Marine lubricants enable the fuel of the future

Abstract

A marine cylinder lubricating oil composition for non-carbon-based fuel marine engines is disclosed. The composition comprises a major amount of oil of lubricating viscosity and a mixture of an overbased phenolic detergent and an overbased calcium sulfonate detergent. The composition is a monograde lubricating oil composition having a TBN of less than 200 mg KOH / g and meeting the January 2015 revised SAE J300 requirements for SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60 monograde lubricants.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Application No. 63 / 450,822, filed March 8, 2023, the disclosure of which is incorporated herein by reference.

[0002] This disclosure relates to marine lubricant additives and lubricant oil compositions containing same. More specifically, the marine lubricant additives and lubricant oil compositions perform well in marine engines operating using non-carbon-based fuels. [Background technology]

[0003] Non-carbon based fuels (e.g., ammonia, hydrogen) are gaining increasing attention as alternative energy sources for marine propulsion. Utilizing non-carbon based fuels such as ammonia will require new engine development, or perhaps modification of existing engines, to account for the differences in fuel and fuel combustion. Consequently, there is a need to develop lubricant formulations that provide good performance and fuel compatibility in alternative fuel marine engines. Summary of the Invention

[0004] In one aspect, there is provided a marine cylinder lubricant composition for a non-carbon-based fuel marine engine, the marine cylinder lubricant composition comprising a major amount of oil of lubricating viscosity and a mixture of an overbased phenolic detergent and an overbased calcium sulfonate detergent, the marine cylinder lubricant composition having a TBN of less than 200 mg KOH / g, and further, the marine engine lubricant composition is a monograde lubricant composition that meets the specifications of the January 2015 revised SAE J300 requirements for SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60 monograde lubricants.

[0005] In yet another aspect, there is provided a method of lubricating a marine two-stroke engine operating using ammonia fuel, the method comprising lubricating the engine with a lubricating oil composition comprising a major amount of oil of lubricating viscosity and a mixture of an overbased phenolic detergent and an overbased calcium sulfonate detergent, wherein the marine cylinder lubricant composition has a TBN of less than 200 mg KOH / g, and further wherein the marine engine lubricant composition is a monograde lubricant composition that meets the specifications of the January 2015 revision of SAE J300 requirements for SAE 40, SAE 50, or SAE 60 monograde lubricants.

[0006] In another further aspect, there is provided a method of improving or maintaining deposit control performance and / or oxidation stability in an ammonia-fueled marine engine, the method comprising lubricating the engine with a lubricating oil composition comprising a major amount of oil of lubricating viscosity and a mixture of an overbased phenolic detergent and an overbased calcium sulfonate detergent, wherein the marine cylinder lubricant composition has a TBN of less than 200 mg KOH / g, and further wherein the marine engine lubricant composition is a monograde lubricant composition that meets the specifications of the January 2015 revised SAE J300 requirements for SAE 40, SAE 50, or SAE 60 monograde lubricants. DETAILED DESCRIPTION OF THE INVENTION

[0007] In this specification, the following words and expressions, if used, have the meanings ascribed to them below.

[0008] "Major amount" means greater than 40 wt.% of the composition.

[0009] "Minor amount" means less than 40 wt.% of the composition.

[0010] The term "on an active ingredient basis" refers to additive materials that are not diluent oils or solvents. Weight percentages throughout this specification are on an active ingredient basis unless otherwise stated or the diluent oil content is given.

[0011] The term "Total Base Number" or "TBN" or "BN" refers to the level of alkalinity in an oil sample, which indicates the ability of a composition to continuously neutralize corrosive acids, according to ASTM Standard No. D2896 or an equivalent procedure. The test measures the change in electrical conductivity, and the results are expressed as mg KOH / g (the number of milligram equivalents of KOH required to neutralize one gram of product). Therefore, a high TBN reflects a strongly overbased product, and consequently, a greater reserve of base to neutralize acids. It should be understood that when TBN values ​​are referred to herein, they are expressed in units of mg KOH / g.

[0012] "Overbased" is used to describe metal-based detergents in which the ratio of the number of equivalents of metal moieties to the number of equivalents of acid moieties is greater than one.

[0013] "Soap" refers to the soap content and the concentration of surfactant anions contributed to the formulation by one or more detergents within the composition. For purposes of this invention, surfactant concentration is reported as millimoles of surfactant per kg of oil.

[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 will be understood that specific reference to each of the various individual and collective combinations and permutations of such elements may not be expressly disclosed, but each is specifically contemplated and described herein.

[0015] The present disclosure relates to marine engine lubricant additive compositions compatible with non-carbon-based fuel engines. The disclosure also relates to lubricant additive compositions having improved oxidation stability, oxidation stability retention, and / or deposit control capabilities, lubricating oil compositions containing the lubricant additive compositions, and methods of using the composition(s).

[0016] The compositions disclosed herein are particularly suitable for ammonia-fueled engines operating under sustained high load conditions. In some embodiments, the engine may be a "low-speed" or "slow-speed" marine engine. In some embodiments, the engine may be a two-stroke crosshead compression-ignition engine. The engine may be a newly designed or modified low-speed two-stroke marine engine fueled by ammonia. An engine classified as "slow-speed" or "slow-speed" may refer to a compression-ignition internal combustion engine operating at a rotational speed of less than 500 revolutions per minute (rpm).

[0017] For purposes of this disclosure, it should be understood that the "ammonia-fueled" engine concept of a large bore compression ignition engine can encompass an engine operating in dual fuel mode, where ammonia can be successfully used in dual fuel mode with diesel fuel or another pilot fuel, and ammonia is introduced into a diesel engine via dual fuel mode where vaporized premixed ammonia (the main fuel) in the combustion chamber is ignited by a pilot fuel (e.g., diesel, kerosene, etc.) as the ignition source.

[0018] Formulation of marine lubricants (e.g., marine cylinder lubricants) generally involves the use of additive technology in conventional base oils or, more recently, bio-based base oils. Some considerations for ammonia-fueled engine formulations include the ability to withstand exposure to ammonia and its reactive combustion products (e.g., NO, NO, HO) without sacrificing critical performance parameters.

[0019] In some embodiments, the lubricating oil compositions disclosed herein are suitable for use as marine cylinder lubricants used to lubricate ammonia-fueled engines. Marine cylinder lubricants are typically formulated to meet SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60 monograde specifications to provide a sufficiently thick lubricant film on the cylinder liner walls at high temperatures. Typically, marine cylinder lubricants have a KOH content of less than 200 mg KOH / g, up to 200 mg KOH / g, or in the range of 2-200 mg KOH / g (e.g., 2-200 mg KOH / g, 5-200 mg KOH / g, 10-200 mg KOH / g, 20-200 mg KOH / g, 30-200 mg KOH / g, 40-200 mg KOH / g, 50-200 mg KOH / g, 60-200 mg KOH / g, 70-200 mg KOH / g, 80-200 mg KOH / g, 90-200 mg KOH / g, 100-200 mg KOH / g, 110-200 mg KOH / g, 120-200 mg KOH / g, 130-200 mg KOH / g, 140-200 mg KOH / g). KOH / g, 150~200mg KOH / g, 160~200mg KOH / g, 170~200mg KOH / g, 180~200mg KOH / g, 190~200mg KOH / g, 2~190mg KOH / g, 5~190mg KOH / g, 10~190mg KOH / g, 20~190mg KOH / g, 30~190mg KOH / g, 40~190mg KOH / g, 50~190mg KOH / g, 60~190mg KOH / g, 70~190mg KOH / g, 80~190mg KOH / g, 90~190mg KOH / g, 100~190mg KOH / g, 110~190mg KOH / g, 120~190mg KOH / g, 130~190mg KOH / g, 140~190mg KOH / g, 150~190mg KOH / g, 160~190mg KOH / g, 170~190mg KOH / g, 180~190mg KOH / g, 2~180mg KOH / g, 5~180mg KOH / g, 10~180mg KOH / g, 15~180mg KOH / g, 20~180mg KOH / g, 30~180mg KOH / g, 40~180mg KOH / g, 50~180mgKOH / g、60~180mg KOH / g、70~180mg KOH / g、80~180mg KOH / g、90~180mg KOH / g、100~180mg KOH / g、110~180mg KOH / g、120~180mg KOH / g、130~180mg KOH / g、140~180mg KOH / g、150~180mg KOH / g、160~180mg KOH / g、2~170mg KOH / g、5~170mg KOH / g、10~170mg KOH / g、15~170mg KOH / g、20~170mg KOH / g、30~170mg KOH / g、40~170mg KOH / g、50~170mg KOH / g、60~170mg KOH / g、70~170mg KOH / g、80~170mg KOH / g、90~170mg KOH / g、100~170mg KOH / g、110~170mg KOH / g、120~170mg KOH / g、130~170mg KOH / g、140~170mg KOH / g、150~170mg KOH / g、160~170mg KOH / g、2~160mg KOH / g、5~160mg KOH / g、10~160mg KOH / g、15~160mg KOH / g、20~160mg KOH / g、30~160mg KOH / g、40~160mg KOH / g、50~160mg KOH / g、60~160mg KOH / g、70~160mg KOH / g、80~160mg KOH / g、90~160mg KOH / g、100~160mg KOH / g、110~160mg KOH / g、120~160mg KOH / g、130~160mg KOH / g、140~160mg KOH / g、150~160mg KOH / g、2~150mg KOH / g、5~150mg KOH / g、10~150mg KOH / g、15~150mg KOH / g、20~150mg KOH / g、30~150mg KOH / g、40~150mg KOH / g、50~150mg KOH / g、60~150mg KOH / g、70~150mg KOH / g、80~150mg KOH / g、90~150mg KOH / g、100~150mg KOH / g、110~150mg KOH / g、120~150mg KOH / g、130~150mg KOH / g、140~150mgKOH / g、2~140mg KOH / g、5~140mg KOH / g、10~140mg KOH / g、from、15~140mg KOH / g、20~140mg KOH / g、30~140mg KOH / g、40~140mg KOH / g、50~140mg KOH / g、60~140mg KOH / g、70~140mg KOH / g、80~140mg KOH / g、90~140mg KOH / g、100~140mg KOH / g、110~140mg KOH / g、120~140mg KOH / g、130~140mg KOH / g、2~130mg KOH / g、5~130mg KOH / g、10~130mg KOH / g、15~130mg KOH / g、20~130mg KOH / g、30~130mg KOH / g、40~130mg KOH / g、50~130mg KOH / g、60~130mg KOH / g、70~130mg KOH / g、80~130mg KOH / g、90~130mg KOH / g、100~130mg KOH / g、110~130mg KOH / g、120~130mg KOH / g、2~120mg KOH / g、5~120mg KOH / g、10~120mg KOH / g、15~120mg KOH / g、20~120mg KOH / g、30~120mg KOH / g、40~120mg KOH / g、50~120mg KOH / g、60~120mg KOH / g、70~120mg KOH / g、80~120mg KOH / g、90~120mg KOH / g、100~120mg KOH / g、110~120mg KOH / g、2~110mg KOH / g、5~110mg KOH / g、10~110mg KOH / g、15~110mg KOH / g、20~110mg KOH / g、30~110mg KOH / g、40~110mg KOH / g、50~110mg KOH / g、60~110mg KOH / g、70~110mg KOH / g、80~110mg KOH / g、90~110mg KOH / g、100~110mg KOH / g、2~100mg KOH / g、5~100mg KOH / g、10~100mg KOH / g、15~100mg KOH / g、20~100mg KOH / g、30~100mg KOH / g、40~100mg KOH / g、50~100mgKOH / g、60~100mg KOH / g、70~100mg KOH / g、80~100mg KOH / g、2~90mg KOH / g、5~90mg KOH / g1~9mg10 KOH / g、20~90mg KOH / g、30~90mg KOH / g、40~90mg KOH / g、50~90mg KOH / g、60~90mg KOH / g、70~90mg KOH / g、80mg KOH / g、80mg KOH / g、 KOH / g、5~80mg KOH / g、10~80mg KOH / g、15~80mg KOH / g、20~80mg KOH / g、30~80mg KOH / g、40~80mg KOH / g、50g0~80mg KOH / g、70~80mg KOH / g、2~70mg KOH / g、5~70mg KOH / g、10~70mg KOH / g、15~70mg KOH / g、20~70mg KOH / g、30~70mg KOH4~70mg KOH / g、50~70mg KOH / g、60~70mg KOH / g、2~60mg KOH / g、5~60mg KOH / g10~60mg KOH / g、15~60mg KOH / g、20~60mg30mg KOH / g KOH / g、40~60mg KOH / g、50~60mg KOH / g、2~50mg KOH / g、5~50mg KOH / g、10~50mg KOH / g、15~50mg KOH / g、20m KOH~50mg、 KOH / g、40~50mg KOH / g、2~40mg KOH / g、5~40mg KOH / g、10~40mg KOH / g、20~40mg KOH / g、30~40mg KOH / g、2~5 / 30mg KOH KOH / g、10~30mg KOH / g、10~30mg KOH / g、15~30mg KOH / g、20~30mg KOH / g、2~20mg KOH / g、5~20mg KOH / g、10~20mg KOH / g、2~15mg KOH / g、5~15mg KOH / g、10~15mg KOH / g、2~10mg KOH / g、5~10mg KOH / g

