Amine-containing polymers and lubricant compositions comprising such polymers and methods of use thereof

Abstract

A functional polymer based on a functionalized styrenic monomer comprising a nitrogen-containing moiety not pendant to the phenyl ring is polymerized from an addition polymerizable monomer composition comprising an amine-derivatized alpha-methylstyrene (ADAMS) monomer according to structure (I). Wherein k is an integer from 1 to 3, preferably 2; wherein R1 is methyl or phenyl, and R2 is benzyl, or wherein R1 is linked to R2 to form a moiety containing a 6-membered ring having four carbons, bearing an O or N-CH3 group at the 4-position of the 6-membered ring; wherein in structure (I), R is hydrogen, a phenyl ring co-linked with the phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, phenyl linked at a single carbon of the phenyl ring, a C1-C4 hydrocarbyl group (e.g., methyl), a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms (e.g., O, N, S, P, Se, and combinations thereof). Methods of using such functional polymers in lubricating oil compositions are also provided. # imgabs0 #

Description

TECHNICAL FIELD

[0001] The present disclosure relates to polymer compositions and methods of using such compositions, which can be derived from monomer compositions containing aromatic and / or conjugated (non-aromatic) structures, each of which contains at least one aminic nitrogen. In particular, such functional monomers can be anionically polymerized to form the functional polymers disclosed herein. The present disclosure also relates to the use of such polymer compositions as additives in lubricant compositions having good dispersing power in engine crankcase applications, especially in compression ignition engine applications. BACKGROUND OF THE INVENTION

[0002] Numerous references disclose nitrogen-containing (amine) groups pendant to the phenyl ring in styrenic monomers / polymers / copolymers. However, monomers and polymers with such side groups are chemically difficult to synthesize reliably / reproducibly. Even when such syntheses can be accomplished, growth problems may exist in the polymerization reactions of monomers containing such amine-functionalized styrenics, either alone or as copolymers with other styrenic monomers.

[0003] Thus, post-polymerization chemical reactions can generally be used to add amine groups to a few monomer repeat units. However, post-polymerization chemistry may generally be accompanied by different problems, even if it can avoid the growth problems of amine-functionalized styrenic monomers.

[0004] Accordingly, it is desirable to develop an unconventional method for pre-polymerizing styrenic monomers that are functionalized, particularly pre-polymerizations of styrenic monomers that are neutral or possibly even enhancing with respect to growth in the polymerization reaction.

[0005] U.S. Patent Nos. 6,486,272, 9,364,825, 10,202,494, and 10,046,285 disclose polymers prepared from styrenic monomers having nitrogen-containing groups pendant to the phenyl ring, all of which patents are hereby incorporated by reference in their entireties. GB Patent No. 1381755 discloses amine-functional monomer compounds but only having acrylamide functional groups. Other examples of potentially relevant publications include but are not necessarily limited to U.S. Patent Nos. 7,790,661, 7,960,320, 8,778,854, and 10,414,999; and PCT Publication No. WO2021 / 127183, all of which documents are hereby incorporated by reference in their entireties.

[0006] Due to the difficulty in preparing and polymerizing styrenic monomers with nitrogen-containing groups attached to the phenyl ring, the applicant has studied other potential structures of functional monomers that are simpler to fabricate and polymerize. These functional monomer compositions containing aromatic and / or conjugated (non-aromatic) structures, each containing at least one amine nitrogen, are described in the related U.S. Provisional Application Serial No. 63 / 483,365, commonly owned and filed on February 6, 2023, the content of which is hereby incorporated by reference in its entirety.

[0007] U.S. Patent No. 2,778,826 (“the ‘826 Schmidle patent”) and the 1955 article by Schmidle and Mansfield titled “The Aminomethylation of Olefins. I. The Reaction of Secondary Amines, Formaldehyde, and Olefins” both disclose various reactions purported to form 3-aryl-3-butenyl-1-amines, in which formaldehyde and secondary amines purportedly form iminium, which reacts with styrenic olefins to form only the terminal (vinylidene) double bond form of amine-functional styrenic. The 1955 article also discloses the amine functionalization of terpenoids such as α- and β-pinene, camphene, and limonene, but does not disclose isoprene or similar conjugated non-aromatic compounds.

[0008] The 1983 article by Cohen and Onopchenko titled “Competing Hydride Transfer and Ene Reactions in the Aminoalkylation of 1-Alkenes with N,N-Dimethylmethyleniminium Ions. A Literature Correction” (partially citing the ‘826 Schmidle patent) further discloses a mechanistic study of the reaction of specific dimethyliminium compounds with styrenic and non-styrenic olefins. Notably, at the beginning of the discussion section, the 1983 article argues that the ‘826 Schmidle patent (and presumably the 1955 article, which contains very similar experiments and results) is in error. However, regarding the aminomethylation of α-methylstyrene, the 1983 article indicates the formation of vinylidene-based products, as well as a significant vinylidene (non-terminal double bond) content and a fairly significant (13% in the case of the dimethylamino form) saturated arylalkane-amine content.

[0009] To the applicant's knowledge, the monomers of the invention disclosed in U.S. Provisional Application Serial No. 63 / 483,365 have not been polymerized previously.

[0010] Based on the above, there is a need to provide functional polymers based on α-substituted functional monomers, in particular functional polymers based on functional monomer compositions containing aromatic and / or conjugated (non-aromatic) structures, each of which contains at least one amine nitrogen, and the functional polymers utilize anionic polymerization processing techniques.

[0011] The emphasis on fuel economy has increased in recent years. One way to improve vehicle fuel economy is to design new lubricating oils that reduce friction while maintaining a good film thickness for durability and wear protection, and also prevent soot-induced viscosity increase. In the attempt to improve fuel economy, the use and specification of low viscosity grades by original equipment manufacturers (OEMs) have become increasingly common. One of the challenges in providing engine oils and / or drivetrain lubricants with these reduced viscosity grades is to maintain cleanliness. Such oils must be able to reduce sludge, provide good soot handling, and provide wear protection while providing the required fuel economy benefits. These goals should be achieved while maintaining low levels of sulfate ash and phosphorus and ensuring seal compatibility. There is a need to provide new engine oils with low viscosity grades that meet these requirements.

[0012] Base oils for lubricants are typically modified by adding additives such as viscosity index improvers (VIIs) and / or dispersants. VIIs can be used to mitigate the degree of change in lubricant viscosity with temperature and are often used in formulating engine and transmission lubricants. Commonly used VIIs typically include polymeric materials that can be derived from ethylene-propylene copolymers, polymethacrylates, hydrogenated styrene-butadiene copolymers, polyisobutylene, etc.

[0013] During engine operation, oil-insoluble oxidation by-products such as soot are produced. Dispersants help keep these by-products suspended or dissolved, thereby reducing their deposition on metal surfaces. Common dispersants include (poly)alkenylsuccinic derivatives, such as hydrocarbon-substituted succinic anhydrides like polyisobutylene succinic anhydride (PIBSA), and hydrocarbon-substituted succinimides such as polyisobutylene succinimide (PIBSA-PAM), such as those derived from the reaction of maleated polyisobutylene with N-phenyl-p-phenylenediamine. Available dispersants include polyisobutenes that have been modified by an ene reaction to include functional groups such as succinimide, hydroxyethylimide, succinate / amide, and oxazoline. Other dispersants include Mannich base derivatives of polybutene, ethylene propylene polymers, and acrylic polymers.

[0014] Some other dispersants are derived from the reaction of maleated poly-α-olefins (such as ethylene-propylene copolymers) and polyamines. U.S. Patent No. 6,107,257 relates to additives for lubricating oil compositions that include multifunctional olefin copolymer viscosity index improvers. Maleic anhydride is reacted or grafted onto the ethylene-propylene copolymer backbone in the presence of a solvent, and then the graft copolymer is reacted with a polyamine such as N-aryl-p-phenylenediamine in the presence of a surfactant to provide a multifunctional olefin copolymer viscosity index improver. Similarly, U.S. Patent No. 6,107,258 relates to multifunctional fuel and lubricant additives derived from the acylation and then amination of copolymers of C3 to C 23 α-olefins.

[0015] Still other dispersants are derived from styrenic copolymers. U.S. Patent No. 6,248,702 discloses the reaction of maleated selectively hydrogenated styrenic block copolymers (Mn 10,000, Ex 1) with aminopropylmorpholine to form a dispersant substance.

[0016] Still other dispersants are derived from copolymers of two different conjugated dienes, such as block copolymers of isoprene and butadiene. U.S. Patent No. 5,780,540 discloses functionalized selectively hydrogenated isoprene-butadiene diblock copolymers in an automotive additive package. Examples show the use of N-phenyl-1,4-phenylenediamine in combination with polyethylene glycol monoalcohol, 4-(3-aminopropyl)morpholine, and / or 3-dibutylaminopropylamine to functionalize maleated 10,000 Mn and / or 20,000 Mn isoprene-butadiene copolymers. Examples 1 and 2 show that the IB copolymer is made with 2,2'-bipyridine, which makes it less likely to have a high 1,4 insertion.

[0017] Similarly, U.S. Patent No. 6,319,881 discloses a functionalized selectively hydrogenated isoprene-butadiene diblock copolymer in an automotive additive package. Example IV shows a maleated selectively hydrogenated isoprene-butadiene diblock copolymer (Mn 15,000) which is reacted with aminopropylmorpholine to form a morpholinopropyl succinimide adduct and then used as a dispersant in an additive package (Example V).

[0018] U.S. Patent No. 5,073,600 relates to a reactive extrusion process for functionalizing (e.g., maleating and then aminating) copolymers of conjugated dienes which typically have an Mn of 500,000 to about 3,000,000. Examples show a hydrogenated "low" molecular weight star polymer of hydrogenated homopolyisoprene having an average of 15 arms (35,000 Mn / arm) reacted in a reactive extruder with maleic anhydride and diethylaminopropylemine.

[0019] There remains a need to provide alternative or improved engine / transmission oil compositions which meet stringent wear tests while also providing improved wear, fuel economy, and dispersancy performance. The present disclosure provides engine oil compositions comprising amine-containing copolymers which reduce wear and also have acceptable soot handling and / or engine / transmission cleanliness. Further, the present disclosure addresses these needs by providing amine-containing copolymers as dispersant viscosity index improvers and their use in lubricating oil compositions to achieve the above-described performance improvements. SUMMARY OF THE INVENTION Summary of the Invention

[0020] In one form, a copolymer is disclosed herein which comprises: (a) 10.0 to 20.0 weight % of amine-derivatized alpha-methyl styrene (ADAMS) repeat units according to Structure (I): Wherein: k is an integer from 1 to 3; R1 is hydrogen or benzyl; R is hydrogen, a phenyl ring co-linked to the shown phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group attached at a single carbon of the shown phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) 80.0 to 90.0% by weight of repeating units corresponding to the reactive form of isoprene, and wherein the peak-average molecular weight of the copolymer is 45.0 to 65.0 kDa.

[0021] In another form, a copolymer is disclosed herein that comprises: (a) 5.0 to 10.0% by weight of amine-derivatized α-methylstyrene (ADAMS) repeating units according to Structure (II): Wherein: k is an integer from 1 to 3; R is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) The balance of 90.0 to 95.0% by weight of repeating units corresponding to the reactive form of isoprene, and wherein the peak-average molecular weight of the copolymer is 24.0 to 42.0 kDa.

[0022] In yet another form, a copolymer is disclosed herein that comprises: (a) 4.0 to 6.0% by weight of amine-derivatized α-methylstyrene (ADAMS) repeating units according to Structure (III): Wherein: k is an integer from 1 to 3; R is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, (b) The balance of 94.0 to 96.0% by weight of repeating units corresponding to the reactive form of isoprene, and wherein the peak-average molecular weight of the copolymer is 36.0 to 46.0 kDa.

[0023] In still another form, a copolymer is disclosed herein that comprises: (a) One or more amine-derivatized α-methylstyrene (ADAMS) repeating units according to Structure (IV): Wherein: k is an integer from 1 to 3; R1 is hydrogen or benzyl; R is hydrogen, a phenyl ring that is co - connected to the indicated phenyl ring at two adjacent ring - carbon positions to form a naphthalene assembly, a phenyl group connected at a single carbon of the indicated phenyl ring, a C1 - C4 hydrocarbon group, a C1 - C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining repeating units corresponding to the reactive form of isoprene.

[0024] The present disclosure also provides a lubricating oil composition comprising or consisting of a blend of the following components: (i) at least 50 wt% of one or more base oils, based on the weight of the lubricating oil composition; (ii) one or more dispersants; (iii) one or more detergents; and (iv) one or more copolymers of any of the four preceding paragraphs.

[0025] The present disclosure also provides a lubricating oil composition comprising or consisting of a blend of the following components: (i) 50 to 99 mass% of one or more base oils, based on the weight of the lubricating oil composition; (ii) 0.01 to 20 wt% of one or more dispersants, based on the total weight of the lubricating oil composition; (iii) 0.10 to 20 mass% of one or more detergents, based on the weight of the lubricating oil composition; and (iv) 0.10 to 20 mass% of one or more of the copolymers described in the preceding paragraph, based on the weight of the lubricating oil composition.

[0026] The present disclosure also provides a method of lubricating an internal combustion engine during operation of the engine, comprising: (i) providing to the crankcase of the internal combustion engine a lubricating oil composition of any of the two preceding paragraphs; (ii) providing fuel to the internal combustion engine; and (iii) combusting the fuel in the internal combustion engine.

[0027] Other aspects of the present disclosure will become apparent from the following detailed description and the examples section. Detailed Description Detailed Description of the Invention

[0028] All numerical values in the detailed description and claims herein are modified by the terms "about" or "substantially" to indicate the value, and account is taken of the experimental errors and variations expected by those of ordinary skill in the art. Overview of the Copolymers

[0029] The present disclosure provides novel polymers and copolymers based on anionic polymerization of functionalized styrenic monomers, the functionalized styrenic monomers including a nitrogen-containing structural moiety that is not pendant to the phenyl ring. Thus, monomers of Structure (I) are developed to obtain a nitrogen-containing functional group on an α-substituted styrenic monomer that is not pendant to the phenyl ring on the styrene unit.

[0030] It should be noted that prior art references generally describe functionalized styrenic monomers having a nitrogen-containing group pendant to the phenyl ring (e.g., "dimethylaminoethylstyrene"), which may be similar to the k=2 monomer structure provided below. However, the prior art does not teach or suggest the α-substituted functional monomers specifically disclosed herein or the functional polymers derived therefrom.

[0031] The functional polymers of the present invention based on functionalized styrenic monomers including a nitrogen-containing structural moiety that is not pendant to the phenyl ring can be polymerized from an addition-polymerizable monomer composition including an amine-derivatized α-methylstyrene (ADAMS) monomer according to Structure (I). where k is an integer from 1 to 3, preferably 2; where R1 is methyl or phenyl, and R2 is benzyl, or where R1 and R2 are connected to form a structural moiety containing a 6-membered ring having four carbons, with an O or N-CH3 group at the 4-position of the 6-membered ring; where in Structure (I), R is hydrogen, a phenyl ring co-connected to the shown phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring connected at a single carbon of the shown phenyl ring, a C1-C4 hydrocarbon group (such as methyl), a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms (such as O, N, S, P, Se, and combinations thereof).

[0032] The functional polymers of the present invention based on functionalized styrenic monomers including a nitrogen-containing structural moiety that is not pendant to the phenyl ring can be polymerized from exemplary ADAMS monomers according to Structure (I), the ADAMS monomers including 1-benzylmethylamino-3-phenylbut-3-ene, 1-benzylphenylamino-3-phenylbut-3-ene, 1-(N-morpholino)-3-phenylbut-3-ene, and 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene.

[0033] In some embodiments, the functional polymers of the present invention based on functionalized styrenic monomers including a nitrogen-containing structural moiety that is not pendant to the phenyl ring can be polymerized from exemplary ADAMS monomers according to Structure (I) and can exhibit a k value of exactly 2.

[0034] For clarity and as used herein, the functional polymers of the present invention based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety not ortho-fused to a phenyl ring can be polymerized from exemplary ADAMS monomers of structure (I) having a vinylidene bond, such as the vinylidene bond derived from the olefinic double bond in α-methylstyrene, which can be reflected, for example, in the -3-ene / -3-enyl language of IUPAC nomenclature.

[0035] The polymer compositions disclosed herein can optionally contain residues of initiators and / or co-initiators used or useful for living or pseudo-living anionic polymerization reactions. Non-limiting examples can include alkyl residues from sec-butyllithium, n-butyllithium, tert-butyllithium, etc. and their combinations, reaction products, and / or degradation products.

[0036] Alkyl residues from initiators can optionally be present at one or more termini of the polymer backbone.

[0037] Initiators that can be used can be alkyl lithium, alkyl sodium, or alkyl potassium compounds, typically in the range of C2 to C12. Alkyl lithium compounds such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, isopentyllithium, sec-pentyllithium, tert-pentyllithium, hexyllithium, or combinations thereof are preferred. Sec-alkyl lithium compounds, such as sec-butyllithium, sec-pentyllithium, or combinations thereof are more preferred. Most preferred is sec-butyllithium. Substituted alkyl lithiums, such as aralkyl lithium compounds, for example benzyllithium, 1-lithioethylbenzene, and 1-lithio-3-methylpentylbenzene can also be used.

[0038] The present invention provides an anionic polymerized polymer of the present invention derived from a functionalized styrenic monomer comprising a nitrogen-containing structural moiety not ortho-fused to a phenyl ring having the following general structure: wherein R1 is methyl or phenyl, and R2 is benzyl, or wherein R1 and R2 are joined to form a structural moiety containing a 6-membered ring having four carbons with an O or N-CH3 group at the 4-position of the 6-membered ring; due to the ease of synthesis of the monomer and its favorable reactivity in polymerization, monomers with k = 2 are preferred. Alternatively, monomers with k ≥ 3 can be used, but they are more complex to prepare and less commercially viable. Alternatively, monomers with k = 1 can be used, but they are difficult to polymerize via anionic polymerization.

[0039] Functionalized styrenic monomers comprising a nitrogen-containing structural moiety not ortho-fused to a phenyl ring can be copolymerized with isoprene.

[0040] Depending on the reactivity ratios of styrene monomers including a nitrogen-containing structural moiety not side-bonded to the phenyl ring and isoprene present in the polymerization reaction, in some cases, the repeating unit of structure (V) and the structure (VII a ), (VII b ) or a combination thereof form an alternating structure. For example, the following reaction, where R1, R2 and R5 have the same meanings as above.

[0041] As an alternating structure formed by the combination of the repeating unit of structure (V) and the structure (VII a ), (VII b ) or a combination thereof will thereby form a larger repeating unit of structure (X a ), (X b ) or a combination thereof. Regarding the polymeric repeating units of structures (VII a ) and (X a ), their double bonds can be in the form of a cis isomer, a trans isomer or a combination thereof.

[0042] where k is an integer from 1 to 3, preferably 2; where R1 is methyl or phenyl, and R2 is benzyl, or where R1 and R2 are joined to form a structural moiety containing a 6-membered ring having four carbons and bearing an O or N-CH3 group at the 4-position of the 6-membered ring; where in structure (I), R is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group (such as methyl), a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms (such as O, N, S, P, Se and combinations thereof).

[0043] In addition, depending on the reactivity ratios of styrene monomers including a nitrogen-containing structural moiety not side-bonded to the phenyl ring and isoprene present in the polymerization reaction, and where there is a molar excess of isoprene present in the polymerization reaction, the polymer in some cases forms a block of repeating units of structure (X a ), (X b ) or a combination thereof, followed by a second block of repeating units of structure (VII a ), (VII b ) or a combination thereof, and there is no structure (IX), (X a ), (X bThe repeating units of ( ). For example, the following reaction, where R1, R2, and R5 have the same meanings as above. Regarding the polymerized repeating units, the double bond can be in the cis isomer form, the trans isomer form, or a combination thereof.

[0044] In some embodiments, additional moieties of the monomer or combinations thereof can be optionally added to the polymerization reaction. In such cases, those monomers added later in the reaction can form one or more blocks of repeating units within the polymer, the blocks having a different composition from those repeating units from the monomers earlier in the polymerization.

[0045] In the case where the polymer contains two blocks of repeating units having different compositions, due to differences in monomer reactivity ratios or due to the sequential addition of monomers to the polymerization reaction, the polymer is described as "diblock". Similarly, when the polymer contains three, four, five, or six blocks of repeating units of different compositions, due to differences in monomer reactivity ratios or due to the sequential addition of monomers to the polymerization reaction, the polymer is described as "triblock", "tetrablock", "pentablock", or "hexablock", respectively.

[0046] In some embodiments, the polymer can be coupled using a multifunctional coupling agent to form a polymer having a star architecture. Many suitable types of these multifunctional compounds have been described in U.S. Patent Nos. 3,595,941; 3,468,972; 3,135,716; 3,078,254, and 3,594,452, the disclosures of which are hereby incorporated by reference in their entireties. The multifunctional coupling agent can optionally be a halogen-substituted or alkoxy-substituted silane, including tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, bis-trimethoxysilylethane, bis-triethoxysilylethane, hexachlorodisiloxane, bis-trichlorosilylethane, 1,6-bis(trichlorosilyl)-hexane, or combinations thereof.

[0047] The preferred coupling agent is a polyalkenyl aromatic coupling agent. The most preferred coupling agent is divinylbenzene. Polyalkenyl aromatic coupling agents capable of forming star polymers are known in the art. See generally Canadian Patent No. 716,645 and U.S. Patent Nos. 4,010,226 and 3,985,830, which are hereby incorporated by reference in their entirety. A detailed description of various such coupling agents is found in U.S. Patent No. 4,391,949, which is hereby incorporated by reference in its entirety. Examples of suitable polyvinyl aromatic compounds are 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5,4'-trivinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,5,6-trivinyl-3,7-diethylnaphthalene, 1,3-divinyl-4,5,6-tributylnaphthalene, 2,2'-divinyl-4-ethyl-4'-propylbiphenyl, and the like, or combinations thereof.

[0048] In the case of coupling polymers using a polyfunctional coupling agent to form a polymer star architecture, the coupling ratio (CR) is used to refer to the amount of polymer that has been crosslinked into a star architecture, i.e., the weight percentage of the star architecture polymer relative to the total weight of the polymer in the sample. In some embodiments, the functional polymers of the present invention based on functionalized styrenic monomers comprising nitrogen-containing structural moieties and including star polymer architectures can have a CR greater than 20%, or greater than 30%, or greater than 40%, or greater than 50%, or greater than 60%, or greater than 70%, or greater than 80%, or greater than 90%, or greater than 95%.

[0049] In one embodiment, the functional polymers of the present invention based on functionalized styrenic monomers comprising nitrogen-containing structural moieties not pendant to the phenyl ring can be a hydrogenated copolymer of 1-benzylmethylamino-3-phenylbut-3-ene and isoprene, which contains from 10.0 to 20.0 weight percent of repeating units corresponding to the reactive form of 1-benzylmethylamino-3-phenylbut-3-ene and has a peak average molecular weight of from 45.0 to 65.0 kDa.

[0050] In one embodiment, the functional polymers of the present invention based on functionalized styrenic monomers comprising nitrogen-containing structural moieties not pendant to the phenyl ring can be a hydrogenated copolymer of 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene and isoprene, which contains from 5.0 to 10.0 weight percent of repeating units corresponding to the reactive form of 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene and has a peak average molecular weight of from 24.0 to 42.0 kDa.

[0051] In one embodiment, the functional polymer of the present invention based on a functionalized styrenic monomer comprising a nitrogen-containing structural moiety not attached laterally to a phenyl ring can be a hydrogenated copolymer of 1-(N-morpholinyl)-3-phenylbut-3-ene and isoprene, which contains 4.0 to 5.0% by weight of repeating units corresponding to the reactive form of 1-(N-morpholinyl)-3-phenylbut-3-ene and has a peak average molecular weight of 36.0 to 46.0 kDa.

[0052] In one embodiment, the functional polymer of the present invention based on a functionalized styrenic monomer comprising a nitrogen-containing structural moiety not attached laterally to a phenyl ring can be a hydrogenated copolymer of 1-benzylphenylamino-3-phenylbut-3-ene and isoprene, which contains 5.0 to 7.0% by weight of repeating units corresponding to the reactive form of 1-benzylphenylamino-3-phenylbut-3-ene and has a peak average molecular weight of 140.0 to 180.0 kDa.

