Ashless additive composition

Abstract

This disclosure describes an ashless lubricant additive that is a tertiary amine-containing compound having the following structure: [Formula 1] JPEG2025512875000019.jpg44141 [In the formula, each R 1 and R 5 are independently a linear or branched monovalent hydrocarbyl group having from 2 to about 20 carbon atoms, and each R 2 , R 3 , and R 4 are independently hydrogen, a linear or branched monovalent hydrocarbyl group having 1 to about 20 carbon atoms, R 2 , R 3 , and R 4 is hydrogen, each m is independently 0 to 2, each p is independently 0 to 2, m+p of each cyclic moiety is 2 to 4, and each n is independently 1 to 6.

Description

[Technical field]

[0001] The present disclosure relates to lubricating oil additives and lubricating oil compositions containing the same. More specifically, the present disclosure describes ashless additives that can increase the total base number in a lubricating oil and / or modify friction and / or improve wear performance. [Background technology]

[0002] Lubricants are often formulated to a specific total base number (TBN) or TBN range. This ensures that the lubricant contains enough base additives and / or detergents to neutralize acidic by-products that can damage engine parts. Traditional base-containing additives, such as overbased phenate and sulfonate detergents, carry with them high amounts of metals, measured in sulfated ash. This presents a challenge as industry and regulatory standards continue to advance ash limits.

[0003] Basic amine additives are an alternative to ash containing overbased metal detergents. At least one problem, commonly found in seals (e.g., Viton seals), is that the amine additives can degrade fluoroelastomers. Basic amine additives, such as succinimide dispersants, contain polyamine head groups that are believed to cause dehydrofluorination of fluoroelastomer seals.

[0004] Certain additives may be multifunctional (eg, friction modifier, anti-wear) and provide multiple performance benefits.

[0005] Therefore, there is a need for a commercially viable ashless additive that is compatible with fluoroelastomer seals. Summary of the Invention

[0006] In one embodiment, an ashless additive composition is provided that includes a tertiary amine-containing compound having the structure: [ka] [In the formula, each R 1 and R 5 are independently a linear or branched monovalent hydrocarbyl group having from 2 to about 20 carbon atoms, and each R 2 , R 3 , and R 4 are independently hydrogen, a linear or branched monovalent hydrocarbyl group having 1 to about 20 carbon atoms, R 2 , R 3 , and R 4 is hydrogen, each m is independently 0 to 4, each p is independently 0 to 4, m+p of each cyclic moiety is independently 2 to 4, and n is independently 1 to 6.

[0007] In another embodiment, there is provided a lubricating oil composition comprising a major amount of a base oil and an ashless tertiary amine-containing compound having the structure: [ka] [In the formula, each R 1 and R 5 are independently a linear or branched monovalent hydrocarbyl group having from 2 to about 20 carbon atoms, and each R 2 , R 3 , and R 4 are independently hydrogen, a linear or branched monovalent hydrocarbyl group having 1 to about 20 carbon atoms, R 2 , R 3 , and R 4 is hydrogen, each m is independently 0 to 4, each p is independently 0 to 4, m+p of each cyclic moiety is independently 2 to 4, and n is independently 1 to 6.

[0008] In yet another aspect, an ashless additive composition comprising: a hydrocarbyl-substituted succinic anhydride represented by the structure: [ka] wherein R is a linear or branched monovalent hydrocarbyl group having from 2 to about 20 carbon atoms. A cyclic polyamine represented by the following structure: [ka] wherein R is a linear or branched monovalent hydrocarbyl group having from 2 to about 20 carbon atoms, m is 0 to 4, p is 0 to 4, m+p is 2 to 4, and n is 1 to 6. and a diamide product obtained by a reaction comprising The ashless additive composition is provided wherein the ratio of hydrocarbyl-substituted succinic anhydride to cyclic polyamine is from about 1.5:1 to about 1.6:1.

