Marine lubricants to assist future fuels

Abstract

A marine cylinder lubricating oil composition for a non-carbon-based fuel driven marine engine is disclosed. The composition includes a high amount of an oil of lubricating viscosity and a mixture of an overbased phenolic-based cleaning agent and an overbased calcium sulfonate cleaning agent. The composition has a TBN of less than 200 mg KOH / g, and is a single grade lubricating oil composition that meets the requirements of the SAE J300 specification revised in January 2015 for SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60 single grade lubricating oil.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 450,822, filed on March 8, 2023, the disclosure of which is incorporated herein by reference. Technical Field

[0003] The present disclosure relates to marine lubricant additives and lubricating oil compositions containing the same. More particularly, the marine lubricant additives and lubricating oil compositions perform well in marine engines running on non-carbon-based fuels. Background Art

[0004] Non-carbon-based fuels (e.g., ammonia, hydrogen) are increasingly being considered as alternative energy sources for marine propulsion. Using non-carbon-based fuels, such as ammonia, requires the development of new engines or the potential modification of conventional engines to account for differences in fuels and fuel combustion. Therefore, there is a need to develop lubricant formulations that provide good performance and fuel compatibility in marine engines powered by alternative fuels. Summary of the Invention

[0005] In one aspect, a marine cylinder lubricating oil composition for a marine engine driven by a non-carbon-based fuel is provided, comprising: a plurality of oils of lubricating viscosity; and a mixture of an overbased phenol-based detergent and an overbased calcium sulfonate detergent; and wherein the marine cylinder lubricating oil composition has a TBN of less than 200 mg KOH / g, and further wherein the marine engine lubricating oil composition is a monograde lubricating oil composition that meets the requirements of the SAE J300 specification, revised January 2015, for SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60 monograde lubricating oils.

[0006] In another aspect, a method of lubricating a marine two-stroke engine operating on ammonia fuel is provided, the method comprising lubricating the engine with a lubricating oil composition comprising: a major amount of an oil of lubricating viscosity; and a mixture of an overbased phenol-based detergent and an overbased calcium sulfonate detergent; and wherein the marine cylinder lubricating oil composition has a TBN of less than 200 mg KOH / g, and further wherein the marine engine lubricating oil composition is a monograde lubricating oil composition that meets the requirements of the SAE J300 specification, revised January 2015, for SAE 40, SAE 50, or SAE 60 monograde lubricants.

[0007] In yet another aspect, there is provided a method of improving or maintaining deposit control performance and / or oxidation stability of an ammonia-fueled marine engine, the method comprising: lubricating the engine with a lubricating oil composition comprising: a major amount of an oil of lubricating viscosity; and a mixture of a high base number phenate detergent and a high base number calcium sulfonate detergent; and wherein the marine cylinder lubricating oil composition has a TBN of less than 200 mg KOH / g, and further wherein the marine engine lubricating oil composition is a single grade lubricating oil composition meeting the requirements of the SAE J300 specification for SAE 40, SAE 50, or SAE 60 single grade lubricating oils as revised in January 2015. DETAILED DESCRIPTION

[0008] In this specification, the following words and phrases have the meanings indicated below, if and when used.

[0009] "Major amount" means greater than 40 percent by weight of the composition.

[0010] "Minor amount" means less than 40 percent by weight of the composition.

[0011] The term "active ingredient-based" means that the additive material is not a diluent oil or solvent. Unless otherwise indicated or a diluent oil content is provided, all weight percentages throughout this specification are based on active ingredients.

[0012] The term "total base number" or "TBN" or "BN" refers to the level of alkalinity in an oil sample, which indicates the ability of the composition to continue to neutralize corrosive acids according to ASTM Standard Number D2896 or equivalent procedure. This test measures the change in conductivity, and the result is expressed in mg KOH / g (the equivalent number of milligrams of KOH needed to neutralize 1 gram of product). Thus, a high TBN reflects a strong overbased product, which therefore requires a higher reserve of base to neutralize acids. When TBN values are introduced herein, it is understood that they are expressed in mg KOH / g.

[0013] "High base number" is used to describe metal detergents in which the ratio of the equivalent number of metal moieties to the equivalent number of acid moieties is greater than 1.

[0014] "soap" refers to the soap content and refers to the concentration of surfactant anions contributed to the formulation by one or more detergents within the composition. For the purposes of this invention, the surfactant concentration is reported in millimoles of surfactant per kg of oil.

[0015] It should be understood that when combinations, subsets, groups, etc. of elements are disclosed (e.g., combinations of components in a composition or combinations of steps in a method), that the combinations are likewise contemplated as if each and every combination and permutation of each and every element that was specifically enumerated and each and every combination and permutation of each and every element that is virtually enumerated by the disclosure were expressly stated.

[0016] The present disclosure relates to marine engine lubricant additive compositions compatible with non-carbon based fuel driven engines. The present 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 compositions.

[0017] The compositions disclosed herein are particularly suitable for use in ammonia fuel driven engines operating under sustained high load conditions. In some embodiments, the engine can be a "low speed" or "slow speed" marine engine. In some embodiments, the engine can be a two-stroke crosshead compression ignition engine. The engine can be a new design or a retrofitted to ammonia fuel driven low speed two-stroke marine engine. Engines classified as "low speed" or "slow speed" can refer to compression ignition internal combustion engines driven at a rotational speed below 500 revolutions per minute (rpm).

[0018] For the purposes of the present disclosure, it is understood that the concept of an "ammonia fuel driven" engine for large bore compression ignition engines can encompass engines operating in dual fuel mode. In compression ignition engines, ammonia can be successfully used in dual fuel mode with diesel or another pilot fuel, where ammonia is introduced into the diesel engine through dual fuel mode, such that the fumigated premixed ammonia (main fuel) in the combustion chamber is ignited by a pilot fuel (e.g., diesel, kerosene, etc.) as an ignition source.

