CN115052958A

CN115052958A - Lubricating composition and method of operating an internal combustion engine

Info

Publication number: CN115052958A
Application number: CN202180012758.5A
Authority: CN
Inventors: B·麦克德莫特; J·L·琼斯; C·J·琼斯; E·E·德尔布里奇
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2020-02-04
Filing date: 2021-02-04
Publication date: 2022-09-13
Also published as: EP4100497A1; US20230151295A1; WO2021158757A1; CA3166808A1

Abstract

The present disclosure generally relates to a lubricating composition having: an oil of lubricating viscosity, a boron-containing additive, a boron-free dispersant, an overbased magnesium-based detergent, an overbased calcium-based detergent, an ashless friction modifier, and optionally other performance additives. The lubricating composition of the present disclosure has a High Temperature High Shear (HTHS) viscosity of less than 2.7mPa-s according to ASTM D4683. The lubricating compositions disclosed herein may achieve one or more of the following: improved fuel economy, reduced corrosion, reduced oxidation, improved cleanliness, and improved wear performance of internal combustion engines.

Description

Lubricating composition and method of operating an internal combustion engine

Technical Field

The present disclosure generally relates to a lubricating composition having: an oil of lubricating viscosity having at least 50 weight percent of a group IV base oil, a mixture of a boron-containing dispersant and a boron-free dispersant, an overbased magnesium-based detergent, an overbased calcium-based detergent, an ashless friction modifier, and optionally other performance additives. The lubricating composition of the present disclosure has a High Temperature High Shear (HTHS) viscosity of less than 2.7mPa-s according to ASTM D4683. The disclosed lubricating composition is suitable for performing one or more of the following: improved fuel economy, reduced corrosion, reduced oxidation, improved cleanliness, improved TBN retention, reduced low speed pre-ignition ("LSPI"), and improved wear performance.

Background

Modern engines are designed to provide ever-improving fuel economy without sacrificing cleanliness or durability. Current and proposed crankcase lubricating oil specifications, such as API SN plus and ILSAC GF-6 for passenger car motor oils and API CK-4 for heavy duty diesel engines, specify increasingly stringent standards to meet government requirements for efficiency. Previous lubricating formulations may not achieve acceptable levels in addressing issues like cleanliness, fuel economy, TBN retention, and/or low speed pre-ignition. Accordingly, there is a need for improved moderate saps lubrication formulations that exhibit one or more of improved cleanliness, fuel economy, and oxidation durability.

Disclosure of Invention

The present disclosure relates generally to a lubricating composition having: an oil of lubricating viscosity having at least 50 weight percent of a group IV base oil, a composition comprising a boron-containing additive, a boron-free dispersant, an overbased magnesium-based detergent, an overbased calcium-based detergent, an ashless friction modifier, and optionally other performance additives. The lubricating composition of the present disclosure has a High Temperature High Shear (HTHS) viscosity of less than 2.7mPa-s according to ASTM D4683. The disclosed lubricating composition is suitable for performing one or more of the following: improved fuel economy, reduced corrosion, reduced oxidation, improved cleanliness, improved TBN retention, reduced low speed pre-ignition ("LSPI"), and improved wear performance.

Another aspect of the present disclosure relates to a method of reducing low speed pre-ignition in a gasoline-fueled internal combustion engine operating at a Brake Mean Effective Pressure (BMEP) of greater than 12 bar and a speed of less than 3,00RPM by supplying to the engine any of the lubricating compositions disclosed herein.

The present disclosure further relates to a method of improving TBN retention of a lubricating composition in a gasoline-fueled internal combustion engine by supplying any one of the lubricating compositions disclosed herein to the engine.

The present disclosure also relates to the use of any of the lubricating compositions disclosed herein for improving one or more of cleanliness, TBN retention, and fuel economy in a gasoline-fueled internal combustion engine.

Detailed Description

The present disclosure relates to lubricating compositions for gasoline-fueled internal combustion engines. The lubricating composition comprises: an oil of lubricating viscosity, wherein at least 50 wt% of the oil is a group III base oil; a boron-containing additive; a boron-free polyisobutenyl succinimide dispersant; an amount of overbased magnesium-based detergent to deliver at least 300ppm of magnesium to the lubricating composition; an amount of an overbased calcium-based detergent to deliver at least 400ppm of calcium to the lubricating composition; an ashless friction modifier; and optionally, other performance additives described herein.

Oil of lubricating viscosity

As used herein, an oil of lubricating viscosity may comprise: natural and synthetic base oils; oils derived from hydrocracking, hydrogenation, and hydrofinishing; unrefined, refined, rerefined base oils, or mixtures thereof. A more detailed description of unrefined, refined and rerefined oils is provided in international publication No. WO2008/147704, paragraphs [0054] to [0056] (similar disclosures are provided in U.S. patent application 2010/197536, see [0072] to [0073 ]). More detailed descriptions of natural and synthetic lubricating oils are described in paragraphs [0058] to [0059] of WO2008/147704, respectively (similar disclosures are provided in U.S. patent application 2010/197536, see [0075] to [0076 ]). Both references are incorporated herein by reference. Synthetic oils may also be produced by Fischer-Tropsch reactions and may typically be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be produced by a Fischer-Tropsch gas-liquid synthesis procedure, as well as other gas-liquid oils.

Suitable oils may be produced from biological sources, i.e. natural sources or by bioengineering methods. This includes naturally occurring oils, such as vegetable oils and triglyceride oils, which can be further refined or purified by standard methods, as well as those oils which can be derived by directly bioconverting natural chemicals into oil or by biologically forming building block precursor molecules which can be further converted into oil by known methods.

Oils of lubricating viscosity may also be defined as set forth in section 1.3, section subtitle 1.3, "Base Stock Categories (Base Stock Categories)", in the 2008 version 4 "Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car and Diesel Engine Oils (Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils)". The API guidelines are also summarized in US patent US 7,285,516 (see column 11, line 64 to column 12, line 10), which is incorporated herein by reference.

Group IV base oils (also known as polyalphaolefins or PAOs) are known in the art and are prepared by oligomerization or polymerization of linear alpha olefins. PAO is a typical water white oil with excellent low temperature viscosity properties (as measured) and a high viscosity index. Typical PAOs suitable for use in an internal combustion engine include PAO-4 and PAO-6, i.e., about 4m each ² S and 6m ² /s。

In one embodiment, the oil of lubricating viscosity may be a base oil, ester or synthetic oil or mixtures thereof comprising API group I to group IV oils. In one embodiment, the oil of lubricating viscosity may be an API group II, group III, group IV oil, ester or synthetic oil or mixtures thereof. In one embodiment, the oil of lubricating viscosity comprises at least 50 wt.%, or at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 100 wt.% of the group III or group IV base oil.

The amount of oil of lubricating viscosity present is typically the balance remaining after subtracting the total amount of additives present in the lubricating composition from 100 wt%. In some embodiments, the oil of lubricating viscosity comprises at least 80 weight percent of the lubricating composition. In other embodiments, the oil of lubricating viscosity comprises at least 80, or at least 81, or at least 85, or at least 87, or at least 89, or at least 91, or at least 93, or at least 95 weight percent of the lubricating composition. In one embodiment, the oil of lubricating viscosity comprises 80 to 87, or 82 to 86, or 83 to 90 weight percent of the lubricating composition.

The lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the present disclosure is in the form of a concentrate (which may be combined with additional oils to form, in whole or in part, a finished lubricant), the weight ratio of these additives to the oil of lubricating viscosity and/or to the diluent oil is included in the range of 1:99 to 99:1 or 80:20 to 10: 90. Typically, the lubricating composition of the present invention comprises at least 50 wt.%, or at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.% of an oil of lubricating viscosity.

In the present disclosure, the lubricating composition may comprise a kinematic viscosity of 2.4m measured at 100 ℃ ² S to 6.4m ² A base oil per second. In some embodiments, the kinematic viscosity is 4.0m ² S to 5.0m ² S or 5.2m ² S to 5.8m ² S or 6.0m ² S to 6.5m ² And s. In other embodiments, the kinematic viscosity is 6.2m ² S or 5.6m ² S or 4.6m ² /s。

Boron-containing additive

The lubricating composition of the present disclosure comprises a boron-containing additive. The boron-containing additive may be in the form of any oil-soluble boron additive, such as a borated polyisobutenyl succinimide dispersant, a borate ester, or any combination thereof.

Borate esters (also known as borate antiwear agents) may be one or more compounds represented by one or more of the following formulas:

wherein each R may independently be an organic group and any two adjacent R groups may together form a cyclic group. Such material may be the product of boric acid and an alcohol. Mixtures of two or more of the foregoing may be used. In one embodiment, each R may independently be a hydrocarbyl group. The total number of carbon atoms in the R group in each formula should be sufficient to render the compound soluble in the base oil. Generally, the total number of carbon atoms in the R group may be at least 8, and in one embodiment at least 10, and in one embodiment at least 12.

In one embodiment, each R group may independently be a hydrocarbyl group of 1 to 100 carbon atoms, and in one embodiment 1 to 50 carbon atoms, and in one embodiment 1 to 30 carbon atoms, and in one embodiment 1 to 10 carbon atoms, provided that the total number of carbons in the R group may be at least 8. Each R group may be the same as each other, but they may also be different. Examples of useful R groups can include isopropyl, n-butyl, isobutyl, pentyl, 1,3 dimethyl-butyl, 2-ethyl-1-hexyl (e.g., from 2-ethylhexanol), isooctyl, decyl, 2-propylheptyl, dodecyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaphthyl, phenylalkyl, naphthylalkyl, alkylphenylalkyl, and alkylnaphthylalkyl.

In some embodiments, the boron-containing additive is present in an amount to deliver at least 75ppm boron to the lubricating composition. In another embodiment, the boron-containing additive is present in an amount to deliver at least 100ppm boron to the lubricating composition. In one embodiment, the boron-containing additive is present in an amount to deliver at least 125ppm boron to the lubricating composition. In some embodiments, the boron-containing additive is present in an amount to deliver at least 150ppm boron to the lubricating composition. In one embodiment, the boron-containing additive is present in an amount to deliver at least 165ppm boron to the lubricating composition. In one embodiment, the boron-containing additive is present in an amount to deliver at least 200ppm boron to the lubricating composition. In one embodiment, the boron-containing additive is present in an amount to deliver 85 to 250ppm boron. In another embodiment, the boron-containing additive is present in an amount to deliver 85 to 200ppm boron to the lubricating composition. In another embodiment, the boron-containing additive is present in an amount to deliver 90 to 175ppm boron to the lubricating composition. In another embodiment, the boron-containing additive is present in an amount to deliver 125 to 200ppm boron to the lubricating composition. In another embodiment, the boron-containing additive is present in an amount to deliver 75 to 175ppm boron to the lubricating composition. In another embodiment, the boron-containing additive is present in an amount to deliver 85 to 160ppm boron to the lubricating composition.

In some embodiments, the boron-containing additive may be a boron-containing polyisobutenyl succinimide dispersant as described herein.

One or more polyisobutenyl succinimide dispersants:

the lubricating composition of the present disclosure also includes a boron-free polyisobutenyl succinimide dispersant and optionally a boron-containing polyisobutenyl succinimide dispersant. References herein to polyisobutylene-based dispersants refer to boron-containing polyisobutenyl succinimide dispersants as well as boron-free polyisobutenyl succinimide dispersants. Except that the boron-containing polyisobutenyl succinimide dispersant is post-treated with a boron compound, as described herein.

