Amine-containing polymer and lubricant composition including such polymer and methods of using them

Abstract

To provide an amine-containing polymer.SOLUTION: There is provided a functional polymer based on a functionalized styrenic monomer containing a nitrogen-containing moiety other than as a pendant to a phenyl ring, polymerized from an addition-polymerizable monomer composition comprising an amine-derivatized alpha-methylstyrene (ADAMS) monomer according to structure (I), where k is an integer from 1 to 3, preferably 2, R1 is a methyl group or a phenyl group, R2 is a benzyl group, or R1 and R2 are connected to form a moiety containing one 6-membered ring having four carbons and one 6-membered ring having an O or N-CH3 group at the 4-position of the 6-membered ring, and R in structure (I) is hydrogen, a phenyl ring co-bonded with the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group bonded to a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group (e.g., a methyl group), or a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms (e.g., O, N, S, P, Se, and combinations thereof). A method of using such a functional polymer in a lubricant composition is also provided.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to polymer compositions that can be derived from monomer compositions comprising aromatic and / or conjugated (non-aromatic) structures each containing at least one amine nitrogen, and methods for using such compositions. 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 that exhibit good dispersibility in engine crankcase applications, particularly compression ignition engine applications.

Background Art

[0002] There are numerous documents that disclose nitrogen-containing (amine) groups pendant to the phenyl ring of styrenic monomers / polymers / copolymers. However, monomers and polymers having such pendant groups can be chemically difficult to synthesize reliably / repeatedly. Even if such a synthesis could be achieved, problems can arise with the propagation within the polymerization reaction, whether alone or as a copolymer with other styrenic monomers, that contain such amine-functionalized styrenic monomers. Thus, it is often possible to use post-polymerization chemical reactions to attach amine groups to a few monomer repeat units. However, in post-polymerization chemical reactions, even if the propagation problems of amine-functionalized styrenic monomers can be avoided, often another problem can arise. Therefore, it is desirable to develop a different method of functionalizing styrenic monomer prepolymers, particularly one that is neutral with respect to propagation within the polymerization reaction or perhaps even enhances propagation. U.S. Patent Nos. 6,486,272, 9,364,825, 10,202,494, and 10,046,285 disclose polymers made from styrene monomers having a nitrogen-containing group pendant to a phenyl ring, and all of these documents are hereby incorporated by reference in their entirety. British Patent No. 1,381,755 discloses amine-functional monomer compounds, but only those having acrylamide functionality. 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 International Publication No. WO 2021 / 127183 Pamphlet. All of these documents are hereby incorporated by reference in their entirety. In view of the difficulties in preparing and polymerizing styrene monomers having a nitrogen-containing group pendant to a phenyl ring, Applicants have explored other potential structures of functional monomers that are simpler in both manufacture and further polymerization. Such functional monomer compositions, each containing an aromatic and / or conjugated (non-aromatic) structure containing at least one amine nitrogen, are described in co-owned related U.S. Patent Application No. 63 / 483,365, filed February 6, 2023, the contents of which are hereby incorporated by reference in their entirety.

[0003] U.S. Patent No. 2,778,826 (the “’826 Schmidle Patent”) and the 1955 paper by Schmidle and Mansfield entitled “The Aminomethylation of Olefins. I. The Reaction of Secondary Amines, Formaldehyde, and Olefins” both disclose various reactions in which 3-aryl-3-butenyl-1-amines are formed, in which formaldehyde and a secondary amine form an iminium, which reacts with a styrenic olefin to form only the terminal (vinylidene) double bond type of the amine-functionalized styrenic material. The 1955 paper also disclosed the amine functionalization of terpenoids such as α- and β-pinene, camphene, and limonene, but did not disclose isoprene or similar conjugated non-aromatic compounds.

[0004] The 1983 paper by Cohen and Onopchenko entitled “Competing Hydride Transfer and Ene Reactions in the Aminoalkylation of 1-Alkenes with N,N-Dimethylmethyleniminium Ions. A Literature Correction” (partially cited in, inter alia, the ’826 Schmidle Patent) further disclosed mechanistic studies of specific dimethyliminium compounds that react with styrenic and non-styrenic olefins. Notably, the 1983 paper states in the opening of the discussion section that there were errors in the ’826 Schmidle Patent (and presumably the 1955 paper, which included experiments and results very similar thereto). Nevertheless, with respect to the aminomethylation of α-methylstyrene, the 1983 paper showed that the vinylidene-based product was produced with a significant vinylenic (not terminal double bond) content and a very significant (13% in the case of the dimethylamino type) saturated arylalkane-amine content.

[0005] To the applicant's knowledge, the monomers of the invention disclosed in U.S. Provisional Patent Application No. 63 / 483,365 have not been polymerized previously. In view of the above, there is a need to provide functional polymers based on alpha-substituted functional monomers, particularly functional polymers based on a functional monomer composition comprising aromatic and / or conjugated (non-aromatic) structures each containing at least one amine nitrogen, using anionic polymerization processing techniques. In recent years, there has been an increasing trend towards emphasizing fuel efficiency. One way to improve the fuel efficiency of vehicles is to design new lubricant oils that reduce friction while maintaining a good film thickness for durability and protect against wear while preventing soot-induced viscosity increase. In attempts to improve fuel efficiency, the use and demand for low-viscosity grades by original equipment manufacturers (OEMs) are becoming increasingly widespread. One of the challenges in providing engine and / or drive train transmission oils with such reduced viscosity grades is to maintain clarity. Such oils must be able to provide the desired fuel efficiency benefits while reducing sludge, providing good soot handling, and providing wear protection. These goals should be achieved while maintaining low levels of sulfuric acid ash and phosphorus, as well as seal compatibility. There is a need to provide new engine oils with low-viscosity grades that meet these requirements.

[0006] The base oil of a lubricant is typically modified by adding additives such as viscosity index improvers (VIIs) and / or dispersants. VIIs can be used to reduce the degree of viscosity change of the lubricant with temperature and are often used in formulating engine and transmission lubricants. Common VIIs typically include polymeric substances that can be derived from, for example, ethylene-propylene copolymers, polymethacrylates, hydrogenated styrene-butadiene copolymers, polyisobutylene, and the like.

[0007] During engine operation, oil-insoluble oxidation by-products, such as soot, are generated. Dispersants assist in maintaining such by-products in suspension or solution, thus reducing the deposition of by-products on metal surfaces. Common dispersants include (poly)alkenyl succinic acid derivatives, such as hydrocarbyl-substituted succinic anhydrides, such as polyisobutylene succinic anhydride (PIBSA), and hydrocarbyl-substituted succinimides, such as polyisobutylene succinimide (PIBSA-PAM), such as those derived from the reaction of maleated polyisobutylene and N-phenyl-p-phenylenediamine. Useful dispersants include polyisobutenes modified by an ene reaction to contain functional groups such as succinimide, hydroxyethylimide, succinic ester / amide, and oxazoline. Other dispersants include polybutene, ethylene-propylene polymers, and Mannich base derivatives of acrylic polymers.

[0008] Other dispersants are derived from the reaction of maleated polyalpha-olefins (e.g., ethylene-propylene copolymers) with polyamines. U.S. Patent No. 6,107,257 relates to additives for lubricating oil compositions containing multifunctional olefin copolymer viscosity index improvers. Maleic anhydride is reacted or grafted with an ethylene-propylene copolymer backbone in the presence of a solvent, and then the grafted 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 acylated and then aminated copolymers of C3-C23 alpha olefins.

[0009] Still other dispersants are derived from styrenic copolymers. U.S. Patent No. 6,248,702 discloses a maleated selectively hydrogenated styrenic block copolymer (Mn 10,000, Example 1) reacted with aminopropylmorpholine to form a dispersant substance. Still other dispersants are derived from copolymers of two different conjugated dienes, for example, block copolymers of isoprene and butadiene. U.S. Patent No. 5,780,540 discloses a functionalized selectively hydrogenated isoprene-butadiene diblock copolymer in an automotive additive package. The examples show that N-phenyl-1,4-phenylenediamine is used in combination with polyethylene glycol monoalcohol, 4-(3-aminopropylmorpholine), and / or 3-dibutylaminopropylamine to functionalize maleated 10,000 Mn and / or 20,000 Mn isoprene-butadiene copolymers. Examples 1 and 2 show that when producing an IB copolymer using 2,2’ dipyridyl, the possibility of having a high 1,4 insertion becomes lower.

[0010] 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) that reacts with aminopropylmorpholine to form a morpholinopropyl succinimide adduct, which is then used as a dispersant in an additive package (Example V). U.S. Patent No. 5,073,600 relates to a reactive extrusion process for functionalizing (e.g., maleating and then aminating) copolymers of conjugated diolefins, typically having an Mn of 500,000 to about 3,000,000. The examples show a hydrogenated “low” molecular weight star polymer of hydrogenated homopolyisoprene having an average of 15 arms (35,000 Mn per arm) that was reacted with maleic anhydride and diethylaminopropylamine in a reactive extruder.

[0011] There is still a need to provide alternative or improved engine / transmission oil compositions that pass severe wear tests while also providing improvements in wear, fuel economy, and dispersancy performance. The present disclosure provides engine oil compositions containing amine-containing copolymers that not only reduce wear but also have acceptable soot handling and / or engine / transmission clarity. Further, the present disclosure provides amine-containing copolymers as dispersant viscosity index improvers and addresses such needs by using them in lubricating oil compositions to achieve the above-described need for performance improvements.

SUMMARY OF THE INVENTION

[0012] In one form, the present specification discloses a copolymer comprising (a) 10.0 to 20.0% by mass of amine-derivatized alpha-methylstyrene (ADAMS) repeat units having Structure (I),

CHEMICAL FORMULA

[0013] In another form, the present specification discloses a copolymer comprising (a) 5.0 to 10.0 mass% of amine-derivatized alpha-methylstyrene (ADAMS) repeat units according to Structure (II),

Chemical Structure

[0014] In yet another form, herein disclosed is a copolymer, (a) 4.0 to 6.0 mass% of amine-derivatized alpha-methylstyrene (ADAMS) repeat units according to Structure (III),

Chemical Structure

[0015] In yet another form, herein, a copolymer is provided, (a) One or more amine - derivatized alpha - methylstyrene (ADAMS) repeat units of structure (IV), [Chemical formula] In the formula, k is an integer from 1 to 3, R1 is hydrogen or a benzyl group, R is hydrogen, a phenyl ring covalently bonded to the phenyl ring in the notation and two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group bonded to a single carbon of the phenyl ring in the notation, a C1 - C4 hydrocarbyl group, a C1 - C6 hydrocarbyl group containing 1 - 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof. One or more amine - derivatized alpha - methylstyrene (ADAMS) repeat units, and (b) The remaining repeat units corresponding to the reaction form of isoprene A copolymer containing them is disclosed.

[0016] Also, herein, a lubricating oil composition is provided that is obtained by including or mixing (i) at least 50 mass% of one or more base oils based on the mass of the lubricating oil composition, (ii) one or more dispersants, (iii) one or more detergents, and (iv) one or more copolymers described in any one of the preceding four paragraphs. Also provided herein is a lubricating oil composition obtained by including or mixing (i) one or more base oils in an amount of 50 to 99% by mass based on the mass of the lubricating oil composition, (ii) one or more dispersants in an amount of 0.01 to 20% by mass based on the total mass of the lubricating oil composition, (iii) one or more detergents in an amount of 0.10 to 20% by mass based on the mass of the lubricating oil composition, and (iv) one or more of the copolymers described in the preceding paragraph in an amount of 0.10 to 20% by mass based on the mass of the lubricating oil composition. Also provided herein is a method for lubricating an internal combustion engine during operation of the engine, the method including (i) supplying to the crankcase of the internal combustion engine the lubricating oil composition described in any one of the preceding two paragraphs, (ii) supplying fuel to the internal combustion engine, and (iii) combusting the fuel in the internal combustion engine. Other aspects of the disclosure will become apparent from the following detailed description and examples section.

DETAILED DESCRIPTION OF THE INVENTION

[0017] All numerical values within the detailed description and claims of this specification are modified by the term “about” or “approximately” such that the indicated values account for experimental error and variations that would be expected by one of ordinary skill in the art. Overview of Copolymers The present disclosure provides novel polymers and copolymers based on the anionic polymerization of functionalized styrenic monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring. Accordingly, monomer of structure (I) was developed to achieve nitrogen-containing functionality other than as a pendant to the phenyl ring of styrene units in alpha-substituted styrenic monomers. It should be noted that the prior art often describes functionalized styrenic monomers having nitrogen-containing groups pendant to the phenyl ring in general terms (e.g., “dimethylaminoethylstyrene”). This may be similar to the k = 2 monomer structure provided below, but the prior art does not teach or suggest the alpha-substituted functional monomers specifically disclosed herein or the functional polymers derived therefrom.

[0018] The functional polymers of the present invention disclosed herein, based on functionalized styrene monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring, can be polymerized from an addition polymerizable monomer composition comprising an amine-derivatized alpha-methylstyrene (ADAMS) monomer according to structure (I).

Chemical formula

[0019] The functional polymers of the present invention disclosed herein, based on functionalized styrene monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring, can be polymerized from exemplary ADAMS monomers according to structure (I). Exemplary ADAMS monomers according to structure (I) include 1-benzylmethylamino-3-phenylbut-3-ene, 1-benzylphenylamino-3-phenylbut-3-ene, 1-(N-morpholinyl)-3-phenylbut-3-ene, and 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene. In some embodiments, the functional polymers of the present invention disclosed herein, based on functionalized styrene monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring, can be polymerized from exemplary ADAMS monomers according to structure (I) and may exhibit exactly a k value of 2. For clarity, as used herein, the functional polymers of the present invention disclosed herein based on functionalized styrene monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring can be polymerized from exemplary ADAMS monomers of structure (I) having a vinylidene bond such as those derived from the olefin double bond of alpha-methylstyrene, which may be reflected in the -3-ene / -3-enyl language of the IUPAC nomenclature, for example.

[0020] The polymer compositions disclosed herein may optionally contain residues of initiators and / or co-initiators used or capable of being used in living or pseudo-living anionic polymerization reactions. Non-limiting examples include alkyl residues derived from sec-butyllithium, n-butyllithium, tert-butyllithium, etc., and combinations, reaction products, and / or decomposition products thereof.

Chemical formula

[0021] Alkyl residues derived from the initiator may optionally be present at one or more ends of the polymer backbone. Initiators that can be used may generally be alkyl lithium compounds, alkyl sodium compounds, or alkyl potassium compounds in the range of C2 to C12. Alkyl lithium compounds, such as methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, iso-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-amyl lithium, iso-amyl lithium, sec-amyl lithium, tert-amyl lithium, hexyl lithium, or combinations thereof are preferred. Secondary alkyl lithium compounds, such as sec-butyl lithium, sec-amyl lithium, or combinations thereof are more preferred. Sec-butyl lithium is most preferred. Substituted alkyl lithiums, such as aralkyl lithium compounds, such as benzyl lithium, 1-lithioethylbenzene, and 1-lithio-3-methylpentylbenzene can also be used.

[0022] This specification provides an anionic polymerization polymer of the present invention derived from a functionalized styrene monomer containing a nitrogen-containing moiety other than as a pendant to a phenyl ring and having the following basic structure.

Chemical formula

[0023] The functionalized styrene monomer containing a nitrogen-containing moiety other than as a pendant to a phenyl ring can copolymerize with isoprene. Depending on the reactivity ratio between the styrene monomer containing a nitrogen-containing moiety other than as a pendant to a phenyl ring and other isoprene present in the polymerization reaction, the repeat unit of structure (V) may, in some cases, be structure (VII a ), (VII b ), or form an alternating structure with the repeat units of these combinations. For example, in the following reaction, R1, R2, and R5 have the same meanings as those shown above.

Chemical formula

[0024] The alternating structure formed as a combination of the repeat unit of structure (V) and structure (VII a ), (VII b ), or combinations thereof thereby forms structure (X a ), (X b) or form larger repeat units of these combinations. Structure (VII a ), and (X a ), for the polymeric repeat units, the double bond may be in the cis isomeric form, the trans isomeric form, or a combination thereof.

Chemical formula

[0025] In addition, depending on the reactivity ratio of the styrene monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring with respect to isoprene present in the polymerization reaction, when a molar excess of isoprene is present during the polymerization reaction, the polymer may, in some cases, have a block of repeat units of structure (X a ), (X b ), or a combination thereof, followed by a second block of repeat units of structure (VII a ), (VII b ), or a combination thereof, and the repeat units of structure (IX), (X a ), (X b ) may not be present. For example, in the following reaction, R1, R2, and R5 have the same meanings as those shown above. For the polymeric repeat units, the double bond may be in the cis isomeric form, the trans isomeric form, or a combination thereof.

Chemical formula

[0026] In some embodiments, the additional portions of the monomers or combinations thereof may optionally be added sequentially to the polymerization reaction. In such cases, the monomers added later in the reaction may form one or more blocks of repeat units within the polymer having a composition different from the repeat units derived from the monomers earlier in the polymerization. As a result of a difference in monomer reactivity ratios or as a result of sequentially adding monomers to the polymerization reaction, if the polymer contains two blocks of repeat units of different compositions, the polymer is described as a "diblock". Similarly, as a result of a difference in monomer reactivity ratios or as a result of sequentially adding monomers to the polymerization reaction, if the polymer contains three, four, five, or six blocks of repeat units of different compositions, the polymer is described as a "triblock", "tetrablock", "pentablock", or "hexablock", respectively.

[0027] In some embodiments, the polymer can be coupled using a polyfunctional coupling agent to form a polymer having a star architecture. Many suitable types of such polyfunctional compounds are 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 entirety. The polyfunctional coupling agent may optionally be a halogen-substituted or alkoxy-substituted silane, including, but not limited to, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, bis-trimethoxy-silylethane, bis-triethoxy-silylethane, hexachlorodisiloxane, bis-trichlorosilylethane, 1,6-bis(trichlorosilyl)-hexane, or combinations thereof.

[0028] Preferred coupling agents are polyalkenyl aromatic coupling agents. The most preferred coupling agent is divinylbenzene. Polyalkenyl aromatic coupling agents capable of forming star polymers are known in the art. In general, reference may be made to Canadian Patent No. 716,645, U.S. Patent No. 4,010,226, and No. 3,985,830. Such documents are hereby incorporated by reference in their entirety. A detailed description of various such coupling agents can be 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, and 2,2'-divinyl-4-ethyl-4'-propylbiphenyl, etc., or combinations thereof.

[0029] When using a multifunctional coupling agent to couple polymers to form a polymer star architecture, the coupling ratio (CR) is used to refer to the amount of polymer crosslinked in the star architecture and means the mass percentage of the polymer of the star architecture relative to the total mass of the polymer in the sample. In some embodiments, the functional polymers of the present invention disclosed herein based on functionalized styrene monomers containing nitrogen-containing moieties and including star polymer architectures may 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%. In one embodiment, the functional polymer of the present invention disclosed herein, based on a functionalized styrene monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, may be a hydrogenated copolymer of 1-benzylmethylamino-3-phenylbut-3-ene and isoprene, comprising 10.0 to 20.0% by mass of repeat units corresponding to the reactive form of 1-benzylmethylamino-3-phenylbut-3-ene and having a peak average molecular weight of 45.0 to 65.0 kDa.

[0030] In one embodiment, the functional polymer of the present invention disclosed herein, based on a functionalized styrene monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, may be a hydrogenated copolymer of 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene and isoprene, comprising 5.0 to 10.0% by mass of repeat units corresponding to the reactive form of 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene and having a peak average molecular weight of 24.0 to 42.0 kDa. In one embodiment, the functional polymer of the present invention disclosed herein, based on a functionalized styrene monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, may be a hydrogenated copolymer of 1-(N-morpholinyl)-3-phenylbut-3-ene and isoprene, comprising 4.0 to 5.0% by mass of repeat units corresponding to the reactive form of 1-(N-morpholinyl)-3-phenylbut-3-ene and having a peak average molecular weight of 36.0 to 46.0 kDa. In one embodiment, the functional polymer of the present invention disclosed herein, based on a functionalized styrene monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, may be a hydrogenated copolymer of 1-benzylphenylamino-3-phenylbut-3-ene and isoprene, comprising 5.0 to 7.0% by mass of repeat units corresponding to the reactive form of 1-benzylphenylamino-3-phenylbut-3-ene and having a peak average molecular weight of 140.0 to 180.0 kDa.

[0031] In some embodiments, the functional polymers of the present invention disclosed herein are based on functionalized styrenic monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring or on functionalized conjugated (non-aromatic) monomers containing nitrogen-containing moieties, and may optionally be further post-polymerization modified to modify their structures. In some embodiments, the post-polymerization modification is hydrogenation. In the methods of the present disclosure, hydrogenation can be carried out by known catalyst systems including heterogeneous and soluble systems. Soluble systems are disclosed in U.S. Patent No. 4,284,835, columns 1, line 65 to column 9, line 16, and U.S. Patent No. 4,980,331, columns 3, line 40 to column 6, line 28, both of which are incorporated herein by reference.

[0032] The hydrogenated copolymers described above may be partially or substantially hydrogenated. In the context of the present disclosure, being partially hydrogenated means that 10% to 90%, or 20% to 90%, or 30% to 90%, or 40% to 90% of the non-aromatic double bonds are saturated. Being substantially hydrogenated means that more than 90%, or more than 92%, or more than 94%, or more than 96%, or more than 98%, or more than 99%, or more than 99.5%, or more than 99.9% of the non-aromatic bonds are saturated.