[0020] The lubricating oil compositions disclosed herein may provide advantageous oxidation control performance. The lubricating oil compositions disclosed herein may either maintain or improve oxidation stability performance when exposed to nitrogen-based contaminants (e.g., ammonia, NO, NO, etc.) present in or generated in ammonia-fueled engines. The lubricating oil compositions disclosed herein may exhibit deposit control capabilities.

[0021] In some embodiments, the lubricating oil composition is contaminated with ammonia. In some embodiments, the lubricating oil composition is contaminated with NO, NO2, and / or water.

[0022] base oil The lubricating oil compositions disclosed herein comprise a base oil. In some embodiments, the base oil is a Group I, II, III (including III+), IV, or V base oil. In some embodiments, the base oil comprises bright stock. Bright stock can be used as a thickener to achieve the correct viscosity. In some embodiments, the lubricating oil compositions disclosed herein comprise a major amount of Group II or higher base stock.

[0023] Groups I, II, III, IV, and V are broad base oil stock categories developed and defined by the American Petroleum Institute (API Publication 1509-Appendix E) to create guidelines for lubricant base oils. 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 but less than 120. Group II base stocks contain 90% or greater saturates, 0.03% or less sulfur, and have a viscosity index of 80 or greater but less than 120. Group III base stocks contain 90% or greater saturates, 0.03% or less sulfur, and have a viscosity index of 120 or greater. Group IV base stocks are polyalphaolefins. Group V base stocks include all other base stocks not included in Groups I, II, III, or IV. Table 1 summarizes the properties of each of these five groups. [Table 1]

[0024] In some embodiments, the lubricating oil compositions disclosed herein comprise a major amount of base stock containing greater than or equal to 90% saturates and less than or equal to 0.03% sulfur.

[0025] In some embodiments, the lubricating oil compositions disclosed herein comprise a major amount of a bio-based base oil derived from a renewable carbon source.

[0026] Bio-based base oil In some embodiments, the lubricating oil composition may comprise a bio-based base oil. A detailed discussion of bio-based base oils can be found in WO / 2021 / 205385, the contents of which are incorporated herein by reference.

[0027] In one aspect, bio-based oils can be described as follows: Base oils derived from bio-based hydrocarbon terpenes (such as myrcene, ocimene, and farnesene), more specifically isoparaffins, are described in PCT Patent Application No. PCT / US2012 / 024926, entitled "Base Oils and Methods for Making the Same," filed February 13, 2012 by Nicholas Ohler et al., published October 18, 2012 as WO2012 / 141784, and assigned to Amyris, Inc. of Emeryville, California. WO2012 / 141784 discloses that terpenes can be obtained from isopentyl pyrophosphate or dimethylallyl pyrophosphate, and the term "terpene" encompasses hemiterpenes, monoterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, tetraterpenes, and polyterpenes. Hydrocarbon terpenes contain only hydrogen and carbon atoms, no heteroatoms (such as oxygen), and in some embodiments have the general formula (C5H8): nwhere n is 1 or greater. A "conjugated terpene" or "conjugated hydrocarbon terpene" refers to a terpene containing at least one conjugated diene moiety. The conjugated diene moiety of a conjugated terpene can have any stereochemistry (e.g., cis or trans) and can be part of a longer conjugated segment of the terpene; for example, the conjugated diene moiety can be part of a conjugated triene moiety. Hydrocarbon terpenes also include monoterpenoids, sesquiterpenoids, diterpenoids, triterpenoids, tetraterpenoids, and polyterpenoids that exhibit the same carbon skeleton as the corresponding terpene but have fewer or more hydrogen atoms than the corresponding terpene (e.g., terpenoids having two fewer, four fewer, or six fewer hydrogen atoms than the corresponding terpene, or two more, four more, or six more hydrogen atoms than the corresponding terpene). Some non-limiting examples of conjugated hydrocarbon terpenes include isoprene, myrcene, a-ocimene, β-ocimene, a-farnesene, β-farnesene, β-springene, geranylfarnesene, neophytadiene, c / s-phyta-1,3-diene, frans-phyta-1,3-diene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II. The terms terpene and isoprenoid may be used interchangeably and refer to a large and diverse class of organic molecules that can be produced by a wide variety of plants and some insects. Some terpenes or isoprenoid compounds can also be produced by microorganisms (including bioengineered microorganisms such as yeast) from organic compounds (such as sugars). Terpenes or isoprenoid compounds can be obtained from a variety of renewable sources, making them useful monomers for making environmentally friendly renewable base oils. In some embodiments, conjugated hydrocarbon terpenes are obtained from microorganisms using renewable carbon sources (such as sugars). Further processing of certain such bio-based base oil stocks has been shown to result in highly useful and superior engine oils.For example, a C15 hydrocarbon containing four double bonds, such as Biofene™ β-farnesene, commercially available from Amyris, Inc. (Emeryville, California), can be pretreated to remove impurities and then hydrogenated to reduce three of the four double bonds to single bonds. The partially hydrogenated intermediate product is then subjected to an oligomerization reaction with linear alpha olefins (LAOs) using a catalyst (e.g., BF3 or BF3 complexes). The resulting intermediate product is a mixture of hydrocarbons ranging from C10 to about C75. This hydrocarbon oligomer mixture is then hydrogenated to reduce the amount of unsaturation. The saturated hydrocarbon mixture is then distilled to obtain a target composition, which is ultimately blended to meet the desired base oil product specifications (e.g., kinematic viscosity at 40°C) for engine oil. Table 2 provides examples of desirable bio-based base oil specifications that can be used to obtain blends suitable for engine oil formulations of one embodiment. Some embodiments of the present disclosure use commercially available bio-based hydrocarbon base oil (hydrogenated reaction product between partially hydrogenated p-3,7,11-trimethyldodeca-1,3,6,10-tetraene and linear C8 to C16 alpha olefins (hydrogenated)) sold under the trade name NOVASPEC (Novvi LLC, Emeryville, CA, United States; (REACH registration number 01-2120031429-59-0000). [Table 2]

[0028] Advantageously, in certain embodiments, at least about 20% of the carbon atoms in the base oil of the engine oil are derived from a renewable carbon source. For example, in one such embodiment, at least about 30% of the carbon atoms in the base oil of the engine oil are derived from a renewable carbon source. By way of further example, in one such embodiment, at least about 40% of the carbon atoms in the base oil of the engine oil are derived from a renewable carbon source. By way of further example, in one such embodiment, at least about 50% of the carbon atoms in the base oil of the engine oil are derived from a renewable carbon source. By way of further example, in one such embodiment, at least about 60% of the carbon atoms in the base oil of the engine oil are derived from a renewable carbon source. By way of further example, in one such embodiment, at least about 70% of the carbon atoms in the base oil of the engine oil are derived from a renewable carbon source. By way of further example, in one such embodiment, at least about 80% of the carbon atoms in the base oil of the engine oil are derived from a renewable carbon source. By way of further example, in one such embodiment, at least about 90% of the carbon atoms in the base oil of the engine oil originate from renewable carbon sources. In some variations, at least about 95%, at least about 97%, at least about 99%, or about 100% of the carbon atoms in the base oil component of the engine oil originate from renewable carbon sources. The origin of the carbon atoms in the reaction product adduct may be determined by any suitable method, including, but not limited to, combining analytical results demonstrating the structure and / or molecular weight of the adduct with the reaction mechanism, or by radiocarbon dating (e.g., by ASTM D6866-12 "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis," which is incorporated herein by reference in its entirety). For example, the modern carbon content of a sample can be determined by measuring the ratio of carbon-14 to carbon-12 isotopes in the bio-based base oil by liquid scintillation counting and / or isotope ratio mass spectrometry using ASTM D6866-12 or another suitable methodology.A measurement of no modern carbon content indicates that all of the carbon is from fossil fuels. Samples derived from renewable carbon sources will show an associated modern carbon content, which can be up to 100%.