[0053] In some embodiments, the functional polymers of the present invention based on functionalized styrenic monomers comprising nitrogen-containing structural moieties not attached laterally to phenyl rings, or based on functionalized conjugated (non-aromatic) monomers comprising nitrogen-containing structural moieties, can optionally be further post-polymerization modified to modify their structures.

[0054] In some embodiments, the post-polymerization modification is hydrogenation. In the methods of the present disclosure, hydrogenation can be carried out by known catalytic systems, including heterogeneous systems and soluble systems. Soluble systems are disclosed in U.S. Patent No. 4,284,835, column 1, line 65 to column 9, line 16, and U.S. Patent No. 4,980,331, column 3, line 40 to column 6, line 28, both of which are incorporated herein by reference.

[0055] The above hydrogenated copolymers can be partially or substantially hydrogenated. In the context of the present disclosure, partial hydrogenation means that 10% to 90%, or 20% to 90%, or 30% to 90%, or 40% to 90% of the non-aromatic double bonds have been saturated. Substantially hydrogenated means that greater than 90%, or greater than 92%, or greater than 94%, or greater than 96%, or greater than 98%, or greater than 99%, or greater than 99.5%, or greater than 99.9% of the non-aromatic bonds have been saturated.

[0056] Other teachings of hydrogenation can be found in Rachapudy et al., Journal of Polymer Science: Polymer Physics Edition, Vol. 17, 1211 - 1222 (1979), which is incorporated herein by reference in its entirety. Table 1 of this article discloses several systems, including palladium on various supports (calcium carbonate, but barium sulfide could also be used). The article by Rachapudy et al. discloses the preparation of homogeneous and heterogeneous catalysts.

[0057] Other teachings of hydrogenation methods and catalysts are disclosed in U.S. Patent Nos. 4,284,835 and 4,980,331, both of which are incorporated herein by reference in their entireties.

[0058] In some embodiments, the post - polymerization modification can be a deprotection reaction that removes a cleavable chemical protecting group from the repeating units of structure (V), (VIII), or a combination thereof. A cleavable chemical protecting group is a chemical group that is inert under the polymerization reaction conditions but can be removed by a post - polymerization chemical reaction to generate a free - NH - or free - NH2 functional group on the ADAMS repeating unit. In one such form, a preferred cleavable chemical protecting group is benzyl and the deprotection reaction is a hydrogenation reaction. Embodiment 1 of the Invention Copolymers and Their Use in Lubricants

[0059] In one form of the inventive copolymers disclosed herein, the copolymer can comprise: (a) 10.0 to 20.0 weight percent of amine - derivatized α - methylstyrene (ADAMS) repeating units according to structure (I):

[0060] wherein: k is an integer from 1 to 3; R1 is hydrogen or benzyl, R is hydrogen, a phenyl ring that is co - connected to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group connected at a single carbon of the indicated phenyl ring, a C1 - C4 hydrocarbon group, a C1 - C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) 80.0 to 90.0 weight percent of repeating units corresponding to the reactive form of isoprene, and wherein the peak average molecular weight of the copolymer is 45.0 to 65.0 kDa. The copolymer can be partially or substantially hydrogenated. In a preferred form, the copolymer has k = 2.

[0061] The copolymer can alternatively include alkyl residues from a monofunctional initiator, the monofunctional initiator including but not limited to alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and being present at one or more ends of the polymer backbone. The alkyl residues from the monofunctional initiator include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, or combinations thereof. The copolymer includes one or more blocks, wherein one or more polymer blocks of the copolymer form a distributed polymer architecture, a diblock, a triblock, a tetrablock, a pentablock, a hexablock, a star polymer architecture, or combinations thereof.

[0062] The copolymer of this embodiment can be used as an additive in a lubricating oil composition. More particularly, the copolymer of this embodiment can be used as a viscosity improver, a friction improver, a dispersant, an antiwear agent, or combinations thereof in a lubricating oil composition. Preferably, the copolymer of this embodiment can be used as a viscosity improver in a lubricating oil composition. More particularly, the lubricating oil composition can comprise the following components or be obtained by mixing the following components: (i) at least 50% by weight of one or more base oils, based on the weight of the lubricating oil composition; (ii) one or more dispersants; (iii) one or more detergents; and (iv) one or more copolymers of this embodiment.

[0063] The lubricating oil composition containing the copolymer of this embodiment can have an SAE viscosity grade of 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40, or 50. Alternatively, the lubricating oil composition of this embodiment can comprise the following components or be obtained by mixing the following components: (i) 50 to 99% by mass of one or more base oils, based on the weight of the lubricating oil composition; (ii) 0.01 to 20% by weight of one or more dispersants, based on the total weight of the lubricating oil composition; (iii) 0.10 to 20% by mass of one or more detergents, based on the weight of the lubricating oil composition; and (iv) 0.10 to 20% by mass of one or more of the copolymers, based on the weight of the lubricating oil composition. Alternatively, the lubricating oil composition of this embodiment can further comprise one, two, three, four, five, six, or more additional additives selected from but not limited to friction improvers; antioxidants; pour point depressants; defoamers; viscosity improvers; corrosion inhibitors and / or rust inhibitors; and antiwear agents.

[0064] Alternatively, the lubricating oil composition of this embodiment may further comprise one, two, three, four, five, six or more of the following: A) one or more friction modifiers in an amount of 0.01 to 5 wt% based on the total weight of the lubricating oil composition; B) one or more antioxidants in an amount of 0.01 to 10 wt% based on the total weight of the lubricating oil composition; C) one or more pour point depressants in an amount of 0.01 to 5 wt% based on the total weight of the lubricating oil composition; D) one or more antifoaming agents in an amount of 0.001 to 5 wt% based on the total weight of the lubricating oil composition; E) one or more viscosity improvers in an amount of 0.001 to 10 wt% based on the total weight of the lubricating oil composition; F) one or more inhibitors and / or rust inhibitors in an amount of 0.0 to 5 wt% based on the total weight of the lubricating oil composition; and / or G) one or more antiwear agents in an amount of 0.001 to 10 wt% based on the total weight of the lubricating oil composition. One or more detergents of the composition may include one or more oil-soluble neutral or overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates and other oil-soluble alkali metal or alkaline earth metal carboxylates. One or more dispersants of the composition may include one or more borated or unborated poly(alkenyl) succinimides, wherein the polyalkyenyl is derived from polyisobutene and the imide is derived from polyamine.

[0065] A lubricating oil composition comprising the copolymer of this embodiment can be used in a method of lubricating an internal combustion engine during engine operation, the method comprising the steps of: (i) providing the lubricating oil composition to the crankcase of the internal combustion engine; (ii) providing fuel in the internal combustion engine; and (iii) combusting the fuel in the internal combustion engine. Non-limiting exemplary fuels include one or more of hydrocarbon fuels, renewable fuels, hydrogen fuels or any blends thereof. The lubricating oil composition of this embodiment can be used as a lubricating oil composition in an internal combustion engine, including but not limited to natural gas engines, gasoline engines, diesel engines and stationary engines. Embodiment 2 of the Invention Copolymers and Their Use in Lubricants

[0066] In another form of the inventive copolymer disclosed herein, the copolymer may comprise: (a) 5.0 to 10.0 wt% of amine-derivatized α-methylstyrene (ADAMS) repeat units according to Structure (II):

[0067] Wherein: k is an integer from 1 to 3; R is hydrogen, a phenyl ring co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining 90.0 to 95.0% by weight of repeating units corresponding to the reactive form of isoprene, and wherein the peak average molecular weight of the copolymer is from 24.0 to 42.0 kDa. The copolymer may be partially or substantially hydrogenated. In a preferred form, the copolymer has k = 2.

[0068] The copolymer may alternatively include alkyl residues from a monofunctional initiator, the monofunctional initiator including, but not limited to, alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and being present at one or more ends of the polymer backbone. Alkyl residues from the monofunctional initiator include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, or combinations thereof. The copolymer includes one or more blocks, wherein one or more polymer blocks of the copolymer form a distributed polymer architecture, a diblock, a triblock, a tetrablock, a pentablock, a hexablock, a star polymer architecture, or combinations thereof.

[0069] The copolymer of this embodiment can also be used as an additive in a lubricating oil composition. More particularly, the copolymer of this embodiment can be used as a viscosity improver, a friction improver, a dispersant, an antiwear agent, or a combination thereof in a lubricating oil composition. Preferably, the copolymer of this embodiment can be used as a viscosity improver in a lubricating oil composition. More particularly, the lubricating oil composition may comprise the following components or be obtained by mixing the following components: (i) at least 50% by weight of one or more base oils, based on the weight of the lubricating oil composition; (ii) one or more dispersants; (iii) one or more detergents; and (iv) one or more copolymers of this embodiment.

[0070] The lubricating oil composition containing the copolymer of this embodiment may have an SAE viscosity grade of 20W-X, 15W-X, 10W-X, 5W-X or 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40 or 50. Alternatively, the lubricating oil composition of this embodiment may comprise the following components or be obtained by mixing the following components: (i) 50 to 99% by mass of one or more base oils, based on the weight of the lubricating oil composition; (ii) 0.01 to 20% by weight of one or more dispersants, based on the total weight of the lubricating oil composition; (iii) 0.10 to 20% by mass of one or more detergents, based on the weight of the lubricating oil composition; and (iv) 0.10 to 20% by mass of one or more of this copolymer, based on the weight of the lubricating oil composition. Alternatively, the lubricating oil composition of this embodiment may further comprise one, two, three, four, five, six or more of the additional additives selected from, but not limited to, friction modifiers; antioxidants; pour point depressants; defoamers; viscosity improvers; corrosion inhibitors and / or rust inhibitors; and antiwear agents.

[0071] Alternatively, the lubricating oil composition of this embodiment may further comprise one, two, three, four, five, six or more of the following: A) 0.01 to 5% by weight of one or more friction modifiers, based on the total weight of the lubricating oil composition; B) 0.01 to 10% by weight of one or more antioxidants, based on the total weight of the lubricating oil composition; C) 0.01 to 5% by weight of one or more pour point depressants, based on the total weight of the lubricating oil composition; D) 0.001 to 5% by weight of one or more defoamers, based on the total weight of the lubricating oil composition; E) 0.001 to 10% by weight of one or more viscosity improvers, based on the total weight of the lubricating oil composition; F) 0.0 to 5% by weight of one or more inhibitors and / or rust inhibitors, based on the total weight of the lubricating oil composition; and / or G) 0.001 to 10% by weight of one or more antiwear agents, based on the total weight of the lubricating oil composition. One or more detergents of the composition may include one or more oil-soluble neutral or overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates and other oil-soluble alkali metal or alkaline earth metal carboxylates. One or more dispersants of the composition may include one or more boronated or unboronated poly(alkenyl)succinimides, where the polyalkenyl is derived from polyisobutene and the imide is derived from polyamine.

[0072] A lubricating oil composition comprising the copolymer of this embodiment can be used in a method of lubricating an internal combustion engine during engine operation, the method comprising the steps of: (i) providing the lubricating oil composition to the crankcase of the internal combustion engine; (ii) providing fuel in the internal combustion engine; and (iii) burning the fuel in the internal combustion engine. Non-limiting exemplary fuels include one or more of hydrocarbon fuels, renewable fuels, hydrogen fuels, or any blend thereof. The lubricating oil composition of this embodiment can be used as a lubricating oil composition in an internal combustion engine, including but not limited to natural gas engines, gasoline engines, diesel engines, and stationary engines. Embodiment 3 of the Invention Copolymers and Their Use in Lubricants

[0073] In yet another form of the inventive copolymer disclosed herein, the copolymer can comprise: (a) 4.0 to 6.0 weight percent of amine-derivatized α-methylstyrene (ADAMS) repeat units according to Structure (III):

[0074] wherein: k is an integer from 1 to 3; R is hydrogen, a phenyl ring co-connected to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group connected at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, (b) the remaining 94.0 to 96.0 weight percent of repeat units corresponding to the reactive form of isoprene, and wherein the copolymer has a peak average molecular weight of 36.0 to 46.0 kDa. The copolymer can be partially or substantially hydrogenated. In a preferred form, the copolymer has k = 2.

[0075] The copolymer can alternatively include alkyl residues from a monofunctional initiator, the monofunctional initiator including but not limited to alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and being present at one or more ends of the polymer backbone. Alkyl residues from the monofunctional initiator include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, or combinations thereof. The copolymer includes one or more blocks, wherein one or more polymer blocks of the copolymer form a distributed polymer architecture, a diblock, a triblock, a tetrablock, a pentablock, a hexablock, a star polymer architecture, or combinations thereof.

[0076] The copolymer of this embodiment can also be used as an additive in a lubricating oil composition. More particularly, the copolymer of this embodiment can be used as a viscosity improver, a friction improver, a dispersant, an antiwear agent, or a combination thereof in a lubricating oil composition. Preferably, the copolymer of this embodiment can be used as a viscosity improver in a lubricating oil composition. More particularly, the lubricating oil composition can comprise the following components or be obtained by mixing the following components: (i) at least 50% by weight of one or more base oils based on the weight of the lubricating oil composition; (ii) one or more dispersants; (iii) one or more detergents; and (iv) one or more copolymers of this embodiment.

[0077] The lubricating oil composition comprising the copolymer of this embodiment can have an SAE viscosity grade of 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40, or 50. Alternatively, the lubricating oil composition of this embodiment can comprise the following components or be obtained by mixing the following components: (i) 50 to 99% by mass of one or more base oils based on the weight of the lubricating oil composition; (ii) 0.01 to 20% by weight of one or more dispersants based on the total weight of the lubricating oil composition; (iii) 0.10 to 20% by mass of one or more detergents based on the weight of the lubricating oil composition; and (iv) 0.10 to 20% by mass of one or more of the copolymers based on the weight of the lubricating oil composition. Alternatively, the lubricating oil composition of this embodiment can further comprise one, two, three, four, five, six, or more of the additional additives selected from, but not limited to, friction improvers; antioxidants; pour point depressants; defoamers; viscosity improvers; corrosion inhibitors and / or rust inhibitors; and antiwear agents.

[0078] Alternatively, the lubricating oil composition of this embodiment may further comprise one, two, three, four, five, six or more of the following: A) one or more friction modifiers in an amount of 0.01 to 5 wt% based on the total weight of the lubricating oil composition; B) one or more antioxidants in an amount of 0.01 to 10 wt% based on the total weight of the lubricating oil composition; C) one or more pour point depressants in an amount of 0.01 to 5 wt% based on the total weight of the lubricating oil composition; D) one or more antifoaming agents in an amount of 0.001 to 5 wt% based on the total weight of the lubricating oil composition; E) one or more viscosity improvers in an amount of 0.001 to 10 wt% based on the total weight of the lubricating oil composition; F) one or more inhibitors and / or rust inhibitors in an amount of 0.0 to 5 wt% based on the total weight of the lubricating oil composition; and / or G) one or more antiwear agents in an amount of 0.001 to 10 wt% based on the total weight of the lubricating oil composition. One or more detergents of the composition may include one or more oil-soluble neutral or overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble alkali metal or alkaline earth metal carboxylates. One or more dispersants of the composition may include one or more borated or unborated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine.

[0079] A lubricating oil composition comprising the copolymer of this embodiment can be used in a method of lubricating an internal combustion engine during engine operation, the method comprising the steps of: (i) providing the lubricating oil composition to the crankcase of the internal combustion engine; (ii) providing fuel in the internal combustion engine; and (iii) burning the fuel in the internal combustion engine. Non-limiting exemplary fuels include one or more of hydrocarbon fuels, renewable fuels, hydrogen fuels, or any blends thereof. The lubricating oil composition of this embodiment can be used as a lubricating oil composition in an internal combustion engine, including but not limited to natural gas engines, gasoline engines, diesel engines, and stationary engines. Embodiment 4 of the Invention Copolymers and Their Use in Lubricants

[0080] In yet another form of the inventive copolymer disclosed herein, the copolymer may comprise: (a) one or more amine-derivatized α-methylstyrene (ADAMS) repeat units according to structure (IV):

[0081] Wherein: k is an integer from 1 to 3; R1 is hydrogen or benzyl, and R is hydrogen, a phenyl ring co - connected to the shown phenyl ring at two adjacent ring - carbon positions to form a naphthalene assembly, a phenyl group connected at a single carbon of the shown phenyl ring, a C1 - C4 hydrocarbon group, a C1 - C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining repeating units corresponding to the reactive form of isoprene. The copolymer may be partially or substantially hydrogenated. In a preferred form, the copolymer has k = 2.

[0082] The copolymer may alternatively include alkyl residues from a monofunctional initiator, the monofunctional initiator including, but not limited to, alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and being present at one or more ends of the polymer backbone. The alkyl residues from the monofunctional initiator include, but are not limited to, methyl, ethyl, n - propyl, isopropyl, n - butyl, isobutyl, sec - butyl, tert - butyl, n - pentyl, isopentyl, sec - pentyl, tert - pentyl, hexyl, or combinations thereof. The copolymer includes one or more blocks, wherein one or more polymer blocks of the copolymer form a distributed polymer architecture, a diblock, a triblock, a tetrablock, a pentablock, a hexablock, a star polymer architecture, or combinations thereof.

[0083] The copolymer of this embodiment can also be used as an additive in a lubricating oil composition. More particularly, the copolymer of this embodiment can be used as a viscosity improver, a friction improver, a dispersant, an anti - wear agent, or a combination thereof in a lubricating oil composition. Preferably, the copolymer of this embodiment can be used as a viscosity improver in a lubricating oil composition. More particularly, the lubricating oil composition may comprise or be a blend of the following components: (i) at least 50 wt% of one or more base oils, based on the weight of the lubricating oil composition; (ii) one or more dispersants; (iii) one or more detergents; and (iv) one or more copolymers of this embodiment.

[0084] The lubricating oil composition containing the copolymer of this embodiment may have an SAE viscosity grade of 20W-X, 15W-X, 10W-X, 5W-X or 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40 or 50. Alternatively, the lubricating oil composition of this embodiment may comprise the following components or be obtained by mixing the following components: (i) 50 to 99% by mass of one or more base oils, based on the weight of the lubricating oil composition; (ii) 0.01 to 20% by weight of one or more dispersants, based on the total weight of the lubricating oil composition; (iii) 0.10 to 20% by mass of one or more detergents, based on the weight of the lubricating oil composition; and (iv) 0.10 to 20% by mass of one or more of this copolymer, based on the weight of the lubricating oil composition. Alternatively, the lubricating oil composition of this embodiment may further comprise one, two, three, four, five, six or more of the additional additives selected from, but not limited to, friction improvers; antioxidants; pour point depressants; defoamers; viscosity improvers; corrosion inhibitors and / or rust inhibitors; and antiwear agents.

[0085] Alternatively, the lubricating oil composition of this embodiment may further comprise one, two, three, four, five, six or more of the following: A) 0.01 to 5% by weight of one or more friction improvers, based on the total weight of the lubricating oil composition; B) 0.01 to 10% by weight of one or more antioxidants, based on the total weight of the lubricating oil composition; C) 0.01 to 5% by weight of one or more pour point depressants, based on the total weight of the lubricating oil composition; D) 0.001 to 5% by weight of one or more defoamers, based on the total weight of the lubricating oil composition; E) 0.001 to 10% by weight of one or more viscosity improvers, based on the total weight of the lubricating oil composition; F) 0.0 to 5% by weight of one or more inhibitors and / or rust inhibitors, based on the total weight of the lubricating oil composition; and / or G) 0.001 to 10% by weight of one or more antiwear agents, based on the total weight of the lubricating oil composition. One or more detergents of the composition may include one or more oil-soluble neutral or overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates and other oil-soluble alkali metal or alkaline earth metal carboxylates. One or more dispersants of the composition may include one or more borated or unborated poly(alkenyl) succinimides, where polyalkyenyl is derived from polyisobutene and imide is derived from polyamine.

[0086] A lubricating oil composition comprising the copolymer of this embodiment can be used in a method of lubricating an internal combustion engine during engine operation, the method comprising the steps of: (i) providing the lubricating oil composition to the crankcase of the internal combustion engine; (ii) providing fuel in the internal combustion engine; and (iii) combusting the fuel in the internal combustion engine. Non-limiting exemplary fuels include one or more of hydrocarbon fuels, renewable fuels, hydrogen fuels, or any blend thereof. The lubricating oil composition of this embodiment can be used as a lubricating oil composition in an internal combustion engine, including but not limited to natural gas engines, gasoline engines, diesel engines, and stationary engines. Method for Manufacturing ADAMS Copolymers

[0087] A novel polymer comprising a functionalized styrenic monomer having a nitrogen-containing structural moiety not side-bonded to a phenyl ring can be prepared by an anionic polymerization method.

[0088] Anionic polymerization methods for monomers that do not include functionalized styrenic monomers having a nitrogen-containing structural moiety not side-bonded to a phenyl ring are well known in the art and are described, for example, in U.S. Patent Nos. 5,736,612, 5,773,521, 8,604,136, and 9,809,671, which are hereby incorporated by reference in their entireties. Anionic polymerization methods generally include at least the following steps: (a) polymerizing one or more monomers in an inert hydrocarbon solvent in the presence of an alkyllithium initiator until substantially complete conversion; (b) optionally adding one or more monomers of the same or different composition in one or more sequential additions, with each sequential addition of the monomer being polymerized until substantially complete conversion; (c) optionally adding a multifunctional coupling agent to couple some or all of the polymers or copolymers; (d) adding a terminator.

[0089] Anionic polymerization is typically initiated with an alkyllithium reagent, most commonly sec-butyllithium, although other mono- and di-functional alkyllithium initiators can also be used [Lintsell et al., Synthesis and characterization of α,ω- and α-functionalized hydrogenated polybutadienes: telechelic and semi-telechelic amine and phosophite terminated polymers, Polymer, Vol. 38, No. 11, 2835 (1997)].

[0090] The monofunctional initiators that can be used can be alkyllithium, alkylsodium or alkylpotassium compounds, typically in the range of C2 to C12. Alkyllithium compounds such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, isopentyllithium, sec-pentyllithium, tert-pentyllithium, hexyllithium or combinations thereof are preferred. Sec-alkyllithium compounds such as sec-butyllithium, sec-pentyllithium or combinations thereof are more preferred. Sec-butyllithium is most preferred. Substituted alkyllithiums such as aralkyllithium compounds, for example benzyllithium, 1-lithioethylbenzene and 1-lithio-3-methylpentylbenzene, can also be used.

[0091] A functionalized styrenic monomer comprising a nitrogen-containing structural moiety not side-bonded to the phenyl ring is copolymerized with isoprene.

[0092] Novel polymers comprising a functionalized styrenic monomer comprising a nitrogen-containing structural moiety not side-bonded to the phenyl ring can be prepared via an anionic polymerization process, wherein the monomer or combination thereof is polymerized in solution in an inert hydrocarbon solvent in the presence of an alkyllithium initiator. The inert hydrocarbon solvent can be any hydrocarbon, typically having 5 to 8 carbons, or a mixture thereof, which does not react with the alkyllithium initiator or the "living" anionic chain ends of the polymer backbone and provides suitable solubility for the product polymer. Non-limiting examples of suitable solvents are cycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, all of which are relatively non-polar. Other suitable solvents are known to those skilled in the art and can be selected to effectuate the polymerization efficiently under the given process conditions, where the polymerization temperature is one of the main factors considered.

[0093] The polymerization is preferably carried out in the presence of a polar additive that reduces the association between ions at the reactive "living" anionic chain ends of the polymer backbone and thereby promotes the polymerization. Non-limiting examples of polar additives can include various ethers (i.e., dimethyl ether, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, anisole, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dimethoxybenzene, 1-methoxy-2-(2-methoxyethoxy)ethane, etc.), various amines (i.e., trimethylamine, triethylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, etc.) or combinations thereof. Among the above polar additives, ethers are preferred. More preferred are diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane or combinations thereof.

[0094] The polymerization reaction conditions for preparing novel polymers of functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-attached to a phenyl ring are generally similar to those commonly used for anionic polymerization. Depending on the monomer and the reaction solvent, the polymerization reaction can be carried out at a temperature of about -80 °C to about 200 °C, or about -40 °C to about 150 °C, preferably about 0 °C to about 100 °C, more preferably about 20 °C to about 90 °C. In some instances, the polymerization of the functionalized monomer and the copolymerization with other monomers and blocks can be carried out at room temperature, or at 15 to 70 °C, or 20 to 60 °C, or 25 to 50 °C, or a combination of the aforementioned temperatures, or at individual temperatures within such ranges.