[0009] In yet another aspect, there is provided a method of operating an internal combustion engine comprising lubricating the engine with a lubricating oil composition comprising a major amount of a base oil of lubricating viscosity and an ashless tertiary amine-containing composition having the structure: [ka] [In the formula, each R 1 and R 5 are independently a linear or branched monovalent hydrocarbyl group having from 2 to about 20 carbon atoms, and each R 2 , R 3 , and R 4 are independently hydrogen, a linear or branched monovalent hydrocarbyl group having 1 to about 20 carbon atoms, R 2 , R 3 , and R 4 is hydrogen, each m is independently 0 to 4, each p is independently 0 to 4, m+p of each cyclic moiety is 2 to 4, and each n is independently 1 to 6. [Brief description of the drawings]

[0010] [Figure 1] 1 shows a graph illustrating one aspect of the invention described in the Examples. [Diagram 2] 1 shows a graph illustrating one aspect of the invention described in the Examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] definition The term "total base number" or "TBN" refers to the amount of base equivalent to milligrams of KOH in 1 gram of sample as measured by ASTM D-2896 test.

[0012] The term "hydrocarbyl" refers to a chemical group or moiety derived from a hydrocarbon, including saturated and unsaturated hydrocarbons. Examples of hydrocarbyl groups include alkenyl, alkyl, polyalkenyl, polyalkyl, phenyl, and the like.

[0013] The terms "oil-soluble" or "oil-dispersible" as used herein do not necessarily indicate that a compound or additive is soluble, dissolvable, miscible, or suspendable in oil in any proportion, but rather mean that it is soluble or stably dispersible in oil to an extent sufficient to exert its intended effect in the environment in which the oil is used, for example. Furthermore, it is possible to incorporate higher levels of a particular additive, if desired, by further incorporating other additives.

[0014] Where combinations, subsets, groups, etc. of elements (e.g., combinations of components in a composition or combinations of steps in a method) are disclosed, it is understood that specific reference to each of the various individual and collective combinations and permutations of those elements is specifically contemplated and described herein, even though it may not be explicitly disclosed.

[0015] The present invention relates to an ashless additive composition that can be used as a TBN source and / or friction modifier and / or antiwear agent in lubricating oils. The additive composition can be used at cost-effective treat rates while maintaining the compatibility of fluoroelastomer seals. In some embodiments, the present invention can be used as a friction modifier to reduce friction and wear of machine components. Other advantages will be apparent from the disclosure herein.

[0016] The ashless additive composition of the present invention comprises the product(s) of a reaction comprising a hydrocarbyl-substituted succinic anhydride and a cyclic polyamine, resulting in a diamide structure characterized by at least two basic tertiary amines.

[0017] The ashless additive compositions of the present invention may be synthesized by any known suitable method, for example, as described in U.S. Patent Publication No. 20180034635 and U.S. Patent No. 7,091,306, which are incorporated herein by reference.

[0018] The reaction may proceed under a variety of conditions. Generally, the hydrocarbyl-substituted succinic anhydride is reacted with the cyclic polyamine at a temperature of about 130°C to 220°C (e.g., 140°C to 200°C, 145°C to 175°C, etc.). More preferably, the temperature may range from about 160°C to 215°C. Generally, the imidization step may be carried out at lower temperatures (e.g., 150°C to 170°C), but it may be necessary to complete the amidation step at higher temperatures (e.g., 200°C to 220°C).

[0019] The reaction can be carried out under an inert atmosphere such as nitrogen or argon. In general, the preferred molar charge of the hydrocarbyl-substituted succinic anhydride to the cyclic polyamine is about 1.4:1 to about 1.7:1, more preferably about 1.5:1 to about 1.6:1. In some embodiments, a charge molar ratio (CMR) of the hydrocarbyl-substituted succinic anhydride to the cyclic polyamine of about 1.55:1 or slightly higher may be desirable due to reaction with any unreacted secondary amine. Secondary amines are believed to be more aggressive to seals. The charge molar ratio is important because too much hydrocarbyl-substituted succinic anhydride can result in monoamide / acid structures instead of diamide structures, while too little can result in monosuccinimide products containing secondary amines.