[0019] Formulating marine lubricating oils (e.g., marine cylinder lubricants) generally involves the use of additive technology in traditional or newer biobased base oils. Some considerations for ammonia fuel driven engine formulations include being able to withstand exposure to ammonia and its reactive combustion products (e.g., NO, NO2, H2O) without sacrificing key performance parameters.

[0020] In some embodiments, the lubricating oil compositions disclosed herein are suitable for use as a marine cylinder lubricant for lubricating ammonia fuel driven engines. Marine cylinder lubricants are typically manufactured to SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60 single grade specifications in order to provide a sufficiently thick lubricant film on the cylinder liner wall at high temperatures. Typically, marine cylinder lubricants have a TBN of less than 200 mg KOH / g, up to 200 mg KOH / g, or ranging from 2 to 200 mg KOH / g (e.g., 2 to 200 mg KOH / g, 5 to 200 mg KOH / g, 10 to 200 mg KOH / g, 20 to 200 mg KOH / g, 30 to 200 mg KOH / g, 40 to 200 mg KOH / g, 50 to 200 mg KOH / g, 60 to 200 mg KOH / g, 70 to 200 mg KOH / g, 80 to 200 mg KOH / g, 90 to 200 mg KOH / g, 100 to 200 mg KOH / g, 110 to 200 mg KOH / g, 120 to 200 mg KOH / g, 130 to 200 mg KOH / g, 140 to 200 mg KOH / g, 150 to 200 mg KOH / g, 160 to 200 mg KOH / g, 170 to 200 mg KOH / g, 180 to 200 mg KOH / g, 190 to 200 mg KOH / g, 2 to 190 mg KOH / g, 5 to 190 mg KOH / g, 10 to 190 mg KOH / g, 20 to 190 mg KOH / g, 30 to 190 mg KOH / g, 40 to 190 mg KOH / g, 50 to 190 mg KOH / g, 60 to 190 mg, 70 to 190 mg, 80 to 190 mg, 90 to 190 mg, 100 to 190 mg KOH / g, 110 to 190 mg KOH / g, 120 to 190 mg KOH / g, 130 to 190 mg KOH / g, 140 to 190 mg KOH / g, 150 to 190 mg KOH / g, 160 to 190 mg KOH / g, 170 to 190 mg KOH / g, 180 to 190 mg KOH / g, 2 to 180 mg KOH / g, 5 to 180 mg KOH / g, 10 to 180 mg KOH / g, 15 to 180 mg KOH / g, 20 to 180 mg KOH / g, 30 to 180 mg KOH / g, 40 to 180 mg KOH / g, 50 to 180 mg KOH / g, 60 to 180 mg KOH / g, 70 to 180 mg KOH / g, 80 to 180 mg KOH / g, 90 to 180 mg KOH / g, 100 to 180 mg KOH / g, 110 to 180 mgmg KOH / g, 120 to 180 mg KOH / g, 130 to 180 mg KOH / g, 140 to 180 mg KOH / g, 150 to 180 mg KOH / g, 160 to 180 mg KOH / g, 2 to 170 mg KOH / g, 5 to 170 mg KOH / g, 10 to 170 mg KOH / g, 15 to 170 mg KOH / g, 20 to 170 mg KOH / g, 30 to 170 mg KOH / g, 40 to 170 mg KOH / g, 50 to 170 mg KOH / g, 60 to 170 mg KOH / g, 70 to 170 mg KOH / g, 80 to 170 mg KOH / g, 90 to 170 mg KOH / g, 100 to 170 mg KOH / g, 110 to 170 mg KOH / g, 120 to 170 mg KOH / g, 130 to 170 mg KOH / g, 140 to 170 mg KOH / g, 150 to 170 mg KOH / g, 160 to 170 mg KOH / g, 2 to 160 mg KOH / g, 5 to 160 mg KOH / g, 10 to 160 mg KOH / g, 15 to 160 mg KOH / g, 20 to 160 mg KOH / g, 30 to 160 mg KOH / g, 40 to 160 mg KOH / g, 50 to 160 mg KOH / g, 60 to 160 mg KOH / g, 70 to 160 mg KOH / g, 80 to 160 mg KOH / g, 90 to 160 mg KOH / g, 100 to 160 mg KOH / g, 110 to 160 mg KOH / g, 120 to 160 mg KOH / g, 130 to 160 mg KOH / g, 140 to 160 mg KOH / g, 150 to 160 mg KOH / g, 2 to 150 mg KOH / g, 5 to 150 mg KOH / g, 10 to 150 mg KOH / g, 15 to 150 mg KOH / g, 