[0095] The polymerization reaction is carried out in a dry inert atmosphere, preferably nitrogen, and can also be carried out at a pressure of about 0 bar to about 10 bar.

[0096] After the polymerization reaction is completed, a terminator can be added to stop the reaction and quench the reactive "living" anionic chain ends of the polymer backbone. The polymerization terminator can be various primary or secondary alcohols or epoxide terminators. Non-limiting examples of various primary or secondary alcohols include methanol, ethanol, isopropanol, 2-ethyl-1-hexanol, etc., or combinations thereof. Non-limiting examples of epoxide terminators include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, etc., or combinations thereof. Among the polymerization terminators, methanol or isopropanol is preferred, except when one or more -OH functional groups are required at one or more ends of the polymer chain (in which case ethylene oxide or propylene oxide is preferred).

[0097] The novel polymers of functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-attached to a phenyl ring can optionally be separated or purified according to various general polymer separation or purification techniques known in the art. For example, the polymerization reaction solution can be poured into a poor solvent for the polymer (such as methanol) to solidify the polymer, or the polymerization reaction solution can be poured into hot water together with steam to remove the solvent by azeotropy (steam stripping) and dry the resulting product.

[0098] To the applicant's knowledge, the monomers of the present invention disclosed in U.S. Provisional Application Serial No. 63 / 483,365 have not been polymerized previously. Concentrates

[0099] A concentrate, also known as an additive package, adpak, or addpack, is a composition having less than 50 wt% (such as less than 40 wt%, such as less than 30 wt%, such as less than 25 wt%, such as less than 20 wt%) base oil and lubricant composition additives (such as those described herein), which is typically subsequently further blended with additional base oil to form a lubricating oil product.

[0100] This disclosure relates to concentrate compositions comprising the following components or obtained by mixing the following components: (a) One or more base oils in an amount of 1 to less than 50 wt% (or 5 to 45 wt%, or 7 to 40 wt%, or 10 to 35 wt%, or 10 to 25 wt%) based on the weight of the lubricating composition; (b) One or more copolymers selected from and comprising the following in an amount of 0.10 to 20 wt% (especially 0.2 to 15 wt%, or 0.5 wt% to 10 wt%, or 1 to 7 wt%) based on the weight of the composition: I. (a) 10.0 to 20.0 wt% of amine-derivatized α-methylstyrene (ADAMS) repeat units according to Structure (I): wherein: k is an integer from 1 to 3; R1 is hydrogen or benzyl, R is hydrogen, a phenyl ring co-connected to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring connected at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) 80.0 to 90.0 wt% of repeat units corresponding to the reactive form of isoprene, and wherein the peak average molecular weight of the copolymer is 45.0 to 65.0 kDa; II. (a) 5.0 to 10.0 wt% of amine-derivatized α-methylstyrene (ADAMS) repeat units according to Structure (II): wherein: k is an integer from 1 to 3; R is hydrogen, a phenyl ring co-connected to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring connected at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining 90.0 to 95.0 wt% of repeat units corresponding to the reactive form of isoprene, and wherein the peak average molecular weight of the copolymer is 24.0 to 42.0 kDa; III. (a) 4.0 to 6.0% by weight of amine-derivatized α-methylstyrene (ADAMS) repeat units according to Structure (III): wherein: k is an integer from 1 to 3; R is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining 94.0 to 96.0% by weight of repeat units corresponding to the reactive form of isoprene, and wherein the peak average molecular weight of the copolymer is 36.0 to 46.0 kDa; IV. (a) One or more amine-derivatized α-methylstyrene (ADAMS) repeat units according to Structure (IV): wherein: k is an integer from 1 to 3; R1 is hydrogen or benzyl, and R is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining repeat units corresponding to the reactive form of isoprene.

[0101] This disclosure relates to concentrate compositions comprising the following components or obtained by mixing the following components: (i) Based on the weight of the composition, 1 to less than 50% by mass (or 5 to 45% by mass, or 7 to 40% by mass, or 10 to 35% by mass, or 10 to 25% by mass) of one or more base oils; (ii) Based on the weight of the composition, 0.10 to 20% by mass (especially 0.15 to 10% by mass, or 0.20% to 5% by mass, or 0.25 to 2% by mass) of one or more detergents; (iii) Based on the weight of the composition, 0.10 to 20% by mass (especially 0.15 to 10% by mass, or 0.20% to 5% by mass, or 0.25 to 2% by mass) of one or more dispersants (such as PIBSA-PAM); and (iv) Based on the weight of the composition, 0.10 to 20% by mass (especially 0.15 to 10% by mass, or 0.20% to 5% by mass, or 0.25 to 2% by mass) of one or more copolymers of the present invention as described herein; (v) Optional additional components, antioxidants, pour point depressants, defoamers, viscosity improvers, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibility agents, additive diluents, base oils, friction improvers (such as organic FMs, such as organic esters, such as fatty acid esters), etc.

[0102] In some embodiments, the concentrate composition may optionally be free of solvents (such as aliphatic or aromatic solvents) and / or free of functionalized base oils.

[0103] The present disclosure also relates to a concentrate composition comprising the following components or obtained by mixing the following components: A) One or more base oils in an amount of 1 to less than 50% by mass (or 5 to 45% by mass, or 7 to 40% by mass, or 10 to 35% by mass, or 10 to 25% by mass) based on the weight of the concentrate composition; B) One or more copolymers of the present invention as described herein in an amount of 0.10 to 20% by mass (especially 0.15 to 10% by mass, or 0.20% to 5% by mass, or 0.25 to 3% by mass) based on the weight of the concentrate composition; C) One or more detergents (such as a blend of detergents) in an amount of 0.1 to 20% by weight (especially 0.5 to 10% by mass, or 2 to 6% by mass) based on the total weight of the concentrate composition; D) Optionally, one or more friction improvers (such as organic friction improvers, such as glycerol monooleate) in an amount of 0.01 to 5% by weight (especially 0.1 to 4% by mass, or 0.25 to 3% by mass, or 0.25 to 0.75% by mass) based on the total weight of the concentrate composition; E) Optionally, one or more antioxidants (such as a blend of antioxidants) in an amount of 0.01 to 20% by weight (especially 0.01 to 15% by mass, or 0.1 to 10% by mass) based on the total weight of the concentrate composition; F) Optionally, one or more pour point depressants (such as a blend of pour point depressants) in an amount of 0.01 to 5% by weight (especially 0.01 to 3% by mass, or 0.1 to 1.5% by mass) based on the total weight of the concentrate composition; G) Optionally, one or more defoamers (such as a blend of defoamers) in an amount of 0.001 to 5% by weight (especially 0.01 to 3% by mass, or 0.02 to 1% by mass) based on the total weight of the concentrate composition; I) Optionally, one or more dispersants (such as a blend of dispersants) in an amount of 0.01 to 40% by weight (especially 0.1 to 30% by mass, or 1 to 20% by mass) based on the total weight of the concentrate composition; K) Optionally, based on the total weight of the lubricating composition, 0.001 to 10% by weight (especially 0.1 to 8% by mass, or 1 to 5% by mass, or 0.25 to 0.75% by mass) of one or more antiwear agents (such as a blend of antiwear agents, such as ZDDP).

[0104] Optionally, the concentrate may be free of functionalized oil.

[0105] In some embodiments, the concentrate composition may optionally be free of solvents (such as aliphatic or aromatic solvents) and / or free of functionalized base oils.

[0106] Optionally, the concentrate may be free of phenolic antioxidants.

[0107] In some embodiments, the concentrate may contain less than 75 ppm boron, or less than 60 ppm boron, or 1 to 70 ppm boron. Alternatively, the concentrate may be free of boron.

[0108] In some embodiments, the concentrate may contain less than 20 (such as 15, such as 10, such as 5, such as 3, such as 1) mass% of functionalized (such as aminated) polybutene (such as polyisobutene), such as PIBSA-PAM. In some embodiments, the concentrate contains, is substantially free of, or is free of functionalized (such as aminated) polybutene (such as polyisobutene), such as PIBSA-PAM.

[0109] In some embodiments, the concentrate may contain an acylated polymer, such as polyisobutene succinic acid, which optionally has a Mn of 500 to 50,000 g / mol, such as 600 to 5,000 g / mol, such as 700 to 3,000 g / mol. In some embodiments, the concentrate may contain an acylated polymer, such as polyisobutene succinic acid, which has a Mn of 500 to 1,600 g / mol, such as 700 to 1,200 g / mol.

[0110] In some embodiments, the concentrate may contain 20 (such as 15, such as 10, such as 5, such as 3, such as 1) mass% or less of block copolymers, such as block, star, random, and / or gradient block copolymers.

[0111] In some embodiments, the concentrate may be substantially free of or free of block copolymers, such as block, star, random, and / or gradient block copolymers.

[0112] In some embodiments, the concentrate may contain 20 mass% or less (such as 15 mass% or less, such as 10 mass% or less, such as 5 mass% or less, such as 3 mass% or less, such as 1 mass% or less) of styrenic copolymers, such as block, star, random, and / or gradient styrenic block copolymers).

[0113] In some embodiments, the concentrate may be substantially free or devoid of styrenic copolymers, such as block, star, random, and / or gradient styrenic block copolymers).

[0114] In some embodiments, the concentrate may comprise less than 20 (such as less than 15, such as 10, such as less than 5, such as less than 3, such as 1) mass% of a functionalized diluent, such as a functionalized oil.

[0115] In some embodiments, the concentrate may be substantially free or devoid of a functionalized diluent, such as a functionalized oil.

[0116] In some embodiments, the concentrate may comprise less than 0.5 (such as less than 0.4, such as less than 0.3, such as less than 0.2, such as 0.1, substantially absent, 0) weight% of secondary and tertiary hydrocarbylamine compounds, based on the weight of the concentrate.

[0117] In some embodiments, the concentrate may be substantially absent or may be devoid of secondary and tertiary hydrocarbylamine compounds.

[0118] In some embodiments, the concentrate may have a kinematic viscosity at 100 °C of less than 1000 cSt, such as less than 500 cSt, such as less than 200 cSt.

[0119] The present disclosure also relates to a method of making a concentrate composition, comprising combining: (a) 1 to less than 50 mass% (or 5 to 45 mass%, or 7 to 40 mass%, or 10 to 35 mass%, or 10 to 25 mass%) of one or more base oils, based on the weight of the lubricating composition; and (b) 0.10 to 20 mass% (particularly 0.2 to 15 mass%, or 0.5 mass% to 10 mass%, or 1 to 7 mass%) of one or more of the copolymers of the present invention described herein, based on the weight of the composition. Lubricating Oil Composition Components and Concentrate Components A. Base Oil

[0120] Base oils useful herein (also referred to as "base stocks", "lubricating oil base stocks", or "oils having lubricating viscosity") may be a single oil or a blend of oils and are typically the major liquid component of a lubricating composition (also referred to as a lubricant), into which additives and optionally additional oils are incorporated to, for example, make a lubricating composition such as a final lubricant composition, a concentrate, or other lubricating composition.

[0121] The base oil can be selected from vegetable oils, animal oils, mineral oils, synthetic lubricating oils, and mixtures thereof. Its viscosity ranges from light distillate mineral oils to heavy lubricating oils, such as gas engine oils, mineral lubricating oils, motor vehicle oils, and heavy diesel engine oils. Generally, the kinematic viscosity of the base oil at 100 °C ("KV100") is from 1 to 30, such as 2 to 25 cSt, such as 5 to 20 cSt (determined according to ASTM D445-19a), especially 1.0 cSt to 10 cSt, 1.5 cSt to 3.3 cSt, 2.7 cSt to 8.1 cSt, 3.0 cSt to 7.2 cSt, or 2.5 cSt to 6.5 cSt. Generally, the high-temperature high-shear (HTHS) viscosity of the base oil at 150 °C is from 0.5 to 20 cP, such as 1 to 10 cP, such as 2 to 5 cP (determined according to ASTM D4683-20).

[0122] Generally, when a lubricating oil base stock is used to manufacture a concentrate, it can advantageously be present in an amount to form a concentrate to obtain a concentrate containing 5 wt% to 80 wt%, 10 wt% to 70 wt%, or 5 wt% to 50 wt% of active ingredient based on the weight of the concentrate.

[0123] Common oils that can be used as base oils include animal oils and vegetable oils (such as castor oil and lard), liquid petroleum, and hydrorefined and / or solvent-treated paraffinic, naphthenic, and mixed paraffin-naphthenic mineral lubricating oils. Oils derived from coal or shale are also available base oils. The base stock can be manufactured using a variety of different methods, including but not limited to distillation, solvent refining, hydroprocessing, oligomerization, esterification, and re-refining.

[0124] Synthetic lubricating oils that can be used as base oils herein include hydrocarbon oils such as homopolymers and copolymers of olefins, known as polyalphaolefins or PAO or Group IV base oils [defined according to API EOLCS1509 (American Petroleum Institute Publication 1509, see Section E.1.3, 19th Edition, January 2021, www.API.org)]. Examples of PAO that can be used as base oils include: poly(ethylene), ethylene-propylene copolymer, polybutene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutene, poly(1-hexene), poly(1-octene), poly(1-decene), C8 to C 20 homopolymers or copolymers of olefins, C8 and / or C 10 and / or C 12 homopolymers or copolymers of olefins, C8 / C 10 copolymers, C8 / C 10 / C 12Copolymer and C 10 / C 12 copolymers, as well as their derivatives, analogs, and homologs.

[0125] In another embodiment, the base oil may comprise a polyalphaolefin, including oligomers of linear olefins having 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, and even more preferably 10 carbon atoms, which have a kinematic viscosity at 100 °C (measured by ASTM D445) of 10 or higher; preferably having a viscosity index ("VI") measured by ASTM D2270 of 100 or higher, preferably 110 or higher, more preferably 120 or higher, more preferably 130 or higher, more preferably 140 or higher; and / or having a pour point of -5 °C or lower (measured by ASTM D97), more preferably -10 °C or lower, more preferably -20 °C or lower.

[0126] In another embodiment, the polyalphaolefin oligomers useful in the present disclosure may comprise C 20 to C 1500 alkanes, preferably C 40 to C 1000 alkanes, preferably C 50 to C 750 alkanes, preferably C 50 to C 500 alkanes. PAO oligomers are in one embodiment C5 to C 14 alpha-olefins, and in another embodiment C6 to C 12 alpha-olefins, and in another embodiment C8 to C 12 alpha-olefin dimers, trimers, tetramers, pentamers, etc. Suitable olefins include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. In one embodiment, the olefin is a combination of 1-octene, 1-decene, and 1-dodecene, or may be substantially 1-decene, and the PAO is a mixture of its dimers, trimers, tetramers, and pentamers (and higher). The available PAOs are more particularly described, for example, in U.S. Patent Nos. 5,171,908 and 5,783,531 and Synthetic Lubricants and High-Performance Functional Fluids 1-52 (Leslie R. Rudnick & Ronald L. Shubkin, ed. Marcel Dekker, Inc. 1999).

[0127] The PAOs useful in the present disclosure typically have a number average molecular weight of from 100 to 21,000 g / mol in one embodiment, from 200 to 10,000 g / mol in another embodiment, from 200 to 7,000 g / mol in yet another embodiment, from 200 to 2,000 g / mol in yet another embodiment, and from 200 to 500 g / mol in yet another embodiment. Desirable PAOs are available as SpectraSyn TM Hi-Vis, SpectraSyn TM Low-Vis, SpectraSyn TM plus, SpectraSyn TM Elite PAO's (ExxonMobil Chemical Company, Houston Texas) and Durasyn PAO's from Ineos Oligomers USA LLC were purchased.

[0128] Synthetic lubricating oils useful as base oils also include hydrocarbon oils such as homopolymers and copolymers of: alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides; and their derivatives, analogs, and homologs.

[0129] Another class of suitable synthetic lubricating oils useful as base oils comprises esters formed by reacting dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, bis(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, docosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and a complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

[0130] The esters useful as synthetic oils herein also include those made from C5 to C 12 monocarboxylic acids and polyols and polyol ethers (such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol).

[0131] Desirable ester base oils are available as EsterexTM purchased from Esters (ExxonMobil Chemical Company, Houston, Texas).

[0132] Silicon-based oils, such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-silicone oils and silicate oils, constitute another class of useful synthetic lubricants that can be used herein; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexakis-(4-methyl-2-ethylhexyl) disiloxane, poly(methyl) siloxane, and poly(methylphenyl) siloxane.

[0133] Other synthetic lubricating oils useful herein include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl decylphosphonate) and polymeric tetrahydrofuran.

[0134] Unrefined oils, refined oils, and re-refined oils can be used in the lubricating compositions of the present disclosure. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil directly obtained from a retorting operation, petroleum directly obtained from distillation, or ester oils directly obtained from an esterification process and used without further treatment are considered unrefined oils. Refined oils are similar to unrefined oils, except that they have been further processed in one or more purification steps to improve one or more properties. Many such purification techniques are used by those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration, and percolation. Re-refined oils are oils obtained by a process similar to the process used to obtain refined oils, where the refined process is applied to a previously refined oil that has been previously put into use. Such re-refined oils are also referred to as regenerated oils or reprocessed oils and are typically further processed to remove spent additives and oil cracking products. Re-refined base oils preferably are substantially free of materials introduced through manufacture, contamination, or previous use.

[0135] Some other examples of available base oils are gas-to-liquid (“GTL”) base oils, i.e., the base oil is an oil derived from hydrocarbons made from synthesis gas containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons generally require further processing to be used as base oils. For example, they can be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed by methods known in the art. For further information on available GTL base oils and their blends, see U.S. Patent No. 10,913,916 (column 4, line 62 to column 5, line 60) and U.S. Patent No. 10,781,397 (column 14, line 54 to column 15, line 5, and column 16, line 44 to column 17, line 55).

[0136] In particular, oils from renewable sources, i.e., those that are partially based on carbon and energy captured from the environment (such as biogenic sources), are available herein.

[0137] Various base oils are generally classified as Group I, Group II, Group III, Group IV, or Group V according to the API EOLCS 1509 definition (American Petroleum Institute Publication 1509, see Section E.1.3, 19th Edition, January 2021, www.API.org). Generally speaking, Group I base stocks have a viscosity index between approximately 80 and 120 and contain more than approximately 0.03% sulfur and / or less than approximately 90% saturates. Group II base stocks have a viscosity index between approximately 80 and 120 and contain less than or equal to approximately 0.03% sulfur and greater than or equal to approximately 90% saturates. Group III base stocks have a viscosity index greater than approximately 120 and contain less than or equal to approximately 0.03% sulfur and greater than approximately 90% saturates. Group IV base stocks include polyalphaolefins (PAOs). Group V base stocks include base stocks not included in Groups I - IV. (The viscosity index is measured by ASTM D 2270, saturates are measured by ASTM D2007, and sulfur is measured by ASTM D5185, D2622, ASTM D4294, ASTM D4927, and ASTM D3120).

[0138] The base oils useful in the formulated lubricating compositions of the present disclosure can be any one, two, three, or more of the various oils described herein. In an ideal embodiment, the base oils useful in the formulated lubricating compositions of the present disclosure are those described as API Group I, Group II, Group III (including Group III+), Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils and mixtures thereof, more preferably those of Group III, Group III+, Group IV, and Group V base oils (due to their excellent volatility, stability, viscosity, and cleanliness characteristics). Small amounts of Group I base stocks are admissible, such as amounts used to dilute additives for incorporation into formulated lubricating oil products, but are typically kept to a minimum, e.g., only amounts related to their use as diluent / carrier oils for additives used on an "as-received" basis. With respect to Group II stocks, more usefully, Group II base stocks are in the higher quality range associated with that stock, i.e., Group II stocks having a viscosity index of 100 to 120.

[0139] The base oils useful herein can be selected from any synthetic oil, natural oil, or re-refined oil (such as those commonly used as crankcase lubricants for spark-ignition and compression-ignition engines). If desired, mixtures of synthetic and / or natural and / or re-refined base oils can be used. If desired, multi-modal mixtures (such as bimodal or trimodal mixtures) of Group I, II, III, IV, and / or V base stocks can be used.

[0140] The base oil or base oil blend used herein preferably has a kinematic viscosity at 100 °C (KV100, measured according to ASTM D445-19a and reported in centistokes (cSt) or its equivalent unit mm2 / s) of about 2 to about 40 cSt, or 3 to 30 cSt, or 4 to 20 cSt, or 5 to 10 cSt at 100 °C, or the base oil or base oil blend can have a kinematic viscosity at 100 °C of 2 to 20 cSt, 2.5 to 2 cSt, preferably about 2.5 cSt to about 9 cSt.

[0141] The base oil or base oil blend preferably has a saturate content of at least 65 mass%, more preferably at least 75 mass%, such as at least 85 mass%, such as at least 90 mass% as determined by ASTM D2007.

[0142] Preferably, the base oil or base oil blend has a sulfur content of less than 1 mass%, preferably less than 0.6 mass%, most preferably less than 0.4 mass%, such as less than 0.3 mass% based on the total mass of the lubricating composition as measured by ASTM D5185.

[0143] In some embodiments, the volatility of the base oil or base oil blend as measured by the Noack test (ASTM D5800, Procedure B) is less than or equal to 30 mass%, such as less than or equal to 25 mass%, such as less than or equal to 20 mass%, such as less than or equal to 16 mass%, such as less than or equal to 12 mass%, such as less than or equal to 10 mass% based on the total mass of the lubricating composition.

[0144] In some embodiments, the viscosity index (VI) of the base oil is at least 95, preferably at least 110, more preferably at least 120, still more preferably at least 125, most preferably about 130 to 240, especially about 105 to 140 (determined by ASTM D2270).

[0145] Base oil can be provided in a major amount and combined with a minor amount of one or more additive components as described below to form a lubricant. This preparation can be achieved by adding the additive directly to the oil or by adding the one or more additives in the form of its concentrate to disperse or dissolve the additive. The additive can be added to the oil by any method known to those skilled in the art before, simultaneously with, or after adding other additives.

[0146] Base oil can be provided in a minor amount and combined with a minor amount of one or more additive components as described below to form an additive concentrate. This preparation can be achieved by adding the additive directly to the oil or by adding the one or more additives in the form of its solution, slurry, or suspension to disperse or dissolve the additive in the oil. The additive can be added to the oil by any method known to those skilled in the art before, simultaneously with, or after adding other additives.

[0147] Base oil generally constitutes the major component of the engine oil lubricant composition of the present disclosure and is typically present in an amount of about 50 to about 99% by weight, preferably about 70 to about 95% by weight, more preferably about 80 to about 95% by weight, based on the total weight of the composition.

[0148] Typically, one or more base oils are present in the lubricant composition in an amount of 32% by weight or more, or 55% by weight or more, or 60% by weight or more, or 65% by weight or more, based on the total weight of the lubricating composition. Typically, one or more base oils are present in the lubricant composition in an amount of 98% by weight or less, more preferably 95% by weight or less, still more preferably 90% by weight or less. Alternatively, one or more base oils are present in the lubricant composition in an amount of 1 to 99% by mass, or 50 to 97% by mass, or 60 to 95% by mass, or 70 to 95% by weight, based on the weight of the lubricating composition.

[0149] The above base oils and their blends can also be used to manufacture concentrates and to manufacture lubricants therefrom.

[0150] Concentrates constitute a convenient means for handling additives before their use and for facilitating the dissolution or dispersion of additives in lubricants. When preparing a lubricant containing more than one type of additive (sometimes referred to as "additive components"), each additive can be incorporated separately in the form of a concentrate. However, in many cases, it is convenient to provide a so-called additive "package" (also referred to as "addpack") that contains one or more of the additives / coconut additives described below in a single concentrate.

[0151] Typically, one or more base oils are present in the concentrate composition in an amount of 50 wt% or less, or 40 wt% or less, or 30 wt% or less, or 20 wt% or less, based on the total weight of the concentrate composition. Typically, one or more base oils are present in the concentrate composition in an amount of 0.1 to 49 mass%, or 5 to 40 mass%, or 10 to 30 mass%, or 15 to 25 mass%, based on the weight of the concentrate composition.

[0152] In some embodiments, the acylation / functionalization reactions described herein can be carried out in the presence of a base oil diluent. As a byproduct, a functionalized base oil can be produced. The oil itself may be acylated and / or functionalized. For example, a maleated base oil or an aminated base oil may be present after the functionalization reactions described herein.

