Ash-free additive composition

Abstract

This disclosure describes an ashless lubricant additive, which is a tertiary amine-containing compound having the structure of formula (I): [Case 1] TIFF2023543939000019.tif53165 where R 1 and R 2 are independently a straight or branched chain monovalent hydrocarbyl group having from 2 to about 20 carbon atoms, each m is independently 0 to 2, each p is independently 0 to 2, and for each cyclic moiety, m+p is 2 to 4, and each n is independently 1 to 6.

Description

[Technical Field]

[0001] This disclosure relates to lubricant additives and lubricant compositions containing lubricant additives. More specifically, this disclosure describes ashless additives that can increase the total base number and / or adjust friction and / or improve wear performance in lubricants. [Background technology]

[0002] Lubricants are often formulated to a specific total base number (TBN) or TBN range. This ensures that the lubricant contains enough basic additives and / or detergents to neutralize acidic byproducts that could damage engine components. Conventional base-containing additives, such as overbasic phenate and sulfonate detergents, contain high levels of metal, which is measured as sulfated ash. This is a challenge as industry and regulatory standards continue to move towards limiting ash content.

[0003] Basic amine additives are alternatives to ash containing overbasic metal cleaning agents. At least one drawback is that amine additives can degrade fluoroelastomers commonly found in seals (e.g., Viton seals). Basic amine additives, such as succinimide dispersants, contain polyamine head groups that are thought to cause dehydrofluoridation in fluoroelastomer seals.

[0004] Certain additives are multifunctional (e.g., friction modifier, wear-resistant) and may offer two or more performance benefits.

[0005] Therefore, there is a need for commercially viable ashless additives that are compatible with fluoroelastomer seals. [Overview of the project]

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

[0007] In another aspect, there is provided a lubricating oil composition comprising a major amount of base oil and an ashless tertiary amine-containing compound having the following structure,

Chemical formula

[0008] In yet another aspect, there is provided an ashless additive composition comprising a diamide product, the hydrocarbyl-substituted succinic anhydride represented by the following structure,

Chemical formula

Chemical formula

[0009] In yet another embodiment, a method for operating an internal combustion engine, the method comprising lubricating the engine with a lubricating oil composition, the lubricating oil composition comprising a large amount of base oil having lubricating viscosity and an ashless tertiary amine having the following structure: [ka] Here, R 1 and R 2 The method is provided wherein m is independently a monovalent hydrocarbyl group having 2 to about 20 carbon atoms in a straight or branched chain, each m is independently 0 to 4, each p is independently 0 to 4, for each cyclic portion m+p is 2 to 4, and each n is independently 1 to 6. [Brief explanation of the drawing]

[0010] [Figure 1] This graph illustrates one aspect of the present invention as described in the examples. [Figure 2] This graph illustrates one aspect of the present invention as described in the examples. [Modes for carrying out the invention]

[0011] definition The term "Total Base Number" or "TBN" refers to the amount of bases equivalent to milligrams of KOH in one gram of sample, as measured by the ASTM D-2896 test.

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

[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 all proportions. Rather, they mean, for example, that the compound is soluble or stably dispersible in oil to a degree sufficient to achieve its intended effect in the environment in which the oil is used. Furthermore, higher levels of specific additive formulations may be possible by further incorporating other additives as needed.

[0014] Where combinations, subsets, or groups of elements are disclosed (for example, combinations of components in a composition or combinations of steps in a method), specific references to various individual and collective combinations and rearrangements of these elements may not be expressly disclosed, but each is understood to be specifically intended and described herein.

[0015] The present invention relates to an ashless additive composition that can be used as a TBN source and / or a friction modifier and / or wear inhibitor in lubricating oils. The additive composition can be used at a cost-effective processing rate while maintaining fluoroelastomer seal compatibility. In some embodiments, the present invention may also be used as a friction modifier to reduce friction and wear in machine parts. Other advantages are evident from the disclosure herein.

[0016] The ashless additive composition of the present invention comprises the product (or multiple product) of a reaction involving hydrocarbyl-substituted succinic anhydride and a cyclic polyamine. As a result, a diamide structure characterized by at least two basic tertiary amines is obtained.