20 to 150 mg KOH / g, 30 to 150 mg KOH / g, 40 to 150 mg KOH / g, 50 to 150 mg KOH / g, 60 to 150 mg KOH / g, 70 to 150 mg KOH / g, 80 to 150 mg KOH / g, 90 to 150 mg KOH / g, 100 to 150 mg KOH / g, 110 to 150 mg KOH / g, 120 to 150 mg KOH / g, 130 to 150 mg KOH / g, 140 to 150 mg KOH / g, 2 to 140 mg KOH / g, 5 to 140 mg KOH / g, 10 to 140 mg KOH / g, 15 to 140 mg KOH / g, 20 to 140 mg KOH / g, 30 to 140 mg KOH / g, 40 to 140 mgmg KOH / g, 60 to 140 mg KOH / g, 70 to 140 mg KOH / g, 80 to 140 mg KOH / g, 90 to 140 mg KOH / g, 100 to 140 mg KOH / g, 110 to 140 mg KOH / g, 120 to 140 mg KOH / g, 130 to 140 mg KOH / g, 2 to 130 mg KOH / g, 5 to 130 mg KOH / g, 10 to 130 mg KOH / g, 15 to 130 mg KOH / g, 20 to 130 mg KOH / g, 30 to 130 mg KOH / g, 40 to 130 mg KOH / g, 50 to 130 mg KOH / g, 60 to 130 mg KOH / g, 70 to 130 mg KOH / g, 80 to 130 mg KOH / g, 90 to 130 mg KOH / g, 100 to 130 mg KOH / g, 110 to 130 mg KOH / g, 120 to 130 mg KOH / g, 2 to 120 mg KOH / g, 5 to 120 mg KOH / g, 10 to 120 mg KOH / g, 15 to 120 mg KOH / g, 20 to 120 mg KOH / g, 30 to 120 mg KOH / g, 40 to 120 mg KOH / g, 50 to 120 mg KOH / g, 60 to 120 mg KOH / g, 70 to 120 mg KOH / g, 80 to 120 mg KOH / g, 90 to 120 mg KOH / g, 100 to 120 mg KOH / g, 110 to 120 mg KOH / g, 2 to 110 mg KOH / g, 5 to 110 mg KOH / g, 10 to 110 mg KOH / g, 15 to 110 mg KOH / g, 20 to 110 mg KOH / g, 30 to 110 mg KOH / g, 40 to 110 mg KOH / g, 50 to 110 mg KOH / g, 60 to 110 mg KOH / g, 70 to 110 mg KOH / g, 80 to 110 mg KOH / g, 90 to 110 mg KOH / g, 100 to 110 mg KOH / g, 2 to 100 mg KOH / g, 5 to 100 mg KOH / g, 10 to 100 mg KOH / g, 15 to 100 mg KOH / g, 20 to 100 mg KOH / g, 30 to 100 mg KOH / g, 40 to 100 mg KOH / g, 50 to 100 mg KOH / g, 60 to 100 mg KOH / g, 70 to 100 mg KOH / g, 80 to 100 mg KOH / g, 90 to 100 mg KOH / g, 2 to 90 mg KOH / g, 5 to 90 mg KOH / g, 10 to 90 mg KOH / g, 15 to 90 mgmg KOH / g, 20 to 90 mg KOH / g, 30 to 90 mg KOH / g, 40 to 90 mg KOH / g, 50 to 90 mg KOH / g, 60 to 90 mg KOH / g, 70 to 90 mg KOH / g, 80 to 90 mg KOH / g, 2 to 80 mg KOH / g, 5 to 80 mg KOH / g, 10 to 80 mg KOH / g, 15 to 80 mg KOH / g, 20 to 80 mg KOH / g, 30 to 80 mg KOH / g, 40 to 80 mg KOH / g, 50 to 80 mg KOH / g, 60 to 80 mg KOH / g, 70 to 80 mg KOH / g, 2 to 70 mg KOH / g, 5 to 70 mg KOH / g, 10 to 70 mg KOH / g, 15 to 70 mg KOH / g, 20 to 70 mg KOH / g, 30 to 70 mg KOH / g, 40 to 70 mg KOH / g, 50 to 70 mg KOH / g, 60 to 70 mg KOH / g, 2 to 60 mg KOH / g, 5 to 60 mg KOH / g, 10 to 60 mg KOH / g, 15 to 60 mg KOH / g, 20 to 60 mg KOH / g, 30 to 60 mg KOH / g, 40 to 60 mg KOH / g, 50 to 60 mg KOH / g, 2 to 50 mg KOH / g, 5 to 50 mg KOH / g, 10 to 50 mg KOH / g, 15 to 50 mg KOH / g, 20 to 50 mg KOH / g, 30 to 50 mg KOH / g, 40 to 50 mg KOH / g, 2 to 40 mg KOH / g, 5 to 40 mg KOH / g, 10 to 40 mg KOH / g, 20 to 40 mg KOH / g, 30 to 40 mg KOH / g, 2 to 30 mg KOH / g, 5 to 30 mg KOH / g, 10 to 30 mg KOH / g, 10 to 30 mg KOH / g, 15 to 30 mg KOH / g, 20 to 30 mg KOH / g, 2 to 20 mg KOH / g, 5 to 20 mg KOH / g, 10 to 20 mg KOH / g, 15 to 20 mg KOH / g, 2 to 15 mg KOH / g, 5 to 15 mg KOH / g, 10 to 15 mg KOH / g, 2 to 10 mg KOH / g, 5 to 10 mg KOH / g, or 2 to 5 mg KOH / g.

