JP2023542926A - Diesel engine lubricating composition and method of use thereof - Google Patents

Abstract

The present disclosure provides diesel engine lubricating compositions and methods of lubricating a diesel engine by providing the engine with the lubricating compositions disclosed herein. The lubricating compositions disclosed herein have a total sulfated ash content of 0.3 to 1.1 wt. % total alkaline earth metal soap and less than 2.7 mPa·s HTHS measured according to ASTM D4683. The lubricating composition can be used to improve one or more of fuel economy and wear protection in diesel engines, particularly heavy duty diesel engines.

Description

The present disclosure provides diesel engine lubricating compositions and methods of lubricating a diesel engine by providing the engine with the lubricating compositions disclosed herein. The lubricating compositions disclosed herein can be used to improve one or more of fuel economy and wear protection, particularly in diesel engines, including heavy duty diesel engines.

Lubricating oil compositions are used for the smooth operation of internal combustion engines. Engine oils for internal combustion engines inter alia (i) lubricate various sliding interfaces between piston rings and cylinder liners, crankshaft and connecting rod bearings, and valve drive mechanisms, including cams and valve lifters; ii) cools the engine; (iii) cleans and disperses combustion products; and (iv) serves to prevent corrosion and resultant rust formation. The stringent requirements for high performance engines in recent years have meant greater demands from the lubricants used in such engines.

There is increasing interest in improving the fuel efficiency of internal combustion engines. Vehicle manufacturers have improved fuel economy through improvements that take advantage of advances in engine design, lubricants that provide better oxidation stability, wear protection, and reduced friction. Heavy duty diesel vehicle operators have been hesitant to adopt lower viscosity grades of engine oil to improve fuel economy. Durability, ie, the ability to keep a vehicle on the road for long periods of time and mileage, is and remains a major concern. Therefore, the most widely used viscosity grades for on-highway heavy duty diesel vehicles were SAE 15W-40, 10W-30, and 5W-30. In recent years, there has been a strong desire to improve the fuel economy of heavy-duty diesel vehicles. Therefore, there is a need to improve the fuel economy of diesel engines without compromising engine durability or adversely affecting lubricant performance, including deposit and soot control and oxidation and corrosion resistance. This is particularly relevant for viscosity grades lighter than the SAE 5W-30 viscosity grade, particularly 0W-20, 0W-16, and 0W12 viscosity grades.

Therefore, to develop lubricating compositions that can be used in diesel engines that can operate under harsh conditions and loads, while reducing the effects of soot and soot-related wear, as well as cleanliness, deposits and better fuel economy. I am interested in

The present disclosure provides an internal combustion engine (typically compressed ignition engine).

The lubricating composition comprises an oil of lubricating viscosity having greater than 50 weight percent (sometimes referred to as "wt%") Group III base oil, Group IV base oil, Group V base oil, or mixtures thereof. The composition further comprises a first PIB succinimide dispersant derived from a PIB of 1800-2500 Mn and a second PIB succinimide dispersant derived from a PIB having an Mn of less than 1600. However, at least one of the first PIB succinimide dispersant and the second PIB succinimide dispersant does not contain boron. The composition further comprises an alkaline earth metal salicylate detergent, such as calcium salicylate, and an alkaline earth metal sulfonate, the alkaline earth metal soap being from 0.1% to 1.2% by weight of the composition. and a phosphorus antiwear agent present in an amount to provide 300 to 900 ppm phosphorus in the lubricating composition.

The lubricating composition has a sulfated ash content of 0.3 to 1.1% by weight, a kinematic viscosity at 100° C. of less than 8.3 cSt, and a total alkaline earth metal soap of 0.6% to 2.1% by weight. and an HTHS of less than 2.7 mPa·s measured according to ASTM D4683.

The present disclosure provides diesel engine lubricating compositions and methods of using the same. The lubricating composition comprises an oil of lubricating viscosity having greater than 50 weight percent of a Group III base oil, a Group IV base oil, a Group V base oil, or mixtures thereof, and a first PIB derived from a PIB of 1800 to 2500 Mn. a succinimide dispersant and a second PIB succinimide dispersant derived from a PIB having an Mn of less than 1600, wherein at least one of the first PIB succinimide dispersant and the second PIB succinimide dispersant is boron-based. The composition further comprises an alkaline earth metal salicylate detergent and an alkaline earth metal sulfonate present in an amount to provide from 0.1% to 1.2% by weight of an alkaline earth metal soap in the lubricating composition. a detergent and a phosphorus antiwear agent present in an amount to provide 300 to 900 ppm phosphorus in the lubricating composition. The lubricating compositions disclosed herein have a total sulfated ash content of 0.3 to 0.9 wt.% or 0.3 to 1.1 wt.% and a total of 0.6 wt.% to 2.1 wt.% Further comprising an alkaline earth metal soap content and an HTHS of less than 2.7 mPa·s measured according to ASTM D4683.
oil of lubricating viscosity

The lubricating compositions disclosed herein include oils of lubricating viscosity. Such oils include natural and synthetic oils, oils derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined oils, refined oils, rerefined oils, or mixtures thereof. A more detailed description of unrefined, refined and rerefined oils is provided in WO 2008/147704, paragraphs [0054]-[0056] (a similar disclosure is provided in US Patent Application No. 2010/ No. 197536, see [0072]-[0073]). A more detailed description of natural and synthetic lubricating oils can be found in paragraphs [0058]-[0059] of WO 2008/147704, respectively (a similar disclosure can be found in US Patent Application No. 2010/197536). (see [0075]-[0076]). Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by the Fischer-Tropsch gas-liquefaction synthesis procedure as well as other gas-liquefaction oils.

Oils of lubricating viscosity are also described in the 2008 “Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils.” As defined in April Edition, Section 1.3 Subheading 1.3 “Base Stock Categories” It can be defined as follows. The API guidelines are also summarized in US Pat. No. 7,285,516 (see column 11, line 64 to column 12, line 10).

Group IV base oils (also known as polyalphaolefins, or PAOs) are known in the art and are prepared by oligomerization or polymerization of linear alphaolefins. PAOs are characteristically water-white oils with excellent low temperature viscosity properties (measured) and high viscosity index. A typical PAO suitable for use in internal combustion engines has ^a Mention may be made of polyalphaolefins having a kinematic viscosity of 1/2 seconds, such as PAO-4 and PAO-6, ie about 4 m ² /sec and 6 m ² /sec, respectively.

In addition to the conventional Group III and Group IV base oils, low levels of some Group V base oils, particularly Group V ester base oils, may be present. Ester-based fluids include esters of monocarboxylic acids and monohydric alcohols; di-esters of diols and monocarboxylic acids and di-esters of dicarboxylic acids and monohydric alcohols; polyol esters of monocarboxylic acids, and monohydric alcohols. Polyesters of alcohols and polycarboxylic acids; and mixtures thereof. Esters can be divided into two broad categories: synthetic and natural.

Synthetic esters include dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, esters of alkylmalonic acids, and alkenylmalonic acids) with any of various monohydric alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol). obtain. Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, and didetyl azelate. Silphthalate, diecoisyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid Examples include complex esters. Other synthetic esters include those made from C5-C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Esters can also be monoesters of monocarboxylic acids and monohydric alcohols.

Natural (or bio-based) esters refer to materials derived from renewable biological resources, organisms, or entities, as distinct from materials derived from petroleum or equivalent raw materials. Natural esters include fatty acid triglycerides, hydrolyzed or partially hydrolyzed triglycerides, or transesterified triglyceride esters, such as fatty acid methyl ester (or FAME). Suitable triglycerides include, but are not limited to, palm oil, soybean oil, sunflower oil, rapeseed oil, olive oil, linseed oil, and related materials. Other triglyceride sources include, but are not limited to, algae, tallow, and zooplankton. A method for producing biolubricants from natural triglycerides is described, for example, in US Patent Application Publication No. 2011/0009300 (A1).

In one embodiment, the lubricant compositions of the present disclosure contain 0.1 to 10 weight percent ester-based fluid, or 0.25 to 5 weight percent, or 0.1 to 2 weight percent ester-based fluid. . In one embodiment, the lubricating composition comprises no more than 5 weight percent ester-based fluid, no more than 2.5 weight percent, or no more than 1 weight percent ester-based fluid. In one embodiment, the lubricant composition is free or substantially free of intentionally added ester-based fluids, ie, contains less than 0.2 weight percent of ester-based fluids.

In one embodiment, the oil of lubricating viscosity may be a base oil comprising an API Group I-IV oil, an ester or synthetic oil, or a mixture thereof. In one embodiment, the oil of lubricating viscosity may be an API Group II, Group III, Group IV oil, ester or synthetic oil, or a mixture thereof. In some embodiments, the oil of lubricating viscosity is at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 100% by weight Group III or Group IV base oil, or a mixture of Group III and Group IV base oils.

The amount of oil of lubricating viscosity present is typically the remainder remaining after subtracting the sum of the amounts of additives and other performance additives of the disclosed compositions from 100% by weight.

The lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. The lubricating compositions described herein (including the additives disclosed herein) may be combined with additional oils to form, in whole or in part, a finished lubricant. When in the form of additives, the ratio of these additives to oils of lubricating viscosity and/or diluent oils ranges from 1:99 to 99:1 by weight, or from 80:20 to 10:90 by weight. Typically, the lubricating compositions described herein include at least 50%, or at least 60%, or at least 70%, or at least 80% by weight oil of lubricating viscosity.