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

[0018] The reaction can proceed under a variety of conditions. Generally, hydrocarbyl-substituted succinic anhydride is reacted with a 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 be in the range of about 160°C to 215°C. Generally, the imidation step can be carried out at a lower temperature (e.g., 150°C to 170°C), but a higher temperature (e.g., 200°C to 220°C) may be necessary to complete the amidation step.

[0019] The reaction can be carried out under an inert atmosphere such as nitrogen or argon. Generally, a suitable molar packing ratio of hydrocarbyl-substituted succinic anhydride to cyclic polyamines 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 packing molar ratio (CMR) of hydrocarbyl-substituted succinic anhydride to cyclic polyamine may be desirable to react with any unreacted secondary amine, with the secondary amine being considered more aggressive to seal. The packing molar ratio is important because too much hydrocarbyl-substituted succinic anhydride may result in a monoamide / acid structure instead of a diamide structure, while too little may result in a monosuccinimide product containing the secondary amine.

[0020] In some embodiments, the reaction can proceed in multiple steps. The total CMR of the hydrocarbyl-substituted succinic anhydride to the cyclic polyamine or cyclic polyamine product is from about 1.4:1 to about 1.7:1, more preferably from about 1.5:1 to about 1.6:1. For example, the first step can include reacting the reactive hydrocarbyl-substituted succinic anhydride with the cyclic polyamine in a 1:1 charge molar ratio to form an imide structure. In the second step, the imide structure is reacted with the hydrocarbyl-substituted succinic anhydride at a charge molar ratio of about 0.5 (succinic anhydride to imide product) 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 given by Structure I.

Chemical formula

[0022] The exact structure of the hydrocarbyl group can depend on many factors. Solubility in oil is an important consideration. Generally, the longer the hydrocarbyl group, the higher the solubility 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 conventional synthesis involves reacting maleic anhydride with an olefin at high temperatures (~200°C).

[0024] According to one embodiment, the cyclic polyamine is represented by structure II. [ka] Here, R 2 R is a monovalent hydrocarbyl group having 2 to approximately 20 carbon atoms in a straight or branched chain, where m is 0 to 4, p is 0 to 4, m+p is 2 to 4, and n is 1 to 6. 2 R may be cyclic or non-cyclic. In some embodiments, R 2 It is saturated. In other embodiments, R 2 It is unsaturated. Cyclic polyamines function as a source of basic tertiary amines.

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

[0026] Suitable examples of cyclic polyamines 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] Here, R 1 and R 2 Each is independently a monovalent hydrocarbyl group having 2 to approximately 20 carbon atoms in a straight or branched chain, where each m is independently 0 to 4, each p is independently 0 to 4, for each cyclic portion, m+p is 2 to 4, and each n is independently 1 to 6.

[0028] Lubricating oil When used as a lubricant additive, the ashless additive composition of the present invention is typically present in the lubricating oil composition at a concentration ranging from about 0.001 to about 20 wt% (without limitation, including 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 oil used as the base oil is selected or blended according to the desired end use and additives in the finished oil to provide a lubricating oil composition having the desired grade of engine oil, for example, 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 SAE viscosity grade.

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

[0031] The definitions of base stock and base oil in this disclosure are the same as those found below: 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% saturated sulfur and / or more than 0.03% sulfur, and have a viscosity index of 80 or greater and less than 120, using the test methods specified in Table E-1. Group II base stocks contain 90% or more saturated sulfur and 0.03% or less sulfur, and have a viscosity index of 80 or greater and less than 120, using the test methods specified in Table E-1. Group III base stocks contain 90% or more saturated sulfur and 0.03% or less sulfur, and have a viscosity index of 120 or greater, using the test methods specified 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] Examples of natural oils include animal oils, vegetable oils (e.g., castor oil and lard), and mineral oils. Animal and vegetable oils with desirable thermal oxidative stability can be used. Among natural oils, mineral oils are preferred. Mineral oils vary considerably depending on their source of origin, for example, whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils also vary depending on the methods used for their production and refining, such as their distillation range, and whether they are straight-run, cracked, hydrorefined, or extracted solvents.