[0021] The lubricating oil compositions disclosed herein can provide advantageous oxidation control performance. The lubricating oil compositions disclosed herein can maintain or improve oxidation stability performance even in the presence of or in the presence of nitrogen-based contaminants (e.g., ammonia, NO, N02, etc.) generated in ammonia fuel driven engines. The lubricating oil compositions disclosed herein can exhibit deposit control capabilities.

[0022] In some embodiments, the lubricating oil composition is contaminated with ammonia. In some embodiments, the lubricating oil composition is contaminated with NO, N02, and / or water.

[0023] Base oil

[0024] The lubricating oil compositions disclosed herein include a base oil. In some embodiments, the base oil is a Group I, Group II, Group III (including Group III+), Group IV, or Group V base oil. In some embodiments, the base oil includes a bright stock. Bright stock can be used as a thickening agent to achieve the correct viscosity. In some embodiments, the lubricating oil compositions disclosed herein comprise a majority of a Group II or higher base oil.

[0025] Group I, Group II, Group III, Group IV, and Group V are base oil broad categories developed and defined by the American Petroleum Institute (API Publication 1509-Addendum E) intended to provide guidance for lubricating base oils. Group I base oils contain less than 90% saturated hydrocarbons and / or greater than 0.03% sulfur, and have a viscosity index greater than or equal to 80 and less than 120. Group II base oils contain greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur, and have a viscosity index greater than or equal to 80 and less than 120. Group III base oils contain greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur, and have a viscosity index greater than or equal to 120. Group IV base oils are polyalphaolefins. Group V base oils include all other base oils not included in Group I, Group II, Group III, or Group IV. Table 1 summarizes the properties of each of the five groups.

[0026] Table 1

[0027] Base Oil Properties

[0028]

[0029]

[0030] (1) ASTM D2007

[0031] (2) ASTM D2622, ASTM D3120, ASTM D4294, or ASTM D4927

[0032] (3) ASTM D2270

[0033] In some embodiments, the lubricating oil compositions disclosed herein comprise a majority of a base oil that contains greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur.

[0034] In some embodiments, the lubricating oil compositions disclosed herein include a major amount of a biobased base oil derived from a renewable carbon source.

[0035] Bio-based base oil

[0036] In some embodiments, the lubricating oil compositions can include a biobased base oil. A detailed discussion of biobased base oils can be found in WO / 2021 / 205385, the contents of which are incorporated herein by reference.

[0037] In one aspect, biobased oils can be described as follows. Base oils, and more specifically isoparaffins derived from biobased hydrocarbon terpenes such as myrcene, ocimene, and famesene have been described in PCT Patent Application No. PCT / US2012 / 024926, entitled “Base Oils and Methods for Making the Same” by Nicholas Ohler et al. filed on February 13, 2012 and published as WO 2012 / 141784 on October 18, 2012, and assigned to Amyris, Inc. of Emeryville, California. WO 2012 / 141784 discloses that terpenes can be derived from isopentyl pyrophosphate or dimethylallyl pyrophosphate, and that the term “terpene” encompasses hemiterpenes, monoterpene, sesquiterpene, diterpene, dipterpene, triterpene, tetraterpene, and polyterpene. Hydrocarbon terpenes contain only hydrogen and carbon atoms, no heteroatoms such as oxygen, and in some embodiments have the general formula (C5H8)n nwhere n is 1 or greater. A “conjugated terpene” or “conjugated hydrocarbon terpene” refers to a terpene that includes 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 monoterpenes, sesquiterpenes, diterpenes, triterpenes, tetraterpenes, and polyterpenes, which exhibit the same carbon skeleton as the corresponding terpene but have fewer or more hydrogen atoms than the corresponding terpene, for example, terpenes having 2 fewer, 4 fewer, or 6 fewer hydrogen atoms than the corresponding terpene, or terpenes having 2 more, 4 more, or 6 more hydrogen atoms than the corresponding terpene. Some non-limiting examples of conjugated hydrocarbon terpenes include isoprene, myrcene, a-ocimene, b-ocimene, a-farnesene, b-farnesene, b-springene, geranyl farnesene, neophytadiene, cis-plant-1,3-diene, frans-plant-1,3-diene, isodehydroisocohumenol, isocohumenol precursor I, and isocohumenol precursor II. The terms terpene and isoprenoid are used interchangeably and are a large and diverse class of organic molecules that can be produced by a variety of plants and some insects. Some terpene or isoprenoid compounds can also be made by microorganisms (including bioengineered microorganisms, such as yeast) from organic compounds such as sugars. Because terpenes or isoprenoid compounds can be obtained from a variety of renewable resources, they are useful monomers for making environmentally friendly and renewable base oils. In some embodiments, the conjugated hydrocarbon terpene is derived from a microorganism that utilizes a renewable carbon source, such as a sugar. It has been found that further processing of certain such bio-based base oils results in very useful and high quality engine oils. For example, a C15 hydrocarbon containing four double bonds, such as Biofene® (commercially available from Amyris, Inc. (Emeryville, CA), can be processed to produce a bio-based base oil that is useful in the production of engine oils. In some embodiments, the conjugated hydrocarbon terpene is derived from a microorganism that utilizes a renewable carbon source, such as a sugar. It has been found that further processing of certain such bio-based base oils results in very useful and high quality engine oils. For example, a C15 hydrocarbon containing four double bonds, such as Biofene® (commercially available from Amyris, Inc. (Emeryville, CA), can be processed to produce a bio-based base oil that is useful in the production of engine oils. TMThe partially hydrogenated intermediate product is then subjected to an oligomerization reaction with linear alpha olefins (LAOs) using a catalyst such as BF3or a BF3complex. Another intermediate product is generated, which consists of a mixture of hydrocarbons from C10to about C75. This oligomeric mixture of hydrocarbons is then hydrogenated to reduce unsaturation. The saturated hydrocarbon mixture is then distilled to obtain the target composition and finally blended to meet the required base oil product specifications for engine oil, such as kinematic viscosity at 40°C. Table 2 lists the required examples of biobased base oil specifications that can be used to produce a blend for an engine oil formulation suitable for one embodiment. In some embodiments of the present disclosure, a commercially available biobased hydrocarbon base oil sold under the trade name NOVASPEC (Novvi LLC, Emeryville, CA; (REACH registration number 01-2120031429-59-0000)) is used (hydrogenation product between partially hydrogenated p-3,7,11-trimethyldodeca-l,3,6,10-tetraene and linear C8-C16alpha olefins, hydrogenated).