In some embodiments, the oil of lubricating viscosity can include a base oil having a kinematic viscosity measured at 100° C. from 2.4 m ² /sec to 6.4 m ² /sec. In some embodiments, the kinematic viscosity is between 3.8 m ² /s and 5.0 m ² /s, or between 5.2 m ² /s and 5.8 m ² /s, or between 6.0 m 2 /s and 6.0 m ² /s. 5 m ² /sec. In other embodiments, the base oil has a kinematic viscosity of 4.5 m ² /sec or 4.3 m ² /sec or 4.2 m ² /sec.
Polyisobutenyl (PIB) succinimide dispersant

The lubricating composition of the present disclosure further comprises a first polyisobutenyl succinimide dispersant and a second polyisobutenyl succinimide dispersant. References herein to polyisobutylene succinimide dispersants refer to both the first polyisobutenyl succinimide dispersant as well as the second polyisobutenyl succinimide dispersant. The difference is that the first polyisobutenyl succinimide dispersant is derived from a polyisobutenyl moiety having a greater number average molecular weight (Mn) than the PIB of the second polyisobutenyl succinimide dispersant.

The first polyisobutenyl succinimide and/or the second polyisobutenyl succinimide dispersant are each made from a polyisobutylene ("PIB") succinimide dispersant that is either a "traditional" PIB or a high vinylidene PIB. can be prepared (or, as used herein, "derived"). The difference between conventional polyolefins and high vinylidene polyolefins can be explained by reference to the production of PIB. Conventional methods for producing PIB involve polymerizing isobutylene in the presence of _AlCl to produce predominantly trisubstituted olefins with only a very small amount (e.g., less than 20 percent) of chains containing terminal vinylidene groups (I). A mixture of polymers containing (III) end groups and tetrasubstituted olefin (IV) end groups is prepared. In another method, isobutylene is polymerized in the presence of a _BF3 catalyst to form a mixture of polymers containing primarily (e.g., at least 70 percent) terminal vinylidene groups, with smaller amounts of tetrasubstituted end groups and other structures. Manufacture. An alternatively produced material, sometimes referred to as "high vinylidene PIB," is also described in US Pat. No. 6,165,235, which is incorporated herein by reference in its entirety. In one embodiment, the polyisobutylene-derived dispersant is a conventional polyisobutylene-derived dispersant. In another embodiment, the polyisobutylene derived dispersant is a high vinylidene succinimide dispersant or a medium vinylidene succinimide dispersant. Polyisobutylene derived dispersants used herein are generally known in the art.

Polyisobutylene-derived acylating agents may be prepared/obtained/obtainable from reaction with maleic anhydride by "ene" or "thermal" reactions (also called direct alkylation). The "ene" reaction mechanism and general reaction conditions are described in "Maleic Anhydride", pages 147-149, B. C. Trivedi and B. C. ed. Culbertson, published by Plenum Press (1982). The polyisobutylene-derived dispersant prepared by a process involving an "ene" reaction is present in less than 50 mol%, or from 0 to less than 30 mol%, or from 0 to less than 20 mol%, or at 0 mol% of the dispersant molecules. Contains a dispersant having a carbocyclic ring. The "ene" reaction may have a reaction temperature of from 180°C to less than 300°C, or from 200°C to 250°C, or from 200°C to 220°C.

Polyisobutylene-derived acylating agents may also be obtained/obtainable from chlorine-assisted processes (often involving Diels-Alder chemistry, leading to the formation of carbocyclic bonds). The process is known to those skilled in the art. The chlorine-assisted process can produce acylating agents with carbocyclic rings present in 50 mole percent or more of the molecule, or from 60 to 100 mole percent. Both thermal and chlorine assisted processes are described in more detail in US Pat. No. 7,615,521, columns 4-5, and Preparative Examples A and B.

The polyisobutylene-derived acylating agent may further be prepared/obtained/obtainable from a free radical process in which the acylating agent reacts with polyisobutylene in the presence of a free radical initiator. Free radical processes of this type are well known in the art and can be carried out in the presence of additional alpha-olefins.

Polyisobutylene-derived acylating agents are produced by reacting polyisobutylene with an acylating agent (i.e., an ethylenically unsaturated carbonyl compound) to form an acylated polyisobutylene, which is further functionalized with an amine or alcohol to form a suitable dispersant. It can be obtained by forming . Suitable acylating agents include maleic anhydride or reactive equivalents thereof (eg, acids or esters) (ie, succinic acid) and reactive equivalents thereof. In one embodiment, polyisobutylene can be reacted with maleic anhydride to form an acylated product with a conversion of 1-2. In one embodiment, monosucane is reacted with an amine such that the desired product comprises a mixture in which all of the anhydrides present in the acylating agent are converted to imides.

The polyisobutylene-derived dispersant has a carbonyl to nitrogen ratio (CO:N ratio) of 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 dispersant comprises 2:1 to 1:10, or 2:1 to 1:5, or 2:1 to 1:2, or 1:1.4 to 1:0.6 CO :N ratio.

The polyisobutylene succinimide dispersants of the present disclosure can be prepared by reaction of 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 hydrocarbylamine component comprises at least one amino group that can be fused with the acyl group to provide a pendant group, and at least one additional group that includes at least one nitrogen, oxygen, or sulfur atom. and at least one aliphatic amine containing. Suitable aliphatic amines include polyethylene polyamines (e.g., tetraethylene pentamine (TEPA), triethylene tetra amine (TETA), pentaethylene hexamine (PEHA), and polyamine bottoms). , N,N-dimethylaminopropylamine (DMAPA), N-(aminopropyl)morpholine, N,N-diisostearylaminopropylamine, ethanolamine, and combinations thereof.

In one embodiment, the hydrocarbylamine component comprises at least one amino group that can be fused with the acyl group to provide a pendant group and at least one additional group that includes at least one nitrogen, oxygen or sulfur atom. at least one aromatic amine containing (i) a nitro-substituted aniline, (ii) a C(O)NR- group, a -C(O)O- group, an -O- group, An amine containing two aromatic moieties linked by a N=N- group, or a -SO2- group, where R is hydrogen or hydrocarbyl, and one of the aromatic moieties carries the condensable amino group. (iii) aminoquinoline, (iv) aminobenzimidazole, (v) N,N-dialkylphenylenediamine, (vi) aminodiphenylamine (also N,N-phenyldiamine), and (vii) ring-substituted benzyl selected from the group consisting of amines;

In one embodiment, the polyether amine compound may include an amine terminated polyether compound. Amine-terminated polyether compounds may include units derived from ethylene oxide, propylene oxide, brene oxide, or some combination thereof. Suitable polyether compounds include the Jeffamine® series of polyether amines available from Huntsman.

In one embodiment, the first polyisobutylene succinimide dispersant can be prepared by the thermal direct alkylation process described herein. In another embodiment, the second polyisobutylene succinimide dispersant can be prepared by the thermal direct alkylation process described herein.

The polyisobutylene-derived dispersants described herein can be further described as having a TBN. In one embodiment, the first polyisobutylene succinimide dispersant has a TBN of 15-25. In another embodiment, the first polyisobutylene succinimide dispersant has a TBN of 15-20. In one embodiment, the second polyisobutylene succinimide dispersant has a TBN of 20-35. In another embodiment, the second polyisobutylene succinimide dispersant has a TBN of 25-30. In one embodiment, the second polyisobutylene succinimide dispersant has a TBN of 27-28.

In one embodiment, the first polyisobutylene succinimide dispersant is derived from PIB having a number average molecular weight in the range of 1720-2200. In another embodiment, the first polyisobutylene succinimide dispersant is derived from PIB having a number average molecular weight in the range of 1800-2100. In one embodiment, the first polyisobutylene succinimide dispersant is derived from PIB having a number average molecular weight in the range of 1850-2150.

In one embodiment, the second polyisobutylene succinimide dispersant is derived from PIB having a number average molecular weight in the range of 750-1600. In another embodiment, the second polyisobutylene succinimide dispersant is derived from PIB having a number average molecular weight in the range of 1000-1600. In one embodiment, the second polyisobutylene succinimide dispersant is derived from PIB having a number average molecular weight in the range of 1200-1600. In one embodiment, the second polyisobutylene succinimide dispersant is derived from PIB having a number average molecular weight in the range of 800-1150. In another embodiment, the second polyisobutylene succinimide dispersant is derived from PIB having a number average molecular weight in the range of 900-1100.

In one embodiment, the first polyisobutylene succinimide dispersant may be present in the lubricating composition in an amount from 0.5% to 10% by weight. In another embodiment, the first polyisobutylene succinimide dispersant may be present in the lubricating composition in an amount from 0.8% to 6% by weight. In one embodiment, the first polyisobutylene succinimide dispersant may be present in the lubricating composition in an amount of 1% to 5% by weight. In one embodiment, the first polyisobutylene succinimide dispersant may be present in the lubricating composition in an amount from 1.1% to 2.2% by weight.

In one embodiment, the second polyisobutylene succinimide dispersant is present in the lubricating composition in an amount of 1% to 5% by weight. In another embodiment, the second polyisobutylene succinimide dispersant is present in the lubricating composition in an amount from 1.5% to 4.8% by weight. In another embodiment, the second polyisobutylene succinimide dispersant is present in the lubricating composition in an amount of 1.8% to 4.6% by weight. In another embodiment, the second polyisobutylene succinimide dispersant is present in the lubricating composition in an amount from 1.9% to 3.3% by weight.