[0033] Examples of synthetic oils include hydrocarbon oils. Examples of hydrocarbon oils include oils derived from polymerized and copolymerized olefins (for example, polybutylene, polypropylene, propylene-isobutylene copolymer, ethylene olefin copolymer, and ethylene alpha-olefin copolymer). Polyalphaolefin (PAO) oil-based stocks are widely used synthetic hydrocarbon oils. As an example, C8-C 14 Olefins, for example, C8, C 10 , C 12 , C 14 PAO derived from olefins or mixtures thereof may also be used.

[0034] Other useful fluids for use as base oils include novel or unconventional base stocks, which are preferably catalytically treated or synthesized to obtain high-performance properties.

[0035] Examples of novel or unconventional base stocks / base oils include base stocks(or more) derived from one or more gas-to-liquid (GTL) materials, as well as isomerized / iso-dewaxed base stocks(or more) derived from natural waxes or waxy feedstocks, mineral and / or non-mineral oil waxy feedstocks, e.g., slack wax, natural wax, and wax stocks, e.g., gas oil, waxy fuel hydrocracker bottom, waxy raffinates, hydrocrackers, thermal crackers, or other mineral, mineral oil, or even non-petroleum-derived waxy materials, e.g., waxy materials received from coal liquefaction or shale oil, and one or more mixtures of such base stocks. Other base oils include coal-to-liquid (CTL) products and alkylnaphthalenes.

[0036] The base oils used in the lubricating oil compositions of this disclosure are oils of API Group I, Group II, Group III, Group IV, and Group V, and mixtures thereof, preferably oils of API Group II, Group III, Group IV, and Group V, and mixtures thereof, more preferably any of the various oils corresponding to base oils of Group III to Group V due to their exceptional volatility, stability, viscosity measurement, and cleanliness characteristics.

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

[0038] The lubricating oil composition may also contain conventional lubricant additives to impart auxiliary functions, giving a 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, anti-wear agents, cleaning agents such as metal cleaners, rust inhibitors, de-hazing agents, de-emulsifiers, friction modifiers, metal deactivators, pour point depressants, viscosity modifiers, defoaming agents, cosolvents, package conforming agents, corrosion inhibitors, dyes, extreme pressure agents, and mixtures thereof. Various additives are known and commercially available. These additives, or compounds similar thereto, can be used for the preparation of the lubricating oil composition of the present invention by conventional blending procedures.

[0039] Each of the aforementioned additives is used in a functionally effective amount to impart the desired properties to the lubricant when used. Therefore, for example, if the additive is an ashless dispersant, the functionally effective amount of this ashless dispersant is sufficient to impart the desired dispersion characteristics to the lubricant. Generally, the concentration of each of these additives when used may range from about 0.001 to about 20 wt%, for example, from about 0.01 to about 10 wt%, unless otherwise specified.

[0040] The following non-limiting embodiments illustrate the present invention. A brief description of how the embodiments were prepared is given below. [Examples]

[0041] Example 1 A 1 L stirred reactor was filled with 550.28 g of the thermal maleation (saponification value = 257 mg KOH / g) of the 9-methylenenonadecane product. The reactor was heated to 150°C under nitrogen sweep. 101.63 g of 1-(2-aminoethyl)piperazine (molecular weight = 129.20 g / mol) was filled with the thermal maleation of the 9-methylenenonadecane product over 45 minutes. The temperature of the mixture was raised to 160°C and maintained for 2 hours. The reaction was carried out under vacuum 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 packed with 1337.1 g of hexadecenyl succinic anhydride (saponification value = 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 maintained for 1 hour. The mixture was then cooled to ambient temperature.

[0043] The following day, the reactive mixture was reheated to 200°C under a vacuum of up to 35 mm Hg. The reactive mixture was held at that temperature for a further 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 filled with 775.84 g of dodecenyl succinic anhydride (saponification value = 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 added to the dodecenyl succinic anhydride over 30 minutes. The temperature of the mixture was raised to 160°C and maintained for 90 minutes. The reaction was carried out under vacuum, reduced to 20 mm Hg for 30 minutes, and then cooled to ambient temperature.

[0045] The following day, 635.01 g of octadecenyl succinic anhydride (saponification value = 317 mg KOH / g) was packed into the reactive mixture at ambient temperature. The reactive mixture was heated to 215°C under a nitrogen sweep and maintained for a further 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 combination of Examples 11, 15, and 16. The product had the following properties: TBN = 84.3 mg KOH / g, Nitrogen = 6.28 wt%.