[0038] Table 2 Exemplary biobased base oil specifications

[0039]

[0040] Advantageously, in certain embodiments, at least about 20% of the carbon atoms in the base oil included in 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 included in 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 included in 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 included in 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 included in 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 included in 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 included in 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 included in the engine oil are derived from a renewable carbon source. In some variations, the carbon atoms of the base oil component of the engine oil include at least about 95%, at least about 97%, at least about 99%, or about 100% derived from a renewable carbon source. The source of carbon atoms in the reaction product adduct can be determined by any suitable method, including but not limited to reaction mechanism in combination with analytical results showing the structure and / or molecular weight of the adduct, or by carbon dating (e.g., according to ASTM D6866-12 "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis," which is incorporated by reference herein in its entirety). For example, using ASTM D6866-12 or another suitable technique, the ratio of carbon 14 to carbon 12 isotopes in the biobased base oil can be measured by liquid scintillation counting and / or isotope ratio mass spectrometry to determine the modern carbon content in the sample. A measurement of no modern carbon content indicates that all of the carbon is derived from fossil fuels. A sample derived from a renewable carbon source will indicate a concomitant amount of modern carbon content, up to 100%.

[0041] In some embodiments of the present disclosure, one or more of the repeating units of the biobased hydrocarbon base oil is a particular species of partially hydrogenated conjugated hydrocarbon terpene. This particular species of partially hydrogenated conjugated terpene can or can 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 catalytic hydrogenation.

[0042] In some embodiments of the present disclosure, the bio-based hydrocarbon base oil can be classified as a Group III+ base oil having greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur and having a viscosity index of greater than or equal to 120.

[0043] Non-limiting examples of specific classes of partially hydrogenated conjugated hydrocarbon terpenes include any of the structures of dihydrofamesene, tetrahydrofamesene, and hexahydrofamesene provided herein; any of the structures of dihydromyrcene and tetrahydromyrcene provided herein; and any of the structures of dihydrolinoleene and tetrahydrolinoleene provided herein.

[0044] One example of a specific class of partially hydrogenated conjugated hydrocarbon terpenes that can be used as a starting material is a terminal olefin having a saturated hydrocarbon tail having structure (A11):

[0045]

[0046] where n = 1, 2, 3, or 4.

[0047] In some variations, the mono-olefin alpha-olefin having structure A11 can be derived from a conjugated hydrocarbon terpene in which the conjugated diene is located at the 1,3- position of the terpene. Examples include those derived from 1,3-diene conjugated hydrocarbon terpenes (e.g., C 10 -C 30 alpha-olefins of conjugated hydrocarbon terpenes, such as famesene, myrcene, linaloeene, pinene, geranyl famesene, neophytadiene, trans-phyt-1,3-diene, or cz’s-phyt-l,3-diene. Another non-limiting example of an alpha-olefin having the general structure A11 includes 3,7,11- trimethyldodecene having structure A12.

[0048]

[0049] The mono-olefin alpha-olefin having structure A11 can be prepared from an appropriate conjugated hydrocarbon terpene using any suitable method. In some variations, the mono-olefin alpha-olefin having structure A11 is produced from a primary alcohol corresponding to the hydrocarbon terpene (e.g., farnesol in the case of famesene, or geraniol in the case of myrcene). The method includes hydrogenating the primary alcohol, forming a carboxylate or carbamate from the hydrogenated alcohol, and pyrolyzing the ester (or heating the ester to drive the elimination reaction) to form the alpha-olefin having a saturated hydrocarbon tail, e.g., for preparing 3,7-dimethyloctene as described in Smith, L. E.; Rouault, G. F., J. Am. Chem. Soc. 1943, 65, 745-750, the entire contents of which are incorporated herein by reference. The primary alcohol of the corresponding hydrocarbon terpene can be obtained using any suitable method.

[0050] Other examples of specific classes of partially hydrogenated conjugated hydrocarbon terpenes that can be used as starting materials are mono-olefins with saturated hydrocarbon tails having structure (A13) or structure (A15):

[0051]

[0052] where n = 1, 2, 3, or 4. The mono-olefins having general structure A13, A15, or A11 can in some cases be derived from conjugated hydrocarbon terpenes having a 1,3-diene moiety, such as myrcene, famesene, pinene, geranyl famesene, neophytadiene, frans-phytol-1,3-diene, or c / sup / / sups-phytol-1,3-diene. Also, in a first step, the conjugate can be functionalized with a protecting group (e.g., by a Diels-Alder reaction), in a second step, the exocyclic olefinic bond is hydrogenated, and in a third step, the protecting group is eliminated. In one non-limiting example of a process for making mono-olefins having structure A13, A15, or A11, a conjugated hydrocarbon terpene having a 1,3-diene is reacted with SO2 in the presence of a catalyst to form a Diels-Alder adduct. The Diels-Alder adduct can be hydrogenated with an appropriate hydrogenation catalyst to saturate the exocyclic olefinic bond. The hydrogenated adduct can be subjected to a reverse Diels-Alder reaction (e.g., by heating, and in some cases in the presence of an appropriate catalyst) to eliminate the sulfone to form a 1,3-diene. The 1,3-diene can then be selectively hydrogenated using a catalyst known in the art to produce mono-olefins having structure A11, A13, or A15, or a mixture of two or more of the foregoing.Non-limiting examples of catalysts for the regioselective hydrogenation of 1,3-dienes are provided in Jong Tae Lee et al., "Regioselective hydrogenation of conjugated dienes catalyzed by hydridopentacyanocobaltate anion using β-cyclodextrin as the phase transfer agent and lanthanide halides as promoters," J. Org. Chem., 1990, 55(6), pp. 1854-1856; V. M. Frolov et al., "Highly active supported palladium catalysts for selective hydrogenation of conjugated dienes into olefins," Reaction Kinetics and Catalysis Letters, 1984, vol. 25, issues 3-4, pp. 319-322; Tungler, A., Hegedus, L., Fodor, K., Farkas, G., Furcht, A., and Karancsi, Z. P. (2003) "Reduction of Dienes and Polyenes," The Chemistry of Dienes and Polyenes, vol. 2 (Z. Rappoport, ed.), John Wiley & Sons, Ltd, Chichester, UK.; and Tungler, A., Hegedus, L., Fodor, K., Farkas, G., Furcht, A., and Karancsi, Z. P., "Reduction of Dienes and Polyenes", Patai's Chemistry of Functional Groups (John Wiley and Sons, Ltd, published online December 15, 2009, each of which is incorporated herein by reference in its entirety. For example, catalysts known in the art for 1,4 hydrogen addition to 1,3-dienes produce mono-olefins having structure A13.In one non-limiting example, the beta-farnesene can be reacted with SO2 in the presence of a catalyst to form a Diels-Alder adduct, which is then hydrogenated, and the sulfone eliminated to form a 1,3-diene, which is then selectively hydrogen added to the 1,3-diene using a catalyst known in the art to form 3,7,1 l-trimethyldodeca-2-ene, 3,7,1 l-trimethyldodeca-1-ene, or 3-methylene-7,1 l-dimethyldodecane, or a mixture of any two or more of the foregoing.