In one embodiment, the first polyisobutylene succinimide dispersant may include a mixture of two or more dispersants, each of the two or more dispersants including, but not limited to, as disclosed herein. The PIB of the first polyisobutylene succinimide dispersant falls within a range that includes Mn, TBN, and treatability. In another embodiment, the first polyisobutylene succinimide dispersant may include a mixture of two dispersants, each of the two dispersants having a first polyisobutylene succinimide dispersant as disclosed herein. PIB of the polyisobutylene succinimide dispersant falls within a range that includes Mn, TBN, and treatability.

In some embodiments, the second polyisobutylene succinimide dispersant may include a mixture of two or more dispersants, each of the two or more dispersants including, but not limited to, those disclosed herein. The PIB Mn, TBN, and treatability of the second polyisobutylene succinimide dispersant, such as: In another embodiment, the second polyisobutylene succinimide dispersant comprises 1% to 5% by weight of a PIB succinimide dispersant derived from PIB having an Mn of 900 to 1100, and 1% to 5% by weight. PIB succinimide dispersants derived from PIB with Mn of 1200-1600.

The lubricating compositions of the present disclosure further provide that at least one of the first polyisobutylene succinimide dispersant and the second polyisobutylene succinimide dispersant is free of boron. In one embodiment, the first polyisobutylene succinimide dispersant is boron-free and the second polyisobutylene succinimide dispersant is boronated. In another embodiment, the first polyisobutylene succinimide dispersant is boronated and the second polyisobutylene succinimide dispersant is boron-free.

In preparing the boron-containing polyisobutylene succinimide dispersants, the first polyisobutylene-derived succinimide dispersant or the second polyisobutylene-derived succinimide dispersant described herein can be prepared by conventional methods including reaction with a boron compound. It can be post-treated to produce a boron-containing polyisobutylene succinimide dispersant. Suitable boron compounds that can be used to borate polyisobutylene-derived dispersants include various forms of boric acid (metaboric acid, _HBO2 , _orthoboric acid, _H3BO3 , and tetraboric acid, _H2B ). ₄ O ₇ ), boron oxide, boron trioxide, and alkyl borates. In one embodiment, the boronating agent is boric acid, which can be used alone or in combination with other boronating agents. Methods of preparing borated dispersants are known in the art. Boronated dispersants are defined as those having 0.1% to 2.5% boron, or 0.1% to 2.0% boron, or 0.2% to 1.5% boron, Alternatively, it can be prepared to contain 0.3 to 1.0% by weight of boron.

In some embodiments, either the first boronated polyisobutylene succinimide dispersant or the second boronated polyisobutylene succinimide dispersant provides at least 25 ppm, or at least 50 ppm, or at least 75 ppm boron to the lubricating composition. It exists in the amount it brings. In another embodiment, either the first borated polyisobutylene succinimide dispersant or the second borated polyisobutylene succinimide dispersant is present in an amount that provides 25 ppm to 400 ppm boron to the lubricating composition. In another embodiment, either the first boronated polyisobutylene succinimide dispersant or the second boronated polyisobutylene succinimide dispersant has a concentration of 25 ppm to 400 ppm, or 50 ppm to 200 ppm, or 75 ppm to 150 ppm, or 78 ppm to 100 ppm. of boron to the lubricating composition.
cleaning agent

The lubricating compositions of the present disclosure further include an alkaline earth metal salicylate detergent and at least one alkaline earth metal sulfonate detergent as described herein. Metal-containing detergents are well known in the art. They are generally composed of metal salts of acidic organic substrates, especially alkali metals and alkaline earth metals. Metal-containing detergents may be neutral, ie, stoichiometric salts of metal and substrate, also called neutral soaps or soaps, or overbased.

Metal overbased detergents, also referred to as overbased detergents, metal-containing overbased detergents, or superbased salts, are intermediates that follow the stoichiometry of metals and certain acidic organic compounds (i.e., the substrates that react with the metals). characterized by a metal content in excess of the amount required for the total Overbased detergents may include one or more of sulfonates, salicylates, non-sulfur-containing phenates, sulfur-containing phenates, and mixtures thereof.

The amount of excess metal to substrate is usually expressed as a metal ratio. The term "metal ratio" refers to the known chemical reactivity and chemistry of two reactants between a hydrocarbyl-substituted organic acid, i.e., a hydrocarbyl-substituted phenol to be overbased, or a mixture thereof, and a basic metal compound. Used in the prior art and herein to define the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in the salt that would be expected to result from a reaction according to stoichiometry. . Thus, for normal or neutral salts (ie soaps) the metal ratio is 1, and for overbased salts the metal ratio is greater than 1, in particular greater than 1.3. The overbased metal detergent can have a metal ratio of 5 to 30, or a metal ratio of 7 to 22, or a metal ratio of 11 to 18, or at least 11.

Metal-containing detergents are further described, for example, in U.S. Pat. As such, "hybrid" detergents formed with mixed surfactant systems containing phenate and/or sulfonate components, such as phenate-salicylate, sulfonate-phenate, sulfonate-salicylate, sulfonate-phenate-salicylate, may be included. For example, if a hybrid sulfonate/salicylate detergent is used, the hybrid detergent would be considered equivalent to the amounts of separate salicylate and sulfonate detergents that introduce similar amounts of salicylate and sulfonate soaps, respectively. . Overbased phenates and salicylates typically have a total base number of 180-450 TBN. Overbased sulfonates typically have a total base number of 250-800, or 300-600. Overbased detergents are known in the art.

Alkylphenols are often used as ingredients in and/or components of overbased detergents. Alkylphenols can be used to prepare phenate, salicylate, salixalate, or saligenin detergents or mixtures thereof. Suitable alkylphenols include para-substituted hydrocarbylphenols. Hydrocarbyl groups are straight or branched chains of 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. It may also be an aliphatic group. In one embodiment, the alkylphenol overbased detergent is prepared from alkylphenols or mixtures thereof that are free or substantially free (ie, contain less than 0.1 weight percent) of p-dodecylphenol. In one embodiment, the lubricating composition contains less than 0.3 weight percent alkylphenol, less than 0.1 weight percent alkylphenol, or less than 0.05 weight percent alkylphenol. In one embodiment, the alkylphenol detergent is a salicylate.
alkaline earth metal salicylates

Salicylate detergents and overbased salicylate detergents can be prepared in at least two different ways. Carbonylation (also called carboxylation) of p-alkylphenols is described in many references, including US Pat. No. 8,399,388. Carbonylation can be followed by overbasing to form an overbased salicylate detergent. Suitable p-alkylphenols include those having straight chain and/or branched hydrocarbyl groups of 1 to 60 carbon atoms, 4 to 34 carbon atoms, 14 to 24 carbon atoms, and combinations thereof. It will be done. Salicylate detergents may also be prepared by alkylation of salicylic acid followed by overbasing, as described in US Pat. No. 7,009,072. Salicylate detergents prepared in this manner are suitable for straight chain and/or branched alkylating agents containing 6 to 50 carbon atoms, 10 to 30 carbon atoms, or 14 to 24 carbon atoms ( (usually 1-olefins). In one embodiment, the overbased detergent is a salicylate detergent. In one embodiment, the salicylate detergent is free (ie, contains less than 0.1 weight percent) of unreacted p-alkylphenol. In one embodiment, salicylate detergents are prepared by alkylation of salicylic acid.

In one embodiment, the alkaline earth metal salicylate detergent has a TBN (KOH/g) of 200-575 or 200-500. In another embodiment, the alkaline earth metal salicylate detergent has a TBN (KOH/g) of 250-350. In one embodiment, the alkaline earth metal salicylate detergent has a metal ratio of 2 to 7, or 2 to 4, or 2.5 to 3.5. In one embodiment, the alkaline earth metal salicylate detergent is present in the lubricating composition in an amount of 0.1 to 5% by weight. In another embodiment, the alkaline earth metal salicylate detergent is present in the lubricating composition in an amount of 0.2-3% by weight. In one embodiment, the alkaline earth metal salicylate detergent is present in the lubricating composition in an amount of 0.5-3% by weight. In one embodiment, the alkaline earth metal salicylate detergent is present in the lubricating composition in an amount of 0.8 to 2.5% by weight. In one embodiment, the calcium alkaline earth metal detergent is present in the lubricating composition in an amount of 0.9-2.3% by weight.

In one embodiment, the alkaline earth metal salicylate detergent may be calcium salicylate, magnesium salicylate, or a combination thereof. In one embodiment, the alkaline earth metal salicylate is calcium salicylate. In one embodiment, the alkaline earth metal salicylate is magnesium salicylate. Calcium salicylate may be present in the lubricant composition in an amount providing 150-1500 ppm calcium, or 250-1100 ppm calcium in the composition. Magnesium salicylate may be present in an amount to provide 100 to 2000 ppm magnesium in the lubricant composition, or 250 to 1750 ppm magnesium, or 300 to 1550 ppm magnesium in the lubricant composition.
Alkaline earth metal sulfonate detergents

The alkaline earth metal sulfonate is a neutral sulfonate salt (metal ratio less than 1.3), a low overbased detergent, such that at least 0.1 weight percent alkaline earth metal soap is present in the lubricant composition. (metal ratio 1.5 to 6), or a highly overbased detergent (metal ratio at least 8), or any combination thereof.

