Silicon-containing compound for lubricant

Abstract

To provide a lubricant composition and a method for lubricating a spark ignition engine, which are effective in reducing the number of low-speed pre-ignition (LSPI) events and maintaining low foam and / or low aeration.SOLUTION: A passenger car motor oil provided includes: one or more base oils of lubricating viscosity; silicon in an amount of about 15 ppm or less, provided from a polydialkylsiloxane antifoam polymer; and additional silicon in an amount of at least about 100 ppm, provided from a silicon-containing compound selected from a siloxane derivative, a silane derivative, or a combination thereof, wherein the silicon-containing compound providing the additional silicon has a molecular weight of about 650 or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to lubricating compositions, and more particularly to lubricating compositions configured to provide low aeration and / or low foaming with an increased silicon content.

Background Art

[0002] Automobile manufacturers continue to demand improvements in efficiency, fluid life, and fuel economy, and thus the requirements for engines, lubricants, and their components continue to increase. Today's engines are often smaller, lighter, and more efficient through technologies designed to improve fuel economy, performance, and output. These requirements also mean that the performance of engine oils must evolve to meet the higher demands of such modern engines and their corresponding performance criteria associated with their unique uses and applications. Such stringent requirements for engine oils often lead lubricant manufacturers to adjust lubricants and their additives to meet certain performance requirements for industrial and / or manufacturer applications. Typically, industry standards and / or automobile manufacturers require certain performance criteria where a lubricant or additive designed for one use or application may not have to meet all performance specifications for different uses or applications. Thus, changing the formulation of a lubricant using different additives often presents the problem that additional additives can improve one set of properties but can degrade another set of performance characteristics.

[0003] For example, compounds containing low concentrations of silicon, such as medium to high molecular weight polydimethylsiloxane polymers, are used in passenger vehicle lubricants for anti-foaming performance. The silicon-containing compounds can also help improve low-speed pre-ignition (LSPI) performance (ASTM D8291). However, depending on the chemical nature and / or treatment rate of silicon, it has been found that some silicon-containing compounds can be harmful to other types of lubricant performance. For example, some silicon-containing compounds can be harmful to foaming and / or aeration depending on the situation. Automobile manufacturers often have strict criteria for evaluating the tendency of oil to entrain free air during engine operation. For example, General Motors has an aeration test as part of its dexos (trademark) engine oil specifications. Other manufacturers have similar criteria. The added silicon useful for the LSPI performance of lubricants can result in lubricants that have difficulty achieving passable performance in other foaming and / or aeration tests required by certain manufacturers, so there can be drawbacks when formulating lubricants to achieve acceptable LSPI performance using added silicon. SUMMARY OF THE INVENTION

[0004] In one approach or embodiment, the present disclosure relates to a lubricating composition for a spark-ignition engine, and in one aspect, to a passenger vehicle motor oil configured to maintain low foaming and / or low aeration during lubrication and, in other aspects, to also maintain acceptable low-speed pre-ignition performance. In some embodiments, the passenger vehicle motor oil comprises one or more base oils of lubricating viscosity, silicon at about 15 ppm or less provided from a polydialkylsiloxane anti-foaming agent polymer, and at least about 100 ppm of additional silicon provided from a silicon-containing compound selected from a siloxane derivative, a silane derivative, or a combination thereof, wherein the silicon-containing compound providing the additional silicon has a molecular weight of about 650 or less.

[0005] In other approaches or embodiments, the passenger car motor oil of the previous paragraph can be combined in any combination with one or more other features or embodiments. These other features or embodiments include one or more of the following: The polydialkylsiloxane defoaming agent polymer is a polydimethylsiloxane polymer having a number average molecular weight of about 50,000 or more; and / or the silicon-containing compound providing additional silicon has 10 or fewer silicon-oxygen bonds per compound; and / or the passenger car motor oil, when operated in a naturally aspirated engine, incorporates less free air compared to a reference motor oil that does not contain the additional silicon provided by the silicon-containing compound; and / or the passenger car motor oil has an average occurrence number of 5 or less according to the Sequence IX low-speed early ignition test of ASTM D8291, and / or a maximum occurrence number of 8 or less according to the Sequence IX low-speed early ignition test of ASTM D8291; and / or the passenger car motor oil contains about 100 to about 300 ppm of additional silicon; and / or the passenger car motor oil contains about 100 to about 250 ppm of additional silicon; and / or the additional silicon is provided by a polyether-modified siloxane, a hydrocarbyl-modified siloxane, or a combination thereof; and / or the additional silicon is provided by a compound of formula II

[0006] [Chemical formula] wherein each R is independently a C1-C4 alkyl group, and R1 is (i) a C6-C 20 alkyl group or (ii) -R2-[O-R3] n -OR4 polyether group, R2 is a C1-C4 hydrocarbyl group, R3 is a C1-C4 hydrocarbyl group, R4 is either hydrogen or a C1-C4 hydrocarbyl group, n is an integer from 1 to 10, and m is an integer of 0 or 1; and / or each R in formula II is a methyl group, and R1 in formula II is C8-C 10It is a hydrocarbyl group, m is an integer of 0; and / or each R in Formula II is a methyl group, R1 in Formula II is a polyether group, R2 is a C3 group, R3 is a C1-C2 group, R4 is hydrogen, m is an integer of 0, n is an integer of 1; and / or each R in Formula II is a methyl group, R1 in Formula II is a polyether group, R2 is a C3 group, R3 is a C1-C2 group, R4 is a methyl group, m is an integer of 1, n is an integer of 1; and / or the additional silicon is provided by a hydrocarbylsilane compound having one or more silyl ether moieties; and / or the additional silicon is provided by a trialkoxyalkylsilane compound; and / or the additional silicon is provided by a triethoxycaprylylsilane compound.

[0007] In yet another approach or embodiment, a method is described herein for lubricating a combustion engine with a motor oil for a passenger vehicle to provide low foaming and / or low aeration with increased levels of silicon. In some aspects, the method also achieves acceptable low speed early ignition performance. In other aspects, the method described herein includes lubricating a combustion engine with a motor oil for a passenger vehicle, the motor oil for a passenger vehicle comprising: (i) one or more base oils of lubricating viscosity, (ii) silicon of about 15 ppm or less provided from a polydialkylsiloxane antifoam polymer, and (iii) at least about 100 ppm of additional silicon provided from a silicon-containing compound selected from a siloxane derivative, a silane derivative, or a combination thereof, the silicon-containing compound providing the additional silicon having a molecular weight of about 650 or less, the motor oil for a passenger vehicle causing less free air to be entrained compared to a reference motor oil that does not contain the additional silicon provided from the silicon-containing compound when operated in a naturally aspirated engine, the additional silicon.

[0008] In other approaches or embodiments, the method of the preceding paragraph may include any combination of other options, features, steps, or embodiments. These other options, features, steps, or embodiments include one or more of the following: The passenger car motor oil has an average occurrence number of 5 or less according to the Sequence IX low-speed early ignition test of ASTM D8291, and / or a maximum occurrence number of 8 or less according to the Sequence IX low-speed early ignition test of ASTM D8291; and / or the polydialkylsiloxane defoaming agent polymer is a polydimethylsiloxane polymer having a number average molecular weight of at least about 50,000; and / or the silicon-containing compound providing additional silicon has 10 or less silicon-oxygen bonds / compound; and / or the passenger car motor oil contains about 100 to about 300 ppm of additional silicon; and / or the passenger car motor oil contains about 100 to about 250 ppm of additional silicon; and / or the additional silicon is provided by a polyether-modified siloxane, a hydrocarbyl-modified siloxane, or a combination thereof; and / or the additional silicon is provided by a compound of formula II

[0009] [Chemical formula] wherein each R is independently a C1-C4 alkyl group, and R1 is (i) a C6-C 20 alkyl group or (ii) -R2-[O-R3] n -OR4 polyether group, R2 is a C1-C4 hydrocarbyl group, R3 is a C1-C4 hydrocarbyl group, R4 is either hydrogen or a C1-C4 hydrocarbyl group, n is an integer from 1 to 10, m is an integer of 0 or 1; and / or each R in formula II is a methyl group, and R1 in formula II is a C8-C 10It is a hydrocarbyl group, m is an integer of 0; and / or each R in Formula II is a methyl group, R1 in Formula II is a polyether group, R2 is a C3 group, R3 is a C1-C2 group, R4 is hydrogen, m is an integer of 0, n is an integer of 1; and / or each R in Formula II is a methyl group, R1 in Formula II is a polyether group, R2 is a C3 group, R3 is a C1-C2 group, R4 is a methyl group, m is an integer of 1, n is an integer of 1; and / or the additional silicon is provided by a hydrocarbylsilane compound having one or more silyl ether moieties; and / or the additional silicon is provided by a trialkoxyalkylsilane compound; and / or the additional silicon is provided by triethoxycaprylylsilane.