[0020] In some embodiments, the reaction may proceed in multiple steps, with the total CMR of hydrocarbyl-substituted succinic anhydride to cyclic polyamine or cyclic polyamine product being about 1.4:1 to about 1.7:1, more preferably about 1.5:1 to about 1.6:1. For example, the first step may involve reacting hydrocarbyl-substituted succinic anhydride with cyclic polyamine at a charge molar ratio of 1:1 to produce an imide structure. In the second step, the imide structure is reacted with hydrocarbyl-substituted succinic anhydride at a charge molar ratio (succinic anhydride to imide product) of about 0.5 to form a diamide structure. The total CMR of the two steps is 1.5:1. The hydrocarbyl-substituted succinic anhydride in the first step and the hydrocarbyl-substituted succinic anhydride in the second step may have the same or different hydrocarbyl groups.

[0021] According to one embodiment, the hydrocarbyl-substituted succinic anhydride is provided by structure I: [ka] [wherein R is a linear or branched monovalent hydrocarbyl group having from 2 to about 20 carbon atoms, e.g., from 10 to 20 carbon atoms, from 12 to 20 carbon atoms, and from 14 to 20 carbon atoms.] In some embodiments, the average number of carbon atoms is about 14 or greater. R can be cyclic or acyclic. In some embodiments, R is saturated. In other embodiments, R is unsaturated.

[0022] The exact structure of the hydrocarbyl group may depend on a variety of factors. Solubility in oil is an important consideration. Generally, the longer the hydrocarbyl group, the more soluble it is in oil.

[0023] Hydrocarbyl-substituted succinic anhydrides are readily available commercially. For example, alkenyl succinic anhydrides are widely used in paper sizing. Conversely, the hydrocarbyl-substituted succinic anhydrides of the present invention can be synthesized by well-established methods. One of the conventional syntheses involves reacting maleic anhydride with olefins at high temperatures (about 200°C).

[0024] According to one embodiment, the cyclic polyamine is represented by structure II: [ka] [wherein R is a linear or branched monovalent hydrocarbyl group having from 2 to about 20 carbon atoms, m is 0 to 4, p is 0 to 4, m+p is 2 to 4, and n is 1 to 6. R can be cyclic or acyclic.] In some embodiments, R is saturated. In other embodiments, R is unsaturated. The cyclic polyamine serves as the source of the basic tertiary amine.

[0025] Many of the polyamines suitable for use in the present invention are commercially available, and others may be prepared by methods well known in the art. For example, methods for preparing amines and their reactions are detailed in Sidgewick's "The Organic Chemistry of Nitrogen", Clarendon Press, Oxford, 1966; Noller's "Chemistry of Organic Compounds", Saunders, Philadelphia, 2nd Ed., 1957; and Kirk-Othmer's "Encyclopedia of Chemical Technology", 2nd Ed., especially Volume 2, pp. 99 116.

[0026] Suitable examples of the cyclic polyamine include, for example, aminoethylpiperazine, aminopropylpiperazine, aminobutylpiperazine, aminoethyldiazepane, aminoethyldiazocane, and suitable derivatives thereof.

[0027] One class of ashless additive compositions may be represented by structure III: [ka] [In the formula, each R 1 and R 5 are independently a linear or branched monovalent hydrocarbyl group having from 2 to about 20 carbon atoms, and each R 2 , R 3 , and R 4 are independently hydrogen, a linear or branched monovalent hydrocarbyl group having 1 to about 20 carbon atoms, R 2 , R 3 , and R 4 is hydrogen, each m is independently 0 to 4, each p is independently 0 to 4, m+p of each cyclic moiety is 2 to 4, and each n is independently 1 to 6.

[0028] Lubricating oil When used as a lubricating oil additive, the ashless additive composition of the present invention is typically present in the lubricating oil composition at a concentration in the range of from about 0.001 to about 20 wt % (including, but not limited to, 0.01 to 5 wt %, 0.2 to 4 wt %, 0.5 to 3 wt %, 1 to 2 wt %, etc.) based on the total weight of the lubricating oil composition.