Alkaline earth metal sulfonate detergents include those described in paragraphs [0026] through [0037] of U.S. Patent Application Publication No. 2005/065045 (assigned as U.S. Patent No. 7,407,919). It may also be a linear alkylbenzene sulfonate detergent. Linear alkylbenzene sulfonate detergents can be particularly useful in helping improve fuel economy. The straight-chain alkyl group may be bonded to the benzene ring at any position along the straight chain of the alkyl group, but in many cases it is bonded at the 2-, 3-, or 4-position of the straight chain, In some cases, it is attached primarily at the 2-position, resulting in a linear alkylbenzene sulfonate detergent.

In one embodiment, the alkaline earth metal sulfonate detergents of the present disclosure are selected from calcium sulfonate detergents and magnesium sulfonate detergents. In another embodiment, the alkaline earth metal sulfonate detergent is a calcium sulfonate detergent. In one embodiment, the calcium sulfonate detergent has a TBN of less than 250 on an oil-free basis. In another embodiment, the calcium sulfonate detergent has a TBN of less than 200, or less than 150, or less than 80. In one embodiment, the calcium sulfonate detergent has a TBN of 50-90. In one embodiment, the calcium sulfonate has a TBN of 120-250 mg KOH/g and a metal ratio of 1.5-5.

In one embodiment, the alkaline earth metal sulfonate detergent is a calcium sulfonate detergent present in the lubricating composition in an amount of 0.1% to 2.0% by weight. In another embodiment, the calcium sulfonate detergent is present in the lubricating composition in an amount of 0.3% to 1.5% by weight.

In one embodiment, the alkaline earth metal sulfonate detergent is a magnesium sulfonate detergent. The magnesium sulfonate may have a TBN (mg KOH/g) of 300 to 800 on an oil-free basis. In some embodiments, the magnesium sulfonate may have a TBN (mg KOH/g) of 400-750. In other embodiments, the magnesium sulfonate may have a TBN (mg KOH/g) of 250-350. In other embodiments, the magnesium sulfonate may have a TBN (mg KOH/g) of 350-375. In one embodiment, the magnesium sulfonate may have a metal ratio of 8-30, 10-25, or 12-18.

In one embodiment, the magnesium sulfonate detergent is present in the lubricating composition in an amount of 0.05% to 0.5% or 0.05 to 0.2% by weight. In another embodiment, the magnesium sulfonate detergent is present in the lubricating composition in an amount of 0.06% to 0.1% or 0.06% to 0.2% by weight.

In one embodiment, the alkaline earth metal sulfonates include at least one neutral or low overbased alkaline earth metal sulfonate (i.e., metal ratio less than 6) and at least one highly overbased alkaline earth metal sulfonate. (metal ratio at least 8).

The alkaline earth metal detergent used herein may be a sulfonate sodium salt, calcium salt, magnesium salt, or a mixture thereof. In one embodiment, the alkaline earth metal sulfonate detergent is a calcium sulfonate detergent, a magnesium sulfonate detergent, or a mixture thereof. In one embodiment, one or more of the calcium sulfonate detergent and the magnesium sulfonate detergent are overbased. In one embodiment, the alkaline earth metal detergent is an overbased calcium sulfonate detergent. In another embodiment, the alkaline earth metal detergent is an overbased magnesium sulfonate detergent. In yet another embodiment, the alkaline earth metal detergent is a mixture of an overbased calcium sulfonate detergent and an overbased magnesium sulfonate detergent. In one embodiment, the alkaline earth metal sulfonate detergent comprises 0.6% to 1.5% by weight of a calcium sulfonate detergent having a TBN of 50 to 200 (mg KOH/g) and a TBN of 400 to 800. (mg KOH/g) in a mixture with 0.04% to 0.1% by weight of an overbased magnesium sulfonate detergent.

The detergent of the disclosed lubricating compositions may include alkaline earth metals provided by the detergent. In one embodiment, the calcium salicylate detergent is present in an amount that provides 150 to 1500 ppm, or 250 to 1100 ppm, or 300 to 800 ppm calcium to the lubricating composition. In embodiments where the alkaline earth metal detergent comprises a calcium sulfonate detergent, the calcium sulfonate detergent may be present in an amount to provide 100 to 1000 ppm, 150 to 800 ppm, or 250 to 650 ppm calcium to the lubricating composition. In embodiments where the alkaline earth metal detergent comprises a magnesium sulfonate detergent, the magnesium sulfonate detergent may be present in an amount to provide 50 to 500, 100 to 425, or 150 to 350 ppm magnesium to the lubricating composition. In some embodiments, the alkaline earth metal detergent comprises a calcium sulfonate detergent, and the total amount of calcium provided to the lubricating composition from the calcium salicylate detergent and the calcium sulfonate detergent is less than or equal to 800-2500, 900-1800, 950-1450 ppm of calcium.

Metal-containing detergents provide sulfated ash to the lubricating composition. Sulfated ash content can be determined by ASTM D874. In one embodiment, the total sulfur ash provided to the lubricating composition from the alkaline earth metal salicylate detergent and the alkaline earth metal detergent is 0.25 to 0.95 weight percent. In other embodiments, the alkaline earth salicylate detergent is present in an amount that provides the lubricating composition with about 0.05 to 0.5 weight percent, or 0.1 to 0.35 weight percent sulfated ash. In another embodiment, the alkaline earth metal detergent is present in an amount that provides the lubricating composition with a sulfated ash content of 0.05 to 0.75, or 0.1 to 0.6 weight percent.

In addition to ash and TBN, overbased detergents provide detergent soaps (also called neutral detergent salts) to lubricating compositions. Soaps, which are matrix metal salts, can act as surfactants in lubricating compositions. In one embodiment, the alkaline earth metal sulfonate detergent comprises 0.1% to 1.5%, or 0.15 to 1.2%, or 0.2% to 0.9% by weight. The sulfonate soap is present in an amount that provides the lubricant composition. In one embodiment, the alkaline earth metal salicylate detergent is 0.3% to 1.4% by weight, or 0.35% to 1.2% by weight, or 0.4% to 1.0% by weight. % salicylate soap to the lubricant composition. In one embodiment, the alkaline earth metal soap may be calcium, magnesium, or any mixture thereof. In one embodiment, the alkaline earth metal sulfonate soap is present in an amount of 0.2% to 0.8% by weight of the lubricant composition, and the alkaline earth metal salicylate soap is present in an amount of 0.2% to 0.8% by weight of the lubricant composition. Present in an amount of 3% to 1.0% by weight. The sum of all alkaline earth metal detergent soaps may be present in an amount of 0.6% to 2.1%, or 0.7% to 1.4% by weight of the lubricant composition. .
anti-wear agent

The lubricating compositions of the present disclosure further include one or more phosphorus-containing antiwear agents.

Phosphorus-containing antiwear agents are well known to those skilled in the art and include metal dialkyl (dithio) phosphates, hydrocarbyl phosphites, hydrocarbyl phosphines, hydrocarbyl phosphonates, alkyl phosphates, amines or ammonium (alkyl) phosphates, and the like. A combination of these can be mentioned.

In one embodiment, the phosphorus-containing antiwear agent may be a metal dialkyldithiophosphate, which may include zinc dialkyldithiophosphate. Such zinc salts are often referred to as zinc dialkyldithiophosphate (ZDDP) or simply zinc dithiophosphate (ZDP). They are well known and readily available to those skilled in the art of lubricant formulation. Further zinc dialkyldithiophosphates can be described as primary zinc dialkyldithiophosphates or secondary zinc dialkyldithiophosphates, depending on the structure of the alcohol used in their preparation. In some embodiments, the composition may include a primary zinc dialkyldithiophosphate. In some embodiments, the composition comprises a zinc secondary dialkyldithiophosphate. In some embodiments, the composition includes a mixture of primary and secondary zinc dialkyldithiophosphates. In some embodiments, component (b) is a mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate, where primary zinc dialkyldithiophosphate versus secondary dialkyldithiophosphate The ratio of zinc acid (by weight) 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:

where R ¹ and R ² are independently hydrocarbyl groups containing 3 to 24 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, and M is an atom A metal having a valence n and generally includes zinc, copper, iron, cobalt, antimony, manganese, and combinations thereof. In one embodiment, R ¹ and R ² are secondary aliphatic hydrocarbyl groups containing 3 to 8 carbon atoms and M is zinc.

In one embodiment, the phosphorus-containing antiwear agent may be a zinc-free phosphorus compound. The zinc-free phosphorus anti-wear agent may contain sulfur or may be sulfur-free. Sulfur-free phosphorus-containing antiwear agents include hydrocarbyl phosphites, hydrocarbyl phosphines, hydrocarbyl phosphonates, alkyl phosphates, amine or ammonium phosphate salts, or mixtures thereof.

In one embodiment, the phosphorus-containing antiwear agent is present in the lubricating composition in an amount that provides 300 ppm to 900 ppm phosphorus to the lubricating composition. In one embodiment, the antiwear agent is ZDDP and is present in the composition in an amount to provide 400 ppm to 850 ppm, or 450 ppm to 800 ppm, or 500 ppm to 800 ppm, or 550 ppm to 780 ppm, or 650 ppm to 780 ppm phosphorus to the lubricating composition. exist.