[0010] In a further approach or embodiment, the use of any embodiment of this summary, specifically, any embodiment of the passenger car motor oil described herein, when operated in a naturally aspirated engine, allows for less free air to be entrained compared to a reference motor oil that does not contain additional silicon provided by a silicon-containing compound (e.g., an aeration test such as those performed by any commercial testing agency such as Southwest Research Institute (SWRI), Intertek, etc., and performance tests such as those specified in the GMW17295 Engine Oil Aeration Evaluation for dexos(™) Oil Qualification test (GMAER) may be mentioned). In still other embodiments of the use, the use of any embodiment of the passenger car motor oil of this summary may also have an average occurrence number of 5 or less and / or a maximum occurrence number of 8 or less according to the Sequence IX low-speed early ignition test of ASTM D8291.

Mode for Carrying Out the Invention

[0011] The present disclosure relates to lubricating compositions and methods of lubricating a spark ignition engine effective to maintain low foaming and / or low aeration during lubrication. It has been discovered that certain treatment rates and certain chemical properties of silicon-containing compounds can effectively reduce foaming and aeration, while in some situations, qualified LSPI performance can also be maintained simultaneously. As used herein, low foaming and / or low aeration refers to the tendency of an oil to entrain free air during engine lubrication, such as the performance requirements in General Motors' dexos™ engine oil specifications or similar standards. Such aeration tests can be performed at any commercial testing facility such as Southwest Research Institute (SWRI), Intertek, and include performance tests such as the Engine Oil Aeration Evaluation for dexos™ Oil Qualification test (GMAER) of GMW 17295 or other similar aeration performance tests.

[0012] In one approach or embodiment, the present disclosure provides a passenger vehicle motor oil configured to provide qualified LSPI performance when including one or more base oils of lubricating viscosity, silicon of about 15 ppm or less provided from a medium to high molecular weight polydialkylsiloxane defoamer polymer such as a polydialkylsiloxane having a number average molecular weight of at least about 50,000 or more, and additional silicon of at least about 100 ppm (in other approaches, about 100 - 300 ppm of additional silicon) provided from a silicon-containing compound such as a selected trisiloxane derivative, a selected silane derivative, or a combination thereof, wherein each of the trisiloxane derivative and / or silane derivative providing the additional silicon has a molecular weight of about 650 or less.

[0013] The lubricants described herein are a combination of silicone from a polydialkylsiloxane antifoam polymer and silicon from a selected additional silicon compound described herein to achieve low air carryover and maintain acceptable LSPI performance. The pass criteria for air carryover (e.g., according to the GMAER evaluation of GMW 17295) typically requires comparing the reference oil run in the same engine with the candidate lubricants described herein. Less air carryover (e.g., a negative intake value) indicates a passing lubricant. The pass criteria for LSPI performance is that the average number of LSPI is 5 or less (and in other approaches, 4 or less, 3 or less, 2 or less, or 1 or less average LSPI) according to the Sequence IX low speed pre-ignition test of ASTM D8291, and / or the total number of LSPI is 8 or less (and in other approaches, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less total number) according to the Sequence IX low speed pre-ignition test of ASTM D8291.

[0014] The passenger vehicle motor oils described herein first contain about 15 ppm or less of silicon provided from a medium to high molecular weight polydialkylsiloxane antifoam polymer. In one approach, the medium to high molecular weight polydialkylsiloxane antifoam polymer has the structure of Formula I below and a number average molecular weight of at least about 50,000, and in other approaches, from about 50,000 to about 200,000:

[0015] [Chemical Formula] In the formula, each R in formula I is independently a C1-C4 alkyl group, preferably a methyl group, and n in formula I is an integer selected to achieve the desired molecular weight. In one approach, the medium to high molecular weight polydialkylsiloxane defoaming agent polymer is preferably a medium to high molecular weight polydimethylsiloxane polymer having the above molecular weight. In some approaches, the polydialkylsiloxane polymer has a degree of polymerization that results in more than 800 silicon-oxygen bonds in the polymer, and in other approaches, it has a degree of polymerization that results in about 800 to about 2000 silicon-oxygen bonds in the polymer. In some approaches, the polydialkylsiloxane defoaming agent polymer can be provided by an additive having a kinematic viscosity of more than about 10,000 cSt at 25°C, and in some approaches, it can be about 10,000 to about 100,000 cSt at 25°C.

[0016] As described above, the passenger car motor oil described herein also contains at least about 100 ppm of additional silicon provided from one or more specific silicon-containing compounds selected from among trisiloxane derivatives, silane derivatives, or combinations thereof, having a molecular weight of 650 grams per mole or less (preferably about 150 to about 450 g / mol, more preferably about 200 to about 420 grams per mole). The silicon-containing compound that provides this additional silicon has only a limited number of silicon-oxygen bonds in the compound, and in some approaches, it has 10 or fewer silicon-oxygen bonds per compound, preferably 6 or fewer silicon-oxygen bonds per compound, and most preferably 4 or fewer silicon-oxygen bonds per compound. The passenger car motor oil described herein preferably contains about 100 to about 300 ppm of this additional silicon, more preferably about 100 to about 250 ppm of this additional silicon.

[0017] In some approaches, the additional silicon is provided by a polyether-modified trisiloxane, a hydrocarbyl-modified trisiloxane, or a combination thereof. For example, the additional silicon is of formula II having a molecular weight of 650 grams per mole or less:

[0018] [Chemistry] can be provided by the compound of formula II, wherein each R in formula II is independently a C1-C4 alkyl group, and R1 in formula II is (i) a C6-C20 alkyl group or (ii) -R2-[O-R3] n -OR4 polyether group, R2 is a C1-C4 hydrocarbyl group, R3 is a C1-C4 hydrocarbyl group, R4 is either hydrogen or a C1-C4 hydrocarbyl group, n is an integer from 1 to 10, and m is an integer of 0 or 1. In some embodiments, each R in formula II can be a methyl group, and R1 in formula II is either a C8-C10 hydrocarbyl group or a polyether group, R2 is a C3-C4 hydrocarbyl group, R3 is a C2-C4 hydrocarbyl group, and n is an integer from 6 to 9. The compound of formula II preferably can have a molecular weight of about 300 to about 650 grams / mol. In polyether form, the compound of formula II can have a molecular weight of about 300 to about 650 g / mol, and in polyalkyl form, the compound of formula II can have a molecular weight of about 300 to about 400 g / mol.

[0019] In some approaches or embodiments, the additional silicon of formula II is such that each R in formula I is a methyl group, and R1 in formula II is a C6-C 10 hydrocarbyl group, preferably a C8-C 10 alkyl group, and m is an integer of 0. The preferred compound of this embodiment has a molecular weight of about 300 to about 350, specifically a molecular weight of 334.

[0020] In other approaches or embodiments, the additional silicon provided by the compound of formula II is such that each R in formula II is a methyl group, R1 in formula II is a polyether group, R2 is a C2-C3 group (preferably a C3 group), each R3 is independently a C1-C2 group (preferably a C2 group), R4 is hydrogen, m is an integer of 0, and n is an integer of 1. The preferred compound of this embodiment has a molecular weight of about 300 to about 350, specifically a molecular weight of 324.

[0021] In yet other embodiments, the additional silicon provided by the compound of Formula II is such that each R of Formula II is a methyl group, R1 of Formula II is a polyether group, R2 is a C2-C3 group (preferably a C3 group), each R3 is a C1-C2 group (preferably a C2 group), R4 is a methyl group, m is an integer of 1, and n is an integer of 1. Preferred compounds of this embodiment have a molecular weight of about 400 to about 450, specifically a molecular weight of 412.

[0022] In yet another approach or embodiment, the additional silicon can be provided by a hydrocarbylsilane compound having one or more silyl ether moieties. For example, the additional silicon can be a trialkoxyalkylsilane compound such as a triethoxycaprylylsilane compound or a similar compound. In other forms, for example, the trialkoxyalkylsilane compound can have a C1-C4 alkoxy group and a C4-C20 straight or branched alkyl group, more preferably a C6-C10 straight alkyl group. In some forms, the additional silicon can be provided by such a hydrocarbylsilane compound, preferably an ethoxylated hydrocarbylsilane compound having a molecular weight of about 250 to about 300 (specifically, a molecular weight of 276), and / or the hydrocarbylsilane compound can have up to 3 silicon-oxygen bonds.

