepared in a reaction containing isatoic anhydride or an alkyl-substituted isatoic anhydride and an aromatic amine selected from the group consisting of xylylenediamine, 4-aminodiphenylamine, 1, 4-dimethylphenylenediamine, and mixtures thereof. In one embodiment, the aromatic amine may be 4 aminodiphenylamine.

The above-mentioned method for preparing the ortho-amino derivative may be carried out at a reaction temperature of 20 ℃ to 180 ℃ or 40 ℃ to 110 ℃. The process may or may not be carried out in the presence of a solvent. Examples of suitable solvents include water, diluent oil, benzene, tert-butyl benzene, toluene, xylene, chlorobenzene, hexane, tetrahydrofuran or mixtures thereof. The reaction may be carried out in air or an inert atmosphere. Examples of suitable inert atmospheres include nitrogen or argon, typically nitrogen.

Carboxylic acid functionalized polymers

The amine functional additive may be the reaction product of an amine having at least 3 or 4 aromatic groups with a carboxyl functional polymer. The resulting product obtained can be described as an amine-functionalized carboxy-functional polymer.

The carboxylic acid functional polymer backbone can be a homopolymer or a copolymer, provided that it contains at least one carboxylic acid function or reactive equivalent of a carboxylic acid function (e.g., anhydride or ester). The carboxylic acid functional polymer may have carboxylic acid functions (or reactive equivalents of carboxylic acid functions) grafted to the backbone, either within the polymer backbone or as end groups on the polymer backbone.

The carboxylic acid functionalized polymer may be polyisobutylene-succinic anhydride, maleic anhydride-styrene copolymer, esters of maleic anhydride-styrene copolymer, α -olefin-maleic anhydride copolymer, or (i) styrene-ethylene- α -olefin polymer, (ii) hydrogenated alkenyl aryl conjugated diene copolymer (i.e., hydrogenated alkenyl arene conjugated diene copolymer, particularly hydrogenated copolymer of styrene-butadiene), (iii) polyolefin grafted with maleic anhydride (particularly ethylene-propylene copolymer), or (iv) maleic anhydride grafted copolymer of isoprene polymer (particularly non-hydrogenated isobutylene-isoprene copolymer or hydrogenated styrene-isoprene polymer), or mixtures thereof.

The carboxylic acid functionalized polymers described herein are known in the lubricant art. For example:

(i) esters of maleic anhydride and styrene-containing polymers are known from us patent 6,544,935;

(ii) grafted styrene-ethylene- α -olefin polymers are taught in International publication WO 01/30947;

(iii) copolymers derived from isobutylene and isoprene have been used to prepare dispersants and are reported in international publication WO 01/98387;

(iv) grafted styrene-butadiene and styrene-isoprene copolymers are described in a number of references, including DE 3,106,959; and U.S. Pat. nos. 5,512,192 and 5,429,758;

(v) polyisobutylene succinic anhydrides have been described in a number of publications, including U.S. Pat. nos. 4,234,435; 3,172,892; 3,215,707, respectively; 3,361,673, respectively; and 3,401,118;

(vi) grafted ethylene-propylene copolymers are described in U.S. patent 4,632,769; 4517104, respectively; and 4,780,228;

(vii) esters of (α -olefin maleic anhydride) copolymers have been described in U.S. Pat. No. 5,670,462;

(viii) copolymers of isobutylene and conjugated dienes (e.g., isobutylene-isoprene copolymers) have been described in U.S. patents 7,067,594 and 7,067,594 and U.S. patent application US 2007/0293409; and

terpolymers of ethylene, propylene and a non-conjugated diene such as dicyclopentadiene or butadiene and are described in U.S. Pat. Nos. 5,798,420 and 5,538,651.

In general, the diene-containing polymers mentioned in (iii), (iv) and (viii), for example butadiene or isoprene, are partially or fully hydrogenated.

Many polymer backbones are also described in "Chemistry and Technology of Lubricants, second edition, edition by R.M.Mortier and S.T.Orszulik Published by Black Academic & Professional. In particular, pages 144-180 discuss a number of polymer backbones (i) - (iv) and (vi) - (viii).

The polymeric backbone (other than polyisobutylene) of the disclosed technology can have a number average molecular weight (by gel permeation chromatography, polystyrene standards) that can be as high as 150,000 or higher, e.g., 1,000 or 5,000 to 150,000 or to 120,000 or 100,000. Examples of suitable number average molecular weight ranges include 10,000 to 50,000, or 6,000 to 15,000, or 30,000 to 50,000. In one embodiment, the number average molecular weight of the polymeric backbone is greater than 5,000, such as greater than 5000 to 150,000. Other combinations of the above molecular weight limits are also contemplated.

When the polymer backbone is polyisobutylene, its number average molecular weight (by gel permeation chromatography, polystyrene standards) may be 350 to 5000, or 550 to 3000 or 750 to 2500. (thus, the polyisobutylene succinic anhydride may be derived from polyisobutylene having any of the aforementioned molecular weights.) the number average molecular weight of commercially available polyisobutylene polymers is 550, 750, 950 and 1000, 1550, 2000 or 2250 some commercially available polyisobutylene polymers may obtain the number average molecular weights shown above by mixing one or more polyisobutylene polymers having different weights.

In one embodiment, the carboxylic acid functionalized polymer may be prepared by reacting a carboxylic acid functionalized polymer with a polymer having at least 3 or 4 aromatic groups, at least one NH₂A functional group and an amine functional additive having at least 2 secondary or tertiary amino groups.

Amine functional additives having at least 3 or 4 aromatic groups can be reacted with the carboxylic acid functional polymer under known reaction conditions. Reaction conditions are known to those skilled in the art for forming imides and/or amides of carboxylic acid functionalized polymers.

By reacting a carboxylic acid-functionalized polymer with a polymer having at least 3 or 4 aromatic groups, at least one NH₂The amine functional carboxylic acid functional polymer obtained/obtainable by reacting a functional group and an amine of at least 2 secondary or tertiary amino groups may in certain embodiments be represented by formula (4) and/or (5):

R¹，R²and U is as previously described;

BB may be a polymer backbone, and may be polyisobutylene, or (i) a hydrogenated alkenyl aryl conjugated diene copolymer (particularly a hydrogenated copolymer of styrene-butadiene), (ii) a polyolefin (particularly an ethylene- α -olefin such as an ethylene-propylene copolymer), (iii) a hydrogenated isoprene polymer (particularly a hydrogenated styrene-isoprene polymer), or (iv) a copolymer of isoprene and isobutylene BB may be substituted with one succinimide group as shown in formulas (4) and (5), or it may be substituted with a plurality of succinimide groups.