The boron-containing polyisobutenyl succinimide and/or boron-free polyisobutenyl succinimide dispersants may each be prepared from a polyisobutylene ("PIB") succinimide dispersant that is either a "conventional" PIB or a high vinylidene PIB. The difference between conventional polyolefins and high vinylidene polyolefins can be illustrated with reference to the production of PIB. In a process to produce conventional PIB, isobutylene is polymerized in the presence of AlCl3 to produce a mixture of polymers comprising predominantly trisubstituted olefin (III) and tetrasubstituted olefin (IV) end groups, only a very small amount (e.g., less than 20%) of which chains contain terminal vinylidene groups (I). In another process, isobutylene is polymerized in the presence of a BF3 catalyst to produce a mixture of polymers containing predominantly (e.g., at least 70%) terminal vinylidene groups having lesser amounts of tetrasubstituted end groups and other structures. Materials produced in an alternative process, sometimes referred to as "high vinylidene PIB", are also described in U.S. patent 6,165,235, which is incorporated herein by reference in its entirety. In one embodiment, the polyisobutylene-based dispersant is a conventional polyisobutylene-based dispersant. In another embodiment, the polyisobutylene-based dispersant is a high or medium vinylidene succinimide dispersant. Polyisobutylene-based dispersants for use herein are well known in the art.

The polyisobutylene-based acylating agent may be prepared/obtained/obtainable by reacting an "ene" or "thermal" reaction with maleic anhydride. The "ene" reaction mechanism and general reaction conditions are summarized in page 147-149 of "Maleic Anhydride (Maleic Anhydride)" edited by b.c. trivedi and b.c. culbertson and published in 1982 by plerian Press (Plenum Press). Polyisobutylene-based dispersants prepared by processes involving "ene" reactions may include dispersants having a carbocyclic ring present on less than 50 mole%, or 0 to less than 30 mole%, or 0 to less than 20 mole%, or 0 mole% of the dispersant molecules. The reaction temperature for the "ene" reaction may be from 180 ℃ to less than 300 ℃, or from 200 ℃ to 250 ℃, or from 200 ℃ to 220 ℃.

Polyisobutene-based acylating agents can also be obtained/obtainable by chlorine-assisted processes, generally involving Diels-Alder (Diels-Alder) chemistry, leading to the formation of carbon ring bonds. Such methods are known to those skilled in the art. The chlorine-assisted process can produce an acylating agent having a carbocyclic ring that is present at 50 mol% or more or 60 to 100 mol% of the molecule. Both thermal and chlorine-assisted processes are described in more detail in U.S. patent No. 7,615,521, columns 4-5, and preparation embodiments a and B.

The polyisobutene-based acylating agent can also be prepared/obtained/obtainable by a free radical process, wherein the acylating agent is reacted with the polyisobutene in the presence of a free radical initiator. Such free radical processes are well known in the art and may be carried out in the presence of additional alpha-olefins.

The polyisobutylene-based acylating agent may be formed by reacting polyisobutylene with an acylating agent, i.e., an ethylenically unsaturated carbonyl compound, to form an acylated polyisobutylene, which may be further functionalized with an amine or alcohol to form a suitable dispersant. Suitable acylating agents include maleic anhydride or reactive equivalents thereof (e.g., acids or esters), i.e., succinic acid and reactive equivalents thereof. In one embodiment, polyisobutylene may be reacted with maleic anhydride to form an acylation product with a conversion of 1-2. In one embodiment, monosuccinic acid is reacted with the amine such that the desired product comprises a mixture in which all of the anhydride present in the acylating agent has been converted to an imide.

The ratio of carbonyl groups to nitrogen (CO: N ratio) of the polyisobutylene-based dispersant may be 5:1 to 1:10, 2:1 to 1:10, or 2:1 to 1:5, or 2:1 to 1: 2. In one embodiment, the ratio of CO to N in the dispersant may be from 2:1 to 1:10, or from 2:1 to 1:5, or from 2:1 to 1:2, or from 1:1.4 to 1: 0.6.

The polyisobutylene-based dispersants as described herein may be further described as having a TBN. In one embodiment, the polyisobutylene-based dispersant has a TBN of 5 to 50. In another embodiment, the polyisobutylene-based dispersant has a TBN of 10 to 40. In yet another embodiment, the polyisobutylene-based dispersant has a TBN of 15 to 30.

The lubricating composition of the present disclosure comprises a polyisobutylene-based dispersant that is a boron-free polyisobutenyl succinimide dispersant as described herein. The boron-free polyisobutenyl succinimide dispersant may be present in the lubricating composition in an amount in the range of from 0.5 wt% to 6.5 wt%. In some embodiments, the boron-free polyisobutenyl succinimide dispersant is present in an amount in the range of from 0.7 wt.% to 6.5 wt.%, or from 1.5 wt.% to 4.1 wt.%, or from 2.0 wt.% to 3.1 wt.%, or from 2.5 wt.% to 2.8 wt.%.

In one embodiment, the boron-free polyisobutenyl succinimide dispersant has a number average molecular weight in the range of 750 to 2500. In some embodiments, the boron-free polyisobutenyl succinimide dispersant has a number average molecular weight in the range of 750 to 1750, or 900 to 1450, or 1050 to 1250, or 1400 to 1600. In other embodiments, the number average molecular weight of the boron-free polyisobutenyl succinimide dispersant may be in the range 1950 to 2500, or 2100 to 2400, or 2200 to 2350.

In one embodiment, the boron-free polyisobutenyl succinimide dispersant comprises a first boron-free polyisobutenyl succinimide dispersant having a number average molecular weight in the range of 750 to 1750 and a second boron-free polyisobutenyl succinimide dispersant having a number average molecular weight in the range of 1950 to 2500. In another embodiment, the first boron-free polyisobutenyl succinimide dispersant has a number average molecular weight in the range of 1150 to 1650 and the second boron-free polyisobutenyl succinimide dispersant has a number average molecular weight in the range of 2100 to 2450. In one embodiment, a first boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount in the range of 0.5 to 4.5 weight percent and a second boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount in the range of 0.2 to 2.0 weight percent. In another embodiment, a first boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount in the range of 1.8 to 2.5 weight percent, and a second boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount in the range of 0.5 to 0.8 weight percent. In one embodiment, the first boron-free polyisobutenyl succinimide dispersant has a number average molecular weight in the range 750 to 1750 and is present in the lubricating composition in an amount in the range 0.5 wt% to 4.5 wt%, and the second boron-free polyisobutenyl succinimide dispersant has a number average molecular weight in the range 1950 to 2500 and is present in the lubricating composition in an amount in the range 0.2 wt% to 2.0 wt%. In one embodiment, the first boron-free polyisobutenyl succinimide dispersant comprises 60% to 90%, or 65% to 85%, or 70% to 80%, or 75% to 80% of the total composition of the first boron-free polyisobutenyl succinimide dispersant and the second boron-free polyisobutenyl succinimide dispersant.

The polyisobutenyl succinimide dispersants of the present invention may be prepared by reacting acylated PIB with a suitable amine compound. Suitable amines include one or more hydrocarbyl amines, amino alcohols, polyether amines, or combinations thereof.

In one embodiment, the hydrocarbyl amine component may include at least one aliphatic amine containing at least one amino group capable of condensing with the acyl group to provide a pendant group and at least one additional group comprising at least one nitrogen, oxygen, or sulfur atom. Suitable aliphatic amines include polyethylene polyamines (such as Tetraethylenepentamine (TEPA), triethylenetetramine (TETA), Pentaethylenehexamine (PEHA), and polyamine bottoms), N-Dimethylaminopropylamine (DMAPA), N- (aminopropyl) morpholine, N-diisostearylaminopropylamine, ethanolamine, and combinations thereof.

In one embodiment, the hydrocarbyl amine component may comprise at least one aromatic amine containing at least one amino group capable of condensing with the acyl group 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 the group consisting of: (i) a nitro-substituted aniline, (ii) an amine comprising two aromatic moieties linked by: a c (O) NR-group, -c (O) O-group, -O-group, N ═ N-group, or-SO 2-group, wherein R is hydrogen or a hydrocarbon group, one of the aromatic moieties bearing said condensable amino group, (iii) aminoquinoline, (iv) aminobenzimidazole, (v) N, N-dialkylphenylenediamine, (vi) aminodiphenylamine (also N, N-phenylenediamine), and (vii) ring-substituted benzylamine.

In one embodiment, the polyether amine compound may comprise an amine terminated polyether compound. The amine-terminated polyether compound may include units derived from ethylene oxide, propylene oxide, butylene oxide, or some combination thereof. Suitable polyether compounds include those available from HensmeiObtained from the company Huntsman

A strain of polyetheramine.

The lubricating composition of the present disclosure also includes a boron-containing polyisobutenyl succinimide dispersant. In preparing a boron-containing polyisobutenyl succinimide dispersant, the polyisobutylene-based dispersants described herein may be post-treated by conventional methods that involve reaction with a boron compound to produce a boron-containing polyisobutenyl succinimide dispersant. Suitable boron compounds that may be used to borate the polyisobutylene-based dispersant include one or more of a variety of agents selected from the group consisting of: boric acid in its various forms, including metaboric acid (HBO2), orthoboric acid (H3BO3) and tetraboric acid (H2B4O7), boron oxide, boron trioxide and alkyl borates. In one embodiment, the borating agent is boric acid, which may be used alone or with other borating agents. Methods of making borated dispersants are known in the art. Borated dispersants may be prepared in such a way that they contain from 0.1 to 2.5 wt% boron, or from 0.1 to 2.0 wt% boron, or from 0.2 to 1.5 wt% boron, or from 0.3 to 1.0 wt% boron.

In one embodiment, the boron-containing polyisobutenyl succinimide dispersant is derived from polyisobutylene having a vinylidene content greater than 70 mole%, or greater than 80 mole%, or greater than 85 mole%, or greater than 90 mole%.

In one embodiment, the boron-containing polyisobutenyl succinimide dispersants have a number average molecular weight in the range of 1750 to 2200, or 1850 to 2150, or 1950 to 2250. The boron-containing polyisobutenyl succinimide dispersant may be present in the lubricating composition in an amount in the range 0.2 wt% to 2.1 wt%, or 0.5 wt% to 1.8 wt%, or 1 wt% to 2.1 wt%, or 1.5 wt% to 1.7 wt%. In some embodiments, the boron-containing polyisobutenyl succinimide dispersant is present in an amount to deliver at least 75ppm boron to the lubricating composition. In another embodiment, the boron-containing polyisobutenyl succinimide dispersant is present in an amount to deliver at least 100ppm boron to the lubricating composition. In one embodiment, the boron-containing polyisobutenyl succinimide dispersant is present in an amount to deliver at least 125ppm boron to the lubricating composition. In some embodiments, the boron-containing polyisobutenyl succinimide dispersant is present in an amount to deliver at least 150ppm boron to the lubricating composition. In one embodiment, the boron-containing polyisobutenyl succinimide dispersant is present in an amount to deliver at least 165ppm boron to the lubricating composition. In one embodiment, the boron-containing polyisobutenyl succinimide dispersant is present in an amount to deliver at least 200ppm boron to the lubricating composition. In one embodiment, the boron-containing polyisobutenyl succinimide dispersant is present in an amount to deliver 125 to 200ppm boron to the lubricating composition.

Metal overbased detergents:

the lubricating composition of the present disclosure comprises an overbased magnesium-based detergent and an overbased calcium-based detergent.

Metal overbased detergents, otherwise known as overbased detergents, metal-containing overbased detergents or overbased salts, are characterized by a metal content in excess of that necessary for neutralization, based on the stoichiometry of the metal with a particular acidic organic compound (i.e., the substrate that reacts with the metal). The overbased detergent may comprise one or more of the following: sulfur-free phenates, sulfur-containing phenates, sulfonates, salicylates, and mixtures thereof.

The amount of excess metal is usually expressed as the ratio of substrate to metal. The term "metal ratio" is used in the prior art and herein and is used to define the ratio of the total stoichiometric amount of metal in an overbased salt to the stoichiometric amount of metal in the salt, which is expected to result from a reaction between a hydrocarbyl-substituted organic acid; the hydrocarbyl-substituted phenol or mixture thereof will be an overbased metal compound and a basic metal compound, in accordance with known chemical reactivity and stoichiometry of the two reactants. Thus, in normal or neutral salts (i.e., soaps), the metal ratio is one, while in overbased salts, the metal ratio is greater than one, specifically, greater than 1.3. The metal ratio of the overbased detergents of the present invention may be from 5 to 30, or from 7 to 22, or at least 11.