[0029] In some embodiments of the present disclosure, one or more repeat units of the bio-based hydrocarbon base oil are a specific type of partially hydrogenated conjugated hydrocarbon terpene. Such a specific type of partially hydrogenated conjugated terpene may or may not be produced by a hydrogenation process. In certain variations, the partially hydrogenated hydrocarbon terpene species is prepared by a method that includes one or more steps in addition to or other than catalytic hydrogenation.

[0030] In some embodiments of the present disclosure, the bio-based hydrocarbon base oil may be classified as a Group III+ base oil having a saturates content of 90% or greater and a sulfur content of 0.03% or less, and may have a viscosity index of 120 or greater.

[0031] Non-limiting examples of specific species of partially hydrogenated conjugated hydrocarbon terpenes include any of the structures provided herein for dihydrofarnesene, tetrahydrofarnesene, and hexahydrofarnesene, any of the structures provided herein for dihydromyrcene and tetrahydromyrcene, and any of the structures provided herein for dihydroocimene and tetrahydroocimene.

[0032] One example of a particular species of partially hydrogenated conjugated hydrocarbon terpene that may have utility as a feedstock is represented by the structure (A11): [ka] where n is 1, 2, 3, or 4.

[0033] In some variations, the monoolefinic alpha-olefin having structure A11 can be derived from a conjugated hydrocarbon terpene (wherein the conjugated diene is in the 1,3 position of the terpene). Examples include 1,3-diene conjugated hydrocarbon terpenes (C 10 ~C 30 Alpha-olefins derived from conjugated hydrocarbon terpenes (such as farnesene, myrcene, ocimene, springene, geranylfarnesene, neophytadiene, trans-phyta-1,3-diene, or cz's-phyta-1,3-diene) are included. Another non-limiting example of an alpha-olefin having the general structure A11 is 3,7,11-trimethyldodecene, which has the structure A12. [ka]

[0034] Monoolefinic alpha-olefins having structure A11 can be prepared from suitable conjugated hydrocarbon terpenes using any suitable method. In some variations, monoolefinic alpha-olefins having structure A11 are obtained from the primary alcohol corresponding to the hydrocarbon terpene (for example, farnesol in the case of farnesene, or geraniol in the case of myrcene). The method includes hydrogenating the primary alcohol, forming a carboxylic acid ester or carbamate ester from the hydrogenated alcohol, and pyrolyzing the ester (or heating the ester to induce an elimination reaction) to form an alpha-olefin having a saturated hydrocarbon tail, as described, for example, in Smith, LE; Rouault, GF, J. Am. Chem. Soc. 1943, 65, 745-750 for the preparation of 3,7-dimethyloctene, which is incorporated herein by reference in its entirety. The primary alcohol of the corresponding hydrocarbon terpene can be obtained using any suitable method.

[0035] Other examples of specific species of partially hydrogenated conjugated hydrocarbon terpenes that may have utility as feedstocks include those represented by structure (A13) or structure (A15):

change

[0036] In yet another example of a particular class of partially hydrogenated hydrocarbon terpenes that may have utility as feedstocks, the terminal olefin of general structure A14 may be made from a 1,3-conjugated diene and a conjugated hydrocarbon terpene having at least one additional olefinic bond (e.g., myrcene, farnesene, springene, or geranylfarnesene), [ka] wherein n=1, 2, 3, or 4. In one non-limiting variation, compounds having structure A14 can be derived from the unsaturated primary alcohol corresponding to the related hydrocarbon terpene (e.g., farnesol in the case of farnesene, or geraniol in the case of myrcene). Exposure of the unsaturated primary alcohol to a suitable catalyst under suitable reaction conditions can result in dehydration of the primary alcohol to form the terminal olefin A14.

[0037] The olefinic feedstocks described herein can contain any useful amount of a particular species (e.g., an alpha-olefin species having structure A11, A12, or A15, a mono-olefin species having structure A13, or an unsaturated terminal olefin species having structure A14) produced either by a partial hydrogenation route or another route (e.g., as described herein). In certain variations, the olefinic feedstock contains at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% of species having structure A11, A12, A13, A14, or A15. In certain variations, the olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7,11-trimethyldodec-1-ene. In certain variations, the olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3-methylene-7,11-dimethyldodecane. In certain variations, the olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7,11-trimethyldodec-2-ene. In certain variations, the olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7,11-trimethyldodeca-1,6,10-triene.In certain variations, the olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7-dimethyloct-1-ene. In certain variations, the olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7-dimethyloct-2-ene. In certain variations, the olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7-dimethylocta-1,6-diene.

[0038] As described herein, in some variations, a hydrocarbon terpene feedstock comprising alpha-olefin or endo-olefin species of partially hydrogenated hydrocarbon terpenes is suitable for catalytic reaction with one or more alpha-olefins to form a mixture of isoparaffins comprising adducts of terpenes and one or more alpha-olefins. In some variations, at least a portion of the mixture of isoparaffins so produced may be used as a base oil.

[0039] In one embodiment, the bio-based oil has at least about 25% carbon atoms in the bio-based base oil that originate from renewable carbon sources as measured by ASTM-D6866-12, or at least about 40% carbon atoms in the bio-based base oil that originate from renewable carbon sources as measured by ASTM-D6866-12, or at least about 50% carbon atoms in the bio-based base oil that originate from renewable carbon sources as measured by ASTM-D6866-12, or at least about 50% carbon atoms in the bio-based base oil that originate from renewable carbon sources as measured by ASTM-D6866-12. The bio-based base oil has at least about 60% carbon atoms from renewable carbon sources as measured by ASTM-D6866-12, or at least about 70% carbon atoms from renewable carbon sources as measured by ASTM-D6866-12, or at least about 80% carbon atoms from renewable carbon sources as measured by ASTM-D6866-12, or at least about 90% carbon atoms from renewable carbon sources as measured by ASTM-D6866-12.

[0040] In one embodiment, the bio-based base oil additionally has an average methyl branching index (methyl branches per 100 carbons) of at least 7, additionally has an average methyl branching index (methyl branches per 100 carbons) of at least 8, additionally has an average methyl branching index (methyl branches per 100 carbons) of at least 9, additionally has an average methyl branching index (methyl branches per 100 carbons) of at least 10, additionally has an average methyl branching index (methyl branches per 100 carbons) of at least 11, and additionally has an average methyl branching index (methyl branches per 100 carbons) of at least 15. Additionally has an average methyl branching index (number of methyl branches per 100 carbons) of at least 20, additionally has an average methyl branching index (number of methyl branches per 100 carbons) of at least 22, additionally has an average methyl branching index (number of methyl branches per 100 carbons) of at least 24, additionally has an average methyl branching index (number of methyl branches per 100 carbons) of at least 26, and additionally has an average methyl branching index (number of methyl branches per 100 carbons) of at least 27.

[0041] In one embodiment, the molecular weight of the bio-based base oil is in the range of 300 g / mol to 800 g / mol, and the molecular weight of the bio-based base oil is in the range of 390 g / mol to 510 g / mol.

[0042] The bio-based base oil contains at least 95% acyclic isoparaffins having a molecular structure in which 25-34% of the total carbon atoms are contained in the branches and less than half of the total isoparaffin branches contain two or more carbon atoms, and the engine oil has a renewable hydrocarbon content of greater than 25% as measured by the ASTM-D6866 method.

[0043] In one embodiment, at least 95 wt% of the bio-based base oil comprises acyclic isoparaffins, and at least 25 wt% of the acyclic isoparaffins are hydrogenated sesquiterpenoid monomer units, or at least 30 wt% of the acyclic isoparaffins are hydrogenated sesquiterpenoid monomer units, or at least 35 wt% of the acyclic isoparaffins are hydrogenated sesquiterpenoid monomer units, or at least 45 wt% of the acyclic isoparaffins are hydrogenated sesquiterpenoid monomer units.

[0044] In one embodiment, the bio-based base oil has greater than 50% biodegradation in 28 days according to OECD 301B test method, the bio-based base oil has greater than 60% biodegradation in 28 days according to OECD 301B test method, and the bio-based base oil has greater than 70% biodegradation in 28 days according to OECD 301B test method.

[0045] In one embodiment, the bio-based base oil is characterized by a viscosity index (VI) greater than 120, as measured according to ASTM D2270-10, and has a branching ratio less than 0.41.

[0046] In one embodiment, the bio-based base oil is characterized by a viscosity index (VI) greater than 120 as measured according to ASTM D2270-10, greater than 40% of the bio-based base oil molecules have greater than 3 methyl branches per molecule, at least 50% of the bio-based base oil molecules have greater than 3 methyl branches per molecule, and at least 60% of the bio-based base oil molecules have greater than 3 methyl branches per molecule.

[0047] In one embodiment, the bio-based base oil is characterized by a viscosity index (VI) greater than 120, as measured according to ASTM D2270-10, and greater than 25% of the bio-based base oil molecules have greater than 6 methyl branches per molecule, at least 30% of the bio-based base oil molecules have greater than 3 methyl branches per molecule, at least 40% of the bio-based base oil molecules have greater than 3 methyl branches per molecule, at least 50% of the bio-based base oil molecules have greater than 3 methyl branches per molecule, and at least 60% of the bio-based base oil molecules have greater than 3 methyl branches per molecule.

[0048] In one embodiment, the bio-based base oil is characterized in having greater than 60% renewable carbon content as measured by ASTM-D6866-12, greater than 70% renewable carbon content as measured by ASTM-D6866-12, greater than 80% renewable carbon content as measured by ASTM-D6866-12, or greater than 90% renewable carbon content as measured by ASTM-D6866-12.

[0049] The base oil has a saturates content of at least 90% as determined by ASTM-D2007-1.

[0050] In one embodiment, the base oil contains at least 50% of its hydrocarbon molecules containing an odd number of carbon atoms per molecule, at least 60% of its hydrocarbon molecules containing an odd number of carbon atoms per molecule, at least 70% of its hydrocarbon molecules containing an odd number of carbon atoms per molecule, and at least 80% of its hydrocarbon molecules containing an odd number of carbon atoms per molecule.

[0051] In one embodiment, the bio-based base oil has greater than 60% biodegradation in 28 days according to OECD 301B test method, and the bio-based base oil has greater than 70% biodegradation in 28 days according to OECD 301B test method.