[0053] In another example of a particular class of partially hydrogenated hydrocarbon terpenes that can be used as a starting material, terminal olefins of general structure A14 can be made from conjugated hydrocarbon terpenes having a 1,3-conjugated diene and at least one additional olefinic bond (e.g., myrcene, farnesene, pinene, or geranyl farnesene):

[0054]

[0055] where n = 1, 2, 3, or 4. In one non-limiting variation, compounds having structure A14 can be derived from an unsaturated primary alcohol corresponding to the relevant hydrocarbon terpene (e.g., farnesol in the case of farnesene, or geraniol in the case of myrcene). The unsaturated primary alcohol can be exposed to a suitable catalyst under suitable reaction conditions to dehydrate the primary alcohol to form the terminal olefin A 14.

[0056] An olefin feedstock as described herein can comprise any useful amount of a particular species (e.g., an a-olefin species having structure A11, A12, or A15, a mono-olefin species having structure A13, or an unsaturated terminal olefin species having structure A14) made by a partial hydrogenation route or by another route, e.g., as described herein. In certain variations, the olefin 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% of a species having structure A11, A12, A13, A14, or A15. In certain variations, the olefin 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% of 3,7,11-trimethyldodeca-l-ene. In certain variations, the olefin 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% of 3-methylene-7,11-dimethyldodecane. In certain variations, the olefin 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% of 3,7,11-trimethyldodeca-2-ene. In certain variations, the olefin 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% of 3,7,11-trimethyldodeca-l,6,10-triene. In certain variations, the olefin 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% of 3,7-dimethyloct-l-ene. In certain variations, the olefin 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% of 3,7-dimethyloct-2-ene. In certain variations, the olefin 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% of 3,7-dimethyloct-l,6-diene.

[0057] As described herein, in some variations, a hydrocarbon terpene feedstock comprising partially hydrogenated hydrocarbon terpene alpha-olefin species or internal olefin species is suitable for catalytic reaction with one or more alpha-olefins to form a mixture of isoparaffins comprising adducts of terpene and one or more alpha-olefins. In some variations, at least a portion of the mixture of isoparaffins so produced can be used as a base oil.

[0058] In one embodiment, the bio-based oil contains: at least about 25% of the carbon atoms in the bio-based base oil originated from a renewable carbon source as measured by ASTM-D6866-12; at least about 40% of the carbon atoms in the bio-based base oil originated from a renewable carbon source as measured by ASTM-D6866-12; at least about 50% of the carbon atoms in the bio-based base oil originated from a renewable carbon source as measured by ASTM-D6866-12; at least about 60% of the carbon atoms in the bio-based base oil originated from a renewable carbon source as measured by ASTM-D6866-12; at least about 70% of the carbon atoms in the bio-based base oil originated from a renewable carbon source as measured by ASTM-D6866-12; at least about 80% of the carbon atoms in the bio-based base oil originated from a renewable carbon source as measured by ASTM-D6866-12; or at least about 90% of the carbon atoms in the bio-based base oil originated from a renewable carbon source as measured by ASTM-D6866-12.

[0059] In one embodiment, the bio-based base oil additionally has an average methyl branch index (number of methyl branches per 100 carbons) of at least 7, an average methyl branch index (number of methyl branches per 100 carbons) of at least 8, an average methyl branch index (number of methyl branches per 100 carbons) of at least 9, an average methyl branch index (number of methyl branches per 100 carbons) of at least 10, an average methyl branch index (number of methyl branches per 100 carbons) of at least 11, an average methyl branch index (number of methyl branches per 100 carbons) of at least 15, an average methyl branch index (number of methyl branches per 100 carbons) of at least 20, an average methyl branch index (number of methyl branches per 100 carbons) of at least 22, an average methyl branch index (number of methyl branches per 100 carbons) of at least 24, an average methyl branch index (number of methyl branches per 100 carbons) of at least 26, an average methyl branch index (number of methyl branches per 100 carbons) of at least 27.

[0060] In one embodiment, the bio-based base oil has a molecular weight in the range of 300 g / mol to 800 g / mol, the bio-based base oil has a molecular weight in the range of 390 g / mol to 510 g / mol.

[0061] The bio-based base oil comprises at least 95% non-cyclic isoparaffins, 25-34% of the total carbon atoms in the molecular structure of which are contained in 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 ASTM-D6866 method.

[0062] 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 sesquiterpene monomer units, at least 30 wt% of the acyclic isoparaffins are hydrogenated sesquiterpene monomer units, at least 35 wt% of the acyclic isoparaffins are hydrogenated sesquiterpene monomer units, or at least 45 wt% of the acyclic isoparaffins are hydrogenated sesquiterpene monomer units.