Metal-containing detergents may also include "hybrid" detergents formed from mixed surfactant systems comprising phenate and/or sulfonate components, such as phenate/salicylate, sulfonate/phenate, sulfonate/salicylate, sulfonate/phenate/salicylate, for example, as described in U.S. patent nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. In the case of, for example, the use of a hybrid sulphonate/phenate detergent, the hybrid detergent will be considered to be equivalent to the amount of different phenate and sulphonate detergents introduced into the same amount of phenate and sulphonate soap respectively. The total base number of overbased phenates and salicylates is typically from 180 to 600 TBN. The total base number of the overbased sulfonates is typically from 250 to 600 or from 500 to 850. Overbased detergents are known in the art.

Alkylphenols are commonly used as ingredients and/or basic building blocks in overbased detergents. The alkyl phenols may be used to prepare phenate, salicylate or salicin detergents or mixtures thereof. Suitable alkylphenols may include para-substituted hydrocarbyl phenols. The hydrocarbyl group can be a straight or branched chain aliphatic group having 1 to 60 carbon atoms, 8 to 40 carbon atoms, 10 to 24 carbon atoms, 12 to 20 carbon atoms, or 16 to 24 carbon atoms. In one embodiment, the alkylphenol overbased detergent is prepared from an alkylphenol or mixture thereof that is free or substantially free (i.e., contains less than 0.1 weight percent) of tetrapropenylphenol, i.e., p-dodecylphenol or PDDP. In one embodiment, the lubricating composition of the present invention contains less than 0.3 weight percent of alkylphenols, less than 0.1 weight percent of alkylphenols, or less than 0.05 weight percent of alkylphenols.

Overbased magnesium-based detergents comprise magnesium salts, or mixtures of phenates, sulphur-containing phenates, sulphonates, salicylates and salicylates thereof. In one embodiment, the overbased magnesium-based detergent is an overbased alkylbenzene sulfonate having a metal ratio of at least 8. In one embodiment, the overbased magnesium-based detergent is present in the lubricating composition to deliver at least 300ppm or at least 330ppm or at least 400ppm magnesium to the lubricating composition. In one embodiment, the overbased magnesium-based detergent is present in the lubricating composition to deliver at least 500ppm of magnesium to the lubricating composition. In another embodiment, the overbased magnesium-based detergent is present in the lubricating composition to deliver at least 600ppm of magnesium to the lubricating composition. In another embodiment, the overbased magnesium-based detergent is present in the lubricating composition to deliver 300 to 1200ppm or 400 to 1200ppm of magnesium to the lubricating composition. In another embodiment, an overbased magnesium-based detergent is present in the lubricating composition to deliver 300 or 700 or 330 or 700 or 400 to 800 magnesium to the lubricating composition.

The overbased magnesium-based detergent may be present in the lubricating composition in an amount of from 0.1 wt% to 1.5 wt%, or from 0.2 wt% to 0.8 wt%, or from 0.2 wt% to 0.4 wt%. In some embodiments, the overbased magnesium-based detergent has a total base number ("TBN") in the range of from 200 to 600 KOH/g. In some embodiments, the overbased magnesium-based detergent has a TBN of from 300 to 500 KOH/g. In other embodiments, the overbased magnesium-based detergent has a TBN of from 600 to 750 KOH/g.

The overbased calcium-based detergents as used in the lubricating compositions of the present disclosure comprise a calcium salt, or a mixture of a salicylate and a salicylate thereof. In one embodiment, the overbased calcium-based detergent has a metal ratio of at least 5. In one embodiment, the overbased calcium-based detergent is present in the lubricating composition to deliver at least 400ppm of calcium to the lubricating composition. In one embodiment, the overbased calcium-based detergent is present in the lubricating composition to deliver at least 500ppm of calcium to the lubricating composition. In another embodiment, the overbased calcium-based detergent is present in the lubricating composition to deliver at least 600ppm of calcium to the lubricating composition. In another embodiment, the overbased calcium-based detergent is present in the lubricating composition to deliver 400 to 1200 or 750 to 1200 or 800 to 1100ppm of calcium to the lubricating composition. In another embodiment, an overbased calcium-based detergent is present in the lubricating composition to deliver 400 to 700 calcium to the lubricating composition.

The overbased calcium-based detergent may be present in the lubricating composition in an amount of from 0.1 wt% to 2.5 wt%, or from 0.3 wt% to 1.5 wt%, or from 0.4 wt% to 0.8 wt%, or from 0.4 wt% to 0.6 wt%. In some embodiments, overbased calcium salicylate detergents have a TBN in the range of 300 to 600 KOH/g. In other embodiments, the overbased calcium salicylate detergents have a TBN in the range of from 350 to 500, or from 100 to 550, or from 250 to 450 KOH/g.

In one embodiment, the calcium-based detergent is an overbased calcium salicylate detergent. In another embodiment, the calcium-based detergent is an overbased calcium salicylate detergent. In another embodiment, the calcium-based detergent is a mixture of a calcium salicylate detergent and a calcium salicylate detergent.

Molybdenum-containing material

In one embodiment, the lubricating composition may contain a molybdenum-containing material, which may also be referred to herein as a molybdenum compound. Molybdenum compounds as lubricant additives are known in the art and may be used for various functions such as antiwear agents, friction modifiers, and antioxidants. The use of molybdenum and sulfur containing compositions as antiwear and antioxidant agents in lubricating oil compositions is known. Such a material may be a molybdenum hydrocarbyl dithiocarbamate. For example, U.S. Pat. No. 4,285,822 discloses a lubricating oil composition containing a molybdenum-and sulfur-containing composition prepared by (1) combining a polar solvent, an acidic molybdenum compound, and an oil-soluble basic nitrogen compound to form a molybdenum-containing complex and (2) contacting the complex with carbon disulfide to form a molybdenum-and sulfur-containing composition. Other molybdenum-containing materials include molybdenum dihydrocarbyl dithiophosphates. However, other molybdenum-containing materials include: mollylamine compounds, as described in U.S. patent No. 6,329,327; organomolybdenum compounds formed from the reaction of a molybdenum source, a fatty oil, and a diamine, as described in U.S. Pat. No. 6,914,037; and trinuclear molybdenum-sulfur complexes, as described in U.S. patent No. 6,232,276. In one embodiment, the molybdenum compound is a molybdenum dithiocarbamate complex, a molybdenum dithiocarbamate dimeric complex, or a trinuclear molybdenum compound.

In certain embodiments, the lubricant formulation includes molybdenum-containing material in an amount to provide 40 to 1200 parts per million by weight of molybdenum to the lubricant, or alternatively 50 to 250, 50 to 500, 60 to 200, 300 to 1000, or 400 to 800 parts per million. The actual amount of molybdenum-containing material will depend in part on the nature and molecular weight of the anion or complexing agent associated with the molybdenum, in a manner that can be readily calculated. In some embodiments, the molybdenum-containing compound is present in the lubricating composition in an amount of from 0 wt% to 1.1 wt%, or from 0.01 wt% to 0.5 wt%, or from 0.03 wt% to 0.35 wt%, or from 0.07 wt% to 0.18 wt%. In some embodiments, the molybdenum-containing compound is present in the lubricating composition in an amount of 0.02 wt% to 0.2 wt%. In other embodiments, the molybdenum-containing compound is present in the lubricating composition in an amount of 0.04 wt% to 0.18 wt%.

Ashless friction modifiers:

the lubricating composition of the present disclosure may further comprise an ashless friction modifier. Friction modifiers that may be suitable for use in exemplary lubricating compositions include fatty acid derivatives, such as amines, esters, epoxides, fatty imidazolines, condensation products of carboxylic acids and polyalkylene-polyamines, and amine salts of alkylphosphoric acids. Friction modifiers are those that do not normally produce any sulfated ash under the conditions of ASTM D874. An additive is said to be "metal-free" if it does not provide metal content to the lubricant composition. As used herein, the term "fatty alkyl" or "fat" with respect to friction modifiers refers to carbon chains having from 8 to 30 carbon atoms, typically straight carbon chains.

In one embodiment, the ashless friction modifier may be represented by the formula:

wherein D and D' are independently selected from the group consisting of-O-),>NH、>NR ²³ By combining together the D and D' groups and in both>R is formed between C ═ O groups ²¹ -N<An imide group formed by radicals; e is selected from-R ²⁴ -O-R ²⁵ -、>CH ₂ 、>CHR ²⁶ 、>CR ²⁶ R ²⁷ 、>C(OH)(CO ₂ R ²² )、>C(CO ₂ R ²² ) ₂ And>CHOR ²⁸ (ii) a Wherein R is ²⁴ And R ²⁵ Is independently selected from>CH ₂ 、>CHR ²⁶ 、>CR ²⁶ R ²⁷ 、>C(OH)(CO ₂ R ²² ) And>CHOR ²⁸ (ii) a q is 0 to 10, with the proviso that when q is 1, E is not>CH ₂ And when n is 2, neither Es is>CH ₂ (ii) a p is 0 or 1; r is ²¹ Independently hydrogen or a hydrocarbyl group, typically containing 1 to 150 carbon atoms, with the proviso that when R is ²¹ P is 0 and q is greater than or equal to 1 when hydrogen is present; r ²² Is a hydrocarbyl group typically containing 1 to 150 carbon atoms; r ²³ 、R ²⁴ 、R ²⁵ 、R ²⁶ And R ²⁷ Independently a hydrocarbyl group; and R is ²⁸ Is hydrogen or a hydrocarbyl group, typically containing from 1 to 150 carbon atoms, or from 4 to 32 carbon atoms, or from 8 to 24 carbon atoms. In certain embodiments, the hydrocarbyl group R ²³ 、R ²⁴ And R ²⁵ May be straight chain or predominantly straight chain alkyl groups. In certain embodiments, the ashless friction modifier is a fatty ester, amide or imide of various hydroxy-carboxylic acids, such as tartaric acid, malic acid, lactic acid, glycolic acid, and mandelic acid. Examples of suitable materials include di (2-ethylhexyl) tartrate (i.e., di (2-ethylhexyl) tartrate), di (C) tartrate ₈ -C ₁₀ ) Di (C) ester, tartrate _12-15 ) Esters, dilinoleoyl tartrate, oleoyl triamides, and oleoyl maleimides.

In certain embodiments, the ashless friction modifier may be selected from a long chain fatty acid derivative of an amine, a fatty ester, or a fatty epoxide; fatty imidazolines, such as condensation products of carboxylic acids with polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartaric acids; a fatty alkyl tartrimide; a fatty alkyl tartaric amide; a fatty phosphate ester; a fatty phosphite; 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 hydroxyalkyl amide; metal salts of fatty acids; metal salts of alkyl salicylates; a fatty oxazoline; a fatty ethoxylated alcohol; condensation products of carboxylic acids with polyalkylene polyamines; or the reaction products of fatty carboxylic acids with guanidine, aminoguanidine, urea or thiourea and their salts.

Useful friction modifiers may also encompass materials such as: sulfurized fatty compounds and soy monoesters of olefins, sunflower oil or 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. In one embodiment, the ashless friction modifier is one or more of an ester, amide, or imide of an alpha-hydroxy carbonyl compound and mixtures thereof.

In one embodiment, the ashless friction modifier is a fatty amine, a fatty amine alkoxylate, an alkoxylated fatty amide or imide, or a combination thereof. In another embodiment, the ashless friction modifier is selected from the group consisting of ethoxylated tallow amine and ethoxylated oleamide.

The ashless friction modifier may be present in the lubricating composition in an amount of from 0.01 wt% to 1.1 wt%, or from 0.1 wt% to 0.5 wt%, or from 0.2 wt% to 0.4 wt%. In some embodiments, the ashless friction modifier is selected from one or more of ethoxylated tallow amine and ethoxylated oleyl amide and is present in the lubricating composition in an amount of from 0.01 wt% to 1.1 wt%, or from 0.1 wt% to 0.5 wt%, or from 0.2 wt% to 0.4 wt%.