[0052] The base oil comprises a bio-based terpene selected from the group consisting of myrcene, ocimene, farnesene, and combinations thereof. In one embodiment, the base oil comprises farnesene. In one embodiment, the bio-based base oil is derived from farnesene. In one embodiment, the bio-based base oil is derived from sugar.

[0053] In one embodiment, the bio-based base oil is a saturated hydrocarbon mixture characterized by NMR with a unique branched structure that makes it suitable for use as a high-quality synthetic base stock. The hydrocarbon mixture possesses outstanding properties (including extremely low volatility, good low-temperature properties, etc.) that are important performance attributes of a high-quality base stock. Specifically, the mixture contains greater than 80% of molecules with even carbon numbers by FIMS. The branching characteristics of the hydrocarbon mixture by NMR include a BP / BI ratio within the range of ≥ -0.6037 (number of internal alkyl branches per molecule) + 2.0. Furthermore, on average, at least 0.3 to 1.5 internal methyl branches are located more than four carbon atoms away from the terminal carbon.

[0054] The bio-based base oil may comprise an oligomerization product of an alpha-alkene. In some embodiments, the oligomerization product may be hydrogenated and / or hydroisomerized.

[0055] In one embodiment, the hydrocarbon mixture described herein is the product of olefin oligomerization and subsequent hydroisomerization. 14 ~C 20 Olefins are oligomerized to form unreacted monomers, dimers (C 28 ~C 40 ), and trimers and oligomers of higher polymerization degree (≧C 42), forming an oligomer distribution consisting of the unreacted monomers. The unreacted monomers are distilled off for reuse in subsequent oligomerizations. The remaining oligomers are then hydroisomerized to achieve the final branched structure described herein.

[0056] In one embodiment, the oligomerization product has the following structure: [ka] wherein n=1 (representing a C16 olefin) or 3 (representing a C18 olefin); R=C16-C18 or H; R1=C9 to C13, R2=C4H 10 It is linear or branched, R3=C9 to C13, a is a value that gives a molecular weight in the range of about 220 to 1020 g / mol.

[0057] lubricating oil composition The lubricating oil compositions of this disclosure can be identified by the Society of Automotive Engineers (SAE) viscosity specifications for engine oils (i.e., the SAE J300 specifications). Table 3 provides a summary of the SAE J300 viscosity grades. [Table 3]

[0058] The lubricating oil compositions of this disclosure may be monograde engine oils, for example, SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60 viscosity grade engine oils.

[0059] additives The lubricating oil compositions of this disclosure may contain one or more performance additives capable of imparting or improving any desirable property of the lubricating oil composition. Any additive known to those skilled in the art may be used in the lubricating oil compositions disclosed herein. Some suitable additives are described by R.M. Mortier et al. "Chemistry and Technology of Lubricants," 3rd Edition, Springer (2010) and L.R. Rudnik "Lubricant Additives: Chemistry and Applications," Second Edition, CRC Press (2009).

[0060] Generally, when used, the concentration of each of the additives in the lubricating oil composition may range from 0.001 to 60 wt.% (e.g., 0.01 to 50 wt.% or 0.05 to 40 wt.%) of the lubricating oil composition. Furthermore, the total amount of additives in the lubricating oil composition may range from 0.001 to 70 wt.% (e.g., 0.01 to 50 wt.% or 0.1 to 40 wt.%) of the lubricating oil composition.

[0061] The lubricating oil compositions may further contain one or more of other commonly used lubricant performance additives, including antioxidants, antiwear agents, metal-based detergents, dispersants, friction modifiers, corrosion inhibitors, demulsifiers, viscosity modifiers, pour point depressants, antifoam agents, thickeners, and others.

[0062] antioxidants Antioxidants retard the oxidative degradation of base oils during use, which can cause deposits on metal surfaces, the presence of sludge, or increased viscosity of the lubricant. Useful antioxidants include hindered phenols, aromatic amines, and sulfurized alkylphenols and their alkali metal and alkaline earth metal salts.

[0063] The hindered phenol antioxidant may contain secondary and / or tertiary butyl groups as sterically hindering groups. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group linking the second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-bis(2,6-di-tert-butylphenol), and 4,4'-methylenebis(2,6-di-tert-butylphenol). The hindered phenol antioxidant may be an ester or addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, where the alkyl group may contain 1 to 18 carbon atoms. The hindered phenol antioxidant may be a 2,6-di-alkyl-phenolic propionic acid ester derivative.

[0064] Non-phenolic antioxidants that can be used include aromatic amine antioxidants (such as diarylamines and alkylated diarylamines). Specific examples of aromatic amine antioxidants include diphenylamines (e.g., N-phenyl-2-naphthylamine, 4,4'-dioctyldiphenylamine, butylated / octylated diphenylamine, nonylated diphenylamine, and octylated N-phenyl-2-naphthylamine).

[0065] In one embodiment, the lubricating oil composition of this disclosure includes a hindered phenol antioxidant, which may be present in the lubricating oil composition at 0 to 10.0 wt.% (e.g., 0.5 to 10.0 wt.%, 0 to 5.0 wt.%, 0.5 to 4.0 wt.%, 0.5 to 4.5 wt.%, 0.5 to 4.0 wt.%, 0.5 to 3.5 wt.%, 0.5 to 3.0 wt.%, 0.5 to 2.5 wt.%, 1.0 to 10.0 wt.%, 1.0 to 4.5 wt.%, 1.0 to 4.0 wt.%, 1.0 to 3.5 wt.%, 1.0 to 3.0 wt.%, or 1.0 to 2.5 wt.%).

[0066] In one embodiment, the lubricating oil composition of this disclosure includes an aminic antioxidant, which may be present in the lubricating oil composition at 0 to 10.0 wt.% (e.g., 0 to 5.0 wt.%, 0.5 to 5.0 wt.%, 0.5 to 4.0 wt.%, 0.5 to 4.5 wt.%, 0.5 to 4.0 wt.%, 0.5 to 3.5 wt.%, 0.5 to 3.0 wt.%, 0.5 to 2.5 wt.%, 1.0 to 4.5 wt.%, 1.0 to 4.0 wt.%, 1.0 to 3.5 wt.%, 1.0 to 3.0 wt.%, or 1.0 to 2.5 wt.%).

[0067] According to the present disclosure, lubricating oil compositions may include a combination of a hindered phenolic antioxidant and an aminic antioxidant, wherein the ratio (by mass percent) of the phenolic antioxidant to the aminic antioxidant may be from 1:1 to 100:1 (e.g., from 1:1 to 75:1, from 1:1 to 50:1, from 1:1 to 25:1, from 1:1 to 1:10, from 1:1 to 8:1, from 1:1 to 6:1, from 1:1 to 5:1, from 1:1 to 4:1, or from 1:1 to 3:1).

[0068] In some embodiments, the lubricating oil composition does not contain an aminic antioxidant, hi some embodiments, the hindered phenol is the only antioxidant present in the lubricating oil composition.

[0069] Anti-wear agents Antiwear agents reduce wear of metal parts. Examples of antiwear agents include phosphorus-containing antiwear / extreme pressure agents (such as metal thiophosphates, phosphoric acid esters and their salts, phosphorus-containing carboxylic acids, esters, ethers, and amides, and phosphites). The antiwear agent may be zinc dialkyldithiophosphate. Non-phosphorus-containing antiwear agents include borate esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins.

[0070] Metallic Detergents Typical detergents are anionic materials containing a long-chain hydrophobic portion of the molecule and a smaller, anionic or oleophobic, hydrophilic portion of the molecule. The anionic portion of the detergent is typically derived from an organic acid, such as a sulfur acid, a carboxylic acid, a phosphorous acid, a phenol, or a mixture thereof. The counterion is typically an alkaline earth metal or alkali metal.

[0071] In some embodiments, the lubricating oil compositions provided herein contain at least an overbased metallic detergent as an additive or additive component. The metallic detergent in the lubricating oil composition can neutralize acidic products in the oil. The metallic detergent can also inhibit the formation of deposits on engine surfaces. Depending on the nature of the acid used, the detergent may have additional functions (e.g., antioxidant properties).

[0072] In certain embodiments, the lubricating oil composition contains a metallic detergent, including either an overbased detergent or a mixture of a neutral detergent and an overbased detergent. The term "overbased" is intended to define an additive containing a metal content in excess of that required by the stoichiometry of the particular metal and particular organic acid used. The excess metal is present in the form of particles of an inorganic base (e.g., hydroxide or carbonate) surrounded by a sheath of metal salt. The sheath helps maintain the particles dispersed in the liquid oil medium. The amount of excess metal is generally expressed as the ratio of the total equivalents of excess metal to the equivalents of organic acid, and is typically in the range of 0.1 to 30.

[0073] Overbased detergents may be further characterized as low overbased, medium overbased, or highly overbased. A low overbased detergent may be, for example, an overbased salt having a TBN of less than 100 mg KOH / g active ingredient. A medium overbased detergent may be, for example, an overbased salt having a TBN of 100 to 250 mg KOH / g active ingredient. A highly overbased detergent may be, for example, an overbased salt having a TBN of more than 250 mg KOH / g active ingredient.

[0074] Some examples of suitable metal-based detergents include sulfurized or non-sulfurized alkyltoluenes, sulfurized or non-sulfurized alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, borated sulfonates, sulfurized or non-sulfurized metal salts of polyhydric hydroxyalkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxyaromatic sulfonates, sulfurized or non-sulfurized alkyl or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of alkyl or alkenyl polyhydric acids, and chemical and physical mixtures thereof. Other examples of suitable metal-based detergents include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates, and combinations thereof. The metal can be any metal suitable for making sulfonate, phenate, salicylate, or phosphonate detergents. Non-limiting examples of suitable metals include alkali metals, alkaline metals, and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li, or the like.

[0075] Metal salts of phenols and sulfurized phenols (e.g., phenate or sulfurized phenate detergents or calcium sulfurized phenate detergents) are prepared by reacting phenols or sulfurized phenols with an appropriate metal compound (such as an oxide or hydroxide). Sulfurized phenols can be prepared by reacting phenols with sulfur or sulfur-containing compounds (such as hydrogen sulfide, sulfur monohalides, or sulfur dihalides) to form a product that is generally a mixture of compounds in which two or more phenols are crosslinked with sulfur-containing bridges. Additional details regarding the general preparation of sulfurized phenates can be found, for example, in U.S. Pat. Nos. 2,680,096, 3,178,368, and 3,801,507, the contents of which are incorporated herein by reference.