[0033] Additional teachings regarding hydrogenation can be found in Rachapudy et al., Journal of Polymer Science: Polymer Physics Edition, Vol. 17, pp. 1211 - 1222 (1979), which is incorporated herein by reference in its entirety. Table 1 of this paper discloses several systems containing palladium supported on various supports (including not only calcium carbonate but also barium sulfide). The paper by Rachapudy et al. discloses the preparation of homogeneous and heterogeneous catalysts. Additional teachings regarding hydrogenation methods and catalysts are disclosed in U.S. Patent Nos. 4,284,835 and 4,980,331, both of which are hereby incorporated by reference in their entirety. In some embodiments, the post-polymerization modification may be a deprotection reaction that removes a cleavable chemical protecting group from the repeat units of structure (V), (VIII), or combinations thereof. A cleavable chemical protecting group means a chemical group that is inert under the polymerization reaction conditions but can be removed by a post-polymerization chemical reaction to yield a free -NH- functional group or a free -NH2 functional group of the ADAMS repeat unit. In one such form, a preferred cleavable chemical protecting group is a benzyl group and the deprotection reaction is a hydrogenation reaction.

[0034] Embodiment 1 of the copolymer of the present invention and use in lubricants In one form of the copolymer of the present invention disclosed herein, the copolymer comprises (a) 10.0 - 20.0% by mass of amine - derivatized alpha - methylstyrene (ADAMS) repeat units according to structure (I),

Chemical formula

[0035] The copolymer may alternatively, but not limited to these, be derived from a monofunctional initiator including alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and may include alkyl residues present at one or more terminals of the polymer backbone. Examples of the alkyl residues derived from the monofunctional initiator include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-amyl group, iso-amyl group, sec-amyl group, tert-amyl group, hexyl group, or combinations thereof. The copolymer includes one or more blocks, and one or more polymer blocks of the copolymer form a dispersed polymer architecture, diblock, triblock, tetrablock, pentablock, hexablock, star polymer architecture, or combinations thereof. The copolymer of this embodiment is useful as an additive for lubricating oil compositions. More specifically, the copolymer of this embodiment can be used as a viscosity modifier, friction modifier, dispersant, antiwear agent, or combinations thereof in lubricating oil compositions. Preferably, the copolymer of this embodiment can be used as a viscosity modifier for lubricating oil compositions. More specifically, the lubricating oil composition may or can be obtained by mixing and containing (i) at least 50% by mass of one or more base oils based on the mass of the lubricating oil composition, (ii) one or more dispersants, (iii) one or more detergents, and (iv) one or more copolymers of this example.

[0036] 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, and 50. Alternatively, the lubricating oil composition of this embodiment may contain (i) one or more base oils in an amount of 50 to 99% by mass based on the mass of the lubricating oil composition, (ii) one or more dispersants in an amount of 0.01 to 20% by mass based on the total mass of the lubricating oil composition, (iii) one or more detergents in an amount of 0.10 to 20% by mass based on the mass of the lubricating oil composition, and (iv) one or more copolymers in an amount of 0.10 to 20% by mass based on the mass of the lubricating oil composition, or can be obtained by mixing them. Alternatively, the lubricating oil composition of this embodiment may further contain one, two, three, four, five, six, or more additional additives selected from, but not limited to, friction modifiers, antioxidants, pour point depressants, defoamers, viscosity modifiers, corrosion inhibitors and / or rust preventives, and antiwear agents.

[0037] Alternatively, the lubricating oil composition of this embodiment contains one or more friction modifiers in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition, one or more antioxidants in an amount of 0.01 to 10% by mass based on the total mass of the lubricating oil composition, one or more pour point depressants in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition, one or more antifoaming agents in an amount of 0.001 to 5% by mass based on the total mass of the lubricating oil composition, one or more viscosity modifiers in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition, one or more inhibitors and / or rust preventives in an amount of 0.0 to 5% by mass based on the total mass of the lubricating oil composition, and / or one or more antiwear agents in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition, and may further contain one, two, three, four, five, six or more thereof. One or more detergents of the composition may contain one or more oil-soluble neutral or overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble carboxylates of alkali metals or alkaline earth metals. One or more dispersants of the composition may contain one or more boricated or non-boricated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from polyamine.

[0038] The lubricating oil composition containing the copolymer of this embodiment is a method for lubricating an internal combustion engine during operation of the engine, and can be used in a method comprising: (i) supplying the lubricating oil composition to the crankcase of the internal combustion engine; (ii) supplying fuel to the internal combustion engine; and (iii) burning the fuel in the internal combustion engine. Non-limiting exemplary fuels include hydrocarbon fuels, renewable fuels, hydrogen fuels, or one or more of any blends thereof. The lubricating oil composition of this embodiment can be used as a lubricating oil composition for internal combustion engines including, but not limited to, natural gas engines, gasoline engines, diesel engines, and stationary engines.

[0039] Embodiment 2 of the copolymer of the present invention and its use in lubricants In another form of the copolymer of the present invention disclosed herein, the copolymer comprises: (a) 5.0 to 10.0% by mass of amine-derivatized alpha-methylstyrene (ADAMS) repeat units according to Structure (II),

Chemical formula

[0040] Alternatively, the copolymer is derived from a monofunctional initiator including, but not limited to, alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and may include an alkyl residue present at one or more terminals of the polymer backbone. Examples of the alkyl residue derived from the monofunctional initiator include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-amyl group, iso-amyl group, sec-amyl group, tert-amyl group, hexyl group, or combinations thereof. The copolymer includes one or more blocks, and one or more polymer blocks of the copolymer form a dispersed polymer architecture, diblock, triblock, tetrablock, pentablock, hexablock, star polymer architecture, or combinations thereof.

[0041] The copolymer of this embodiment is also useful as an additive for lubricating oil compositions. More specifically, the copolymer of this embodiment can be used as a viscosity modifier, friction modifier, dispersant, antiwear agent, or combinations thereof in lubricating oil compositions. Preferably, the copolymer of this embodiment can be used as a viscosity modifier for lubricating oil compositions. More specifically, the lubricating oil composition may or can be obtained by mixing (i) at least 50% by mass of one or more base oils based on the mass of the lubricating oil composition, (ii) one or more dispersants, (iii) one or more detergents, and (iv) one or more copolymers of this example.

[0042] 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 contain (i) one or more base oils in an amount of 50 to 99% by mass based on the mass of the lubricating oil composition, (ii) one or more dispersants in an amount of 0.01 to 20% by mass based on the total mass of the lubricating oil composition, (iii) one or more detergents in an amount of 0.10 to 20% by mass based on the mass of the lubricating oil composition, and (iv) one or more copolymers in an amount of 0.10 to 20% by mass based on the mass of the lubricating oil composition, or can be obtained by mixing them. Alternatively, the lubricating oil composition of this embodiment may further contain one, two, three, four, five, six, or more additional additives selected from, but not limited to, friction modifiers, antioxidants, pour point depressants, antifoaming agents, viscosity modifiers, corrosion inhibitors and / or rust preventives, and antiwear agents.

[0043] Alternatively, the lubricating oil composition of this embodiment comprises: A) one or more friction modifiers in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition; B) one or more antioxidants in an amount of 0.01 to 10% by mass based on the total mass of the lubricating oil composition; C) one or more pour point depressants in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition; D) one or more antifoaming agents in an amount of 0.001 to 5% by mass based on the total mass of the lubricating oil composition; E) one or more viscosity modifiers in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition; F) one or more inhibitors and / or rust preventives in an amount of 0.0 to 5% by mass based on the total mass of the lubricating oil composition; and / or G) one or more antiwear agents in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition, and may further contain one, two, three, four, five, six or more thereof. 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 carboxylates of alkali metals or alkaline earth metals. One or more dispersants of the composition may include one or more boricated or non-boricated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from polyamine.

[0044] The lubricating oil composition containing the copolymer of this embodiment is a method for lubricating an internal combustion engine during operation of the engine, and can be used in a method including: (i) supplying the lubricating oil composition to the crankcase of the internal combustion engine; (ii) supplying fuel to 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 for internal combustion engines including, but not limited to, natural gas engines, gasoline engines, diesel engines, and stationary engines.

[0045] Embodiment 3 of the copolymer of the present invention and use in lubricants In yet another form of the copolymer of the invention disclosed herein, the copolymer comprises (a) 4.0 to 6.0% by mass of amine-derivatized alpha-methylstyrene (ADAMS) repeat units according to structure (III),

Chemical formula

[0046] Alternatively, the copolymer is derived from a monofunctional initiator including, but not limited to, alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and may contain alkyl residues present at one or more terminals of the polymer backbone. Examples of alkyl residues derived from monofunctional initiators include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-amyl group, iso-amyl group, sec-amyl group, tert-amyl group, hexyl group, or combinations thereof. The copolymer includes one or more blocks, and one or more polymer blocks of the copolymer form a dispersed polymer architecture, diblock, triblock, tetrablock, pentablock, hexablock, star polymer architecture, or combinations thereof.

[0047] The copolymer of this embodiment is also useful as an additive for lubricating oil compositions. More specifically, the copolymer of this embodiment can be used as a viscosity modifier, a friction modifier, 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 modifier for a lubricating oil composition. More specifically, the lubricating oil composition may or can be obtained by mixing (i) at least 50% by mass of one or more base oils based on the mass of the lubricating oil composition, (ii) one or more dispersants, (iii) one or more detergents, and (iv) one or more copolymers of this example.

[0048] 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 or can be obtained by mixing (i) 50 to 99% by mass of one or more base oils based on the mass of the lubricating oil composition, (ii) 0.01 to 20% by mass of one or more dispersants based on the total mass of the lubricating oil composition, (iii) 0.10 to 20% by mass of one or more detergents based on the mass of the lubricating oil composition, and (iv) 0.10 to 20% by mass of one or more copolymers based on the mass of the lubricating oil composition. Alternatively, the lubricating oil composition of this embodiment may further contain one, two, three, four, five, six, or more additional additives selected from, but not limited to, friction modifiers, antioxidants, pour point depressants, antifoaming agents, viscosity modifiers, corrosion inhibitors and / or rust preventives, and antiwear agents.

[0049] Alternatively, the lubricating oil composition of this embodiment comprises: A) one or more friction modifiers in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition; B) one or more antioxidants in an amount of 0.01 to 10% by mass based on the total mass of the lubricating oil composition; C) one or more pour point depressants in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition; D) one or more antifoaming agents in an amount of 0.001 to 5% by mass based on the total mass of the lubricating oil composition; E) one or more viscosity modifiers in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition; F) one or more inhibitors and / or rust inhibitors in an amount of 0.0 to 5% by mass based on the total mass of the lubricating oil composition; and / or G) one or more antiwear agents in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition, and may further contain one, two, three, four, five, six or more thereof. One or more detergents in the composition may include one or more oil-soluble neutral or overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble carboxylates of alkali metals or alkaline earth metals. One or more dispersants in the composition may include one or more boricated or non-boricated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from polyamine.

[0050] The lubricating oil composition containing the copolymer of this embodiment is a method for lubricating an internal combustion engine during operation of the engine, and can be used in a method comprising: (i) supplying the lubricating oil composition to the crankcase of the internal combustion engine; (ii) supplying fuel to 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 for internal combustion engines including, but not limited to, natural gas engines, gasoline engines, diesel engines, and stationary engines.

[0051] Embodiment 4 of the copolymer of the present invention and its use in lubricants In yet another form of the copolymer of the present invention disclosed herein, the copolymer comprises (a) one or more amine-derivatized alpha-methylstyrene (ADAMS) repeat units of structure (IV),

Chemical formula

[0052] Alternatively, the copolymer is derived from a monofunctional initiator including, but not limited to, alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and may contain alkyl residues present at one or more terminals of the polymer backbone. Examples of alkyl residues derived from monofunctional initiators include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-amyl group, iso-amyl group, sec-amyl group, tert-amyl group, hexyl group, or combinations thereof. The copolymer includes one or more blocks, and one or more polymer blocks of the copolymer form a dispersed polymer architecture, diblock, triblock, tetrablock, pentablock, hexablock, star polymer architecture, or combinations thereof.

[0053] The copolymer of this embodiment is also useful as an additive for a lubricating oil composition. More specifically, the copolymer of this embodiment can be used as a viscosity modifier, a friction modifier, 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 modifier for a lubricating oil composition. More specifically, the lubricating oil composition may or can be obtained by mixing (i) at least 50% by mass of one or more base oils based on the mass of the lubricating oil composition, (ii) one or more dispersants, (iii) one or more detergents, and (iv) one or more copolymers of this example.

[0054] 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 or can be obtained by mixing (i) 50 to 99% by mass of one or more base oils based on the mass of the lubricating oil composition, (ii) 0.01 to 20% by mass of one or more dispersants based on the total mass of the lubricating oil composition, (iii) 0.10 to 20% by mass of one or more detergents based on the mass of the lubricating oil composition, and (iv) 0.10 to 20% by mass of one or more copolymers based on the mass of the lubricating oil composition. Alternatively, the lubricating oil composition of this embodiment may further contain one, two, three, four, five, six, or more additional additives selected from, but not limited to, friction modifiers, antioxidants, pour point depressants, antifoaming agents, viscosity modifiers, corrosion inhibitors and / or rust preventives, and anti-wear agents.

[0055] Alternatively, the lubricating oil composition of this embodiment comprises: A) one or more friction modifiers in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition; B) one or more antioxidants in an amount of 0.01 to 10% by mass based on the total mass of the lubricating oil composition; C) one or more pour point depressants in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition; D) one or more antifoaming agents in an amount of 0.001 to 5% by mass based on the total mass of the lubricating oil composition; E) one or more viscosity modifiers in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition; F) one or more inhibitors and / or rust inhibitors in an amount of 0.0 to 5% by mass based on the total mass of the lubricating oil composition; and / or G) one or more antiwear agents in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition, and may further contain one, two, three, four, five, six or more thereof. 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 carboxylates of alkali metals or alkaline earth metals. One or more dispersants of the composition may include one or more boricated or non-boricated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from polyamine.

[0056] The lubricating oil composition containing the copolymer of this embodiment is a method for lubricating an internal combustion engine during operation of the engine, and can be used in a method including: (i) supplying the lubricating oil composition to the crankcase of the internal combustion engine; (ii) supplying fuel to the internal combustion engine; and (iii) burning the fuel in the internal combustion engine. Non-limiting and 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 for internal combustion engines including, but not limited to, natural gas engines, gasoline engines, diesel engines, and stationary engines.

[0057] Method for Producing an ADAMS Copolymer Novel polymers of functionalized styrenic monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring can be produced by anionic polymerization.

[0058] Anionic polymerization methods in which there are no functionalized styrenic monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring are generally 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 entirety. 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 conversion is substantially complete; (b) optionally, adding one or more monomers of the same or different composition in one or more sequential additions to allow polymerization of each sequential addition of said monomers until conversion is substantially complete; (c) optionally, adding a polyfunctional coupling agent to couple some or all of the polymer or copolymer; (d) adding a terminating agent.

[0059] Anionic polymerization is generally initiated using an alkyllithium reagent, most frequently sec-butyllithium, although other monofunctional and difunctional alkyllithium initiators can 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)]. The monofunctional initiator that can be used may generally be an alkyllithium compound, an alkylsodium compound, or an alkylpotassium compound in the range of C2 - C12. Alkyllithium compounds, such as, for example, methyllithium, ethyllithium, n - propyllithium, isopropyllithium, n - butyllithium, iso - butyllithium, sec - butyllithium, tert - butyllithium, n - amylithium, iso - amylithium, sec - amylithium, tert - amylithium, hexyllithium, or combinations thereof are preferred. Secondary alkyllithium compounds, such as, for example, sec - butyllithium, sec - amylithium, or combinations thereof are more preferred. sec - Butyllithium is most preferred. Substituted alkyllithium, such as aralkyllithium compounds, such as benzyllithium, 1 - lithioethylbenzene, and 1 - lithio - 3 - methylpentylbenzene can also be used.

[0060] The functionalized styrenic monomer containing a nitrogen - containing moiety other than as a pendant to the phenyl ring can be copolymerized with isoprene. The novel polymer of the functionalized styrenic monomer containing a nitrogen - containing moiety other than as a pendant to the phenyl ring can be prepared by an anionic polymerization method in which the monomer or combinations thereof are polymerized in a solution of an inert hydrocarbon solvent in the presence of an alkyllithium initiator. The inert hydrocarbon solvent does not react with the alkyllithium initiator or the "living" anionic chain ends of the polymer backbone and provides suitable solubility characteristics to the product polymer, and may generally be any hydrocarbon having 5 - 8 carbon atoms or mixtures thereof. Non - limiting examples of suitable solvents are cyclic alkanes, such as, for example, 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 function effectively under a given set of process conditions, and one of the main factors to be considered would be the polymerization temperature.

[0061] The polymerization is preferably carried out in the presence of a polar additive that reduces the association between the ions of the reactive "living" anionic chain ends of the polymer backbone, thereby facilitating the polymerization. Non-limiting examples of polar additives include various ethers (i.e., dimethyl ether, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, anisole, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dimethoxybenzene, and 1-methoxy-2-(2-methoxyethoxy)ethane, etc.), various amines (i.e., trimethylamine, triethylamine, N,N,N',N'-tetramethylethylenediamine, and N,N,N',N'',N''-pentamethyldiethylenetriamine, etc.), or combinations thereof. Of the above polar additives, ethers are preferred. Diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, or combinations thereof are more preferred.

[0062] Polymerization reaction conditions for preparing novel polymers of functionalized styrenic monomers containing nitrogen-containing moieties other than as pendants to a phenyl ring are typically similar to those commonly used for anionic polymerization. Depending on the monomer and reaction solvent, the polymerization reaction can be carried out at a temperature of about -80°C to about 200°C, alternatively 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 cases, the polymerization of functionalized monomers and copolymerization with other monomers and blocks can be carried out at room temperature, or alternatively at 15-70°C, alternatively at 20-60°C, alternatively at 25-50°C, or a combination of such aforementioned temperatures, or individual temperatures within such ranges.

[0063] The polymerization reaction is carried out under a dry inert atmosphere, preferably under nitrogen, and may be carried out under a pressure in the range of about 0 bar to about 10 bar. Once the polymerization reaction is complete, a terminating agent may be added to stop the reaction and quench the reactive "living" anionic chain ends of the polymer backbone. The polymerization terminating agent may be any of various primary or secondary alcohols or epoxide terminating agents. Non-limiting examples of various primary or secondary alcohols include methanol, ethanol, isopropanol, and 2-ethyl-1-hexanol, etc., or combinations thereof. Non-limiting examples of epoxide terminating agents include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, and phenyl glycidyl ether, etc., or combinations thereof. Among the polymerization terminating agents, if one or more -OH functional groups are desired at one or more ends of the polymer chain, ethylene oxide or propylene oxide is preferred, and except for that case, methanol or isopropanol is preferred. The novel polymers of functionalized styrenic monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring may optionally be isolated or purified by various common polymer isolation or purification techniques known in the art, such as pouring the polymerization reaction solution into a poor solvent for the polymer, such as methanol, to solidify the polymer, or pouring the polymerization reaction solution into hot water together with steam to remove the solvent by azeotropy (steam stripping) and drying the resulting product. The inventive monomers disclosed in U.S. Patent Application No. 63 / 483,365 have not been polymerized previously to the best of the applicant's knowledge.

[0064] Concentrate A concentrate, also referred to as an additive package, adpak, or addpack, has less than 50% by weight (e.g., less than 40% by weight, e.g., less than 30% by weight, e.g., less than 25% by weight, e.g., less than 20% by weight) of a base oil and lubricant composition additives (e.g., those described herein) and is typically a composition that is then further blended with additional base oil to form a lubricating oil product.

[0065] The present disclosure relates to (a) one or more base oils in an amount of from 1 to less than 50% by weight (alternatively 5 to 45% by weight, alternatively 7 to 40% by weight, alternatively 10 to 35% by weight, alternatively 10 to 25% by weight) based on the weight of the lubricating composition, (b) 0.10 to 20% by weight (in particular 0.2 to 15% by weight, alternatively 0.5% to 10% by weight, alternatively 1 to 7% by weight) of the following, based on the weight of the composition: I. (a) 10.0 to 20.0% by weight of amine-derivatized alpha-methylstyrene (ADAMS) repeat units of structure (I),

Chemical formula

Chemical formula

[0066] The present disclosure is a concentrate composition, (i) Based on the mass of the composition, 1 to less than 50% by mass (alternatively 5 to 45% by mass, alternatively 7 to 40% by mass, alternatively 10 to 35% by mass, alternatively 10 to 25% by mass) of one or more base oils, (ii) Based on the mass of the composition, 0.10 to 20% by mass (particularly 0.15 to 10% by mass, alternatively 0.20% to 5% by mass, alternatively 0.25 to 2% by mass) of one or more detergents, (iii) Based on the mass of the composition, 0.10 to 20% by mass (particularly 0.15 to 10% by mass, alternatively 0.20% to 5% by mass, alternatively 0.25 to 2% by mass) of one or more dispersants (e.g., PIBSA-PAM), and (iv) Based on the mass of the composition, 0.10 to 20% by mass (particularly 0.15 to 10% by mass, alternatively 0.20% to 5% by mass, alternatively 0.25 to 2% by mass) of one or more of the copolymers of the present invention described herein, (v) Optional additional components, antioxidants, pour point depressants, antifoaming agents, viscosity modifiers, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibility agents, additive diluent base oils, friction modifiers (e.g., organic FMs, e.g., organic esters, e.g., fatty acid esters), etc. It relates to a concentrate composition obtained by including or mixing

[0067] In an embodiment, the concentrate composition may optionally not contain a solvent (e.g., an aliphatic solvent or an aromatic solvent) and / or may not contain a functionalized base oil.