[0023] As shown in the following examples, the passenger vehicle motor oil described herein contains a low treat rate of medium to high molecular weight polydialkylsiloxane defoamer polymer (e.g., 15 ppm or less), and thus, when the selected treat rate of the specific additional silicon is at least about 100 ppm, preferably about 100 ppm to about 300 ppm, more preferably about 100 ppm to about 250 ppm of the additional silicon having the selected chemical properties described above, the lubricant achieves acceptable foaming performance and / or aeration performance and simultaneously maintains acceptable LSPI performance. In other approaches, the fluids described herein can have a total silicon of about 100 to about 350 ppm provided by both a defoamer polymer and a compound containing the additional silicon described herein. In some approaches, the weight ratio of silicon from the compound containing the additional silicon to silicon from the medium to high molecular weight polydialkylsiloxane defoamer polymer can be from about 6:1 to about 15:1, and in other approaches, from about 6:1 to about 13:1, or at least from about 6:1 to about 12.9:1 or less, about 12.1:1 or less, about 12:1 or less, or about 11.5:1 or less.

[0024] Base oil or base oil blend: The base oil used in the passenger vehicle motor oil described herein can be an oil of lubricating viscosity and can be selected from any of the API Group I - V base oils defined in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. In one approach, the base oil of the lubricating composition described herein can be a blend of an API Group II base oil and an API Group III base oil. Surprisingly, when following the fluid element relationships described above, even lower quality base oils can be used in the lubricants described herein. The five base oil groups are generally shown in Table 1 below.

[0025]

Table 1

[0026] Groups I, II, and III are mineral oil process stocks. The base oils of Group IV contain true synthetic molecular species produced by the polymerization of olefinically unsaturated hydrocarbons. Many of the Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, or may be natural oils such as vegetable oils. The Group III base oils are derived from mineral oils, but it should be noted that due to the stringent processing these fluids undergo, their physical properties become very similar to those of some true synthetic oils such as PAO. Thus, oils derived from Group III base oils may be referred to as synthetic fluids in the industry. Group II+ may include high viscosity index Group II.

[0027] The base oil blend used in the disclosed lubricating oil compositions can be mineral oil, animal oil, vegetable oil, synthetic oil, synthetic oil blend, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and re-refined oils, and mixtures thereof.

[0028] Unrefined oils are those derived from natural, mineral, or synthetic sources without or with very little further refining treatment. Refined oils are similar to unrefined oils except that they have been treated in one or more refining steps that can result in the improvement of one or more properties. Examples of suitable refining techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, osmosis, etc. Oils refined to a quality suitable for food use may or may not be useful. Edible oils may sometimes also be called white oils. In some embodiments, the lubricating oil composition does not contain edible oil or white oil.

[0029] Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained in a similar manner to refined oils using the same or similar processes. Often, these oils are additionally treated by techniques aimed at removing used additives and oil degradation products.

[0030] Mineral oil can include oil obtained by excavation, or from plants and animals, or any mixture thereof. For example, such oils can include castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum, and solvent-treated or acid-treated mineral lubricating oils of paraffinic, naphthenic, or mixed paraffin-naphthenic type, but are not limited thereto. Such oils may be partially hydrogenated or fully hydrogenated if desired. Oils derived from coal or shale can also be useful.

[0031] Useful synthetic lubricating oils include hydrocarbon oils, such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymer); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs and homologs thereof, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0032] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decanephosphonic acid), or polymeric tetrahydrofuran. Synthetic oils may be produced by the Fischer-Tropsch reaction and may typically be hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by a Fischer-Tropsch gas-liquid synthesis procedure, as well as other gas-liquid oils.

[0033] The major amount of base oil contained in the lubricating composition can be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, provided that the major amount of base oil is other than that resulting from the provision of additive components or viscosity index improvers in the composition. In another embodiment, the major amount of base oil contained in the lubricating composition can be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, provided that the major amount of base oil is other than that resulting from the provision of additive components or viscosity index improvers in the composition.

[0034] The amount of oil of lubricating viscosity present can be the remaining balance after subtracting 100% by weight from the total amount of performance additives including viscosity index improvers and / or pour point depressants and / or other top treatment additives. For example, the oil of lubricating viscosity that can be present in the final fluid can be a major amount, such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0035] In some methods or embodiments, the base oil system herein includes one or more of Group I to Group V base oils and can have a KV100 of about 2 to about 20 cSt, in other methods about 2 to about 10 cSt, about 2.5 to about 6 cSt, in still other methods about 2.5 to about 3.5 cSt, and in other methods about 2.5 to about 4.5 cSt. (ASTM D445)

[0036] As used herein, the terms "oil composition", "lubricating composition", "lubricating oil composition", "lubricating oil", "lubricant composition", "fully formulated lubricant composition", "lubricant", and "lubricating and cooling fluid" are considered synonymous and fully interchangeable terms that refer to a finished lubricating product that includes a major amount of base oil component and minor amounts of detergents and other optional components.

[0037] Optional Additives: The lubricating oil composition described herein may also contain a number of optional additives in combination with an antifoam polymer and the above-described additional silicon-containing compound. These optional additives are described in the following paragraphs.

[0038] Dispersants: The lubricating oil composition may optionally contain one or more dispersants or mixtures thereof. Dispersants do not contain metals that form ash before being mixed into the lubricating oil composition and typically do not contribute to ash when added to the lubricant, and are thus often known as ashless dispersants. Ashless dispersants are characterized in that the polar group is bonded to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or to about 5,000, or to about 3,000 as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Patent No. 7,897,696 or U.S. Patent No. 4,234,435. The alkenyl substituent can be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines (typically poly(ethyleneamine)).

[0039] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, higher homologues such as diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), and pentaethylamine hexamine (PEHA).

[0040] Suitable heavy polyamines include small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but mainly include polyalkylene-polyamine mixtures containing six or more nitrogen atoms, two or more primary amines per molecule, and oligomers with a broader range of branching than conventional polyamine mixtures. The heavy polyamine preferably contains polyamine oligomers having seven or more nitrogen atoms per molecule and two or more primary amines per molecule. The heavy polyamine contains more than 28% by weight (for example, more than 32% by weight) of total nitrogen and 120 to 160 grams of equivalent of primary amine groups per equivalent.

[0041] In some approaches, suitable polyamines are generally known as PAM and contain mixtures of ethyleneamines in which TEPA and pentaethylenehexamine (PEHA) are the major part of the polyamine and are usually less than about 80%.

[0042] Typically, PAM has 8.7 to 8.9 milliequivalents of primary amine per gram (115 to 112 grams of equivalent per equivalent of primary amine) and a total nitrogen content of about 33 to 34% by weight. A heavier cut of PAM oligomers that contains substantially no TEPA and only trace amounts of PEHA but mainly contains more than six nitrogen atoms and oligomers with a broader range of branching may produce a dispersant with improved dispersibility.

[0043] In embodiments, the disclosure further includes at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000, or to about 5,000, or to about 3,000 as determined by GPC. The polyisobutylene succinimide can be used alone or in combination with other dispersants.

[0044] In some embodiments, when polyisobutylene is included, the polyisobutylene can have a terminal double bond content of more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, or more than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0045] When determined by GPC, HR-PIB having a number average molecular weight in the range of about 900 to about 3000 can be suitable. Such HR-PIB is commercially available or can be synthesized by the polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride as described in U.S. Patent No. 4,152,499 to Boerzel, et al. and U.S. Patent No. 5,739,355 to Gateau, et al. When HR-PIB is used in the above-mentioned thermal ene reaction, the HR-PIB can result in a higher conversion rate during the reaction and a lower amount of precipitate formation due to the increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0046] In one embodiment, the present disclosure further includes at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). PIBSA can have an average of about 1.0 to about 2.0 succinic acid moieties per polymer.

[0047] The active ingredient percentage of alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0048] The percent conversion of the polyolefin is calculated from the active ingredient % using the formulas in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0049] Unless otherwise stated, all percentages are by weight and all molecular weights are number average molecular weights determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having a number average molecular weight of 180 to about 18,000 as a calibration standard).

[0050] In one embodiment, the dispersant can be derived from polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant can be derived from an olefin maleic anhydride copolymer. As an example, the dispersant can be described as poly-PIBSA. In embodiments, the dispersant can be derived from an anhydride grafted onto an ethylene-propylene copolymer.