In addition to formulas (4) and (5), additional structures may be formed, including terpolymers, tetramers, higher order polymers, or mixtures thereof. The amino groups shown in the formulae (4) and (5) may also be substituted in whole or in part by amines of the formulae (2a), (3), (3a) or mixtures thereof.

When BB can be polyisobutylene, the resulting carboxylic acid functionalized polymer can typically be polyisobutylene succinic anhydride. Typically, w may be 1 to 5 or 1 to 3 as defined for formula (1).

When BB may not be polyisobutylene and have maleic anhydride (or other carboxylic acid functional groups) grafted thereon, the grafted maleic anhydride group or groups may be the succinimide of an amine when reacted with an amine. The number of succinimide groups may be 1 to 40, or 2 to 40, or 3 to 20.

The amine-functionalized carboxylic acid-functionalized polymer may be prepared by reacting a carboxylic acid-functionalized polymer derived from a maleic anhydride-styrene copolymer, an ester of a maleic anhydride-styrene copolymer, an α -olefin maleic anhydride copolymer, or a mixture thereof, with a carboxylic acid-functionalized polymer having at least 3 or 4 aromatic groups, at least one NH₂Functional groups and at least 2 secondary or tertiary amino groups. Generally, this type of product can be described as an alternating copolymer. In the alternating copolymer, one or more of the maleic anhydride derived groups may have a group represented by formula (6):

wherein R is¹，R²And U As previously described, the group of formula (6) may be bonded to a component of the polymer backbone through one or two wavy bonds as shown on the above maleic acid ring structure. When only one wavy bond is bonded to the polymer, the second wavy bond may be hydrogen.

The amine-containing groups of formula (6) may also be replaced by amines of formula (3) or mixtures thereof.

In one embodiment, the amine-functionalized carboxylic acid-functionalized polymer may be derived from a polyisobutylene polymer backbone (represented by PIB in formula 7 below). A more detailed description of the polyisobutylene polymer backbone is described in the foregoing description.

Examples of suitable structures of anthranilic acid derivatives derived from polyisobutylene, anthranilic acid derivatives, and 4-aminodiphenylamine may be represented by formula (7):

in one embodiment, the amine-functionalized carboxylic acid-functionalized polymer may be derived from one of the aromatic amines and a non-polyisobutylene polymer backbone. An example of a suitable structure of an anthranilic acid derivative derived from 4-aminodiphenylamine can be represented by formula (8):

wherein BB may be a polymer (typically BB may be an ethylene-propylene copolymer derived from an ethylene-propylene copolymer). As shown, BB is grafted with maleic anhydride and functionalized to form an imide group, u may be the number of graft units within [ ], typically u may be 1 to 2000, or 1 to 500 or 1 to 250, or 1 to 50, 1 to 20, 1 to 10, or 1 to 4.

A more detailed description of amine-functionalized carboxylic acid-functionalized polymers is described in International application PCT/US2008/082944 (based on U.S. provisional application 60/987499), see in particular preparation examples 1 to 25 disclosed in [0013] to [0021], [0027] to [0091] and [0111] to [0135 ]. The present disclosure provides an in depth discussion of possible structures and methods for preparing amine functionalized carboxylic acid functionalized polymers.

Generally, the amine-functionalized additive may be based on polyisobutylene defined by BB in formula (4) or formula (5) above.

In one embodiment, the non-borated dispersant containing an amine having at least 3 or 4 aromatic groups may be represented by formula (1) reacted with a polyisobutylene anhydride.

When present, the non-borated dispersant may be present at 0.25 wt% to 8 wt%, or 0.5 wt% to 5 wt%, 1 wt% to 4.5 wt%, or 1.6 wt% to 2.5 wt% of the lubricating composition.

Dispersant viscosity modifiers

The lubricating composition of the disclosed technology in one embodiment further comprises a dispersant viscosity modifier. When present, the dispersant viscosity modifier may be present at 0.01 wt% to 3 wt%, or 0.05 wt% to 1.5 wt%, or 0.1 wt% to 1 wt%, or 0.1 to 0.5 wt%. In one embodiment, the lubricating composition disclosed herein further comprises a dispersant viscosity modifier

Dispersant viscosity modifiers may include functionalized polyolefins such as ethylene-propylene copolymers that have been functionalized with acylating agents such as maleic anhydride and amines; polymethacrylates functionalized with amines, or styrene-maleic anhydride copolymers reacted with amines. More detailed descriptions of dispersant viscosity modifiers are disclosed in International publication WO2006/015130 or U.S. Pat. Nos. 4,863,623; 6,107,257; 6,107,258; 6,117,825, respectively; and US7,790,661. In one embodiment, the dispersant viscosity modifier may include those disclosed in U.S. Pat. No. 4,863,623 (see column 2, line 15 to column 3, line 52) or International publication WO2006/015130 (see page 2, paragraph [0008] and preparation examples described in paragraphs [0065] to [0073 ]).

In one embodiment, the dispersant viscosity modifier comprises an olefin copolymer further functionalized with a dispersant amine group. Typically, the olefin copolymer may be an ethylene-propylene copolymer.

The olefin copolymer has a number average molecular weight of 5000 to 100,000, or 7500 to 60,000, or 8000 to 45,000.

The dispersant amine groups may be prepared/derivatized by reacting an olefin copolymer (typically an ethylene-propylene copolymer) with an acylating agent (typically maleic anhydride) and an aromatic amine having a primary or secondary amino group. Typically, the dispersant viscosity modifier may be an ethylene-propylene copolymer acylated with maleic anhydride and reacted with an aromatic amine.

The formation of dispersant viscosity modifiers is well known in the art. Dispersant viscosity modifiers may include, for example, those described in U.S. Pat. No. 7,790,661 column 2, line 48 to column 10, line 38.

In one embodiment, the dispersant viscosity modifier may be prepared by grafting an olefinic carboxylic acylating agent to 15 to 80 mole percent ethylene, 20 to 85 mole percent C_3-10α -monoolefin and 0 to 15 mole percent of a non-conjugated diene or triene, said polymer having an average molecular weight of 5000 to 500,000, and further reacting said graft polymer with an amine, typically an aromatic amine.