Formulation additives:

the lubricating composition as described herein may further contain one or more additives as described below:

an antiwear agent:

the antiwear agent comprises a phosphorus-containing compound and a phosphorus-free compound.

Phosphorus-containing antiwear agents are well known to those skilled in the art and include metal dialkyl (dithiophosphate) phosphates, hydrocarbyl phosphites, hydrocarbyl phosphines, hydrocarbyl phosphonates, alkyl phosphate esters, (alkyl) amine or ammonium (alkyl) phosphate salts, and combinations thereof.

In one embodiment, the phosphorus-containing antiwear agent may be a metal dialkyl dithiophosphate, which may comprise zinc dialkyl dithiophosphate. Such zinc salts are commonly referred to as zinc dialkyldithiophosphates (ZDDPs) or simply Zinc Dithiophosphates (ZDPs). Which are well known and readily available to those skilled in the art of lubricant formulations. Other zinc dialkyldithiophosphates may be described as primary or secondary zinc dialkyldithiophosphates, depending on the structure of the alcohol used in their preparation. In some embodiments, the compositions of the present disclosure may comprise a zinc primary dialkyldithiophosphate. In some embodiments, the composition comprises a secondary zinc dialkyldithiophosphate. In some embodiments, the composition comprises a mixture of primary and secondary zinc dialkyldithiophosphates. In some embodiments, component (b) is a mixture of primary and secondary zinc dialkyldithiophosphates, wherein the ratio (by weight) of primary zinc dialkyldithiophosphate to secondary zinc dialkyldithiophosphate is at least 1:1, or even at least 1:1.2, or even at least 1:1.5 or 1:2, or 1: 10.

Examples of suitable metal dialkyldithiophosphates include metal salts of the formula:

R ¹ and R ² Is an independent hydrocarbyl group containing 3 to 24 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms; m is a metal of valence n, typically including zinc, copper, iron, cobalt, antimony, manganese, and combinations thereof. In one embodiment, R ¹ And R ² Is a secondary aliphatic hydrocarbyl group containing 3 to 8 carbon atoms, and M is zinc. Suitable hydrocarbyl groups may be selected from isopropyl, n-butyl, sec-butyl, pentyl (also referred to as pentyl), methylpentyl, 1, 4-diMethylbutyl (derived from 4-methylpent-2-ol), n-hexyl, isooctyl, 2-ethylhexyl, and combinations thereof.

The ZDDP may be present in the composition in an amount to deliver 0.01 wt.% to 0.12 wt.% of phosphorus to the lubricating composition. The ZDDP can be present in an amount to deliver at least 100ppm, or at least 300ppm, or at least 500ppm of phosphorus to the composition up to no more than 1200ppm, or no more than 1000ppm, or no more than 800ppm of phosphorus to the composition. Further, the ZDDP may be present in the lubricating composition in an amount to deliver 200ppm to 1000ppm, or 450ppm to 800ppm, or 600ppm to 800ppm of phosphorus to the lubricating composition.

In one embodiment, the phosphorus-containing antiwear agent may be a zinc-free phosphorus compound. The zinc-free phosphorus antiwear agent may contain sulfur or may be sulfur-free. The sulfur-free, phosphorus-containing antiwear agent comprises hydrocarbyl phosphite, hydrocarbyl phosphine, hydrocarbyl phosphonate, alkyl phosphate ester, amine phosphate salt, or ammonium phosphate salt, or mixtures thereof.

In one embodiment, the antiwear agent may be a phosphorus-free compound. Examples of suitable phosphorus-free antiwear agents include: titanium compounds, hydroxy-carboxylic acid derivatives such as esters, amides, imides or amines or ammonium salts, sulfurized olefins, (thio) carbamate-containing compounds such as (thio) carbamates, (thio) carbamate amides, (thio) carbamate ethers, alkylene-coupled (thio) carbamates and bis (S-alkyl (dithio) carbamoyl) disulfides. Suitable hydroxy-carboxylic acid derivatives include tartaric acid derivatives, malic acid derivatives, citric acid derivatives, glycolic acid derivatives, lactic acid derivatives and mandelic acid derivatives.

In one embodiment, the antiwear agent may include a tartrate or tartrimide, as disclosed in International publication WO 2006/044411 or Canadian patent CA 1183125. The tartrate or tartrimide may contain alkyl ester groups in which the sum of the carbon atoms in the alkyl groups is at least 8. In one embodiment, the antiwear agent may comprise a citrate salt as disclosed in U.S. patent application 20050198894.

The antiwear agent may be represented by the formula:

wherein Y and Y' are each independently-O-,>NH、>NR ³ or by Y and Y' groups, in both>With formation of one R between C ═ O groups ¹ -N<An imide group formed by the group; x is independently-Z-O-Z' -, or,>CH ₂ 、>CHR ⁴ 、>CR ⁴ R ⁵ 、>C(OH)(CO ₂ R ² )、>C(CO ₂ R ² ) ₂ Or is or>CHOR ⁶ (ii) a Z and Z' are independently>CH ₂ 、>CHR ⁴ 、>CR ⁴ R ⁵ 、>C(OH)(CO ₂ R ² ) And>CHOR ⁶ (ii) a n is 0 to 10, and when n is 1, X is not>CH ₂ When n is 2, neither X is>CH ₂ (ii) a m is 0 or 1; r ¹ Is an independent hydrogen or hydrocarbyl group, usually containing 1 to 150 carbon atoms, with the proviso that when R is ¹ When is hydrogen, m is 0 and n is greater than or equal to 1; r ² Is a hydrocarbyl group typically containing 1 to 150 carbon atoms; r ³ 、R ⁴ And R ⁵ Is an independent hydrocarbyl group; and R is ⁶ Independently hydrogen or a hydrocarbyl group typically containing 1 to 150 carbon atoms.

The phosphorus-free antiwear agent may be present at 0 wt% to 3 wt%, or 0.1 wt% to 1.5 wt%, or 0.5 wt% to 1.1 wt% of the lubricating composition.

The antiwear agent comprising phosphorus, or a mixture may be present at 0.15 wt% to 6 wt%, or 0.2 wt% to 3.0 wt%, or 0.5 wt% to 1.5 wt% of the lubricating composition.

Another class of additives includes oil soluble titanium compounds, as disclosed in US 7,727,943 and US 2006/0014651. The oil soluble titanium compound may serve 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 is a titanium (IV) alkoxide. The titanium alkoxide is formed from a monohydric alcohol, a polyhydric alcohol, or a mixture thereof. The monoalkanol can have 2 to 16, or 3 to 10 carbon atoms. In one embodiment, the titanium alkoxide is titanium (IV) isopropoxide. In one embodiment, the titanium alkoxide is titanium (IV) 2-ethylhexanoate. 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 is oleic acid.

Ashless antioxidant

The compositions of the present disclosure may comprise an ashless antioxidant. The ashless antioxidant may comprise one or more of the following: arylamines, diarylamines, alkylated arylamines, alkylated diarylamines, phenols, hindered phenols, sulfurized olefins, or mixtures thereof. In one embodiment, the lubricating composition comprises an antioxidant or a mixture thereof. The antioxidant may be present at least 0.9 wt.%, or 0.9 wt.% to 2.5 wt.%, or 1.1 wt.% to 2.0 wt.%, or 1.2 wt.% to 7 wt.%, or 1.2 wt.% to 6 wt.%, or 1.5 wt.% to 5 wt.% of the lubricating composition.

The diarylamine or alkylated diarylamine may be phenyl-alpha-naphthylamine (PANA), alkylated diphenylamine or alkylated phenylnaphthylamine or mixtures thereof. The alkylated diphenylamines may include dinonylated diphenylamine, nonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, didecylated diphenylamine, decyldiphenylamine, and mixtures thereof. In one embodiment, the diphenylamine may comprise nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, or mixtures thereof. In one embodiment, the alkylated diphenylamine may comprise nonyl diphenylamine or dinonyl diphenylamine. The alkylated diarylamine may comprise octyl, dioctyl, nonyl, dinonyl, decyl, or didecylphenylnaphthylamine.

The diarylamine antioxidant may be present at 0.1% to 10%, 0.35% to 5%, or even 0.5% to 2% of the lubricating composition on a weight basis.

The phenolic antioxidant may be a simple alkylphenol, a hindered phenol or a coupled phenolic compound.

Hindered phenol antioxidants generally contain secondary and/or tertiary butyl groups asA sterically hindered group. The phenolic group may be further substituted with a hydrocarbyl group (typically a straight or branched chain 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, 4-dodecyl-2, 6-di-tert-butylphenol or butyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate. In one embodiment, the hindered phenol antioxidant may be an ester and may comprise, for example, Irganox from Ciba (Ciba) ^TM L-135。

The coupled phenol typically contains two alkylphenols coupled with an alkylene group to form a bisphenol compound. Examples of suitable coupled phenol compounds include 4,4 '-methylenebis- (2, 6-di-tert-butylphenol), 4-methyl-2, 6-di-tert-butylphenol, 2' -bis- (6-tert-butyl-4-heptylphenol); 4,4' -bis (2, 6-di-tert-butylphenol), 2,2' -methylenebis (4-methyl-6-tert-butylphenol) and 2,2' -methylenebis (4-ethyl-6-tert-butylphenol).

The phenol may comprise polyhydroxy aromatic compounds and their derivatives. Examples of suitable polyhydroxy aromatic compounds include esters and amides of gallic acid, 2, 5-dihydroxybenzoic acid, 2, 6-dihydroxybenzoic acid, 1, 4-dihydroxy-2-naphthoic acid, 3, 5-dihydroxy naphthoic acid, 3, 7-dihydroxy naphthoic acid, and mixtures thereof.

In one embodiment, the phenolic antioxidant comprises a hindered phenol. In another embodiment, the hindered phenol is derived from 2, 6-di-tert-butylphenol.

In one embodiment, the lubricating composition comprises a phenolic antioxidant in the range of 0.01 wt% to 5 wt%, or 0.1 wt% to 4 wt%, or 0.2 wt% to 3 wt%, or 0.5 wt% to 2 wt% of the lubricating composition.

Sulfurized olefins are well known commercial materials and sulfurized olefins that are substantially free of nitrogen, i.e., contain no nitrogen functionality, are readily available. The olefinic compounds which can be sulfurized are diverse in nature. They contain at least one olefinic double bond, which is defined as a non-aromatic double bond; i.e. one connecting two aliphatic carbon atoms. These materials typically have sulfur bonds with 1 to 10 sulfur atoms, for example 1 to 4 or 1 or 2. Suitable sulfurized olefins include sulfurized alpha olefins having from 10 to 22 carbon atoms, sulfurized isobutylene, sulfurized diisobutylene, 4-carbobutoxycyclohexene, and combinations thereof.

Ashless antioxidants may be used alone or in combination. In one embodiment, two or more different antioxidants are used in combination such that at least 0.1 weight percent of each of the at least two antioxidants, and wherein the combined amount of ashless antioxidants is from 1.2 to 7 weight percent. In one embodiment, at least 0.25 wt.% to 3 wt.% of each ashless antioxidant may be present.

Additional metal-based detergents:

in addition to the magnesium-based and calcium-based detergents described above, the lubricating composition according to the present disclosure may further contain one or more additional metal-based detergents. Further metal based detergents would be different detergents from magnesium based and calcium based detergents even though they may contain the same metal salts, i.e. magnesium sulphonate detergent and magnesium phenate would be considered different detergents. Metal-based detergents are as described above; however, the additional metal-based detergent may be an alkali or alkaline earth metal salt, including sodium, calcium, magnesium salts, or mixtures of their phenates, sulphur-containing phenates, sulphonates, salilates and salicylates. The additional metal-based detergent may be a neutral or overbased detergent. The additional metal-based detergent may be present in the lubricating composition at 0.2 wt% to 15 wt%, or 0.3 wt% to 10 wt%, or 0.3 wt% to 8 wt%, or 0.4 wt% to 3 wt%.