[0029] The oils used as base oils are selected or blended depending on the desired end use and the additives to be included in the finished oil to provide a lubricating oil composition having a desired grade of engine oil, for example, a Society of Automotive Engineers (SAE) viscosity grade of 0W, 0W-8, 0W-16, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, or 15W-40.

[0030] An oil of lubricating viscosity (sometimes referred to as a "base stock" or "base oil") is the primary liquid component of a lubricating oil into which additives and possibly other oil ingredients are blended to produce, for example, the final lubricating oil (or lubricating oil composition). Base oils useful for making concentrates and for making lubricating oil compositions therefrom may be selected from natural (vegetable, animal, or mineral) and synthetic lubricating oils and mixtures thereof.

[0031] The definitions of base stocks and base oils in this disclosure are similar to those set forth in American Petroleum Institute (API) Publication 1509 Annex E ("API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils," December 2016). Group I base stocks contain less than 90% saturates and / or more than 0.03% sulfur and have a viscosity index of 80 or greater and less than 120, using the test methods set forth in Table E-1. Group II base stocks contain 90% or greater saturates and 0.03% or less sulfur and have a viscosity index of 80 or greater and less than 120, using the test methods set forth in Table E-1. Group III base stocks contain 90% or greater saturates and 0.03% or less sulfur and have a viscosity index of 120 or greater, using the test methods set forth in Table E-1. Group IV base stocks are polyalphaolefins (PAOs). Group V base stocks include all other base stocks not included in Groups I, II, III, or IV.

[0032] Natural oils include animal oils, vegetable oils (e.g., castor oil and lard oil), and mineral oils. Animal and vegetable oils with favorable thermo-oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely according to their crude source, e.g., paraffinic, naphthenic, or mixed paraffinic and naphthenic. Oils derived from coal or shale are also useful. Natural oils also vary according to the methods used to produce and refine them, e.g., their distillation range, and whether they are straight run, cracked, hydrorefined, or solvent extracted.

[0033] Synthetic oils include hydrocarbon oils, such as polymerized and copolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alpha olefin copolymers). Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oils. Examples include C8-C 14 Olefins, e.g. C8, C 10 , C 12 , C 14 In some cases, PAOs derived from olefins, or mixtures thereof may be utilized.

[0034] Other useful fluids for use as base oils include unconventional or unconventional base stocks, preferably catalytically processed or synthetically prepared to provide high performance properties.

[0035] Unconventional or unconventional base stocks / base oils include one or more base stock(s) derived from gas-to-liquids (GTL) materials, as well as natural wax or waxy feeds, mineral and / or non-mineral waxy feedstocks (such as slack wax), natural wax, and isomerized / isomerized dewaxed base stock(s) derived from waxy materials (such as gas oil, waxy fuel hydrocracker bottoms, waxy raffinate, hydrocracked oil, pyrolysis oil, or other minerals, mineral oils, or even non-petroleum derived waxy materials such as waxy materials derived from coal liquids or shale oil), as well as mixtures of these base stocks. Other base oils include coal-to-liquids (CTL) products and alkyl naphthalenes.

[0036] The base oils for use in the lubricating oil compositions of the present disclosure can be any of the various oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils, and mixtures thereof, with API Group II, Group III, Group IV, and Group V oils, and mixtures thereof, being preferred, and Group III to Group V base oils being more preferred due to their superior volatility, stability, viscosity, and detergency characteristics.

[0037] Typically, the base oil has a viscosity of 1.5 to 35 mm at 100°C. 2 / s (e.g., 1.5 to 25 mm 2 / s, 2.0~20mm 2 / s, or 2.0 to 15 mm 2 / s) range of kinematic viscosity (ASTM D445).

[0038] The lubricating oil composition of the present invention may also contain conventional lubricating oil additives to provide auxiliary functions, resulting in the finished lubricating oil composition in which these additives are dispersed or dissolved.For example, the lubricating oil composition may be blended with antioxidants, ashless dispersants, antiwear agents, detergents such as metal detergents, rust inhibitors, anti-foaming agents, demulsifiers, friction modifiers, metal deactivators, pour point depressants, viscosity modifiers, antifoaming agents, co-solvents, package compatibilizers, corrosion inhibitors, dyes, extreme pressure agents, etc., and mixtures thereof.Various additives are known and commercially available.These additives or their analogues may be used in the preparation of the lubricating oil composition of the present invention by conventional mixing procedures.