[0051] A preferred class of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants that can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can react with functionalized OCPs is described in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383 and / or is commercially available.

[0052] One class of suitable dispersants can also be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Patent No. 3,634,515.

[0053] Suitable classes of dispersants can also be high molecular weight esters or semi-ester amides. Suitable dispersants can also be post-treated by reaction with any of a variety of agents by conventional methods. Among these are boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. U.S. Patent No. 7,645,726, U.S. Patent No. 7,214,649, and U.S. Patent No. 8,048,831 are hereby incorporated by reference in their entirety.

[0054] In addition to the post-treatment of carbonate and boric acid, the compounds can all be post-treated or further post-treated by various post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Patent No. 5,241,003, which is incorporated herein by reference. Such treatments include the following. Inorganic phosphoric acid or anhydride (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Patent No. 3,502,677); phosphorus pentasulfide; boron compounds as already described above (e.g., U.S. Patent Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Patent Nos. 3,708,522 and 4,948,386); epoxides, polyepoxides, or thioepoxides (e.g., U.S. Patent Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Patent No. 3,458,530); carbon disulfide (e.g., U.S. Patent No. 3,256,185); glycidol (e.g., U.S. Patent No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Patent Nos. 3,312,619, 3,865,813, and British Patent No. 1,065,595); organic sulfonic acids (e.g., U.S. Patent No. 3,189,544 and British Patent No. 2,140,811); alkenyl cyanide (e.g., U.S. Patent Nos. 3,278,550 and 3,366,569); diketene (e.g., U.S. Patent No. 3,546,243); diisocyanate (e.g., U.S. Patent No. 3,573,205); alkanesultone (e.g., U.S. Patent No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Patent No. 3,954,639); cyclic lactones (e.g., U.S. Patent Nos. 4,617,138, 4,645,515, 4,668,246, 4,963,275, and 4,971,711);Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. 2,140,811); hydroxy-protected dichlorocarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460); cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected dichlorocarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Patent Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Patent Nos. 4,482,464, 4,521,318, 4,713,189); oxidizing agents (e.g., U.S. Patent No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Patent No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Patent Nos. 3,390,086, 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Patent No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Patent Nos. 3,649,229, 5,030,249, 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acid (e.g., U.S. Patent No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acids (e.g., U.S. Patent No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids, followed by formaldehyde and phenol (e.g., U.S. Patent No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids and, followed by aliphatic dicarboxylic acids (e.g., U.S. Patent No. 4,663,064); combinations of formaldehyde and phenol, and, followed by glycolic acid (e.g., U.S. Patent No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid and, followed by diisocyanates (e.g., U.S. Patent No. 4,713,191); combinations of inorganic acids or anhydrides of phosphorus or their partial or total sulfur analogs and boron compounds (e.g., U.S. Patent No. 4,857,214); combinations of organic diacids, followed by unsaturated fatty acids, and, followed by nitrosoaromatic amines, optionally followed by boron compounds, and, followed by glycolating agents (e.g., U.S. Patent No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Patent No. 4,963,278); combinations of aldehydes and triazoles, followed by boron compounds (e.g., U.S. Patent No. 4,981,492); combinations of cyclic lactones and boron compounds (e.g., U.S. Patent No. 4,963,275 and No. 4,971,711). Here, the patents mentioned above are incorporated herein in their entirety.;

[0055] The TBN of a suitable dispersant can be about 10 to about 65 mg KOH / g dispersant on an oil-free basis, comparable to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluted oil. The TBN is measured by the method of ASTM D2896.;

[0056] In still other embodiments, the optional dispersant additive can be a hydrocarbyl-substituted succinamide dispersant or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide dispersant or succinimide dispersant can be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, provided that the hydrocarbyl substituent of the succinamide dispersant or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of from about 250 to about 5,000 as measured by GPC using polystyrene as a calibration standard.

[0057] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0058]

Chemical formula

[0059] When present, the dispersant can be used in an amount sufficient to provide up to about 20 wt% based on the final weight of the lubricating oil composition. Another amount of dispersant that can be used is from about 0.1 wt% to about 15 wt%, or from about 0.1 wt% to about 10 wt%, about 0.1 to 8 wt%, or from about 1 wt% to about 10 wt%, or from about 1 wt% to about 8 wt%, or from about 1 wt% to about 6 wt% based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A mixture of a single type or two or more types of dispersants in any desired ratio can be used.

[0060] Antioxidant: The lubricating oil composition herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamine, alkylated phenyl-alpha-naphthylamine, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds can be used alone or in combination.

[0061] The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as the sterically hindering group. The phenol group may be further substituted with a crosslinking group that binds to a hydrocarbyl group and / or a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant can be an ester and may include, for example, Irganox™ L-135 available from BASF or an adduct derived from 2,6-di-tert-butylphenol and an alkyl acrylate, where the alkyl group may contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant can be an ester and may include Ethanox™ 4716 available from Albemarle Corporation.

[0062] Useful antioxidants can include diarylamines and high molecular weight phenols. In embodiments, the lubricating oil composition can contain a mixture of a diarylamine and a high molecular weight phenol, and thus each antioxidant can be present in an amount sufficient to provide up to about 5 wt% based on the final weight of the lubricating oil composition. In embodiments, the antioxidant can be a mixture of about 0.3 to about 1.5 wt% diarylamine and about 0.4 to about 2.5 wt% high molecular weight phenol based on the final weight of the lubricating oil composition.

[0063] Examples of suitable olefins that can be sulfided to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, and their dimers, trimers, and tetramers are particularly useful olefins. Alternatively, the olefin can be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester such as butyl acrylate.

[0064] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. Fatty acids are often obtained from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as alpha-olefins.

[0065] In another alternative embodiment, the antioxidant composition also contains a molybdenum-containing antioxidant in addition to the phenolic and / or amine antioxidants discussed above. When a combination of these three antioxidants is used, preferably, the ratio of the treatment rates of the phenol, amine, and molybdenum-containing components is (0 to 3):(0 to 3):(0 to 3).

[0066] One or more antioxidants may be present in the range of about 0 wt% to about 20 wt%, or about 0.1 wt% to about 10 wt%, or about 1 wt% to about 5 wt% of the lubricating oil composition.

[0067] Antiwear agent: The lubricating oil composition herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphate esters or salts thereof; phosphate esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds such as thiocarbamate esters, alkylene-bonded thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof, but are not limited thereto. A suitable antiwear agent can be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are fully described by European Patent No. 612839. The metal in the dialkyldithiophosphate salt can be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent can be zinc dialkyldithiophosphate.

[0068] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-bonded thiocarbamates, and bis(S-alkyl dithiocarbamyl) disulfides. The tartrates or tartrimides may contain alkyl-ester groups, but the total number of carbon atoms on the alkyl groups can be at least 8. In one embodiment, the antiwear agent may include citrates.

[0069] The antiwear agent can be present in the lubricating oil composition in an amount ranging from about 0 wt% to about 15 wt%, or about 0.01 wt% to about 10 wt%, or about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt%.

[0070] Boron-containing compounds: The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include boric esters, boric acid fatty amines, boric acid epoxides, boronated detergents, and boronated dispersants such as boronated succinimide dispersants as disclosed in U.S. Patent No. 5,883,057. When present, the boron-containing compounds can be used in an amount sufficient to provide up to about 8 wt%, about 0.01 wt% to about 7 wt%, about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt% of the lubricating oil composition.

[0071] Detergent: The lubricating oil composition may optionally further contain one or more neutral detergents, low-base detergents, or overbased detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphoric acids, alkylphenols, sulfur-bonded alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in detail in numerous patent publications, including U.S. Patent No. 7,732,390 and the references cited therein.

[0072] The detergent base can be salted with an alkali metal or alkaline earth metal such as calcium, magnesium, potassium, sodium, lithium, barium, or a mixture thereof, but is not limited thereto. In some embodiments, the detergent does not contain barium. In some embodiments, the detergent may contain trace amounts of other metals such as magnesium or calcium in an amount of 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali metal salts or alkaline earth metal salts of petroleum sulfonic acids and long-chain mono- or di-alkylaryl sulfonic acids whose aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include calcium phenolate, sulfur-containing calcium phenolate, calcium sulfonate, calcium carlexarate, calcium salexarate, calcium salicylate, calcium carboxylate, calcium phosphate, mono- and / or di-thiophosphate calcium, calcium alkylphenol, calcium sulfur-bonded alkylphenol compound, calcium methylene-bridged phenol, magnesium phenolate, sulfur-containing magnesium phenolate, magnesium sulfonate, magnesium carlexarate, magnesium salexarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, mono- and / or di-thiophosphate magnesium, magnesium alkylphenol, magnesium sulfur-bonded alkylphenol compound, magnesium methylene-bridged phenol, sodium phenolate, sulfur-containing sodium phenolate, sodium sulfonate, sodium carlexarate, sodium salexarate, sodium salicylate, sodium carboxylate, sodium phosphate, mono- and / or di-thiophosphate sodium, sodium alkylphenol, sodium sulfur-bonded alkylphenol compound, or sodium methylene-bridged phenol, but are not limited thereto.