[0076] The sulfur used to form the sulfide compound can have any allotropic form of sulfur. The sulfur can be present as molten sulfur, or as a solid (e.g., powder or particulate), or as a solid suspension in a compatible hydrocarbon liquid.

[0077] In some embodiments, the use of calcium hydroxide as the calcium base is desirable due to its ease of handling (e.g., as compared to calcium oxide) and the superior results that can be obtained from calcium hydroxide. Other calcium bases (e.g., calcium alkoxides) can also be used.

[0078] Suitable alkyl phenols that can be used are those in which the alkyl substituent contains a sufficient number of carbon atoms to render the resulting alkyl phenate (e.g., overbased calcium sulfurized alkyl phenate) composition oil-soluble. Oil solubility can be imparted by a single long chain alkyl substitution or by a combination of alkyl substituents. Typically, the alkyl phenol used is a mixture of different alkyl phenols (e.g., C 20 ~C 24 In one embodiment, the alkylphenol compound is derived from an isomerized normal alpha-olefin alkyl group having from about 10 to about 40 carbon atoms per molecule, with an alpha-olefin isomerization level of from about 0.1 to about 0.4. The isomerization level can be determined by the method described in U.S. Pat. No. 1,148,5928, the contents of which are incorporated herein by reference. In one embodiment, the isomerized normal alpha-olefin has from about 20 to about 24 carbon atoms. In one embodiment, the alkylphenol compound is derived from an alkyl group that is a branched olefinic propylene oligomer or mixture thereof having from about 9 to about 80 carbon atoms. In one embodiment, the branched olefinic propylene oligomer or mixture thereof has from about 9 to about 40 carbon atoms. In one embodiment, the branched olefinic propylene oligomer or mixture thereof has from about 9 to about 18 carbon atoms. In one embodiment, the branched olefinic propylene oligomer or mixture thereof has from about 9 to about 12 carbon atoms.

[0079] In one embodiment, suitable alkylphenol compounds include distilled cashew nut shell liquid (CNSL) or hydrodistilled CNSL. Distilled CNSL is a mixture of biodegradable meta-hydrocarbyl-substituted phenols, including cardanol, in which the hydrocarbyl groups are linear and unsaturated. Catalytic hydrogenation of distilled CNSL produces a mixture of meta-hydrocarbyl-substituted phenols that is primarily enriched in 3-pentadecylphenol.

[0080] The alkylphenol may be a para-, meta-, or ortho-alkylphenol. In certain embodiments, such as when an overbased product is desired, the alkylphenol is preferably predominantly para-alkylphenol, with no more than about 45 mole percent of the alkylphenol being ortho-alkylphenol, and more preferably no more than about 35 mole percent of the alkylphenol being ortho-alkylphenol. Alkylhydroxytoluenes or xylenes and other alkylphenols having one or more alkyl substituents in addition to at least one long-chain alkyl substituent can also be used. In the case of distilled cashew nut shell liquid, catalytic hydrogenation of the distilled CNSL produces a mixture of meta-hydrocarbyl-substituted phenols.

[0081] Generally, the selection of alkylphenols can be based on the properties desired in the marine engine lubricating oil composition, particularly TBN and oil solubility. Additional information regarding the preparation of suitable alkylphenols can be found, for example, in U.S. Patent Nos. 5,024,773, 5,320,763, 5,318,710, and 5,320,762, each of which is incorporated herein by reference.

[0082] As noted, certain embodiments of lubricating oil formulations may utilize one or more sulfonate detergents, either alone or in combination with other sulfonates (e.g., combinations of highly overbased sulfonates and low overbased sulfonates), as well as other detergents. Sulfonates may be prepared from sulfonic acids, which may be obtained by sulfonation of alkyl-substituted aromatic hydrocarbons (such as those obtained from petroleum fractionation) or by alkylation of aromatic hydrocarbons. Examples of alkyl-substituted aromatic hydrocarbons that may be sulfonated include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl, or their halogen derivatives. Alkylation may be carried out in the presence of a catalyst with an alkylating agent having from 3 to more than 70 carbon atoms. Alkaryl sulfonates typically contain from 9 to 80 or more carbon atoms per alkyl-substituted aromatic moiety, preferably from 16 to 60, more preferably from 16 to 30, and most preferably from 20 to 24 carbon atoms.

[0083] In one embodiment, the lubricating oil formulation may utilize a combination of highly and lowly overbased sulfonates derived from the alkylation of toluene.

[0084] The oil-soluble sulfonates or alkaryl sulfonic acids may be neutralized with metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates, and ethers. The amount of metal compound is selected taking into account the desired TBN of the final product.

[0085] Detergents may also include "hybrid" or "composite" detergents formed with mixed surfactant systems containing phenate and / or sulfonate components (e.g., phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, sulfonate / phenate / salicylate), as described, for example, in U.S. Patent Nos. 6,429,178, 6,429,179, and 6,153,565. Detergents may also include methylene-bridged polyphenol compositions prepared by reacting phenol with formaldehyde or its reversible polymer, optionally sulfurizing the methylene-bridged intermediate, and then reacting the intermediate with an excess of a metal base to obtain the methylene-bridged polyphenol phenate composition. In one embodiment, the methylene-bridged polyphenol phenate composition may be further reacted with an epoxide. In one embodiment, the methylene-bridged polyphenol phenate composition is not sulfurized.

[0086] In one or more embodiments, the lubricating oil composition comprises a phenolic detergent that is an overbased sulfurized calcium phenate detergent. In one or more embodiments, the lubricating oil composition comprises an overbased sulfurized calcium phenate detergent having a TBN of less than 250 mg KOH / g. In one or more embodiments, the lubricating oil composition comprises an overbased sulfurized calcium phenate detergent that is not derived from tetrapropenyl phenol. In one or more embodiments, the lubricating oil composition comprises a phenolic detergent that is an overbased sulfurized calcium phenate detergent derived from an isomerized normal-alpha-olefin alkyl group having from about 10 to about 40 carbon atoms per molecule.

[0087] Generally, the amount of detergent may be from about 0.001 wt.% to about 60 wt.% (such as from about 0.05 wt.% to about 40 wt.%, such as from about 0.05 wt.% to about 30 wt.%, such as from about 0.05 wt.% to about 25 wt.%, from about 0.1 wt.% to about 20 wt.%, from about 0.01 to 15 wt.%, and from about 0.01 to about 10 wt.%) based on the total weight of the marine lubricating oil composition.

[0088] In one or more embodiments, the lubricating oil composition comprises a low overbased calcium sulfonate detergent, a medium overbased calcium sulfonate detergent, and / or a highly overbased calcium sulfonate detergent, or combinations thereof, present in an amount to provide the lubricating oil composition with a sulfonate soap content of 10 mmol / kg or more (e.g., 10 mmol / kg to 140 mmol / kg, 10 mmol / kg to 100 mmol / kg, 10 mmol / kg to 80 mmol / kg, 25 mmol / kg to 140 mmol / kg, 30 mmol / kg to 140 mmol / kg, 30 mmol / kg to 100 mmol / kg, 40 mmol / kg to 100 mmol / kg, 40 mmol / kg to 80 mmol / kg, or 50 mmol / kg to 100 mmol / kg sulfonate soap).

[0089] In one or more embodiments, the lubricating oil composition comprises a low overbased calcium sulfonate detergent, a medium overbased calcium sulfonate detergent, and / or a high overbased calcium sulfonate detergent, or a combination thereof, wherein the TBN contribution from the sulfonate detergent to the total detergent BN contribution is greater than about 20%, greater than about 25% (e.g., 25-95%, 25-90%, 25-85%, 25-80%, 30-80%).

[0090] In one or more embodiments, the lubricating oil composition comprises a low overbased calcium sulfonate detergent, a medium overbased calcium sulfonate detergent, and / or a high overbased calcium sulfonate detergent, or a combination thereof, wherein the TBN contribution from the sulfonate detergent to the total detergent BN contribution is greater than about 20%, and further wherein the sulfonate detergent is present in an amount such that the sulfonate soap content in the lubricating oil composition is from 25 mmol / kg to 140 mmol / kg.

[0091] In one or more embodiments, the lubricating oil composition comprises a low overbased calcium sulfonate detergent, a medium overbased calcium sulfonate detergent, and / or a high overbased calcium sulfonate detergent, or a combination thereof, wherein the TBN contribution from the sulfonate detergent to the total detergent BN contribution is from 20 to 95%, and further wherein the sulfonate detergent is present in an amount such that the sulfonate soap content in the lubricating oil composition is from 25 mmol / kg to 140 mmol / kg.

[0092] In one embodiment, the phenolic detergent contribution can come from one or more phenolic detergents with similar or different TBN levels, and in one embodiment, the sulfonate soap contribution can come from one or more sulfonate detergents with similar or different TBN levels (e.g., a combination of low and high overbased).

[0093] Other additional detergents may also be present in the lubricating oil composition in any suitable amount (such as 0.1 to 45 wt.% or 0.5 to 30 wt.% of the lubricating oil composition).

[0094] Ashless Dispersant Dispersants are additives whose primary function is to hold solid and liquid contaminants in suspension, thereby passivating them and reducing sludge deposits as well as engine deposits. For example, dispersants maintain in suspension oil-insoluble materials that result from oxidation during lubricant use, thereby preventing sludge flocculation and precipitation or deposition on metal engine parts.

[0095] Dispersants are typically "ashless"—nonmetallic organic materials that do not substantially form ash upon combustion, as opposed to metal-containing, i.e., ash-forming, materials. Dispersants contain long hydrocarbon chains with polar heads, the polarity resulting from the inclusion of at least one nitrogen, oxygen, or phosphorus atom. The hydrocarbon is an oleophilic group, e.g., having 40 to 500 carbon atoms, that confers oil solubility. Thus, ashless dispersants may contain an oil-soluble polymer backbone.

[0096] A preferred class of olefin polymers is constituted by polybutylene, specifically polyisobutylene (PIB) or poly-n-butylene (such as may be prepared by polymerization of C4 refinery streams).