Additional friction modifiers

The lubricating composition may contain one or more additional friction modifiers other than those described in the foregoing compositions or combinations thereof. Examples of one or more additional friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or epoxides; fatty imidazolines, such as condensation products of carboxylic acids with polyalkylene-polyamines; and amine salts of alkylphosphoric acids. As used herein, the term fat may mean having a C8-22 straight chain alkyl group. In one embodiment, the friction modifier may be a monoglyceride, such as glycerol monooleate, or a triglyceride, such as sunflower oil, soybean oil, or combinations thereof.

The additional friction modifier may be present in the lubricating composition at 0.01 wt% to 2 wt%, or 0.05 wt% to 1 wt%, or 0.1 wt% to 0.5 wt%.

Polymeric viscosity modifiers:

the lubricating composition may comprise a polymeric viscosity modifier, a dispersant viscosity modifier other than the present invention, or a combination thereof. Dispersant viscosity modifiers are generally understood to be functionalized, i.e., derivatized, forms of polymers similar to polymeric viscosity modifiers.

The polymeric viscosity modifier may be an olefin (co) polymer, a poly (meth) acrylate (PMA), or a mixture thereof. In one embodiment, the polymeric viscosity modifier is an olefin (co) polymer.

The olefin polymer may be derived from isobutylene or isoprene. In one embodiment, the olefin polymer is prepared from ethylene and higher olefins in the range of C3 to C10 alpha monoolefins, for example, the olefin polymer may be prepared from ethylene and propylene.

In one embodiment, the olefin polymer may be a polymer of: from 15 to 80 mol% ethylene, for example from 30 mol% to 70 mol% ethylene, and from 20 to 85 mol% of a C3 to C10 monoolefin, such as propylene, for example from 30 to 70 mol% propylene or higher monoolefin. Terpolymer variations of olefin copolymers may also be used, and may contain up to 15 mol% of a non-conjugated diene or triene. The non-conjugated diene or triene may have from 5 to about 14 carbon atoms. The non-conjugated diene or triene monomer may be characterized by the presence of a vinyl group in the structure and may include cyclic and bicyclic compounds. Representative dienes include 1, 4-hexadiene, 1, 4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1, 5-heptadiene, and 1, 6-octadiene.

In one embodiment, the olefin copolymer may be a copolymer of ethylene, propylene, and butene. The polymer may be prepared by polymerizing a mixture of monomers comprising ethylene, propylene, and butylene. These polymers may be referred to as copolymers or terpolymers. The terpolymer may comprise about 5 mol% to 20 mol% or about 5 mol% to 10 mol% structural units derived from ethylene; comprises about 60 to 90 mol% or about 60 to 75 mol% structural units derived from propylene; and from about 5 mol% to 30 mol% or from about 15 mol% to 30 mol% structural units derived from butene. The butenes may include any isomer or mixture thereof, such as n-butenes, isobutenes, or mixtures thereof. The butene may include butene-1. Commercial sources of butene may include butene-1 as well as butene-2 and butadiene. The butenes may include a mixture of butene-1 and isobutene, where the weight ratio of butene-1 to isobutene is about 1:0.1 or less. The butene can include butene-1 and is free or substantially free of isobutene.

In one embodiment, the olefin copolymer may be a copolymer of ethylene and butene. The polymer may be prepared by polymerizing a mixture of monomers comprising ethylene and butene, wherein the monomer composition is free or substantially free of propylene monomers (i.e., comprises less than 1 weight percent intentionally added monomers). The copolymer may include 30 to 50 mol% structural units derived from butene; and from 50 mol% to 70 mol% of structural units derived from ethylene. The butenes may include a mixture of butene-1 and isobutene, where the weight ratio of butene-1 to isobutene is about 1:0.1 or less. The butene may include butene-1 and be free or substantially free of isobutene.

Useful olefin polymers, especially ethylene-alpha-olefin copolymers, have a number average molecular weight in the range of 4500 to 500,000, e.g., 5000 to 100,000, or 7500 to 60,000, or 8000 to 45,000.

The formation of functionalized ethylene-alpha-olefin copolymers is well known in the art, such as those described in U.S. Pat. No. 7,790,661 column 2, line 48 to column 10, line 38. Additional details of similar functionalized ethylene-alpha-olefin copolymers are found in international publication WO2006/015130 or U.S. patent 4,863,623; 6,107,257; 6,107,258; 6,117,825, respectively; and US 7,790,661. In one embodiment, the functionalized ethylene-a-olefin copolymer may comprise those described 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 lubricating composition comprises a Dispersant Viscosity Modifier (DVM). The DVM may comprise an olefin polymer that has been modified by the addition of a polar moiety.

Olefin polymers are functionalized by modifying the polymer with the addition of polar moieties. In one useful embodiment, the functionalized copolymer is the reaction product of an olefin polymer grafted with an acylating agent. In one embodiment, the acylating agent may be an ethylenically unsaturated acylating agent. Useful acylating agents are typically α, β unsaturated compounds having at least one olefinic bond (prior to reaction) and at least one, e.g., two carboxylic acid (or anhydride thereof) groups or polar groups convertible to the carboxyl group by oxidation or hydrolysis. The acylating agent is grafted onto the olefin polymer to give two carboxylic acid functions. Examples of useful acylating agents include maleic anhydride, chloromaleic anhydride, itaconic anhydride, or reactive equivalents thereof, e.g., the corresponding dicarboxylic acids such as maleic acid, fumaric acid, cinnamic acid, (meth) acrylic acid, esters of these compounds, and acid chlorides of these compounds.

In one embodiment, the functionalized ethylene-a-olefin copolymers include olefin copolymers grafted with acyl groups further functionalized with hydrocarbyl amine, hydrocarbyl alcohol groups, amino or hydroxyl terminated polyether compounds, and mixtures thereof.

Amine functionality can be added to an olefin polymer by reacting an olefin copolymer (typically an ethylene-alpha-olefin copolymer, such as an ethylene-propylene copolymer) with an acylating agent (typically maleic anhydride) and a hydrocarbyl amine having a primary or secondary amino group. In one embodiment, the hydrocarbyl amine may be selected from aromatic amines, aliphatic amines, and mixtures thereof.

In one embodiment, the hydrocarbyl amine component may comprise at least one aromatic amine comprising at least one amino group capable of condensing with the acyl group 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 the group consisting of: (i) a nitro-substituted aniline, (ii) an amine comprising two aromatic moieties linked by: (iv) a c (O) NR-group, -c (O) O-group, -O-group, N ═ N-group, or-SO 2-group, wherein R is hydrogen or a hydrocarbon group, one of the aromatic moieties having the condensable amino group, (iii) aminoquinoline, (iv) aminobenzimidazole, (v) N, N-dialkylphenylenediamine, (vi) aminodiphenylamine (also N-phenyl-phenylenediamine), and (vii) ring-substituted benzylamine.

In another embodiment, the polar moiety added to the functionalized ethylene-a-olefin copolymer may be derived from an alkyl alcohol group containing at least one hydroxyl group capable of condensing with the acyl group to provide a pendant group and at least one additional group comprising at least one nitrogen, oxygen, or sulfur atom. The alcohol functional group may be added to the olefin polymer by reacting the olefin copolymer with an acylating agent (typically maleic anhydride) and a hydrocarbon alcohol. The hydrocarbon alcohol may be a polyol compound. Suitable hydrocarbyl polyols include ethylene and propylene glycols, Trimethylolpropane (TMP), pentaerythritol, and mixtures thereof.

In another embodiment, the polar moiety added to the functionalized ethylene-a-olefin copolymer may be an amine terminated polyether compound, a hydroxyl terminated polyether compound, and mixtures thereof. The hydroxyl-terminated or amine-terminated polyether may be selected from the group comprising: polyethylene glycol, polypropylene glycol, a mixture of one or more amine terminated polyether compounds containing units derived from ethylene oxide, propylene oxide, butylene oxide, or some combination thereof. Suitable polyether compounds include polyalkylene glycol compounds

Strain, UCON of polyether compound available from Dow Chemical ^TM Preparation of OSP strain, a polyetheramine available from Huntsman (Huntsman)

And (5) strain.

In one embodiment, the lubricating composition may comprise a poly (meth) acrylate polymer viscosity modifier. As used herein, the term "(meth) acrylate" and its cognates mean methacrylate or acrylate, as will be readily understood.

In one embodiment, the poly (meth) acrylate polymer is prepared from a monomer mixture comprising (meth) acrylate monomers having alkyl groups of different lengths. The (meth) acrylate monomer may contain an alkyl group that is a linear or branched group. The alkyl group can contain 1 to 24 carbon atoms, for example 1 to 20 carbon atoms.

The poly (meth) acrylate polymers described herein are formed from monomers derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-methylpentyl (meth) acrylate, 2-propylheptyl (meth) acrylate, 2-butyloctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, 3-isopropylheptyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, 2-isopropylheptyl (meth) acrylate, decyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl acrylate, methyl (meth) acrylate, methyl, Dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltrodecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 5-isopropylheptadecyl (meth) acrylate, 4-tert-butyloctadecyl (meth) acrylate, 5-ethyloctadecyl (meth) acrylate, 3-isopropyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, (meth) acrylates derived from unsaturated alcohols, such as oleyl (meth) acrylate; and cycloalkyl (meth) acrylates, such as 3-vinyl-2-butylcyclohexyl (meth) acrylate or bornyl (meth) acrylate.

Further examples of monomers include alkyl (meth) acrylates having long-chain alcohol-derived groups, which can be obtained, for example, by reaction of (meth) acrylic acid (by direct esterification) or methyl (meth) acrylate (by transesterification) with long-chain fatty alcohols, where reaction mixtures of esters, such as (meth) acrylates, with alcohol groups having various chain lengths are generally obtained. These fatty alcohols include menthane

7911、

7900 and

1100, a first step of processing; of Imperial Chemical Industries (ICI)

79; of Condea (now known as Sasol)

1620、

610 and

810; from Ethyl Corporation

610 and

810; of Shell AG

79、

911 and

25L; of Condea Augusta in Milan

125; from Hangao, now called German Kening

And

and of Yujin Kolman

7-11 and

91。

in one embodiment, the poly (meth) acrylate polymer includes a dispersant monomer; dispersant monomers include those monomers that can be copolymerized with the (meth) acrylate monomers and contain one or more heteroatoms in addition to the carbonyl group of the (meth) acrylate. The dispersant monomer may comprise a nitrogen-containing group, an oxygen-containing group, or a mixture thereof.

The oxygen-containing compound may comprise hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate, 4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2, 5-dimethyl-1, 6-hexanediol (meth) acrylate, 1, 10-decanediol (meth) acrylate, carbonyl-containing (meth) acrylates such as 2-carboxyethyl (meth) acrylate, carboxymethyl (meth) acrylate, oxazolidinyl ethyl (meth) acrylate, N- (methacryloyloxy) formamide, propyl (meth) acrylate, N-methacryloylmorpholine, N-methacryloyl-2-pyrrolidone, N- (2-methacryloyl-oxyethyl) -2-pyrrolidone, N-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-ethyl (meth) acrylate, N- (methacryloyloxy) methyl (meth) acrylate, N-methacryloylmorpholine, N-2-pyrrolidone, N- (2-methacryloyl-oxyethyl) -2-pyrrolidone, N- (2-pyrrolidone, N-hydroxy-methyl) acrylate, N- (2-hydroxyethyl (meth) acrylate, N-hydroxy-methyl) acrylate, N- (2-methyl) acrylate, N-methyl) methyl acrylate, N-methyl (meth) acrylate, N-methyl (meth) acrylate, N-methyl acrylate, N-2-methyl acrylate, N, or N, or N, N, N- (3-methacryloxypropyl) -2-pyrrolidone, N- (2-methacryloxypentadecyl) -2-pyrrolidone, N- (3-methacryloxy-heptadecyl) -2-pyrrolidone; glycol di (meth) acrylates such as 1, 4-butanediol (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-ethoxyethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or mixtures thereof.