In one embodiment, the phosphorus-containing antiwear agent is present in an amount of 0.2-2%, or 0.3-1.3%, or 0.5-0.95% by weight of the lubricant composition. do.
Other performance additives

The lubricating composition comprises an oil of lubricating viscosity, a first PIB succinimide dispersant, a second succinimide dispersant, a calcium salicylate detergent, an alkaline earth metal detergent, a phosphorus antiwear agent, and optionally ( may be prepared by mixing one or more performance additives (as described herein below).

Other performance additives include metal deactivators, viscosity modifiers, friction modifiers, antiwear agents, corrosion inhibitors, extreme pressure agents, antioxidants, antifoaming agents, demulsifiers, pour point depressants, At least one of a seal swell agent and a mixture thereof is included. Typically, fully formulated lubricating oils contain one or more of these performance additives.

In further embodiments, the lubricating composition comprises an antioxidant, the antioxidant comprising a phenolic or aminic antioxidant or a mixture thereof. Antioxidants include diarylamines, alkylated diarylamines, hindered phenols, or mixtures thereof. When present, individual antioxidants independently range from 0.1% to 3%, or from 0.5% to 2.75%, or from 1% to 2.5% by weight of the lubricating composition. Present in % by weight.

The diarylamine or alkylated diarylamine may be phenyl-α-naphthylamine (PANA), alkylated diphenylamine, or alkylated phenylnaphthylamine, or mixtures thereof. Alkylated diphenylamines include di-nonylated diphenylamine, nonyldiphenylamine, octyldiphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyldiphenylamine, and mixtures thereof. In one embodiment, the diphenylamine can include nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, or mixtures thereof. In another embodiment, the alkylated diphenylamine includes nonyldiphenylamine or dinonyldiphenylamine. Alkylated diarylamines include octyl, dioctyl, nonyl, dinonyl, decyl or didecylphenylnaphthylamine.

Hindered phenolic antioxidants often contain secondary and/or tertiary butyl groups as sterically hindering groups. The phenol group may be further substituted with a hydrocarbyl group (typically a linear or branched alkyl) 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, 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester, such as Irganox™ L-135 from Ciba. Suitable hindered phenolic esters include hydrocarbyl esters of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid, such as those having 3 to 18 carbon atoms, or 4 to 12 carbon atoms. or hydrocarbyl esters containing from 6 to 10 carbon atoms. A more detailed description of suitable ester-containing hindered phenolic antioxidant chemistry is found in US Pat. No. 6,559,105.

In one embodiment, the lubricating composition contains a friction modifier. Friction modifiers include long chain fatty acid derivatives of amines, long chain fatty esters, or derivatives of long chain fatty epoxides; fatty imidazolines; amine salts of alkyl phosphoric acids; fatty alkyl tartrates; fatty alkyl tartarimides; fatty alkyl tartaramides; glycolates; aliphatic glycolamides; and combinations thereof.

As used herein, the term "fatty alkyl" or "fat" with respect to friction modifiers means a carbon chain having 10 to 24 carbon atoms, typically a straight carbon chain, which is It may be saturated or unsaturated.

Examples of suitable friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines, such as condensation products of carboxylic acids with polyalkylene-polyamines; amine salts of alkyl phosphoric acids; tartrate fatty acids. Alkyl; fatty alkyl tartarimide; fatty alkyl tartaramide; fatty phosphonate; fatty phosphite; borated phospholipid, borated fatty epoxide; glycerol ester; borated glycerol ester; fatty amine; alkoxylated fatty amine; borated alkoxylated fat Amines; hydroxyl and polyhydroxy fatty amines, including tertiary hydroxy fatty amines; hydroxyalkylamides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; aliphatic ethoxylated alcohols; carboxylic acids and polyalkylene polyamines or reaction products of fatty carboxylic acids with guanidine, aminoguanidine, urea or thiourea, and salts thereof.

Friction modifiers may also include materials such as sulfurized fatty compounds and olefins, molybdenum compounds such as molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salt molybdic acid compounds, and molybdenum post-treated succinimide dispersants. Molybdenum dithiocarbamate may be a mononuclear, dinuclear, or trinuclear complex. Suitable molybdenum compounds may be present as Mo(IV) complexes, or Mo(V) complexes, or Mo(VI) complexes, or combinations thereof, and are available from Adeka Co. Commercially available materials include Sakura-lube 525 from Vanderbilt Chemicals LLC and Molyvan (copyright) 855 from Vanderbilt Chemicals LLC.

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. Suitable triglycerides include vegetable oils such as soybean oil or sunflower oil.

The ashless friction modifier contains 0.01 to 2.5% by weight, or 0.1 to 0.5% by weight, or 0.3 to 2.0% by weight, or 0.5 to 0.9% by weight. may be present in the lubricating composition in any amount.

The lubricating composition optionally further comprises at least one antiwear agent other than the phosphorus-containing antiwear agents described above. Examples of suitable antiwear agents include titanium compounds, tartrates, tartarimides, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamate ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithio carbamyl) disulfide. The antiwear agent may, in one embodiment, include a tartrate or tartarimide as disclosed in WO 2006/044411 or Canadian Patent No. 1183125. The tartrate or tartarimide may contain an alkyl-ester group in which the total number of carbon atoms on the alkyl group is at least 8. The antiwear agent, in one embodiment, can include citrate as disclosed in US Patent Application No. 2005/0198894.

Another class of additives includes oil-soluble titanium compounds, such as those disclosed in US Patent No. 7,727,943 and US Patent Application Publication No. 2006/0014651. Oil-soluble titanium compounds can function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or two or more of these functions. In one embodiment, the oil-soluble titanium compound is a titanium (IV) alkoxide. Titanium alkoxides are formed from monohydric alcohols, polyols or mixtures thereof. Monovalent alkoxides may 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-ethylhexoxide. 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, and often the fatty acid is oleic acid.

In one embodiment, the oil-soluble titanium compound is a titanium carboxylate. In a further embodiment, the titanium (IV) carboxylate is titanium neodecanoate.

Extreme Pressure (EP) agents that are soluble in oil include sulfur- and chlorosulfur-containing EP agents, dimercaptothiadiazole or _CS2 derivatives of dispersants (typically succinimide dispersants), chlorinated hydrocarbon EP agents. derivatives of agents and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; sulfurized olefins (e.g. sulfurized isobutylene), hydrocarbyl-substituted 2,5-di-mercapto-1,3,4-thiadiazole or oligomers thereof, organic sulfides and polysulfides (e.g. , dibenzyl-disulfide, bis-(chlorobenzyl) disulfide, dibutyltetrasulfide, sulfurized methyl esters of oleic acid, sulfurized alkylphenols, sulfurized dipentene, sulfurized terpenes, and sulfurized Diels-Alder adducts); phosphorus sulfide hydrocarbons, e.g. phosphorus sulfide and turpentine or methyl oleate; phosphite esters such as dihydrocarbons and trihydrocarbon phosphites, such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene substituted phenol phosphite; metal thiocarbamates such as zinc dioctyl dithiocarbamate and barium heptyl-phenol dioic acid; amine salts of alkyl and dialkyl phosphates or derivatives, such as amine salts of the reaction products of dialkyldithiophosphoric acids and propylene oxide, followed by further reaction with _P2O5 , and mixtures thereof (as described in U.S. Pat. No. 3,197,405 ₎ . (such as).

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

Polymeric viscosity index improvers, also referred to as viscosity modifiers (VMs) or dispersant viscosity modifiers (DVMs), may be useful in the compositions disclosed herein. Dispersant viscosity modifiers can generally be understood as functionalized or derivatized forms of polymers similar to polymeric viscosity modifiers. The polymeric viscosity modifier may be an olefin (co)polymer, poly(meth)acrylate (PMA), or a mixture thereof. In one embodiment, the polymeric viscosity modifier is an olefin (co)polymer or a dispersant viscosity modifier derived therefrom.

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

Useful olefin polymers, particularly ethylene-a-olefin copolymers, have number average molecular weights in the range of 4500 to 500,000, such as 5000 to 100,000, or 7500 to 60,000, or 8000 to 45,000. .

The formation of functionalized ethylene-a-olefin copolymers is well known in the art and is described, for example, in U.S. Pat. No. 7,790,661, column 2, line 48 to column 10, line 38. It is. Additional detailed descriptions of similar functionalized ethylene-a-olefin copolymers can be found in WO 2006/015130 or US Pat. , No. 258, No. 6,117,825; and No. 7,790,661. In one embodiment, the functionalized ethylene-a-olefin copolymer is a functionalized ethylene-a-olefin copolymer in US Pat. See paragraph [0008], preparation examples may include those described in paragraphs [0065] to [0073]).

In one embodiment, the lubricating composition includes a dispersant viscosity modifier (DVM). DVMs may include olefin polymers modified by the addition of polar moieties.

Olefin polymers are functionalized by modifying the polymer through 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 can be an ethylenically unsaturated acylating agent. Useful acylating agents typically have at least one ethylene bond (prior to reaction) and at least one, e.g. two, carboxylic acid (or anhydride) groups or convertible to such carboxyl groups by oxidation or hydrolysis. It is an α,β-unsaturated compound with a polar group. An acylating agent is grafted onto the olefin polymer to provide two carboxylic acid functional groups. Examples of useful acylating agents include maleic anhydride, chloromaleic anhydride, itaconic anhydride, or reactive equivalents thereof, such as maleic acid, fumaric acid, cinnamic acid, (meth)acrylic acid, etc. dicarboxylic acids, esters of these compounds, and acid chlorides of these compounds.