[0153] It is contemplated that the functionalized base oil may comprise an acylated oil.

[0154] It is contemplated that the functionalized base oil may comprise a reaction product of an acylated oil and an amine to form an amide, an imide, or a combination thereof.

[0155] It is contemplated that the functionalized base oil may comprise an acylated oil and a reaction product of an acylated oil and an amine to form an amide, an imide, or a combination thereof.

[0156] In some embodiments, the lubricating oil composition and / or the concentrate composition may comprise a functionalized base oil, such as an acylated oil and / or a reaction product of an acylated oil and an amine or alcohol to form an amide, an imide, an ester, or a combination thereof, in an amount of 40 wt% or less, or 20 wt% or less, or 10 wt% or less, or 5 wt% or less, based on the total weight of the concentrate composition. Typically, one or more functionalized base oils, such as an acylated oil and / or a reaction product of an acylated oil and an amine or alcohol (to form an amide, an imide, an ester, or a combination thereof) are present in the concentrate in an amount of 0.01 to 40 mass%, or 0.1 to 20 mass%, or 1 to 10 mass%, or 1.5 to 5 mass%, based on the weight of the concentrate composition.

[0157] Typically, one or more functionalized base oils, such as an acylated oil and / or a reaction product of an acylated oil and an amine or alcohol (to form an amide, an imide, an ester, or a combination thereof) are present in the lubricating oil composition in an amount of 0.01 to 40 mass%, or 0.1 to 20 mass%, or 1 to 10 mass%, or 1.5 to 5 mass%, based on the weight of the lubricating oil composition.

[0158] In some embodiments, the functionalized oil may be present in the lubricating oil composition in an amount of 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt%.

[0159] In some embodiments, the functionalized oil may be present in the concentrate composition at 3 mass% or less, preferably 2 mass% or less, preferably 1 mass% or less, preferably 0.1 mass% or less, preferably 0 mass%, based on the weight of the concentrate composition.

[0160] In some embodiments, the acylation / functionalization reactions described herein may be carried out in a solvent-containing medium. As a by-product, a functionalized solvent may be produced. The solvent itself may be acylated and / or functionalized. In some embodiments, the acylated and / or functionalized solvent may be present in the concentrate composition at 3 mass% or less, preferably 2 mass% or less, preferably 1 mass% or less, preferably 0.1 mass% or less, preferably 0 mass%, based on the weight of the concentrate composition. In some embodiments, the functionalized solvent may be present in the lubricating oil composition at 3 mass% or less, preferably 2 mass% or less, preferably 1 mass% or less, preferably 0.1 mass% or less, preferably 0 mass%, based on the weight of the lubricating oil composition. B. Functionalized Polymer

[0161] The present disclosure relates to a functionalized polymer comprising a polymer having an Mn (GPC-PS) of about 10,000 g / mol or higher, such as 20,000 g / mol or higher, such as 25,000 g / mol or higher, such as 30,000 g / mol or higher, such as 35,000 g / mol or higher before functionalization. Alternatively, the functionalized polymer comprises a polymer having an Mn (GPC-PS) of 10,000 to 300,000 g / mol, such as 20,000 to about 150,000 g / mol, such as 30,000 to about 125,000 g / mol, such as 35,000 to about 100,000 g / mol, such as 40,000 to 80,000 g / mol before functionalization. The polymer before functionalization may have an Mw / Mn of less than 2 (such as less than 1.6, such as less than 1.5, such as 1.4 or lower, such as 1 to 1.3, such as 1.0 to 1.25, such as 1.0 to 1.2, such as 1.0 to 1.15, such as 1.0 to 1.1, as determined by GPC-PS). The polymer before functionalization may comprise repeating units of one or more olefins having 4 to 5 carbon atoms (preferably conjugated dienes having 4 to 5 carbon atoms). Before functionalization, the C 4-5 polymer is preferably fully or partially saturated (such as fully or partially hydrogenated). The functionalized polymer can be obtained by reacting the C 4-5 polymer with an acylating agent to form an acylated polymer and then reacting the acylated polymer with an amine or an alcohol to form an amide, imide, ester or a combination thereof. The functionalized polymer can also be obtained by reacting an acylated C 4-5 polymer (such as a commercially available maleated fully or partially hydrogenated C4-5 obtained by reacting a (co)polymer with an amine to form an amide, imide, or a combination thereof.

[0162] This disclosure further relates to a C as described herein 4-5 saturated (e.g., hydrogenated) polymer functionalized with amide, imide, and / or ester of a conjugated diene, which is obtained by reacting a completely or partially saturated (e.g., completely or partially hydrogenated) polymer of a conjugated diene having an Mw / Mn of less than 2 with an acylating agent, such as maleic acid or maleic anhydride, and then reacting the acylated polymer with an amine (e.g., polyamine) to form an imide, amide, or a combination thereof. 4-5 obtained by reacting a completely or partially saturated (e.g., completely or partially hydrogenated) polymer of a conjugated diene with an acylating agent, such as maleic acid or maleic anhydride, and then reacting the acylated polymer with an amine (e.g., polyamine) to form an imide, amide, or a combination thereof.

[0163] This disclosure relates to a polymer containing one or more amine side groups and comprising the following components or obtained by mixing the following components: at least partially (preferably completely) hydrogenated C 4-5 olefin polymer with an acylating agent, such as maleic acid or maleic anhydride, and then reacting the acylated polymer with a polyamine to form an imide, amide, or a combination thereof.

[0164] In some embodiments, the functionalized polymer is not prepared in an aromatic solvent (such as benzene or toluene), or the aromatic solvent is present at 2 wt% or less (such as 1 wt% or less, such as 0.5 wt% or less) based on the weight of the solvent, diluent, and polymer.

[0165] In some embodiments, the functionalized polymer is not prepared in an alkylated naphthylenic solvent, or the alkylated naphthylenic solvent is present at 5 wt% or less (such as 3 wt% or less, such as 1 wt% or less) based on the weight of the solvent, diluent, and polymer.

[0166] The polymers that can be used herein to prepare the functionalized polymer can be homopolymers of butadiene, isoprene, etc.

[0167] In some embodiments, the polymers that can be used herein to prepare the functionalized polymer can be homopolymers of isoprene, or copolymers of isoprene and less than 5 mol% (such as less than 3 mol%, such as less than 1 mol%, such as less than 0.1 mol%) of comonomers.

[0168] The polymers useful herein for preparing functionalized polymers can be copolymers of isoprene and one or more of the following: styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, and 3,5-decadiene, [optionally, the comonomer is present in less than 20 mol%, less than 5 mol%, such as less than 3 mol%, such as less than 1 mol%, such as less than 0.1 mol%].

[0169] Typically, the polymerized conjugated diene polymers useful herein for preparing functionalized polymers include a mixture of 1,4- and 1,2-insertions (also known as 2,1-insertions; for butadiene, 1,2-insertion is the same as 3,4-insertion). As measured by 1HNMR, the polymerized conjugated diene polymers useful herein for preparing functionalized polymers contain at least about 50% 1,4-insertion, such as at least about 75% 1,4-insertion, such as at least about 80% 1,4-insertion, such as at least about 90% 1,4-insertion, such as at least about 95% 1,4-insertion, such as at least 98% 1,4-insertion, based on the total amount of 2,1-insertion, 1,4-insertion, and 3,4-insertion based on isoprene. For the purposes of this disclosure, 1) the phrase "1,4-insertion" includes 1,4- and 4,1-insertions, 2) the phrase "2,1-insertion" includes 2,1- and 1,2-insertions, and 3) the phrase "3,4-insertion" includes 3,4- and 4,3-insertions.

[0170] Optionally, styrene repeating units may be absent in the polymers useful herein for preparing functionalized polymers. Optionally, styrene repeating units may be absent in the functionalized hydrogenated / saturated polymers.

[0171] Optionally, butadiene repeating units may be absent in the polymers useful herein for preparing functionalized polymers. Optionally, butadiene repeating units may be absent in the functionalized hydrogenated / saturated polymers.

[0172] Optionally, the polymers useful herein for preparing functionalized polymers may not be homopolybutene. Optionally, the functionalized hydrogenated / saturated polymers may not be homopolybutene.

[0173] Optionally, the polymers useful herein for preparing functionalized polymers may not be homopolyisobutene. Optionally, the functionalized hydrogenated / saturated polymers may not be homopolyisobutene.

[0174] Optionally, the polymers useful herein for preparing functionalized polymers may not be copolymers of isoprene and butadiene. Optionally, the functionalized hydrogenated / saturated polymers may not be copolymers of isoprene and butadiene.

[0175] The polymers useful herein for preparing functionalized polymers and / or the functionalized polymers may be homopolymers or copolymers. The copolymer may be a random copolymer, a gradient block copolymer, a star copolymer, or a block copolymer. The block copolymer is formed from a monomer mixture comprising one or more first monomers (such as isobutene), wherein, for example, the first monomer forms a discrete block of the polymer, which is attached to a second discrete block of the polymer formed from a second monomer (such as butadiene). Although the block copolymer has substantially discrete blocks formed from monomers, the gradient block copolymer may consist of a relatively pure first monomer at one end and a relatively pure second monomer at the other end. The middle of the gradient block copolymer may be more of a gradient composition of these two monomers.

[0176] The polymers useful herein for preparing functionalized polymers may generally have a Mn (GPC-PS) of from 20,000 to 150,000 g / mol, or from 20,000 to about 150,000 g / mol, or from 30,000 to about 125,000 g / mol, or from 35,000 to about 100,000 g / mol, or from 40,000 to 80,000 g / mol.

[0177] The polymers useful herein for preparing functionalized polymers may generally have an Mw / Mn (determined by GPC-PS) of from 1 to 2, or greater than 1 to less than 2, or from 1.1 to 1.8, or from 1.2 to 1.5. Alternatively, the polymers useful herein for preparing functionalized polymers may generally have an Mw / Mn of 1 or greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.5, such as less than 1.4, such as less than 1.3, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0178] The polymers useful for preparing functionalized polymers may have an Mz (determined by GPC-PS) (GPC-PS) of from 20,000 to 150,000 g / mol, or from 20,000 to about 150,000 g / mol, or from 30,000 to about 125,000 g / mol, or from 35,000 to about 100,000 g / mol, or from 40,000 to 80,000 g / mol, or from 40,000 to 60,000 g / mol.

[0179] The polymers useful for preparing functionalized polymers herein may have a glass transition temperature (Tg) of -25 °C or lower, such as -40 °C or lower, such as -50 °C or lower, as determined by differential scanning calorimetry (DSC) using a Perkin Elmer or TA Instrument Thermal Analysis System (heating the sample from ambient temperature to 210 °C at 10 °C / min and holding at 210 °C for 5 minutes, then cooling to -40 °C at 10 °C / min and holding for 5 minutes).

[0180] The polymers useful for preparing functionalized polymers herein generally have a residual unsaturation of less than 3%, such as less than 2%, such as less than 1%, such as less than 0.5%, such as less than 0.25%, based on the number of double bonds in the non-hydrogenated polymer.

[0181] The polymers useful for preparing functionalized polymers herein generally have a residual metal (such as Li, Co, and Al) content of less than 100 ppm, such as less than 50 ppm, such as less than 25 ppm, such as less than 10 ppm, such as less than 5 ppm. Hydrogenation

[0182] The C of the polymers useful for preparing functionalized polymers herein 4-5 The polymers can be partially or fully hydrogenated by hydrogenating agents known to those of ordinary skill in the art. For example, saturated or partially saturated polymers can be prepared as follows: (a) providing a C containing unsaturations (such as double bonds or triple bonds) 4-5a polymer; and (b) hydrogenating at least a portion or all of the unsaturations (such as double or triple bonds) in the polymer in the presence of a hydrogenating reagent. In some embodiments, the polymer is fully hydrogenated. In some embodiments, the polymer is partially hydrogenated. In some embodiments, the polymer is saturated (hydrogenated) at 50% or higher, such as 60% or higher, such as 70% or higher, such as 80% or higher, such as 90% or higher, such as 95% or higher, such as 98% or higher, such as 99% or higher, such as 50 to 100% saturation (hydrogenation), as determined by the ozone absorption method described by Martino N. Smits and Dirkman Hoefman, Quantitative Determination of Olefinic Unsaturation by Measurement of Ozone Absorption, Analytical Chemistry Vol 44, No. 9, page 1688, 1972, Martino N. Smits.

[0183] In some embodiments, the hydrogenating reagent can be hydrogen in the presence of a hydrogenation catalyst. In some embodiments, the hydrogenation catalyst is Pd, Pd / C, Pt, PtO2, Ru(PPh3)2Cl2, Raney nickel, or a combination thereof. In some embodiments, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd / C. In a further embodiment, the catalyst can comprise or be 10% Pd / C in a high-pressure reaction vessel, and the hydrogenation reaction is allowed to proceed to completion. Typically, after completion, the reaction mixture can be washed, concentrated, and dried to obtain the corresponding hydrogenated product. Alternatively, any reducing agent that can reduce a C═C bond to a C—C bond can also be used. For example, an olefin polymer can be hydrogenated by treatment with hydrazine in an oxygen atmosphere in the presence of a catalyst such as 5-ethyl-3-methyl-10H-phenothiazin-10-yl perchlorate to obtain the corresponding hydrogenated product. The reduction reaction with hydrazine is disclosed in Imada et al., J Am. Chem. Soc., 127, pages 14544-14545, (2005), which is hereby incorporated by reference. Acylation

[0184] Fully or partially saturated (hydrogenated) polymers can be chemically modified (functionalized) to provide polymers having at least one polar functional group such as, but not limited to, halogen, epoxy, hydroxyl, amino, imino, mercapto, imido, carboxyl, and sulfonic acid groups or combinations thereof. The functionalized polymers can be further modified to provide a more desired functional type. In a preferred case, the fully or partially hydrogenated polymer is functionalized by a method that includes reacting the fully or partially hydrogenated polymer with an unsaturated carboxylic acid (or its derivative such as maleic anhydride) to provide an acylated polymer (which can then be further functionalized as described below).

[0185] In some embodiments, a carboxylic acid functionality or its reactive equivalent is grafted onto the polymer to form an acylated polymer. Generally, an ethylenically unsaturated carboxylic acid material is grafted onto the polymer backbone. These materials attached to the polymer typically contain at least one double bond (before reaction) and at least one, such as two, carboxylic acid (or its anhydride) groups or polar groups that can be converted to the carboxyl group by oxidation or hydrolysis. Maleic anhydride or its derivatives are suitable. It is grafted onto the polymer to provide two carboxylic acid functionalities. Examples of additional unsaturated carboxylic acid materials include itaconic anhydride or the corresponding dicarboxylic acids such as maleic acid, fumaric acid, and their esters, and cinnamic acid and its esters.

[0186] The ethylenically unsaturated carboxylic acid material can be grafted onto the polymer in a variety of ways. It can be grafted onto the polymer in solution or in a substantially pure (molten) form, with or without a free radical initiator. The free radical-initiated grafting of the ethylenically unsaturated carboxylic acid material can also be carried out in a solvent such as hexane or mineral oil. It can be carried out at an elevated temperature of 100 °C to 250 °C, such as 120 °C to 190 °C, or 150 °C to 180 °C, for example above 160 °C.

[0187] Free radical initiators that can be used include peroxides, hydroperoxides, and azo compounds, typically those having a boiling point greater than about 100 °C and thermally decomposing within the grafting temperature range to provide free radicals. Representatives of these free radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hex-3-yne-2,5-bis(tert-butylperoxide). The initiator can be used in an amount of 0.005 wt% to 1 wt% based on the weight of the reaction mixture solution. The grafting can be carried out in an inert atmosphere, such as under a nitrogen blanket. The resulting acylated polymer intermediate is characterized by having a carboxylic acid acylation functionality as part of its structure.

[0188] In some embodiments, the acylated polymer can have two or more anhydride groups per polymer molecule and can exhibit less than 10% gel. Alternatively, the acylated polymer can have less than two anhydride groups per polymer molecule and can exhibit less than 10% gel. (See also column 17, line 14 - column 18, line 11 of U.S. Patent No. 5,429,758).

[0189] Alternatively, in some embodiments, the acylated polymer may have a gel content of less than about 5 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or 0 wt%, where the gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as the extractant. The percentage of soluble and insoluble (gel) materials in the polymer composition is determined by soaking a sample of the polymer film nominally 0.5 mm thick in cyclohexane at 23 °C for 48 hours or refluxing the film sample in boiling xylene for half an hour, removing the solvent, weighing the dry residue, and calculating the amounts of soluble and insoluble (gel) materials. This method is generally described in U.S. Patent No. 4,311,628, which is incorporated herein by reference. For the purposes of this disclosure, the gel content is measured using boiling xylene, unless the sample is insoluble in xylene, in which case the cyclohexane method is used.

[0190] In some embodiments, the acylated polymer may have a saponification value (SAP) of 5 g / KOH or higher, such as 10 g / KOH or higher, such as 20 g / KOH or higher, such as 30 g / KOH or higher, such as 50 g / KOH or higher, such as 10 to 60 g / KOH, such as 20 to 40 g / KOH, as determined by ASTM D94.

[0191] In some embodiments, the acylated polymer composition may have less than 5 wt% of unreacted acylating agent (such as maleic anhydride), such as less than 4 wt%, such as less than 3 wt%, such as less than 1 wt%, such as less than 0.5 wt%, such as less than 0.25 wt%, such as less than 0.1 wt%, based on the weight of the acylated polymer composition (i.e., polymer, acylating agent, and diluent).

[0192] In some embodiments, the acylation reaction described herein may be carried out in a base oil diluent. As a byproduct, a functionalized base oil may be produced. The oil itself may be acylated. For example, a maleated base oil may be present after the acylation reaction described herein.

[0193] It is contemplated that the functionalized base oil may comprise an acylated oil and / or a reaction product of an acylated oil with an amine to form an amide, imide, or a combination thereof.

[0194] Preferably, the acylated oil and / or the reaction product of the acylated oil with an amine or an alcohol (to form an amide, imide, ester, or a combination thereof) may be present in the concentrate in an amount of 40 wt% or less, or 20 wt% or less, or 10 wt% or less, or 5 wt% or less, or 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt% (such as 0 to 40 wt%, or 0.01 to 40 wt%, or 0.1 to 20 wt%, or 1 to 10 wt%, or 1.5 to 5 wt%) based on the weight of the concentrate composition.

[0195] Preferably, one or more functionalized base oils, such as the acylated oil and / or the reaction product of the acylated oil with an amine or an alcohol (to form an amide, imide, ester, or a combination thereof) may be present in the lubricating oil composition in an amount of 0.01 to 40 wt%, or 0.1 to 20 wt%, or 1 to 10 wt%, or 1.5 to 5 wt% (such as 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt%) based on the weight of the lubricating oil composition.

[0196] In some embodiments, the acylation reaction described herein is carried out in a solvent-containing medium. As a by-product, an acylated / functionalized solvent may be produced. In some embodiments, the acylated and / or functionalized solvent may be present in the concentrate composition in an amount of 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt%. In some embodiments, the functionalized solvent may be present in the lubricating oil composition in an amount of 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt% based on the weight of the lubricating oil composition.

[0197] In some embodiments, the acylating agent may be added in a manner that minimizes side reactions (such as reactions with the base oil or other diluents present in the reaction vessel).

[0198] In some embodiments, an acylation reaction can occur where an acylating agent (such as maleic acid or maleic anhydride) is added in a continuous or semi - continuous (such as batch) feed stream (e.g., added in controlled relatively equal portions over the reaction time, or in larger and / or smaller portions at different points in the reaction) to minimize functionalized base oil and other side reactions. As an example, the acylating agent can be added in a continuous manner where the amounts of the polymer and the acylating agent are added in a controlled stoichiometric amount. As another example, the polymer can be added to the reaction vessel in a batch manner while the acylating agent is added slowly or in a semi - continuous manner (such as added in 2 or more, such as 5 or more, such as 10 or more, such as 20 or more, such as 30 or more, such as 40 or more, such as 50 or more, such as 60 or more discrete amounts or portions). Alternatively, the polymer can be divided into X portions and added to the reaction vessel, while the acylating agent is divided into 1.5X or more (such as 2X or more, such as 5X or more, such as 10X or more, such as 20X or more, such as 30X or more, such as 40X or more, such as 50X or more, such as 60X or more) portions. The same effect can also be achieved by diluting or concentrating the polymer solution and / or the acylating agent solution to the same or different extents.

[0199] Preferably, the acylating agent can be added in a manner that minimizes side reactions, such as in a continuous or semi - continuous manner.

[0200] The reaction can also be run to minimize side reactions by using a high - concentration polymer (such as 45 wt% or higher, or 50 wt% or higher, or 55 wt% or higher, or 60 wt% or higher) in a diluent in a batch, semi - continuous or continuous reactor operation. For example, a polymer (such as a hydrogenated isoprene polymer, such as a hydrogenated homopolyisoprene) can be introduced as a solution or suspension (such as a slurry) in a diluent (such as an oil (e.g., a base oil, such as Group I, II, III, IV, and / or V base oils, such as Group II and / or Group III base oils) or an alkane solvent or diluent or a combination thereof) into a batch, semi - continuous or continuous reactor operation, where the polymer can be present in the solution or suspension at 45 wt% or more (such as 50 wt% or more, or 55 wt% or more, or 60 wt% or more) based on the weight of the polymer and the diluent.

[0201] In some embodiments, side reactions can be minimized as follows: 1) adding the acylating agent in a continuous or semi - continuous manner, and / or 2) introducing the polymer as a solution or suspension in a diluent into a batch, semi - continuous or continuous reactor operation, where the polymer is present at 45 wt% or more based on the weight of the polymer and the diluent.

[0202] In some embodiments, side reactions are minimized, optionally by adding the acylating agent in a continuous or semi - continuous manner, and / or by introducing a fully or partially hydrogenated polymer (such as an isoprene polymer) as a solution or suspension in a diluent into a batch, semi - continuous or continuous reactor operation, the solution or suspension comprising 45 wt% or more (such as 50 wt% or more, or 55 wt% or more, or 60 wt% or more) of the fully or partially hydrogenated polymer based on the weight of the fully or partially hydrogenated polymer and the diluent.

[0203] In some embodiments, side reactions are minimized, optionally by adding the acylating agent in a continuous or semi - continuous manner, and by introducing a fully or partially hydrogenated polymer (such as an isoprene polymer) as a solution or suspension in a diluent into a batch, semi - continuous or continuous reactor operation, the solution or suspension comprising 45 wt% or more (such as 50 wt% or more, or 55 wt% or more, or 60 wt% or more) of the fully or partially hydrogenated polymer based on the weight of the fully or partially hydrogenated polymer and the diluent. Functionalization

[0204] In some embodiments, an acylated polymer can react with an alcohol or an amine to form an amide, an imide, an ester, or a combination thereof. The reaction can consist of condensations to form imides, amides, semi - amides, amide - esters, diesters, or amine salts. A primary amino group will generally condense to form an amide, or an imide in the case of maleic anhydride. It should be noted that the amine can have a single primary amino group or multiple primary amino groups.

[0205] Suitable amines can include one or more aromatic amines, such as amines in which a carbon atom of the aromatic ring structure is directly attached to the amino nitrogen. The amine can also be aliphatic. In some embodiments, the aliphatic amines can be used alone, or in combination with each other or with aromatic amines. In some embodiments, the amount of aromatic amine can be a major or minor amount compared to the amount of non - aromatic amine, or in some cases, the composition can be substantially free of aromatic amines. Alternatively, the composition can be substantially free of aliphatic amines.

[0206] Examples of aromatic amines useful herein include one or more N - arylphenylenediamines represented by the following formula: wherein R7 is H, —NHaryl, —NHalkaryl, or a branched or straight - chain hydrocarbon group having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxy, aralkyl, or alkaryl; R9 is —NH2, —(NH(CH2) n ) mNH2, —NH-alkyl, —NH-arylalkyl, —CH2-aryl-NH2, where n and m each have a value of from about 1 to about 10; and R8 is hydrogen, or an alkyl, alkenyl, alkoxy, arylalkyl or alkaryl group having from about 4 to about 24 carbon atoms.

[0207] Suitable N-aryl-phenylenediamines include N-phenyl-phenylenediamine (NPPDA), such as N-phenyl-4,4-phenylenediamine, N-phenyl-1,3-phenylenediamine and N-phenyl-1,2-phenylenediamine and N-naphthyl-1,4-phenylenediamine. Other derivatives of NPPDA may also be included, such as N-propyl-N'-phenyl-phenylenediamine.