The nitrogen-containing compound may be (meth) acrylamide or a nitrogen-containing (meth) acrylate monomer. Examples of suitable nitrogen-containing compounds include N, N-dimethylacrylamide, N-vinylcarboxamides such as N-vinylformamide, vinylpyridine, N-vinylacetamide, N-vinylpropionamide, N-vinylhydroxy-acetamide, N-vinylimidazole, N-vinylpyrrolidone, N-vinylcaprolactam, dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminobutylacrylamide, dimethylaminopropyl methacrylate (DMAPMA), dimethylaminopropyl acrylamide, dimethyl-aminopropyl methacrylamide, dimethylaminoethyl acrylamide or mixtures thereof.

The dispersant monomer may be present in an amount up to 5 mol% of the monomer composition of the (meth) acrylate polymer. In one embodiment, the poly (meth) acrylate is present in an amount of 0 to 5 mol%, 0.5 to 4 mol%, or 0.8 to 3 mol% of the polymer composition. In one embodiment, the poly (meth) acrylate is free or substantially free of dispersant monomers.

In one embodiment, the poly (meth) acrylate comprises a block copolymer or a tapered block copolymer. The block copolymer is formed from a monomer mixture comprising one or more (meth) acrylate monomers, wherein, for example, a discrete block of a polymer formed from a first (meth) acrylate monomer is linked to a second discrete block of a polymer formed from a second (meth) acrylate monomer. While the block copolymer has substantially discrete blocks formed from monomers in the monomer mixture, the tapered block copolymer may be comprised of a relatively pure first monomer at one end and a relatively pure second monomer at the other end. The middle of the tapered block copolymer is more of a gradient composition of the two monomers.

In one embodiment, the poly (meth) acrylate polymer (P) is a block or tapered block copolymer comprising at least one polymer block (B) that is insoluble or substantially insoluble in the base oil ₁ ) And a second polymer block (B) soluble or substantially soluble in the base oil ₂ )。

In one embodiment, the poly (meth) acrylate polymer may have a configuration selected from linear, branched, hyperbranched, crosslinked, star-shaped (also referred to as "radial"), or combinations thereof. Star or radial refers to multi-arm polymers. Such polymers include (meth) acrylate-containing polymers comprising 3 or more arms or branches, which in some embodiments contain at least about 20, or at least 50 or 100 or 200 or 350 or 500 or 1000 carbon atoms. The arms are typically attached to a multivalent organic moiety that acts as a "core" or "coupler". Multi-arm polymers may be referred to as radial or star polymers, or even "comb" polymers, or polymers that otherwise have multiple arms or branches as described herein.

The linear poly (meth) acrylates in random, block, or other form may have a weight average molecular weight (M) of 1000 to 400,000 daltons, 1000 to 150,000 daltons, or 15,000 to 100,000 daltons _w ). In one embodiment, the poly (meth) acrylate may be a linear block copolymer having a Mw of 5,000 to 40,000 daltons or 10,000 to 30,000 daltons.

Radial, crosslinked or star copolymers may be derived from linear random or diblock copolymers having molecular weights as described above. The star polymer may have a weight average molecular weight of 10,000 to 1,500,000 daltons, or 40,000 to 1,000,000 daltons, or 300,000 to 850,000 daltons.

In one embodiment, the lubricating composition may comprise a vinyl aromatic diene copolymer. The vinyl aromatic diene copolymer may be a linear or radial block copolymer. In one embodiment, the vinyl aromatic diene copolymer may be a hydrogenated styrene- (conjugated diene) block copolymer.

In various embodiments, the block copolymer may be a hydrogenated styrene-butadiene copolymer or a hydrogenated styrene-isoprene copolymer. Both block copolymers are known in the art and are disclosed, for example, in EP 2001983A for hydrogenated styrene-butadiene (Price et al) and in U.S. Pat. No. 5,490,945 for hydrogenated styrene-isoprene (Smith et al).

The butadiene block of the hydrogenated styrene-butadiene copolymer can be prepared by 1, 2-addition or 1, 4-addition, as disclosed in EP 2001983A, 1, 2-addition being preferred. The use of 1, 2-addition results in butadiene blocks having from 20 mol% to 80 mol%, or from 25 mol% to 75 mol%, or from 30 mol% to 70 mol%, or from 40 mol% to 65 mol% of repeating units of branched alkyl groups, since the initially formed pendant unsaturated or vinyl groups become alkyl branches upon hydrogenation.

The lubricating composition may comprise from 0.05 wt% to 2 wt%, or from 0.08 wt% to 1.8 wt%, or from 0.1 to 1.2 wt% of one or more polymeric and/or dispersant viscosity modifiers as described herein.

Alkoxylated hydrocarbyl phenols:

the lubricating composition described herein may further comprise an alkoxylated hydrocarbyl phenol. The alkoxylated hydrocarbyl phenol may be represented by the formula:

wherein

Each R ² Independently hydrogen or a hydrocarbyl group of 1 to 6 carbon atoms;

R ³ is hydrogen, a hydrocarbyl radical of 1 to 24 carbon atoms or is represented by-C (═ O) R ⁵ The acyl group as represented by (a) or (b),

R ⁵ is a hydrocarbyl group of 1 to 24 carbon atoms;

each R ⁴ Independently a hydrocarbyl group of 1 to 220 carbon atoms, wherein at least one R ⁴ Containing 35 to 140 or 40 to 96 carbon atoms;

n is 1 to 10; and is

m is 1 to 3.

In another embodiment, the alkoxylated hydrocarbyl phenol may be represented by the formula:

wherein each R ² Independently hydrogen or a hydrocarbyl group of 1 to 6 carbon atoms;

R ³ is hydrogen, a hydrocarbyl radical of 1 to 24 carbon atoms or is represented by-C (═ O) R ⁵ An acyl group represented by;

R ⁵ is a hydrocarbyl group of 1 to 24 carbon atoms;

R ⁴ is a polyisobutenyl group having a number average molecular weight of 550 to 2300; and is provided with

n is 1 to 10.

In some embodiments, the alkoxylated hydrocarbyl phenol may be present in an amount of from 0.01 wt% to 5 wt%, or from 0.05 wt% to 3 wt%, or from 0.1 wt% to 1.5 wt% of the lubricating composition. In other embodiments, the alkoxylated hydrocarbyl phenol is present in an amount of 0.1 wt% to 1.5 wt% of the lubricating composition.

Other performance additives:

various embodiments of the compositions disclosed herein may optionally include one or more additional performance additives. These additional performance additives may include one or more metal deactivators, friction modifiers, corrosion inhibitors, extreme pressure agents, foam inhibitors, demulsifiers, pour point depressants, seal swell agents, and any combination or mixture thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives, and often a set of multiple performance additives. However, such performance additives are included based on the application of the lubricating composition, and the particular performance additives and their therapeutic rates will be apparent to one of ordinary skill in the art in view of this disclosure.

In one embodiment, the lubricating composition may further include a molybdenum compound. The molybdenum compound may be selected from the group consisting of: molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof. The molybdenum compound may provide 0 to 1000ppm, or 5 to 1000ppm, or 10 to 750ppm, or 5ppm to 300ppm, or 20ppm to 250ppm molybdenum to the lubricating composition.

Other performance additives such as corrosion inhibitors include those described in paragraphs 5 to 8 of U.S. application No. US05/038319, publication No. WO2006/047486, octyl octanoamide, condensation products of dodecenyl succinic acid or anhydride, and condensation products of fatty acids such as oleic acid with polyamines. In one embodiment, the corrosion inhibitor comprises

(registered trademark of the Dow chemical company) corrosion inhibitors.

The corrosion inhibitor may be a homopolymer or copolymer of propylene oxide.

The corrosion inhibitors are described in more detail in The product Manual published by The Dow Chemical Company under The Table number 118-01453-0702 AMS. The product manual is entitled "SYNALOX Lubricants, High Performance polyethylene glycols for Demanding Applications" (SYNALOX Lubricants, High-Performance polyols for Demanding Applications).

The lubricating composition may also contain a metal deactivator including a benzotriazole derivative (typically tolytriazole), a dimercaptothiadiazole derivative, 1,2, 4-triazole, benzimidazole, 2-alkyldithiobenzothiazole or 2-alkyldithiobenzothiazole; a foam inhibitor comprising a copolymer of ethyl acrylate and 2-ethylhexyl acrylate and vinyl acetate; demulsifiers comprising trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides, and (ethylene oxide-propylene oxide) polymers; and pour point depressants comprising maleic anhydride-styrene esters, polymethacrylates, polyacrylates, or polyacrylamides.

Pour point depressants useful in the lubricating compositions disclosed herein also comprise a polyalphaolefin, an ester of maleic anhydride-styrene, a poly (meth) acrylate, a polyacrylate, or a polyacrylamide.

In various embodiments, the lubricating composition may have a composition as set forth in the following table:

in one embodiment, the lubricating composition may have: (i) a sulfur content of 0.3 wt.% or less, (ii) a phosphorus content of 0.15 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 may have: (i) a sulfur content of 0.3 wt.% or less, (ii) a phosphorus content of 0.09 wt.% or less, and (iii) a sulfated ash content of 0.5 wt.% to 0.9 wt.% or less. In another embodiment, the lubricating composition may have at least one of: (i) a sulfur content of 0.2 wt.% to 0.4 wt.% or less, (ii) a phosphorus content of 0.05 wt.% to 0.15 wt.% or less, and (iii) a sulfated ash content of 0.5 wt.% to 1.5 wt.% or less.

The lubricating composition disclosed herein has a kinematic viscosity at 100 ℃ of from 5 to 12cSt (mm) ² S) and a kinematic viscosity at 40 ℃ of 40 to 50cSt (mm) ² In s). In another embodiment, the lubricating composition has a kinematic viscosity at 100 ℃ of 6 to 10cSt (mm) ² S) and a kinematic viscosity at 40 ℃ of from 40 to 47cSt (mm) ² /s)。

The lubricating composition as described herein has a high temperature high shear viscosity (HTHS) of less than 2.7mPa-s measured at 150 ℃ according to ASTM D4683. In one embodiment, the HTHS viscosity is less than 2.65 mPa-s. In another embodiment, the HTHS of the lubricating composition is less than 2.5 mPa-s. In another embodiment, the HTHS of the lubricating composition is less than 2.3 mPa-s.

In another embodiment, the HTHS of the lubricating composition is 1.5 to 2.7 mPa-s. In another embodiment, the HTHS of the lubricating composition is 1.5 to 2.5 mPa-s. In another embodiment, the HTHS of the lubricating composition is 1.5 to 2.2 mPa-s. In another embodiment, the HTHS of the lubricating composition is 1.8 to 2.5 mPa-s. In another embodiment, the HTHS of the lubricating composition is 1.8 to 2.2 mPa-s. In another embodiment, the HTHS of the lubricating composition is 1.9 to 2.3 mPa-s. In another embodiment, the HTHS of the lubricating composition is 1.9 to 2.1 mPa-s.

The lubricating composition described herein can have an evaporation loss (also referred to as Noack volatility) of less than 20 wt%, as measured by ASTM D5800 and CEC L-40-93. In one embodiment, the lubricating composition has an evaporation loss of less than 10 wt% to 20 wt%, or 11 wt% to 19 wt%.

In one embodiment, the lubricating composition described herein has an HTHS of 1.5 to 2.2 and a Noack volatility of 9 to 13 weight percent, as measured by ASTM D5800 and CEC L-40-93. In another embodiment, the lubricating composition described herein has an HTHS of 1.5 to 2.2, and a Noack volatility from 10 wt% to 12 wt%, as measured by ASTM D5800 and CEC L-40-93. In another embodiment, the lubricating composition described herein has an HTHS of 1.9 to 2.1 and a Noack volatility of 9 wt.% to 13 wt.%, as measured by ASTM D5800 and CEC L-40-93. In another embodiment, the lubricating composition described herein has an HTHS of 1.9 to 2.1 and a Noack volatility of 10 wt.% to 12 wt.%, as measured by ASTM D5800 and CEC L-40-93.