In one embodiment, the functionalized ethylene-α-olefin copolymer comprises an olefin copolymer grafted with acyl groups, which is further grafted with hydrocarbyl amines, hydrocarbyl alcohol groups, amino- or hydroxy-terminated polyether compounds, and mixtures thereof. Sensualized.

In one embodiment, the hydrocarbyl amine can be selected from aromatic amines, aliphatic amines, and mixtures thereof. In one embodiment, the hydrocarbylamine component comprises at least one amino group that can be fused with the acyl group to provide a pendant group and at least one additional group that includes at least one nitrogen, oxygen or sulfur atom. at least one aromatic amine containing (i) a nitro-substituted aniline, (ii) a C(O)NR- group, a -C(O)O- group, an -O- group, N=N- group, or an amine containing two aromatic moieties linked by a -SO2- group, where R is hydrogen or hydrocarbyl, and one of the aromatic moieties carries the condensable amino group. , (iii) aminoquinoline, (iv) aminobenzimidazole, (v) N,N-dialkylphenylenediamine, (vi) aminodiphenylamine (also N-phenylphenylenediamine), and (vii) ring-substituted benzylamine, and (viii) selected from the group consisting of methylene-linked dimers of aminodiphenylamine.

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

In one embodiment, poly(meth)acrylate polymers are prepared from monomer mixtures that include (meth)acrylate monomers with alkyl groups of varying lengths. (Meth)acrylate monomers may contain alkyl groups that are linear or branched groups. Alkyl groups may contain 1 to 24 carbon atoms, for example 1 to 20 carbon atoms.

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

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

In one embodiment, the poly(meth)acrylate polymer (P) comprises at least one polymer block (Bi) that is insoluble or substantially insoluble in the base oil and a second polymer block (Bi) that is soluble or substantially soluble in the base oil. It is a block or tapered block copolymer containing the polymer block (B2).

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

The linear poly(meth)acrylates may be random, block, or otherwise and have a weight average molecular weight (Mw) of 1000 to 400,000 Daltons, 1000 to 150,000 Daltons, or 15,000 to 100,000 Daltons. May have. 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 can be derived from linear random or diblock copolymers having the above molecular weights. 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.

Another class of polymeric viscosity modifiers are styrene-diene (SD) copolymers, such as styrene isoprene (SI) and styrene butadiene (SBR). Styrene-diene copolymers may be linear or radial (star) and generally contain one or more discrete blocks of styrene bonded to one or more discrete blocks of hydrogenated diene. .

The lubricating composition may contain from 0.05% to 2%, or from 0.08% to 1.2%, or from 0.1 to 0.8% by weight of one or more polymeric viscosity modifiers and/or A dispersant viscosity modifier may also be included.

Pour point depressants that may be useful in the compositions disclosed herein include polyalphaolefins, esters of maleic anhydride-styrene copolymers, poly(meth)acrylates, polyacrylates or polyacrylamides. .

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

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

Seal swelling agents include the sulfolene derivatives Exxon Necton-37™ (FN 1380) and Exxon Mineral Seal Oil™ (FN 3200).

The lubricating composition may further include one or more dispersants different from the dispersants of the first PIB succinimide dispersant and the second PIB succinimide dispersant of the compositions disclosed herein. Such dispersants include succinimide dispersants, Mannich dispersants, polyolefin succinates, amides, or ester-amides different from those of the described compositions, or mixtures thereof.

The additional dispersant may be a PIB succinimide, similar to the dispersion medium of the described composition, derived from polyisobutylene having a number average molecular weight of 800 Daltons to 2600 Daltons. Additional dispersants may be present to facilitate soot treatment or as a source of ashless TBN. Soot dispersants may be functionalized with aromatic (poly)amines. Dispersants used as TBN boosters typically have a high TBN, such as greater than 80 mg KOH/g, greater than 95 mg KOH/g, or even greater than 110 mg KOH/g.

Additional dispersants may be present in an amount of 0.05-2%, or 0.1-1.1%, or 0.2-0.8% by weight of the lubricant composition.
industrial use

The lubricating compositions disclosed herein are suitable for use in diesel engines. Diesel engines are classified by Gross Vehicle Weight Rating (GVWR). GVWR includes the maximum rated weight of the vehicle and cargo, including passengers. GVWR applies to trucks or trailers, but not the two combined; this is a separate rating called Gross Combined Weight Rating (GCWR). The GVWR of various classes of diesel engines is shown in the table below.

Light vehicles are classified into classes 1 to 3. Class 2A vehicles are typically referred to as "light duty" vehicles, and Class 2B vehicles are often referred to as "light duty" vehicles.

Medium-sized vehicles refer to vehicles classified into classes 4 to 6. Large vehicles are vehicles classified into class 7 and class 8.

There are distinct differences between classes of vehicles as they relate to operating conditions. Differences in size mean that more highly classified vehicles have engines that experience significantly different operating conditions such as load, oil temperature, duty cycle and engine speed. Heavy-duty diesel engines are designed to maximize torque for transporting payloads at maximum fuel economy, while passenger cars (low-class vehicles) are designed to maximize torque for transporting payloads at maximum fuel economy. It is designed to. The design purpose of a transportation versus commutation engine results in differences in hardware design and in the stresses placed on the lubricant for engine protection and lubrication purposes. Another distinct design difference is the revolution per minute (RPM) at which each engine operates for conveyance versus commutation. Heavy duty diesel engines, such as a typical 12-13 liter truck engine, typically do not exceed 2200 rpm, while passenger car engines can go up to 4500 rpm.

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

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

In one embodiment, the sulfated ash content may be 0.2-1.2% by weight of the lubricating composition. The lubricating compositions disclosed herein have a sulfated ash content of 0.2-1.2%, or 0.3-1.1%, or 0.4-0.8% by weight. obtain.

As used herein, TBN value is (total base number) as determined by the methodology described in ASTM D4739 (Buffers).

The lubricating composition may be characterized as having a total base number (TBN) content of at least 3, or at least 4, or at least 5 mg KOH/g.

The lubricating composition can be characterized as having a total base number (TBN) content of 5 to 10 mg KOH/g, or 5 to 8.5 mg KOH/g.

The lubricating compositions disclosed herein have a kinematic viscosity of 2.5 to 8.3, or 3.5 to 6.5 cSt (mm ² /sec) as measured by ASTM D-445 at 100°C; It has a kinematic viscosity of 15-30 cSt (mm ² /sec) at 40°C. In another embodiment, the lubricating composition has a kinematic viscosity of 2.5-6.5 or 3-5.5 cSt (mm ² /s) at 100°C and 15-25 cSt (mm ² /s) at 40°C. It has a kinematic viscosity of

The lubricating compositions disclosed herein have a temperature of less than 2.6 mPa·s, or less than 2.5 mPa·s, or less than 2.3 mPa·s, or less than 2.1 mPa·s, as measured by ASTM D4683 at 150°C. It has a high temperature, high shear (HTHS) of less than s. In another embodiment, the HTHS of the lubricating composition is between 1.4 and 2.5 mPa.s, or between 1.6 and 2.1 mPa.s, or between 1.8 and 2.1 mPa.s, or between 1.9 and 2.1 mPa.s. It is 2.0 mPa·s.

The lubricating composition may have an SAE viscosity grade of 0W-Y, where Y may be 12, 16, or 20. In one embodiment, the lubricating composition has an SAE viscosity grade of 0W-12.

The internal combustion engines disclosed herein may have steel surfaces on the cylinder bore, cylinder block, or piston rings.

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

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

The present disclosure further relates to a method of lubricating a diesel engine by supplying the engine with any one of the lubricating compositions disclosed herein. In one embodiment, the method includes lubricating a diesel engine by providing a lubricating composition to the engine, the lubricating composition comprising greater than 50 weight percent of Group III base oil, Group IV base oil, or a mixture thereof, a first PIB succinimide dispersant derived from a PIB of 1800 to 2500 Mn, and a second PIB succinimide dispersant derived from a PIB having an Mn of less than 1600; wherein at least one of the first PIB succinimide dispersant and the second PIB succinimide dispersant is boron-free, the composition further comprising a calcium salicylate detergent and a lubricating composition containing 0.3% by weight of the lubricating composition. % to 2.1% by weight alkaline earth metal sulfonate detergent, and a phosphorus antiwear agent present in an amount to provide 300 to 900 ppm phosphorus to the lubricating composition. The lubricating composition further comprises a total sulfated ash content of 0.3-0.9% by weight and an HTHS of less than 2.7 mPa·s as measured according to ASTM D4683.

Another embodiment provides a lubricating composition disclosed herein for improving at least one of wear protection and fuel economy in a compression ignition internal combustion engine (typically a heavy duty diesel internal combustion engine). Provide for the use of any one of the following.

In different embodiments, the lubricating compositions disclosed herein can have compositions as described in the table below.

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

The series of 0W-12 engine lubricants in Group III base oils of lubricating viscosity contain the additives listed above, as well as polymeric viscosity modifiers, corrosion inhibitors, pour point depressants, and other performance additives such as: (Table 1). Elements are included to indicate relative equivalence of compositions.