In another embodiment, the dispersant viscosity modifier may be the reaction product of (a) and (b): (a) a polymer comprising carboxylic acid functions or reactive equivalents thereof, said polymer having a number average molecular weight greater than 5,000; (b) an amine component comprising at least one aromatic amine containing at least one amino group capable of condensing with the carboxylic acid function to provide a pendant group and at least one additional group comprising at least one nitrogen, oxygen, or sulfur atom, wherein the aromatic amine may be selected from (i) nitro substituted anilines, (ii) aniline substituted with a group selected from the group consisting of a-c (O) -NR-group, -c (O) -O-group, -N ═ groupN-radical or-SO₂-an amine of two aromatic moieties linked by a group, wherein R may be hydrogen or a hydrocarbyl group, one of said aromatic moieties having said condensable amino group, (iii) an aminoquinoline, (iv) an aminobenzimidazole, (v) an N, N-dialkylphenylenediamine, (vi) an aminodiphenylamine (also known as N, N-phenylenediamine) and (vii) a ring-substituted benzylamine.

The aromatic amine of the dispersant viscosity modifier may also include NH which may be represented by the general structure₂-Ar or T-NH-Ar wherein T may be an alkyl or aryl group and Ar may be an aryl group, including nitrogen or amino substituted aryl groups and Ar groups, including any of the following structures

And a plurality of non-fused or linked aromatic rings. In these and related structures, among the other groups disclosed herein, R^v，R^viAnd R^viiMay independently be-H, -C_1-18Alkyl, nitro, -NH-Ar, -N ═ N-Ar, -NH-CO-Ar, OOC-C_1-18Alkyl, -COO-C₁₈Alkyl, -OH, -O- (CH)₂CH₂O)_nC_1-18Alkyl and O (CH)₂CH₂O)_nAr (where n may be 0 to 10).

Aromatic amines include those wherein a carbon atom of an aromatic ring structure is directly attached to an amino nitrogen. The amine may be a monoamine or a polyamine. The aromatic ring is typically a mononuclear aromatic ring (i.e., an aromatic ring derived from benzene), but may include fused aromatic rings, particularly those derived from naphthalene. Examples of aromatic amines include aniline, N-alkylanilines such as N-methylaniline and N-butylaniline, bis (p-methylphenyl) amine, 4-aminodiphenylamine, N-dimethylphenylenediamine, naphthylamine, 4- (4-nitrophenylazo) aniline (disperse orange 3), sulfadimidine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide (N- (4-aminophenyl) acetamide)), 4 amino-2-hydroxy-benzoic acid phenyl ester (phenylaminosalicylate), (4-amino-phenyl) -benzamide, various benzylamines such as 2, 5-dimethoxybenzylamine, 4-phenylazoaniline and substituted forms of these. Other examples include p-ethoxyaniline, p-dodecylaniline, cyclohexyl-substituted naphthylamine and thienyl-substituted anilines. Examples of other suitable aromatic amines include amino-substituted aromatics and amines in which the amine nitrogen is part of an aromatic ring, such as 3-aminoquinoline, 5-aminoquinoline and 8-aminoquinoline. Also included are aromatic amines, such as 2-aminobenzimidazole, which contain one 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-aminopropylimidazole. Other amines include 2, 5-dimethoxybenzylamine.

Additional aromatic amines and related compounds are disclosed in U.S. Pat. nos. 6,107,257 and 6,107,258; some of these include aminocarbazole, benzimidazole, aminoindole, aminopyrrole, amino-indazolone, aminoPyridine, mercaptotriazole, aminophenothiazine, aminopyridine, aminopyrazine, aminopyrimidine, pyridine, pyrazine, pyrimidine, aminothiadiazole, aminothiothiadiazole and aminobenzotriazole. Other suitable amines include 3-amino-N- (4-anilinophenyl) -N-isopropyl butanamide and N- (4-anilinophenyl) -3- { (3-aminopropyl) - (cocoalkyl) amino } butanamide. Other aromatic amines that may be used include various aromatic amine dye intermediates containing multiple aromatic rings connected by, for example, an amide structure. Examples include materials having the general structure:

and isomeric variants thereof, wherein R^viiiAnd R^ixIndependently an alkyl or alkoxy group, such as methyl, methoxy or ethoxy. In one case, R^viiiAnd R^ixAre all-OCH₃This material is known as Fast BlueRR [ CAS #6268-05-9 [ ]]。

In another example, R^ixMay be-OCH₃，R^viiiMay be-CH₃And the material is known as FastViolet B [99-21-8]. When R is^viiiAnd R^ixWhen both are ethoxy, the material is FastBlue BB [120-00-3]. U.S. patent 5,744,429 discloses other aromatic amine compounds, particularly aminoalkylphenothiazines. N-aromatic substituted amide compounds, such as those disclosed in U.S. patent application 2003/0030033A1, may also be used for the purposes of the disclosed technology. Suitable aromatic amines include those in which the amine nitrogen is a substituent on an aromatic carboxylic acid compound, i.e., the nitrogen is not sp in the aromatic ring²Is hybridized.

The aromatic amine may also comprise an amine formed by reacting an aldehyde with 4-aminodiphenylamine. The resulting amine can be described as having at least 4 aromatic groups, at least one-NH₂An alkylene-coupled amine having a functional group and at least 2 secondary or tertiary amino groups. The aldehyde may be aliphatic, alicyclic or aromatic. The aliphatic aldehydes may be linear or branched. Examples of suitable aromatic aldehydes include benzaldehyde or o-vanillin. Examples of aliphatic aldehydes include formaldehyde (or reactive equivalents thereof such as formalin or paraformaldehyde), acetaldehyde or propionaldehyde. Typically, the aldehyde may be formaldehyde or benzaldehyde. Alternatively, the aromatic amines may be prepared by the process described in BerichtederDeutschen Chemischen Gesellschaft (1910), 43,728-39.

Aromatic amines formed by coupling an aldehyde and 4-aminodiphenylamine are described in european patent application EP 2401348A and may also be represented by the formula:

wherein each variable is

R¹May be hydrogen or C_1-5Alkyl (typically hydrogen);

R²may be hydrogen or C_1-5Alkyl (typically hydrogen);

u may be an aliphatic, cycloaliphatic or aromatic group, provided that when U may be aliphatic, the aliphatic group may be a linear or branched alkylene group containing 1 to 5 or 1 to 2 carbon atoms; and

w may be 0 to 9 or 0 to 3 or 0 to 1 (typically 0).