[0073] Overbased detergent additives are well known in the art and can be alkali or alkaline earth metal overbased detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

[0074] The term "overbased" relates to metal salts such as metal salts of sulfonic acids, carboxylic acids, and phenols where the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion level greater than 100% (i.e., such salts can contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard salt", "neutral salt"). In many cases, the expression "metal ratio", abbreviated as MR, is used to indicate the ratio of the total chemical equivalent of the metal in the overbased salt to the chemical equivalent of the metal in the neutral salt, according to known chemical reactivity and stoichiometry. In the standard or neutral salt, the metal ratio is 1, but in the overbased salt, the MR is greater than 1. They are generally referred to as overbased, highly basic, or superbasic salts and can be salts of organic sulfuric acids, carboxylic acids, or phenols.

[0075] The overbased detergent of the lubricating oil composition can have a total base number (TBN) of about 200 mg KOH / g or more, or as a further example, about 250 mg KOH / g or more, or about 350 mg KOH / g or more, or about 375 mg KOH / g or more, or about 400 mg KOH / g or more. The TBN is measured by the method of ASTM D2896.

[0076] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased calcium sulfur-containing phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salixarate, overbased calcium salicylate, overbased calcium carboxylate, overbased calcium phosphate, overbased calcium mono- and / or di-thiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-bonded alkylphenol compound, overbased calcium methylene-bridged phenol, overbased magnesium phenate, overbased magnesium sulfur-containing phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylate, overbased magnesium phosphate, overbased magnesium mono- and / or di-thiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-bonded alkylphenol compound, or overbased magnesium methylene-bridged phenol.

[0077] Overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 mg KOH / g to about 350 mg KOH / g when measured by the method of ASTM D2896. When such a detergent composition is formed in an inert diluent, such as a process oil, usually a mineral oil, the total base number reflects the basicity of the overall composition including the diluent and any other materials (e.g., accelerators, etc.) that may be included in the detergent composition.

[0078] Overbased detergents can have a metal-to-substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective for reducing or preventing rust in an engine or other automotive parts such as a transmission or gears. The detergent can be present in the lubricating composition at from about 0 wt% to about 10 wt%, or from about 0.1 wt% to about 8 wt%, or from about 1 wt% to about 4 wt%, or greater than about 4 wt% up to about 8 wt%.

[0079] Extreme Pressure Agents: The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Extreme Pressure (EP) agents soluble in oil include sulfur and chlorosulfur-containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyldisulfide, bis(chlorobenzyl)disulfide, dibutyltetrasulfide, methyl ester of sulfurized oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels - Alder adducts; phosphorus-sulfurized hydrocarbons such as the reaction product of phosphorus sulfide with terpentin or methyl oleate; dihydrocarbyl and trihydrocarbyl phosphites, for example, phosphate esters such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphoric acids, including, for example, amine salts of the reaction product of dialkyldithiophosphoric acid and propylene oxide; and mixtures thereof.

[0080] Friction modifier: The lubricating oil composition herein may also optionally contain one or more friction modifiers. Suitable friction modifiers can include those containing metals and those not containing metals, such as imidazoline, amide, amine, succinimide, alkoxylated amine, alkoxylated ether amine, amine oxide, amide amine, nitrile, betaine, quaternary amine, imine, amine salt, aminoguanidine, alkanolamide, phosphonate, metal-containing compound, glycerol ester, sulfurized fatty compound and olefin, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid ester, ester or partial ester of a polyol and one or more aliphatic or aromatic carboxylic acids, etc., but are not limited thereto.

[0081] Suitable friction modifiers can contain a hydrocarbyl group selected from a straight-chain, branched-chain, or aromatic hydrocarbyl group, or a mixture thereof, which can be saturated or unsaturated. The hydrocarbyl group can be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl group can range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier can be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester can be a mono-ester, or di-ester, or (tri)glyceride. The friction modifier can be a long-chain fatty amide, long-chain fatty ester, long-chain fatty epoxide derivative, or long-chain imidazoline.

[0082] Other suitable friction modifiers can include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols and can generally include polar end groups (such as carboxyl or hydroxyl) covalently bonded to lipophilic hydrocarbon chains. Examples of organic ashless nitrogen-free friction modifiers are generally known as glycerol monooleate (GMO), which can contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, which is hereby incorporated by reference in its entirety.

[0083] Aminic friction modifiers can include amines or polyamines. Such compounds can have hydrocarbyl groups that are linear, either saturated or unsaturated, or mixtures thereof, and can contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds can have hydrocarbyl groups that are linear, either saturated, unsaturated, or mixtures thereof. These can contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0084] Amines and amides can be used as such or in the form of adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid, or mono-, di-, or tri-alkyl borates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is hereby incorporated by reference in its entirety.

[0085] The friction modifier can optionally be present in ranges such as from about 0 wt% to about 10 wt%, or from about 0.01 wt% to about 8 wt%, or from about 0.1 wt% to about 4 wt%.

[0086] Molybdenum-containing components: The lubricating oil composition herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional performance of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organic molybdenum compounds, and / or mixtures thereof. Examples of molybdenum sulfide include molybdenum disulfide. Molybdenum disulfide can be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound can be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound can be molybdenum dithiocarbamate.

[0087] Suitable examples of molybdenum compounds that can be used include commercially available materials sold under trademark names such as Molyvan® 822, Molyvan® A, Molyvan® 2000, and Molyvan® 855 from R.T. Vanderbilt Co., Ltd., and Adeka Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Patent Nos. 5,650,381, Reissue Patent Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entireties of which are incorporated herein by reference.

[0088] Additionally, the molybdenum compound can be an acidic molybdenum compound. Those included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, the composition can provide molybdenum by, for example, a molybdenum / sulfur complex of a basic nitrogen compound as described in U.S. Patent Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and International Publication No. 94 / 06897, the foregoing patent documents being incorporated herein by reference in their entirety.

[0089] Another class of suitable organic molybdenum compounds are trinuclear molybdenum compounds, such as the formula Mo3S k L n Q z of compounds and mixtures thereof, where S represents sulfur, L represents independently selected ligands having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is from 1 to 4, k varies from 4 to 7, Q is a neutral electron donating compound, such as selected from the group of water, amines, alcohols, phosphines, and ethers, z is in the range from 0 to 5, including non-stoichiometric values. Among the organic groups of all the ligands, at least 21 total carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms, may be present. Additional suitable molybdenum compounds are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in its entirety.

[0090] The oil-soluble molybdenum compound can be present in an amount sufficient to provide from about 0.5 ppm to about 2000 ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 550 ppm, from about 5 ppm to about 300 ppm, or from about 20 ppm to about 250 ppm of molybdenum.

[0091] Transition metal-containing compound: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or a metalloid. The transition metal may include, but is not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0092] In an embodiment, the oil-soluble transition metal-containing compound can function as an antiwear agent, a friction modifier, an antioxidant, an adhesion control additive, or one or more of these functions. In an embodiment, the oil-soluble transition metal-containing compound can be an oil-soluble titanium compound such as titanium(IV) alkoxide. Among the titanium-containing compounds that can be used or can be used therefor in the preparation of the oil-soluble materials in the technology of the present disclosure, there are various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes such as titanium phenate; titanium carboxylates such as titanium(IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium(IV)(triethanolaminato)isopropoxide, but are not limited thereto. Other forms of titanium included in the disclosed technology include titanium phosphates such as titanium dithiophosphate (e.g., dialkyldithiophosphate) and titanium sulfonate (e.g., alkylbenzene sulfonate), or generally reaction products of titanium compounds forming salts such as oil-soluble salts with various acid materials. Thus, the titanium compounds can be derived, inter alia, from organic acids, alcohols, and glycols. The Ti compounds can also exist in a dimeric or oligomeric form containing a Ti-O-Ti structure. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques known to those skilled in the art. These can exist as solids or liquids at room temperature depending on the particular compound. These can also be provided in solution form in a suitable inert solvent.