In one embodiment, the lubricating composition described herein has an HTHS of 1.8 to 2.2, and a Noack volatility of 13 wt% to 20 wt%, as measured by ASTM D5800 and CEC L-40-93. In one embodiment, the lubricating composition described herein has an HTHS of 1.8 to 2.2 and a Noack volatility of 14 wt% to 19 wt%, as measured by ASTM D5800 and CEC L-40-93. In one embodiment, the lubricating composition described herein has an HTHS of 1.9 to 2.1 and a Noack volatility of 13 wt% to 20 wt%, as measured by ASTM D5800 and CEC L-40-93. In one embodiment, the lubricating composition described herein has an HTHS of 1.9 to 2.1 and a Noack volatility of 14 wt% to 19 wt%, as measured by ASTM D5800 and CEC L-40-93.

The lubricating composition containing the dispersant additive package has a TBN of 4 to 14mg KOH/g. In another embodiment, the lubricating TBN is from 5 to 10 or from 6 to 8mg KOH/g.

The present disclosure further provides a method of lubricating an internal combustion engine by supplying to the engine a lubricating composition as disclosed herein. In one embodiment, the internal combustion engine is a gasoline fueled engine. In another embodiment, the internal combustion engine is a diesel engine. Typically, a lubricant is added to the lubrication system of an internal combustion engine, and then during its operation, the lubricating composition is delivered to critical portions of the engine that require lubrication.

The above lubricating composition may be used in internal combustion engines having steel or aluminium surfaces, typically steel surfaces, and may also be coated, for example, with a diamond-like carbon (DLC) coating.

Internal combustion engines may be equipped with an emission control system or a turbocharger. Examples of emission control systems include Diesel Particulate Filters (DPF), Gasoline Particulate Filters (GPF), systems employing Selective Catalytic Reduction (SCR), and combinations thereof.

The internal combustion engine may be of the port injection (PFI) or direct injection type. In one embodiment, the internal combustion engine is a gasoline direct injection engine (GDI). Direct injection engines are characterized by direct injection of fuel, such as gasoline, into the cylinders. This is different from Port Fuel Injection (PFI) and may result in higher efficiency, higher compression, and/or higher mean effective brake pressure than a similar PFI engine.

In one embodiment, the internal combustion engine is equipped with a turbocharger, a supercharger, or a combination thereof. Both turbochargers and superchargers are used to increase the volumetric efficiency of the engine, i.e., the volume of air that fills the cylinders relative to the volume of the cylinders. Turbochargers and superchargers operate by forcing more air into the cylinders, thereby producing higher torque at a given displacement, and thus higher BMEP. In addition to improving engine efficiency, turbochargers and superchargers also increase the likelihood of random pre-ignition, especially at lower speeds.

The lubricating composition disclosed herein may be used to lubricate an internal combustion engine operating at a Brake Mean Effective Pressure (BMEP) of greater than 12 bar and a speed of less than 3,000rpm by supplying the lubricating composition to the engine. In some embodiments, the internal combustion engine is a Turbocharged Direct Injection (TDi) engine.

Method embodiments of the present disclosure may include supplying to an internal combustion engine a lubricating composition comprising: an oil of lubricating viscosity comprising at least 50 wt% of a group IV base oil; a boron-containing polyisobutenyl succinimide dispersant; a boron-free polyisobutenyl succinimide dispersant; an amount of overbased magnesium-based detergent to deliver at least 300ppm or at least 400ppm magnesium to the lubricating composition; an amount of an overbased calcium-based detergent to deliver at least 400ppm of calcium to the lubricating composition; an ashless friction modifier; and optionally, other additives, wherein the lubricating composition has a High Temperature High Shear (HTHS) viscosity of less than 3.0mpa.s according to ASTM D4683.

As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the rest of the molecule and having a predominantly hydrocarbon character including one or more double bonds. Examples of hydrocarbyl groups include: hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents and aromatic substituents substituted with aromatic, aliphatic, and alicyclic groups, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);

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 (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); hetero substituents, that is, substituents that, while having a predominantly hydrocarbon character in the context of this invention, contain other atoms in the ring or chain otherwise composed of carbon atoms in addition to carbon, and encompass substituents such as pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. Typically, for every ten carbon atoms in the hydrocarbyl group, no more than two or no more than one non-hydrocarbon substituent will be present; alternatively, non-hydrocarbon substituents may not be present in the hydrocarbyl group.

The present disclosure is not limited to the particular embodiments described herein, which are intended as illustrations of various aspects. It will be apparent to those skilled in the art that many modifications and variations can be made to the technology of the present invention without departing from the spirit or scope thereof. Functionally equivalent methods and components within the scope of the present disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. The disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds or compositions, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

As used herein, the singular forms "a", "an" and "the" include plural references unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Nothing in this disclosure should be construed as an admission that the embodiments described in this disclosure are not entitled to antedate such disclosure by virtue of prior invention. The term "including" as used herein means "including but not limited to".

Although various compositions, methods, and devices have been described in terms of "comprising" various components or steps (which are to be interpreted as meaning "including, but not limited to"), the compositions, methods, and devices may also "consist essentially of" or "consist of" the various components and steps, and such terms should be interpreted as defining an inherently closed group of members.

With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. Various singular/plural permutations may be expressly set forth herein for the sake of clarity.

It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as "open" terms (e.g., the term "including" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles "a" or "an" limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the claim includes the introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an" (e.g., "a" and/or "an" should be interpreted to mean "at least one" or "one or more"); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the bare recitation of "two recitations," without other modifiers, means at least two recitations, or two or more recitations). Further, where a convention analogous to "at least one of A, B and C, etc." is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B and C" would include, but not be limited to, systems having only a, only B, only C, A and B together, a and C together, B and C together, and/or A, B and C together, etc.). In cases where a convention analogous to "A, B or at least one of C, etc." is used, in general, such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B or C" would include but not be limited to systems having a alone, B alone, C, A and B together alone, a and C together, B and C together, and/or A, B and C together, etc.). Those skilled in the art will further appreciate that virtually any disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase "a or B" will be understood to include the possibility of "a" or "B" or "a and B".

In addition, where features or aspects of the present disclosure may be described in terms of Markush (Markush) groups, those skilled in the art will recognize that the present disclosure is thereby also described in terms of any single member or subgroup of members of the Markush group.

As will be understood by those skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily identified as fully descriptive and the same range can be broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein may be readily broken down into a lower third, a middle third, and an upper third, etc. Those skilled in the art will also understand that all language, such as "at most," "at least," and the like, includes the recited number and refers to ranges that can be subsequently broken down into the sub-ranges discussed above. Finally, as will be understood by those of skill in the art, a range encompasses each individual member. Thus, for example, a group having 1-3 wt.% refers to a group having 1,2, or 3 wt.%. Similarly, a group having 1-5 wt.% refers to a group having 1,2, 3, 4, or 5 wt.%, and so on, including all points therebetween.

As used herein, the term "about" means that the value of a given amount is within ± 20% of the stated value. In other embodiments, the values are within ± 15% of the stated values. In other embodiments, the values are within ± 10% of the stated values. In other embodiments, the values are within ± 5% of the stated values. In other embodiments, the values are within ± 2.5% of the stated values. In other embodiments, the values are within ± 1% of the stated values.

As used herein, "weight percent," unless otherwise specified, refers to weight percent based on the total weight of the composition.

The present disclosure is applicable to lubricant formulations that exhibit one or more of improved cleanliness ratings, improved fuel economy, reduced low speed pre-ignition ("LSPI"), and improved TBN retention relative to lubricant formulations that do not include the additives of the lubrication formulations of the present disclosure. It is expected that cleanliness levels, improved fuel economy, reduced low speed pre-ignition ("LSPI"), and improved TBN retention can be measured and compared under industry standard tests, as will be apparent to one of ordinary skill in the art in view of this disclosure. The foregoing may be better understood by reference to the following examples:

examples

Embodiments will be further illustrated by the following examples, which illustrate particularly advantageous embodiments. While examples are provided to illustrate certain embodiments, they are not intended to be limiting.

Lubricating composition

A series of 0W-12 engine additive formulations were prepared containing the above described dispersant and detergent additives as well as conventional additives including friction modifiers, antiwear agents, polymeric viscosity modifiers, antioxidants (a combination of phenolic acid esters and diarylamines), and other performance additives as described below (table 1). The calcium, magnesium, phosphorus, sulfur and ash contents of each example are also partially listed in the table to indicate that each example has similar amounts of these materials to make an appropriate comparison of comparative examples and examples according to embodiments described herein. High Temperature High Shear (HTHS) viscosity (CEC L-36-90) and Noack evaporation loss (CEC L-40-93) were also included to further illustrate the effect of base oils and additives.

¹ TABLE 1 lubricating compositions

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

2-overbased calcium salicylate (TBN 485mg KOH/g; metal ratio 5.5)

3-overbased magnesium alkylbenzenesulfonate (TBN 690mg KOH/g: metal ratio 14)

4-Polyisobutenylsuccinimide dispersants prepared by the chlorine method from 980Mn PIB (TBN 115mg KOH/g)

Composition of 5-oleyl tartrate imide, trialkyl borate and succinimide dispersant (0.46% boron)

6-nonylated diphenylamines

7-additional additives used in the examples contain antifoam, pour point depressant, and a quantity of diluent oil

The ability of the lubricating compositions to improve engine cleanliness (deposits), improve fuel economy, and improve corrosion control was evaluated. Cleanliness was evaluated in the Volkswagen TDI deposit cleanliness Engine test (CEC L-78-99) and the Volkswagen FSI Valve deposit test (PV 1481). The Volkswagen TDI engine test rated the piston cleanliness (excellent) and ring adhesion of the lubricant. Fuel economy was evaluated in the audi EA888 fuel economy test (PV 1496). Corrosion control was evaluated in the PV1401 humidity cabinet test.

TABLE 2 deposit and Fuel Economy Performance test

Oxidation and corrosion control were also evaluated in the biodiesel oxidation bench test (CEC L-109) and High Temperature Corrosion Bench Test (HTCBT) according to ASTM D6594. In the biodiesel oxidation test, kinematic viscosity was measured at 100 ℃ at various time intervals at the beginning of and during the test to evaluate the oxidation resistance of the lubricating oil composition when contaminated with the biodiesel fuel fraction (B10).

¹ TABLE 3 lubricating compositions

2-overbased calcium salicylate (TBN 485mg KOH/g; metal ratio 5.5)

3-overbased calcium salicylate (TBN 300mg KOH/g: metal ratio 2.9)

4-overbased magnesium alkylbenzenesulfonate (TBN 690mg KOH/g: metal ratio 14)

5-Polyisobutenylsuccinimide dispersants prepared by the chlorine method from 980Mn PIB (TBN 115mg KOH/g)

Composition of 6-oleyl tartrate imide, trialkyl borate and succinimide dispersant (0.46% boron)

7-nonylated diphenylamine.

8-additional additives used in the examples include defoamers, pour point depressants, corrosion inhibitors, and include a quantity of diluent oil.