1. All treatment rates presented are oil-free unless otherwise specified. 2. Polyisobutenyl succinimide dispersant (TBN 54 mg KOH/g) prepared from 2300 Mn low vinylidene PIB by chlorine Diels-Alder method
3. Borated analogs of the above dispersants (1% boron by weight)
4. PIB succinimide aromatic amine soot dispersant 5. Polyisobutenyl succinimide dispersant (TBN 26 mg KOH/g) prepared from high vinylidene 2000Mn PIB by thermal enalkylation
Polyisobutenyl succinimide dispersant prepared from 6.980Mn PIB (TBN 25mg KOH/g)
7. Polyisobutenyl succinimide dispersant prepared from high vinylidene 1550Mn PIB by thermal enalkylation (TBN 17mg KOH/g)
8. Overbased calcium alkylbenzene sulfonate (TBN 520mg KOH/g, 48% substrate)
9. Calcium overbased alkyl salicylate detergent (TBN 300mg KOH/g, metal ratio 2.8)
10. Low TBN Calcium Alkylbenzene Sulfonate Detergent (TBN 170mg KOH/g, 84% Substrate, Metal Ratio 2.7)
11. A combination of diarylamines, hindered phenols, and sulfurized olefins.
12. Combination of low Mn (10 kDa) and high Mn (60 kDa) substituted ethylene-propylene copolymers functionalized with aromatic amines 13. Premixture of oleyl tartarimide (44 wt.%), boronating agent, basic nitrogen, and compatibilizer (0.46 wt.% boron, TBN 17 mg KOH/g)
14. Sulfur-bridged molybdenum (V) dimer, dithiocarbamate complex (commercially available as Sakuralube 525 from Adeka)
15. Other additives include pour point depressants, foam inhibitors, and low levels of corrosion inhibitors and compatibilizers.

The lubrication examples in Table 1 are evaluated for improved fuel economy and ability to prevent/reduce wear. The results are summarized along with other chemical and physical properties related to performance (Table 2). Fuel economy improvement is measured according to the Volvo D13TC fuel economy test. In this test, improvement is determined in comparison to a preselected reference oil. In these data, Example 8 (EX8) was selected as the reference oil.

Abrasion resistance (also called durability) was determined on a high frequency reciprocating rig (HFRR) available from PCS Instruments. HFRR conditions for evaluation were 500 g load, 75 minutes duration, 1000 micrometer stroke, 20 Hertz frequency, and 105° C. temperature. Wear and contact potential are then measured.

The results obtained indicate that the lubricant composition is capable of providing improved fuel economy while maintaining and even improving wear control.

The lubricant compositions described herein further provide cleanliness, deposit control, and oxidation control in suitable bench tests. Deposit performance can be measured according to the Thermo-Oxidation Engine Oil Simulation Test (TEOST 33) as set forth in ASTM D6335. The results of the TEOST 33 test indicate the number of milligrams of deposits after operating the engine oil at high temperatures. Lower TEOST 33 results indicate improved resistance to deposit formation. This lubricating composition can be tested for deposit control in a Panel Coker heated to 325°C with a sump temperature of 105°C and a splash/bake cycle of 120 seconds/45 seconds. Air flow is 350 ml/min, spindle speed is 1000 rpm, and the test lasts 4 hours. The oil is spread onto an aluminum panel and then evaluated optically by a computer. Performance ranges from 0% (black panel) to 100% (clean panel).

The fuel economy of the disclosed lubricating compositions was determined by any of the following: M111 Fuel Economy Test (CEC L-54-96), Daimler OM501LA Fuel Economy Test, NEDC MB Fuel Economy Test, and ILSAC Sequence VI Engine Test. or can be tested according to one and may have improvements. Friction performance may also be evaluated in any of several High Frequency Reciprocating Rig (HFRR) bench tests, such as ASTM D6079.

Unless otherwise stated herein, references to processing rates or amounts of ingredients present in the lubricating compositions disclosed herein are quoted on an oil-free basis, i.e., on the amount of active material. Ru.

As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary meaning as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly bonded to the remainder of the molecule and having predominantly hydrocarbon character, including one or more double bonds. Examples of hydrocarbyl groups include hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), cycloaliphatic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic, and cycloaliphatic Substituted aromatic substituents as well as cyclic substituents where the ring is completed via another part of the molecule (e.g. two substituents taken together to form a ring); substituted hydrocarbon substituents, i.e. , in the context of the present invention, substituents containing non-hydrocarbon groups which do not change the predominantly hydrocarbon nature of the substituents, such as halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); heterosubstituents, i.e., in the context of the present invention, have predominantly hydrocarbon character but contain other than carbon in a ring or chain otherwise composed of carbon atoms, and pyridyl , furyl, thienyl, and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. Generally, there will be no more than 2, or no more than 1 non-hydrocarbon substituent for every 10 carbon atoms in the hydrocarbyl group; alternatively, no non-hydrocarbon substituents may be present in the hydrocarbyl group. good.

This disclosure is not to be limited with respect to the particular embodiments described in this application, which are intended as illustrations of various aspects. Many modifications and variations can be made without departing from the spirit and scope of the invention, as will be apparent to those skilled in the art. Functionally equivalent methods and components within the scope of the 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 be within the scope of the appended claims. This 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 may, of course, vary. It should also 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 is to be construed as an admission that the embodiments described in this disclosure are not entitled to antedate such disclosure by virtue of prior invention. As used herein, the term "comprising" means "including, but not limited to."

Although various compositions, methods, and devices are described in terms of "comprising" (which is taken to mean "including, but not limited to") various components or steps, the compositions, methods, and the device may further "consist essentially of" or "consist of" various components and steps, and such terminology should be construed to define an essentially closed group of elements.

With respect to the use of virtually any plural and/or singular term herein, those skilled in the art will be able to convert from the plural to the singular and/or the singular as appropriate to the context and/or use. can be converted to plural form. Various singular/plural conversions may be expressly set forth herein for clarity.

In general, the terms used herein, and particularly the terms used in the appended claims (e.g., the body of the appended claims), are generally intended as "open" terms (e.g., " The term "including" should be construed as "including, but not limited to," the term "having" should be construed as "having at least," and the term "including" should be construed as "including, but not limited to." It will be understood by those of ordinary skill in the art that the term should be construed as ``but not limited to''. If a particular number of claim statements to be introduced is intended, such intent will be expressly stated in the claim, and in the absence of such statement, one skilled in the art will know that no such intent exists. will be further understood by For example, as an aid to understanding, the following appended claims may include the use of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such a phrase is prohibited even if the same claim includes the introductory phrase "one or more" or "at least one" and an indefinite article such as "a" or "an". Introducing a claim statement with "a" or "an" does not limit any particular claim containing such introduced claim statement to embodiments containing only one such statement. shall not be construed as implying (eg, "a" and/or "an" should be construed to mean "at least one" or "one or more"). The same applies to the use of definite articles used to introduce claim statements. In addition, even where a specific number of claim statements being introduced is explicitly stated, one skilled in the art should understand that such statement should be interpreted to mean at least the recited number. (e.g., the express statement "two statements" without other modifiers means at least two statements, or more than one statement). Further, when a convention similar to "at least one of A, B, and C, etc." is used, such construction is generally intended in the sense that one of ordinary skill in the art would understand the convention. (For example, "a system having at least one of A, B, and C" includes only A, only B, only C, both A and B, both A and C, both B and C, and (including, but not limited to, systems having both A, B, and C). When a convention similar to "at least one of A, B, or C, etc." is used, such construction is generally intended in the sense that a person skilled in the art would understand the convention (e.g. , "a system having at least one of A, B, or C" means only A, only B, only C, both A and B, both A and C, both B and C, and/or (including, but not limited to, systems having both A, B, and C). Substantially any disjunctive word and/or phrase that presents two or more alternative terms, whether in the specification, claims, or drawings, includes one of the terms, any of the terms, It will be further understood by those skilled in the art that it should be understood to include the possibility of including either or both terms. For example, the phrase "A or B" will be understood to include the possibilities "A" or "B" or "A and B."

In addition, where a feature or aspect of the present disclosure may be described with respect to a Markush group, those skilled in the art will recognize that the disclosure may thereby also be described with respect to any individual element or subgroup of elements of the Markush group. will.

As will be understood by those skilled in the art, for any and all purposes, including in connection with providing a written description, all ranges disclosed herein also include each and every possible subrange and combination of subranges. do. Any enumerated range is sufficient to describe and enable the same range to be broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. can be easily recognized as As a non-limiting example, each range discussed herein can be easily broken down into a lower third, a middle third, an upper third, and so on. As those skilled in the art will understand, all phrases such as "up to", "at least", etc. refer to ranges that are inclusive of the recited number and that can subsequently be broken down into subranges, as discussed above. Finally, as will be understood by those skilled in the art, ranges include each individual element. Thus, for example, a group having 1 to 3% by weight refers to a group having 1, 2, or 3% by weight. Similarly, a group having 1 to 5% by weight refers to a group having 1, 2, 3, 4, or 5% by weight, etc., and includes everything in between.

Additionally, when stated ranges are provided for processing rates, such ranges are intended to include processing rates for individual components and/or mixtures of components. Thus, for example, a range of 1 to 3% by weight indicates that a given component may be present in a range of 1 to 3% by weight, or that a mixture of similar components may be present in a range of 1 to 3% by weight. plan.