[0093] In one embodiment, titanium can be supplied as a Ti-modified dispersant such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride such as alkenyl- (or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly or reacted with any of several materials such as (a) a polyamine-based succinimide / amide dispersant having a free condensable -NH functional group; (b) components of a polyamine-based succinimide / amide dispersant, namely, an alkenyl (or alkyl) succinic anhydride and a polyamine; (c) a hydroxy-containing polyester dispersant prepared by reaction of a substituted succinic anhydride with a polyol, an amino alcohol, a polyamine, or a mixture thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents such as an alcohol, an amino alcohol, an ether alcohol, a polyether alcohol or a polyol, or a fatty acid, but the product can be used directly to impart Ti to a lubricating oil or further reacted with a succinic acid dispersant as described above. By way of example, 1 part (mole) of tetraisopropyl titanate can be reacted with about 2 parts (mole) of polyisobutene-substituted succinic anhydride at 140-150 °C for 5-6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can be further reacted at 150 °C for 1.5 hours with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) to produce a titanium-modified succinimide dispersant.

[0094] Another titanium-containing compound can be the reaction product of a titanium alkoxide and a C6-C 25 carboxylic acid. The reaction product can be represented by the following formula:

[0095] [Chemical formula] (wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms) or by the following formula:

[0096] [Chemical formula] (wherein m + n = 4, n ranges from 1 to 3, R4 is an alkyl moiety having from 1 to 8 carbon atoms, R1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from hydrocarbyl groups containing from 1 to 6 carbon atoms), or the titanium compound has the following formula:

[0097] [Chemical formula] (wherein x ranges from 0 to 3, R1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms, R2 and R3 are the same or different and are selected from hydrocarbyl groups containing from about 1 to 6 carbon atoms, and R4 is selected from the group consisting of H, C6 - C 25 any of the carboxylic acid moieties).

[0098] Suitable carboxylic acids can include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, etc.

[0099] In an embodiment, the oil - soluble titanium compound can be present in the lubricating oil composition in an amount to provide from about 0 to about 3000 weight ppm of titanium, or from 25 to about 1500 weight ppm of titanium, or from about 35 weight ppm to about 500 weight ppm of titanium, or from about 50 ppm to about 300 ppm.

[0100] Viscosity Index Improver: The lubricating oil composition herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. The viscosity index improver may include star polymers, and suitable examples are described in U.S. Patent Application Publication No. 20120101017(A1).

[0101] The lubricating oil composition herein may optionally contain one or more dispersant viscosity index improvers in addition to or instead of the viscosity index improver. Suitable dispersant viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine, polymethacrylates functionalized with an amine, or esterified maleic anhydride-styrene copolymers reacted with an amine.

[0102] The total amount of the viscosity index improver and / or the dispersant viscosity index improver may be about 0 wt% to about 20 wt%, about 0.1 wt% to about 15 wt%, about 0.1 wt% to about 12 wt%, or about 0.5 wt% to about 10 wt% of the lubricating oil composition.

[0103] Other Optional Additives: Other additives may be selected to perform one or more functions required for the lubricating fluid. Further, one or more of the aforementioned additives may be multifunctional and may provide additional functions in addition to or other than the functions described herein.

[0104] The lubricating oil composition according to the present disclosure may optionally contain other performance additives. The other performance additives may be additional to the specific additives of the present disclosure and / or may include one or more of a metal deactivator, a viscosity index improver, a detergent, an ashless TBN booster, a friction modifier, an antiwear agent, a corrosion inhibitor, a rust inhibitor, a dispersant, a dispersant viscosity index improver, an extreme pressure agent, an antioxidant, a foam inhibitor, a demulsifier, an emulsifier, a pour point depressant, a seal swell agent, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0105] Suitable metal deactivators include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam inhibitors including copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers including trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; and pour point depressants including esters of maleic anhydride-styrene, polymethacrylate, polyacrylate, or polyacrylamide may be mentioned.

[0106] Suitable rust inhibitors can be a single compound or a mixture of compounds having the property of suppressing corrosion of the iron metal surface. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and serotic acid, and oil-soluble polycarboxylic acids including dimeric and trimeric acids such as those produced from tall oil fatty acid, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid, wherein the alkenyl group contains about 10 or more carbon atoms. Another useful type of acidic corrosion inhibitor is a half-ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group and an alcohol such as polyglycol. The corresponding semi-amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0107] When present, the rust inhibitor can be used in an amount sufficient to provide from about 0 wt% to about 5 wt%, from about 0.01 wt% to about 3 wt%, from about 0.1 wt% to about 2 wt% based on the final weight of the lubricating oil composition.

[0108] Generally speaking, suitable lubricants containing detergent metals herein can contain additive components within the ranges listed in the following table.

[0109]

Table 2

[0110] The percentages of the above components represent the weight percentages of the components based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used when formulating the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferred to use an additive concentrate (i.e., an additive plus a diluent such as a hydrocarbon solvent) to blend all of the components simultaneously. A fully formulated lubricating oil conventionally contains a dispersant / inhibitor package or DI package and an additive package as referred to herein that supplies the properties required in the formulation.

[0111] Definitions For the purposes of this disclosure, chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed. Additionally, general principles of organic chemistry are described in “Organic Chemistry”, Thomas Sorrell, University Science Books, Sausolito: 1999, and “March’s Advanced Organic Chemistry”, 5th Ed., Ed.: Smith, M.B. and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are incorporated herein by reference.

[0112] As described herein, a compound can be optionally substituted with one or more substituents as generally illustrated above, or as illustrated by a particular class, subclass, and species of this disclosure.

[0113] Unless otherwise apparent from the context, the term “major amount” is understood to mean an amount of 50 weight percent or more, e.g., about 80 to about 98 weight percent, based on the total weight of the composition. Also, as used herein, the term “minor amount” is understood to mean an amount less than 50 weight percent based on the total weight of the composition.

[0114] As used herein, the terms "hydrocarbyl group" or "hydrocarbyl" are used in their ordinary meaning well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly bonded to the rest of the molecule and mainly having hydrocarbon characteristics. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl) substituents, cycloaliphatic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic-substituted, and cycloaliphatic-substituted aromatic substituents, and cyclic substituents where the ring is completed through another part of the molecule (e.g., two substituents together form a cycloaliphatic radical); (2) substituted hydrocarbon substituents, i.e., in the context of the present disclosure, non-hydrocarbon groups (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy) that do not mainly change the hydrocarbon substituent; (3) hetero substituents, i.e., in the context of the present disclosure, substituents that mainly have hydrocarbon characteristics while containing something other than carbon in the ring or chain or are otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. Generally, there are two or fewer non-hydrocarbon substituents per ten carbon atoms in the hydrocarbyl group, or as a further example, only one non-hydrocarbon substituent is present, and in some embodiments, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

[0115] As used herein, the term "aliphatic" includes the terms alkyl, alkenyl, and alkynyl, each of which is optionally substituted as described below.

[0116] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing from 1 to 12 (e.g., 1 to 8, 1 to 6, or 1 to 4) carbon atoms. The alkyl group can be linear or branched. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or 2-ethylhexyl. The alkyl group can be substituted with one or more substituents such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic) carbonyl, (alicyclic) carbonyl, or (heteroalicyclic) carbonyl], nitro, cyano, amide [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylaminoalkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, or heteroalicyclic amino], sulfonyl [e.g., aliphatic -SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide, oxo, carboxy, carbamoyl, alicyclic oxy, heterocycloaliphatic oxy, aryloxy, heteroaryloxy, aralkyloxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy, i.e., optionally substituted.While not limiting, some examples of substituted alkyl include carboxyalkyl (e.g., HOOC-alkyl, alkoxycarbonylalkyl, and alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl)alkyl, (sulfonylamino)alkyl (e.g., (alkyl-SO2-amino)alkyl), aminoalkyl, amidoalkyl, (alicyclic)alkyl, or haloalkyl.