[0047] Comparative Example A (Baseline) A baseline lubricant formulation was formed containing an ashless dispersant, an alkaline earth metal carboxylate, a sulfonate, a phenate cleaning agent, zinc dithiophosphate, a non-dispersant viscosity index improver, an antioxidant, an anti-foaming agent, and a pour point depressant.

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

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

[0050] The results indicate that lubricating oil compositions containing aminoethylpiperazine-based additives did not significantly degrade sealing performance in 1, 2, or 3 TBN.

[0051] Comparative example B This sample is an automotive engine oil containing conventional amine-containing additives.

[0052] Example 5 This sample uses the ashless additive of the present invention (C) instead of conventional amine-containing additives. 18 This is the same as Comparative Example B, except that the reaction product of succinic anhydride and aminoethylpiperazine was used.

[0053] The results of the seal compatibility test are shown in Table 2 below. [Table 2]

[0054] High-temperature corrosion bench test (HTCBT) Using ASTM D6594 HTCBT, engine lubricants were evaluated to determine their tendency to corrode various metals, specifically lead and copper alloys widely used in cam followers and bearings. Four metal samples—copper, lead, tin, and phosphor bronze—were immersed in engine oil. The oil was heated to a high temperature (170°C) and air (5 l / h) was blown onto it for a certain period of time (168 h).

[0055] Copper samples and stressed oil were tested to investigate corrosion and corrosion products, respectively. The concentrations of copper, lead, and tin in new and stressed oil, along with the individual changes in metal concentrations, are reported. To "pass," the lead concentration must not exceed 120 ppm, and the copper concentration must not exceed 20 ppm.

[0056] A copy of this test method can be obtained from ASTM International at 100 Barr Harbor Drive, PO Box 0700, West Conshohocken, Pa. 19428-2959.

[0057] The results for HTCBT are summarized in Table 3 below. [Table 3]

[0058] The lubricant samples were tested using a high-frequency reciprocating rig (HFRR) test to investigate their wear performance.

[0059] Comparative example C Comparative Example C includes a baseline lubricant.

[0060] Example 6 Example 6 includes the baseline lubricating oil of Comparative Example C and the ashless additive of the present invention (C 18It contains the reaction product of succinic anhydride and aminoethylpiperazine.

[0061] Example 7 Example 7 includes the lubricating oil of Comparative Example C and a conventional amine-containing additive.

[0062] Samples containing the ashless additive composition of the present invention (Comparative Example D, Examples 8 and 9) were tested in automatic transmission fluid. Static torque was measured using the JASO SAE#2 friction test. Figure 2 shows the SAE#2 results.

[0063] Comparative example D This sample contains baseline automatic transmission fluid and C 20 The reaction product contains succinic anhydride and diethylenetriamine (DETA) in a 2:1 packing molar ratio. The processing rate is 1.0 wt%.

[0064] Example 8 This sample contains the baseline automatic transmission fluid used in Comparative Example D, and C 18 The reaction product contains succinic anhydride and aminoethylpiperazine in a packing molar ratio of 1.6:1. The processing rate is 1.0 wt%.

[0065] Example 9 This sample contains the baseline automatic transmission fluid used in Comparative Example D, and C 20 The reaction product contains succinic anhydride and aminoethylpiperazine in a packing molar ratio of 1.6:1. The processing rate is 1.19 wt%.

[0066] All documents mentioned herein are incorporated herein by reference and include any priority documents and / or test procedures, to the extent that they do not conflict with the text. As is evident from the above summary and specific embodiments, the forms of this disclosure are illustrative and described, but various modifications can be made without departing from the spirit and scope of this disclosure. Therefore, this disclosure is not intended to be limited thereto.

[0067] For simplicity, this specification explicitly discloses only certain ranges. However, a range from any lower bound may be combined with any upper bound to enumerate ranges not explicitly listed, similarly, a range from any lower bound may be combined with any other lower bound to enumerate ranges not explicitly listed, and similarly, a range from any upper bound may be combined with any other upper bound to enumerate ranges not explicitly listed. Furthermore, a range includes all points or individual values ​​between its endpoints, even if they are not explicitly listed. Thus, all points or individual values, combined with any other points or individual values ​​or any other lower or upper bound, can function as their own lower or upper bounds to enumerate ranges not explicitly listed.