[0068] Further, the present disclosure provides a concentrate composition comprising: A) one or more base oils in an amount of 1 to less than 50% by mass (alternatively 5 to 45% by mass, alternatively 7 to 40% by mass, alternatively 10 to 35% by mass, alternatively 10 to 25% by mass) based on the mass 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 (particularly 0.15 to 10% by mass, alternatively 0.20% by mass to 5% by mass, alternatively 0.25 to 3% by mass) based on the mass of the concentrate composition; C) one or more detergents (e.g., a blend of detergents) in an amount of 0.1 to 20% by mass (particularly 0.5 to 10% by mass, alternatively 2 to 6% by mass) based on the total mass of the concentrate composition; D) optionally, one or more friction modifiers (e.g., an organic friction modifier such as glycerol monooleate) in an amount of 0.01 to 5% by mass (particularly 0.1 to 4% by mass, alternatively 0.25 to 3% by mass, alternatively 0.25 to 0.075% by mass) based on the total mass of the concentrate composition; E) optionally, one or more antioxidants (e.g., a blend of antioxidants) in an amount of 0.01 to 20% by mass (particularly 0.01 to 15% by mass, alternatively 0.1 to 10% by mass) based on the total mass of the concentrate composition; F) optionally, one or more pour point depressants (e.g., a blend of pour point depressants) in an amount of 0.01 to 5% by mass (particularly 0.01 to 3% by mass, alternatively 0.1 to 1.5% by mass) based on the total mass of the concentrate composition; G) optionally, one or more antifoaming agents (e.g., a blend of antifoaming agents) in an amount of 0.001 to 5% by mass (particularly 0.01 to 3% by mass, alternatively 0.02 to 1% by mass) based on the total mass of the concentrate composition; I) optionally, one or more dispersants (e.g., a blend of dispersants) in an amount of 0.01 to 40% by mass (particularly 0.1 to 30% by mass, alternatively 1 to 20% by mass) based on the total mass of the concentrate composition; (K) Based on the total mass of the lubricating composition, one or more antiwear agents (e.g., a blend of antiwear agents, e.g., ZDDP) in an amount of 0.001 to 10% by mass (particularly 0.1 to 8% by mass, alternatively 1 to 5% by mass, alternatively 0.25 to 0.75% by mass). It relates to a concentrate composition obtained by including or mixing such.

[0069] Optionally, the concentrate may not contain a functionalized oil. In an embodiment, the concentrate composition may optionally not contain a solvent (e.g., an aliphatic solvent or an aromatic solvent) and / or may not contain a functionalized base oil. Optionally, the concentrate may not contain a phenolic antioxidant. In an embodiment, the concentrate may contain boron in an amount less than 75 ppm, alternatively less than 60 ppm, alternatively 1 to 70 ppm. Alternatively, the concentrate may not contain boron. In an embodiment, the concentrate may contain less than 20 (e.g., 15, e.g., 10, e.g., 5, e.g., 3, e.g., 1) mass% of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), e.g., PIBSA - PAM. In an embodiment, the concentrate substantially does not contain a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), e.g., PIBSA - PAM, or the concentrate does not contain a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), e.g., PIBSA - PAM.

[0070] In an embodiment, the concentrate may optionally contain an acylated polymer having an Mn of 500 to 50,000 g / mol, e.g., 600 to 5,000 g / mol, e.g., 700 to 3000 g / mol, e.g., polyisobutylene succinic acid. In an embodiment, the concentrate may contain an acylated polymer having an Mn of 500 to 1600 g / mol, e.g., 700 to 1200 g / mol, e.g., polyisobutylene succinic acid. In an embodiment, the concentrate may contain 20 (e.g., 15, e.g., 10, e.g., 5, e.g., 3, e.g., 1) mass % or less of a block copolymer, such as a block, star, random, and / or tapered block copolymer. In an embodiment, the concentrate may substantially not contain a block copolymer, such as a block, star, random, and / or tapered block copolymer, or there may be no block copolymer, such as a block, star, random, and / or tapered block copolymer in the concentrate.

[0071] In an embodiment, the concentrate may contain 20 mass % or less (e.g., 15 mass % or less, e.g., 10 mass % or less, e.g., 5 mass % or less, e.g., 3 mass % or less, e.g., 1 mass % or less) of a styrenic copolymer, such as a block, star, random, and / or tapered styrenic block copolymer. In an embodiment, the concentrate may not substantially contain a styrenic copolymer, such as a block, star, random, and / or tapered styrenic block copolymer, or there may be no styrenic copolymer, such as a block, star, random, and / or tapered styrenic block copolymer in the concentrate. In an embodiment, the concentrate may contain less than 20 mass % (e.g., less than 15 mass %, e.g., 10 mass %, e.g., less than 5 mass %, e.g., less than 3 mass %, e.g., 1 mass %) of a functionalized diluent, such as a functionalized oil. In an embodiment, the concentrate may not substantially contain a functionalized diluent, such as a functionalized oil, or there may be no functionalized diluent, such as a functionalized oil in the concentrate. In an embodiment, the concentrate may contain less than 0.5 mass % (e.g., less than 0.4 mass %, e.g., less than 0.3 mass %, e.g., less than 0.2 mass %, e.g., 0.1 mass %, substantially not present, or zero mass %) of a secondary hydrocarbylamine compound and a tertiary hydrocarbylamine compound based on the mass of the concentrate.

[0072] In an embodiment, the concentrate may substantially lack a secondary hydrocarbylamine compound and a tertiary hydrocarbylamine compound, or the concentrate may not contain a secondary hydrocarbylamine compound and a tertiary hydrocarbylamine compound. In an embodiment, 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. The present disclosure also relates to a method for producing a concentrated composition comprising combining (a) one or more base oils in an amount of 1 to less than 50% by weight (alternatively 5 to 45% by weight, alternatively 7 to 40% by weight, alternatively 10 to 35% by weight, alternatively 10 to 25% by weight) based on the mass of the lubricating composition, and (b) 0.10 to 20% by weight (particularly 0.2 to 15% by weight, alternatively 0.5% to 10% by weight, alternatively 1 to 7% by weight) of one or more of the copolymers of the present invention described herein based on the mass of the composition.

[0073] Lubricating oil composition components and concentrate components A. Base oil Base oils useful herein (also referred to as "base stocks", "lubricating oil base stocks", or "lubricating viscosity oils") may be a single oil or a blend of multiple oils and are typically the major liquid component of a lubricating composition, also called a lubricant, to which additives and optionally additional oils are blended to produce, for example, a lubricating composition, such as a final lubricant composition, a concentrate, or other lubricating composition. The base oil can be selected from vegetable oils, animal oils, mineral oils, synthetic lubricating oils, and mixtures thereof. In terms of viscosity, the base oil can range from light distillate mineral oils to heavy lubricating oils, such as those for gas engine oils, mineral lubricating oils, power vehicle oils, and large diesel oils. Generally, the kinematic viscosity of the base oil at 100 °C (“KV100”) is determined in accordance with ASTM D445-19a and is in the range of 1 to 30, for example 2 to 25 cSt, for example 5 to 20 cSt, in particular 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 viscosity (HTHS) of the base oil at 150 °C is determined in accordance with ASTM D4683-20 and is in the range of 0.5 to 20 cP, for example 1 to 10 cP, for example 2 to 5 cP.

[0074] Typically, when producing a concentrate using a lubricating oil base stock, the lubricating oil base stock may advantageously be present in a concentrate-forming amount that results in a concentrate containing 5% to 80%, 10% to 70%, or 5% to 50% by mass of active ingredient, based on the mass of the concentrate. General oils useful as base oils include animal and vegetable oils (e.g., castor oil and lard oil), liquid petroleum, and paraffinic, naphthenic, and paraffinic-naphthenic mixed type hydrorefined and / or solvent-treated mineral lubricating oils. Oils derived from coal or shale are also useful base oils. The base stock can be produced using a variety of different methods including, but not limited to, distillation, solvent refining, hydrotreating, oligomerization, esterification, and re-refining.

[0075] Synthetic lubricating oils useful herein as base oils include hydrocarbon oils such as polyalphaolefins or PAO or Group IV base oils, which are homopolymers and copolymers of olefins [see API EOLCS 1509 definition (API Publication 1509, Section E.1.3, 19th Edition, January 2021, www.API.org)]. Examples of PAO useful as base oils include poly(ethylene), copolymers of ethylene and propylene, polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene), C8~C 20 Homopolymers or copolymers of alkenes, C8 and / or C 10 And / or C 12 Homopolymers or copolymers of alkenes, C8 / C 10 Copolymers, C8 / C 10 / C 12 Copolymers, and C 10 / C 12 Copolymers, and derivatives, analogs, and homologs thereof.

[0076] In another embodiment, the base oil has a kinematic viscosity at 100 °C (measured by ASTM D445) of 10 or more, preferably, as determined by ASTM D2270, a viscosity index ("VI") of 100 or more, preferably 110 or more, more preferably 120 or more, more preferably 130 or more, more preferably 140 or more, and / or a pour point (measured by ASTM D97) of -5 °C or less, more preferably -10 °C or less, more preferably -20 °C or less, and may include a polyalphaolefin containing oligomers of linear olefins having 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, more preferably 10 carbon atoms.

[0077] In another embodiment, the polyalphaolefin oligomers useful in the present disclosure are C 20 ~C 1500 Paraffins, preferably C 40 ~C 1000 Paraffins, preferably C50 ~C 750 Paraffin, preferably C 50 ~C 500 may contain paraffin. The PAO oligomer, in one embodiment, is C5-C 14 alpha-olefin, and in another embodiment C6-C 12 alpha-olefin, and in another embodiment C8-C 12 dimers, trimers, tetramers, pentamers, etc. of alpha-olefins. 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 alternatively may be substantially 1-decene, and the PAO is a mixture of these dimers, trimers, tetramers, and pentamers (and higher order species). Useful PAOs are described in more detail, for example, in U.S. Patent Nos. 5,171,908 and 5,783,531, and on pages 1-52 of Synthetic Lubricants and High-Performance Functional Fluids (edited by Leslie R. Rudnick & Ronald L. Shubkin, Marcel Dekker, Inc., 1999).

[0078] The PAOs useful in the present disclosure typically have a number average molecular weight of, in one embodiment, 100-21,000 g / mol, in another embodiment 200-10,000 g / mol, in yet another embodiment 200-7,000 g / mol, in yet another embodiment 200-2,000 g / mol, and in yet another embodiment 200-500 g / mol. Desirable PAOs are commercially available as SpectraSyn™ Hi-Vis, SpectraSyn™ Low-Vis, SpectraSyn™ plus, SpectraSyn™ Elite PAO (ExxonMobil Chemical Company, Houston, Texas) and Durasyn PAO from Ineos Oligomers USA LLC.

[0079] Synthetic lubricating oils useful as base oils include hydrocarbon oils such as homopolymerized and copolymerized alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (e.g., biphenyl, terphenyl, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides; as well as derivatives, analogs, and homologs thereof. Another suitable type of synthetic lubricating oil useful as a base oil includes esters of 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) reacted with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of such esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl 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.

[0080] Esters useful as synthetic oils herein include those made from C5 to C 12 monocarboxylic acids and polyols, as well as polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Desirable ester base oils are commercially available as Esterex (trademark) esters (ExxonMobil Chemical Company, Houston, Texas). Silicon-based oils, such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysilicone oils and silicate oils, constitute another useful type of synthetic lubricants useful herein. Such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl) disiloxane, poly(methyl) siloxane, and poly(methylphenyl)-siloxane.

[0081] Other synthetic lubricating oils useful herein include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid), and polymeric tetrahydrofuran.

[0082] Unrefined oils, refined oils, and re-refined oils can be used in the lubricating compositions of the present disclosure. Unrefined oils are oils obtained directly from natural or synthetic sources without further refining treatment. For example, shale oil obtained directly from a retorting operation, petroleum obtained directly from distillation, or ester oils obtained directly 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 refining steps to improve one or more properties. Many such refining techniques, such as distillation, solvent extraction, acid or base extraction, filtration, and percolation, are used by those skilled in the art. Re-refined oils are oils obtained by a method similar to the method used to obtain refined oils, to which a refining method is applied to what was once a refined oil that had been previously used in service. Such re-refined oils are also called regenerated oils or reprocessed oils and are often additionally treated to remove spent additives and oil decomposition products. Re-refined base oils preferably substantially do not contain substances introduced by manufacture, contamination, or previous use.

[0083] Other examples of useful base oils are gas-to-liquid (GTL) base oils, i.e., base oils that are derived from hydrocarbons produced from synthesis gas (''syn gas'') containing H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing to be useful as base oils. For example, such hydrocarbons may be hydroisomerized, hydrocracked and hydroisomerized, dewaxed, or hydroisomerized and dewaxed by methods known in the art. Further information regarding useful GTL base oils and blends thereof can be found in 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).

[0084] In particular, herein, oils derived from renewable resources, i.e., carbon and energy captured from the environment, e.g., based in part on biological resources, are useful. Various base oils are often classified as Group I, II, III, IV, or V according to the API EOLCS 1509 definition (American Petroleum Institute Publication 1509, Section E.1.3, 19th Edition, January 2021, www.API.org). Generally speaking, Group I base stocks have a viscosity index of about 80 - 120 and contain more than about 0.03% sulfur and / or less than about 90% saturates. Group II base stocks have a viscosity index of about 80 - 120 and contain about 0.03% or less sulfur and about 90% or more saturates. Group III base stocks have a viscosity index higher than about 120 and contain about 0.03% or less sulfur and more than about 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 D2270, saturates are measured by ASTM D2007, and sulfur is measured by ASTM D5185, D2622, ASTM D4294, ASTM D4927, and ASTM D3120).

[0085] The base oils for use in the formulated lubricating compositions useful in the present disclosure are any one, two, three, or more of the various oils described herein. In a preferred embodiment, the base oils for use in the formulated lubricating compositions useful in 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 Group III, Group III+, IV, and Group V base oils because of their excellent volatility, stability, viscosity, and clarity characteristics. Small amounts of Group I base stock, for example, in an amount used to dilute additives for blending into a formulated lubricating oil product, can be tolerated but are typically minimized, for example, to an amount only relevant to use as a diluent / carrier oil for the additives used on a "received" basis. With respect to Group II stock, it is more useful for the Group II base stock to be in a higher quality range in relation to that stock, i.e., a Group II stock having a viscosity index in the range of 100 - 120.

[0086] The base oils useful herein can be selected from either synthetic oils, natural oils, or re-refined oils (e.g., those typically used as crankcase lubricants for spark-ignition engines and compression-ignition engines). Optionally, mixtures of synthetic base oils and / or natural base oils and / or re-refined base oils may be used. Optionally, multimodal mixtures (e.g., bimodal or trimodal mixtures) of Group I, II, III, IV, and / or V base stocks may be used. The base oil or base oil blend used in this specification preferably has a kinematic viscosity at 100 °C (KV100, measured according to ASTM D445-19a and reported in units of centistokes (cSt) or mm2 / s equivalent thereto) of about 2 to about 40 cSt, alternatively 3 to 30 cSt, alternatively 4 to 20 cSt at 100 °C, alternatively 5 to 10 cSt. Alternatively, the base oil or base oil blend may 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. The base oil or base oil blend preferably has a saturation content of at least 65% by mass, more preferably at least 75% by mass, such as at least 85% by mass, such as at least 90% by mass, as determined by ASTM D2007.

[0087] Preferably, the base oil or base oil blend has a sulfur content of less than 1% by mass, preferably less than 0.6% by mass, most preferably less than 0.4% by mass, such as less than 0.3% by mass, based on the total mass of the lubricating composition, as measured by ASTM D5185. In an embodiment, the volatility of the base oil or base oil blend is 30% by mass or less, such as 25% by mass or less, such as 20% by mass or less, such as 16% by mass or less, such as 12% by mass or less, such as 10% by mass or less, based on the total mass of the lubricating composition, as measured by the Noack test (ASTM D5800, Procedure B). In an embodiment, the viscosity index (VI) of the base oil is at least 95, preferably at least 110, more preferably at least 120, even more preferably at least 125, most preferably about 130 to 240, particularly about 105 to 140 (determined by ASTM D2270). A large amount of base oil may be provided in combination with one or more small amounts of additive components as described hereinafter that constitute the lubricant. This preparation can be achieved by adding the additive directly to the oil, or by adding one or more additives in the form of their concentrates and dispersing or dissolving the additives. The additives can be added to the oil by any method known to those skilled in the art, either before the addition of other additives, simultaneously with the addition, or after the addition.

[0088] The base oil may be provided in small amounts in combination with one or more small amounts of additive components as described below that make up the additive concentrate. This preparation can be achieved by adding the additive directly to the oil or by adding one or more additives in the form of their solutions, slurries, or suspensions to disperse or dissolve the additives in the oil. The additives can be added to the oil by any method known to those skilled in the art, either before, simultaneously with, or after the addition of other additives. The base oil typically constitutes the main component of the engine oil lubricant composition of the present disclosure and is typically present in an amount in the range of about 50 to about 99% by mass, preferably about 70 to about 95% by mass, more preferably about 80 to about 95% by mass, based on the total mass of the composition.

[0089] Typically, one or more base oils are present in the lubricating composition in an amount of 32% by mass or more, alternatively 55% by mass or more, alternatively 60% by mass or more, alternatively 65% by mass or more, based on the total mass of the lubricating composition. Typically, one or more base oils are present in the lubricating composition in an amount of 98% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less. Alternatively, one or more base oils are present in the lubricating composition in an amount of 1 to 99% by mass, alternatively 50 to 97% by mass, alternatively 60 to 95% by mass, alternatively 70 to 95% by mass, based on the mass of the lubricating composition.

[0090] The base oils described above and their blends are also useful in the production of concentrates and in the production of lubricants therefrom. The concentrate is a convenient means for facilitating the handling of additives before use and the dissolution or dispersion of additives in lubricants. When preparing a lubricant containing more than one type of additive (sometimes referred to as an "additive component"), 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 called an "add pack") containing one or more additives / coconut additives as described below in a single concentrate.

[0091] Typically, one or more base oils are present in the concentrate composition in an amount of 50% by mass or less, alternatively 40% by mass or less, alternatively 30% by mass or less, alternatively 20% by mass or less, based on the total mass of the concentrate composition. Typically, one or more base oils are present in the concentrate composition in an amount of 0.1 to 49% by mass, alternatively 5 to 40% by mass, alternatively 10 to 30% by mass, alternatively 15 to 25% by mass, based on the mass of the concentrate composition. In embodiments, the acylation / functionalization reactions described herein may occur in the presence of a base oil diluent. As a by-product, a functionalized base oil may be produced. The oil itself may be acylated and / or functionalized. After the functionalization reactions described herein, for example, a maleated base oil or an aminated base oil may be present. It is contemplated that the functionalized base oil may include an acylated oil. It is contemplated that the functionalized base oil may include a reaction product of an acylated oil and an amine that forms an amide, imide, or a combination thereof. It is contemplated that the functionalized base oil may include both an acylated oil and a reaction product of an acylated oil and an amine that forms an amide, imide, or a combination thereof.

[0092] In embodiments, the lubricating oil composition and / or the concentrate composition may include a functionalized base oil, for example, an acylated oil and / or a reaction product of an acylated oil and an amine or alcohol that forms an amide, imide, ester, or a combination thereof, in an amount of 40% by mass or less, alternatively 20% by mass or less, alternatively 10% by mass or less, alternatively 5% by mass or less, based on the total mass of the concentrate composition. Typically, one or more functionalized base oils, for example, an acylated oil and / or a reaction product of an acylated oil and an amine or alcohol that forms an amide, imide, ester, or a combination thereof, are present in the concentrate in an amount of 0.01 to 40% by mass, alternatively 0.1 to 20% by mass, alternatively 1 to 10% by mass, alternatively 1.5 to 5% by mass, based on the mass of the concentrate composition.

[0093] Typically, one or more functionalized base oils, such as acylated oils, and / or reaction products of acylated oils with amines or alcohols that form amides, imides, esters, or combinations thereof are present in the lubricating oil composition in an amount of 0.01 to 40 wt%, alternatively 0.1 to 20 wt%, alternatively 1 to 10 wt%, alternatively 1.5 to 5 wt% based on the mass of the lubricating oil composition. In 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% based on the mass of the lubricating oil composition.

[0094] In embodiments, the functionalized oil 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% based on the mass of the concentrate composition. In embodiments, the acylation / functionalization reactions described herein may occur in a solvent-containing medium. As a by-product, a functionalized solvent may be formed. The solvent itself may be acylated and / or functionalized. In 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% based on the mass of the concentrate composition. In 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 mass of the lubricating oil composition.