[0063] In one embodiment, the bio-based base oil has greater than 50% biodegradation within 28 days according to the OECD 301B test method; the bio-based base oil has greater than 60% biodegradation within 28 days according to the OECD 301B test method; the bio-based base oil has greater than 70% biodegradation within 28 days according to the OECD 301B test method.

[0064] In one embodiment, the bio-based base oil is characterized by a viscosity index (VI) of greater than 120, as measured according to ASTM D2270-10, and a branch ratio of less than 0.41.

[0065] In one embodiment, the bio-based base oil is characterized by a viscosity index (VI) of greater than 120, as measured according to ASTM D2270-10, and greater than 40% of the bio-based base oil molecules have more than 3 methyl branches per molecule, at least 50% of the bio-based base oil molecules have more than 3 methyl branches per molecule, at least 60% of the bio-based base oil molecules have more than 3 methyl branches per molecule,

[0066] In one embodiment, the bio-based base oil is characterized by a viscosity index (VI) of greater than 120, as measured according to ASTM D2270-10, and greater than 25% of the bio-based base oil molecules have more than 6 methyl branches per molecule, at least 30% of the bio-based base oil molecules have more than 3 methyl branches per molecule, at least 40% of the bio-based base oil molecules have more than 3 methyl branches per molecule, at least 50% of the bio-based base oil molecules have more than 3 methyl branches per molecule, at least 60% of the bio-based base oil molecules have more than 3 methyl branches per molecule.

[0067] In one embodiment, the bio-based base oil is characterized as having a renewable carbon content greater than 60% as measured by ASTM-D6866-12, a renewable carbon content greater than 70% as measured by ASTM-D6866-12, a renewable carbon content greater than 80% as measured by ASTM-D6866-12, a renewable carbon content greater than 90% as measured by ASTM-D6866-12.

[0068] The base oil has a saturates content of at least 90% as determined by ASTM-D2007-1.

[0069] In one embodiment, at least 50% of the hydrocarbon molecules comprised by the base oil comprise an odd number of carbon atoms per molecule, at least 60% of the hydrocarbon molecules comprised by the base oil comprise an odd number of carbon atoms per molecule, at least 70% of the hydrocarbon molecules comprised by the base oil comprise an odd number of carbon atoms per molecule, at least 80% of the hydrocarbon molecules comprised by the base oil comprise an odd number of carbon atoms per molecule.

[0070] In one embodiment, the bio-based base oil has greater than 60% biodegradation within 28 days according to the OECD 301B test method; greater than 70% biodegradation within 28 days according to the OECD 301B test method.

[0071] 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 a sugar.

[0072] In one aspect, the bio-based base oil is a mixture of saturated hydrocarbons having a unique branching structure as characterized by NMR that makes it suitable for use as a high quality synthetic base oil. The hydrocarbon mixture has outstanding properties including very low volatility, good low temperature properties, etc. that are important performance attributes of high quality base oils. Specifically, the mixture comprises greater than 80% of molecules with even carbon numbers according to FIMS. The branching characteristics of the hydrocarbon mixture as measured by NMR include a BP / BI value in the range of > -0.6037 (number of internal alkyl branches per molecule) + 2.0. Further, on average, at least 0.3 to 1.5 internal methyl branches are located more than four carbons from the terminal carbon.

[0073] The bio-based base oil can include oligomerization products of a-olefins. In some embodiments, the oligomerization products can be hydrogenated and / or hydroisomerized.

[0074] In one embodiment, the hydrocarbon mixture described herein is the product of olefin oligomerization and subsequent hydroisomerization. The C14 to C 20 Olefins are oligomerized to form an oligomer distribution consisting of unreacted monomer, dimers (C 28 -C 40 ), trimers, and higher oligomers (> C 42 ). The unreacted monomer is distilled off for possible reuse in subsequent oligomerization reactions. The remaining oligomers are then subjected to hydroisomerization to obtain the final branched structures described herein.

[0075] In one embodiment, the oligomerization product can have the following structure:

[0076]

[0077] wherein

[0078] n = 1 (representing a C16 olefin) or 3 (representing a C18 olefin)

[0079] R = C16-C18 or H

[0080] R1= C9-C13

[0081] R2= C4H 10 linear or branched

[0082] R3= C9-C13

[0083] a is a value that results in a molecular weight range from about 220 to 1020 g / mol.

[0084] Lubricating oil composition

[0085] The lubricating oil compositions of the present disclosure can be identified by the Society of Automotive Engineers (SAE) viscosity standards for engine oils (i.e., SAE J300 standards). Table 3 summarizes the SAE J300 viscosity grades.

[0086] Table 3

[0087]

[0088] (1) ASTM D5293

[0089] (2) ASTM D4684

[0090] (3) ASTM D445

[0091] (4) ASTM D4683, ASTM D4741, ASTM D5481, or CEC L-36-90

[0092] (5) for 0W-40, 5W-40, and 10W-40 grades

[0093] (6) for 15W-40, 20W-40, 25W-40, and 40 grades

[0094] The lubricating oil composition of the present disclosure can be a single grade engine oil, such as a SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60 viscosity grade engine oil.

[0095] Additive

[0096] The lubricating oil composition of the present disclosure can contain one or more performance additives capable of imparting or improving any desired property of the lubricating oil composition. Any additive known to those skilled in the art can be used in the lubricating oil compositions disclosed herein. Some suitable additives have been described by R. M. Mortier et al. “Chemistry and Technology of Lubricants,” 3rdEdition, Springer (2010) and L. R. Rudnik “Lubricant Additives: Chemistry and Applications,” 2ndEdition, CRC Press (2009).