[0068] Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever there is a transitional phrase “comprising” before a composition, element, or group of elements, it is understood that the same composition or group of elements accompanied by the transitional phrases “essentially become from,” “consist of,” “selected from a group consisting of,” or “is” is intended to precede the enumeration of the composition, element, or element(s), and vice versa.

[0069] The terms "a" and "" are understood to include both singular and plural forms when used in this specification.

[0070] Various terms have been defined above. Unless a term used in a claim is defined above, the broadest definition given to that term by a person skilled in the art should be given, as reflected in at least one publication or granted patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to all jurisdictions where incorporation is permitted, provided that such disclosures do not conflict with this application.

[0071] As described herein, this disclosure is illustrative and descriptive. Furthermore, although this disclosure illustrates and describes only preferred embodiments, as stated above, this disclosure can, of course, be used in a variety of other combinations, modifications, and environments, and can be modified or altered within the scope of the ideas expressed herein. The ideas expressed herein are commensurate with the teachings and / or skill or knowledge of the art described herein. While the foregoing is directed toward embodiments of this disclosure, other and further embodiments of this disclosure can be conceived without departing from its basic scope, the scope of which is determined by the following claims.

[0072] Where combinations, subsets, or groups of elements are disclosed (for example, combinations of components in a composition or combinations of steps in a method), specific references to various individual and collective combinations and rearrangements of these elements may not be expressly disclosed, but each is understood to be specifically intended and described herein.

[0073] The embodiments described above are intended to further illustrate the best known modes of carrying out the invention and to enable those skilled in the art to use the disclosure in such or other embodiments with various modifications required for specific applications or uses. Therefore, this description is not intended to limit the embodiments disclosed herein. The appended claims are also intended to be interpreted as including alternative embodiments. Furthermore, [1] to

[15] below are all embodiments or aspects of the present invention. [1] A composition of ashless additives, The compound contains a tertiary amine having the following structure: [ka] Here, R 1 and R 2 The ashless additive composition wherein each is independently a monovalent linear or branched hydrocarbyl group having 2 to about 20 carbon atoms, each m is independently 0 to 4, each p is independently 0 to 4, for each cyclic portion m+p is 2 to 4, and each n is independently 1 to 6. [2] The monovalent hydrocarbyl group in the linear or branched chain is branched C 12 ~C 20 The ashless additive composition described in [1], wherein the alkenyl group is [1]. [3] The monovalent hydrocarbyl group in the linear or branched chain is branched C 18 ~C 20 The ashless additive composition described in [1], wherein the alkenyl group is [1]. [4] A lubricating oil composition, A large amount of base oil, A compound containing an ashless tertiary amine having the following structure,

change

[10] A ashless additive composition containing a diamide product, A hydrocarbyl-substituted succinic anhydride represented by the following structure,

change

change

[11] The ashless additive composition according to

[10] , wherein the piperazine is aminoethylpiperazine, aminopropylpiperazine, aminobutylpiperazine, aminoethyldiazepane, or aminoethyldiazocan.

[12] A method for adjusting friction within an engine, the method comprising lubricating the engine with a lubricating oil composition, the lubricating oil composition is A large amount of base oil with lubricating viscosity, A composition of ashless additives having the following structure, comprising:

change

[13] The monovalent hydrocarbyl group in the linear or branched chain is branched C 12 ~C 20 The method described in

[12] , which is an alkenyl group.

[14] The monovalent hydrocarbyl group in the linear or branched chain is branched C 18 ~C 20 The method described in

[12] , which is an alkenyl group.

[15] A method for increasing the total base number in a lubricating oil, the method comprising blending a base oil with an ashless additive composition having the following structure,

change

Claims

1. A composition of ashless additives, The compound contains a tertiary amine having the following structure: 【Chemistry 1】 Here, R １ and R ２ The ashless additive composition wherein each is independently a monovalent hydrocarbyl group having 2 to 20 carbon atoms in a linear or branched chain, each m is independently 0 to 4, each p is independently 0 to 4, for each cyclic portion m+p is 2 to 4, and each n is independently 1 to 6.