TABLE 4 Oxidation and Corrosion testing

	EX1	EX2	EX6	EX7	EX8
						Biodiesel oxidation (CEC L-109)
KV 100-test Start (m) ² /s)	5.68	5.66	5.39	5.29	5.31
						KV100 at 72 hours	6.66	6.97	6.08	6.13	6.02
Increase in KV at 72 hours%	17.1	23.1	14.9	16.08	13.4
						KV100 at 144 hours	7.57	8.79	6.8	6.91	6.81
Increase in KV at 144 hours%	33.1	55.1	28.5	30.65	28.2
						KV100 at 168 hours	8.06	10.03	7.08	7.27	7.23
Increase in KV at 168 hours%	41.9	77.2	33.8	37.5	36.0
						KV100 at 216 hours	9.59	15.73	7.83	8.19	8.49
Increase in KV at 216 hours%	68.6	177.8	48.0	54.9	59.9
						HTCBT(ASTM D6594)
Copper change (ppm)	7.8	13	55	10	12
						Lead variation (ppm)	15.9	14.6	31	19	7
Grade of copper strip	1A	1A	4A	1A	1B

TABLE 5 deposit, Oxidation, and Fuel Economy Performance tests

	EX9	EX10	EX11	EX12	EX13	EX14
							VW TDI
Average piston cleanliness rating	57	61	55	53	54	59
							Ring bonding	0	0	0	0	0	0
Audi EA888
							Oil consumption-before reference test (g)	575.9	580.5	582.2	580.0	577.9	578.6
Oil consumption-candidate test (g)	562.5	572.5	567.1	572.7	563.2	569.6
							Oil consumption-after reference test (g)	575.4	580.9	581.6	580.5	578.8	577.9
Difference pre-reference-candidate (g)	13.39	7.96	15.1	7.35	14.73	8.98
							Fuel economy improvement (%)	2.32	1.37	2.59	1.27	2.55	1.55
Base drift (%)	0.10	0.08	0.10	0.07	0.15	0.12
							Biodiesel Oxidation (CEC L-109)	575.92	580.48	582.18	580.05	577.9
KV 100-test Start (m) ² /s)	5.42	7.10	5.29	7.16		7.18
							KV100 at 72 hours	6.24	8.22	6.08	8.24		8.11
Increase in KV at 72 hours%	15.1	15.9	14.9	15.1		12.9
							KV100 at 144 hours		9.66	6.77	9.16		9.35
Increase in KV at 144 hours%		36.1	28.0	27.9		30.2
							KV100 at 168 hours		10.4	7.06	9.65		10.0
Increase in KV at 168 hours%		46.1	33.4	34.8		39.3
							KV100 at 216 hours		12.3	7.80	10.8		12.3
Increase in KV at 216 hours%		73.0	47.4	50.2		71.7

The results show that compositions with lower HTHS viscosity provide improved fuel economy without sacrificing oxidation durability, cleanliness or corrosion control.

Claims

1. An internal combustion engine lubricating composition comprising:

an oil of lubricating viscosity;

a boron-containing additive;

a boron-free polyisobutenyl succinimide dispersant;

an amount of overbased magnesium-based detergent to deliver at least 300ppm of magnesium to the lubricating composition;

an amount of an overbased calcium-based detergent to deliver at least 400ppm of calcium to the lubricating composition; and

an ashless friction modifier for a friction modifier,

wherein the lubricating composition has a High Temperature High Shear (HTHS) viscosity of less than 2.7mPa-s according to ASTM D4683.

2. The composition of claim 1, wherein the oil of lubricating viscosity comprises at least 60, or at least 70, or at least 80 weight percent of group IV base oil.

3. The lubricating composition of claim 1 or claim 2, wherein the boron-containing additive is a boron-containing succinimide dispersant.

4. The lubricating composition of claim 3, wherein the boron-containing succinimide dispersant is derived from a polyisobutylene having a vinylidene content of greater than 70 mol%.

5. The lubricating composition of claim 4, wherein the boron-containing succinimide is derived from a polyolefin having a number average molecular weight of 1750 to 2200.

6. The lubricating composition of any preceding claim, wherein the boron-containing succinimide dispersant is present in the lubricating composition in an amount of 0.2 wt% to 2.1 wt%.

7. The lubricating composition of any one of claims 3 to 6, wherein the boron-containing succinimide dispersant is present in the lubricating composition in an amount of 0.5 wt% to 1.8 wt%.

8. The lubricating composition of any one of claims 3 to 7, wherein the boron-containing succinimide dispersant is present in the lubricating composition in an amount of 1 to 2.1 wt%.

9. The lubricating composition of any one of claims 3 to 8, wherein the boron-containing succinimide dispersant is present in the lubricating composition in an amount of 1.5 wt% to 1.7 wt%.

10. The lubricating composition of any preceding claim, wherein the boron-free polyisobutenyl succinimide dispersant has a number average molecular weight of 750 to 2500.

11. The lubricating composition of any preceding claim, wherein the boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount of from 0.5 wt% to 6.5 wt%.

12. The lubricating composition of any preceding claim, wherein the boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount of from 0.7 wt% to 6.5 wt%.

13. The lubricating composition of any preceding claim, wherein the boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount of from 1.5 wt% to 4.1 wt%.

14. The lubricating composition of any preceding claim, wherein the boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount of from 2.0 wt% to 3.1 wt%.

15. The lubricating composition of any preceding claim, wherein the boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount from 2.5 wt% to 2.8 wt%.

16. The lubricating composition of any preceding claim, wherein the boron-free polyisobutenyl succinimide dispersant comprises a first boron-free polyisobutenyl succinimide dispersant having a number average molecular weight of 750 to 1750 and a second boron-free polyisobutenyl succinimide dispersant having a number average molecular weight of 1950 to 2500.

17. The lubricating composition of claim 14, wherein the first boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount of 0.5 to 4.5, and the second boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount of 0.2 to 2.0.

18. The lubricating composition of claim 13, wherein the first boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount of 1.8 to 2.5 and the second boron-free polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount of 0.5 to 0.8.

19. The lubricating composition of any preceding claim, wherein the overbased magnesium-based detergent is present in the lubricating composition in an amount of 0.1 to 1.5 wt%.

20. The lubricating composition of any preceding claim, wherein the overbased magnesium-based detergent is present in the lubricating composition in an amount of 0.2 wt% to 0.8 wt%.

21. The lubricating composition of any preceding claim, wherein the overbased magnesium-based detergent is present in the lubricating composition in an amount of from 0.2 wt% to 0.4 wt%.

22. The lubricating composition of any preceding claim, wherein the overbased magnesium based detergent is an overbased alkylbenzene sulfonate detergent having a metal ratio of at least 8.

23. The lubricating composition of any preceding claim, wherein the overbased magnesium-based detergent has a TBN (KOH/g) of greater than 200.

24. The lubricating composition of any preceding claim, wherein the overbased magnesium based detergent has a TBN (KOH/g) of from 200 to 600.

25. The lubricating composition of any preceding claim, wherein the overbased magnesium-based detergent has a TBN (KOH/g) of from 300 to 500.

26. The lubricating composition of any preceding claim, wherein the overbased magnesium-based detergent delivers from 300ppm to 800ppm magnesium to the lubricating composition.

27. The lubricating composition of any preceding claim, wherein the overbased magnesium-based detergent delivers from 330ppm to 700ppm magnesium to the lubricating composition.

28. The lubricating composition of any one of claims 1 to 25, wherein the overbased magnesium-based detergent delivers at least 400ppm magnesium to the lubricating composition.

29. The lubricating composition of any preceding claim, wherein the overbased calcium-based detergent is present in the lubricating composition in an amount of from 0.1 wt% to 2.5 wt%.

30. The lubricating composition of any preceding claim, wherein the overbased calcium-based detergent is present in the lubricating composition in an amount of from 0.3 wt% to 1.5 wt%.

31. The lubricating composition of any preceding claim, wherein the overbased calcium-based detergent is present in the lubricating composition in an amount of from 0.6 wt% to 1.1 wt%.

32. The lubricating composition of any preceding claim, wherein the overbased calcium-based detergent has a metal ratio of at least 5.

33. The lubricating composition of any preceding claim, wherein the overbased calcium-based detergent has a TBN (KOH/g) of 100 to 550.

34. The lubricating composition of any preceding claim, wherein the overbased calcium-based detergent has a TBN (KOH/g) of 250 to 450.

35. The lubricating composition of any preceding claim, wherein the overbased calcium-based detergent delivers from 750ppm to 1200ppm of calcium to the lubricating composition.

36. The lubricating composition of any preceding claim, wherein the overbased calcium-based detergent delivers 800ppm to 1100ppm of calcium to the lubricating composition.

37. The lubricating composition of any preceding claim, wherein the overbased calcium-based detergent is selected from an overbased calcium salicylate (calcium salicylate) detergent, an overbased calcium salicylate detergent, or a mixture thereof.

38. The lubricating composition of any preceding claim, wherein the overbased calcium-based detergent is an overbased calcium salicylate detergent.

39. The lubricating composition of any preceding claim, wherein the overbased calcium-based detergent comprises a mixture of an overbased calcium salicylate detergent and an overbased calcium salicylate detergent.

40. The lubricating composition of any preceding claim, further comprising an ashless antioxidant.

41. The lubricating composition of claim 40, wherein the ashless antioxidant is present in an amount of 0.2 wt% to 2.1 wt%.

42. The lubricating composition of any one of claims 40 to 41, wherein the ashless antioxidant is present in an amount of 0.3 wt% to 1.5 wt%.

43. The lubricating composition of any preceding claim, wherein the ashless friction modifier is an ethoxylated amine.

44. The lubricating composition of 43, wherein the ethoxylated amine is selected from the group consisting of ethoxylated tallow amine and ethoxylated oleyl amide.

45. The lubricating composition of any preceding claim, wherein the ashless friction modifier is present in the lubricating composition in an amount of from 0.01 wt% to 1.1 wt%.

46. The lubricating composition of any preceding claim, wherein the ashless friction modifier is present in the lubricating composition in an amount of from 0.1 wt% to 0.5 wt%.

47. The lubricating composition of any preceding claim, wherein the ashless friction modifier is present in the lubricating composition in an amount of from 0.2 wt% to 0.4 wt%.

48. The lubricating composition of any preceding claim further comprising an amount of zinc dialkyldithiophosphate antiwear agent to deliver 200 to 1000ppm of phosphorus to the lubricating composition.

49. The lubricating composition of claim 48 wherein the zinc dialkyldithiophosphate antiwear agent delivers 450 to 800ppm phosphorus to the lubricating composition.

50. The lubricating composition of claim 48 wherein the zinc dialkyldithiophosphate antiwear agent delivers 600 to 800ppm phosphorus to the lubricating composition.

51. The lubricating composition of any preceding claim, wherein the lubricating composition is free or substantially free of tetrapropenylphenol (pddp) and derivatives thereof.

52. The lubricating composition of any preceding claim, further comprising an alkoxylated hydrocarbyl phenol.

53. The lubricating composition of claim 52, wherein the alkoxylated hydrocarbyl phenol is represented by the formula:

R ³ is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms or is represented by-C (═ O) R ⁵ An acyl group represented by;

R ⁵ is a hydrocarbyl group of 1 to 24 carbon atoms;

n is 1 to 10.

54. The lubricating composition of any one of claims 52 or 53, wherein the alkoxylated hydrocarbyl phenol is present in the lubricating composition in an amount in the range of from 0.01 wt% to 5 wt%, or from 0.05 wt% to 3 wt%, or from 0.1 wt% to 1.5 wt%.

55. The lubricating composition of any preceding claim, wherein the lubricating composition has an HTHS of less than 2.5.

56. The lubricating composition of any preceding claim, wherein the lubricating composition has an HTHS of between 1.5 and 2.2.

57. The lubricating composition of any preceding claim, wherein the lubricating composition has an HTHS of between 1.9 and 2.1.

58. The lubricating composition of any one of claims 56 to 57, wherein the lubricating composition further comprises a Noack volatility of from 9 wt% to 13 wt% or from 10 wt% to 12 wt% according to one or more of ASTM D5800 and CED L-40-93.

59. The lubricating composition of any one of claims 1 to 56, wherein the lubricating composition has an HTHS of between 1.8 and 2.2.

60. The lubricating composition of claim 59, wherein the lubricating composition further comprises a Noack volatility of 13 to 20 wt% or 14 to 19 wt% according to one or more of ASTM D5800 and CED L-40-93.

61. A method of lubricating an internal combustion engine, the method comprising supplying to the internal combustion engine a lubricating composition according to any preceding claim.

62. The method of claim 61, wherein the internal combustion engine is selected from the group consisting of a gasoline internal combustion engine and a diesel internal combustion engine.

63. Use of a composition according to any one of claims 1 to 60 in an internal combustion engine for achieving one or more of: improved fuel economy, reduced corrosion, reduced oxidation, improved cleanliness, improved TBN retention, reduced LSPI, and improved wear performance.