[0208] In some embodiments, the amine that reacts with the acylated polymer is an amine having at least 3 or 4 aryl groups and can be represented by the following formula: where, independently of each variable, R 1 can be hydrogen or C l to C5 alkyl (usually hydrogen); R 2 can be hydrogen or C l to C5 alkyl (usually hydrogen); U can be an aliphatic, alicyclic or aromatic group, provided that when U is aliphatic, the aliphatic group can be a linear or branched alkylene group containing 1 to 5, or 1 to 2 carbon atoms; and w can be 1 to 10, or 1 to 4, or 1 to 2 (usually 1).

[0209] Other examples of aromatic amines include aniline, N-alkyl anilines such as N-methyl aniline and N-butyl aniline, di-(p-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitrophenylazo)aniline (disperse orange 3), sulfamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl salicylate), N-(4-amino-5-methoxy-2-methylphenyl)-benzamide (fast violet B), N-(4-amino-2,5-dimethoxyphenyl)-benzamide (fast blue RR), N-(4-amino-2,5-diethoxyphenyl)-benzamide (fast blue BB), N-(4-aminophenyl)-benzamide and 4-phenylazoaniline. Suitable amines are mentioned in U.S. Patent No. 7,790,661 and incorporated herein by reference.

[0210] In some embodiments, the compound that condenses with the acylated polymer can be represented by the following formula: where X is an alkylene group containing from about 1 to about 4 carbon atoms; R2 , R 3 and R 4 are hydrocarbon groups. wherein X is an alkylene group containing from about 1 to about 4 carbon atoms; R 3 and R 4 are hydrocarbon groups.

[0211] Alternatively, the amine can be an amine having at least 4 aromatic groups and an aldehyde (such as formaldehyde). The aromatic amine can be represented by the following formula: wherein, R 1 is hydrogen or C 1-5 alkyl (usually hydrogen); R 2 is hydrogen or C 1-5 alkyl (usually hydrogen); U is an aliphatic, alicyclic or aromatic group, provided that when U is aliphatic, the aliphatic group can be a linear or branched alkylene group containing 1, 2, 3, 4 or 5, or 1 to 2 carbon atoms; and w is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, such as 0, 1, 2 or 3, or 0 or 1 (usually 0). For further information on such amines, see, for example, US2017 / 0073606, page 5, paragraphs

[0064] -

[0070] and European Patent No. 2 401 348.

[0212] Examples of compounds that can condense with an acylating agent and further have a tertiary amino group can include, but are not limited to: dimethylaminopropylamine, N,N-dimethyl-aminopropylamine, N,N-diethyl-aminopropylamine, N,N-dimethyl-aminoethylamine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, isobutylenediamine, pentanediamine, hexanediamine, heptanediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine and bis(hexamethylene)triamine, diaminobenzene, diaminopyridine or mixtures thereof. Compounds that can condense with an acylating agent and further have a tertiary amino group can further include aminoalkyl-substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, 3',3-amino-bis(N,N-dimethylpropylamine). Another example of a compound that can condense with an acylating agent and have a tertiary amino group includes alkanolamines, including but not limited to triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-di-ethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine.

[0213] In some embodiments, the polymer can react with a polyether aromatic compound. Generally, the polyether aromatic compound has at least two functional groups, each capable of reacting with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester, or a mixture thereof. In some embodiments, the polyether aromatic compound is derived from an aromatic compound containing at least one amine group, and wherein the polyether is capable of reacting with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester.

[0214] Examples of suitable polyether aromatic amines include compounds having the following structures: wherein A represents an aromatic aminic moiety, wherein the ether group is linked via at least one amine group on the aromatic structural moiety; R1 and R6 are independently hydrogen, alkyl, alkaryl, aralkyl or aryl or a mixture thereof; R2, R3, R4 and R5 are independently hydrogen or an alkyl group containing from about 1 to about 6 carbon atoms or a mixture thereof; a and x are independently integers from about 1 to about 50.

[0215] The acylated polymer can react with a polyetheramine or a polyether polyamine. Typical polyetheramine compounds contain at least one ether unit and are chain-terminated with at least one amine structural moiety. The polyether polyamines can be based on polymers derived from C2-C6 epoxides such as ethylene oxide, propylene oxide and butylene oxide. Examples of polyether polyamines are sold under the Jeffamine TM brand and are available from Huntsman Corporation.

[0216] Amines that can be used in combination with the acylated polymer herein include one or more of the following: N-phenylenediamines (such as N-phenyl-1,4-phenylenediamine, N-phenyl-p-phenylenediamine (also known as 4-aminodiphenylamine, ADPA), N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-phenylenediamine), nitroanilines (such as 3-nitroaniline), N-phenylethylenediamines (such as N1-phenylethane-1,2-diamine), N-aminophenylacetamides (such as N-(4-aminophenyl)acetamide), morpholinopropylamines (such as 3-morpholinopropan-1-amine) and aminoethylpiperazines (such as 1-(2-aminoethyl)piperazine).

[0217] In some embodiments, the functionalization (such as amination) reactions described herein can be carried out in a diluent (such as a base oil or an alkane solvent). As a by-product, a functionalized diluent (such as a functionalized base oil) can be produced. It is contemplated that the functionalized diluent (such as a functionalized base oil) may contain the reaction product of an acylated diluent (such as an acylated base oil) with an amine to form an amide, an imide or a combination thereof.

[0218] Preferably, the reaction product of an acylation diluent (such as an acylated oil) with an amine or an alcohol (to form an amide, imide, ester, or a combination thereof) can be present in the concentrate in an amount of 40 wt% or less, or 20 wt% or less, or 10 wt% or less, or 5 wt% or less, or 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt% (such as 0 to 40 wt%, or 0.01 to 40 wt%, or 0.1 to 20 wt%, or 1 to 10 wt%, or 1.5 to 5 wt%) based on the weight of the concentrate composition.

[0219] Preferably, one or more functionalized base oils, such as the reaction product of an acylation diluent (such as an acylated base oil) with an amine or an alcohol (to form an amide, imide, ester, or a combination thereof), can be present in the lubricating oil composition in an amount of 0.01 to 40 wt%, or 0.1 to 20 wt%, or 1 to 10 wt%, or 1.5 to 5 wt% (such as 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt%) based on the weight of the lubricating oil composition.

[0220] In some embodiments, the functionalization (such as amination) reaction described herein can be carried out in a solvent-containing medium. As a by-product, a functionalized solvent can be produced. In some embodiments, the functionalized solvent can be present in the concentrate composition in an amount of 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt% based on the weight of the concentrate composition. In some embodiments, the functionalized solvent can be present in the lubricating oil composition in an amount of 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt% based on the weight of the lubricating oil composition.

[0221] In some embodiments, the acylated base oil / solvent can be removed before functionalization. Functionalized Polymers

[0222] The functionalized polymer can be a C4 or C5 olefin, such as a homopolymer of butadiene and isoprene.

[0223] In some embodiments, the functionalized polymer can be a homopolymer of isoprene, or a copolymer of isoprene and a comonomer in an amount less than 5 mol% (such as less than 3 mol%, such as less than 1 mol%, such as less than 0.1 mol%).

[0224] The functionalized polymer can comprise or be a copolymer of isoprene and one or more of the following: styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, and 3,5-decadiene, (optionally, the comonomer is present in less than 20 mol%, less than 5 mol%, such as less than 3 mol%, such as less than 1 mol%, such as less than 0.1 mol%).

[0225] In some embodiments, the functionalized polymer comprises 10 (such as 9, such as 8, such as 7, such as 6, such as 5, such as 4, such as 3, such as 2, such as 1) wt% or less of styrene monomer based on the weight of the functionalized polymer.

[0226] In some embodiments, styrene repeat units may be absent in the functionalized polymer.

[0227] In some embodiments, the functionalized polymer can be a block copolymer or a gradient block copolymer that does not contain a styrene block.

[0228] In some embodiments, the functionalized polymer can be a block copolymer or a gradient block copolymer that comprises isoprene (or consists of or consists essentially of isoprene).

[0229] In some embodiments, the functionalized polymer can be a block copolymer or a gradient block copolymer that comprises 50 wt% or more of isoprene based on the weight of the copolymer.

[0230] In some embodiments, the functionalized polymer can be a block copolymer or a gradient block copolymer that comprises C 4-5 conjugated diene (or consists of or consists essentially of C 4-5 conjugated diene), preferably comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt% or more of C 4-5 conjugated diene based on the weight of the copolymer. 4-5 conjugated diene of the block copolymer or gradient block copolymer.

[0231] In some embodiments, the functionalized polymer can be a copolymer comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) weight percent or more isoprene, based on the weight of the copolymer.

[0232] In some embodiments, the functionalized polymer can be a copolymer comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) weight percent or more butadiene, based on the weight of the copolymer.

[0233] In some embodiments, the functionalized polymer can be a copolymer comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) weight percent or more butadiene and isoprene, based on the weight of the copolymer.

[0234] In some embodiments, the functionalized polymer can be a diblock copolymer comprising at least one isoprene homopolymer or copolymer block.

[0235] Optionally, no butadiene repeat units may be present in the functionalized polymer.

[0236] Optionally, the functionalized polymer may not be homopolyisobutene.

[0237] Optionally, the functionalized polymer may not be a copolymer of isoprene and butadiene.

[0238] Typically, the polymerized conjugated dienes in the functionalized polymer include monomer units that have been inserted into the growing polymer chain by conjugated addition and non-conjugated addition. In some embodiments, as measured by 13 13C NMR, based on the total number of conjugated additions and non-conjugated insertions, the functionalized polymer contains at least about 50% of the insertions by conjugated addition, such as at least about 75% of the insertions by conjugated addition, such as about 80% of the insertions by conjugated addition, such as about 85% to about 100% of the insertions by conjugated addition.

[0239] The insertion of isoprene most typically occurs by 2,1 insertion, 1,4 insertion (trans and cis), and 3,4 insertion of isoprene. (Measurement of the insertion geometry by 1 1H NMR). By 1For the ¹H NMR measurement, the functionalized isoprene polymer contains at least about 50% of 1,4-insertion, such as at least about 75% of 1,4-insertion, such as at least about 80% of 1,4-insertion, such as at least about 90% of 1,4-insertion, such as at least about 95% of 1,4-insertion, such as at least 98% of 1,4-insertion, based on the total amount of 2,1-insertion, 1,4-insertion and 3,4-insertion based on isoprene. For the present disclosure, 1) the phrase "1,4-insertion" includes 1,4- and 4,1-insertion, 2) the phrase "2,1-insertion" includes 2,1- and 1,2-insertion, and 3) the phrase "3,4-insertion" includes 3,4- and 4,3-insertion.

[0240] The functionalized polymer can be a homopolymer or a copolymer. Optionally, the functionalized polymer comprises a homopolymer or copolymer of isoprene. The copolymer can be a random copolymer, a gradient block copolymer, a star copolymer or a block copolymer.

[0241] The functionalized polymer can generally have a Mn (GPC-PS) of 20,000 to 150,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol.

[0242] The polymer before functionalization can generally have a Mn / Mw (GPC-PS) of 1.0 to 2, such as 1.1 to 1.5, such as 1.1 to 1.3, such as 1.1 to 1.2. As the functionalization proceeds, broadening of Mw / Mn may occur.

[0243] The functionalized polymer can generally have a Mw / Mn (GPC-PS) of 1 to 3, or 1 to 2, or greater than 1 to less than 2, or 1.05 to 1.9, or 1.10 to 1.8, or 1.10 to 1.7, or 1.12 to 1.6, or 1.13 to 1.5, or 1.15 to 1.4, or 1.15 to 1.3. Alternatively, the functionalized polymer can generally have a Mw / Mn of 1 or greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.4, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0244] In some embodiments, the functionalized polymer can have a saponification number (SAP) of 25 (such as 28, such as 30, such as 32, such as 34) mgKOH / g or higher as determined by ASTM D94.

[0245] In some embodiments, the functionalized polymer can contribute 17% or more (such as 20% or more, such as 17 to 40%, such as 20 to 30%) of the saponification value of the lubricating oil composition.

[0246] In some embodiments, the functionalized polymer can have an average functionality of 1.4 to 20 FG grafts / polymer chain as determined by GPC-PS, such as 1.4 to 15 FG grafts / polymer chain, such as 3 to 12.5 FG grafts / polymer chain, such as 4 to 10 FG grafts / polymer chain.

[0247] The functionalized polymer can have an average functionality of 15 (such as 14, 13, 12, 11, 10, 9, 8, 7, or 6) or fewer FG grafts / polymer chain as determined by GPC-PS.

[0248] The functionalized polymer can have an average functionality of 1 (such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) or more FG grafts / polymer chain as determined by GPC-PS.

[0249] The functionalized polymer can have an average functionality of 1 (such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) to 15 (such as 14, 13, 12, 11, 10, 9, 8, 7, or 6) FG grafts / polymer chain as determined by GPC-PS.

[0250] In some embodiments, the functionalized polymer can have an aromatic content of 5% or less, such as 3% or less, such as 1% or less, such as 0% based on the weight of the polymer.

[0251] In some embodiments, the functionalized polymer can comprise a branched C monomer acylated polymer having an Mw / Mn of 2 or less, such as 1 to 2.0 as determined by GPC-PS and having a Mn of 20,000 to 500,000 g / mol. 4-5 monomer.

[0252] In some embodiments, the functionalized polymer may have a number average molecular weight (Mn) of 20,000 (such as 25,000, such as 30,000, such as 35,000, such as 40,000) g / mol or higher as determined by GPC-PS.

[0253] In some embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of 50,000 (such as 40,000, such as 35,000) g / mol or lower as determined by GPC-PS. In some embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of 1000 to 50,000 g / mol, such as 5000 to 40,000 g / mol as determined by GPC-PS.

[0254] In some embodiments, the functionalized polymer may have a z-average molecular weight (Mz) (GPC-PS) of 5000 to 150,000 g / mol, such as 10,000 to 150,000 g / mol, such as 15,000 to 70,000 g / mol, such as 20,000 to 150,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol, or 40,000 to 60,000 g / mol.

[0255] In some embodiments, the functionalized polymer may have a gel content of less than about 5 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt% or 0 wt%, where the gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as the extractant. The percentages of soluble and insoluble (gel) materials in the polymer composition are determined as described herein.

[0256] In some embodiments, the functionalized polymer may have a functionality distribution (Fd) value of 3.5 or lower (such as 3.4 or lower, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS). The functionality distribution (Fd) value is determined as described in the Examples section below, and the average functionality of 1.4 to 20 FG grafts / polymer chain, such as 1.4 to 15 FG grafts / polymer chain, such as 3 to 12.5 FG grafts / polymer chain, such as 4 to 10 FG grafts / polymer chain as determined by GPC-PS.

[0257] The present disclosure relates to amide, imide and / or ester functionalized C-containing4-5 Hydrogenated / saturated polymers of olefins (consisting essentially of C 4-5 olefins or consisting of C 4-5 olefins), having an Mw / Mn of less than 2, a functionality distribution (Fd) value of 3.5 or lower (such as 3.4 or lower, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, determined by GPC-PS), and wherein if the polymer before functionalization is a C4 olefin polymer, such as polyisobutylene, polybutadiene or a copolymer thereof (preferably polyisobutylene or a copolymer of isobutylene and butadiene), the C4 olefin polymer has an Mn (GPC-PS) of 10,000 g / mol or higher, and if the polymer before functionalization is a C4 / C5 copolymer of isoprene and butadiene, the Mn of the copolymer is greater than 25,000 Mn (GPC-PS).

[0258] The present disclosure also relates to amide, imide and / or ester functionalized hydrogenated / saturated polymers comprising 90 mol% or more of isoprene repeat units, having an Mw / Mn of less than 2, a functionality distribution (Fd) value of 3.5 or lower (such as 3.4 or lower, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, determined by GPC-PS), and wherein the polymer before functionalization has an Mn (GPC-PS) of 30,000 g / mol or higher.

[0259] The present disclosure also relates to amide, imide and / or ester functionalized hydrogenated / saturated isoprene homopolymers, having an Mw / Mn of less than 2, a functionality distribution (Fd) value of 3.5 or lower (such as 3.4 or lower, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, determined by GPC-PS), and wherein the polymer before functionalization has an Mn (determined by GPC-PS) of 30,000 g / mol or higher.

[0260] The lubricating composition according to the present disclosure may further comprise one or more additives, such as detergents, friction modifiers, antioxidants, pour point depressants, defoamers, viscosity improvers, dispersants, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibilizers, additive diluent base oils, etc. Specific examples of such additives are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, Volume 14, pages 477 - 526, and several will be discussed in more detail below. C. Detergents

[0261] The lubricating composition may comprise one or more metal detergents (such as blends of metal detergents), also known as "detergent additives". Metal detergents generally act both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head and a long hydrophobic tail, the polar head comprising a metal salt of an acidic organic compound. The salt may contain stoichiometric amounts of metal, in which case they are generally described as normal or neutral salts and generally have a total base number ("TBN", measured by ASTM D2896) of up to 150 mg KOH / g, such as 0 to 80 (or 5 - 30) mg KOH / g. Large amounts of metal base can be incorporated by reacting an excess metal compound (such as an oxide or hydroxide) with an acidic gas (such as carbon dioxide). Such detergents, sometimes referred to as overbased, can have a TBN of 100 mg KOH / g or higher (such as 200 mg KOH / g or higher) and generally have a TBN of 250 mg KOH / g or higher, such as 300 mg KOH / g or higher, such as 200 to 800 mg KOH / g, 225 to 700 mg KOH / g, 250 to 650 mg KOH / g, or 300 to 600 mg KOH / g, such as 150 to 650 mg KOH / g.

[0262] Suitable detergents include metal, especially alkali metals (Group 1 metals such as Li, Na, K, Rb) or alkaline earth metals (Group 2 metals such as Be, Mg, Ca, Sr, Ba), especially sodium, potassium, lithium, calcium and magnesium, such as oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates and other oil-soluble carboxylates of Ca and / or Mg. In addition, the detergent may comprise a hybrid detergent containing any combination of sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates and naphthenates containing sodium, potassium, lithium, calcium or magnesium or other oil-soluble carboxylates of Group 1 and / or 2 metals.

[0263] Preferably, the detergent additive useful in the present disclosure comprises a calcium and / or magnesium metal salt. The detergent can be a calcium and / or magnesium carboxylate (such as a salicylate), sulfonate or phenate detergent. More preferably, the detergent additive is selected from magnesium salicylate, calcium salicylate, magnesium sulfonate, calcium sulfonate, magnesium phenate, calcium phenate and hybrid detergents and / or combinations thereof comprising two, three, four or more of these detergents.

[0264] The metal-containing detergent may also include "hybrid" detergents formed with mixed surfactant systems including phenate and / or sulfonate components, such as phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, sulfonate / phenate / salicylate, as described, for example, in U.S. Patent Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. When using, for example, a hybrid sulfonate / phenate detergent, the hybrid detergent is considered equivalent to the amount of separate phenate and sulfonate detergents introducing similar amounts of phenate and sulfonate soaps, respectively.

[0265] The overbased metal-containing detergent can be a sodium, calcium, magnesium salt or a mixture thereof of phenate, sulfur-containing phenate, sulfonate, salixarates and salicylate. The overbased phenates and salicylates typically have a total base number of 180 to 650 mg KOH / g, such as 200 to 450 TBN mg KOH / g. The overbased sulfonates typically have a total base number of 250 to 600 mg KOH / g, or 300 to 500 mg KOH / g. In some embodiments, the sulfonate detergent can be mainly a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as described in paragraphs

[0026] to

[0037] of U.S. Patent Application Publication No. 2005 / 065045 (granted as U.S. Patent No. 7,407,919). The overbased detergent can be present in an amount of 0 wt% to 15 wt%, or 0.1 wt% to 10 wt%, or 0.2 wt% to 8 wt%, or 0.2 wt% to 3 wt% based on the lubricating composition. For example, in a heavy-duty diesel engine, the detergent can be present in an amount of 2 wt% to 3 wt% of the lubricating composition. For a passenger car engine, the detergent can be present in an amount of 0.2 wt% to 1 wt% of the lubricating composition.

[0266] The detergent additive can comprise one or more magnesium sulfonate detergents. The magnesium detergent can be a neutral salt or an overbased salt. Suitably, the magnesium detergent is an overbased magnesium sulfonate having a TBN of 80 to 650 mg KOH / g (ASTM D2896), such as 200 to 500 mg KOH / g, such as 240 to 450 mg KOH / g.

[0267] Alternatively, the detergent additive is magnesium salicylate. Suitably, the magnesium detergent is a magnesium salicylate having a TBN of 30 to 650 mg KOH / g (ASTM D2896), such as 50 to 500 mg KOH / g, such as 200 to 500 mg KOH / g, such as 240 to 450 mg KOH / g, or 150 mg KOH / g or less, such as 100 mg KOH / g or less.

[0268] Alternatively, the detergent additive is a combination of magnesium salicylate and magnesium sulfonate.

[0269] The magnesium detergent provides 200 - 4000 ppm of magnesium atoms, suitably 200 - 2000 ppm, 300 to 1500 or 450 - 1200 ppm of magnesium atoms (ASTM D5185) to its lubricating composition.

[0270] The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents.

[0271] A combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents provides to its lubricating composition: 1) 200 - 4000 ppm of magnesium atoms, suitably 200 - 2000 ppm, 300 to 1500 ppm or 450 - 1200 ppm of magnesium atoms (ASTM D5185), and 2) at least 500 ppm, preferably at least 750 ppm, more preferably at least 900 ppm of atomic calcium, such as 500 - 4000 ppm, preferably 750 - 3000 ppm, more preferably 900 - 2000 ppm of atomic calcium (ASTM D5185).

[0272] The detergent may comprise one or more calcium detergents, such as calcium carboxylates (e.g., salicylates), sulfonates or phenates detergents.

[0273] Suitably, the calcium detergent has a TBN of 30 to 700 mgKOH / g (ASTM D2896), such as 50 to 650 mgKOH / g, such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g, or 150 mgKOH / g or lower, such as 100 mgKOH / g or lower, or 200 mgKOH / g or higher, or 300 mgKOH / g or higher, or 350 mgKOH / g or higher.

[0274] Suitably, the calcium detergent is calcium salicylate, calcium sulfonate or calcium phenate having a TBN of 30 to 700 mgKOH / g, 30 to 650 mgKOH / g (ASTM D2896), such as 50 to 650 mgKOH / g, such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g, or 150 mgKOH / g or lower, such as 100 mgKOH / g or lower, or 200 mgKOH / g or higher, or 300 mgKOH / g or higher, or 350 mgKOH / g or higher.

[0275] Calcium detergents are typically present in an amount sufficient to provide at least 500 ppm, preferably at least 750 ppm, more preferably at least 900 ppm atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide no greater than 4000 ppm, preferably no greater than 3000 ppm, more preferably no greater than 2000 ppm atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide 500 - 4000 ppm, preferably 750 - 3000 ppm, more preferably 900 - 2000 ppm atomic calcium to the lubricating oil composition (ASTM D5185).

[0276] Suitably, the total atomic weight of the metals of the detergents in the lubricating compositions from all aspects of the present disclosure is no greater than 5000 ppm, preferably no greater than 4000 ppm, more preferably no greater than 2000 ppm (ASTM D5185). The total atomic metal of the detergents in the lubricating oil compositions from all aspects of the present disclosure is suitably at least 500 ppm, preferably at least 800 ppm, more preferably at least 1000 ppm (ASTM D5185). The total atomic metal of the detergents in the lubricating oil compositions from all aspects of the present disclosure is suitably 500 to 5000 ppm, preferably 500 to 3000 ppm, more preferably 500 to 2000 ppm (ASTM D5185).

[0277] Sulfonate detergents can be prepared from sulfonic acids, which are typically obtained by sulfonation of alkyl-substituted aromatics such as those obtained by fractionation of petroleum or by alkylation of aromatics. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene. Alkylation can be carried out with an alkylating agent having from about 3 to more than 70 carbon atoms in the presence of a catalyst. Alkaryl sulfonates typically contain from about 9 to about 80 or more carbon atoms per alkyl-substituted aromatic structural moiety, preferably from about 16 to about 60 carbon atoms. The oil-soluble sulfonate or alkaryl sulfonic acid can be neutralized with metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and ethers. The amount of the metal compound is selected considering the desired TBN of the final product, but is typically about 100 to 220 mass% (preferably at least 125 mass%) of the stoichiometric requirement.