[0095] B. Functionalized Polymer The present disclosure relates to a functionalized polymer comprising a polymer having an Mn of about 10,000 g / mol or more, such as 20,000 g / mol or more, such as 25,000 g / mol or more, such as 30,000 g / mol or more, such as 35,000 g / mol or more (GPC-PS) before functionalization. Alternatively, the functionalized polymer comprises a polymer having an Mn 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 (GPC-PS) before functionalization. The polymer before functionalization may have an Mw / Mn of less than 2 (determined by GPC-PS, such as less than 1.6, such as less than 1.5, such as less than 1.4, 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). The polymer before functionalization may contain repeat units of one or more olefins having 4 to 5 carbon atoms (preferably a conjugated diene having 4 to 5 carbon atoms). Before functionalization, the C 4~5 polymer is preferably fully or partially saturated (e.g., fully or partially hydrogenated). The functionalized polymer is C 4~5 obtainable by reacting the polymer with an acylating agent to form an acylated polymer, and then reacting the acylated polymer with an amine or alcohol to form an amide, imide, ester, or a combination thereof. The functionalized polymer is an acylated C 4~5 polymer (e.g., a commercially available maleated fully or partially hydrogenated C 4~5 polymer) can also be obtained by reacting it with an amine to form an amide, imide, or a combination thereof.

[0096] The present disclosure provides a fully or partially saturated (e.g., fully or partially hydrogenated) polymer of a conjugated diene having an Mw / Mn of less than 2, which is obtained by reacting with an acylating agent, such as maleic acid or maleic anhydride, and then reacting the acylated polymer with an amine (e.g., a polyamine) to form an imide, amide, or a combination thereof, as described herein. 4~5 C4~5 It further relates to amide, imide, and / or ester functionalized saturated (e.g., hydrogenated) polymers of conjugated dienes. This disclosure includes a C olefin polymer that contains one or more pendant amine groups and is at least partially (preferably completely) hydrogenated 4~5 relates to polymers that involve mixing an 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, an amide, or a combination thereof, or that result therefrom.

[0097] In embodiments, the functionalized polymer is not prepared in an aromatic solvent (e.g., benzene or toluene), or the aromatic solvent is present at 2 wt% or less (e.g., 1 wt% or less, e.g., 0.5 wt% or less) based on the mass of the solvent, diluent, and polymer. In embodiments, the functionalized polymer is not prepared in an alkylated naphthalene-based solvent, or the alkylated naphthalene-based solvent is present at 5 wt% or less (e.g., 3 wt% or less, e.g., 1 wt% or less) based on the mass of the solvent, diluent, and polymer. Polymers useful herein for preparing the functionalized polymer may be homopolymers such as butadiene or isoprene. In embodiments, the polymers useful herein for preparing the functionalized polymer may be homopolymers of isoprene, or copolymers of isoprene and less than 5 mol% (e.g., less than 3 mol%, e.g., less than 1 mol%, e.g., less than 0.1 mol%) of a comonomer.

[0098] Polymers useful herein for preparing functionalized polymers may be copolymers of isoprene with one or more of 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 at 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%].

[0099] Generally, 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; in the case of butadiene, 1,2-insertion is the same as 3,4-insertion). The polymerized conjugated diene polymers useful herein for preparing functionalized polymers are 1 Based on the sum of 2,1 insertions, 1,4 insertions, and 3,4 insertions of isoprene as measured by 1H NMR, contain at least about 50% 1,4-insertions, such as at least about 75% 1,4 insertions, such as at least about 80% 1,4 insertions, such as at least about 90% 1,4 insertions, such as at least about 95% 1,4 insertions, such as at least 98% 1,4 insertions. 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 insertions and 4,3 insertions.

[0100] Optionally, the polymers useful herein for preparing functionalized polymers may be free of styrene repeat units. Optionally, the functionalized hydrogenated / saturated polymers may be free of styrene repeat units. Optionally, the polymers useful herein for preparing functionalized polymers may be free of butadiene repeat units. Optionally, the functionalized hydrogenated / saturated polymers may be free of butadiene repeat units. Optionally, the polymers useful herein for preparing functionalized polymers need not be homopolybutylene. Optionally, the functionalized hydrogenated / saturated polymers need not be homopolybutylene.

[0101] Optionally, the polymers useful herein for preparing functionalized polymers need not be homopolyisobutylene. Optionally, the functionalized hydrogenated / saturated polymers need not be homopolyisobutylene. Optionally, the polymers useful herein for preparing functionalized polymers need not be copolymers of isoprene and butadiene. Optionally, the functionalized hydrogenated / saturated polymers need not be copolymers of isoprene and butadiene. The polymers and / or functionalized polymers useful herein for preparing functionalized polymers may be homopolymers or copolymers. Copolymers may be random copolymers, tapered block copolymers, star copolymers, or block copolymers. Block copolymers are formed from a monomer mixture containing one or more first monomers (e.g., isobutylene), e.g., the first monomer forms an individual block of the polymer that is joined to a second individual block of the polymer formed from a second monomer (e.g., butadiene). Block copolymers have substantially distinct blocks formed from monomers, while tapered block copolymers may be composed of a relatively pure first monomer at one end and a relatively pure second monomer at the other end. The intermediate portion of the tapered block copolymer may have an increasing gradient composition of the two monomers.

[0102] Polymers useful herein for preparing functionalized polymers typically may have an Mn of 20,000 to 150,000 g / mol, alternatively 20,000 to about 150,000 g / mol, alternatively 30,000 to about 125,000 g / mol, alternatively 35,000 to about 100,000 g / mol, alternatively 40,000 to 80,000 g / mol (GPC-PS). Polymers useful herein for preparing functionalized polymers typically may have an Mw / Mn (determined by GPC-PS) of 1 to 2, alternatively greater than 1 and less than 2, alternatively 1.1 to 1.8, alternatively 1.2 to 1.5. Alternatively, polymers useful herein for preparing functionalized polymers typically may have an Mw / Mn of 1 or more and less than 2 (e.g., less than 1.8, e.g., less than 1.7, e.g., less than 1.6, e.g., less than 1.5, e.g., less than 1.4, e.g., less than 1.3, e.g., less than 1.2, e.g., less than 1.15, e.g., less than 1.12, e.g., less than 1.10).

[0103] The polymers used for preparing functionalized polymers may have an Mz (determined by GPC-PS) of 20,000 to 150,000 g / mol, alternatively 20,000 to about 150,000 g / mol, alternatively 30,000 to about 125,000 g / mol, alternatively 35,000 to about 100,000 g / mol, alternatively 40,000 to 80,000 g / mol, alternatively 40,000 to 60,000 g / mol (GPC-PS). Polymers useful herein for preparing functionalized polymers may have a glass transition temperature (Tg) of -25°C or lower, e.g., -40°C or lower, e.g., -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, holding at 210°C for 5 minutes, then cooling to -40°C at 10°C / min and holding for 5 minutes). Polymers useful herein for preparing functionalized polymers typically have less than 3% residual unsaturation, based on the number of double bonds in the unhydrogenated polymer, such as less than 2%, such as less than 1%, such as less than 0.5%, such as less than 0.25%. Polymers useful herein for preparing functionalized polymers typically have a residual metal (e.g., 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.

[0104] Hydrogenation C useful herein for preparing functionalized polymers 4~5 The polymers can be partially or fully hydrogenated with any hydrogenating agent known to those skilled in the art. For example, a saturated or partially saturated polymer can be a polymer having (a) a C 4~5 The method can be prepared by (b) providing a polymer, and (b) hydrogenating at least some or all of the unsaturation (e.g., double or triple bonds) of the polymer in the presence of a hydrogenation agent. In some embodiments, the polymer is fully hydrogenated. In some embodiments, the polymer is partially hydrogenated. In some embodiments, the polymer is 50% or more saturated (hydrogenated), such as 60% or more, such as 70% or more, such as 80% or more, such as 90% or more, such as 95% or more, such as 98% or more, such as 99% or more, such as 50-100% saturated (hydrogenated), as determined by the ozone adsorption method described in Martino N. Smits and Dirkman Hoefman, Quantitative Determination of Olefinic Unsaturation by Measurement of Ozone Absorption, Analytical Chemistry Vol. 44, No. 9, p. 1688, 1972 Martino N. Smits.

[0105] In embodiments, the hydrogenation reagent may 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 embodiments, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd / C. In a further embodiment, the catalyst may contain 10% Pd / C in a high-pressure reaction vessel or be 10% Pd / C, and the hydrogenation reaction can proceed until completion. Generally, after completion, the reaction mixture can be washed, concentrated, and dried to obtain the corresponding hydrogenation product. Alternatively, any reducing agent capable of reducing a C═C bond to a C—C bond can be used. For example, an olefin polymer can be hydrogenated by hydrazine treatment in the presence of a catalyst under an oxygen atmosphere, such as 5-ethyl-3-methylrhodanine perchlorate, to obtain the corresponding hydrogenation product. The reduction reaction with hydrazine is disclosed in Imada et al., J Am. Chem. Soc., Vol. 127, pp. 14544-14545 (2005). This document is incorporated herein by reference.

[0106] Acylation A fully or partially saturated (hydrogenated) polymer can be chemically modified (functionalized) to provide a polymer having at least one polar functional group, such as, but not limited to, halogen, epoxy, hydroxy, amino, nitrilo, mercapto, imide, carboxy, and sulfonic acid groups, or a combination thereof. The functionalized polymer can be further modified to impart a more desirable type of functionality. Preferably, the fully or partially hydrogenated polymer is functionalized by a method comprising reacting the fully or partially hydrogenated polymer with an unsaturated carboxylic acid (or a derivative thereof, such as maleic anhydride) to provide an acylated polymer (which may then be further functionalized as described below).

[0107] In some embodiments, a carboxylic acid functionality or its reactive equivalent is grafted onto a polymer to form an acylated polymer. Typically, an ethylenically unsaturated carboxylic acid substance is grafted onto the polymer backbone. Such substances to be attached to the polymer typically contain at least one ethylene bond (before reaction) and at least one, for example two, carboxylic acid (or its anhydride) groups, or polar groups convertible to said carboxyl groups by oxidation or hydrolysis. Maleic anhydride or its derivatives are suitable. It is grafted onto the polymer to impart two carboxylic acid functionalities. Examples of additional unsaturated carboxylic acid substances include itaconic anhydride, or the corresponding dicarboxylic acids, such as maleic acid, fumaric acid, and their esters, and cinnamic acid and its esters.

[0108] The ethylenically unsaturated carboxylic acid substance can be grafted onto the polymer in a number of ways. The ethylenically unsaturated carboxylic acid substance can be grafted onto the polymer in solution or in an essentially pure (melted) form, with or without using a radical initiator. The free-radical induced grafting of the ethylenically unsaturated carboxylic acid substance can also be carried out in a solvent, such as hexane or mineral oil. The free-radical induced grafting of the ethylenically unsaturated carboxylic acid substance may be carried out at a high temperature in the range of 100 °C to 250 °C, for example 120 °C to 190 °C or 150 °C to 180 °C, such as above 160 °C.

[0109] Free radical initiators that can be used include peroxides, hydroperoxides, and azo compounds, typically those having a boiling point higher than about 100 °C and decomposing thermally within the grafting temperature range to provide free radicals. Representative examples of such free radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hexa-3-yne-2,5-bis-tert-butylperoxide. The initiator can be used in an amount of 0.005% to 1% by weight based on the weight of the reaction mixture solution. The grafting may be carried out in an inert atmosphere, for example, under a nitrogen blanket. The resulting acylated polymer intermediate is characterized by having carboxylic acid acylation functional groups as part of its structure. In embodiments, the acylated polymer may have two or more anhydride groups per polymer molecule and less than 10% may exhibit gel. Alternatively, the acylated polymer may have less than two anhydride groups per polymer molecule and less than 10% may exhibit gel. (See also column 17, line 14 to column 18, line 11 of U.S. Patent No. 5,429,758). Alternatively, in some embodiments, the acylated polymer may have a gel content of less than about 5%, less than 3%, less than 2%, less than 1%, less than 0.5%, less than 0.1%, or 0% by weight, and 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 by immersing a polymer thin film specimen of nominal thickness 0.5 mm in cyclohexane at 23 °C for 48 hours or refluxing the thin film specimen in boiling xylene for 30 minutes, removing the solvent, weighing the dry residue, and calculating the amounts of soluble and insoluble (gel) materials. This method is outlined in U.S. Patent No. 4,311,628, which is incorporated herein by reference. For the purposes of the present disclosure, the gel content is measured using boiling xylene, and if the sample does not dissolve in xylene, the cyclohexane method is used.

[0110] In an embodiment, the saponification value (SAP) of the acylated polymer may be 5 g / KOH or more, for example 10 g / KOH or more, for example 20 g / KOH or more, for example 30 g / KOH, 50 g / KOH or more, for example 10 to 60 g / KOH, for example 20 to 40 g / KOH as determined by ASTM D94. In an embodiment, the acylated polymer composition may have less than 5% by mass, for example less than 4% by mass, for example less than 3% by mass, for example less than 1% by mass, for example less than 0.5% by mass, for example less than 0.25% by mass, for example less than 0.1% by mass of unreacted acylating agent (e.g., maleic anhydride) based on the mass of the acylated polymer composition (i.e., polymer, acylating agent, and diluent). In an embodiment, the acylation reaction described herein may occur in a base oil diluent. As a byproduct, a functionalized base oil may be produced. The oil itself may be acylated. After the acylation reaction described herein, for example, maleated base oil may be present.

[0111] It is contemplated that the functionalized base oil may include an acylated oil and / or a reaction product of an acylated oil and an amine that forms an amide, imide, or a combination thereof. Preferably, the acylated oil and / or the reaction product of an acylated oil and an amine or alcohol that forms an amide, imide, ester, or a combination thereof may be present in the concentrate composition in an amount of 40% by mass or less, alternatively 20% by mass or less, alternatively 10% by mass or less, alternatively 5% by mass or less, alternatively 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass (e.g., 0 to 40% by mass, alternatively 0.01 to 40% by mass, alternatively 0.1 to 20% by mass, alternatively 1 to 10% by mass, alternatively 1.5 to 5% by mass) based on the mass of the concentrate composition. Preferably, one or more functionalized base oils, such as acylated oils, and / or reaction products of acylated oils with amines or alcohols that form amides, imides, esters, or combinations thereof, are present in the lubricating oil composition in an amount of 0.01 to 40 wt%, alternatively 0.1 to 20 wt%, alternatively 1 to 10 wt%, alternatively 1.5 to 5 wt% (e.g., 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 mass of the lubricating oil composition.

[0112] In embodiments, the acylation reactions described herein occur in a solvent-containing medium. As a by-product, an acylated / functionalized solvent may be formed. In 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% based on the mass of the concentrate composition. In 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 mass of the lubricating oil composition. In embodiments, the acylating agent can be added to minimize side reactions (e.g., reactions with base oils or other diluents present in the reaction vessel). In an embodiment, the acylation reaction can be caused by adding an acylating agent (e.g., maleic acid or maleic anhydride) in a continuous or semi-continuous (e.g., intermittent) flow (e.g., controlled to be in relatively equal amounts over the reaction time or in larger and / or smaller amounts at various points in the reaction) to minimize the 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 and the acylating agent can be added slowly or in a semi-continuous manner (e.g., the acylating agent is added in separate amounts or portions more than 2 times, e.g., more than 5 times, e.g., more than 10 times, e.g., more than 20 times, e.g., more than 30 times, e.g., more than 40 times, e.g., more than 50 times, e.g., more than 60 times). Alternatively, the polymer can be added to the reaction vessel in X portions and the acylating agent can be added in more than 1.5X portions (e.g., more than 2X portions, e.g., more than 5X portions, e.g., more than 10X portions, e.g., more than 20X portions, e.g., more than 30X portions, e.g., more than 40X portions, e.g., more than 50X portions, e.g., more than 60X 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.

[0113] Preferably, the acylating agent may be added in a continuous or semi-continuous manner, for example, so as to minimize side reactions. The reaction can also be carried out to minimize side reactions by using a high concentration of polymer in a diluent, for example, 45% by mass or more, or 50% by mass or more, or 55% by mass or more, or 60% by mass, in batch, semi - continuous, or continuous reactor operation. For example, a polymer (e.g., a hydrogenated isoprene polymer, e.g., hydrogenated homo - polyisoprene) can be introduced as a solution or suspension (e.g., a slurry) in a diluent (e.g., an oil (e.g., a base oil, e.g., Group I, II, III, IV, and / or V base oil, e.g., Group II and / or Group III base oil) or an alkane solvent or diluent, or a combination thereof) into batch, semi - continuous, or continuous reactor operation, and the polymer may be present in the solution or suspension at 45% by mass or more (or 50% by mass or more, or 55% by mass or more, or 60% by mass or more) based on the mass of the polymer and the diluent.

[0114] In embodiments, side reactions can be minimized by 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 in which the polymer is present at 45% by mass or more based on the mass of the polymer and the diluent, in batch, semi - continuous, or continuous reactor operation. In embodiments, optionally, by adding the acylating agent in a continuous or semi - continuous manner and / or introducing a fully or partially hydrogenated polymer (e.g., an isoprene polymer) as a solution or suspension in a diluent containing 45% by mass or more (or 50% by mass or more, or 55% by mass or more, or 60% by mass or more) of the fully or partially hydrogenated polymer based on the mass of the fully or partially hydrogenated polymer and the diluent, into batch, semi - continuous, or continuous reactor operation, side reactions are minimized.

[0115] In an embodiment, optionally, by adding an acylating agent in a continuous or semi - continuous manner, and introducing a fully or partially hydrogenated polymer (e.g., isoprene polymer) as a solution or suspension in a diluent containing 45% by mass or more (or 50% by mass or more, or 55% by mass or more, or 60% by mass or more) of the fully or partially hydrogenated polymer based on the mass of the fully or partially hydrogenated polymer and the diluent into a batch, semi - continuous, or continuous reactor operation, side reactions are minimized.

[0116] Functionalization In an embodiment, the acylated polymer can be reacted with an alcohol or an amine to form an amide, imide, ester, or a combination thereof. The reaction may consist of a condensation to form an imide, amide, semi - amide, amide - ester, diester, or amine salt. Typically, a primary amino group will condense to form an amide, or in the case of maleic anhydride, an imide will be formed. Note that the amine may have a single primary amino group or multiple primary amino groups.

[0117] Suitable amines can include one or more aromatic amines, for example, amines in which a carbon atom of an aromatic ring structure is directly bonded to the amino nitrogen. Also, the amine may be aliphatic. In an embodiment, the aliphatic amine can be used alone, or in combination with each other, or in combination with an aromatic amine. The amount of the aromatic amine may be large or small compared to the amount of the non - aromatic amine in some embodiments, or in some cases, the composition may not substantially contain an aromatic amine. Alternatively, the composition may not substantially contain an aliphatic amine.

[0118] Examples of aromatic amines that can be used herein include the following formula:

Chemical formula

[0119] Suitable N-aryl phenylenediamines include N-phenyl phenylenediamine (NPDA), for example, 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, such as N-propyl-N'-phenyl phenylenediamine, may also be included.

[0120] In an embodiment, the amine reacted with the acylated polymer is an amine having at least 3 or 4 aromatic groups, of the following formula:

Chemical formula

[0121] Other examples of aromatic amines include the following: aniline, N-alkyl aniline such as N-methyl aniline and N-butyl aniline, di-(para-methylphenyl) amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitro-phenylazo) aniline (Disperse Orange 3), sulfamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenylaminosalicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (Fast Violet B), N-(4-amino-2,5-dimethoxy-phenyl)-benzamide (Fast Blue RR), N-(4-amino-2,5-diethoxy-phenyl)-benzamide (Fast Blue BB), N-(4-amino-phenyl)-benzamide, and 4-phenylazoaniline. Suitable amines are referenced in U.S. Patent No. 7,790,661, which is incorporated herein by reference.

[0122] In an embodiment, the compound to be condensed with the acylated polymer can be represented by the following formula.

Chemical formula

Chemical formula

[0123] Alternatively, the amine may be an amine having at least four aromatic groups and an aldehyde (e.g., formaldehyde). The aromatic amine has the following formula:

Chemical formula

[0064] to

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

[0124] It can be condensed with an acylating agent. Examples of compounds further having a tertiary amino group include, but are not limited to, the following: dimethylaminopropylamine, N,N-dimethyl-aminopropylamine, N,N-diethyl-aminopropylamine, N,N-dimethyl-aminoethylamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, isomeric butylenediamine, pentanediamine, hexanediamine, heptanediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine, and bis(hexamethylene)triamine, diaminobenzene, diaminopyridine, or a mixture thereof. Examples of compounds that can be condensed with an acylating agent and further have a tertiary amino group include aminoalkyl-substituted heterocyclic compounds, such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-di-amino-N-methyldipropylamine, 3’,3-aminobis(N,N-dimethylpropylamine). Another example of a compound that can be condensed with an acylating agent and has a tertiary amino group includes, but is not limited to, alkanolamines including triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-di-ethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine.

[0125] In an embodiment, the polymer may be reacted with a polyether aromatic compound. Typically, the polyether aromatic compound will have 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 an embodiment, the polyether aromatic compound is derived from an aromatic compound containing at least one amine group, and the polyether is capable of reacting with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester.

[0126] Examples of suitable polyether aromatic amines include compounds having the following structures.

Chemical formula

[0127] The acylated polymer may be reacted 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 moiety. The polyether polyamine may be based on a polymer derived from C2 - C6 epoxides, such as ethylene oxide, propylene oxide, and butylene oxide. Examples of polyether polyamines are sold under the Jeffamine (trademark) brand and are commercially available from Huntsman Corporation.

[0128] Amines useful herein for combination with an acylated polymer include one or more of the following: N - phenyldiamines (e.g., 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 (e.g., 3 - nitroaniline), N - phenylethane - diamines (e.g., N1 - phenylethane - 1,2 - diamine), N - aminophenylacetamides (e.g., N - (4 - aminophenyl)acetamide), morpholinopropanamine (e.g., 3 - morpholinopropan - 1 - amine), and aminoethylpiperazine (e.g., 1 - (2 - aminoethyl)piperazine).