[0117] As used herein, the term "alkenyl" refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like an alkyl group, an alkenyl group can be linear or branched. Examples of alkenyl groups include, but are not limited to, allyl, isoprenyl, 2-butenyl, and 2-hexenyl. An alkenyl group can be optionally substituted with one or more substituents such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic) carbonyl, (alicyclic) carbonyl, or (heteroalicyclic) carbonyl], nitro, cyano, amide [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylaminoalkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, heteroalicyclic amino, or aliphatic sulfonylamino], sulfonyl [e.g., alkyl-SO2-, alicyclic-SO2-, or aryl-SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide, oxo, carboxy, carbamoyl, alicyclic oxy, heteroalicyclic oxy, aryloxy, heteroaryloxy, aralkyloxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy. Some examples of substituted alkenyls include, but are not limited to, cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aralkenyl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (e.g., (alkyl-SO2-amino)alkenyl), aminoalkenyl, amidoalkenyl, (alicyclic)alkenyl, or haloalkenyl.

[0118] As used herein, the term "alkynyl" refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and having at least one triple bond. The alkynyl group can be linear or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. The alkynyl group can be optionally substituted with one or more substituents such as aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxy, cyano, halo, hydroxy, sulfo, mercapto, sulfanyl [e.g., aliphatic sulfanyl or alicyclic sulfanyl], sulfinyl [e.g., aliphatic sulfinyl or alicyclic sulfinyl], sulfonyl [e.g., aliphatic -SO2-, aliphatic amino -SO2-, or alicyclic -SO2-], amide [e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, arylaminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (cycloalkylalkyl)carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino, or heteroarylaminocarbonyl], urea, thiourea, sulfamoyl, sulfamide, alkoxycarbonyl, alkylcarbonyloxy, alicyclic, heterocycloalicyclic, aryl, heteroaryl, acyl [e.g., (alicyclic)carbonyl or (heterocycloalicyclic)carbonyl], amino [e.g., aliphatic amino], sulfoxy, oxo, carboxy, carbamoyl, (alicyclic)oxy, (heterocycloalicyclic)oxy, or (heteroaryl)alkoxy.

[0119] As used herein, the term "amino" refers to -NR X R Y wherein R X and R YEach of them is independently hydrogen, alkyl, cycloalkyl, (cycloalkyl)alkyl, aryl, aralkyl, heterocycloalkyl, (heterocycloalkyl)alkyl, heteroaryl, carboxy, sulfanyl, sulfinyl, sulfonyl, (alkyl)carbonyl, (cycloalkyl)carbonyl, ((cycloalkyl)alkyl)carbonyl, arylcarbonyl, (aralkyl)carbonyl, (heterocycloalkyl)carbonyl, ((heterocycloalkyl)alkyl)carbonyl, (heteroaryl)carbonyl, or (heteroaralkyl)carbonyl, each of which is defined herein and optionally substituted. Examples of amino groups include alkylamino, dialkylamino, or arylamino. When the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is represented by -NR X -. R X is synonymous with those defined above.

[0120] As used herein, a "cycloalkyl" group refers to a saturated carbocyclic monocyclic or bicyclic (fused or bridged) ring of 3 to 10 (e.g., 5 to 10) carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cubyl, octahydroindenyl, decahydronaphthyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, bicyclo[3.3.1]nonyl, bicyclo[3.3.2.]decyl, bicyclo[2.2.2]octyl, adamantyl, or ((aminocarbonyl)cycloalkyl)cycloalkyl.

[0121] As used herein, the term "heterocycloalkyl" refers to a 3- to 10-membered monocyclic or bicyclic (fused or bridged) (e.g., 5- to 10-membered monocyclic or bicyclic) saturated ring structure, where one or more of the ring atoms is a heteroatom (e.g., N, O, S, or combinations thereof). Examples of heterocycloalkyl groups include piperidyl, piperazinyl, tetrahydropyranyl, tetrahydrofuryl, 1,4-dioxolanyl, 1,4-dithianyl, 1,3-dioxolanyl, oxazolidyl, isoxazolidyl, morpholinyl, thiomorpholinyl, octahydrobenzofuryl, octahydrochromenyl, octahydrothiochromenyl, octahydroindolyl, octahydropyridinyl, decahydroquinolinyl, octahydrobenzo[b]thiophenyl, 2-oxa-bicyclo[2.2.2]octyl, 1-aza-bicyclo[2.2.2]octyl, 3-aza-bicyclo[3.2.1]octyl, and 2,6-dioxa-tricyclo[3.3.1.0]nonyl. Monocyclic heterocycloalkyl groups can be fused to a phenyl moiety to form structures such as tetrahydroisoquinoline, which would be classified as heteroaryls.

[0122] As used herein, the term "heteroaryl" refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 15 ring atoms, where one or more of the ring atoms are heteroatoms (e.g., N, O, S, or combinations thereof), and the monocyclic ring system is aromatic or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. The heteroaryl group includes a benzo-fused ring system having 2 to 3 rings. For example, the benzo-fused group includes benzo fused with 1 or 2 4- to 8-membered heterocyclic aliphatic moieties (e.g., indolizinyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl or isoquinolinyl). Some examples of heteroaryl include pyridyl, 1H-indazolyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuryl, isoquinolinyl, benzothiazolyl, xanthene, thioxanthene, phenothiazine, dihydroindole, benzo[1,3]dioxole, benzo[b]furyl, benzo[b]thiophenyl, indazolyl, benzimidazolyl, benzothiazolyl, puryl, cinnolyl, quinolinyl, quinazolinyl, cinnolyl, phthalazinyl, quinazolinyl, quinoxalinyl, isoquinolinyl, 4H-quinolizinyl, benzo-1,2,5-thiadiazole, or 1,8-naphthyridyl.

[0123] Without limitation, examples of monocyclic heteroaryl include furyl, thiophenyl, 2H-pyrrolyl, pyrrolyl, oxazolyl, thazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3,4-thiadiazolyl, 2H-pyranyl, 4-H-pyranyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazolyl, pyrazinyl, or 1,3,5-triazinyl. Monocyclic heteroaryls are numbered according to standard chemical nomenclature.

[0124] Examples of bicyclic heteroaryl include indolizinyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, isoquinolinyl, indolizinyl, isoindolyl, indolyl, benzo[b]furyl, benzo[b]thiophenyl, indazolyl, benzimidazolyl, benzothiazolyl, purinyl, 4H-quinolizinyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 1,8-naphthyridinyl, or pteridinyl. The bicyclic heteroaryl is numbered according to standard chemical nomenclature.

[0125] As used herein, the term "treatment rate" refers to the weight percentage of components in motor oil for passenger cars.

[0126] The weight average molecular weight (Mw) and number average molecular weight (Mn), or any other molecular weight, can be determined using a gel permeation chromatography (GPC) instrument obtained from Waters or a similar instrument, and data processed with Waters Empower Software or similar software. The GPC instrument may be provided with a Waters separation module and a Waters refractive index detector (or any similar optional instrument). The GPC operating conditions can include a guard column, four Agilent PLgel columns (length 300 × 7.5 mm, particle size 5 μm, and pore size in the range of 100 to 10,000 Å), and a column temperature of about 40 °C. Unstabilized HPLC grade tetrahydrofuran (THF) can be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument can be calibrated with commercially available poly(methyl methacrylate) (PMMA) standards having a narrow molecular weight distribution in the range of 960 to 1,568,000 g / mol. The calibration curve can be extrapolated for samples having a mass of less than 500 g / mol. The sample and PMMA standards can be dissolved in THF, prepared at a concentration of 0.1 to 0.5 wt%, and used without filtration. The GPC measurement is also described in U.S. Patent No. 5,266,223, which is incorporated herein by reference. The GPC method additionally provides molecular weight distribution information. See also, for example, W.W. Yau, J.J. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is incorporated herein by reference.

Example

[0127] A better understanding of the present disclosure and its many advantages can be obtained by using the following examples. The following examples are illustrative and do not limit it in any way in terms of scope or spirit. Those skilled in the art will readily understand that variations of the components, methods, steps, and devices described in these examples can be used. Unless otherwise specified, or unless it is clear from the context throughout the following examples and the present disclosure, all percentages, ratios, and parts in the present disclosure are by weight.

[0128] The compositions of the present invention and the comparative compositions were subjected to an aeration test according to an aeration test suitable for meeting General Motors dexos (trademark) requirements such as GMW17295, which can be carried out at test facilities such as Southwest Research Institute (SWRI) and Intertek. The aeration test included measuring the air entrainment amount after lubrication for a set period and comparing it with a reference lubricant. Table 3 below provides the fluids evaluated for this example. All lubricants contained the same API Group III base oil blend, detergent inhibitor package, and viscosity modifier. Each of the lubricants in Table 3 contained about 15 ppm of silicon from a high molecular weight (e.g., 60,000 Daltons or more) polydimethylsiloxane antifoam polymer having a viscosity of at least about 12,500 cSt at 25°C. Tables 3 and 4 show the influence of the selection of the chemical nature of silicon and the silicon treatment rate of various other silicon-providing compounds on the aeration performance. The only material change in each lubricant was the additive evaluated for the additional silicon compound and its treatment rate, as shown in the following table. The aeration pass criterion in Table 4 is less air entrainment, i.e., a separation score less than 0.