[0278] Metal salts of phenols and thiophenols are prepared by reaction with suitable metal compounds such as oxides or hydroxides and can be obtained as neutral or overbased products by methods well known in the art. Thiophenols can be prepared by reacting phenols with sulfur or sulfur-containing compounds such as hydrogen sulfide, sulfur monohalide or sulfur dihalide to form products which are usually mixtures of compounds in which two or more phenols are bridged by sulfur-containing bridges.

[0279] Carboxylate detergents such as salicylates can be prepared by reacting aromatic carboxylic acids such as C 5-100 -, C 9-30 -, C 14-24 alkyl-substituted hydroxybenzoic acids with suitable metal compounds such as oxides or hydroxides and can be obtained as neutral or overbased products by methods well known in the art. The aromatic structural part of the aromatic carboxylic acid may contain heteroatoms such as nitrogen and oxygen. Preferably, the structural part contains only carbon atoms; more preferably, the structural part contains six or more carbon atoms; for example, benzene is a preferred structural part. The aromatic carboxylic acid may contain one or more aromatic structural parts fused or linked via an alkylene bridge such as one or more benzene rings.

[0280] Preferred substituents in oil-soluble salicylic acids are alkyl substituents. In alkyl-substituted salicylic acids, the alkyl advantageously contains from 5 to 100, preferably from 9 to 30, especially from 14 to 20 carbon atoms. If there is more than one alkyl, the average number of carbon atoms in all alkyls is preferably at least 9 to ensure sufficient oil solubility.

[0281] In some embodiments, the ratio of detergent atomic metal to atomic molybdenum in the lubricating oil composition can be less than 3:1, such as less than 2:1.

[0282] Furthermore, since metal organic and inorganic base salts used as detergents can contribute to the sulfate ash content of the lubricating oil composition, in embodiments of the present disclosure, the amount of such additives is minimized. To maintain a low sulfur content, salicylate detergents can be used and the lubricating compositions herein can comprise one or more salicylate detergents (the detergents are preferably used in an amount of from 0.05 to 20.0% by weight, more preferably from 1.0 to 10.0% by weight, and most preferably from 2.0 to 5.0% by weight based on the total weight of the lubricating composition).

[0283] As determined by ASTM D874, based on the total weight of the lubricating composition, the total sulfate ash content of the lubricating compositions herein is generally not greater than 2.0% by weight, or at a level not greater than 1.0% by weight, or at a level not greater than 0.8% by weight.

[0284] In addition, it is useful that each detergent independently has a TBN value (total base number) measured by ISO 3771 in the range of 10 to 700 mg KOH / g, 10 to 500 mg KOH / g, or in the range of 100 to 650, or in the range of 10 to 500 mg KOH / g, or in the range of 30 to 350 mg KOH / g, or in the range of 50 to 300 mg KOH / g.

[0285] Sulfonate detergents (such as Ca and / or Mg sulfonate detergents) may be present in an amount that provides 0.1 wt% to 1.5 wt%, or 0.15 to 1.2 wt%, or 0.2 wt% to 0.9 wt% sulfonate soap to the lubricant composition.

[0286] Salicylate detergents (such as Ca and / or Mg salicylate detergents) are present in an amount that provides 0.3 wt% to 1.4 wt%, or 0.35 wt% to 1.2 wt%, or 0.4 wt% to 1.0 wt% salicylate soap to the lubricant composition.

[0287] Sulfonate soap may be present in an amount of 0.2 wt% to 0.8 wt% of the lubricant composition, and salicylate soap may be present in an amount of 0.3 wt% to 1.0 wt% of the lubricant composition.

[0288] All alkaline earth metal detergent soaps in total may be present in an amount of 0.6 wt% to 2.1 wt%, or 0.7 wt% to 1.4 wt% of the lubricant composition.

[0289] Typically, a lubricating composition formulated for a heavy-duty diesel engine contains from about 0.1 to about 10 mass%, or from about 0.5 to about 7.5 mass%, or from about 1 to about 6.5 mass% of detergents based on the lubricating composition.

[0290] Typically, a lubricating composition formulated for passenger-car engines contains from about 0.1 to about 10 mass%, or from about 0.5 to about 7.5 mass%, or from about 1 to about 6.5 mass% of detergents based on the lubricating composition.

[0291] Typically, a lubricating composition formulated for a driveline (such as a transmission) contains from about 0.1 to about 10 mass%, or from about 0.5 to about 7.5 mass%, or from about 2 to about 6.5 mass% of detergents based on the lubricating composition. D. Friction modifiers

[0292] A friction modifier is any material or fluid containing such a material that can change the coefficient of friction of a surface lubricated with any lubricant. If desired, friction modifiers, also known as friction reducers or lubricity agents or oiliness agents, and other such reagents that change the ability of a base oil, formulated lubricating composition, or functional fluid to condition the coefficient of friction of the lubricated surface can be effectively used in combination with the base oils or lubricating compositions of the present disclosure. Friction modifiers that reduce the coefficient of friction are particularly advantageously combined with the base oils and lubricating compositions of the present disclosure.

[0293] Exemplary friction modifiers can include, for example, organometallic compounds or materials or mixtures thereof. Exemplary organometallic friction modifiers useful in the lubricating oil formulations of the present disclosure include, for example, tungsten and / or molybdenum compounds such as molybdenum amines, molybdenum diamines, organotungstates, molybdenum dithiocarbamates, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, etc., and mixtures thereof. Examples of useful molybdenum-containing compounds can conveniently include molybdenum dithiocarbamate, trinuclear molybdenum compounds (such as those described in PCT Publication No. WO 98 / 26030), sulfides of molybdenum, and molybdenum dithiophosphate.

[0294] Other known friction modifiers contain oil-soluble organomolybdenum compounds. Such organomolybdenum friction modifiers also provide antioxidant and antiwear benefits to lubricating oil compositions. Examples of such oil-soluble organomolybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphites, xanthates, thioxanthates, sulfides, etc., and mixtures thereof. Particularly preferred are molybdenum dithiocarbamate, dialkyldithiophosphate molybdenum, alkylxanthate molybdenum, and alkylthioxanthate molybdenum.

[0295] In addition, the molybdenum compound can be an acidic molybdenum compound. These compounds react with basic nitrogen compounds as measured by the ASTM test D664 or D2896 titration procedure and are generally hexavalent. Include 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.

[0296] Molybdenum compounds useful in the compositions of the present disclosure include organomolybdenum compounds of the formulas Mo(R"OCS2)4 and Mo(R"SCS2)4, where R" is an organic group selected from alkyl, aryl, aralkyl, and alkoxyalkyl groups generally having from 1 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and most preferably an alkyl group having from 2 to 12 carbon atoms. Particularly preferred are the dialkyldithiocarbamates of molybdenum.

[0297] Another class of organomolybdenum compounds useful in the lubricating compositions of the present disclosure are trinuclear molybdenum compounds, particularly those of the formula Mo3S k L n Q z and mixtures thereof, where L is an independently selected ligand having an organic group with a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n ranges from 1 to 4, k ranges from 4 to 7, Q is selected from neutral electron-donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. There should be at least 21 carbon atoms in all ligands / organic groups, such as at least 25, at least 30, or at least 35 carbon atoms.

[0298] Lubricating oil compositions useful in all aspects of the present disclosure preferably contain at least 10 ppm, at least 30 ppm, at least 40 ppm, and more preferably at least 50 ppm of molybdenum. Suitably, lubricating oil compositions useful in all aspects of the present disclosure contain no more than 1000 ppm, no more than 750 ppm, or no more than 500 ppm of molybdenum. Lubricating oil compositions useful in all aspects of the present disclosure preferably contain 10 to 1000, such as 30 to 750, or 40 to 500 ppm of molybdenum (measured as molybdenum atoms).

[0299] For more information on available Mo-containing friction modifiers, see U.S. Patent No. 10,829,712 (column 8, line 58 to column 11, line 31).

[0300] Ashless friction modifiers can be present in the lubricating oil compositions of the present disclosure and are well-known and include esters formed by reacting carboxylic acids and acid anhydrides with alkanols and amine-based friction modifiers. Other available friction modifiers generally include polar end groups (such as carboxyl or hydroxyl groups) covalently bonded to lipophilic hydrocarbon chains. Esters of carboxylic acids and acid anhydrides with alkanols are described in U.S. Patent No. 4,702,850. Examples of other conventional organic friction modifiers are described by M. Belzer in "Journal of Tribology" (1992), volume 114, pages 675 - 682 and by M. Belzer and S. Jahanmir in "Lubrication Science" (1988), volume 1, pages 3 - 26. Generally, the total amount of organic ashless friction modifiers in the lubricants according to the present disclosure is not more than 5% by mass, preferably not more than 2% by mass, and more preferably not more than 0.5% by mass, based on the total mass of the lubricating oil composition.

[0301] Exemplary friction modifiers useful in the lubricating compositions described herein include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.

[0302] Exemplary alkoxylated fatty acid esters include, for example, polyoxyethylene stearates, fatty acid polyglycol esters, etc. These may include polyoxypropylene stearates, polyoxybutylene stearates, polyoxyethylene isostearates, polyoxypropylene isostearates, polyoxyethylene palmitates, etc.

[0303] Exemplary alkanolamides include, for example, diethyl alkanolamide laurate, diethyl alkanolamide palmitate, etc. These may include diethyl alkanolamide oleate, diethyl alkanolamide stearate, diethyl alkanolamide oleate, polyethoxylated alkylamides, polypropoxylated alkylamides, etc.

[0304] Exemplary polyol fatty acid esters include, for example, glycerol monooleate, saturated mono-, di- and triglycerides, glycerol monostearate, etc. These may include polyol esters, polyol esters containing hydroxyl groups, etc.

[0305] Exemplary borated glycerol fatty acid esters include, for example, borated glycerol monooleate, borated saturated mono-, di- and triglycerides, borated glycerol monostearate, etc. In addition to glycerol polyols, these may also include trimethylolpropane, pentaerythritol, sorbitan, etc. These esters may be polyol monocarboxylic acid esters, polyol dicarboxylic acid esters and sometimes, polyol tricarboxylic acid esters. Preferred may be glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monostearate, glycerol distearate and glycerol tristearate and the corresponding glycerol monopalmitate, glycerol dipalmitate and glycerol tripalmitate, as well as the respective isostearates, linoleates, etc. Ethoxylated, propoxylated and / or butoxylated fatty acid esters of polyols (especially using glycerol as the base polyol) may be used herein.

[0306] Exemplary fatty alcohol ethers include, for example, stearyl ethers, myristyl ethers, etc. Alcohols (including those having C3 to C 50 carbon numbers) may be ethoxylated, propoxylated or butoxylated to form the corresponding fatty alkyl ethers. The underlying alcohol portion may preferably be stearyl, myristyl, C 11 -C 13 hydrocarbons, oleyl, isostearyl, etc.

[0307] Useful concentrations of friction improvers can be from 0.01 wt% to 5 wt%, or from about 0.01 wt% to about 2.5 wt%, or from about 0.05 wt% to about 1.5 wt%, or from about 0.051 wt% to about 1 wt%. The concentration of the molybdenum-containing material is typically described as the Mo metal concentration. A favorable concentration of Mo can be from 25 ppm to 700 ppm or more, and the generally preferred range is 50 - 200 ppm. All types of friction improvers can be used alone or in combination with the materials of the present disclosure. Mixtures of two or more friction improvers or mixtures of friction improvers with alternative surface-active materials are generally also desirable. For example, a combination of a Mo-containing compound with a polyol fatty acid ester (such as glycerol monooleate) can be used for this purpose. E. Antioxidants

[0308] Antioxidants retard the oxidative degradation of base oils during use. Such degradation can lead to deposits on metal surfaces, the presence of sludges, an increase in viscosity in lubricants, etc. A wide variety of oxidation inhibitors can be used in lubricating oil compositions. See, for example, Lubricants and Related Products, Klamann, Wiley VCH, 1984; U.S. Patent Nos. 4,798,684 and 5,084,197.

[0309] Available antioxidants include hindered phenols. These phenolic antioxidants can be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols containing sterically hindered hydroxyl groups, and these include derivatives of dihydroxyaryl compounds where the hydroxyl groups are in the ortho or para positions to each other. Typical phenolic antioxidants include hindered phenols substituted with C 6+ alkyl groups and alkylene-coupled derivatives of these hindered phenols. Examples of phenolic materials of this type include 2-tert-butyl-4-heptylphenol; 2-tert-butyl-4-octylphenol; 2-tert-butyl-4-dodecylphenol; 2,6-di-tert-butyl-4-heptylphenol; 2,6-di-tert-butyl-4-dodecylphenol; 2-methyl-6-tert-butyl-4-heptylphenol; and 2-methyl-6-tert-butyl-4-dodecylphenol. Other available hindered mono-phenolic antioxidants can include, for example, hindered 2,6-di-alkyl-phenolic propionate derivatives. Bisphenolic antioxidants can also be advantageously used herein. Examples of ortho-coupled phenols include: 2,2'-bis(4-heptyl-6-tert-butyl-phenol); 2,2'-bis(4-octyl-6-tert-butyl-phenol); and 2,2'-bis(4-dodecyl-6-tert-butyl-phenol). Para-coupled bisphenols include, for example, 4,4'-bis(2,6-di-tert-butylphenol) and 4,4'-methylene-bis(2,6-di-tert-butylphenol).

[0310] An effective amount of one or more catalytic antioxidants can also be used. The catalytic antioxidants comprise an effective amount of a) one or more oil-soluble polymetallic organic compounds; and an effective amount of b) one or more substituted N,N'-diaryl-o-phenylenediamine compounds, or c) one or more hindered phenolic compounds; or a combination of b) and c). The catalytic antioxidants useful herein are more fully described in U.S. Patent No. 8,048,833.

[0311] Non-phenolic oxidation inhibitors that can be used include aromatic amine antioxidants, which can be used as such or in combination with phenolics. Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines, such as aromatic monoamines of the formula R8R9R 10 N, where R8 is an aliphatic, aromatic or substituted aromatic group, R9 is an aromatic or substituted aromatic group, and R 10 is H, alkyl, aryl or R 11 S(O)XR 12 where R 11 is alkylene, alkenylene or aralkylene, R 12 is alkyl or alkenyl, aryl or alkaryl, and x is 0, 1 or 2. The aliphatic group R8 can contain from 1 to about 20 carbon atoms, preferably from about 6 to 12 carbon atoms. The aliphatic group is usually a saturated aliphatic group. Preferably, both R8 and R9 are aromatic or substituted aromatic groups, and the aromatic group can be a polycyclic aromatic group, such as naphthyl. The aromatic groups R8 and R9 can be linked together with other groups such as S.

[0312] Typical aromatic amine antioxidants have an alkyl substituent containing at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl and decyl. Generally, the aliphatic group does not contain more than about 14 carbon atoms. General types of amine antioxidants that can be used in the present composition include diphenylamine, phenylnaphthylamine, phenothiazine, imidodibenzyls and diphenylbenzidine. Mixtures of two or more aromatic amines can also be used. Polymer amine antioxidants can also be used. Specific examples of aromatic amine antioxidants that can be used in the present disclosure include: p,p'-dioctyldiphenylamine; tert-octylphenyl-α-naphthylamine; phenyl-α-naphthylamine; and p-octylphenyl-α-naphthylamine.

[0313] Sulfur-containing antioxidants can also be used herein. In particular, one or more oil-soluble or oil-dispersible sulfur-containing antioxidants can be used as antioxidant additives. For example, sulfurized alkylphenols and their alkali metal or alkaline earth metal salts are also antioxidants that can be used herein. Suitably, the lubricating oil composition of the present disclosure can comprise the one or more sulfur-containing antioxidants in an amount that provides 0.02 to 0.2, preferably 0.02 to 0.15, more preferably 0.02 to 0.1, and even more preferably 0.04 to 0.1 mass % sulfur based on the total mass of the lubricating oil composition. Optionally, the oil-soluble or oil-dispersible sulfur-containing antioxidant is selected from sulfurized C4 to C 25 olefins, sulfurized aliphatic (C7 to C 29 ) hydrocarbon-based fatty acid esters, ashless sulfurized phenolic antioxidants, sulfur-containing organomolybdenum compounds, and combinations thereof. For further information on sulfurized materials that can be used as antioxidants herein, see U.S. Patent No. 10,731,101 (column 15, line 55 to column 22, line 12).

[0314] Antioxidants that can be used herein include hindered phenols and / or arylamines. These antioxidants can be used independently by type or in combination with each other.

[0315] Typical antioxidants include: Irganox TM L67, ETHANOX TM 4702, Lanxess Additin TM RC 7110; ETHANOX TM 4782J; Irganox TM 1135, Irganox TM 5057, sulfurized lard and palm oil fatty acid methyl esters.

[0316] The antioxidant additive can be used in an amount of about 0.01 to 10 (or 0.01 to 5, or 0.01 to 3) weight %, or about 0.03 to 5 weight %, or 0.05 to less than 3 weight % based on the weight of the lubricating composition.

[0317] The compositions according to the present disclosure can contain additives that have different listed functions and also have a secondary effect as antioxidants (e.g., phosphorus-containing antiwear agents such as ZDDP can also have an antioxidant effect). For determining the amount of antioxidant in the lubricating oil composition or concentrate herein, these additives are not counted as antioxidants. F. Pour Point Depressants

[0318] If desired, conventional pour point depressants (also known as lubricating oil flow improvers) can be added to the compositions of the present disclosure. These pour point depressants can be added to the lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid can flow or be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyacrylamides, condensation products of halogenated paraffins and aromatic compounds, carboxylic acid vinyl ester polymers, and terpolymers of dialkyl fumarates, fatty acid vinyl esters, and allyl vinyl ethers. U.S. Patent Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe available pour point depressants and / or their preparation. Such additives can be used in amounts of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%, based on the weight of the lubricating composition. G. Antifoaming Agents

[0319] Antifoaming agents can advantageously be added to the lubricant compositions described herein. These reagents prevent or delay the formation of stable foams. Silicones and / or organic polymers are typical antifoaming agents. For example, polysiloxanes, such as silicon oil or polydimethylsiloxane, provide antifoaming properties.

[0320] Antifoaming agents are commercially available and can be used in minor amounts, such as 5 wt% or less, 3 wt% or less, 1 wt% or less, 0.1 wt% or less, such as 5 wt% to 0.1 ppm, such as 3 wt% to 0.5 ppm, such as 1 wt% to 10 ppm.

[0321] For example, it is possible that the lubricating oil composition contains an antifoaming agent containing polyalkylsiloxane, such as polydialkylsiloxane, where the alkyl is C1-C 10 alkyl, such as polydimethylsiloxane (PDMS), also known as silicone oil. Alternatively, the siloxane is poly(R 3 ) siloxane, where R 3 is one or more identical or different linear, branched, or cyclic hydrocarbon groups, such as alkyl or aryl groups, which typically have 1 to 20 carbon atoms. It is possible that, for example, the lubricating oil composition contains a polymeric siloxane compound according to Formula 1 below, where R 1 and R 2 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, phenyl, naphthyl, alkyl-substituted phenyl, or its isomers (such as methyl, phenyl), and n is from 2 to 1000, such as 50 to 450, or such as 40 to 100.

[0322] Additionally or alternatively, it is possible that the lubricating oil composition comprises an organomodified siloxane (OMS), such as a siloxane modified with an organic group such as a polyether (e.g., an ethylene - propylene oxide copolymer), a long - chain hydrocarbon group (e.g., C 11 -C 100 alkyl) or an aryl group (e.g., C6 - C 14 aryl). It is possible that, for example, the lubricating oil composition comprises an organomodified siloxane compound according to formula 1, where n is from 2 to 2000, such as from 50 to 450 (or such as from 40 to 100), and where R 1 and R 2 are the same or different, and optionally where R 1 and R 2 are each independently an organic group, such as an organic group selected from polyethers (e.g., ethylene - propylene oxide copolymers), long - chain hydrocarbon groups (e.g., C 11 -C 100 alkyl) or aryl groups (e.g., C6 - C 14 aryl). Preferably, one of R 1 and R 2 is CH3. Formula 1

[0323] Based on the total weight of the lubricant composition, the siloxane according to formula 1 is incorporated to provide from about 0.1 to less than about 30 ppm Si, or from about 0.1 to about 25 ppm Si, or from about 0.1 to about 20 ppm Si, or from about 0.1 to about 15 ppm Si, or from about 0.1 to about 10 ppm Si. More preferably, it is in the range of about 3 - 10 ppm Si.

[0324] In some embodiments, the silicone defoamers useful herein are available from Dow Corning Corporation and Union Carbide Corporation, such as Dow Corning FS-1265 (1000 centistokes), Dow Corning DC-200, and Union Carbide UC-L45. The silicone defoamers useful herein include polydimethylsiloxane, phenyl-methyl polysiloxane, linear, cyclic, or branched siloxanes, silicone polymers and copolymers, and / or organo-silicone copolymers. Silicone polyether copolymer defoamers available from OSI Specialties, Inc. of Farmington Hills, Michigan may also be used in place of or in addition to. One such material is sold as SILWET-L-7220.

[0325] Acrylate polymer defoamers may also be used herein. Typical acrylate defoamers include the polyacrylate defoamer designated PC-1244 available from Monsanto Polymer Products Co. The preferred acrylate polymer defoamers useful herein are PX TM 3841 (i.e., an alkyl acrylate polymer), also known as Mobilad TM C402.

[0326] In some embodiments, a combination of a silicone defoamer and an acrylate defoamer may be used, such as at a weight ratio of silicone defoamer / acrylate defoamer of from about 5:1 to about 1:5, see for example U.S. Patent Application Publication No. 2021 / 0189283. H. Viscosity Improvers

[0327] Viscosity modifiers (also known as viscosity index improvers or viscosity improvers) may be included in the lubricating compositions described herein. Viscosity improvers provide high and low temperature operability to the lubricant. These additives provide shear stability at elevated temperatures and acceptable viscosities at low temperatures. Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters, and viscosity improver dispersants that can act both as viscosity improvers and dispersants. The typical molecular weights of these polymers are between about 10,000 and 1,500,000 g / mol, more typically between about 20,000 and 1,200,000 g / mol, and even more typically between about 50,000 and 1,000,000 g / mol.

[0328] Examples of suitable viscosity improvers are linear or star polymers and copolymers of methacrylates, butadienes, olefins or alkylated styrenes. Polyisobutene is a commonly used viscosity improver. Another suitable viscosity improver is polymethacrylate (e.g., copolymers of alkyl methacrylates of various chain lengths), some formulations of which also act as pour point depressants. Other suitable viscosity improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (e.g., copolymers of acrylates of various chain lengths). Specific examples include styrene-isoprene or styrene-butadiene based polymers with molecular weights from 50,000 to 200,000 g / mol.

[0329] Copolymers that can be used as viscosity improvers include those available under the trade name "PARATONE" TM [[ID=5"]](such as "PARATONE" TM 8921", "PARATONE" TM 68231" and "PARATONE" TM 8941") available from Chevron Oronite Company LLC; those available under the trade name "HiTEC" TM (such as HiTEC TM 5850B and HiTEC TM 5777) available from Afton Chemical Corporation; and those available under the trade name "Lubrizol" TM 7067C" available from The Lubrizol Corporation. Hydrogenated polyisoprene star polymers that can be used as viscosity improvers in this article include those available from Infineum International Limited, such as those available under the trade name "SV200" TM " and "SV600" TM ". Hydrogenated diene-styrene block copolymers that can be used as viscosity improvers in this article are available from Infineum International Limited, such as those available under the trade name "SV 50" TM ".

[0330] Polymers that can be used as viscosity improvers in this article include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, such as those available under the trade name "Viscoplex" TM "(e.g., Viscoplex TMThose obtained from Evonik Industries, or available under the trade name Asteric TM (e.g., Lubrizol TM 87708 and Lubrizol TM 87725) star polymers obtained from Lubrizol Corporation.

[0331] Vinyl aromatic-containing polymers that can be used as viscosity improvers herein can be derived from vinyl aromatic monomers such as styrenic monomers such as styrene. Exemplary vinyl aromatic-containing copolymers useful herein can be represented by the general formula: A - B, where A is a polymeric block mainly derived from vinyl aromatic monomers (such as styrene), and B is a polymeric block mainly derived from conjugated diene monomers (such as isoprene).