In one embodiment, the aromatic amine comprises 4 aminodiphenylamine, aldehyde (typically formaldehyde) coupled 4-aminodiphenylamine, nitroaniline (3-nitroaniline), dispersed orange-3 (DO3), or mixtures thereof.

The lubricating composition may be prepared by adding the product of the process described herein to an oil of lubricating viscosity, optionally in the presence of other performance additives (as described below).

Other Performance additives

The lubricating compositions of the disclosed technology optionally comprise other performance additives. Other performance additives include at least one of metal deactivators, viscosity modifiers, friction modifiers, antiwear agents, corrosion inhibitors, extreme pressure agents, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

In one embodiment, the friction modifier may be selected from a long chain fatty acid derivative of an amine, a long chain fatty acid ester, or a derivative of a long chain fatty epoxide; a fatty imidazoline; amine salts of alkylphosphoric acids; a fatty alkyl tartrate; a fatty alkyl tartrimide; a fatty alkyl tartaric amide; fatty glycolate; and fatty hydroxyacetamides. The friction modifier may be present at 0 wt% to 6 wt%, or 0.01 wt% to 4 wt%, or 0.05 wt% to 2 wt%, or 0.1 wt% to 2 wt% of the lubricating composition.

As used herein, the term "fatty alkyl" or "fat" refers to a carbon chain having from 10 to 22 carbon atoms, typically a straight carbon chain, relative to the friction modifier.

Examples of suitable friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene polyamines; amine salts of alkylphosphoric acids; a fatty alkyl tartrate; a fatty alkyl tartrimide; a fatty alkyl tartaric amide; a fatty phosphonate ester; fatty phosphites; borated phospholipids, borated fatty epoxides; a glyceride; borating the glyceride; a fatty amine; an alkoxylated fatty amine; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines, including tertiary hydroxyl fatty amines; a hydroxyalkylamide; metal salts of fatty acids; metal salts of alkyl salicylates; a fatty oxazoline; a fatty ethoxylated alcohol; condensation products of carboxylic acids and polyalkylene polyamines; or from the reaction products of fatty carboxylic acids with guanidine, aminoguanidine, urea or thiourea and salts thereof.

Friction modifiers may also include materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or soy oil monoesters of polyols and aliphatic carboxylic acids.

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.

The lubricating composition optionally further comprises at least one antiwear agent.

Examples of suitable anti-wear agents include titanium compounds, tartrates, tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized olefins, metal dihydrocarbyl dithiophosphates (e.g., zinc dialkyldithiophosphate), phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thio-carbamates, and bis (S-alkyldithiocarbamoyl) disulfides. In one embodiment, the antiwear agent may comprise a tartrate or tartrimide, as disclosed in International publication WO2006/044411 or Canadian patent CA 1183125. The tartrate or tartrimide may contain alkyl ester groups, wherein the sum of the carbon atoms on the alkyl groups may be at least 8. The antiwear agent may include, in one embodiment, a citrate ester as disclosed in U.S. patent application 2005/0198894.

Another class of additives comprises oil soluble titanium compounds, as disclosed in US7,727,943 and US 2006/0014651. The oil soluble titanium compound may be used as an antiwear agent, a friction modifier, an antioxidant, a deposit control additive, or more than one of these functions. In one embodiment, the oil soluble titanium compound may be a titanium (IV) alkoxide. The titanium alkoxide may be formed from a monohydric alcohol, a polyhydric alcohol, or mixtures thereof. The monoalkoxides may have 2 to 16 or 3 to 10 carbon atoms. In one embodiment, the titanium alkoxide may be titanium (IV) isopropoxide. In one embodiment, the titanium alkoxide may be titanium (IV) diethylhexyloxide. In one embodiment, the titanium compound comprises an alkoxide of a vicinal 1, 2-diol or polyol. In one embodiment, the 1, 2-vicinal diol comprises a fatty acid monoester of glycerol, typically the fatty acid may be oleic acid.

In one embodiment, the oil soluble titanium compound may be a titanium carboxylate. In another embodiment, the titanium (IV) carboxylate may be titanium neodecanoate.

In one embodiment, the lubricating composition may further comprise a phosphorus-containing antiwear agent. Typically, the phosphorus-containing antiwear agent may be a zinc dialkyldithiophosphate, a phosphite, a phosphate, a phosphonate, and an ammonium phosphate salt, or mixtures thereof. Zinc dialkyldithiophosphates are known in the art. The antiwear 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.

In one embodiment, the lubricating composition may further comprise a phosphorus-containing antiwear agent based on zinc dialkyldithiophosphate, or mixtures thereof.

When present, the zinc dialkyldithiophosphate can be present in an amount to supply 100ppm to 1000ppm, or 200ppm to 900ppm, or 350ppm to 900ppm of phosphorus.

The zinc dialkyldithiophosphate may be derived from aliphatic or aromatic hydrocarbon alcohols; a hydrocarbyl group; the alcohol may be a primary or secondary alcohol. Zinc dialkyldithiophosphates (or ZDDP) derived from secondary alcohols are considered secondary ZDDP. ZDDP derived from primary alcohols are considered primary ZDDP. ZDDP prepared from a mixture of primary and secondary alcohols is considered a mixed primary/secondary ZDDP. In one embodiment, the ZDDP may be represented by the following structure:

wherein each R may independently be a primary or secondary hydrocarbyl group containing 1 to 24, for example 2 to 12, carbon atoms and includes groups such as alkyl, alkenyl, aryl, arylalkyl, alkylaryl and cycloaliphatic hydrocarbyl groups. In one embodiment, R may be an alkyl group having 2 to 8 carbon atoms. R may be, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, and butenyl.

The R group of the zinc dithiophosphate may be derived from, for example, primary alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, octadecanol, propenol, butenol, 2-ethylhexanol; secondary alcohols such as isopropanol, sec-butanol, isobutanol, 3-methylbutan-2-ol, 2-pentanol, 4-methyl-2-pentanol, 2-hexanol, 3-hexanol, pentanol, aryl alcohols such as phenol, substituted phenols (in particular alkylphenols such as butylphenol, octylphenol, nonylphenol, dodecylphenol), disubstituted phenols. Certain diols may also be used in the preparation of ZDDP; suitable primary glycols include esters of ethylene glycol, propylene glycol, and polyhydric alcohols such as glycerol monooleate, and combinations thereof. ZDDP can be prepared from a combination of primary alcohols and primary diols.