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

Unless otherwise specified, "wt%" as used herein shall refer to weight percent based on the total weight of the composition on an oil-free basis.

As described below, the number average molecular weights of dispersant viscosity modifiers and viscosity modifiers have been determined using known methods such as GPC analysis using polystyrene standards. Methods for determining the molecular weight of polymers are well known. This method is described, for example, below. (i) P. J. Flory, "Principles of Polymer Chemistry", Cornell University Press 91953), Chapter VII, pp 266-315, or (ii) "Macromolecules, an In "Production to Polymer Science", F. A. Bovey and F. H. Winslow, Editors, Academic Press (1979), pp 296-312.

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

Claims (50)

a diesel engine lubricating composition having more than 50 weight percent of a Group III base oil, a Group IV base oil, a Group V base oil, or a mixture thereof;
a first PIB succinimide dispersant derived from 1800-2500 Mn PIB;
a second PIB succinimide dispersant derived from a PIB having an Mn of less than 1600, wherein at least one of the first PIB succinimide dispersant and the second PIB succinimide dispersant is free of boron. ,
The composition further comprises an alkaline earth metal salicylate detergent;
an alkaline earth metal sulfonate detergent present in an amount to provide 0.1% to 1.2% by weight alkaline earth metal soap in the lubricating composition;
a phosphorus antiwear agent present in an amount providing 300 to 900 ppm phosphorus in the lubricating composition;
The lubricating composition has a total sulfated ash content of 0.3 to 1.1 wt.%, a kinematic viscosity at 100° C. of less than 8.3 cSt, and a total alkaline earth content of 0.6 wt.% to 2.1 wt.%. A composition having a metallic soap and an HTHS of less than 2.7 mPa·s measured according to ASTM D4683. The composition of claim 1, wherein the first PIB succinimide dispersant has a TBN (KOH/g) of 15-25. 3. The composition of claim 1 or 2, wherein the first PIB succinimide dispersant has a TBN (KOH/g) of 15-20. The composition according to any one of claims 1 to 3, wherein the PIB of the first PIB succinimide dispersant has a number average molecular weight of 1750 to 2200 Mn. A composition according to any one of claims 1 to 4, wherein the PIB of the first PIB succinimide dispersant has a number average molecular weight of 1800 to 2100 Mn. The composition according to any one of claims 1 to 5, wherein the PIB of the first PIB succinimide dispersant has a number average molecular weight of 1850 to 2150 Mn. A composition according to any preceding claim, wherein the first PIB succinimide dispersant is present in the lubricating composition in an amount of 0.5% to 10% by weight. A composition according to any preceding claim, wherein the first PIB succinimide dispersant is present in the lubricating composition in an amount of 0.8% to 6% by weight. A composition according to any preceding claim, wherein the first PIB succinimide dispersant is present in the lubricating composition in an amount of 1% to 5% by weight. A composition according to any preceding claim, wherein the first PIB succinimide dispersant is present in the lubricating composition in an amount of 1.5% to 5% by weight. Composition according to any one of claims 1 to 10, wherein the first PIB succinimide dispersant is prepared by a thermal direct alkylation process. Composition according to any one of claims 1 to 11, wherein the first PIB succinimide dispersant comprises a mixture of two dispersants. Composition according to any one of claims 1 to 12, wherein the second PIB succinimide dispersant is derived from PIB having a number average molecular weight of 750-1600. Composition according to any one of claims 1 to 13, wherein the second PIB succinimide dispersant is derived from PIB having a number average molecular weight of 1000-1600. Composition according to any one of the preceding claims, wherein the second PIB succinimide dispersant is derived from PIB having a number average molecular weight of 1200-1600. 14. The composition of claim 13, wherein the second PIB succinimide dispersant is derived from PIB having a number average molecular weight of 800-1150. 17. The composition of claim 13 or 16, wherein the second PIB succinimide dispersant is derived from PIB having a number average molecular weight of 900-1100. Composition according to any one of claims 1 to 17, wherein the second PIB succinimide dispersant is prepared by a thermal direct alkylation process. the second PIB succinimide dispersant in an amount of 1 to 5%, or 1.5 to 4.8%, or 1.8 to 4.6%, or 1.9 to 4.6% by weight; A composition according to any one of claims 1 to 18, wherein the composition is present in the lubricating composition. The second PIB succinimide dispersant comprises 1-5% by weight of a PIB succinimide dispersant derived from a PIB with an Mn of 900-1100 and 1-5% by weight of a PIB succinimide dispersant derived from a PIB with an Mn of 1200-1600. % PIB succinimide dispersant. Composition according to any one of claims 1 to 20, wherein the second PIB succinimide dispersant has a TBN (KOH/g) of 20 to 35. Composition according to any one of claims 1 to 21, wherein the second PIB succinimide dispersant has a TBN (KOH/g) of 25 to 30. Composition according to any one of claims 1 to 22, wherein the second PIB succinimide dispersant has a TBN (KOH/g) of 27 to 28. A composition according to any one of claims 1 to 23, wherein the first PIB succinimide dispersant is boronated. A composition according to any one of claims 1 to 23, wherein the second PIB succinimide dispersant is boronated. 25. or claim 24, wherein the first borated dispersant and the second borated dispersant are independently present in an amount to provide 25 to 400 (or 50 to 200) ppm by weight boron to the lubricating composition. 25. The composition according to 25. A composition according to any one of claims 1 to 26, wherein the alkaline earth metal salicylate detergent has a TBN (KOH/g) of 200 to 575 or 200 to 500. A composition according to any one of claims 1 to 27, wherein the alkaline earth metal salicylate is a calcium salicylate detergent having a TBN (KOH/g) of 250 to 350. A composition according to any one of claims 1 to 28, wherein the alkaline earth metal salicylate detergent has a metal ratio of 2 to 7, or 2 to 4, or 2.5 to 3.5. A composition according to any one of claims 1 to 29, wherein the alkaline earth metal sulfonate detergent is selected from calcium sulfonate detergents and magnesium sulfonate detergents. A composition according to any preceding claim, wherein the alkaline earth metal sulfonate detergent is a calcium sulfonate detergent. 32. The composition of claim 31, wherein the calcium sulfonate detergent has a TBN (KOH/g) of less than 200. 33. The composition of claim 31 or 32, wherein the calcium sulfonate detergent has a TBN (KOH/g) of less than 150, or less than 100, or less than 80. A composition according to any one of claims 31 to 33, wherein the calcium sulfonate detergent has a TBN (KOH/g) of 50 to 90. Any of claims 31 to 34, wherein the calcium sulfonate detergent is present in the lubricant composition in an amount of 0.5% to 2.0%, or 0.6% to 1.5% by weight. The composition according to item 1. A composition according to any preceding claim, wherein the alkaline earth metal sulfonate detergent is an overbased magnesium sulfonate detergent. 37. Any one of claims 1-29 and 36, wherein the overbased magnesium sulfonate detergent has a TBN (KOH/g) of 200-500, or 250-400, or 250-350, or 350-375. The composition described in. Claims 1-29, wherein the overbased magnesium sulfonate detergent is present in the lubricating composition in an amount from 0.05% to 0.2%, or from 0.06% to 0.1%, by weight. 36. The composition according to any one of 37. The alkaline earth metal sulfonate has a TBN of 250 to 350 (KOH/g) with 0.6% to 1.5% by weight of a calcium sulfonate detergent having a TBN (KOH/g) of 50 to 100. Composition according to any one of claims 1 to 30, comprising a mixture with 0.05% to 0.1% by weight of an overbased magnesium sulfonate detergent. 40. The total alkaline earth metal soap of the lubricating composition is from 0.6% to 1.5% or from 0.7% to 1.4% by weight. Composition of. Claims 1 to 4, wherein the phosphorus antiwear agent is zinc dialkyldithiophosphate in an amount that provides the lubricating composition with 400 ppm to 850 ppm, or 450 ppm to 800 ppm, or 500 ppm to 800 ppm, or 550 ppm to 780 ppm, or 650 ppm to 780 ppm. 41. The composition according to any one of 40. 42. A composition according to any one of claims 1 to 41, wherein the total sulfated ash content is between 0.3 and 0.9% by weight, or between 0.4 and 0.8% by weight. 43. A composition according to any one of claims 1 to 42, wherein the HTHS is less than 2.5, or less than 2.3, or less than 2.1. Any one of claims 1 to 43, wherein the HTHS is 1.4 to 2.5, or 1.6 to 2.1, or 1.8 to 2.1, or 1.9 to 2.0. The composition described in Section. A composition according to any one of claims 1 to 44, further comprising an ashless friction modifier. 46. The composition of any one of claims 1 to 45, further comprising a dispersant other than the first PIB succinimide dispersant and the second PIB succinimide dispersant. 47. A composition according to any one of claims 1 to 46, further comprising one or more additional additives selected from antioxidants, foam inhibitors, and corrosion inhibitors. The composition according to any one of claims 1 to 47, wherein the kinematic viscosity at 100° C. is 2.5 to 8.3 cSt or 3.5 to 6.5 cSt. A method of lubricating a diesel engine, comprising supplying the engine with a lubricant composition according to any one of claims 1 to 48. Use of a lubricating composition according to any one of claims 1 to 48 for improving one or more of fuel economy in a diesel engine and wear protection in a diesel engine.