[0039] Each of the aforementioned additives, when used, is used in a functionally effective amount to impart the desired properties to the lubricating oil. Thus, for example, if the additive is an ashless dispersant, a functionally effective amount of the ashless dispersant is an amount sufficient to impart the desired dispersant properties to the lubricating oil. In general, the concentration of each of these additives, when used, can range from about 0.001 to about 20% by weight, for example, from about 0.01 to about 10% by weight, unless otherwise specified.

[0040] The following non-limiting examples are illustrative of the present invention. A brief description of how the examples were prepared is provided. EXAMPLES

[0041] Example 1 A 1 L stirred reactor was charged with 550.28 g of the thermally maleated 9-methylenenonadecane product (saponification number = 257 mg KOH / g). The reactor was heated to 150°C under a nitrogen sweep. 101.63 g of 1-(2-aminoethyl)piperazine (molecular weight = 129.20 g / mol) was charged to the thermally maleated 9-methylenenonadecane product over 45 minutes. The temperature of the mixture was increased to 160°C and maintained for 2 hours. The reaction was evacuated to 20 mm Hg for 30 minutes. The product had the following properties: TBN = 80.3 mg KOH / g, nitrogen = 5.21 wt%.

[0042] Example 2 A 4 L stirred reactor was charged with 1337.1 g of hexadecenyl succinic anhydride (saponification number = 352 mg KOH / g) and 338.67 g of 1-(2-aminoethyl)piperazine (molecular weight = 129.20 g / mol). The reactor was heated to 195°C under a nitrogen sweep and held for 1 hour. The mixture was then cooled to ambient temperature.

[0043] The next day, the reaction mixture was reheated to 200° C. while applying a vacuum to 35 mm Hg. The reaction mixture was held at temperature for an additional 2.5 hours. The product had the following properties: TBN=90.14 mg KOH / g, Nitrogen=6.56 wt %.

[0044] Example 3 A 4 L stirred reactor was charged with 775.84 g of dodecenyl succinic anhydride (saponification number = 414 mg KOH / g). The reactor was heated to 150°C under a nitrogen sweep. 385.94 g of 1-(2-aminoethyl)piperazine (molecular weight = 129.20 g / mol) was charged to the dodecenyl succinic anhydride over 30 minutes. The temperature of the mixture was increased to 160°C and maintained for 90 minutes. The reaction was evacuated to 20 mm Hg for 30 minutes and then cooled to ambient temperature.

[0045] The next day, 635.01 g of octadecenyl succinic anhydride (saponification number = 317 mg KOH / g) was charged into the reaction mixture at ambient temperature. The reaction mixture was heated to 215°C under a nitrogen sweep and maintained for an additional 4.5 hours. The product had the following properties: TBN = 109 mg KOH / g, nitrogen = 7.08 wt%.

[0046] Example 4 This example is a composite of products obtained from three separate reactions: 1) A 4 L stirred reactor was charged with 2019.1 g of octadecenyl succinic anhydride (saponification number = 317 mg KOH / g) and 460.59 g of 1-(2-aminoethyl)piperazine (molecular weight = 129.20 g / mol). The reactor was heated to 215°C under a nitrogen sweep and held for 2 hours. The reaction was evacuated to 10 mm Hg for 30 minutes. 2) A 4 L stirred reactor was charged with 2083.1 g of octadecenyl succinic anhydride (saponification number = 317 mg KOH / g) and 475.20 g of 1-(2-aminoethyl)piperazine (molecular weight = 129.20 g / mol). The reactor was heated to 215°C over 2 hours while purging the vapor space with nitrogen. The reaction mixture was maintained at temperature for 2 hours. The reaction was evacuated to 20 mm Hg for 30 minutes. 3) A 4 L stirred reactor was charged with 2087.4 g of octadecenyl succinic anhydride (saponification number = 317 mg KOH / g) and 476.41 g of 1-(2-aminoethyl)piperazine (molecular weight = 129.20 g / mol). The reactor was heated to 210°C over 2 hours while purging the vapor space with nitrogen. The reaction mixture was maintained at temperature for 2 hours. The reaction was evacuated to 40-50 mmHg for 30 minutes. The combined product had the following properties: TBN=84.3 mg KOH / g, nitrogen=6.28 wt %.