In one embodiment, the R groups of the ZDDP may independently be primary alkyl groups, secondary alkyl groups, aryl groups, or mixtures thereof.

In one embodiment, the R group of the ZDDP may be a secondary alkyl group.

Extreme Pressure (EP) agents include oil-soluble compounds, including sulfur and chlorothiogen-containing EP agents, CS of dimercaptothiadiazoles or dispersants, typically succinimide dispersants₂Derivatives, derivatives of chlorinated hydrocarbon EP agents and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; sulfurized olefins (e.g., sulfurized isobutylene), hydrocarbyl-substituted 2, 5-dimercapto-1, 3, 4-thiadiazoles or oligomers thereof, organic sulfides and polysulfides such as dibenzyldisulfide, bis (chlorobenzyl) disulfide, dibutyl tetrasulfide, methyl oleate sulfide, sulfurized alkylphenols, sulfurized dipentene, sulfurized terpenes, and sulfurized diels-alder adducts; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters such as di-and trihydrocarbon phosphites, for example dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; diamyl phenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene-substituted phenol phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol; amine salts or derivatives of alkyl and dialkyl phosphoric acids, including, for example, the reaction of a dialkyl dithiophosphoric acid with propylene oxide and subsequent further reaction with P₂O₅Amine salts of the reaction products of the reaction; and mixtures thereof (as described in US 3,197,405).

Suds suppressors useful in the disclosed technology compositions include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexyl acrylate with optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers.

Pour point depressants useful in the disclosed technology compositions include poly α olefins, esters of maleic anhydride-styrene copolymers, poly (meth) acrylates, polyacrylates, or polyacrylamides.

Demulsifiers include trialkyl phosphates, as well as various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide or mixtures thereof.

Metal deactivators include derivatives of benzotriazole (usually tolyltriazole), 1,2, 4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole. Metal deactivators may also be described as corrosion inhibitors.

The seal swelling agent comprises sulfolene (sulfolene) derivative Exxon Neon-37^TM(FN1380) and Exxon Mineral Seal Oil^TM(FN 3200)。

Industrial applications

The internal combustion engine may be a four-stroke engine. The internal combustion engine may or may not have an exhaust gas recirculation system. The internal combustion engine may be equipped with an emission control system or a turbocharger. Examples of emission control systems include Diesel Particulate Filters (DPFs) or systems employing Selective Catalytic Reduction (SCR).

The lubricating composition can be characterized as having (i) a sulfur content of 0.5 wt% or less, (ii) a phosphorus content of 0.1 wt% or less, (iii) a sulfated ash content of 0.5 wt% to 1.5 wt% or less.

The lubricating composition can be characterized as having at least one of (i) a sulfur content of 0.2 wt% to 0.4 wt% or less, (ii) a phosphorus content of 0.08 wt% to 0.15 wt%, and (iii) a sulfated ash content of 0.5 wt% to 1.5 wt% or less.

The lubricating composition may be characterized as having a sulphated ash content of 0.5 wt% to 1.2 wt%.

The lubricating composition may have a total sulphated ash content of 1.2 wt% or less.

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

In one embodiment, the lubricating composition can be characterized as having (i) a sulfur content of 0.5 wt.% or less, (ii) a phosphorus content of 0.15 wt.% or less, (iii) a sulfated ash content of 0.5 wt.% to 1.5 wt.% or less.

The lubricating composition can be characterized as having (i) a sulfur content of 0.2 wt% to 0.4 wt% or less, (ii) a phosphorus content of 0.08 wt% to 0.15 wt%, and (iii) a sulfated ash content of 0.5 wt% to 1.5 wt% or less.

The lubricating composition can have an SAE viscosity grade of XW-Y, where X can be 0, 5, 10, or 15; y may be 16, 20, 30 or 40.

The internal combustion engine disclosed herein may have a steel surface on the cylinder bore, block or piston rings.

The internal combustion engine may have a surface of steel or an aluminium alloy or an aluminium composite.

Typically, compression ignition internal combustion engines have a maximum load mass in excess of 3,500 kg.

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

A series of 15W-40 engine lubricants were prepared in group II base oils of lubricating viscosity containing the above additives as well as conventional additives including polymeric viscosity modifiers, ashless succinimide dispersants, overbased detergents and other performance additives as follows (Table 1). The phosphorus, sulfur and ash content of each example is also listed in the table to show that each example has similar amounts of these materials, thus providing a suitable comparison between the comparative and inventive examples.

Watch-lubricating composition¹

1-unless otherwise indicated, all amounts mentioned above are in weight percent and on an oil-free basis.

2-overbased alkylbenzene sulfonate (TBN 520mg KOH/g)

3-Low overbased alkylbenzene sulfonate with TBN of 160mg KOH/g

4-overbased calcium phenate sulphide having a TBN content of 420mg KOH/g

5-conventional polyisobutenyl succinimide dispersants aminated with polyethylene polyamine (PIB Mn. about.2200; TBN54mg KOH/g)

6-conventional polyisobutenyl succinimide dispersants aminated with polyaromatic polyamines (PIB Mn. about.2200; TBN. about.0 mg KOH/g)

7-borated polyisobutenyl succinimide dispersant (PIB Mn 1200; TBN 90mg KOH/g; 2.85 wt% B)

8-borated polyisobutenyl succinimide dispersant (PIB Mn-2200; TBN54 mgKOH/g; 0.6 wt% B)

9-other additives include low levels of corrosion inhibitors, foam inhibitors and pour point depressants

The lubricants were evaluated for deposit control, copper and lead corrosion, and friction and wear in a series of bench tests and engine tests. Deposit control was evaluated using industry standard tests TEOST 33C (ASTM D6335), MHT TEOST (ASTM D7097B), Caterpillar 1K (ASTM D6750) single cylinder engine test and Mack T-12 engine test. Corrosion was evaluated using an extended version of the high temperature corrosion bench test (HTCBT as described in ASTM D6594) run for 168 hours, with the following table showing the results after the dual length HTCBT test) extended to 336 hours, OM501LA-CEC L-101-08, OM646LA-CEC L-099-08, and Mack T-12(ASTM D7422) engine tests, according to the procedures of ASTM D6594. Wear and friction were evaluated using a reciprocating tester bench test and a GM 6.5L roller follower wear test (RFWT, astm d 5966). Engine tests may include those run under the test procedures described above, with typical test parameters for each test being shown in the following table.