[0129]

Table 3

[0130] [Table 4]

[0131] As used in this specification and the appended claims, it should be noted that the singular forms "a", "an", and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, reference to "an antioxidant" includes two or more different antioxidants. As used herein, the term "comprising" and its grammatical variations are intended to be non-limiting such that the listing of items in a list does not exclude other similar items that may be substituted or added to the items in the list.

[0132] For the purposes of this specification and the appended claims, unless otherwise indicated, all amounts, percentages, or ratios used in this specification and the claims, and all numbers representing other values, should be understood to be modified in all instances by the term "about". Thus, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the reported number of significant digits and by applying ordinary rounding techniques.

[0133] It should be understood that each component, compound, substituent, or parameter disclosed herein is disclosed for use alone or in combination with one or more of any other component, compound, substituent, or parameter disclosed herein.

[0134] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosed range having the same number of significant figures. Thus, for example, the range of 1 to 4 should be interpreted as a clear disclosure not only of the values 1, 2, 3, and 4, but also of any range of such values.

[0135] It should be further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range for the same component, compound, substituent, or parameter. Thus, the present disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it should also be further understood that any range between the endpoint values within a broad range is also contemplated herein. Thus, the range of 1 to 4 also means ranges such as 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0136] Furthermore, the specific amounts / values of components, compounds, substituents, or parameters disclosed in the details or examples should be interpreted as a disclosure of either the lower or upper limit of a range, and thus can form a range for that component, compound, substituent, or parameter in combination with any other lower or upper limit or specific amount / value in the ranges for the same component, compound, substituent, or parameter disclosed elsewhere in this application.

[0137] Although specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not now contemplated or that may not be presently contemplated by the applicants or other persons of ordinary skill in the art may arise. Accordingly, the appended claims that have been filed, and the appended claims as may be amended, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. 1. A passenger car motor oil configured to maintain low foam and / or low aeration during lubrication, said passenger car motor oil comprising: one or more base oils of lubricating viscosity; about 15 ppm or less of silicon provided by a polydialkylsiloxane antifoam polymer; at least about 100 ppm additional silicon provided by a silicon-containing compound selected from a siloxane derivative, a silane derivative, or a combination thereof, wherein the silicon-containing compound providing the additional silicon has a molecular weight of about 650 or less.

2. 10. The passenger car motor oil of claim 1, wherein the polydialkylsiloxane antifoam polymer is a polydimethylsiloxane polymer having a number average molecular weight of about 50,000 or greater, and / or the silicon-containing compound providing the additional silicon has 10 or fewer silicon-oxygen bonds per compound, and / or the passenger car motor oil, when operated in a naturally aspirated engine, entrains less free air compared to a benchmark motor oil that does not include the additional silicon provided by the silicon-containing compound.

3. 3. The passenger car motor oil of claim 2, wherein the passenger car motor oil has an average number of occurrences according to the Sequence IX Slow Pre-Ignition Test of ASTM D8291 less than or equal to 5 and / or a maximum number of occurrences according to the Sequence IX Slow Pre-Ignition Test of ASTM D8291 less than or equal to 8.

4. 2. The passenger car motor oil of claim 1, wherein said passenger car motor oil contains from about 100 to about 300 ppm of said added silicon, preferably said passenger car motor oil contains from about 100 to about 250 ppm of said added silicon.

5. The additional silicon is provided by a polyether-modified siloxane, a hydrocarbyl-modified siloxane, or a combination thereof, and / or the additional silicon is provided by a compound of formula II: 【Chemistry 1】 During the ceremony, Each R is independently C １ ~C ４ is an alkyl group, R １ (i) C ６ ~C ２０ an alkyl group, or (ii) -R ２ -[O-R] ３ ] ｎ -OR ４ R is a polyether group; ２ is C １ ~C ４ is a hydrocarbyl group, R ３ is C １ ~C ４ is a hydrocarbyl group, R ４ is hydrogen or C １ ~C ４ is any of the hydrocarbyl groups, 2. The passenger car motor oil of claim 1, wherein n is an integer from 1 to 10 and m is an integer of 0 or 1.

6. Each R in formula II is a methyl group; １ is C ８ ~C １０ 6. The passenger car motor oil of claim 5, wherein m is a hydrocarbyl group and m is an integer equal to 0.

7. Each R in formula II is a methyl group; １ is a polyether group, R ２ is C ３ group, R ３ is C １ ~C ２ group, R ４ 6. The passenger car motor oil of claim 5, wherein m is an integer equal to 0 and n is an integer equal to 1.

8. Each R in formula II is a methyl group; １ is a polyether group, R ２ is C ３ group, R ３ is C １ ~C ２ group, R ４ 6. The passenger car motor oil of claim 5, wherein m is an integer equal to 1 and n is an integer equal to 1.

9. 2. The passenger car motor oil of claim 1, wherein the additional silicon is provided by a hydrocarbyl silane compound having one or more silyl ether moieties, preferably the additional silicon is provided by a trialkoxyalkyl silane compound, and most preferably the additional silicon is provided by a triethoxycaprylyl silane compound.

10. 1. A method for lubricating a combustion engine with a passenger vehicle motor oil to provide low foam and / or low aeration with an increased concentration of silicon, said method comprising: lubricating the combustion engine with the passenger car motor oil comprising: (i) one or more base oils of lubricating viscosity; (ii) about 15 ppm or less of silicon provided from a polydialkylsiloxane antifoam polymer; and (iii) at least about 100 ppm of additional silicon provided from a silicon-containing compound selected from a siloxane derivative, a silane derivative, or a combination thereof, wherein the silicon-containing compound providing the additional silicon has a molecular weight of about 650 or less; wherein said passenger car motor oil, when operated in a naturally aspirated engine, has a lower amount of free air entrained compared to a benchmark motor oil not containing said added silicon provided from a silicon-containing compound.

11. 11. The method of claim 10, wherein the passenger car motor oil has an average number of occurrences according to the Sequence IX Slow Pre-Ignition Test of ASTM D8291 of 5 or less and / or a maximum number of occurrences according to the Sequence IX Slow Pre-Ignition Test of ASTM D8291 of 8 or less.

12. 11. The method of claim 10, wherein the polydialkylsiloxane antifoam polymer is a polydimethylsiloxane polymer having a number average molecular weight of at least about 50,000, and / or the silicon-containing compound providing the additional silicon has 10 or fewer silicon-oxygen bonds / compound, and / or the passenger car motor oil comprises from about 100 to about 300 ppm of the additional silicon, preferably from about 100 to about 250 ppm of the additional silicon.

13. The additional silicon is provided by a polyether-modified siloxane, a hydrocarbyl-modified siloxane, or a combination thereof, and / or the additional silicon is provided by a compound of formula II: 【Chemistry 2】 During the ceremony, Each R is independently C １ ~C ４ is an alkyl group, R １ (i) C ６ ~C ２０ an alkyl group, or (ii) -R ２ -[O-R] ３ ] ｎ -OR ４ R is a polyether group; ２ is C １ ~C ４ is a hydrocarbyl group, R ３ is C １ ~C ４ is a hydrocarbyl group, R ４ is hydrogen or C １ ~C ４ is any of the hydrocarbyl groups, The method of claim 10, wherein n is an integer from 1 to 10 and m is an integer of 0 or 1.

14. Each R in formula II is a methyl group; １ is C ８ ~C １０ each R of formula II is a hydrocarbyl group and m is an integer equal to 0; or each R of formula II is a methyl group; １ is a polyether group, R ２ is C ３ group, R ３ is C １ ~C ２ group, R ４ is hydrogen, m is an integer equal to 0, and n is an integer equal to 1; or each R in formula II is a methyl group; １ is a polyether group, R ２ is C ３ group, R ３ is C １ ~C ２ group, R ４ The method of claim 13, wherein: is a methyl group; m is an integer equal to 1; and n is an integer equal to 1.

15. 11. The method of claim 10, wherein the additional silicon is provided by a hydrocarbyl silane compound having one or more silyl ether moieties, or the additional silicon is provided by a trialkoxyalkyl silane compound, or the additional silicon is provided by triethoxycaprylyl silane.

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