[0097] Dispersants include, for example, derivatives of long-chain hydrocarbon-substituted carboxylic acids, such as derivatives of high molecular weight hydrocarbyl-substituted succinic acids. A notable group of dispersants is constituted by hydrocarbon-substituted succinimides, which are made, for example, by reacting the above acids (or derivatives) with nitrogen-containing compounds, advantageously polyalkylene polyamines (such as polyethylene polyamines). A typical commercially available polyisobutylene-based succinimide dispersant contains a polyisobutylene polymer having a number average molecular weight in the range of 900 to 2500, functionalized with maleic anhydride, and derivatized with a polyamine having a molecular weight of 100 to 350.

[0098] Other suitable dispersants include succinate esters and succinate ester-amides, Mannich bases, polyisobutylene succinic acid (PIBSA), and other related components.

[0099] Succinate esters are formed by the condensation reaction between hydrocarbyl-substituted succinic anhydrides and alcohols or polyols. For example, the condensation product of hydrocarbyl-substituted succinic anhydrides with pentaerythritol is a useful dispersant.

[0100] Succinic acid ester-amides are formed by the condensation reaction between hydrocarbon-substituted succinic anhydrides and alkanolamines. For example, suitable alkanolamines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines, and polyalkenylpolyamines (such as polyethylenepolyamines). One example is propoxylated hexamethylenediamine.

[0101] Mannich bases are made from the reaction of an alkylphenol, formaldehyde, and a polyalkylenepolyamine. The molecular weight of the alkylphenol can range from 800 to 2500.

[0102] Nitrogen-containing dispersants may be post-treated by conventional methods to enhance their properties by reaction with any of a variety of agents, including boron compounds (e.g., boric acid) and cyclic carbonates (e.g., ethylene carbonate).

[0103] In one embodiment, the dispersant is a polyalkenyl bis-succinimide dispersant, wherein the polyalkenyl substituent is derived from a polyalkene group having a number average molecular weight of about 1500 to about 3000. In one embodiment, the dispersant is a non-borated, post-treated polyalkenyl bis-succinimide dispersant. In one embodiment, the dispersant is post-treated with ethylene carbonate. In one embodiment, the dispersant is a non-post-treated polyalkenyl bis-succinimide dispersant, wherein the polyalkenyl substituent is derived from a polyalkene group having a number average molecular weight of about 1000 to about 1500. In one embodiment, the dispersant is present in the lubricating composition at 0.05 to 10.0 wt.% (e.g., 0.1 to 10.0 wt.%, 0.1 to 5.0 wt.%, 0.2 to 10 wt.%, or 0.2 to 5.0 wt.%).

[0104] friction modifiers Friction modifiers are any material(s) capable of altering the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s). Friction modifiers include alkoxylated fatty amines, borated fatty epoxides, fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters, and fatty imidazolines. As used herein, the term "fatty" refers to a hydrocarbon chain having 10 to 22 carbon atoms, typically a straight hydrocarbon chain.

[0105] Other known friction modifiers include oil-soluble organo-molybdenum compounds. Such organo-molybdenum friction modifiers also provide antioxidant and anti-wear properties to lubricating oil compositions. Suitable oil-soluble organo-molybdenum compounds have a molybdenum sulfur core. Examples include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and mixtures thereof. The molybdenum compounds may be di- or tri-nuclear.

[0106] Corrosion inhibitors Corrosion inhibitors protect lubricated metal surfaces from chemical attack by water or other contaminants. Suitable corrosion inhibitors include polyoxyalkylene polyols and their esters, polyoxyalkylene phenols, thiadiazoles, and anionic alkylsulfonic acids.

[0107] Viscosity modifier Viscosity modifiers provide high and low temperature operability to lubricants. While such additives increase the viscosity of the oil composition at high temperatures, thereby increasing film thickness, they have limited effect on viscosity at low temperatures.

[0108] Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters, and viscosity index improver dispersants, which function as both viscosity index improvers and dispersants. Typical molecular weights of such polymers are in the range of 1000 to 1,000,000 (e.g., 2000 to 500,000 or 25,000 to 100,000).

[0109] Examples of suitable viscosity improvers are polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (e.g., copolymers of alkyl methacrylates of various chain lengths), which, depending on the formulation, can also function 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 molecular weights of 50,000 to 200,000.

[0110] Pour Point Depressants Pour point depressants lower the minimum temperature at which a fluid will flow or can be poured. Suitable pour point depressants include C8 to C18 dialkyl fumarate / vinyl acetate copolymers, polyalkyl methacrylates, and the like.

[0111] Anti-foaming agent Antifoam agents retard the formation of stable foam. Examples of suitable antifoam agents include polysiloxanes, polyacrylates, and the like.

[0112] thickener The thickener can increase the viscosity of the lubricating oil composition to achieve the desired viscosity grade. Any suitable thickener can be used, such as bright stock (BS), polyisobutylene (PIB), polymethacrylate (PMA), or olefin copolymer (OCP).

[0113] PIB is a commercially available material from several manufacturers. Polyisobutylene typically has a number average molecular weight of 800 to 5000 (e.g., 1000 to 2500) and a viscosity of 200 to 5000 mm 2 / s (e.g., 200 to 1000 mm 2It is a viscous, oil-miscible liquid with a kinematic viscosity at 100°C of 100°C (1 / s). The amount of PIB added to a lubricating oil composition will typically be 1 to 20 wt.% (e.g., 2 to 15 wt.% or 4 to 12 wt.% on an active ingredient basis) of the finished oil.

[0114] The olefin copolymer is generally present at 0.1 wt.% or more (e.g., 0.1-12 wt.%) of the lubricating oil composition on an active ingredient basis. In certain embodiments, the OCP is present at 0.2-10 wt.%, 0.3-9 wt.%, 0.4-8 wt.%, or 0.5-7 wt.% of the lubricating oil composition on an active ingredient basis. In yet further embodiments, the OCP is present at 0.5-12.0 wt.%, 0.5-5 wt.%, or 1-2 wt.% of the lubricating oil composition on an active ingredient basis. In another further embodiment, the OCP is present at 1.0 wt.% or greater (e.g., 1.0-12.0 wt.%, 1.0 wt.%-5 wt.%, 1.3 wt.%-4.5 wt.%, 1.5 wt.%-4.0 wt.%, 2.0-12.0 wt.%, or 2.0 wt.%-3.5 wt.%) of the lubricating oil composition on an active ingredient basis.

[0115] In certain embodiments, the olefin copolymer is a copolymer (such as an ethylene-propylene copolymer composition) based on ethylene units and alpha-olefin (e.g., normal alpha-olefin, isomerized alpha-olefin) units. Other alpha-olefins suitable in place of propylene or in combination with ethylene and propylene to form terpolymers or tetrapolymers include, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and branched-chain alpha-olefins (such as 4-methyl-1-pentene, 4-methyl-1-hexene, 4-methylpentene-1,4,4-dimethyl-1-pentene, 6-methylheptene-1, and mixtures thereof).

[0116] The following non-limiting examples illustrate the present invention. A brief description of how the examples were prepared is provided. [Example]

[0117] The effects of ammonia fuel and its combustion products on the MCL package were investigated.

[0118] Virgin test oil samples containing the MCL additive package were contaminated with ammonia using an experimental aging procedure. The aging procedure mimics the interaction between marine lubricants and ammonia to assess the impact on bench test performance of marine lubricants. The wt.% nitrogen in the aged test oils was measured to demonstrate that nitrogen uptake occurs as a result of ammonia exposure.

[0119] Differential scanning calorimetry (DSC), modified IP-48 (MIP-48), and Komatsu Hot Tube (KHT) bench tests were used to evaluate both virgin and aged test oils.

[0120] Marine cylinder lubricant Marine cylinder lubricants were prepared by blending 15BN and 40BN MCL packages in various types of base oil mixtures.

[0121] Base oil blend A consisted of a major amount of API Group I 600N base oil and a minor amount of API Group I XOM2500 bright stock as a viscosity enhancer.

[0122] Base oil blend B consisted of a major amount of bio-based base oil SynNova 9® (a plant-derived sustainable synthetic base oil (SSBO) with a viscosity of 9.5 cSt at 100°C, commercially available as a Group III+ base oil derived 100% from renewable carbon sources), a small amount of API Group I XOM2500 bright stock thickener, and some high molecular weight polyisobutene (PIB2300) to maintain equal amounts of bright stock and to compensate for the viscosity loss resulting from using the lower viscosity SSBO.

[0123] Base oil blend C consisted of a major amount of Chevron RLOP 600R API Group II base oil and a minor amount of API Group I XOM2500BS bright stock as a viscosity enhancer.