[0332] The vinyl aromatic-containing polymers that can be used as viscosity improvers can have a kinematic viscosity at 100 °C of 20 cSt or lower, such as 15 cSt or lower, such as 12 cSt or lower, but can be diluted (such as in Group I, II, and / or III base oils) to a higher kinematic viscosity at 100 °C, such as up to 40 cSt or higher, such as 100 cSt or higher, such as 1000 cSt or higher, such as 1000 to 2000 cSt.

[0333] Typically, the viscosity improver can be used in an amount of about 0.01 to about 10 wt%, such as about 0.1 to about 7 wt%, such as 0.1 to about 4 wt%, such as about 0.2 to about 2 wt%, such as about 0.2 to about 1 wt%, and such as about 0.2 to about 0.5 wt% based on the total weight of the formulated lubricant composition.

[0334] The viscosity improver is typically added as a concentrate in a large amount of diluent oil. The "as delivered" viscosity improver typically contains 20 wt% to 75 wt% of active polymer for polymethacrylate or polyacrylate polymers, or 8 wt% to 20 wt% of active polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers in the "as delivered" polymer concentrate. I. Dispersant

[0335] During engine operation, oil-insoluble oxidation by-products are produced. The dispersant helps keep these by-products in solution, thereby reducing their deposition on metal surfaces. The dispersants used in the formulations of the lubricating compositions herein can be ashless or ash-forming in nature. The dispersant is preferably ashless. So-called ashless dispersants are organic materials that form substantially no ash upon combustion. For example, metal-free dispersants or borated metal-free dispersants are considered ashless. In contrast, metal-containing detergents tend to form ash upon combustion.

[0336] The dispersants useful herein generally contain polar groups attached to relatively high molecular weight hydrocarbon chains. The polar groups generally contain at least one element of nitrogen, oxygen or phosphorus. Typical hydrocarbon chains contain from 40 to 500, such as 50 to 400 carbon atoms. (Poly)alkenylsuccinic Derivative Dispersants of (Poly)alkenylsuccinic derivatives

[0337] A particularly useful class of dispersants includes (poly)alkenyl succinic derivatives typically made by the reaction of a succinic compound (usually a hydrocarbyl-substituted succinic anhydride) substituted by a long-chain hydrocarbyl group with a polyhydroxy or polyamino compound. The long-chain hydrocarbyl group that constitutes the lipophilic part of the molecule (which provides oil solubility) is usually a polyisobutylene group (the long-chain hydrocarbyl group, such as a polyisobutylene group, typically has a Mn of from 400 to 3000 g / mol, such as 450 to 2500 g / mol). Many examples of this type of dispersant are known in the art and in the literature. Exemplary U.S. patents describing such dispersants include U.S. Patent Nos. 3,172,892; 3,214,5707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersants are described in U.S. Patent Nos. 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. Further descriptions of the dispersants useful herein can be found, for example, in European Patent Applications Nos. 0 471 071 and 0 451 380, which are hereby incorporated by reference.

[0338] Hydrocarbyl-substituted succinic acids and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimides, succinic esters or succinic ester amides prepared by the reaction of a hydrocarbyl-substituted succinic acid or anhydride compound (which typically has at least 25 carbon atoms, such as 28 to 400 carbon atoms in the hydrocarbyl substituent) with at least 1 equivalent of a polyhydroxy or polyamino compound, such as an alkylene amine, are particularly useful herein. The hydrocarbyl-substituted succinic acids and hydrocarbyl-substituted succinic anhydride derivatives may have a number average molecular weight of at least 400 g / mol, such as at least 900 g / mol, such as at least 1500 g / mol, such as 400 to 4000 g / mol, such as 800 to 3000, such as 2000 to 2800 g / mol, such as about 2100 to 2500 g / mol, and such as about 2200 to about 2400 g / mol.

[0339] The succinimides particularly useful herein are formed by a condensation reaction between 1) a hydrocarbyl-substituted succinic anhydride, such as polyisobutylene succinic anhydride (PIBSA); and 2) a polyamine (PAM). Examples of suitable polyamines include: polyhydrocarbyl polyamines, polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof. Examples of polyamines include tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8 or 9 nitrogen atoms per molecule. Mixtures in which the average number of nitrogen atoms per polyamine molecule is greater than 7 are generally referred to as heavy polyamines or H-PAMs and are available under trade names such as HPA TM and HPA-X TM from Dow Chemical, under the name E-100 TM from Huntsman Chemical, etc. Examples of hydroxy-substituted polyamines include N-hydroxyalkyl-alkylene polyamines, such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine, and / or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. Patent No. 4,873,009. Examples of polyoxyalkylene polyamines include polyoxyethylene and / or polyoxypropylene diamines and triamines (and their co-oligomers) having an average Mn of about 200 to about 5000 g / mol. Products of this type are available under the trade name Jeffamine TM and can be obtained. Representative examples of available succinimides are shown in U.S. Patent Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; 3,652,616; 3,948,800; and 6,821,307; and Canadian Patent No. 1,094,044.

[0340] The dispersant may comprise one or more optionally borated higher molecular weight (Mn 1600 g / mol or higher, such as 1800 to 3000 g / mol) succinimides and one or more optionally borated lower molecular weight (Mn less than 1600 g / mol) succinimides, wherein the higher molecular weight may be 1600 to 3000 g / mol, such as 1700 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 1850 to 2300 g / mol; the lower molecular weight may be 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol, such as 900 to 1150 g / mol, such as 900 to 1000 g / mol. The higher molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 0.5 to 10 wt%, or 0.8 to 6 wt%, or 1.0 to 5 wt%, or 1.5 to 5 wt%, or 1.5 to 4.0 wt%; the lower molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 1 to 5 wt%, or 1.5 to 4.8 wt%, or 1.8 to 4.6 wt%, or 1.9 to 4.6 wt%, or 2 wt% or higher, such as 2 to 5 wt%. The lower molecular weight succinimide may differ from the higher molecular weight succinimide by 500 g / mol or higher, such as by 750 g / mol or higher, such as by 1000 g / mol or higher, such as by 1200 g / mol or higher, such as by 500 to 3000 g / mol, such as by 750 to 2000 g / mol, such as by 1000 to 1500 g / mol.

[0341] The succinate esters useful as dispersants include those formed by the condensation reaction between a hydrocarbyl-substituted succinic anhydride and an alcohol or polyol. For example, the condensation product of a hydrocarbyl-substituted succinic anhydride and pentaerythritol is a useful dispersant.

[0342] The succinate amides useful herein are formed by the condensation reaction between a hydrocarbyl-substituted succinic anhydride and an alkanolamine. Suitable alkanolamines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines, and polyalkenylpolyamines, such as polyethylenepolyamines and / or propoxylated hexamethylenediamine. Representative examples are shown in U.S. Patent No. 4,426,305.

[0343] Hydrocarbyl-substituted succinic anhydride (such as PIBSA) esters of hydrocarbyl-bridged aryloxy alcohols can also be used as dispersants herein. For information on such dispersants, see U.S. Patent No. 7,485,603, particularly columns 2, line 65 to column 6, line 22 and column 23, line 40 to column 26, line 46. In particular, the PIBSA ester of methylene-bridged naphthoxy ethanol (i.e., 2-hydroxyethyl-1-naphthol ether (or hydroxy-terminated naphthol ethylene oxide oligomer ether)) can be used herein.

[0344] The molecular weight of the hydrocarbyl-substituted succinic anhydride used in the preceding paragraphs is generally from 350 to 4000 g / mol, such as from 400 to 3000 g / mol, such as from 450 to 2800 g / mol, such as from 800 to 2500 g / mol. The above (poly)alkenyl succinic derivatives can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.

[0345] The dispersant can be present in the lubricant in an amount of 0.1% to 20% by mass of the composition, such as 0.2 to 15% by mass, such as 0.25 to 10% by mass, such as 0.3 to 5% by mass, such as 1.0% to 3.0% by mass of the lubricating oil composition.

[0346] The above (poly)alkenyl succinic derivatives can also be post-reacted with boron compounds such as boric acid, borate esters or highly boronated dispersants to form boronated dispersants which generally have from about 0.1 to about 5 moles of boron / mole of dispersant reaction product.

[0347] Dispersants useful herein include boronated succinimides, including those derivatives from mono-succinimides, bis-succinimides and / or mixtures of mono-succinimides and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group having a Mn of from about 300 to about 5000 g / mol, or from about 500 to about 3000 g / mol, or from about 1000 to about 2000 g / mol, such as polyisobutene, or mixtures of such hydrocarbylene groups, usually having high terminal vinyl.

[0348] The boron-containing dispersant can be present in the lubricating composition in an amount of 0.01% to 20% by weight, or 0.1% to 15% by weight, or 0.1% to 10% by weight, or 0.5% to 8% by weight, or 1.0% to 6.5% by weight, or 0.5% to 2.2% by weight.

[0349] The boron-containing dispersant can be present in an amount providing 15 ppm to 2000 ppm, or 25 ppm to 1000 ppm, or 40 ppm to 600 ppm, or 80 ppm to 350 ppm boron to the composition.

[0350] The borated dispersant can be used in combination with a non-borated dispersant and can be the same or different compound as the non-borated dispersant. In one embodiment, the lubricating composition can include one or more boron-containing dispersants and one or more non-borated dispersants, wherein the total amount of the dispersants can be 0.01 wt% to 20 wt%, or 0.1 wt% to 15 wt%, or 0.1 wt% to 10 wt%, or 0.5 wt% to 8 wt%, or 1.0 wt% to 6.5 wt%, or 0.5 wt% to 2.2 wt% of the lubricating composition, and wherein the ratio of the borated dispersant to the non-borated dispersant can be 1:10 to 10:1 (weight:weight) or 1:5 to 3:1 or 1:3 to 2:1.

[0351] The dispersant can include one or more borated or un-borated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM").

[0352] The dispersant can include one or more PIBSA-PAMs, wherein the PIB is derived from polyisobutene having a Mn of 600 to 5000, such as 700 to 4000, such as 800 to 3000, such as 900 to 2500 g / mol, and the polyamine is derived from a hydrocarbyl-substituted polyamine, such as tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule. The dispersant can be borated, typically at a level of up to 4 mass%, such as 1 to 3 mass%. The dispersant can include one or more borated PIBSA-PAMs and one or more non-borated PIBSA-PAMs. The dispersant can include one or more borated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more non-borated PIBSA-PAMs derived from PIB having a Mn greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol). The dispersant can include one or more non-borated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more borated PIBSA-PAMs derived from PIB having a Mn greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol).

[0353] The dispersant may comprise PIBSA derived from PIB having a Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol) and one or more boronated or non-boronated PIBSA-PAMs derived from PIB having a Mn of 700 to 5000 g / mol.

[0354] The dispersant may comprise PIBSA derived from PIB having a Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol), one or more boronated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol), and one or more non-boronated PIBSA-PAMs derived from PIB having a Mn greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol). The dispersant may comprise PIBSA derived from PIB having a Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol), one or more non-boronated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol), and one or more boronated PIBSA-PAMs derived from PIB having a Mn greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol).

[0355] The dispersant may comprise one or more boronated or non-boronated PIBSA-PAMs and one or more PIBSA esters of a hydrocarbyl-bridged aryloxy alcohol.

[0356] The dispersant may comprise one or more boronated PIBSA-PAMs and one or more non-boronated PIBSA-PAMs.

[0357] The dispersant may comprise one or more optionally borated higher molecular weight (Mn 1600 g / mol or higher, such as 1800 to 3000 g / mol) PIBSA-PAMs and one or more optionally borated lower molecular weight (Mn less than 1600 g / mol) PIBSA-PAMs, wherein the higher molecular weight may be 1600 to 3000 g / mol, such as 1700 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 1850 to 2300 g / mol; the lower molecular weight may be 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol, such as 900 to 1150 g / mol, such as 900 to 1000 g / mol. The higher molecular weight PIBSA-PAM dispersant may be present in the lubricating composition in an amount of 0.5 to 10 wt%, or 0.8 to 6 wt%, or 1.0 to 5 wt%, or 1.5 to 5 wt% or 1.5 to 4.0 wt%; the lower molecular weight PIBSA-PAM dispersant may be present in the lubricating composition in an amount of 1 to 5 wt%, or 1.5 to 4.8 wt%, or 1.8 to 4.6 wt%, or 1.9 to 4.6 wt%, or 2 wt% or higher, such as 2 to 5 wt%. Mannich Base Dispersants

[0358] The Mannich base dispersants useful herein are generally made by the reaction of an amine component, a hydroxyaromatic compound (substituted or unsubstituted, such as alkyl-substituted) (such as an alkylphenol), and an aldehyde (such as formaldehyde). See U.S. Patent Nos. 4,767,551 and 10,899,986. Processing aids and catalysts, such as oleic acid and sulfonic acid, may also be part of the reaction mixture. Representative examples are shown in U.S. Patent Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; 3,803,039; 4,231,759; 9,938,479; 7,491,248; and 10,899,986 and PCT Publication No. WO 01 / 42399. (Poly)methacrylate or (Poly)acrylate Derivative Dispersants

[0359] Polyacrylate or polymethacrylate derivatives are another class of dispersants useful herein. These dispersants are generally prepared by reacting a nitrogen-containing monomer with a methacrylate or acrylate containing 5-25 carbon atoms in the ester group. Representative examples are shown in U.S. Patent Nos. 2,100,993 and 6,323,164. Polyacrylate and polymethacrylate dispersants are generally of lower molecular weight.

[0360] The lubricating compositions of the present disclosure generally contain from 0.1% to 20% by mass, such as from 0.2% to 15% by mass, such as from 0.25% to 10% by mass, such as from 0.3% to 5% by mass, such as from 2.0% to 4.0% by mass of the dispersant of the composition. Alternatively, the dispersant may be present at from 0.1% to 5% by weight, or from 0.01% to 4% by weight of the lubricating composition.

[0361] For further information on the dispersants available herein, see U.S. Patent No. 10,829,712, column 13, line 36 to column 16, line 67, and U.S. Patent No. 7,485,603, column 2, line 65 to column 6, line 22, column 8, line 25 to column 14, line 53, and column 23, line 40 to column 26, line 46.

[0362] The compositions according to the present disclosure may contain additives having different recited functions and also having a secondary effect as a dispersant (e.g., the above-mentioned component B functionalized polymers may also have a dispersant effect). For determining the amount of the dispersant in the lubricating oil composition or concentrate herein, these additives are not counted as dispersants. J. Corrosion inhibitor / Rust inhibitor

[0363] Corrosion inhibitors can be used to mitigate the corrosion of metals and are generally also referred to as metal deactivators or metal passivators. Some corrosion inhibitors can also be characterized as antioxidants.

[0364] Suitable corrosion inhibitors can include nitrogen- and / or sulfur-containing heterocyclic compounds such as triazoles (e.g., benzotriazole), substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and derivatives of any one or more thereof. A specific corrosion inhibitor is benzotriazole represented by the following structure: wherein R 8 is absent (hydrogen) or may be a linear or branched, saturated or unsaturated C1 to C 20A hydrocarbyl or substituted hydrocarbyl group. It may contain a ring structure that is alkyl or aryl in nature and / or contain heteroatoms such as N, O, or S. Examples of suitable compounds may include benzotriazole, alkyl-substituted benzotriazoles (such as tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles, alkylaryl- or arylalkyl-substituted benzotriazoles, etc., and combinations thereof. For example, the triazole may comprise or be benzotriazole and / or alkylbenzotriazole, where the alkyl contains from 1 to about 20 carbon atoms, or from 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors may comprise or be benzotriazole, tolyltriazole, and / or optionally substituted benzotriazole, such as Irgamet available from BASF of Ludwigshafen, Germany. TM 39. Preferred corrosion inhibitors may comprise or be benzotriazole and / or tolyltriazole.

[0365] Additionally or alternatively, the corrosion inhibitor may include one or more substituted thiadiazoles of the following structures: wherein, R 15 and R 16 are independently hydrogen or a hydrocarbyl group, which group may be aliphatic or aromatic, including cyclic, cycloaliphatic, aralkyl, aryl, and alkaryl, and wherein each w is independently 1, 2, 3, 4, 5, or 6 (preferably 2, 3, or 4, such as 2). These substituted thiadiazoles are derived from 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecules. Many derivatives of DMTD have been described in the art, and any such compounds may be included in the fluids used in the present disclosure. For example, U.S. Patent Nos. 2,719,125; 2,719,126; and 3,087,937 describe the preparation of various 2,5-bis-(hydrocarbyldithio)-1,3,4-thiadiazoles.

[0366] Still additionally or alternatively, the corrosion inhibitor may include one or more other DMTD derivatives, such as carboxylic acid esters, wherein R 15 and R 16 may be connected to the sulfide sulfur atom via a carbonyl group. The preparation of these sulfur-containing ester DMTD derivatives is described, for example, in U.S. Patent No. 2,760,933. DMTD derivatives made by the condensation of DMTD with an α-haloaliphatic carboxylic acid having at least 10 carbon atoms are described, for example, in U.S. Patent No. 2,836,564. This method produces DMTD derivatives, wherein R 15 and R 16 are HOOC-CH(R 19 )-(R 19DMTD derivatives further prepared by amidation or esterification of these terminal carboxylic acid groups are also useful.

[0367] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in U.S. Pat. No. 3,663,561.

[0368] One class of DMTD derivatives may include a mixture of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-alkyldithio-1,3,4-thiadiazole. Such a mixture may be marketed under the trade name HiTEC TM 4313 is sold and available from Afton Chemical Company.

[0369] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in U.S. Pat. No. 3,663,561.

[0370] One class of DMTD derivatives may include a mixture of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-alkyldithio-1,3,4-thiadiazole. Such a mixture may be marketed under the trade name HiTEC TM 4313 is sold and available from Afton Chemical Company.

[0371] Additionally or alternatively, the corrosion inhibitor may include a compound having the structure B(OR 46 )3 trifunctional borate ester, wherein each R 46 Since the borate ester is generally ideally compatible with the non-aqueous medium of the composition, each R 46 In particular, it may comprise or be a hydrocarbyl C1-C8 moiety. For compositions in which the non-aqueous medium comprises or is a lubricating oil base stock, for example, better compatibility may generally be achieved when the hydrocarbyl moieties are each at least C4. Non-limiting examples of such corrosion inhibitors therefore include, but are not limited to, triethyl borate, tripropyl borate such as triisopropyl borate, tributyl borate such as tri-tert-butyl borate, tripentyl borate, trihexyl borate, trioctyl borate such as tri-(2-ethylhexyl) borate, monohexyl dibutyl borate, and the like, and combinations thereof.

[0372] When used, the corrosion inhibitor may comprise a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof.

[0373] When needed, the corrosion inhibitor can be used in any effective amount, but when used, it can generally be used in an amount of about 0.001% to 5.0% by weight, such as 0.005% to 3.0% by weight or 0.01% to 1.0% by weight, based on the weight of the composition. Alternatively, such an additive can be used in an amount of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight, based on the weight of the lubricating composition.

[0374] In some embodiments, the composition containing 3,4-oxypyridinone can be substantially free (e.g., 0, or less than 0.001% by weight, 0.0005% by weight or less, no intentional addition and / or absolutely free) of triazole, benzotriazole, substituted thiadiazole, imidazole, thiazole, tetrazole, hydroxyquinoline, oxazoline, imidazoline, thiophene, indole, indazole, quinoline, benzoxazine, dithiol, oxazole, oxatriazole, pyridine, piperazine, triazine, its derivatives, its combinations or all corrosion inhibitors.

[0375] The composition according to the present disclosure may contain additives having different listed functions and also having a secondary effect as a corrosion inhibitor (e.g., the above-mentioned component B functionalized polymer may also have a corrosion inhibitor effect). For determining the amount of corrosion inhibitor in the lubricating oil composition or concentrate herein, these additives are not counted as corrosion inhibitors. K. Antiwear agent

[0376] The lubricating oil composition of the present disclosure may contain one or more antiwear agents that can reduce friction and excessive wear. Any antiwear agent known to those of ordinary skill in the art can be used in the lubricating oil composition. Non-limiting examples of suitable antiwear agents include zinc dialkyl dithiophosphate, metal (e.g., Pb, Sb, Mo, etc.) salts of dithiophosphoric acid, metal (e.g., Zn, Pb, Sb, Mo, etc.) salts of dithiocarbamic acid, metal (e.g., Zn, Pb, Sb, etc.) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphate esters or thiophosphate esters, reaction products of dicyclopentadiene and dithiophosphoric acid, and combinations thereof. Based on the total weight of the lubricating oil composition, the amount of the antiwear agent can be about 0.01% to about 5% by weight, about 0.05% to about 3% by weight, or about 0.1% to about 1% by weight.

[0377] In some embodiments, the antiwear agent is or comprises a metal salt of a dialkyldithiophosphoric acid, such as a zinc dialkyldithiophosphate compound. The metal of the metal salt of the dialkyldithiophosphoric acid can be an alkali metal or an alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the metal salt of the dialkyldithiophosphoric acid has from about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

[0378] Available antiwear agents also include substituted or unsubstituted thiophosphoric acids, the salts of which include zinc-containing compounds, such as zinc dithiophosphate compounds selected from dialkyl-, diaryl-, and / or alkylaryl-dithiophosphates.

[0379] Metal alkyl thiophosphates, more particularly zinc dialkyldithiophosphates in which the metal component is zinc, or zinc dialkyldithiophosphate (ZDDP) can be useful components of the lubricating compositions of the present disclosure. ZDDP can be derived from primary alcohols, secondary alcohols, or mixtures thereof. ZDDP compounds generally have the formula Zn[SP(S)(OR1)(OR2)]2, where R1 and R2 are C1-C 18 alkyl groups, preferably C2-C 12 alkyl groups. These alkyl groups can be straight chain or branched. The alcohols used in ZDDP can be 2-propanol, butanol, sec-butanol, pentanol, hexanol, such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, alkylated phenols, etc. Mixtures of secondary alcohols or mixtures of primary and secondary alcohols can be used. Alkyl aryls can also be used. Available zinc dithiophosphates include secondary zinc dithiophosphates, such as those available from The Lubrizol Corporation under the trade names "LZ677A", "LZ 1095", and "LZ 1371", from Chevron Oronite under the trade name "OLOA 262", and from Afton Chemical under the trade name "HITEC" TM 7169.

[0380] In some embodiments, the zinc compound can be a zinc dithiocarbamate complex, such as zinc dithiocarbamate shown by the following formula: where each R IIndependently, it is a linear, cyclic or branched, saturated or unsaturated aliphatic hydrocarbon structural moiety having from 1 to about 10 carbon atoms, n is 0, 1 or 2, L is a ligand that saturates the zinc coordination layer, and x is 0, 1, 2, 3 or 4. In certain embodiments, the ligand L is selected from water, hydroxide, ammonia, amino, amido, alkylthiolate, halide, and combinations thereof.

[0381] Antiwear additives, such as ZDDP and / or zinc carbamate, are typically used in an amount of from about 0.4 wt% to about 1.2 wt%, preferably from about 0.5 wt% to about 1.0 wt%, more preferably from about 0.6 wt% to about 0.8 wt%, based on the total weight of the lubricating composition, although more or less may typically be used advantageously. Preferably, the antiwear additive is ZDDP, preferably secondary ZDDP, and is present in an amount of about 0.6 to 1.0 wt% of the total weight of the lubricating composition.

[0382] Antiwear additives useful herein also include boron-containing compounds such as borates, boronated fatty amines, boronated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates, and boronated overbased metal salts.