2. The monovalent hydrocarbyl group in the linear or branched chain is branched C １２ ~C ２０ The ashless additive composition according to claim 1, wherein the alkenyl group is...

3. The monovalent hydrocarbyl group in the linear or branched chain is branched C １８ ~C ２０ The ashless additive composition according to claim 1, wherein the alkenyl group is...

4. A lubricating oil composition, A large amount of base oil, A compound containing an ashless tertiary amine having the following structure, 【Chemistry 2】 Here, R １ and R ２ The lubricating oil composition wherein each is independently a monovalent hydrocarbyl group having 2 to 20 carbon atoms in a straight or branched chain, each m is 0 to 4, each p is 0 to 4, for each cyclic portion m+p is 2 to 4, and each n is independently 1 to 6.

5. The linear or branched monovalent hydrocarbyl group is a branched C １２ -C ２０ alkenyl group, and the lubricating oil composition according to claim 4.

6. The monovalent hydrocarbyl group in the linear or branched chain is branched C １８ ~C ２０ The lubricating oil composition according to claim 4, wherein the alkenyl group is...

7. The lubricating oil composition according to claim 4, wherein the tertiary amine-containing compound is present in an amount of 0.1 to 2 wt% by weight of the lubricating oil composition.

8. The lubricating oil composition according to claim 4, wherein the lubricating oil composition is a hydraulic oil, a slide way lubricant, an automatic transmission fluid, a continuously variable transmission fluid, a battery electric vehicle, a hybrid electric vehicle transmission fluid, or a gear oil.

9. The lubricating oil composition according to claim 4, further comprising a friction modifier, an ashless wear-resistant additive, an antioxidant, a metal deactivator, a seal swell additive, an anti-foaming agent, or a viscosity modifier.

10. A ashless additive composition containing a diamide product, A hydrocarbyl-substituted succinic anhydride represented by the following structure, 【Transformation 3】 R １ The hydrocarbyl-substituted succinic anhydride is a monovalent hydrocarbyl group having 2 to 20 carbon atoms in a straight or branched chain, A cyclic polyamine represented by the following structure, 【Chemistry 4】 Here, R ２ The diamide product of the reaction with the cyclic polyamine comprises a monovalent hydrocarbyl group having 2 to 20 carbon atoms in a straight or branched chain, where m is 0 to 4, p is 0 to 4, m+p is 2 to 4, and n is 1 to 6. The ashless additive composition wherein the ratio of hydrocarbyl-substituted succinic anhydride to cyclic polyamine is 1.5:1 to 1.6:

1.

11. The ashless additive composition according to claim 10, wherein the piperazine is aminoethylpiperazine, aminopropylpiperazine, aminobutylpiperazine, aminoethyldiazepane, or aminoethyldiazocan.

12. A method for adjusting friction within an engine, the method comprising lubricating the engine with a lubricating oil composition, the lubricating oil composition is A large amount of base oil with lubricating viscosity, A composition of ashless additives having the following structure, comprising: 【Transformation 5】 Here, R １ and R ２ The method wherein m is independently a monovalent hydrocarbyl group having 2 to 20 carbon atoms in a straight or branched chain, each m is independently 0 to 4, each p is independently 0 to 4, and for each cyclic portion, m+p is 2 to 4, and each n is independently 1 to 6.

13. The monovalent hydrocarbyl group in the linear or branched chain is branched C １２ ~C ２０ The method according to claim 12, wherein the alkenyl group is...

14. The monovalent hydrocarbyl group in the linear or branched chain is branched C １８ ~C ２０ The method according to claim 12, wherein the alkenyl group is...

15. A method for increasing the total base number in a lubricating oil, the method comprising blending a base oil with an ashless additive composition having the following structure, 【Transformation 6】 Here, R １ and R ２ The method wherein m is independently a monovalent hydrocarbyl group having 2 to 20 carbon atoms in a straight or branched chain, each m is independently 0 to 4, each p is independently 0 to 4, and for each cyclic portion, m+p is 2 to 4, and each n is independently 1 to 6.

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