[0124] Below is a summary of the resulting test oil samples containing marine additive packages and base oil blends. Example 1 (40BN SAE 50 MCL with a KV of 18.5 cSt at 100°C) a) Additive package 1 - 9.0 wt.% oil concentrate (40 wt.% diluent oil) of overbased calcium sulfurized phenate (derived from propylene tetramer) having a TBN of 116BN, 60 mmol / kg sulfonate soap derived from a mixture of low and high overbased calcium sulfonate detergents, 1000 MW polyisobutylene-derived bis-succinimide dispersant, and 1.5 wt.% antioxidant system having a combination of a hindered phenolic antioxidant and a diphenylamine amine antioxidant. The TBN contribution from the sulfonate detergent was 72% of the total detergent BN. b) Base oil mixture A - (78.1 wt.% base oil blend) contained 54.7 wt.% API Group I 600N base oil and 23.4 wt.% API Group I XOM2500BS bright stock as a viscosity enhancer. Example 2 (40BN SAE 50 MCL with a KV of 18.5 cSt at 100°C) a) Additive package 1 - 9.0 wt.% oil concentrate (40 wt.% diluent oil) of overbased calcium sulfurized phenate (derived from propylene tetramer) having a TBN of 116BN, 60 mmol / kg sulfonate soap derived from a mixture of low and high overbased calcium sulfonate detergents, 1000 MW polyisobutylene-derived bis-succinimide dispersant, and 1.5 wt.% antioxidant system having a combination of a hindered phenolic antioxidant and a diphenylamine amine antioxidant. The TBN contribution from the sulfonate detergent was 72% of the total detergent BN. b) Base oil blend B- (78.1 wt.%) contained 50.2 wt.% of bio-based base oil SynNova9® (a 100% renewable and bio-based sustainable synthetic base oil (SSBO) with a viscosity of 9.5 cSt at 100°C), 23.4 wt.% of API Group I XOM2500BS bright stock thickener, and 4.5 wt.% of high molecular weight polyisobutene (PIB2300). Example 3 (40BN SAE 50 MCL with a KV of 18.5 cSt at 100°C) a) Additive Package 2 - 9.0 wt.% oil concentrate (40 wt.% diluent) of overbased calcium sulfurized phenate (derived from propylene tetramer) having a TBN of 260, 9.0 wt.% oil concentrate (40 wt.% diluent) of overbased calcium sulfurized phenate (derived from propylene tetramer) having a TBN of 116 BN, 70 mmol / kg sulfonate soap derived from a mixture of low and high overbased calcium sulfonate detergents, 1000 MW polyisobutylene-derived bis-succinimide dispersant, and 1.5 wt.% antioxidant system having a combination of a hindered phenolic antioxidant and a diphenylamine amine antioxidant. The TBN contribution from the sulfonate detergent was 70% of the total detergent BN. b) Base oil mixture A - (75.8 wt.% base oil blend) contained 52.2 wt.% API Group I 600N base oil and 23.6 wt.% API Group I XOM2500BS bright stock as a viscosity enhancer. Example 4 (40BN SAE 50 MCL with a KV of 18.5 cSt at 100°C) a) Additive Package 2 - 9.0 wt.% oil concentrate (40 wt.% diluent) of overbased calcium sulfurized phenate (derived from propylene tetramer) having a TBN of 260, 9.0 wt.% oil concentrate (40 wt.% diluent) of overbased calcium sulfurized phenate (derived from propylene tetramer) having a TBN of 116 BN, 70 mmol / kg sulfonate soap derived from a mixture of low and high overbased calcium sulfonate detergents, 1000 MW polyisobutylene-derived bis-succinimide dispersant, and 1.5 wt.% antioxidant system having a combination of a hindered phenolic antioxidant and a diphenylamine amine antioxidant. The TBN contribution from the sulfonate detergent was 70% of the total detergent BN. b) Base oil blend B- (75.8 wt%) contained 48.1 wt.% of bio-based base oil SynNova9® (a 100% renewable and bio-based sustainable synthetic base oil (SSBO) with a viscosity of 9.5 cSt at 100°C), 23.6 wt.% of API Group I XOM2500BS bright stock thickener, and 4.1 wt.% of high molecular weight polyisobutene (PIB2300). Example 5 (40BN SAE 50 MCL with a KV of 18.5 cSt at 100°C) a) Additive package 6 - 2.5 wt.% oil concentrate (40 wt.% diluent) of overbased calcium sulfurized phenate (derived from propylene tetramer) having a TBN of 260, 14.0 wt.% oil concentrate (40 wt.% diluent) of overbased calcium sulfurized phenate (derived from propylene tetramer) having a TBN of 116 BN, 30 mmol / kg sulfonate soap derived from a blend of low and high overbased calcium sulfonate detergents, and a bis-succinimide dispersant derived from 1000 MW polyisobutylene. The TBN contribution from the sulfonate detergent was 43% of the total detergent BN. b) Base Oil Blend C - (77.6 wt.% base oil blend) 60.3 wt.% Chevron RLOP 600R API Group II base oil and 17.4 wt.% API Group I XOM2500BS bright stock as a thickener. Example 6 (40BN SAE 50 MCL with a KV of 18.5 cSt at 100°C) a) Additive package 7-95 oil concentrate (20 wt.% diluent oil) of 23.5 wt.% overbased calcium sulfurized phenate (derived from C20-24 isomerized olefins) with a TBN of 95, 27 mmol / kg sulfonate soap derived from a blend of low and high overbased calcium sulfonate detergents, and a bis-succinimide dispersant derived from 1000 MW polyisobutylene. The TBN contribution from the sulfonate detergent was 43% of the total detergent TBN. b) Base Oil Blend C - (71.0 wt.% base oil blend) 57.3 wt.% Chevron RLOP 600R API Group II base oil and 13.7 wt.% API Group I XOM2500BS bright stock as a thickener. Example 7 (15BN SAE 50 MCL with a KV of 18.5 cSt at 100°C) a) Additive package: 2.7 wt.% oil concentrate (20 wt.% diluent oil) of overbased calcium sulfurized phenate (derived from C20-24 isomerized olefins) with a TBN of 8-95, 15 mmol / kg sulfonate soap derived from a blend of low and high overbased calcium sulfonate detergents, and a bis-succinimide dispersant derived from 1000 MW polyisobutylene. The TBN contribution from the sulfonate detergent was 81% of the total detergent TBN. b) Base Oil Mixture C - (93.8 wt.% base oil blend) 52.4 wt.% Chevron RLOP 600R API Group II base oil and 41.4 wt.% API Group I XOM2500BS bright stock as a thickener. Example 8 (15BN SAE 50 MCL with a KV of 18.5 cSt at 100°C) a) Additive package: 8.8 wt.% oil concentrate (20 wt.% diluent oil) of overbased calcium sulfurized phenate (derived from C20-24 isomerized olefins) with a TBN of 9-95, 10 mmol / kg sulfonate soap derived from a blend of low and high overbased calcium sulfonate detergents, and a bis-succinimide dispersant derived from 1000 MW polyisobutylene. The TBN contribution from the sulfonate detergent was 42% of the total detergent BN. b) Base Oil Blend C - (88.9 wt.% base oil blend) 53.0 wt.% Chevron RLOP 600R API Group II base oil and 35.9 wt.% API Group I XOM2500BS bright stock as a thickener. Comparative Example A (40BN SAE 50 MCL with a KV of 18.5 cSt at 100°C) a) Additive Package 3 (Single Phenate) - 14.8 wt.% oil concentrate (40 wt.% diluent) of overbased calcium sulfurized phenate (derived from propylene tetramer) having a TBN of 260, 1.0 wt.% oil concentrate (40 wt.% diluent) of overbased calcium sulfurized phenate (derived from propylene tetramer) having a TBN of 116 BN, and 1.0 wt.% bis-succinimide dispersant derived from 1000 MW polyisobutylene. The TBN contribution from the sulfonate detergent was 0% of the total detergent BN. b) Base Oil Blend C - (83.8 wt.% base oil blend) 55.2 wt.% Chevron RLOP 600R API Group II base oil and 28.6 wt.% API Group I XOM2500BS bright stock as a thickener. Comparative Example B (40BN SAE 50 MCL with a KV of 18.5 cSt at 100°C) a) Additive Package 4 (Single Sulfonate) - 50 mmol / kg sulfonate soap derived from a mixture of low and high overbased calcium sulfonate detergents, 1000 MW polyisobutylene-derived bis-succinimide dispersant. The TBN contribution from the sulfonate detergent was 100% of the total detergent BN. b) Base Oil Blend C - (89.2 wt.% base oil blend) 53.9 wt.% Chevron RLOP 600R API Group II base oil and 35.4 wt.% API Group I XOM2500BS bright stock as a thickener. Comparative Example C (15BN SAE 50 MCL with a KV of 18.5 cSt at 100°C) a) Additive Package 5 (Single Phenate) - Oil concentrate (20 wt.% diluent oil) of overbased calcium sulfurized phenate (derived from C20-24 isomerized olefins) with a TBN of 95, containing 15.6 wt.% of a bis-succinimide dispersant derived from 1000 MW polyisobutylene. The TBN contribution from the sulfonate detergent was 0% of the total detergent TBN. b) Base Oil Blend C - (84.0 wt.% base oil blend) 53.4 wt.% Chevron RLOP 600R API Group II base oil and 30.6 wt.% API Group I XOM2500BS bright stock as a thickener.

[0125] Aging treatment protocol To demonstrate the effects of ammonia fuel and its combustion products, test oils were aged in an NH3 atmosphere. The aged products were then subjected to bench testing to provide insight into lubricant performance.

[0126] The aging process involved aging 15BN and 40BN marine cylinder lubricants with gaseous ammonia (NH3) at high temperature (180°C) for extended periods of time. After verifying that the increased nitrogen content in the samples was at least about 600 ppm, a series of bench tests were performed.

[0127] "Soap" refers to the soap content and the concentration in millimoles / kg of surfactant anions contributed to the formulation by one or more detergents in the composition. For purposes of this invention, surfactant concentration is reported as millimoles of surfactant per kg of additive concentrate. The soap, or surfactant, content of a detergent additive can be determined as follows: Step 1: Determine the equivalent % (by weight) of calcium as sulfonate soap according to ASTM D4251. The resulting value is [Wt.% calcium / 100] in the following formula, or in other words, the wt.% equivalent of calcium as soap in 100 g of additive concentrate. Step 2: Once you have determined the % calcium as sulfonate soap, calculate the number of surfactant anions, or "soaps," in mmol / kg using the following formula: [Wt.% calcium / 100]*[1000g / Kg]*[1 mole calcium / 40g calcium]*[2 moles surfactant anion / mol calcium]*[1000 mmol / mol] = mmol surfactant "soap" / kg of additive concentrate

[0128] DSC oxidation test DSC testing is used to evaluate the thin film oxidation stability of test oils according to ASTM D-6186. During the test, the heat flow to and from the test oil in the sample cup is compared to a reference cup. The oxidation onset temperature is the temperature at which oxidation of the test oil begins. The oxidation induction time is the time at which oxidation of the test oil begins. A longer oxidation induction time indicates better performance. The oxidation reaction is exothermic and is clearly indicated by heat flow. The oxidation induction time (in minutes) is calculated to evaluate the thin film oxidation stability of the test oil.

[0129] Modified Institute of Petroleum 48 (MIP-48) Test The MIP-48 test measures the degree of stability of a lubricant against oxidation-based viscosity growth. The MIP-48 test consists of a thermal and an oxidation part. During both parts of the test, the sample is heated for a set period of time. During the thermal part of the test, nitrogen is passed through the heated oil sample for 24 hours. In parallel, during the oxidation part of the test, air is passed through the heated oil sample for 24 hours. The samples are cooled, and the viscosities of both samples are determined. The viscosity increase of the test oil caused by oxidation is determined and corrected for the effects of heat. The oxidation-based viscosity increase of each marine lubricating oil composition was calculated by subtracting the kinematic viscosity of the nitrogen-blown sample at 200°C from the kinematic viscosity of the air-blown sample at 200°C and dividing the result by the kinematic viscosity of the nitrogen-blown sample at 200°C. This is done to correct for potential evaporation effects or any other thermal effects during the test, thereby focusing on the impact of oxidation. The result of this correction can be a negative value. The better the stability of the test oil against oxidation-based viscosity growth, the smaller the resulting absolute value. Table 1 below shows the results of the MIP-48 study.