[0129] In embodiments, the functionalization (e.g., amination) reactions described herein may occur in a diluent (e.g., base oil or alkane solvent). As a by - product, a functionalized diluent (e.g., functionalized base oil) may be produced. It is contemplated that the functionalized diluent (e.g., functionalized base oil) may include reaction products of an acylated diluent (e.g., acylated base oil) and an amine that form amides, imides, or combinations thereof.

[0130] Preferably, the reaction products of an acylated diluent (e.g., acylated oil) and an amine or alcohol that form amides, imides, esters, or combinations thereof may be present in the concentrate in an amount of 40 wt% or less, alternatively 20 wt% or less, alternatively 10 wt% or less, alternatively 5 wt% or less, alternatively 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt% (e.g., 0 - 40 wt%, alternatively 0.01 - 40 wt%, alternatively 0.1 - 20 wt%, alternatively 1 - 10 wt%, alternatively 1.5 - 5 wt%) based on the mass of the concentrate composition.

[0131] Preferably, the reaction product of an acylating diluent (such as an acylated base oil) and an amine or alcohol that forms one or more functionalized base oils, such as amides, imides, esters, or combinations thereof, may be present in the lubricating oil composition in an amount of 0.01 to 40% by mass, alternatively 0.1 to 20% by mass, alternatively 1 to 10% by mass, alternatively 1.5 to 5% by mass (such as 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass) based on the mass of the lubricating oil composition.

[0132] In embodiments, the functionalization (such as amination) reaction described herein may occur in a solvent-containing medium. As a by-product, a functionalized solvent may be formed. In embodiments, the functionalized solvent may be present in the concentrate composition in an amount of 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass based on the mass of the concentrate composition. In embodiments, the functionalized solvent may be present in the lubricating oil composition in an amount of 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass based on the mass of the lubricating oil composition. In embodiments, the acylated base oil / solvent may be removed prior to functionalization.

[0133] Functionalized polymer The functionalized polymer may be a homopolymer of a C4 or C5 olefin, such as butadiene and isoprene. In embodiments, the functionalized polymer may 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%).

[0134] The functionalized polymer may or may not contain a copolymer with isoprene and one or more of 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%, for example less than 3 mol%, for example less than 1 mol%, for example less than 0.1 mol%). In embodiments, the functionalized polymer contains styrene monomer at 10 (for example 9, for example 8, for example 7, for example 6, for example 5, for example 4, for example 3, for example 2, for example 1) mass% or less based on the mass of the functionalized polymer.

[0135] In embodiments, the functionalized polymer may not have styrene repeat units. In embodiments, the functionalized polymer may be a block or tapered block copolymer that does not contain a styrene block. In embodiments, the functionalized polymer may be a block or tapered block copolymer that contains isoprene (or consists of or is essentially composed of isoprene). In embodiments, the functionalized polymer may be a block or tapered block copolymer that contains 50 mass% or more of isoprene based on the mass of the copolymer. In embodiments, the functionalized polymer is C 4~5 containing conjugated diene (or C 4~5Consisting of conjugated dienes or essentially consisting of C 4~5 conjugated dienes), preferably at least 50 (e.g., 60, e.g., 70, e.g., 80, e.g., 90, e.g., 95, e.g., 98) mass % of C based on the mass of the copolymer 4~5 It may be a block or tapered block copolymer containing conjugated dienes. In an embodiment, the functionalized polymer may be a copolymer containing at least 50 (e.g., 60, e.g., 70, e.g., 80, e.g., 90, e.g., 95, e.g., 98) mass % of isoprene based on the mass of the copolymer.

[0136] In an embodiment, the functionalized polymer may be a copolymer containing at least 50 (e.g., 60, e.g., 70, e.g., 80, e.g., 90, e.g., 95, e.g., 98) mass % of butadiene based on the mass of the copolymer. In an embodiment, the functionalized polymer may be a copolymer containing at least 50 (e.g., 60, e.g., 70, e.g., 80, e.g., 90, e.g., 95, e.g., 98) mass % of butadiene and isoprene based on the mass of the copolymer. In an embodiment, the functionalized polymer may be a diblock copolymer containing at least one block of an isoprene homopolymer or copolymer. Optionally, the functionalized polymer may not have butadiene repeat units. Optionally, the functionalized polymer may not be homopolyisobutylene. Optionally, the functionalized polymer may not be a copolymer of isoprene and butadiene.

[0137] Generally, the polymerized conjugated dienes in the functionalized polymer include monomer units inserted into the growing polymer chain by conjugate addition and non-conjugate addition. In an embodiment, the functionalized polymer is 13 Based on the total number of conjugate addition insertions and non-conjugate addition insertions measured by C NMR, it includes at least about 50% conjugate addition insertions, e.g., at least about 75% conjugate addition insertions, e.g., about 80% conjugate addition insertions, e.g., about 85% - about 100% conjugate addition insertions. Isoprene insertion most often occurs by 2,1 insertion, 1,4 insertion (trans and cis), and 3,4 insertion of isoprene. (Measurement of the insertion geometry is 1 determined by 1H NMR.) The functionalized isoprene polymer is 1 measured by 1H NMR and contains 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 sum of 2,1 insertion, 1,4 insertion, and 3,4 insertion of 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.

[0138] The functionalized polymer may be a homopolymer or a copolymer. Optionally, the functionalized polymer contains a homopolymer or copolymer of isoprene. The copolymer may be a random copolymer, a tapered block copolymer, a star copolymer, or a block copolymer. The functionalized polymer may typically have an Mn of 20,000 - 150,000 g / mol, alternatively 20,000 - about 150,000 g / mol, alternatively 30,000 - about 125,000 g / mol, alternatively 35,000 - about 100,000 g / mol, alternatively 40,000 - 80,000 g / mol (GPC-PS).

[0139] The polymer before functionalization may typically have an Mn / Mw (GPC-PS) of 1.0 - 2, such as 1.1 - 1.5, such as 1.1 - 1.3, such as 1.1 - 1.2. As functionalization occurs, there may be Mw / Mn broadening.

[0140] The functionalized polymer may typically have an Mw / Mn (GPC-PS) of 1 to 3, alternatively 1 to 2, alternatively greater than 1 and less than 2, alternatively 1.05 to 1.9, alternatively 1.10 to 1.8, alternatively 1.10 to 1.7, alternatively 1.12 to 1.6, alternatively 1.13 to 1.5, alternatively 1.15 to 1.4, alternatively 1.15 to 1.3. Alternatively, the functionalized polymer may typically have an Mw / Mn greater than 1 or greater than 1 and less than 2 (e.g., less than 1.8, e.g., less than 1.7, e.g., less than 1.6, e.g., less than 1.4, e.g., less than 1.2, e.g., less than 1.15, e.g., less than 1.12, e.g., less than 1.10).

[0141] In an embodiment, the functionalized polymer may have a saponification value (SAP) of 25 (e.g., 28, e.g., 30, e.g., 32, e.g., 34) mg KOH / g or more as determined by ASTM D94. In an embodiment, the functionalized polymer can contribute 17% or more (e.g., 20% or more, e.g., 17 - 40%, e.g., 20 - 30%) to the saponification value of the lubricating oil composition. In an embodiment, the functionalized polymer may have an average functionality of 1.4 to 20 FG grafts / polymer chain, e.g., 1.4 to 15 FG grafts / polymer chain, e.g., 3 to 12.5 FG grafts / polymer chain, e.g., 4 to 10 FG grafts / polymer chain as determined by GPC-PS. The functionalized polymer may have an average functionality of 15 (e.g., 14, 13, 12, 11, 10, 9, 8, 7, or 6) FG grafts / polymer chain or less as determined by GPC-PS.

[0142] The functionalized polymer may have an average functionality of 1 (e.g., 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) FG grafts / polymer chain or more as determined by GPC-PS. The functionalized polymer may have an average functionality of 1 (e.g., 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 (14, 13, 12, 11, 10, 9, 8, 7, or 6) FG grafts / polymer chain as determined by GPC-PS. In embodiments, the functionalized polymer may have an aromatic content of 5% or less, such as 3% or less, such as 1% or less, such as 0%, based on the mass of the polymer.

[0143] In embodiments, the functionalized polymer has an Mn of 20,000 to 500,000 g / mol as determined by GPC-PC and has a branched-chain C with an Mw / Mn of 2 or less, such as 1 to 2.0. 4~5 It may contain an acylated polymer of the monomer. In embodiments, the functionalized polymer may have a number average molecular weight (Mn) of 20,000 (e.g., 25,000, e.g., 30,000, e.g., 35,000, e.g., 40,000) g / mol or more as determined by GPC-PS. In embodiments, the functionalized polymer may have a mass average molecular weight (Mw) of 50,000 (e.g., 40,000, e.g., 35,000) g / mol or less as determined by GPC-PS. In embodiments, the functionalized polymer may have a mass average molecular weight (Mw) of 1000 to 50,000 g / mol, such as 5000 to 40,000 g / mol as determined by GPC-PS. In embodiments, the functionalized polymer may have a z average molecular weight (Mz) 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, alternatively 20,000 to about 150,000 g / mol, alternatively 30,000 to about 125,000 g / mol, alternatively 35,000 to about 100,000 g / mol, alternatively 40,000 to 80,000 g / mol, alternatively 40,000 to 60,000 g / mol (GPC-PS).

[0144] In 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%, and the gel content is measured by determining the amount of material extractable from the polymer by using boiling xylene (or cyclohexane) as an extractant. The percentages of soluble and insoluble (gel) materials in the polymer composition are determined as described herein. In embodiments, the functionalized polymer may have a functionality distribution (Fd) value of 3.5 or less (determined by GPC-PS, e.g., 3.4 or less, e.g., 1 - 3.3, e.g., 1.1 - 3.2, e.g., 1.2 - 3.0, e.g., 1.4 - 2.9). The functionality distribution (Fd) value is determined as shown in the Examples section below, and the average functionality is determined by GPC-PS to be 1.4 - 20 FG grafts / polymer chain, e.g., 1.4 - 15 FG grafts / polymer chain, e.g., 3 - 12.5 FG grafts / polymer chain, e.g., 4 - 10 FG grafts / polymer chain.

[0145] The present disclosure relates to an amide, imide, and / or ester functionalized hydrogenated / saturated polymer containing (consisting essentially of or consisting of) olefins, wherein the polymer before functionalization is a C4 olefin polymer, e.g., polyisobutylene, polybutadiene, or a copolymer thereof (preferably polyisobutylene or a copolymer of isobutylene and butadiene), the C4 olefin polymer has a Mn of 10,000 g / mol or more (GPC-PS), and when 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), and has an Mw / Mn of less than 2 and a functionality distribution (Fd) value of 3.5 or less (measured by GPC-PS, e.g., 3.4 or less, e.g., 1 - 3.3, e.g., 1.1 - 3.2, e.g., 1.2 - 3.0, e.g., 1.4 - 2.9). 4~5 an amide, imide, and / or ester functionalized hydrogenated / saturated polymer containing (consisting essentially of or consisting of) olefins, wherein the polymer before functionalization is a C4 olefin polymer, e.g., polyisobutylene, polybutadiene, or a copolymer thereof (preferably polyisobutylene or a copolymer of isobutylene and butadiene), the C4 olefin polymer has a Mn of 10,000 g / mol or more (GPC-PS), and when 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).

[0146] The present disclosure also relates to amide, imide, and / or ester-functionalized hydrogenated / saturated polymers that contain 90 mol% or more of isoprene repeat units and have a functionality distribution (Fd) value of less than 2 for Mw / Mn and 3.5 or less (measured by GPC-PS, e.g., 3.4 or less, e.g., 1 to 3.3, e.g., 1.1 to 3.2, e.g., 1.2 to 3.0, e.g., 1.4 to 2.9), wherein the polymer before functionalization has a Mn of 30,000 g / mol or more (GPC-PS). The present disclosure also relates to amide, imide, and / or ester-functionalized hydrogenated / saturated homopolymers of isoprene that have a functionality distribution (Fd) value of less than 2 for Mw / Mn and 3.5 or less (determined by GPC-PS, e.g., 3.4 or less, e.g., 1 to 3.3, e.g., 1.1 to 3.2, e.g., 1.2 to 3.0, e.g., 1.4 to 2.9), wherein the polymer before functionalization has a Mn of 30,000 g / mol or more (determined by GPC-PS).

[0147] The lubricating compositions according to the present disclosure may further contain one or more additives, such as detergents, friction modifiers, antioxidants, pour point depressants, defoamers, viscosity modifiers, dispersants, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibility agents, additive diluent base oils, and the like. Specific examples of such additives are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, Volume 14, pages 477 - 526, and some are considered in more detail below.

[0148] C. Detergents The lubricating composition may contain one or more metal detergents (e.g., a blend of metal detergents), also referred to as "detergent additives". Metal detergents typically function 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 contain a polar head with a long-chain hydrophobic tail, and the polar head contains a metal salt of an acidic organic compound. Such salts may contain substantially stoichiometric amounts of metal, in which case such salts are usually described as normal or neutral salts and typically will have a total base number (TBN, measured by ASTM D2896) of up to 150 mg KOH / g, e.g., 0 to 80 (or 5 to 30) mg KOH / g. A large amount of metal base can be incorporated by reacting an excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide). Such detergents are sometimes referred to as overbased and may have a TBN of 100 mg KOH / g or more (e.g., 200 mg KOH / g or more), typically 250 mg KOH / g or more, e.g., 300 mg KOH / g or more, e.g., 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, e.g., 150 to 650 mg KOH / g.

[0149] Suitable detergents include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble carboxylates of metals, particularly alkali metals (Group 1 metals, e.g., Li, Na, K, Rb) or alkaline earth metals (Group 2 metals, e.g., Be, Mg, Ca, Sr, Ba), particularly sodium, potassium, lithium, calcium, and magnesium, e.g., Ca and / or Mg. Further, the detergent may include hybrid detergents containing any combination of sodium salts, potassium salts, lithium salts, calcium salts, or magnesium salts of sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates, or other oil-soluble carboxylates of Group 1 and / or Group 2 metals. Preferably, the detergent additives useful in the present disclosure include calcium and / or magnesium metal salts. The detergent may be calcium and / or magnesium carboxylate (e.g., salicylic acid), calcium and / or magnesium sulfonate, or calcium and / or magnesium 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 containing two, three, four, or more of these detergents, and / or combinations thereof.

[0150] Also, examples of the metal-containing detergent include "hybrid" detergents formed from mixed surfactant systems containing phenate and / or sulfonate components, such as phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, sulfonate / phenate / salicylate, as described in U.S. Patent Nos. 6,429,178, 6,429,179, 6,153,565, and 6,281,179. For example, when a hybrid sulfonate / phenate detergent is used, the hybrid detergent is considered to be in the same amount as the amount of the separate phenate detergent and sulfonate detergent that introduce similar amounts of phenate soap and sulfonate soap, respectively.

[0151] The overbased metal-containing detergent may be a sodium salt, calcium salt, magnesium salt, or a mixture thereof of phenate, sulfur-containing phenate, sulfonate, salicylate, and salicylate. The overbased phenate and salicylate typically have a total base number of 180 to 650 mg KOH / g, such as 200 to 450 TBN mg KOH / g. The overbased sulfonate typically has a total base number of 250 to 600 mg KOH / g, or 300 to 500 mg KOH / g. In an embodiment, the sulfonate detergent may be mainly a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described in paragraphs

[0026] to

[0037] of US Patent Application Publication No. 2005 / 065045 (and granted as US Patent No. 7,407,919). The overbased detergent may be present in an amount of 0% to 15% by weight, or 0.1% to 10% by weight, or 0.2% to 8% by weight, or 0.2% to 3% by weight based on the lubricating composition. For example, in a large diesel engine, the detergent may be present in an amount of 2% to 3% by weight of the lubricating composition. In the case of a passenger car engine, the detergent may be present in an amount of 0.2% to 1% by weight of the lubricating composition.

[0152] The detergent additive may include one or more magnesium sulfonate detergents. The magnesium detergent may be a neutral salt or an overbased salt. Preferably, 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. Alternatively, the detergent additive is magnesium salicylate. Preferably, the magnesium detergent is 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 alternatively 150 mg KOH / g or less, such as 100 mg KOH / g or less.

[0153] Alternatively, the detergent additive is a combination of magnesium salicylate and magnesium sulfonate. The magnesium detergent provides 200 to 4000 ppm of magnesium atoms, preferably 200 to 2000 ppm, 300 to 1500 ppm, or 450 to 1200 ppm of magnesium atoms to the lubricating composition (ASTM D5185). The detergent composition may (or may consist of) include a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents. A combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents provides to the lubricating composition: 1) 200 to 4000 ppm of magnesium atoms, preferably 200 to 2000 ppm, 300 to 1500 ppm, or 450 to 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, for example 500 to 4000 ppm, preferably 750 to 3000 ppm, more preferably 900 to 2000 ppm of atomic calcium (ASTM D5185). The detergent may include one or more calcium detergents, such as calcium carboxylate (e.g., salicylic acid) detergents, calcium sulfonate detergents, or calcium phenate detergents.

[0154] Preferably, the calcium detergent has a TBN of 30 to 700 mg KOH / g (ASTM D2896), such as 50 to 650 mg KOH / g, such as 200 to 500 mg KOH / g, such as 240 to 450 mg KOH / g, or alternatively 150 mg KOH / g or less, such as 100 mg KOH / g or less, or 200 mg KOH / g or more, or 300 mg KOH / g or more, or 350 mg KOH / g or more. Preferably, the calcium detergent is calcium salicylate, calcium sulfonate, or calcium phenate having a TBN of 30 to 700 mg KOH / g, 30 to 650 mg KOH / g (ASTM D2896), for example 50 to 650 mg KOH / g, for example 200 to 500 mg KOH / g, for example 240 to 450 mg KOH / g, or alternatively 150 mg KOH / g or less, for example 100 mg KOH / g or less, or 200 mg KOH / g or more, or 300 mg KOH / g or more, or 350 mg KOH / g or more. The calcium detergent is typically present in an amount sufficient to provide at least 500 ppm, preferably at least 750, more preferably at least 900 ppm of atomic calcium to the lubricating oil composition (ASTM D5185). When present, any calcium detergent is preferably present in an amount sufficient to provide up to 4000 ppm, preferably up to 3000 ppm, more preferably up to 2000 ppm of atomic calcium to the lubricating oil composition (ASTM D5185). When present, any calcium detergent is preferably present in an amount sufficient to provide 500 to 4000 ppm, preferably 750 to 3000 ppm, more preferably 900 to 2000 ppm of atomic calcium to the lubricating oil composition (ASTM D5185).

[0155] Preferably, the total atomic weight of the metal derived from the detergent in the lubricating composition according to all aspects of the present disclosure is 5000 ppm or less, preferably 4000 ppm or less, more preferably 2000 ppm or less (ASTM D5185). The total amount of metal atoms derived from the detergent in the lubricating oil composition according to all aspects of the present disclosure is preferably at least 500 ppm, preferably at least 800 ppm, more preferably at least 1000 ppm (ASTM D5185). The total amount of metal atoms derived from the detergent in the lubricating oil composition according to all aspects of the present disclosure is preferably 500 to 5000 ppm, preferably 500 to 3000 ppm, more preferably 500 to 2000 ppm (ASTM D5185).

[0156] Sulfonate detergents can typically be prepared from sulfonic acids obtained by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from the fractional distillation of petroleum, or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl, or halogen derivatives thereof, such as chlorobenzene, chlorotoluene, and chloronaphthalene. The alkylation can be carried out in the presence of a catalyst using an alkylating agent having from about 3 to more than 70 carbon atoms. Alkaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms, per alkyl-substituted aromatic moiety. 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 typically ranges from about 100 to 220% by weight (preferably at least 125% by weight) of the stoichiometrically required amount.

[0157] Metal salts of phenol and sulfurized phenol are prepared by reaction with a suitable metal compound, such as an oxide or hydroxide, and neutral or overbased products can be obtained by methods well known in the art. Sulfurized phenol is prepared by reacting phenol with sulfur or a sulfur-containing compound, such as hydrogen sulfide, sulfur monohalide, or sulfur dihalide, to form a product that is generally a mixture of compounds in which two or more phenols are bridged by sulfur-containing linkages. Carboxylate detergents, such as salicylates, are prepared from aromatic carboxylic acids (e.g., C 5~100 , C 9~30 , C 14~24It can be prepared by reacting an alkyl-substituted hydroxybenzoic acid with a suitable metal compound, such as an oxide or hydroxide, and neutral or overbased products can be obtained by methods well known in the art. The aromatic moiety of the aromatic carboxylic acid may contain heteroatoms, such as nitrogen and oxygen. Preferably, this moiety contains only carbon atoms, and more preferably, this moiety contains 6 or more carbon atoms. For example, a preferred moiety is benzene. The aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, which are condensed or connected via an alkylene bridge.