TABLE 2 bench test results

Comparative example

The results obtained indicate that the lubricating composition may have at least one of deposit control, wear control, and/or Cu/Pb corrosion control.

It is known that some of the above materials may interact in the final formulation such that the components of the final formulation may be different from the components initially added. The products formed thereby, including products formed when using the lubricant compositions of the presently disclosed technology in their intended use, may not be easily described. However, all such modifications and reaction products are intended to be included within the scope of the presently disclosed technology; the disclosed technology includes lubricant compositions prepared by mixing the above components.

Each of the documents mentioned above is incorporated herein by reference. Except in the examples, or where otherwise explicitly indicated, all numbers in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word "about". Unless otherwise specified, each chemical or composition referred to herein should be interpreted as a commercial grade material, which may contain isomers, by-products, derivatives, and other such materials that are normally understood to be present in the commercial grade. However, unless otherwise specified, the amount of each chemical component does not include any solvent or diluent oil, which may be typically present in commercial materials. It is understood that the upper and lower amounts, ranges and specific limits described herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used with ranges or amounts for any of the other elements.

As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its conventional sense, as is well known to those skilled in the art. In particular, it refers to a group having a carbon atom directly attached to the rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent; and hetero substituents, that is, substituents that similarly have a predominantly hydrocarbon character in the ring or chain but contain elements other than carbon. More detailed definitions of the term "hydrocarbyl substituent" or "hydrocarbyl group" are described in paragraphs [0118] to [0119] of international publication WO2008147704 or similar definitions are described in paragraphs [0137] to [0141] of published application US 2010-0197536.

As described below, the number average molecular weights of the dispersant viscosity modifier and viscosity modifier have been determined using known methods such as GPC analysis using polystyrene standards. Methods for determining the molecular weight of polymers are well known. These methods are described, for example, in: (i) flory, "Principles of Polymer Chemistry", Cornell university Press 91953), Chapter VII, pp 266-; or (ii) "Macromolecules, a Introduction to Polymer Science", F.A. Bovey and F.H. Winslow, Editors, Academic Press (1979), p.296-.

While the invention has been described in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. It is, therefore, to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

1. A method of lubricating a compression ignition internal combustion engine having a maximum loaded mass in excess of 2700kg, comprising supplying to the engine a lubricating composition comprising:

an oil of lubricating viscosity, which oil has,

an alkaline earth metal sulphonate detergent of 300TBN or higher having a metal ratio of 10 to 40,

an alkaline earth metal sulphonate detergent having a metal ratio of from 3 to 9 and a TBN (measured by ASTM D2896-11) of from 81 to 180mg KOH/g,

wherein the sulphonate detergent provides a total amount of sulphonate matrix to the lubricating composition of from 0.8 wt% to 3 wt%, or from 0.9 wt% to 3 wt%, or from 1 wt% to 3 wt%,

0.1 to 1.2 wt.% of an antioxidant, wherein at least 20 wt.% of the antioxidant is a phenolic antioxidant,

the borated compound is present in an amount to supply 25ppm to 300ppm boron, the borated compound being selected from

A borate ester, a salt of a carboxylic acid,

borated dispersant, and

wherein,

the lubricating composition has a TBN (measured by ASTM D2896-11) of 6.5 to 15mg KOH/g.

2. A method of lubricating a compression ignition internal combustion engine having a maximum loaded mass in excess of 2700kg, comprising supplying to the engine a lubricating composition comprising:

an oil of lubricating viscosity, which oil has,

borate ester present in an amount to supply 75ppm to 200ppm or 75ppm to 150ppm boron,

to 1.2 wt.% of an antioxidant, wherein at least 20 wt.% of the antioxidant is a phenolic antioxidant,

wherein,

3. A method of lubricating a compression ignition internal combustion engine having a maximum loaded mass in excess of 2700kg, comprising supplying to the engine a lubricating composition comprising:

an oil of lubricating viscosity, which oil has,

a borated dispersant present in an amount to supply 125ppm to 250ppm boron,

wherein,

4. The method of any preceding claim, wherein the lubricating composition is characterized by (i) a sulfur content of 0.5 wt% or less, (ii) a phosphorus content of 0.1 wt% or less, and (iii) a sulfated ash content of 0.5 wt% to 1.5 wt% or less.

5. The method of any preceding claim, wherein the lubricating composition is characterized by at least one of: (i) a sulfur content of 0.2 wt.% to 0.4 wt.% or less, (ii) a phosphorus content of 0.08 wt.% to 0.15 wt.%, and (iii) a sulfated ash content of 0.5 wt.% to 1.5 wt.% or less.

6. The method of any preceding claim, wherein the lubricating composition is characterized by a sulphated ash content of from 0.9 wt% to 1.4 wt%, or from 1.05 wt% to 1.2 wt%.

7. The method of any preceding claim, wherein the oil of lubricating viscosity comprises API group I, II, III, IV, V or mixtures thereof.

8. The method of any preceding claim, wherein the oil of lubricating viscosity comprises API group I, II, III, IV or mixtures thereof.

9. The method of any preceding claim, wherein the oil of lubricating viscosity comprises API group I, II, III or mixtures thereof.

10. The method of any preceding claim, wherein the oil of lubricating viscosity comprises API group I, II or a mixture thereof.

11. The method of any preceding claim, wherein the oil of lubricating viscosity comprises API group I.

12. The method of any preceding claim, wherein the oil of lubricating viscosity comprises API group II.

13. The method of any preceding claim, wherein the lubricating composition comprises an antioxidant, wherein the phenolic antioxidant comprises at least 40 wt%, or at least 50 wt%, typically from 45 wt% to 90 wt%, or from 55 wt% to 80 wt% of the antioxidant.

14. The method of any preceding claim, wherein the lubricating composition comprises an aminic antioxidant, typically a diarylamine or an alkylated diarylamine, and comprising phenyl- α -naphthylamine (PANA), an alkylated diphenylamine or an alkylated phenylnaphthylamine, or mixtures thereof.

15. A process according to any preceding claim, wherein the amine antioxidant comprises up to 60 wt%, or up to 50 wt%, of the antioxidant, typically from 5 wt% to 55 wt% or from 10 to 45 wt% of the antioxidant.

16. A method as claimed in any preceding claim, wherein the lubricating composition comprises a sulphurised olefin antioxidant, such as sulphurised 4-butenyloxycyclohexene, or a sulphurised olefin, or mixtures thereof.