[0047] Sealing performance Comparative Example A (Baseline) A baseline lubricating oil formulation was formed containing ashless dispersants, alkaline earth metal carboxylate, sulfonate, and phenate detergents, zinc dithiophosphates, non-dispersant viscosity index improvers, antioxidants, antifoam agents, and pour point depressants.

[0048] The lubricating oil compositions of Examples 1-4 were tested for compatibility with fluorocarbon elastomer seals in a Volkswagen (VW) bench test (PV3344) by suspending fluorocarbon test specimens in an oil solution. The solution was then heated at 150°C for 168 hours. The changes in volume, hardness (PH), tensile strength (TS), and elongation (EL) of each sample were measured.

[0049] The test results of the compatibility test (friction performance results of DC AK6 seal) are summarized in Table 1 below. [Table 1]

[0050] Comparative example B The sample is an automotive engine oil containing a conventional amine-containing additive.

[0051] Example 5 This sample compares the conventional amine-containing additive with the ashless additive of the present invention (C 18 Identical to Comparative Example B, except that ethyl acetate (the reaction product of succinic anhydride and aminoethylpiperazine) was replaced with ethyl acetate.

[0052] The seal compatibility results are shown in Table 2 below. [Table 2]

[0053] High Temperature Corrosion Bench Test (HTCBT) The ASTM D6594 HTCBT test was used to evaluate engine lubricating oils to determine their tendency to corrode various metals, especially lead-copper alloys commonly used in cam followers and bearings. Four metal samples - copper, lead, tin, and phosphorus bronze - were immersed in engine oil. The oil was heated to 170°C and then blown out with air (5l / h) for a set period of time (168 hours).

[0054] The copper coupons and aged oil were tested for corrosion and corrosion products, respectively. The concentrations of copper, lead, and tin in the new and aged oils are reported, along with the change in each metal concentration. To be considered a "pass," the lead concentration must not exceed 120 ppm and the copper concentration must not exceed 20 ppm.

[0055] Copies of this test method may be obtained from ASTM International, 100 Barr Harbor Drive, PO Box 0700, West Conshohocken, Pa. 19428-2959.

[0056] The results for HTCBT are summarized in Table 3 below. [Table 3]

[0057] Wear performance The lubricant samples were also tested for wear performance using a High Frequency Reciprocating Rig (HFRR) test.

[0058] Comparative example C Comparative Example C includes a baseline lubricant.

[0059] Example 6 Example 6 is a comparison of the baseline lubricant of Comparative Example C and the ashless additive of the present invention (C 18 (Reaction product of succinic anhydride and aminoethylpiperazine).

[0060] Example 7 Example 7 includes the lubricant of Comparative Example C and a conventional amine-containing additive.

[0061] Friction modifier performance Samples containing the ashless additive compositions of the present invention (Comparative Example D, Examples 8 and 9) were tested in automatic transmission fluids. Static torque was measured using the JASO SAE#2 friction test. Figure 2 shows the SAE#2 results.

[0062] Comparative example D This sample consisted of a baseline automatic transmission fluid and 20 It contains the reaction product of succinic anhydride and diethylenetriamine (DETA) at a charge molar ratio of 2:1. The treat rate is 1.0 wt%.

[0063] Example 8 This sample is a comparison of the baseline automatic transmission fluid used in Comparative Example D and C 18 It contains the reaction product of succinic anhydride and aminoethylpiperazine at a charge mole ratio of 1.6:1. The treat rate is 1.0 wt%.