[0158] Preferred substituents in oil-soluble salicylic acid are alkyl substituents. In alkyl-substituted salicylic acid, the alkyl group advantageously contains 5 to 100 carbon atoms, preferably 9 to 30 carbon atoms, particularly 14 to 20 carbon atoms. When more than one alkyl group is present, the average number of carbon atoms of all alkyl groups is preferably at least 9 in order to ensure reasonable oil solubility. In embodiments, the ratio of detergent metal to atomic molybdenum in the lubricating oil composition may be less than 3:1, such as less than 2:1. Furthermore, since the metal organic and inorganic base salts used as detergents can contribute to the sulfuric acid 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 level, salicylate detergents can be used, and the lubricating compositions herein may contain one or more salicylate detergents (the detergents are preferably used in an amount in the range of 0.05 to 20.0% by mass, more preferably in the range of 1.0 to 10.0% by mass, and most preferably in the range of 2.0 to 5.0% by mass, based on the total mass of the lubricating composition).

[0159] The total sulfuric acid ash content of the lubricating compositions herein, determined by ASTM D874, is typically 2.0% by mass or less, alternatively 1.0% by mass or less, alternatively 0.8% by mass or less, based on the total mass of the lubricating composition. Furthermore, each of the detergents independently preferably has a TBN (total base number) value in the range of 10 to 700 mg KOH / g, 10 to 500 mg KOH / g, alternatively in the range of 100 to 650, alternatively in the range of 10 to 500 mg KOH / g, alternatively in the range of 30 to 350 mg KOH / g, alternatively in the range of 50 to 300 mg KOH / g, as measured by ISO 3771. The sulfonate detergent (e.g., Ca and / or Mg sulfonate detergent) may be present in the lubricant composition in an amount that delivers 0.1 wt% to 1.5 wt%, or 0.15% to 1.2 wt%, or 0.2 wt% to 0.9 wt% of the sulfonate soap.

[0160] The salicylate detergent (e.g., Ca and / or Mg salicylate detergent) is present in the lubricant composition in an amount that delivers 0.3 wt% to 1.4 wt%, or 0.35 wt% to 1.2 wt%, or 0.4 wt% to 1.0 wt% of the salicylate soap. The sulfonate soap may be present in the lubricant composition in an amount of 0.2 wt% to 0.8 wt%, and the salicylate soap may be present in the lubricant composition in an amount of 0.3 wt% to 1.0 wt%. The total of all alkaline earth metal detergent soaps may be present in the lubricant composition in an amount of 0.6 wt% to 2.1 wt%, or 0.7 wt% to 1.4 wt%. Typically, a lubricating composition formulated for use in a large diesel engine contains about 0.1 to about 10 wt%, alternatively about 0.5 to about 7.5 wt%, alternatively about 1 to about 6.5 wt% of a detergent, based on the lubricating composition.

[0161] Typically, a lubricating composition formulated for use in a passenger car engine contains about 0.1 to about 10 wt%, alternatively about 0.5 to about 7.5 wt%, alternatively about 1 to about 6.5 wt% of a detergent, based on the lubricating composition. Typically, a lubricating composition formulated for use in a drive train (e.g., a transmission) contains about 0.1 to about 10 wt%, alternatively about 0.5 to about 7.5 wt%, alternatively about 2 to about 6.5 wt% of a detergent, based on the lubricating composition.

[0162] D. Friction Modifiers A friction modifier is any one or more substances that can change the coefficient of friction of a surface lubricated by a fluid containing any lubricant or such substances. Friction modifiers, also known as friction reducers or lubricity agents or oiliness agents, and other such agents that can change the properties of a base oil, formulated lubricating composition, or functional fluid to adjust the coefficient of friction of the lubricated surface can be effectively used, if necessary, in combination with the base oils or lubricating compositions of the present disclosure. It is particularly advantageous to combine friction modifiers that lower the coefficient of friction with the base oils and lubricating compositions of the present disclosure. Exemplary friction modifiers can include, for example, organometallic compounds or substances or mixtures thereof. Exemplary organometallic friction modifiers useful in the lubricating oil formulations of the present disclosure can include, for example, tungsten and / or molybdenum compounds such as molybdenum amines, molybdenum diamines, organotungstenates, molybdenum dithiocarbamates, molybdenum dithiophosphates, molybdenum amine complexes, and molybdenum carboxylates, etc., and mixtures thereof. Examples of useful molybdenum-containing compounds can conveniently include molybdenum dithiocarbamates such as the trinuclear molybdenum compounds described in WO 98 / 26030 pamphlet, sulfides of molybdenum, and molybdenum dithiophosphates.

[0163] Other known friction modifiers include oil-soluble organomolybdenum compounds. Such organomolybdenum friction modifiers can also provide antioxidant and antiwear benefits to lubricating oil compositions. Examples of such oil-soluble organomolybdenum compounds can include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, and sulfides, etc., and mixtures thereof. Particularly preferred are molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum alkylxanthates, and molybdenum alkylthioxanthates. In addition, the molybdenum compound may be an acidic molybdenum compound. Such compounds react with basic nitrogen compounds and are typically hexavalent as measured by the ASTM test D664 or D2896 titration procedure. Molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates, and other molybdenum salts, such as sodium hydrogen molybdate, MoOC l4 , MoO2Br2, Mo2O3C l6 , molybdenum trioxide, or similar acidic molybdenum compounds are included.

[0164] Molybdenum compounds useful in the compositions of the present disclosure include organic molybdenum compounds of the formulas Mo(R″OCS2)4 and Mo(R″SCS2)4, where R″ is generally an organic group selected from the group consisting of alkyl, aryl, aralkyl, and alkoxyalkyl having from 1 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and most preferably alkyl having from 2 to 12 carbon atoms. Particularly preferred are dialkyldithiocarbamates of molybdenum. Another group of organic molybdenum compounds useful in the lubricating compositions of the present disclosure are trinuclear molybdenum compounds, particularly those of the formula Mo3SkLnQz, and mixtures thereof, where L is an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is from 1 to 4, k is in the range of 4 to 7, Q is selected from the group consisting of neutral electron donor compounds such as water, amines, alcohols, phosphines, and ethers, z is in the range of 0 to 5, and includes non-stoichiometric values. All ligands / organic groups should have at least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms.

[0165] 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, more preferably at least 50 ppm of molybdenum. Suitably, lubricating oil compositions useful in all aspects of the present disclosure contain 1000 ppm or less, 750 ppm or less, or 500 ppm or less of molybdenum. Lubricating oil compositions useful in all aspects of the present disclosure preferably contain 10 to 1000 ppm, such as 30 to 750 ppm, or 40 to 500 ppm of molybdenum (measured as molybdenum atoms). For further information regarding useful friction modifiers containing Mo, see U.S. Patent No. 10,829,712 (column 8, line 58 to column 11, line 31). The lubricating oil compositions of the present disclosure may contain ashless friction modifiers, which are generally known and include esters formed by reacting carboxylic acids and anhydrides with alkanols and amine-based friction modifiers. Other useful friction modifiers generally include polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to a lipophilic hydrocarbon chain. Esters of carboxylic acids and anhydrides with alkanols are described in U.S. Patent No. 4,702,850. Examples of other conventional organic friction modifiers are described in "Journal of Tribology" (1992), Vol. 114, pp. 675 - 682 by M. Belzer, and in "Lubrication Science" (1988), Vol. 1, pp. 3 - 26 by M. Belzer and S. Jahanmir. Typically, the total amount of organic ashless friction modifiers in the lubricants according to the present disclosure does not exceed 5% by mass, preferably does not exceed 2% by mass, more preferably does not exceed 0.5% by mass based on the total mass of the lubricating oil composition.

[0166] Exemplary friction modifiers useful in the lubricating compositions described herein include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, glycerol borate fatty acid esters, fatty alcohol ethers, and mixtures thereof. Exemplary alkoxylated fatty acid esters include, for example, polyoxyethylene stearate and fatty acid polyglycol esters. Such examples include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, and polyoxyethylene palmitate. Exemplary alkanolamides include, for example, diethyl alkanolamide laurate and diethyl alkanolamide palmitate (palmic acid). Such examples include diethyl alkanolamide oleate, diethyl alkanolamide stearate, diethyl alkanolamide oleate, polyethoxylated hydrocarbylamide, and polypropoxylated hydrocarbylamide.

[0167] Exemplary polyol fatty acid esters include, for example, glycerol monooleate, saturated mono-, di-, and triglyceride esters, and glycerol monostearate. Such examples include polyol esters and hydroxyl-containing polyol esters. Exemplary glycerol borate fatty acid esters include, for example, glycerol monooleate borate, saturated mono-, di-, and triglyceride esters borate, and glycerol monostearate borate, etc. In addition to glycerol polyols, such substances may include trimethylolpropane, pentaerythritol, and sorbitan, etc. Such esters may be polyol monocarboxylic acid esters, polyol dicarboxylic acid esters, and in some cases polyol tricarboxylic acid esters. Preferred are glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monooleate, glycerol distearate, and glycerol tristearate, as well as the corresponding glycerol monopalmitate, glycerol dipalmitate, and glycerol tripalmitate, and their respective isostearates and linoleates, etc. In this specification, in particular, ethoxylated, propoxylated, and / or butoxylated fatty acid esters of polyols in which glycerol is used as the base polyol are useful.

[0168] Exemplary aliphatic alcohol ethers include, for example, stearyl ether and myristyl ether, etc. Alcohols having a carbon number of C3 to C 50 can be ethoxylated, propoxylated, or butoxylated to form the corresponding fatty alkyl ethers. The base alcohol moiety is preferably stearyl, myristyl, C 11 to C 13 hydrocarbons, oleyl, and isostearyl, etc. The useful concentration of the friction modifier may be in the range of 0.01% to 5% by mass, or about 0.01% to about 2.5% by mass, or about 0.05% to about 1.5% by mass, or about 0.051% to about 1% by mass. The concentration of the molybdenum-containing substance is often described in terms of the Mo metal concentration. The advantageous concentration of Mo may be in the range of 25 ppm to 700 ppm or higher, and in many cases, the preferred range is 50 to 200 ppm. Any type of friction modifier can be used alone or in combination with the substances of the present disclosure. In many cases, a mixture of two or more friction modifiers, or a mixture of a friction modifier and an alternative surfactant, is also desirable. In this specification, for example, a combination of a Mo-containing compound and a polyol fatty acid ester, such as glycerol monooleate, is useful.

[0169] E. Antioxidants Antioxidants retard the oxidative degradation of the base oil during service. Such degradation can lead to deposits on metal surfaces, the presence of sludge, and an increase in the viscosity of the lubricant. A wide variety of oxidation inhibitors are useful 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.

[0170] Useful antioxidants include hindered phenols. Such phenolic antioxidants may be ashless (metal-free) phenolic compounds, or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenolic compounds containing sterically hindered hydroxyl groups, and examples of such compounds include derivatives of dihydroxyaryl compounds in which the hydroxyl groups are in the ortho or para positions to each other. Typical phenolic antioxidants include C 6+Hindered phenols substituted with an alkyl group and alkylene coupling derivatives of such hindered phenols can be mentioned. Examples of this type of phenolic substance include 2-t-butyl-4-heptylphenol, 2-t-butyl-4-octylphenol, 2-t-butyl-4-dodecylphenol, 2,6-di-t-butyl-4-heptylphenol, 2,6-di-t-butyl-4-dodecylphenol, 2-methyl-6-t-butyl-4-heptylphenol, and 2-methyl-6-t-butyl-4-dodecylphenol. Other useful hindered monophenolic antioxidants can include, for example, hindered 2,6-di-alkyl-phenolic propionate esters derivatives. In this specification, bis-phenolic antioxidants can also be advantageously used. Examples of ortho-coupling phenols include 2,2'-bis(4-heptyl-6-t-butyl-phenol), 2,2'-bis(4-octyl-6-t-butyl-phenol), and 2,2'-bis(4-dodecyl-6-t-butyl-phenol). Examples of para-coupling bisphenols include, for example, 4,4'-bis(2,6-di-t-butyl-phenol) and 4,4'-methylene-bis(2,6-di-t-butyl-phenol).

[0171] An effective amount of one or more catalytic antioxidants can also be used. The catalytic antioxidant includes 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 phenol compounds or a combination of both b) and c). The catalytic antioxidants useful in this specification are described in more detail in U.S. Patent No. 8,048,833. Non-phenolic antioxidants that can be used can include aromatic amine antioxidants, which can be used either as such or in combination with phenolic substances. Typical examples of non-phenolic antioxidants include alkylated and non-alkylated aromatic amines, for example, of the formula R8R9R 10Aromatic monoamines of N are exemplified, in the formula, R8 is an aliphatic group, an aromatic group, or a substituted aromatic group, R9 is an aromatic group or a substituted aromatic group, R 10 is H, alkyl, aryl, or R 11 S(O)XR 12 wherein, R 11 is an alkylene group, an alkenylene group, or an aralkylene group, R 12 is an alkyl group, or an alkenyl group, an aryl group, or an alkaryl group, and x is 0, 1, or 2. The aliphatic group R8 may contain from 1 to about 20 carbon atoms, preferably about 6 to 12 carbon atoms. The aliphatic group is typically a saturated aliphatic group. Preferably, both R8 and R9 are aromatic groups or substituted aromatic groups, and the aromatic group may be a condensed ring aromatic group, such as naphthyl. The aromatic groups R8 and R9 may be combined with other groups, such as S.

[0172] Typical aromatic amine antioxidants have an alkyl substituent of at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic group will not contain more than about 14 carbon atoms. General types of amine antioxidants useful in the present composition include diphenylamine, phenylnaphthylamine, phenothiazine, imidodibenzyl, and diphenylphenylenediamine. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used. Specific examples of aromatic amine antioxidants useful in the present disclosure include p,p'-dioctyldiphenylamine, t-octylphenyl-alpha-naphthylamine, phenyl-alpha-naphthylamine, and p-octylphenyl-alpha-naphthylamine.

[0173] In this specification, sulfur-containing antioxidants are also useful. In particular, one or more oil-soluble or oil-dispersible sulfur-containing antioxidants can be used as antioxidant additives. For example, alkylphenol sulfides and their alkali metal salts or alkaline earth metal salts are also useful antioxidants in this specification. Preferably, the lubricating oil composition of the present disclosure contains 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, even more preferably 0.04 to 0.1% by mass of sulfur to the lubricating oil composition based on the total mass of the lubricating oil composition. Optionally, the oil-soluble or oil-dispersible sulfur-containing antioxidant is sulfurized C4-C 25 olefins, sulfurized aliphatic (C7-C 29 ) hydrocarbyl fatty acid esters, ashless sulfurized phenolic antioxidants, sulfur-containing organic molybdenum compounds, and combinations thereof. For further information regarding sulfide materials useful as antioxidants in this specification, see U.S. Patent No. 10,731,101 (column 15, line 55 to column 22, line 12).

[0174] Useful antioxidants in this specification include hindered phenols and / or arylamines. Such antioxidants can be used individually or in combination with each other for each type. Typical antioxidants include Irganox™ L67, Ethanox™ 4702, Lanxess Additin™ RC7110; Ethanox™ 4782J; Irganox™ 1135, Irganox™ 5057, sulfurized lard oil, and palm oil fatty acid methyl ester. The antioxidant additive can be used in an amount of about 0.01 to 10 (alternatively about 0.01 to 5, alternatively 0.01 to 3) mass%, alternatively 0.03 to 5 mass%, alternatively less than 0.05 to 3 mass% based on the mass of the lubricating composition. The compositions according to the present disclosure may include additives having various notational functions that also have a secondary effect as antioxidants (for example, phosphorus-containing antiwear agents (e.g., ZDDP) can also exhibit an antioxidant effect). Such additives are not included in the antioxidants for the purpose of determining the amount of antioxidants in the lubricating oil composition or concentrate herein.

[0175] F. Pour Point Depressant Conventional pour point depressants (also known as lubricating oil flow improvers) can be added to the compositions of the present disclosure as needed. Adding such a pour point depressant to the lubricating composition of the present disclosure can lower the lowest temperature at which the fluid will flow or can be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyaryl amides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkyl fumarates, vinyl esters of fatty acids, 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 useful pour point depressants and / or their preparation. Such additives 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.

[0176] G. Antifoaming Agent Advantageously, an antifoaming agent can be added to the lubricant compositions described herein. Such agents prevent or delay the formation of stable bubbles. Silicones and / or organic polymers are typical antifoaming agents. For example, polysiloxanes, such as silicone oil or polydimethylsiloxane, provide antifoaming properties. Defoamers are commercially available and can be used in small amounts, for example, 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.1% by mass or less, for example, 5% by mass to 0.1 ppm, for example, 3% by mass to 0.5 ppm, for example, 1% by mass to 10 ppm.

[0177] For example, the lubricating oil composition is a defoamer containing polyalkylsiloxane, for example, polydialkylsiloxane, and for example, the alkyl is C1 - C 10 It may contain a defoamer that is an alkyl group, for example, polydimethylsiloxane (PDMS), also known as silicone oil. Alternatively, the siloxane is a poly(R 3 ) siloxane, and R 3 is typically one or more of the same or different linear, branched, or cyclic hydrocarbyls having 1 to 20 carbon atoms, such as alkyl or aryl. For example, the lubricating oil composition contains a polymeric siloxane compound according to the following formula 1, 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 isomers thereof (e.g., methyl, phenyl), and n is 2 - 1000, for example, 50 - 450, alternatively for example 40 - 100.

[0178] In addition or alternatively, the lubricating oil composition may contain an organically modified siloxane (OMS), for example, a polyether (e.g., ethylene - propylene oxide copolymer), a long-chain hydrocarbyl (e.g., C 11 - C 100 alkyl), or a siloxane modified with an organic group such as aryl (e.g., C6 - C 14 aryl). For example, the lubricating oil composition contains an organically modified siloxane compound according to formula 1, where n is 2 - 2000, for example, 50 - 450 (alternatively for example 40 - 100), and R 1 and R 2 are the same or different, and optionally, R 1 and R 2Each of them is independently an organic group, such as a polyether (e.g., ethylene-propylene oxide copolymer), a long-chain hydrocarbyl (e.g., C 11 ~C 100 alkyl), or an aryl (e.g., C6~C 14 aryl), which is an organic group selected from. Preferably, one of R 1 and R 2 is CH3. [Chemical formula] Formula 1

[0179] Based on the total mass of the lubricating composition, the siloxane according to Formula 1 is incorporated to provide about 0.1 to less than about 30 ppm of Si, or about 0.1 to about 25 ppm of Si, or about 0.1 to about 20 ppm of Si, or about 0.1 to about 15 ppm of Si, or about 0.1 to about 10 ppm of Si. More preferably, it is in the range of about 3 to 10 ppm of Si. In embodiments, silicone defoamers useful herein, such as Dow Corning FS-1265 (1000 centistokes), Dow Corning DC-20, and Union Carbide UC-L45, etc., are available from Dow Corning Corporation and Union Carbide Corporation. Silicone defoamers useful herein include polydimethylsiloxane, phenyl-methylpolysiloxane, linear, cyclic, or branched siloxanes, silicone polymers and copolymers, and / or organosilicone copolymers. Also, a siloxane polyether copolymer defoamer available from OSI Specialties, Inc. in Farmington Hills, Michigan can be substituted or included. One such substance is sold as SILWET-L-7220.

[0180] In this specification, an acrylate polymer defoamer can also be used. Typical acrylate defoamers include polyacrylate defoamers available from Monsanto Polymer Products Co., known as PC-1244. A preferred acrylate polymer defoamer useful in this specification is commercially available from Dorf Ketl and is PX(trademark)3841 (i.e., an alkyl acrylate polymer), also called Mobilad(trademark)C402. In embodiments, a combination of a silicone defoamer and an acrylate defoamer can be used, for example, at a mass ratio of silicone defoamer to acrylate defoamer of about 5:1 to about 1:5. See, for example, U.S. Patent Application Publication No. 2021 / 0189283.

[0181] H. Viscosity Modifiers A viscosity modifier (also referred to as a viscosity index improver or a viscosity enhancer) can be included in the lubricating compositions described herein. Viscosity modifiers provide high-temperature and low-temperature operability to lubricants. Such additives impart shear stability at high temperatures and an acceptable viscosity at low temperatures. Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters, and viscosity-modifying dispersants that can function as both viscosity modifiers and dispersants. The typical molecular weight of such polymers is from about 10,000 to 1,500,000 g / mol, more typically from about 20,000 to 1,200,000 g / mol, and even more typically from about 50,000 to 1,000,000 g / mol.

[0182] Examples of suitable viscosity modifiers are linear or star polymers and copolymers of methacrylate, butadiene, olefin, or alkylated styrene. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (e.g., copolymers of alkyl methacrylates of various chain lengths), and some of its formulations also serve as pour point depressants. Other suitable viscosity modifiers 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 polymers with a molecular weight of 50,000 to 200,000 g / mol.

[0183] Examples of copolymers useful as viscosity modifiers include those commercially available under the trade name "PARATONE™" from Chevron Oronite Company LLC (e.g., "PARATONE™ 8921", PARATONE™ 68231, and "PARATONE™ 8941"), those commercially available under the trade name "HiTEC™" from Afton Chemical Corporation (e.g., HiTEC™ 5850B and HiTEC™ 5777), and those commercially available under the trade name "Lubrizol™ 7067C" from The Lubrizol Corporation. Examples of hydrogenated polyisoprene star polymers useful as viscosity modifiers in this specification include those commercially available from Infineum International Limited under, for example, the trade names "SV200™" and "SV600™". Examples of hydrogenated diene-styrene block copolymers useful as viscosity modifiers in this specification are commercially available from Infineum International Limited under, for example, the trade name "SV50™".