17. The process of any preceding claim, wherein the sulfurized olefin antioxidant constitutes up to 60 wt%, or up to 50 wt%, of the antioxidant, typically from 5 wt% to 55 wt% or from 10 to 45 wt% of the antioxidant.

18. The method of any preceding claim, wherein the antioxidant comprises a phenolic or aminic antioxidant or a mixture thereof, and wherein the antioxidant is present at 0.1 wt% to 3 wt%, or 0.5 wt% to 2.75 wt%, or 1 wt% to 2.5 wt%.

19. The method of any preceding claim, wherein the lubricating composition is characterized by a Total Base Number (TBN) content of from 7 to 14, or from 7.5 to 12mg KOH/g.

20. The method of any preceding claim, wherein the lubricating composition is characterized by a Total Base Number (TBN) content of from 8 to 10mg KOH/g.

21. The method of any preceding claim, wherein the total amount of substrate supplied by the calcium sulphonate detergent is from 1.05 to 1.2 wt%, or from 1.05 to 1.1 wt% of the lubricating composition.

22. The method of any preceding claim, wherein the metal ratio of the alkali metal sulphonate detergent of 300TBN or higher is from 15 to 30, or from 20 to 30, or from 22 to 25.

23. The method of any preceding claim, wherein the alkaline earth metal sulphonate detergent of 300TBN or higher is a calcium or magnesium sulphonate detergent, typically a calcium sulphonate detergent.

24. The method of any preceding claim, wherein the calcium sulfonate detergent having a metal ratio of 10 to 40 has a TBN of 350 to 500, or 375 to 425.

25. The method of any preceding claim, wherein the alkaline earth metal sulphonate detergent has a metal ratio of from 3 to 9, and a TBN of from 81 to 130mg KOH/g or from 82 to 100mg KOH/g or from 85 to 95mg KOH/g.

26. The method of any preceding claim, wherein the metal ratio of the alkaline earth metal sulphonate detergent is from 3 to 9 and is a calcium or magnesium sulphonate detergent, typically a calcium sulphonate detergent.

27. The method of any preceding claim, wherein the alkaline earth metal sulphonate detergent having a metal ratio of from 3 to 9 has a metal ratio of from 4 to 8 or greater than 5 to 8.

28. The method of any preceding claim, wherein both the sulphonate detergent having a metal ratio of from 3 to 9 and the sulphonate detergent having a metal ratio of from 10 to 40 are calcium sulphonate detergents.

29. The method of any preceding claim, wherein the lubricating composition comprises 0 wt% to 0.2 wt%, or 0 wt% to 0.1 wt% of the phenolic based detergent.

30. The method of claim 29, wherein the lubricating composition comprises 0 wt% of the phenolic-based detergent.

31. The method of any of claims 29 to 30, wherein the phenolic based detergent is a phenate.

32. The method of any of claims 29 to 31, wherein the phenolic based detergent is selected from phenates and salicylates.

33. The method of any preceding claim 29 to 32, wherein the phenolic based detergent is selected from the group consisting of phenates, salicylates, and salixarates.

34. The method of any one of claims 29 to 33 wherein the phenate is a non-sulfur containing phenate, a sulfur containing phenate, or a "hybrid" detergent formed with a mixed surfactant system, wherein the hybrid detergent is a mixed phenate-salicylate, a sulfonate-phenate, or a sulfonate-phenate-salicylate.

35. The method of any preceding claim, wherein the lubricating composition further comprises a dispersant viscosity modifier, and is typically present at 0.01 wt% to 3 wt%.

36. The method of claim 35, wherein the dispersant viscosity modifier is an olefin copolymer further functionalized with a dispersant amine group.

37. The process of any of claims 35 to 36, wherein the olefin copolymer is an ethylene-propylene copolymer.

38. The method of any of claims 35 to 37 wherein the olefin copolymer has a number average molecular weight of 5000 to 100,000, or 7500 to 60,000, or 8000 to 45,000.

39. A method according to any one of claims 35 to 38 wherein the dispersant amine groups are derived from the reaction of an olefin copolymer with an acylating agent and an aromatic amine having a primary or secondary amino group.

40. A method according to claim 39 wherein the aromatic amine comprises 4-aminodiphenylamine, aldehyde (typically formaldehyde) -coupled 4-aminodiphenylamine, nitroaniline, dispersed orange-3 (DO3) or mixtures thereof.

41. The method of any of claims 35 to 40 wherein the dispersant viscosity modifier is prepared by grafting an olefinic carboxylic acylating agent to 15 to 80 mole% ethylene, 20 to 85 mole% C_3-10α -monoolefin, and 0 to 15 mole percent of a non-conjugated diene or triene, and further reacting said graft polymer with an amine, said polymer having an average molecular weight of 5000 to 500,000.

42. A method as claimed in any one of claims 35 to 41, wherein the dispersant viscosity modifier is the reaction product of: (a) a polymer comprising carboxylic acid functions or reactive equivalents thereof, said polymer having a number 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 the carboxylic acid functionality to provide a pendant group and at least one additional group comprising at least one nitrogen, oxygen, or sulfur atom, wherein the aromatic amine is selected from (i) nitro-substituted(iii) an aniline comprising a group formed by-c (O) NR-, c (O) O-group, -N ═ N-group or-SO₂-an amine of two aromatic moieties linked by a group, wherein R is hydrogen or a hydrocarbyl group, one of said aromatic moieties having a condensable amino group, (iii) an aminoquinoline, (iv) an aminobenzimidazole, (v) an N, N-dialkylphenylenediamine, and (vi) a ring-substituted benzylamine.

43. A method as claimed in any of claims 35 to 42, in which the dispersant viscosity modifier is present at 0.05 wt% to 1.5 wt%, or 0.1 wt% to 1 wt%, or 0.1 to 0.5 wt%.

44. The method of any preceding claim, wherein the lubricating composition further comprises a non-borated dispersant, which is typically present at 0.25 wt% to 8 wt%, or 0.5 wt% to 5 wt%, 1 wt% to 4.5 wt%, or 1.6 wt% to 2.5 wt% of the lubricating composition.

45. The method of claim 44, wherein the non-borated dispersant is an amine-functionalized additive, wherein the amine-functionalized additive is derived from an amine having at least 3 or 4 aromatic groups.