[0064] Example 9 This sample is a comparison of the baseline automatic transmission fluid used in Comparative Example D and C 20 It contains the reaction product of succinic anhydride and aminoethylpiperazine in a charge mole ratio of 1.6:1. The treat rate is 1.19 wt%.

[0065] All documents described herein are incorporated herein by reference, including any priority documents and / or test procedures, unless inconsistent with the text. As is apparent from the general description and specific embodiments set forth above, although several forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, the present disclosure is not intended to be limited thereby.

[0066] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit may be combined with any upper limit to enumerate a range that is not explicitly stated, and a range from any lower limit may be combined with any other lower limit to enumerate a range that is not explicitly stated, and a range from any upper limit may be combined with any other upper limit to enumerate a range that is not explicitly stated. Furthermore, a range includes every point or individual value between its endpoints, even if not explicitly enumerated. Thus, every point or individual value may be combined with other points or individual values, or with other lower or upper limits, to serve as its own lower or upper limit, to enumerate a range that is not explicitly stated.

[0067] Similarly, the term "comprising" is considered synonymous with the term "including." Similarly, whenever the transitional phrase "comprising" precedes a composition, element, or group of elements, it is understood to also contemplate the same composition or group of elements with the transitional phrase "consisting essentially of," "consisting of," "selected from the group consisting of," or "is," preceding the description of the composition, element, or group of elements, and vice versa.

[0068] As used herein, the terms "a" and "the" are understood to encompass the plural as well as the singular.

[0069] Various terms are defined above. To the extent that a term used in the claims is not defined above, it should be given the broadest definition that a person skilled in the relevant art would give that term, as reflected in at least one printed publication or issued patent. Furthermore, all patents, test methods, and other documents cited in this application are incorporated by reference in their entirety to the extent such disclosure is not inconsistent with this application and in all jurisdictions where such incorporation is permitted.

[0070] The foregoing description of the disclosure illustrates and describes the disclosure. Moreover, the disclosure shows and describes only the preferred embodiments, but as noted above, it is to be understood that the disclosure can be used in various other combinations, modifications, and environments, and that changes or modifications are possible within the scope of the concepts expressed herein, consistent with the teachings above and / or the skill or knowledge of the relevant art. While the foregoing is directed to embodiments of the disclosure, other and further embodiments of the disclosure can be devised without departing from the basic scope thereof, the scope of which is determined by the claims that follow.

[0071] Where combinations, subsets, groups, etc. of elements (e.g., combinations of components in a composition or combinations of steps in a method) are disclosed, it is understood that specific reference to each of the various individual and collective combinations and permutations of those elements is specifically contemplated and described herein, even though it may not be explicitly disclosed.

[0072] The embodiments described herein above are further intended to further describe the best mode known for carrying out the invention and to enable others skilled in the art to utilize the present disclosure in such or other embodiments, with various modifications necessary for a particular application or use. Therefore, the description is not intended to be limited to the forms disclosed herein. Also, it is intended that the appended claims be construed to include alternative embodiments.

Claims

1. An ashless additive composition comprising a tertiary amine-containing compound having the structure: 【Chemistry 1】 [In the formula, each R １ and R ５ are independently linear or branched monovalent hydrocarbyl groups having from 2 to about 20 carbon atoms, and each R ２ , R ３ , and R ４ are independently hydrogen, a linear or branched chain monovalent hydrocarbyl group having from 1 to about 20 carbon atoms, R ２ , R ３ , and R ４ is hydrogen, each m is independently 0 to 4, each p is independently 0 to 4, m+p of each cyclic moiety is 2 to 4, and each n is independently 1 to 6.

2. The linear or branched monovalent hydrocarbyl group is １２ ~C ２０ 2. The ashless additive composition of claim 1, wherein the alkyl group is an alkenyl group.

3. The linear or branched monovalent hydrocarbyl group is １８ ~C ２０ 2. The ashless additive composition of claim 1, wherein the alkyl group is an alkenyl group.