[0184] Polymers useful as viscosity modifiers herein include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, such as those available under the trade name “Viscoplex™” (e.g., Viscoplex™ 6-954) from Evnoik Industries, or star polymers available under the trade name Asteric™ (e.g., Lubrizol™ 87708 and Lubrizol™ 87725) from Lubrizol Corporation. Vinyl aromatic-containing polymers useful as viscosity modifiers herein can be derived from vinyl aromatic hydrocarbon 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 hydrocarbon monomers (e.g., styrene), and B is a polymeric block mainly derived from conjugated diene monomers (e.g., isoprene).

[0185] Vinyl aromatic-containing polymers useful as viscosity modifiers may have a kinematic viscosity at 100 °C of 20 cSt or less, such as 15 cSt or less, such as 12 cSt or less, but may be diluted to a higher kinematic viscosity at 100 °C, such as 40 cSt or more, such as 100 cSt or more, such as 1000 cSt or more, such as 1000 - 2000 cSt (e.g., in Group I, II, and / or III base stocks). Typically, the viscosity modifier 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%, such as about 0.2 to about 0.5 wt% based on the total mass of the formulated lubricant composition. Viscosity modifiers are typically added as concentrates to large amounts of diluent oil. The "as-received" viscosity modifier typically contains 20% to 75% by weight of active polymer in the case of polymethacrylate or polyacrylate polymers, or 8% to 20% by weight of active polymer in the case of olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers in the "as-received" polymer concentrate.

[0186] I. Dispersants During engine operation, oil-insoluble oxidation by-products are formed. Dispersants assist in keeping these by-products in solution and thus reduce their deposition on metal surfaces. The dispersants used in formulating the lubricating compositions herein may be ashless in nature or ash-forming. Preferably, the dispersants are ashless. So-called ashless dispersants are organic substances that do not substantially form ash upon combustion. For example, non-metal-containing dispersants or boronated metal-free dispersants are considered ashless. In contrast, metal-containing detergents tend to form ash upon combustion. Dispersants useful herein typically contain polar groups attached to relatively high molecular weight hydrocarbon chains. The polar groups typically contain at least one element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain 40 to 500, for example 50 to 400, carbon atoms.

[0187] (Poly)alkenyl succinic acid derivative dispersants Particularly useful types of dispersants typically include long-chain hydrocarbyl-substituted succinic compounds, usually (poly)alkenyl succinic derivatives produced by the reaction of a hydrocarbyl-substituted succinic anhydride with a polyhydroxy or polyamino compound. The long-chain hydrocarbyl groups that constitute the lipophilic portion of the molecule imparting solubility in the oil are often polyisobutylene groups (typically, long-chain hydrocarbyl groups, such as polyisobutylene groups, have a Mn of 400 to 3000 g / mol, such as 450 to 2500 g / mol). Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U.S. patents in which such dispersants are described 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, and 5,705,458. Further descriptions of dispersants useful herein can be found, for example, in European Patent Applications Nos. 0 471 071 and 0 451 380, and such documents are hereby incorporated by reference for this purpose.

[0188] Hydrocarbyl-substituted succinic acids and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimides, succinate esters, or succinate ester amides prepared by reacting a hydrocarbon-substituted succinic acid or anhydride compound (typically having at least 25 carbon atoms, e.g., 28 to 400 carbon atoms in the hydrocarbon substituent) with at least 1 equivalent of a polyhydroxy or polyamino compound (e.g., an alkylene amine) are particularly useful herein. Hydrocarbyl-substituted succinic acids and hydrocarbyl-substituted succinic anhydride derivatives may have a number average molecular weight of at least 400 g / mol, e.g., at least 900 g / mol, e.g., at least 1500 g / mol, e.g., 400 to 4000 g / mol, e.g., 800 to 3000, e.g., 2000 to 2800 g / mol, e.g., about 2100 to 2500 g / mol, e.g., about 2200 to about 2400 g / mol.

[0189] The succinimides that are particularly useful herein are formed by the condensation reaction of 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 tetraethylene pentamine, pentaethylene hexamine, tetraethylene pentamine (TEPA), pentaethylene hexamine (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-PAM and may be commercially available under trade names such as HPA (trademark) and HPA-X (trademark) of Dow Chemical Company, E-100 (trademark) of Huntsman Chemical Company, 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 having an average Mn of about 200 to about 5000 g / mol and / or polyoxypropylene diamines and triamines (and their co-oligomers). Products of this type are commercially available under the trade name Jeffamine (trademark). Representative examples of useful 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.

[0190] The dispersant may contain one or more succinimides of higher molecular weight (Mn 1600 g / mol or more, for example 1800 - 3000 g / mol) which may be boronated, and one or more succinimides of lower molecular weight (Mn less than 1600 g / mol) which may be boronated. The higher molecular weight may be 1600 - 3000 g / mol, for example 1700 - 2800 g / mol, for example 1800 - 2500 g / mol, for example 1850 - 2300 g / mol. The lower molecular weight may be less than 600 - 1600 g / mol, for example 650 - 1500 g / mol, for example 700 - 1400 g / mol, for example 800 - 1300 g / mol, for example 850 - 1200 g / mol, for example 900 - 1150 g / mol, for example 900 - 1000 g / mol. The higher molecular weight succinimide dispersant may be present in the lubricating composition at 0.5 - 10% by mass, or 0.8 - 6% by mass, or 1.0 - 5% by mass, or 1.5 - 5% by mass, or 1.5 - 4.0% by mass. The lower molecular weight succinimide dispersant may be present in the lubricating composition at 1 - 5% by mass, or 1.5 - 4.8% by mass, or 1.8 - 4.6% by mass, or 1.9 - 4.6% by mass, or 2% by mass or more, for example 2 - 5% by mass. The lower molecular weight succinimide may differ from the higher molecular weight succinimide by 500 g / mol or more, for example 750 g / mol or more, for example 1000 g / mol or more, for example 1200 g / mol, for example 500 - 3000 g / mol, for example 750 - 2000 g / mol, for example 1000 - 1500 g / mol.

[0191] Useful succinic esters as dispersants include those formed by the condensation reaction of a hydrocarbyl-substituted succinic anhydride with an alcohol or a polyol. For example, the condensation product of a hydrocarbyl-substituted succinic anhydride and pentaerythritol is a useful dispersant. The succinic acid ester amides useful herein are formed by the condensation reaction of a hydrocarbyl-substituted succinic anhydride with an alkanolamine. Suitable alkanolamines include ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines, and polyalkenyl polyamines such as polyethylene polyamines and / or propoxylated hexamethylenediamine. Representative examples are shown in U.S. Patent No. 4,426,305.

[0192] Hydrocarbyl-substituted succinic anhydride (e.g., PIBSA) esters of hydrocarbyl-bridged aryloxy alcohols are also useful herein as dispersants. Information regarding such dispersants can be found in 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 naphthyloxyethanol (i.e., 2-hydroxyethyl-1-naphthol ether (or hydroxy-terminated ethylene oxide oligomer ether of naphthol)) is useful herein.

[0193] The molecular weight of the hydrocarbyl-substituted succinic anhydride used in the preceding paragraphs will typically be in the range of 350 to 4000 g / mol, such as 400 to 3000 g / mol, such as 450 to 2800 g / mol, such as 800 to 2500 g / mol. The above (poly)alkenyl succinic acid derivatives may be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid. The dispersant may be present in the lubricant in an amount of 0.1% to 20% by weight of the composition, such as 0.2 to 15% by weight of the lubricating oil composition, such as 0.25 to 10% by weight, such as 0.3 to 5% by weight, such as 1.0% to 3.0% by weight.

[0194] The above (poly)alkenyl succinic acid derivatives can also be post-reacted with boron compounds such as boric acid, boric acid esters, or highly boronated dispersants to form boronated dispersants having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product. Useful dispersants in this specification include borated succinimides containing derivatives derived from monosuccinimide, bis-succinimide, and / or mixtures of monosuccinimide and bis-succinimide. Hydrocarbyl succinimide is derived from a hydrocarbylene group, for example, polyisobutylene having an Mn of about 300 to about 5000 g / mol, or about 500 to about 3000 g / mol, or about 1000 to about 2000 g / mol, or a mixture of such hydrocarbylene groups often having a high terminal vinyl group. The boron-containing dispersant may be present in the lubricating composition at 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.

[0195] The boron-containing dispersant may be present in an amount that delivers 15 ppm to 2000 ppm, or 25 ppm to 1000 ppm, or 40 ppm to 600 ppm, or 80 ppm to 350 ppm of boron to the composition. The borated dispersant can be used in combination with a non-borated dispersant, which may be the same compound or a different compound as the non-borated dispersant. In one embodiment, the lubricating composition may contain one or more boron-containing dispersants and one or more non-borated dispersants. The total amount of the dispersant may be 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 of the lubricating composition. The ratio of the borated dispersant to the non-borated dispersant may be 1:10 to 10:1 (weight:weight), or 1:5 to 3:1, or 1:3 to 2:1. The dispersant may include one or more borated or non-borated poly(alkenyl) succinimides, where the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine, one or more borated or non-borated poly(alkenyl) succinimides ("PIBSA-PAM").

[0196] The dispersant is one or more PIBSA-PAMs, where the PIB is derived from polyisobutylene having an 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 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 may contain one or more PIBSA-PAMs. The dispersant may typically be borated at a level of up to 4% by weight, such as 1 to 3% by weight. The dispersant may contain one or more borated PIBSA-PAMs and one or more non-borated PIBSA-PAMs. The dispersant may contain one or more borated PIBSA-PAMs derived from PIB having an Mn of 700 to 1800 g / mol (e.g., 800 to 1500 g / mol), and one or more non-borated PIBSA-PAMs derived from PIB having an Mn greater than 1800 and up to 5000 g / mol (e.g., 2000 to 3000 g / mol). The dispersant may contain one or more non-borated PIBSA-PAMs derived from PIB having an Mn of 700 to 1800 g / mol (e.g., 800 to 1500 g / mol), and one or more borated PIBSA-PAMs derived from PIB having an Mn greater than 1800 and up to 5000 g / mol (e.g., 2000 to 3000 g / mol).

[0197] The dispersant may contain PIBSA derived from PIB having an Mn of 700 to 5000 g / mol (e.g., 800 to 3000 g / mol) and one or more borated or non-borated PIBSA-PAMs derived from PIB having an Mn of 700 to 5000 g / mol. The dispersant may include PIBSA derived from PIB having an Mn of 700 to 5000 g / mol (for example, 800 to 3000 g / mol), and one or more boric acid-modified PIBSA-PAMs derived from PIB having an Mn of 700 to 1800 g / mol (for example, 800 to 1500 g / mol), and one or more non-boric acid-modified PIBSA-PAMs derived from PIB having an Mn greater than 1800 and up to 5000 g / mol (for example, 2000 to 3000 g / mol). The dispersant may include PIBSA derived from PIB having an Mn of 700 to 5000 g / mol (for example, 800 to 3000 g / mol), one or more non-boric acid-modified PIBSA-PAMs derived from PIB having an Mn of 700 to 1800 g / mol (for example, 800 to 1500 g / mol), and one or more boric acid-modified PIBSA-PAMs derived from PIB having an Mn greater than 1800 and up to 5000 g / mol (for example, 2000 to 3000 g / mol).

[0198] The dispersant may include one or more PIBSA-esters of one or more boric acid-modified or non-boric acid-modified PIBSA-PAMs and hydrocarbyl crosslinked aryloxy alcohols. The dispersant may include one or more boric acid-modified PIBSA-PAMs and one or more non-boric acid-modified PIBSA-PAMs. The dispersant may contain one or more PIBSA-PAMs with a higher molecular weight (Mn 1600 g / mol or more, for example 1800 - 3000 g / mol) that may be boronated, and one or more PIBSA-PAMs with a lower molecular weight (Mn less than 1600 g / mol) that may be boronated. The higher molecular weight may be 1600 - 3000 g / mol, for example 1700 - 2800 g / mol, for example 1800 - 2500 g / mol, for example 1850 - 2300 g / mol. The lower molecular weight may be less than 600 - 1600 g / mol, for example 650 - 1500 g / mol, for example 700 - 1400 g / mol, for example 800 - 1300 g / mol, for example 850 - 1200 g / mol, for example 900 - 1150 g / mol, for example 900 - 1000 g / mol. The higher molecular weight PIBSA-PAM dispersant may be present in the lubricating composition at 0.5 - 10% by mass, or 0.8 - 6% by mass, or 1.0 - 5% by mass, or 1.5 - 5% by mass, or 1.5 - 4.0% by mass. The lower molecular weight PIBSA-PAM dispersant may be present in the lubricating composition at 1 - 5% by mass, or 1.5 - 4.8% by mass, or 1.8 - 4.6% by mass, or 1.9 - 4.6% by mass, or 2% by mass or more, for example 2 - 5% by mass.

[0199] Dispersant of Mannich base The Mannich base dispersants useful herein are typically made from the reaction of an amine component, a hydroxyaromatic compound (substituted or unsubstituted, e.g., alkyl-substituted), such as an alkylphenol, and an aldehyde, such as formaldehyde. See U.S. Patent Nos. 4,767,551 and 10,899,986. Also, processing aids and catalysts, such as oleic acid and sulfonic acid, may 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 International Publication No. 01 / 42399 pamphlet.

[0200] Dispersants of polymethacrylate or polyacrylate derivatives Polymethacrylate or polyacrylate derivatives are another type of dispersant useful herein. Such dispersants are typically prepared by reacting a nitrogen-containing monomer with a methacrylic acid ester or acrylic acid ester containing 5 to 25 carbon atoms in the ester group. Representative examples are shown in U.S. Patent Nos. 2,100,993 and 6,323,164. Polymethacrylate and polyacrylate dispersants are typically of lower molecular weight. The lubricating compositions of the present disclosure typically contain from 0.1 wt% to 20 wt% of the composition, e.g., from 0.2 to 15 wt% of a lubricating oil composition, e.g., from 0.25 to 10 wt%, e.g., from 0.3 to 5 wt%, e.g., from 2.0 wt% to 4.0 wt% of a dispersant. Alternatively, the dispersant may be present at from 0.1 wt% to 5 wt% or from 0.01 wt% to 4 wt% of the lubricating composition.

[0201] For further information regarding dispersants useful herein, see column 13, line 36 to column 16, line 67 of U.S. Patent No. 10,829,712 and 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 of U.S. Patent No. 7,485,603. The compositions according to the present disclosure may include additives having various notation functions that also have a secondary effect as a dispersant (for example, the component B-functionalized polymer described above can also exhibit a dispersant effect). Such additives are not included in the dispersant for the purpose of determining the amount of the dispersant in the lubricating oil composition or concentrate herein.

[0202] J. Corrosion inhibitor / Rust preventive Corrosion inhibitors can be used to reduce the corrosion of metals and are often alternatively referred to as metal deactivators or metal passivators. Some corrosion inhibitors may alternatively be characterized as antioxidants. Suitable corrosion inhibitors 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 of these. A specific corrosion inhibitor has the following structure:

Chemical formula

[0203] In addition or alternatively, the corrosion inhibitor may include one or more substituted thiadiazoles represented by the structure:

Chemical formula

[0204] Further, in addition to or alternatively, the corrosion inhibitor may include one or more other derivatives of DMTD, such as 15 and 16 may include carboxylic acid esters in which R 15 and 16 are bonded to the sulfide sulfur atom via a carbonyl group. The preparation of such thioester-containing DMTD derivatives is described, for example, in U.S. Patent No. 2,760,933. DMTD derivatives produced by condensation of DMTD with an alpha-halogenated aliphatic carboxylic acid having at least 10 carbon atoms are described, for example, in U.S. Patent No. 2,836,564. By this method, DMTD derivatives in which 19 and 19 is HOOC-CH(R 19 )-(R 19 is a hydrocarbyl group) are produced. DMTD derivatives further produced by amidation or esterification of such terminal carboxylic acid groups may also be useful.

[0205] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561. Examples of DMTD derivatives include mixtures of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such mixtures are sold under the trade name HiTEC™ 4313 and are commercially available from Afton Chemical Company. The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561. Examples of DMTD derivatives include mixtures of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such mixtures are sold under the trade name HiTEC™ 4313 and are commercially available from Afton Chemical Company.

[0206] Still further, in addition to or in place of, the corrosion inhibitor may include a trifunctional borate having the structure B(OR 46 )3, where each R 46 may be the same or different. Since the borate is typically desirably compatible with the non-aqueous medium of the composition, each R 46 may in particular include a hydrocarbyl C1-C8 moiety or be a hydrocarbyl C1-C8 moiety. For example, in the case of a composition where the non-aqueous medium comprises or is a lubricating oil base stock, typically better compatibility can be achieved when the hydrocarbyl moieties are each at least C4. Thus, non-limiting examples of such corrosion inhibitors 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, and monohexyl dibutyl borate, and combinations thereof. When used, the corrosion inhibitor may include a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof.

[0207] If desired, the corrosion inhibitor can be used in any effective amount, but when used, typically, based on the mass of the composition, it can be used in an amount of about 0.001% to 5.0% by mass, such as 0.005% to 3.0% by mass, or 0.01% to 1.0% by mass. Alternatively, such an additive can be used in an amount of about 0.01 to 5% by mass, preferably about 0.01 to 1.5% by mass, based on the mass of the lubricating composition. In some embodiments, the 3,4-oxypyridinone-containing composition may not substantially contain a triazole, a benzotriazole, a substituted thiadiazole, an imidazole, a thiazole, a tetrazole, a hydroxyquinoline, an oxazoline, an imidazoline, a thiophene, an indole, an indazole, a quinoline, a benzoxazine, a dithiol, an oxazole, an oxatriazole, a pyridine, a piperazine, a triazine, derivatives thereof, combinations thereof, or any corrosion inhibitor (e.g., 0, or less than 0.001% by mass, 0.0005% by mass or less, intentionally not added, and / or not contained at all). The compositions according to the present disclosure may include additives having various marking functions that also have a secondary effect as a corrosion inhibitor (e.g., the component B functionalized polymer described above can also exhibit a corrosion inhibitor effect). Such additives are not included in the corrosion inhibitor for the purpose of determining the amount of the corrosion inhibitor in the lubricating oil composition or concentrate herein.

[0208] K. Antiwear Agent 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 skilled in the art can be used in the lubricating oil composition. Non-limiting examples of suitable antiwear agents include zinc dithiophosphate, metal salts of dithiophosphates (e.g., metals such as Pb, Sb, and Mo), metal salts of dithiocarbamates (e.g., metals such as Zn, Pb, Sb, and Mo), metal salts of fatty acids (e.g., metals such as Zn, Pb, and Sb), boron compounds, phosphate esters, phosphite esters, amine salts of phosphate esters or thiophosphate esters, reaction products of dicyclopentadiene and thiophosphoric acid, and combinations thereof. The amount of the antiwear agent may range from about 0.01% by mass to about 5% by mass, from about 0.05% by mass to about 3% by mass, or from about 0.1% by mass to about 1% by mass based on the total mass of the lubricating oil composition.

[0209] In embodiments, the antiwear agent is or includes a metal salt of dihydrocarbyl dithiophosphate, such as a zinc dialkyldithiophosphate compound. The metal of the metal salt of dihydrocarbyl dithiophosphate may 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 dihydrocarbyl dithiophosphate has about 3 to about 22 carbon atoms, about 3 to about 18 carbon atoms, about 3 to about 12 carbon atoms, or about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched. Also, useful antiwear agents include substituted or unsubstituted thiophosphoric acids, and examples of these salts include zinc-containing compounds, such as zinc dialkyldithiophosphate, zinc diaryldithiophosphate, and / or zinc alkylaryldithiophosphate compounds selected from zinc dithiophosphate compounds.

[0210] Metal alkyl thiophosphates and more particularly zinc dialkyldithiophosphates or zinc dialkyldithiophosphates (ZDDP) where the metal component is zinc 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 are generally of the formula Zn[SP(S)(OR1)(OR2)]2 where R1 and R2 are C1-C 18 alkyl groups, preferably C2-C 12 alkyl groups. Such alkyl groups may be straight-chain or branched-chain. Alcohols used for ZDDP can be 2-propanol, butanol, secondary butanol, pentanol, hexanol, for example, 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, and alkylated phenols and the like. Mixtures of secondary alcohols or mixtures of primary and secondary alcohols may be used. Alkylaryl groups can also be used. Useful zinc dithiophosphates include those commercially available under the trade names "LZ 677A", "LZ 1095", and "LZ 1371" from The Lubrizol Corporation, those commercially available under the trade name "OLOA 262" from Chevron Oronite, and those commercially available under the trade name "HiTEC™ 7169" from Afton Chemical and the like, secondary zinc dithiophosphates.

[0211] In embodiments, the zinc compound can be a zinc dithiocarbamate complex, for example, of the formula:

Chemical formula

[0212] Antiwear additives such as ZDDP and / or zinc carbamate are typically used in amounts of about 0.4 wt% to about 1.2 wt%, preferably about 0.5 wt% to about 1.0 wt%, more preferably about 0.6 wt% to about 0.8 wt% based on the total mass of the lubricating composition, although in many cases more or less amounts can be advantageously used. 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 mass of the lubricating composition. Also, antiwear additives useful herein include boron-containing compounds such as borate esters, boronated aliphatic amines, boronated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates, and boronated overbased metal salts. The compositions according to the present disclosure may include additives having various notational functions that also have a secondary effect as antiwear agents (for example, the component B-functionalized polymers described above can also exhibit an antiwear agent effect). Such additives are not included in the antiwear agent for the purpose of determining the amount of antiwear agent in the lubricating oil composition or concentrate herein.