[0130] Komatsu Hot Tube (KHT) Test The Komatsu Hot Tube Test is a lubrication industry bench test that measures the high-temperature detergency and thermal and oxidative stability of lubricating oils. During the test, a specific amount of test oil is pumped upward through a glass tube placed inside an oven set to a specific temperature. Air is introduced into the oil stream before the oil enters the tube, causing it to flow upward along with the oil. Marine lubricating oils are evaluated at temperatures between 300 and 320°C. After cooling and rinsing, the test result is determined by comparing the amount of lacquer deposited in the glass test tube with a rating scale ranging from 1.0 (very dark) to 10.0 (completely clear). Results are reported in multiples of 0.5. If the glass tube becomes completely blocked with deposits, the test result is recorded as "blocked." Blockage occurs when the result is less than 1.0; in this case, the lacquer is very thick and dark, but still allows fluid flow, albeit at a rate completely unsatisfactory for usable oil.

[0131] Each of the finished oil lubricants of Examples 1-4 was evaluated for oxidation-based viscosity increase using the MIP-48 test, with the virgin oil being evaluated first, followed by the NH3-aged oil. Table 4 below shows the results for each of the Examples. [Table 4]

[0132] Referring to Table 4, ammonia (NH3) aging at 180°C had only a minimal effect on the marine cylinder lubricating compositions of the present invention. Each ammonia-aged test oil exhibited stability against oxidation-based viscosity increase compared to the virgin test oil before aging, as evidenced by relatively stable % viscosity increase. This demonstrates the compatibility of the cylinder lubricants of the present invention with ammonia fuel. In some cases, as seen in Examples 2, 3, and 4, the ammonia-aged oils exhibited lower % viscosity increase than the virgin test oils, indicating a directionally improved stability against oxidation-based viscosity increase. Overall, the absolute % viscosity increase was lower for virgin and aged test oils containing a major amount of SSBO base oil (Examples 2 and 4) than for those containing a major amount of conventional API Group I base oil, indicating improved stability against oxidation-based viscosity increase.

[0133] Each of the NH3-aged Group II finished oil lubricants of Comparative Examples A-B and Examples 5-6 was evaluated for oxidation-based viscosity increase using the MIP-48 test, for high-temperature detergency using the KHT test, and for oxidation stability using the DSC test. Table 5 below shows the results for each of the examples. [Table 5]

[0134] Referring to Table 5, Examples 5 and 6, when exposed to ammonia aging, experienced a reduced % viscosity increase (indicating improved stability against oxidation-based viscosity increase), a longer oxidation induction time, and improved KHT ratings (demonstrating improved oxidation stability and deposit performance) over the Comparative Example.

[0135] Each of the NH3-aged Group II finished oil lubricants of Comparative Example C and Examples 7-8 was evaluated for high temperature detergency using the KHT test. Table 6 below shows the results for each of the Examples. [Table 6]

[0136] Referring to Table 6, the 15BN Group II based formulations of Examples 7 and 8, when exposed to ammonia aging, improved their KHT test ratings over the comparative examples, demonstrating improved deposit performance.

[0137] For the sake of brevity, only certain ranges are explicitly disclosed herein.However, a range from any lower limit can be combined with any upper limit to describe a range that is not explicitly stated; in addition, a range from any lower limit can be combined with any other lower limit to describe a range that is not explicitly stated; and a range from any upper limit can be combined with any other upper limit to describe a range that is not explicitly stated.Furthermore, a range includes every point or individual value between its endpoints, even if not explicitly stated.Therefore, every point or individual value can act as a unique lower limit or upper limit in combination with any other point or individual value or any other lower limit or upper limit, to describe a range that is not explicitly stated.

[0138] Similarly, the term "comprising" is considered synonymous with the term "including." Similarly, whenever a composition, element, or group of elements is preceded by the transitional phrase "comprising," it will be understood that the inventors also contemplate that same composition or group of elements with the transitional phrase "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is" preceding the description of the composition, element, or elements, and vice versa.

[0139] It will be understood that the terms "a" and "the", as used herein, encompass the plural as well as the singular.

[0140] Various terms are defined above. If a term used in a claim is not defined above, it should be given the broadest definition given to that term by one of ordinary skill in the relevant art as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, 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 for all jurisdictions where such incorporation is permitted.

[0141] The foregoing description of the present disclosure illustrates and describes the present disclosure. Moreover, while the present disclosure shows and describes only preferred embodiments, it will be understood, as noted above, that the present disclosure is capable of use in various other combinations, modifications, and environments, and is capable of changes or modifications within the scope of the concepts expressed herein commensurate with the above teachings and / or the skill or knowledge of the relevant art. While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the present disclosure may be devised without departing from the basic scope thereof, which scope is determined by the following claims.

[0142] 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 will be understood that specific reference to each of the various individual and collective combinations and permutations of such elements may not be expressly disclosed, but each is specifically contemplated and described herein.

[0143] The embodiments described herein above illustrate the best mode known for its practice and are further intended to enable those skilled in the art to utilize the present disclosure in such or other embodiments with various modifications required for particular applications or uses. Therefore, the description is not intended to limit it to the form disclosed herein. Also, it is intended that the appended claims be construed to include alternative embodiments.

Claims

1. 1. A marine cylinder lubricating oil composition for a non-carbon-based fuel marine engine, comprising: (a) a major amount of oil of lubricating viscosity; (b) a mixture of an overbased phenolic detergent and an overbased calcium sulfonate detergent; wherein the marine cylinder lubricant composition has a TBN of less than 200 mg KOH / g, and further wherein the marine engine lubricant composition is a monograde lubricant composition that meets the specifications of the January 2015 revised SAE J300 requirements for SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60 monograde lubricants.

2. 10. The marine cylinder lubricating oil composition of claim 1, wherein the lubricating oil composition is contaminated with ammonia.

3. 2. The marine cylinder lubricating oil composition of claim 1, wherein the oil of lubricating viscosity is a base oil having greater than or equal to 90% saturates and less than or equal to 0.03% sulfur, and has a viscosity index of 120 or greater.

4. 10. The marine cylinder lubricating oil composition of claim 1, further comprising an ashless dispersant.

5. 10. The marine cylinder lubricating oil composition of claim 1, further comprising a mixture of a phenolic antioxidant and an aminic antioxidant.

6. 10. The marine cylinder lubricating oil composition of claim 1, wherein the composition has a BN level of 15 to 80 mg KOH / g.

7. 2. The marine cylinder lubricating oil composition of claim 1, wherein the phenolic detergent is an overbased calcium sulfurized phenate.

8. 2. The marine cylinder lubricating oil composition of claim 1, wherein the sulfonate detergent is one or more sulfonate detergents and the TBN contribution from the sulfonate detergent to the total detergent BN contribution is from 20 to 95%.

9. 2. The marine cylinder lubricating oil composition of claim 1, wherein the sulfonate detergent is one or more sulfonate detergents, and the sulfonate detergents are present in an amount to provide a sulfonate soap content in the lubricating oil composition of from 10 mmol / kg to 140 mmol / kg.

10. 1. A method of lubricating a marine two-stroke engine operating using ammonia fuel, comprising: (a) a major amount of oil of lubricating viscosity; (b) a mixture of an overbased phenolic detergent and an overbased calcium sulfonate detergent; wherein the marine cylinder lubricant composition has a TBN of less than 200 mg KOH / g, and wherein the marine engine lubricant composition is a monograde lubricant composition that meets the specifications of the January 2015 revised SAE J300 requirements for SAE 40, SAE 50, or SAE 60 monograde lubricants.

11. 11. The method of claim 10, wherein the oil of lubricating viscosity is a base oil having greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur, and has a viscosity index of 120 or greater.

12. 11. The method of claim 10, wherein the oil of lubricating viscosity contains greater than or equal to 90% saturates and less than or equal to 0.03 wt.% sulfur.

13. The method of claim 10, wherein the lubricating oil composition has a BN level of 15 to 80 mg KOH / g.

14. The method of claim 10, wherein the lubricating oil composition further comprises an ashless dispersant.

15. 11. The method of claim 10, wherein the lubricating oil composition further comprises a mixture of a phenolic antioxidant and an aminic antioxidant.

16. 11. The marine cylinder lubricating oil composition of claim 10, wherein the phenolic detergent is an overbased calcium sulfurized phenate.

17. 11. The marine cylinder lubricating oil composition of claim 10, wherein the sulfonate detergent is one or more sulfonate detergents and the TBN contribution from the sulfonate detergent to the total detergent BN contribution is from 20 to 95%.

18. 11. The marine cylinder lubricating oil composition of claim 10, wherein the sulfonate detergent is one or more sulfonate detergents, and the sulfonate detergents are present in an amount to provide a sulfonate soap content in the lubricating oil composition of from 10 mmol / kg to 140 mmol / kg.

19. 1. A method for improving or maintaining deposit control performance and / or oxidation stability in an ammonia-fueled marine engine, comprising: (a) a major amount of oil of lubricating viscosity; (b) a mixture of an overbased phenolic detergent and an overbased calcium sulfonate detergent; wherein the marine cylinder lubricant composition has a TBN of less than 200 mg KOH / g, and wherein the marine engine lubricant composition is a monograde lubricant composition that meets the specifications of the January 2015 revised SAE J300 requirements for SAE 40, SAE 50, or SAE 60 monograde lubricants.

20. 20. The method of claim 19, wherein the oil of lubricating viscosity is a base oil having greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur, and has a viscosity index of 120 or greater.

21. 20. The method of claim 19, wherein the oil of lubricating viscosity contains greater than or equal to 90% saturates and less than or equal to 0.03 wt.% sulfur.

22. 20. The method of claim 19, wherein the lubricating oil composition has a BN level of 15 to 80 mg KOH / g.

23. 20. The method of claim 19, wherein the lubricating oil composition further comprises an ashless dispersant.

24. 20. The method of claim 19, wherein the lubricating oil composition further comprises a mixture of a phenolic antioxidant and an aminic antioxidant.

25. 20. The marine cylinder lubricating oil composition of claim 19, wherein the phenolic detergent is an overbased calcium sulfurized phenate.

26. 20. The marine cylinder lubricating oil composition of claim 19, wherein the sulfonate detergent is one or more sulfonate detergents and the TBN contribution from the sulfonate detergent to the total detergent BN contribution is from 20 to 95%.

27. 20. The marine cylinder lubricating oil composition of claim 19, wherein the sulfonate detergent is one or more sulfonate detergents, and the sulfonate detergents are present in an amount to provide a sulfonate soap content in the lubricating oil composition of from 10 mmol / kg to 140 mmol / kg.

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