4. a major amount of base oil; and an ashless tertiary amine-containing compound having the structure: 【Chemistry 2】 [In the formula, each R １ and R ５ are independently linear or branched monovalent hydrocarbyl groups having from 2 to about 20 carbon atoms, and each R ２ , R ３ , and R ４ are independently hydrogen, a linear or branched chain monovalent hydrocarbyl group having from 1 to about 20 carbon atoms, R ２ , R ３ , and R ４ is hydrogen, each m is 0 to 4, each p is 0 to 4, m+p of each cyclic moiety is 2 to 4, and each n is independently 1 to 6.

5. The linear or branched monovalent hydrocarbyl group is １２ ~C ２０ The lubricating oil composition of claim 4, wherein the alkyl group is an alkenyl group.

6. The linear or branched monovalent hydrocarbyl group is １８ ~C ２０ The lubricating oil composition of claim 4, wherein the alkyl group is an alkenyl group.

7. The lubricating oil composition of claim 4, wherein the tertiary amine-containing compound is present at about 0.1 to 2 weight percent of the weight of the lubricating oil composition.

8. 5. The lubricating oil composition of claim 4, wherein the lubricating oil composition is a hydraulic fluid, a slideway lubricant, an automatic transmission fluid, an infinitely variable transmission fluid, a battery electric vehicle, a hybrid electric vehicle transmission fluid, or a gear oil.

9. 5. The lubricating oil composition of claim 4, further comprising a friction modifier, an ashless antiwear additive, an antioxidant, a metal deactivator, a seal swell additive, an antifoam agent, or a viscosity modifier.

10. 1. An ashless additive composition comprising: a hydrocarbyl-substituted succinic anhydride represented by the structure: 【Chemistry 3】 wherein R is a linear or branched monovalent hydrocarbyl group having from 2 to about 20 carbon atoms. A cyclic polyamine represented by the following structure: 【Chemistry 4】 wherein R is a linear or branched monovalent hydrocarbyl group having from 2 to about 20 carbon atoms, m is 0 to 4, p is 0 to 4, m+p is 2 to 4, and n is 1 to 6. and a diamide product obtained by a reaction comprising The ashless additive composition wherein the ratio of said hydrocarbyl-substituted succinic anhydride to said cyclic polyamine is from about 1.5:1 to about 1.6:

1.

11. 11. The ashless additive composition of claim 10, wherein the piperazine is aminoethyl piperazine, aminopropyl piperazine, aminobutyl piperazine, aminoethyl diazepane, or aminoethyl diazocane.

12. 1. A method for adjusting friction in an engine, comprising: a major amount of a base oil of lubricating viscosity; an ashless additive composition having the structure: 【Chemistry 5】 [In the formula, each R １ and R ５ are independently linear or branched monovalent hydrocarbyl groups having from 2 to about 20 carbon atoms, and each R ２ , R ３ , and R ４ are independently hydrogen, a linear or branched chain monovalent hydrocarbyl group having from 1 to about 20 carbon atoms, R ２ , R ３ , and R ４ is hydrogen, each m is independently 0 to 4, each p is independently 0 to 4, m+p of each cyclic moiety is 2 to 4, and each n is independently 1 to 6. lubricating said engine with a lubricating oil composition comprising:

13. The linear or branched monovalent hydrocarbyl group is １２ ~C ２０ The method of claim 12, wherein the alkyl group is an alkenyl group.

14. The linear or branched monovalent hydrocarbyl group is １８ ~C ２０ The method of claim 12, wherein the alkyl group is an alkenyl group.

15. 1. A method for increasing the total base number in a lubricating oil, comprising: A base oil, an ashless additive composition having the structure: 【Chemistry 6】 [In the formula, each R １ and R ５ are independently linear or branched monovalent hydrocarbyl groups having from 2 to about 20 carbon atoms, and each R ２ , R ３ , and R ４ are independently hydrogen, a linear or branched chain monovalent hydrocarbyl group having from 1 to about 20 carbon atoms, R ２ , R ３ , and R ４ is hydrogen, each m is independently 0 to 4, each p is independently 0 to 4, m+p of each cyclic moiety is 2 to 4, and each n is independently 1 to 6. The method comprising:

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