[0383] The compositions according to the present disclosure may contain additives having different recited functions and also having a secondary effect as an antiwear agent (e.g., the component B functionalized polymers described above may also have an antiwear effect). For determining the amount of antiwear agent in the lubricating oil compositions or concentrates herein, these additives are not counted as antiwear agents. L. Demulsifiers

[0384] Demulsifiers useful herein include those described in U.S. Patent No. 10,829,712 (column 20, lines 34 to 40). Generally, a small amount of demulsifying component can be used herein. Preferred demulsifying components are described in European Patent No. 330522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a diepoxide with a polyol. Such additives can be used in an amount of from about 0.001 to 5 wt%, preferably from about 0.01 to 2 wt%. M. Seal compatibilizers

[0385] Other optional additives include seal compatibilizers such as organophosphates, aromatic esters, aromatic hydrocarbons, esters (such as butyl benzyl phthalate), and polybutenyl succinic anhydride. Such additives can be used in amounts of from about 0.001 to 5 wt%, preferably from about 0.01 to 2 wt%. In some embodiments, the seal compatibilizer is a seal swelling agent such as PIBSA (polyisobutenyl succinic anhydride). N. Extreme Pressure Agents

[0386] The lubricating oil compositions of the present disclosure may contain one or more extreme pressure agents that prevent seizure of sliding metal surfaces under extreme pressure conditions. Any extreme pressure agent known to those of ordinary skill in the art can be used in the lubricating oil composition. Generally, an extreme pressure agent is a compound that can chemically bond with a metal to form a surface film that prevents welding of asperities in opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents include sulfided animal or vegetable fats or oils, sulfided animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfided olefins, dihydrocarbyl polysulfides, sulfided Diels - Alder adducts, sulfided dicyclopentadiene, sulfided or co - sulfided mixtures of fatty acid esters and mono - unsaturated olefins, co - sulfided blends of fatty acids, fatty acid esters, and α - olefins, functionally substituted dihydrocarbyl polysulfides, thioaldehydes, thioketones, episulfides, sulfur - containing acetal derivatives, co - sulfided blends of terpenes and acyclic olefins, polysulfide olefin products, amine salts of phosphate esters or thiophosphate esters, and combinations thereof. Based on the total weight of the lubricating oil composition, the amount of the extreme pressure agent can range from about 0.01 wt% to about 5 wt%, from about 0.05 wt% to about 3 wt%, or from about 0.1 wt% to about 1 wt%. O. Non - base oil unsaturated hydrocarbons

[0387] The lubricating oil compositions of the present disclosure may contain one or more unsaturated hydrocarbons. These unsaturated hydrocarbons are different from any base oils (Group I, II, III, IV, and / or V lubricating oil base stocks) and / or viscosity improvers that may be present in the composition and always have at least one unsaturation per molecule (usually only one in the case of linear α - olefins or LAO). Without being bound by theory, the unsaturation can provide antioxidant functionality and / or sulfur capture functionality, which can supplement and / or replace one or more antioxidant additives and / or one or more corrosion inhibitor additives, but unsaturated hydrocarbons (LAO) generally do not provide only antioxidant functionality and only corrosion inhibition functionality in the lubricating oil composition. Non - limiting examples of unsaturated hydrocarbons can include one or more unsaturated C 12 -C 60 hydrocarbons (such as C 12 -C 48 hydrocarbons, C 12 -C 36Hydrocarbon, C 12 -C 30 Hydrocarbon or C 12 -C 24 hydrocarbon). When there is only one unsaturation, the unsaturated hydrocarbon can be referred to as a linear α-olefin (LAO). Other non-limiting examples of unsaturated hydrocarbons can include polyisobutene oligomers / polymers and / or blends thereof that retain (or are modified after polymerization to exhibit) (near) terminal unsaturation. When present, the unsaturated hydrocarbon (LAO) can be present in an amount of 0.01 to 5 wt% (particularly 0.1 to 3 mass%, or 0.1 to 1.5 mass%) based on the total weight of the lubricating oil composition.

[0388] When the lubricating oil composition contains one or more of the additives discussed above, the additives are typically incorporated into the composition in an amount sufficient to enable them to perform their intended function. Typical amounts of such additives useful in the present disclosure, particularly for crankcase lubricants, are shown in the table below.

[0389] It should be noted that many additives are shipped by additive manufacturers as concentrates containing one or more additives together with a certain amount of base oil or other diluent. Thus, the weights in the table below and other amounts mentioned herein refer to the amount of the active ingredient (i.e., the undiluted portion of the ingredient). The weight percentages (mass%) shown below are based on the total weight of the lubricating oil composition. Typical amounts of optional lubricating oil components

[0390] The above additives are typically commercially available materials. These additives can be added independently, but are usually pre-blended in packages available from lubricating oil additive suppliers. Additive packages with various compositions, ratios, and properties are available and the selection of an appropriate package will take into account the intended use of the final composition. Fuels

[0391] The present disclosure also relates to a method of lubricating an automotive internal combustion engine during engine operation, which includes: (i) providing the lubricating composition described herein to the crankcase of the automotive internal combustion engine; (ii) providing a hydrocarbon fuel in the automotive internal combustion engine; and (iii) combusting the fuel in the automotive internal combustion engine, such as a spark-ignition or compression-ignition two-stroke or four-stroke reciprocating engine, such as a diesel engine or a passenger car engine (such as a spark-ignition internal combustion engine).

[0392] The present disclosure also relates to a fuel composition comprising the lubricating oil composition described herein and a hydrocarbon fuel, wherein the fuel may be derived from petroleum and / or biological sources (“biofuel” or “renewable fuel”). In some embodiments, the fuel comprises 0.1 to 100% by mass of renewable fuel, or 1 to 75% by mass of renewable fuel, or 5 to 50% by mass of renewable fuel, based on the total mass of the renewable fuel and the petroleum-derived fuel.

[0393] Renewable fuel components are generally made from vegetable oils (such as palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oils (such as algal oil), animal fats (such as cooking oil, animal fat and / or fish fat) and / or biogas. Renewable fuel refers to biofuels made from biological resources formed by contemporary biological processes. In one embodiment, the renewable fuel component is made by a hydrotreating process. Hydrotreating involves various reactions in which molecular hydrogen reacts with other components or the components undergo molecular transformation in the presence of molecular hydrogen and a solid catalyst. The reactions include, but are not limited to, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrocracking and isomerization. The renewable fuel component can have different distillation ranges to provide the desired properties for the component according to the intended use. Uses

[0394] The lubricating compositions of the present disclosure can be used to lubricate mechanical engine components by adding a lubricant thereto, particularly in internal combustion engines, such as spark-ignition or compression-ignition two-stroke or four-stroke reciprocating engines. Generally, they are crankcase lubricants, such as passenger car motor oils or heavy-duty diesel engine lubricants.

[0395] In particular, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of a compression-ignition internal combustion engine, such as a heavy-duty diesel engine.

[0396] In particular, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of a spark-ignition turbocharged internal combustion engine.

[0397] In some embodiments, the lubricating oil of the present disclosure is used in a spark-assisted high-compression internal combustion engine, and when used in a high-compression spark-ignition internal combustion engine, the lubricating oil composition of the present disclosure can be used to lubricate the high-compression spark-ignition engine.

[0398] In some embodiments, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of an engine of a heavy-duty diesel vehicle (i.e., a heavy-duty diesel vehicle having a gross vehicle weight of more than 10,000 pounds).

[0399] In some embodiments, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of a passenger car diesel engine.

[0400] In particular, the lubricating oil formulations of the present disclosure are particularly useful for compression ignition internal combustion engines that use low viscosity oils such as API FA-4 and future oil categories where wear protection of the valve train becomes challenging, i.e., heavy duty diesel engines. Additional Embodiments / EP Clauses

[0401] 1. A copolymer comprising one or more of the following: I. (a) 10.0 to 20.0 wt% of amine derivatized α-methylstyrene (ADAMS) repeat units according to Structure (I): wherein: k is an integer from 1 to 3; R1 is hydrogen or benzyl, R is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) 80.0 to 90.0 wt% of repeat units corresponding to the reactive form of isoprene, and wherein the peak average molecular weight of the copolymer is 45.0 to 65.0 kDa; II. (a) 5.0 to 10.0 wt% of amine derivatized α-methylstyrene (ADAMS) repeat units according to Structure (II): wherein: k is an integer from 1 to 3; R is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining 90.0 to 95.0 wt% of repeat units corresponding to the reactive form of isoprene, and wherein the peak average molecular weight of the copolymer is 24.0 to 42.0 kDa; III. (a) 4.0 to 6.0 wt% of amine derivatized α-methylstyrene (ADAMS) repeat units according to Structure (III): wherein: k is an integer from 1 to 3; R is hydrogen, a phenyl ring that is co - connected to the indicated phenyl ring at two adjacent ring - carbon positions to form a naphthalene assembly, a phenyl group connected at a single carbon of the indicated phenyl ring, a C1 - C4 hydrocarbyl group, a C1 - C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining 94.0 to 96.0 wt% of repeating units corresponding to the reactive form of isoprene, and wherein the peak average molecular weight of the copolymer is from 36.0 to 46.0 kDa; IV. (a) One or more amine - derivatized α - methylstyrene (ADAMS) repeating units according to structure (IV): wherein: k is an integer from 1 to 3; R1 is hydrogen or benzyl, R is hydrogen, a phenyl ring that is co - connected to the indicated phenyl ring at two adjacent ring - carbon positions to form a naphthalene assembly, a phenyl group connected at a single carbon of the indicated phenyl ring, a C1 - C4 hydrocarbyl group, a C1 - C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining repeating units corresponding to the reactive form of isoprene.

[0402] 2. The copolymer of clause 1, wherein the copolymer is partially or substantially hydrogenated.

[0403] 3. The copolymer of clause 1 or 2, wherein k = 2.

[0404] 4. The copolymer of clauses 1 - 3, further comprising alkyl residues from a monofunctional initiator selected from alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and present at one or more termini of the polymer backbone.

[0405] 5. The copolymer of clause 4, wherein the alkyl residues from the monofunctional initiator include methyl, ethyl, n - propyl, isopropyl, n - butyl, isobutyl, sec - butyl, tert - butyl, n - pentyl, isopentyl, sec - pentyl, tert - pentyl, hexyl, or combinations thereof.

[0406] 6. The copolymer of clauses 1 - 5, wherein one or more polymer blocks of the copolymer form a distributed polymer architecture, a diblock, a triblock, a tetrablock, a pentablock, a hexablock, a star polymer architecture, or combinations thereof.

[0407] 7. A lubricating oil composition comprising or consisting of a blend of the following components: (i) at least 50 wt% of one or more base oils, based on the weight of the lubricating oil composition; (ii) one or more dispersants; (iii) one or more detergents; and (iv) one or more copolymers of clauses 1 - 6.

[0408] 8. The lubricating oil composition of clause 7, wherein the composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40, or 50.

[0409] 9. The lubricating oil composition of clauses 7-8, comprising the following components or obtained by mixing the following components: (i) 50 to 99% by mass of one or more base oils, based on the weight of the lubricating oil composition; (ii) 0.01 to 20% by weight of one or more dispersants, based on the total weight of the lubricating oil composition; (iii) 0.10 to 20% by mass of one or more detergents, based on the weight of the lubricating oil composition; and (iv) 0.10 to 20% by mass of one or more of the copolymers, based on the weight of the lubricating oil composition.

[0410] 10. The lubricating oil composition of clauses 7-9, further comprising one, two, three, four, five, six, or more of the additional additives selected from friction modifiers; antioxidants; pour point depressants; defoamers; viscosity improvers; corrosion inhibitors and / or rust inhibitors; and antiwear agents.

[0411] 11. The lubricating oil composition of clauses 7-10, further comprising one, two, three, four, five, six, or more of the following: A) 0.01 to 5% by weight of one or more friction modifiers, based on the total weight of the lubricating oil composition; B) 0.01 to 10% by weight of one or more antioxidants, based on the total weight of the lubricating oil composition; C) 0.01 to 5% by weight of one or more pour point depressants, based on the total weight of the lubricating oil composition; D) 0.001 to 5% by weight of one or more defoamers, based on the total weight of the lubricating oil composition; E) 0.001 to 10% by weight of one or more viscosity improvers, based on the total weight of the lubricating oil composition; F) 0.0 to 5% by weight of one or more inhibitors and / or rust inhibitors; and / or G) 0.001 to 10% by weight of one or more antiwear agents, based on the total weight of the lubricating oil composition.

[0412] 12. The lubricating oil composition of clauses 7-11, wherein the one or more detergents comprise one or more oil-soluble neutral or overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble alkali metal or alkaline earth metal carboxylates.

[0413] 13. The lubricating oil composition of clauses 7-12, wherein the one or more dispersants comprise one or more boronated or non-boronated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from polyamine.

[0414] 14. A method of lubricating an internal combustion engine during engine operation, comprising: (i) providing to the crankcase of the internal combustion engine the lubricating oil composition of clauses 7 - 13; (ii) providing fuel in the internal combustion engine; and (iii) combusting the fuel in the internal combustion engine.

[0415] 15. The method of clause 14, wherein the fuel is one or more of a hydrocarbon fuel, a renewable fuel, a hydrogen fuel, or any blend thereof.

[0416] 16. The method of clauses 14 - 15, wherein the engine is a diesel engine.

[0417] The present invention will now be described by way of non - limiting examples only. Examples Test Procedures

[0418] Gel permeation chromatography (GPC) samples were prepared by dissolving samples of the crude reaction mixture or separated polymer product in tetrahydrofuran (THF) with the goal of a final sample concentration of 1.0 - 5.0 mg polymer / ml THF. GPC was carried out in a constant solvent mode using stabilized THF as the mobile phase. Unless otherwise stated, all polymer Mp, Mn, Mw, Mz values are reported relative to PS standards. Unless otherwise stated, all molecular weights were determined by gel permeation chromatography using polystyrene standards and reported as peak average molecular weights (Mp) in kDa / mol. Molecular weight values of the polymer before and after hydrogenation were reported. "A.I.", "ai", "a.i.", and "ai" are the weight % of the active ingredient unless otherwise stated.

[0419] KV100 is the kinematic viscosity measured at 100 °C according to ASTM D445 - 19a.

[0420] Phosphorus, boron, calcium, zinc, molybdenum, magnesium, and sulfur contents were measured by ASTM D5185.

[0421] High temperature high shear viscosity ("HTHS" or "HTHS150") was determined at 150 °C according to ASTM D4683 and reported in cPs.

[0422] Unless otherwise stated, the Cold Cranking Simulator ("CCS") at - 25 °C is a measure of the cold - start characteristics of the crankcase lubricant and is determined as described in ASTM D5293 - 92.

[0423] Cummins ISB Engine Test. According to the Cummins ISB Engine Test, ASTM D7484-21 determines valve train wear protection in a 5.9L 6-cyl diesel engine equipped with exhaust gas recirculation. The Cummins ISB test is a two-stage test. In Stage A, for 100 hours, the engine runs with a retarded fuel-injection timing according to the ASTM procedure to generate excessive soot. During Stage B, for 250 hours, the engine runs under cyclic conditions according to the ASTM procedure to induce valve train wear. The oil performance is determined by evaluating the crosshead weight loss (mg) measured as detailed in Section 8.1.5 of ASTM D7484-21, the tappet weight loss (mg) measured as detailed in Section 8.1.6 of ASTM D7484-21, and the camshaft wear (μm) averaged over 12 lobes measured using a Mitutoyo Snap Gauge and a Mitutoyo digital indicator as detailed in Section 8.1.7 of ASTM D7484-21. Materials Polymer Examples The following ADAMS-isoprene copolymer samples were prepared according to the general method detailed above. Component Tables Example 1: Cummins ISB Valve Train Wear Protection Test

[0424] Oils A, B, and a comparative oil C were prepared and tested for valve train wear protection according to the above Cummins ISB engine test. The data are reported in Table 1. Table 1 Example 2: Soot-Induced Viscosity Control Bench Test

[0425] A 2.0 wt% solution of the selected isolated ADAMS-isoprene copolymer in a Group II base oil (KV 100 6 cSt) was prepared by mixing appropriate amounts of the finished components with the base oil and heating to 75 °C for 1 - 3 hours until the polymer was completely dissolved.

[0426] A 9.0 wt% suspension of carbon black (Vulcan XC72R) in the ADAMS-isoprene copolymer solution was prepared by weighing 45.5 g of the 2.0 wt% polymer solution and adding it to a 100 mL beaker containing 4.5 g of Vulcan XC72R carbon black. The suspension was mixed at 90 °C for 16 hours and then at 100 °C for 1 hour under an air atmosphere via overhead stirring (200 - 400 rpm).

[0427] The soot-induced viscosity growth experiment was conducted on a Haake RS600 rheometer controlled by Haake RheoWin Job Manager software (version 4.30.0028) using the following conditions in Table 2: Table 2. Sootification Rheology Method

[0428] The dynamic viscosity of the sample under the final shear sweep was used to compare the soot dispersing power of different components diluted to 2.0 wt% active polymer in Group III base oils. The viscosity (η, Pa-s) was measured at approximate shear rates of 2.1 ± 0.1, 4.1 ± 0.1, and 8.1 ± 0.1 s -1 as described in Table 3 below. Table 3. Soot-Induced Viscosity Increase Data

[0429] All documents described herein are hereby incorporated by reference to the extent that they are not inconsistent with the present disclosure, including any priority documents and / or test procedures. From the foregoing general description and specific embodiments, it will be apparent that, although forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended to limit the invention hereby. The term "comprising" specifies the presence of the recited element, step, integer or component, but does not preclude the presence or addition of one or more other elements, steps, integers, components or combinations thereof. Accordingly, the term "comprising" is considered synonymous with the term "including". Similarly, whenever a composition, element or group of elements is preceded by the connecting word "comprising", it should be understood that the same composition or group of elements preceded by the connecting words "consisting essentially of", "consisting of", "selected from" or "may be", "might be", "is" is contemplated, and vice versa. Except for the well-known terms that "comprising" means "including the matter recited and any other matter" [open] and "consisting of" means "including only the matter recited" [closed], the term "consisting essentially of" should be understood to be semi-inclusive and means, according to United States judicial interpretation, including the matter recited and other matters that do not materially affect the basic and novel properties.

[0430] The applicant has attempted to disclose all embodiments and applications of the disclosed subject matter that are reasonably foreseeable. However, there may be some unforeseen, non-substantive modifications that are still equivalent. Although the invention has been described in connection with its specific exemplary embodiments, it will be apparent that, in view of the foregoing description, many changes, modifications and variations will be obvious to those skilled in the art without departing from the spirit or scope of the present disclosure. Accordingly, the present disclosure is intended to embrace all such changes, modifications and variations of the foregoing detailed description.

[0431] All patents, test procedures and other documents cited herein, including priority documents, are hereby incorporated by reference in their entirety to the extent that such disclosure is not inconsistent with the present invention and in all jurisdictions in which such incorporation is permitted.

[0432] When numerical lower and upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.

Claims

1. A copolymer comprising one or more of the following: I. (a) 10.0 to 20.0 wt% of amine - derivatized α - methylstyrene (ADAMS) repeat units according to structure (I): Wherein: k is an integer from 1 to 3; R1 is hydrogen or benzyl, R is hydrogen, a phenyl ring co - connected to the indicated phenyl ring at two adjacent ring - carbon positions to form a naphthalene assembly, a phenyl group connected at a single carbon of the indicated phenyl ring, a C1 - C4 hydrocarbon group, a C1 - C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) 80.0 to 90.0 wt% of repeat units corresponding to the reactive form of isoprene, and wherein the peak average molecular weight of the copolymer is 45.0 to 65.0 kDa; II. (a) 5.0 to 10.0 wt% of amine - derivatized α - methylstyrene (ADAMS) repeat units according to structure (II): wherein: k is an integer from 1 to 3; R is hydrogen, a phenyl ring co - connected to the indicated phenyl ring at two adjacent ring - carbon positions to form a naphthalene assembly, a phenyl group connected at a single carbon of the indicated phenyl ring, a C1 - C4 hydrocarbon group, a C1 - C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining 90.0 to 95.0 wt% of repeat units corresponding to the reactive form of isoprene, and wherein the peak average molecular weight of the copolymer is 24.0 to 42.0 kDa; III. (a) 4.0 to 6.0 wt% of amine - derivatized α - methylstyrene (ADAMS) repeat units according to structure (III): wherein: k is an integer from 1 to 3; R is hydrogen, a phenyl ring co - connected to the indicated phenyl ring at two adjacent ring - carbon positions to form a naphthalene assembly, a phenyl group connected at a single carbon of the indicated phenyl ring, a C1 - C4 hydrocarbon group, a C1 - C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining 94.0 to 96.0 wt% of repeat units corresponding to the reactive form of isoprene, and wherein the peak average molecular weight of the copolymer is 36.0 to 46.0 kDa; or IV. (a) One or more amine - derivatized α - methylstyrene (ADAMS) repeat units according to structure (IV): wherein: k is an integer from 1 to 3; R1 is hydrogen or benzyl, R is hydrogen, a phenyl ring co - connected to the indicated phenyl ring at two adjacent ring - carbon positions to form a naphthalene assembly, a phenyl group connected at a single carbon of the indicated phenyl ring, a C1 - C4 hydrocarbon group, a C1 - C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, and (b) the remaining repeat units corresponding to the reactive form of isoprene.

2. The copolymer according to claim 1, wherein the copolymer is partially or substantially hydrogenated.

3. The copolymer according to claim 1 or 2, wherein k = 2.

4. The copolymer according to claims 1 - 3 further comprises an alkyl residue from a monofunctional initiator selected from alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and is present at one or more ends of the polymer backbone.

5. The copolymer according to claim 4, wherein the alkyl residue from the monofunctional initiator comprises methyl, ethyl, n - propyl, isopropyl, n - butyl, isobutyl, sec - butyl, tert - butyl, n - pentyl, isopentyl, sec - pentyl, tert - pentyl, hexyl, or combinations thereof.

6. The copolymer according to claims 1 - 5, wherein one or more polymer blocks of the copolymer form a distributed polymer architecture, diblock, triblock, tetrablock, pentablock, hexablock, star polymer architecture, or combinations thereof.

7. A lubricating oil composition comprising the following components or obtained by mixing the following components: (i) at least 50 wt% of one or more base oils, based on the weight of the lubricating oil composition; (ii) one or more dispersants; (iii) one or more detergents; and (iv) one or more copolymers according to claims 1 - 6.

8. The lubricating oil composition according to claim 7, wherein the composition has an SAE viscosity grade of 20W - X, 15W - X, 10W - X, 5W - X, or 0W - X, where X represents any one of 8, 12, 16, 20, 30, 40, or 50.

9. The lubricating oil composition according to claims 7 - 8, comprising the following components or obtained by mixing the following components: (i) 50 to 99 mass% of one or more base oils, based on the weight of the lubricating oil composition; (ii) 0.01 to 20 wt% of one or more dispersants, based on the total weight of the lubricating oil composition; (iii) 0.10 to 20 mass% of one or more detergents, based on the weight of the lubricating oil composition; and (iv) 0.10 to 20 mass% of one or more of the copolymers, based on the weight of the lubricating oil composition.

10. The lubricating oil composition according to claims 7 - 9, which further comprises one, two, three, four, five, six, or more additional additives selected from friction modifiers; antioxidants; pour point depressants; defoamers; viscosity improvers; corrosion inhibitors and / or rust inhibitors; and anti - wear agents.

11. The lubricating oil composition according to claims 7-10, further comprising one, two, three, four, five, six or more of the following: A) one or more friction modifiers in an amount of 0.01 to 5% by weight, based on the total weight of the lubricating oil composition; B) 0.01 to 10 wt% of one or more antioxidants, based on the total weight of the lubricating oil composition; C) 0.01 to 5 wt% of one or more pour point depressants, based on the total weight of the lubricating oil composition; D) 0.001 to 5 wt% of one or more defoamers, based on the total weight of the lubricating oil composition; E) 0.001 to 10 wt% of one or more viscosity improvers, based on the total weight of the lubricating oil composition; F) 0.0 to 5 wt% of one or more inhibitors and / or rust inhibitors, based on the total weight of the lubricating oil composition; and / or G) 0.001 to 10 wt% of one or more anti - wear agents, based on the total weight of the lubricating oil composition.

12. The lubricating oil composition according to claim 7-11, wherein the one or more detergents comprise one or more oil-soluble neutral or overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble alkali metal or alkaline earth metal carboxylates.

13. The lubricating oil composition according to claim 7-12, wherein the one or more dispersants comprise one or more boronated or non-boronated poly(alkenyl)succinimides, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from polyamine.

14. A method for lubricating an internal combustion engine during engine operation, comprising: (i) Supplying the lubricating oil composition according to claim 7-13 to the crankcase of an internal combustion engine; (ii) Supplying fuel in the internal combustion engine; and (iii) Burning the fuel in the internal combustion engine.

15. The method according to claim 14, wherein the fuel is one or more of a hydrocarbon fuel, a renewable fuel, a hydrogen fuel, or any blend thereof.

16. The method according to claim 14-15, wherein the engine is a diesel engine.

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