46. The method of claim 45, wherein the amine-functionalized additive is derived from a compound having at least 4 aromatic groups and having at least one-NH group₂An amine having a functional group and at least 2 secondary or tertiary amino groups.

47. A method according to any one of claims 45 to 46 wherein the amine having at least 3 or 4 aromatic groups is represented by the formula:

R¹is hydrogen or C_1-5An alkyl group;

R²is hydrogen or C_1-5An alkyl group;

u is an aliphatic, cycloaliphatic or aromatic group, with the proviso that when U is aliphatic, the aliphatic group is a linear or branched alkylene group containing 1 to 5 or 1 to 2 carbon atoms; and is

w is 1 to 10, or 1 to 4, or 1 to 2, or 1.

48. A method according to any one of claims 45 to 47 wherein the amine having at least 3 or 4 aromatic groups is bis [ p- (p-aminophenylamino) phenyl ] -methane, 2- (7-amino-acridin-3-ylmethyl) -N-4- {4- [4- (4-amino-phenylamino) -benzyl ] -phenyl } -benzene-1, 4-diamine, or a mixture thereof.

49. A process according to any one of claims 45 to 47 wherein the amine functionalised additive is a product obtained/obtainable by reacting an amine having at least 3 or 4 aromatic groups with a carboxylic acid functionalised polymer.

50. The process according to claim 45, wherein the amine-functionalised additive is derived from an amine having at least 3 or 4 aromatic groups, which is obtained/obtainable by a process comprising: reacting (1) isatoic anhydride or an alkyl-substituted isatoic anhydride with (2) an aromatic amine having at least two aromatic groups and a primary or reactive secondary amino group.

51. The method of any preceding claim 45 to 50 wherein the carboxylic acid functionalized polymer is polyisobutylene-succinic anhydride, maleic anhydride-styrene copolymer, an ester of maleic anhydride-styrene copolymer, α -olefin-maleic anhydride copolymer, or (i) styrene-ethylene- α -olefin polymer, (ii) hydrogenated alkenyl aryl conjugated diene copolymer, (iii) polyolefin grafted with maleic anhydride, or (iv) a maleic anhydride grafted copolymer of hydrogenated isoprene polymer or mixtures thereof.

52. A method as set forth in any one of claims 45 to 51 wherein the carboxylic acid functional polymer is polyisobutylene succinic anhydride.

53. A method according to claim 52 wherein the polyisobutylene succinic anhydride is derived from polyisobutylene having a number average molecular weight in the range of 350 to 5000, or 550 to 3000 or 750 to 2500.

54. The method of any one of claims 1,2 or 4 to 51 wherein the boron-containing compound is a borate ester represented by the formula:

wherein each R is independently an organic group, and any two adjacent R groups may together form a cyclic group, or

Wherein the boron-containing compound is a borate ester represented by the formula

R, R therein¹、R²、R³And R⁴Independently a hydrocarbyl group having 1 to 12 carbon atoms; and R is⁵And R⁶Independently an alkylene group having from 1 to 6 carbon atoms and in one embodiment 2 to 4 carbon atoms.

55. The method of any one of claims 1,2 or 4 to 51 wherein the boron-containing compound is a borate ester represented by the formula:

wherein: r¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Independently hydrogen or hydrocarbyl groups, typically wherein each hydrocarbyl group may contain 1 to 12 or 1 to 4 carbon atoms.

56. The method of any one of claims 1,2 or 4 to 51 wherein the boron-containing compound is a borate ester comprising at least one alkyl group having 10 to about 32 carbon atoms, said alkyl group having a branch at β or higher, said borate ester being present in an amount to provide about 1 to about 1000ppm by weight boron to the lubricant composition.

57. The method as recited in claim 56, wherein the borate ester comprises a plurality of alkyl groups each independently having 10 to about 32 carbon atoms, the alkyl groups having a branch at β or higher.

58. The method of claim 57 wherein the alkyl group is branched at position β.

59. The method of any one of claims 57 to 58, wherein the alkyl group has a structure represented by-CH₂-CH(R¹)(R²) Structure of (a) wherein R¹Is an alkyl group having from 7 to about 18 carbon atoms, and R²To have a ratio R¹Alkyl groups of a smaller number of carbon atoms.

60. The method of any one of claims 57 to 58, wherein the alkyl group has a structure represented by-CH₂-CH(R¹)(R²) Structure of (a) wherein R¹Is an alkyl group having from 7 to about 18 carbon atoms, and R²To have a ratio R¹Alkyl with two fewer carbon atoms.

61. The method according to claim 60, wherein the alkyl group is a 2-propylheptyl group, a 2-butyloctyl group, a 2-hexyldecyl group, or a 2-octyldodecyl group.

62. The method of any preceding claim 1,2, or 4 to 51, wherein the borate ester is represented by one or more of the following formulae: (RO)₃B or

(RO)₂B-O-B(OR)₂，

Or

Wherein each R is independently an alkyl group having from 10 to about 32 carbon atoms and has a branch at the β or higher position.

63. The method of any preceding claim 1,2, or 4 to 51, wherein the borate ester comprises a trialkyl borate.

64. The method of claim 63, wherein the borate ester comprises a material represented by the following structure.

65. The method of any preceding claim, wherein the lubricating composition further comprises a zinc dialkyldithiophosphate.

66. The method of claim 65 wherein the zinc dialkyl dithiophosphate is a primary zinc dialkyl dithiophosphate, or a secondary zinc dialkyl dithiophosphate.

67. The method according to claim 66, wherein the zinc dialkyldithiophosphate is represented by the structure:

wherein each R can independently be a primary or secondary hydrocarbyl group containing 1 to 24 or 2 to 12 carbon atoms, typically the hydrocarbyl groups are alkyl, alkenyl, aryl, aralkyl, alkaryl, and alicyclic hydrocarbyl groups.

68. The method of any of claims 65 to 67 wherein the zinc dialkyl dithiophosphate is a secondary zinc dialkyl dithiophosphate.

69. The method of any of claims 65 to 68 wherein the zinc dialkyldithiophosphate is present in a supply of 100ppm to 1000ppm, or 200ppm to 900ppm, or 350ppm to 900ppm phosphorus.

70. The method according to any one of the preceding claims, wherein the internal combustion engine has a steel surface on the cylinder bore, cylinder block or piston ring.

71. A method according to any one of the preceding claims, wherein the internal combustion engine has a surface of steel or an aluminium alloy or an aluminium composite.