[0213] L. Demulsifier Useful anti-emulsifiers in this specification include those described in U.S. Patent No. 10,829,712 (column 20, lines 34 to 40). In this specification, typically a small amount of anti-emulsifying component can be used. Preferred anti-emulsifying components are described in European Patent No. 330,522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol. Such additives can be used in an amount of about 0.001 to 5% by weight, preferably about 0.01 to 2% by weight.

[0214] M. Seal compatibility agent Other optional additives include seal compatibility agents such as organic phosphates, aromatic esters, aromatic hydrocarbons, esters (e.g., butyl benzyl phthalate), and polybutenyl succinic anhydride. Such additives can be used in an amount of about 0.001 to 5% by weight, preferably about 0.01 to 2% by weight. In an embodiment, the seal compatibility agent is a sea swell agent such as PIBSA (polyisobutenyl succinic anhydride).

[0215] N. Extreme pressure agent The lubricating oil composition of the present disclosure may contain one or more extreme pressure agents capable of preventing seizure of a sliding metal surface under extreme pressure conditions. Any extreme pressure agent known to those skilled in the art can be used in the lubricating oil composition. Generally, an extreme pressure agent is a compound that can chemically combine with a metal to form a surface film that prevents welding of the irregularities of the opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents include the following: sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and mono-unsaturated olefins, co-sulfurized blends of fatty acids, fatty acid esters, and alpha-olefins, functional group-substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, episulfide compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpenes and acyclic olefins, and polysulfide olefin products, amine salts of phosphoric esters or thiophosphoric esters, and combinations thereof. The amount of the extreme pressure agent may range from about 0.01% by mass to about 5% by mass, from about 0.05% by mass to about 3% by mass, or from about 0.1% by mass to about 1% by mass based on the total mass of the lubricating oil composition.

[0216] O. Non-base stock unsaturated hydrocarbons The lubricating oil composition of the present disclosure may contain one or more unsaturated hydrocarbons. Such unsaturated hydrocarbons are different from any base oil (lubricating oil base stock of Group I, II, III, IV, and / or V) and / or viscosity modifier that may be present in the composition, and always have at least one unsaturation per molecule (typically only one in the case of linear alpha-olefins or LAO). Without being bound by theory, the unsaturation can provide antioxidant functionality and / or sulfur scavenging functionality that can complement and / or replace one or more antioxidant additives and / or one or more corrosion inhibitor additives, but the unsaturated hydrocarbon (LAO) will typically not be the only antioxidant or the only corrosion inhibitor in the lubricating oil composition. Non-limiting examples of unsaturated hydrocarbons include one or more unsaturated C 12 ~C 60 hydrocarbons (e.g., C 12 ~C 48 hydrocarbons, C 12 ~C 36 hydrocarbons, C 12 ~C 30 hydrocarbons, or C 12 ~C 24 hydrocarbons). When there is only one unsaturation, the unsaturated hydrocarbon may be referred to as a linear alpha-olefin (LAO). Other non-limiting examples of unsaturated hydrocarbons include oligomers / polymers of polyisobutylene that retain (or are post-polymerization modified to exhibit) terminal (nearby) unsaturation, and / or blends thereof. The unsaturated hydrocarbon (LAO), if present, may be present in an amount of 0.01 to 5% by mass (in particular, 0.1 to 3% by mass, alternatively 0.1 to 1.5% by mass) based on the total mass of the lubricating oil composition.

[0217] When the lubricating oil composition contains one or more of the additives discussed above, the additives are typically blended into the composition in an amount sufficient to perform their intended function. Typical amounts of such additives useful in the present disclosure, particularly for use in crankcase lubricants, are shown in the following table. Note that many additives are shipped from additive manufacturers as concentrates containing one or more additives together with a certain amount of base oil or other diluent. Accordingly, the amounts by mass in the tables below, as well as the other amounts referred to herein, refer to the amounts of the active ingredients (i.e., the undiluted portions of the components). The mass percentages (mass %) shown below are based on the total mass of the lubricating oil composition.

Table 1

[0218] The above-mentioned additives are typically commercially available substances. Such additives may be added independently, but are usually pre-mixed in packages that can be obtained from suppliers of lubricating oil additives. Additive packages with various components, ratios, and characteristics are available, and the appropriate package will be selected considering the use of the final composition.

[0219] Fuel The present disclosure relates to a method for lubricating an automotive internal combustion engine during engine operation, comprising: (i) supplying the lubricating composition described herein to the crankcase of the automotive internal combustion engine; (ii) supplying a hydrocarbon fuel to 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 vehicle engine (e.g., a spark-ignition combustion engine). The present disclosure also relates to a fuel composition comprising the lubricating oil composition and the hydrocarbon fuel described herein, wherein the fuel may be derived from petroleum and / or a biological source (a "biofuel" or "renewable fuel"). In embodiments, the fuel comprises 0.1 to 100% by mass of renewable fuel, alternatively 1 to 75% by mass of renewable fuel, alternatively 5 to 50% by mass of renewable fuel, based on the total mass of the renewable fuel and the petroleum-derived fuel. 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 a biological source (a "biofuel" or "renewable fuel"). In embodiments, the fuel comprises 0.1 to 100% by mass of renewable fuel, alternatively 1 to 75% by mass of renewable fuel, alternatively 5 to 50% by mass of renewable fuel, based on the total mass of the renewable fuel and the petroleum-derived fuel.

[0220] Renewable fuel components are typically produced from vegetable oils (e.g., palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oils (e.g., algal oil), animal fats (e.g., cooking oil, animal fat, and / or fish oil), and / or biogas. Renewable fuels refer to biofuels produced from biological resources formed by modern biological processes. In one embodiment, the renewable fuel component is produced by a hydrotreating process. Hydrotreating includes 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. Reactions include, but are not limited to, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrocracking, and isomerization. The renewable fuel component may have various distillation ranges that provide the desired properties to the component depending on the intended purpose.

[0221] Use The lubricating compositions of the present disclosure can be used for lubricating mechanical engine parts of internal combustion engines, particularly spark-ignition or compression-ignition two-stroke or four-stroke reciprocating engines, by adding lubricants thereto. Typically, the lubricating compositions of the present disclosure are crankcase lubricants, such as passenger car motor oils or large diesel engine lubricating oils.

[0222] In particular, the lubricating compositions of the present disclosure are preferably used for lubricating the crankcase of a compression-ignition internal combustion engine, such as a large diesel engine. In particular, the lubricating compositions of the present disclosure are preferably used for lubricating the crankcase of a spark-ignition turbocharged internal combustion engine. In an embodiment, 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 is useful for lubricating a high compression spark-ignition engine. In an embodiment, the lubricating composition of the present disclosure is preferably used for lubricating the crankcase of an engine of a large diesel vehicle (i.e., a large diesel vehicle having a gross vehicle weight rating of 4535.9 kg (10,000 pounds) or more). In an embodiment, the lubricating composition of the present disclosure is preferably used for lubricating the crankcase of a passenger car diesel engine. In particular, the lubricating oil formulation of the present disclosure is particularly useful in compression ignition internal combustion engines, i.e., large diesel engines, where valve train wear protection is an issue, using low viscosity oils such as API FA-4 and future oil categories.

[0223] Additional Embodiments / EP Clauses 1. A copolymer, comprising the following: I. (a) 10.0 to 20.0 mass% of amine-derivatized alpha-methylstyrene (ADAMS) repeat units according to structure (I),

Chemical formula

Chemical formula

[0224] 2. The copolymer according to clause 1, which is partially or substantially hydrogenated. 3. The copolymer according to clause 1 or 2, wherein k = 2. 4. The copolymer according to clauses 1 to 3, which is derived from a monofunctional initiator selected from the group consisting of alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and further contains an alkyl residue present at one or more terminals of the polymer backbone. 5. The copolymer according to clause 4, wherein the alkyl residue derived from the monofunctional initiator includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an iso-amyl group, a sec-amyl group, a tert-amyl group, a hexyl group, or combinations thereof.

[0225] 6. One or more polymer blocks of the copolymer form a dispersed polymer architecture, a diblock, a triblock, a tetrablock, a pentablock, a hexablock, a star polymer architecture, or combinations thereof. The copolymer according to clauses 1 to 5.

[0226] 7. A lubricating oil composition comprising (i) at least 50% by mass, based on the mass of the lubricating oil composition, of one or more base oils, (ii) one or more dispersants, (iii) one or more detergents, and (iv) one or more copolymers as described in clauses 1 to 6, or a lubricating oil composition obtained by mixing them.

[0227] 8. The lubricating oil composition according to 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.

[0228] 9. The lubricating oil composition according to clause 7 or 8, comprising (i) 50 to 99% by mass, based on the mass of the lubricating oil composition, of one or more base oils, (ii) 0.01 to 20% by mass, based on the total mass of the lubricating oil composition, of one or more dispersants, (iii) 0.10 to 20% by mass, based on the mass of the lubricating oil composition, of one or more detergents, and (iv) 0.10 to 20% by mass, based on the mass of the lubricating oil composition, of one or more copolymers, or a lubricating oil composition obtained by mixing them.

[0229] 10. The lubricating oil composition according to clauses 7 to 9, further comprising one, two, three, four, five, six, or more additional additives selected from the group consisting of friction modifiers, antioxidants, pour point depressants, defoamers, viscosity modifiers, corrosion inhibitors and / or rust preventives, and antiwear agents.

[0230] 11. One or more friction modifiers in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition, B) one or more antioxidants in an amount of 0.01 to 10% by mass based on the total mass of the lubricating oil composition, C) one or more pour point depressants in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition, D) one or more defoamers in an amount of 0.001 to 5% by mass based on the total mass of the lubricating oil composition, E) one or more viscosity modifiers in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition, F) one or more inhibitors and / or rust inhibitors in an amount of 0.0 to 5% by mass based on the total mass of the lubricating oil composition, and / or G) one or more antiwear agents in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition, further comprising one, two, three, four, five, six, or more than that of the lubricating oil composition according to clauses 7 to 10.

[0231] 12. One or more detergents include one or more oil-soluble neutral or overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble carboxylates of alkali metals or alkaline earth metals, the lubricating oil composition according to clauses 7 to 11. 13. One or more dispersants include one or more boricated or non-boricated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from polyamine, the lubricating oil composition according to clauses 7 to 12.

[0232] 14. A method for lubricating an internal combustion engine during operation of the engine, comprising the steps of: (i) supplying the lubricating oil composition according to clauses 7 to 13 to the crankcase of the internal combustion engine; (ii) supplying fuel to the internal combustion engine; and (iii) burning the fuel in the internal combustion engine. 15. The fuel is one or more of hydrocarbon fuel, renewable fuel, hydrogen fuel, or any blend thereof, the method according to clause 14. 16. The engine is a diesel engine, the method according to clause 14 or 15. Hereinafter, the present invention will be described by way of non-limiting examples only.

Example

[0233] Test procedure A sample of either the crude reaction mixture or the isolated polymer product was dissolved in tetrahydrofuran (THF) to a final sample concentration of 1.0 - 5.0 mg polymer / ml THF to prepare a gel permeation chromatography (GPC) sample. GPC was performed in isocratic mode using stabilized THF as the mobile phase. The Mp, Mn, Mw, and Mz values of the polymer are all reported relative to PS standards, unless otherwise specified. All molecular weights are peak average molecular weights (Mp) determined by gel permeation chromatography using polystyrene standards and reported in kDa / mol, unless otherwise stated. Molecular weight values are reported for both the pre-hydrogenated polymer and the post-hydrogenated polymer. "A.I.", "ai", "a.i.", and "ai" are % by mass active ingredient, unless otherwise indicated.

[0234] KV100 is the kinematic viscosity measured at 100 °C according to ASTM D445-19a.

[0235] The contents of phosphorus, boron, calcium, zinc, molybdenum, magnesium, and sulfur are measured by ASTM D5185.

[0236] The high temperature high shear viscosity ("HTHS" or "HTHS150") is determined at 150 °C according to ASTM D4683 and reported in cPs.

[0237] Unless otherwise indicated, the cold cranking simulator ("CCS") at -25 °C is a measure of the cold cranking properties of the crankcase lubricant and is determined as described in ASTM D5293-92.

[0238] Cummins ISB Engine Test. Valve train wear protection was determined in a Cummins ISB engine test in a 5.9L six-cylinder diesel engine equipped with an exhaust gas recirculation device, according to ASTM D7484-21. The Cummins ISB test is a two-stage test. In Stage A, the engine was operated for 100 hours with the fuel injection timing retarded to produce excessive soot, according to the ASTM protocol. In Stage B, the engine was operated for 250 hours under cycle conditions according to the ASTM protocol to induce valve train wear. Oil performance was determined by evaluating the crosshead mass loss (mg) measured as detailed in Section 8.1.5 of ASTM D7484-21, the tappet mass 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. Substance Polymer Example The following ADAMS-isoprene copolymer samples were prepared according to the basic method in the above detailed description.

Table 2

Table 3

[0239] Example 1 Cummins ISB Test for Valve Train Wear Protection. Oils A, B, and comparative oil C were prepared and tested for valve train wear protection according to the Cummins ISB engine test described above. The data is reported in Table 1.

Table 4

[0240] Example 2 Soot-induced Viscosity Control Bench Test By mixing appropriate amounts of the final components and base oil, a 2.0 wt% solution of the selected isolated ADAMS-isoprene copolymer in Group II base oil (KV 100 6 cSt) was prepared and heated to 75 °C for 1 - 3 hours until the polymer was completely dissolved.

[0241] 45.5 g of the 2.0 wt% polymer solution was weighed and added to a 100 ml beaker containing 4.5 g of Vulcan XC72R carbon black to prepare a suspension of 9.0 wt% carbon black (Vulcan XC72R) in the ADAMS-isoprene copolymer solution. The suspension was mixed at 90 °C for 16 hours with an overhead stirrer (200 - 400 rpm) and then at 100 °C for 1 hour under an air atmosphere.

[0242] Using a Haake RS600 rheometer controlled by Haake RheoWin Job Manager software (version 4.30.0028), a soot-induced viscosity increase experiment was carried out using the conditions in Table 2 below.

Table 5

[0243] Using the kinematic viscosity of the sample in the final shear sweep, the soot dispersibility of various components diluted with 2.0 wt% of the active polymer in Group III base oil was compared. The viscosity (η, Pa-s) was measured at an approximate shear rate of 2.1 ± 0.1, 4.1 ± 0.1, and 8.1 ± 0.1 seconds -1 as described in Table 3 below.

Table 6

[0244] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference to the extent not inconsistent with the text. As should be apparent from the above basic description and the specific embodiments, although the forms of the present invention are illustrated and described, various modifications can be made without departing from the spirit and scope of the present invention. Accordingly, the present invention is not intended to be limited thereby. The term "comprising" specifies the presence of the described feature, step, integer, or component, but does not exclude the presence or addition of one or more other features, steps, integers, components, or groups thereof. Therefore, the term "comprising" is considered to be essentially synonymous with the term "including". Similarly, whenever the transitional phrase "comprising" precedes a composition, element, or group of elements, it is always contemplated that the same composition or group of elements having the transitional phrases "consisting essentially of", "consisting of", "selected from the group of consisting of", or "can be", "may be", "is" preceding the description of the composition, element, or plurality of elements are also contemplated, and vice versa should be understood. The well-known term "comprising" means "including the following and any other things" [open], "consisting of" means "including only the following" [closed], whereas the term "consisting essentially of" is understood to be semi-inclusive according to US judicial interpretation and means including the following and other things that do not substantially affect the basic and novel characteristics.

[0245] The applicant has attempted to disclose all reasonably foreseeable embodiments and applications of the subject matter of the present disclosure. However, there may be modifications that are unforeseeable and not substantial, yet still equivalents. Although the invention has been described in connection with its particular exemplary embodiments, it will be apparent to those skilled in the art that, in light of the foregoing description, numerous changes, modifications, and variations can be made 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.

[0246] 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 within the scope of all jurisdictions in which such incorporation is permitted.

[0247] When numerical lower and upper limits are recited herein, ranges from any lower limit to any upper limit are contemplated.

Claims

1. A copolymer, comprising the following: I. (a) 10.0 to 20.0% by mass of amine-derivatized alpha-methylstyrene (ADAMS) repeat units having structure (I), 【Chemical 1】 wherein k is an integer from 1 to 3, and R 1 is hydrogen or a benzyl group, and R is hydrogen, a phenyl ring covalently bonded to the phenyl ring shown so as to form a naphthalene assembly at two adjacent ring carbon positions, a phenyl group bonded to a single carbon of the phenyl ring shown, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, 10.0 to 20.0% by mass of an amine-derivatized alpha-methylstyrene (ADAMS) repeat unit, and (b) 80.0 to 90.0% by mass of a repeat unit corresponding to the reactive form of isoprene, and the peak average molecular weight of the copolymer is 45.0 to 65.0 kDa, II. (a) 5.0 to 10.0% by mass of amine-derivatized alpha-methylstyrene (ADAMS) repeat units having structure (II), 【Chemical Formula 2】 wherein k is an integer from 1 to 3, and R is hydrogen, a phenyl ring covalently bonded to the phenyl ring shown and two adjacent ring carbon positions so as to form a naphthalene assembly, a phenyl group bonded to a single carbon of the phenyl ring shown, a C1-C4 hydrocarbyl group, O, N, S, P, Se, and a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of these and combinations thereof, 5.0 to 10.0% by mass of amine-derivatized alpha-methylstyrene (ADAMS) repeat units, and (b) the remaining 90.0 to 95.0% by mass of repeat units corresponding to the reaction form of isoprene, and the peak average molecular weight of the copolymer is 24.0 to 42.0 kDa, III. (a) 4.0 to 6.0% by mass of amine-derivatized alpha-methylstyrene (ADAMS) repeat units having structure (III), 【Chemical Formula 3】 wherein k is an integer from 1 to 3, and R is hydrogen, a phenyl ring covalently bonded to the phenyl ring shown and two adjacent ring carbon positions so as to form a naphthalene assembly, a phenyl group bonded to a single carbon of the phenyl ring shown, a C1-C4 hydrocarbyl group, O, N, S, P, Se, and a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of these and combinations thereof, 4.0 to 6.0% by mass of amine-derivatized alpha-methylstyrene (ADAMS) repeat units, and (b) the remaining 94.0 to 96.0% by mass of repeat units corresponding to the reaction form of isoprene, and the peak average molecular weight of the copolymer is 36.0 to 46.0 kDa, IV. (a) One or more amine-derivatized alpha-methylstyrene (ADAMS) repeat units having structure (IV), 【Chemical Formula 4】 wherein k is an integer from 1 to 3, and R 1 is hydrogen or a benzyl group, and R is hydrogen, a phenyl ring covalently bonded to the phenyl ring represented to form a naphthalene assembly at two adjacent ring carbon positions, a phenyl group bonded to a single carbon of the phenyl ring represented, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, one or more amine-derivatized alpha-methylstyrene (ADAMS) repeat units, and (b) the remaining repeat units corresponding to the reactive form of isoprene A copolymer comprising one or more of the above.

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

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

4. The copolymer according to any one of claims 1 to 3, which is derived from a monofunctional initiator selected from the group consisting of alkyllithium, alkylsodium, alkylpotassium, and combinations thereof, and further contains an alkyl residue present at one or more terminals of the polymer backbone.

5. The copolymer according to claim 4, wherein the alkyl residue derived from the monofunctional initiator includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an iso-amyl group, a sec-amyl group, a tert-amyl group, a hexyl group, or a combination thereof.

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

7. A lubricating oil composition comprising (i) at least 50% by mass of one or more base oils based on the mass of the lubricating oil composition, (ii) one or more dispersants, (iii) one or more detergents, and (iv) one or more copolymers according to any one of claims 1 to 6, or obtained by mixing them.

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 claim 7 or 8, comprising (i) 50 to 99% by mass of the one or more base oils based on the mass of the lubricating oil composition, (ii) 0.01 to 20% by mass of the one or more dispersants based on the total mass of the lubricating oil composition, (iii) 0.10 to 20% by mass of the one or more detergents based on the mass of the lubricating oil composition, and (iv) 0.10 to 20% by mass of the one or more copolymers based on the mass of the lubricating oil composition, or obtained by mixing them.

10. The lubricating oil composition according to any one of claims 7 to 9, further comprising one, two, three, four, five, six, or more additional additives selected from the group consisting of a friction modifier, an antioxidant, a pour point depressant, an antifoaming agent, a viscosity modifier, a corrosion inhibitor and / or a rust preventive agent, and an antiwear agent.

11. A) one or more friction modifiers in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition; B) one or more antioxidants in an amount of 0.01 to 10% by mass based on the total mass of the lubricating oil composition; C) one or more pour point depressants in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition; D) one or more antifoaming agents in an amount of 0.001 to 5% by mass based on the total mass of the lubricating oil composition; E) one or more viscosity modifiers in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition; F) one or more inhibitors and / or rust preventive agents in an amount of 0.0 to 5% by mass based on the total mass of the lubricating oil composition, and / or G) one or more antiwear agents in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition, the lubricating oil composition according to any one of claims 7 to 10, further comprising one, two, three, four, five, six, or more of them.

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

13. The lubricating oil composition according to any one of claims 7 to 12, wherein the one or more dispersants include one or more boricated or non-boricated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine.

14. A method for lubricating an internal combustion engine during operation of the engine, comprising the steps of: (i) supplying the lubricating oil composition according to any one of claims 7 to 13 to the crankcase of the internal combustion engine; (ii) supplying fuel to 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 or 15, wherein the engine is a diesel engine.

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