[0097] Generally, when used, the concentration of each additive in the lubricating oil composition can range from 0.001 to 60 wt% of the lubricating oil composition (e.g., 0.01 to 50 wt%, or 0.05 to 40 wt%). Further, the total amount of additives in the lubricating oil composition can range from 0.001 to 70 wt% of the lubricating oil composition (e.g., 0.01 to 50 wt%, or 0.1 to 40 wt%).

[0098] The lubricating oil composition of the present invention can additionally contain one or more of other commonly used lubricating oil performance additives, including antioxidants, antiwear agents, metal deactivators, dispersants, friction modifiers, corrosion inhibitors, demulsifiers, viscosity modifiers, pour point depressants, foam inhibitors, thickening agents, and the like.

[0099] Antioxidant

[0100] Antioxidants can retard the oxidative degradation of the base oil during use. Such degradation can result in the appearance of deposits, sludge on metal surfaces, or an increase in the viscosity of the lubricant. Useful antioxidants include hindered phenols, aromatic amines, and sulfurized alkyl phenols and their alkali metal and alkaline earth metal salts.

[0101] Hindered phenolic antioxidants can contain a sec-butyl and / or a tert-butyl group as a steric hindering group. The phenolic group can be further substituted with a hydrocarbyl group and / or a bridging group to a second aromatic group. Examples of suitable hindered phenolic 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 phenolic antioxidant can be an ester or addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, where the alkyl group can contain 1 to 18 carbon atoms. The hindered phenolic antioxidant can be a 2,6-di-alkyl-phenolic propionic acid ester derivative.

[0102] Non-phenolic antioxidants that can be used include aromatic amine antioxidants, such as diaryl amines and alkylated diaryl amines. Specific examples of aromatic amine antioxidants include diphenylamine (e.g., N-phenyl-2-naphthylamine, 4,4'-dioctyldiphenylamine, butylated / octylated diphenylamine, nonylated diphenylamine, and octylated N-phenyl-2-naphthylamine).

[0103] In one embodiment, the lubricating oil composition of the present disclosure includes a hindered phenolic antioxidant. The hindered phenolic antioxidant can be present in the lubricating oil composition at 0 to 10.0 wt% (e.g., at 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%).

[0104] In one embodiment, the lubricating oil composition of the present disclosure includes an amine antioxidant. The amine antioxidant can be present in the lubricating oil composition at 0 to 10.0 wt% (e.g., at 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%).

[0105] According to the present disclosure, the lubricating oil composition can include a combination of a hindered phenolic antioxidant and an amine antioxidant. The combination can provide a ratio (in mass percent) of phenolic antioxidant to amine antioxidant of 1 : 1 to 100: 1 (e.g., 1 : 1 to 75: 1, 1 : 1 to 50: 1, 1 : 1 to 25: 1, 1 : 1 to 1 : 10, 1 : 1 to 8: 1; 1 : 1 to 6: 1; 1 : 1 to 5: 1; 1 : 1 to 4: 1; or 1 : 1 to 3: 1).

[0106] In some embodiments, the lubricating oil composition does not contain an amine antioxidant. In some embodiments, the hindered phenol is the only antioxidant present in the lubricating oil composition.

[0107] Antiwear agent

[0108] Anti-wear agents reduce the wear of metal parts. Examples of anti-wear agents include phosphorus-containing anti-wear / extreme pressure agents such as metal thiophosphates, phosphates and salts thereof, phosphorus-containing carboxylic acids, esters, ethers, and amides; and phosphites. The anti-wear agent can be zinc dialkyldithiophosphate. Non-phosphorus-containing anti-wear agents include borate esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins.

[0109] Metal cleaner

[0110] 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 usually derived from an organic acid such as sulfuric acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof. The counterion is usually an alkaline earth metal or alkali metal.

[0111] In some embodiments, the lubricating oil composition provided herein comprises at least a high base number metal detergent as an additive, or additive component. The metal detergent in the lubricating oil composition can neutralize acidic products in the oil. The metal detergent can also prevent the formation of deposits on the surfaces of the engine. Depending on the nature of the acid used, the detergent can have additional functions, such as antioxidant properties.

[0112] In certain aspects, the lubricating oil composition contains a metal detergent, including a high base number detergent or a mixture of neutral and high base detergents. The term "high base number" is intended to define an additive that contains more than the stoichiometrically required amount of metal for the particular metal and particular organic acid used. The excess metal is present in the form of an inorganic base particle (e.g., hydroxide or carbonate) coated with a layer of metal salt. The role of this coating is to keep the particle dispersed in the liquid oily medium. The amount of excess metal is usually expressed as the ratio of the total equivalents of excess metal to the equivalents of the organic acid, and is typically in the range of 0.1 to 30.

[0113] Overbased detergents can be further characterized as low overbased, medium overbased, or high overbased. A low overbased detergent can be, for example, an overbased salt based on an active ingredient having a TBN of less than 100 mg KOH / g. A medium overbased detergent can be, for example, an overbased salt based on an active ingredient having a TBN of 100 to 250 mg KOH / g. A high overbased detergent can be, for example, an overbased salt based on an active ingredient having a TBN of greater than 250 mg KOH / g.

[0114] Some examples of suitable metal detergents include sulfided or un-sulfided alkyl toluenes, sulfided or un-sulfided alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, borated sulfonates, sulfided or un-sulfided metal salts of polyhydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, sulfided or un-sulfided alkyl or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of alkyl or alkenyl polyacids, and chemical and physical mixtures thereof. Other examples of suitable metal detergents include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates, and combinations thereof. The metal can be any metal suitable for making a sulfonate, phenate, salicylate, or phosphonate detergent. Non-limiting examples of suitable metals include alkali metals, alkaline earth metals, and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li, and the like.

[0115] Metal salts of phenols and sulfided phenols (e.g., phenate or sulfided phenate detergents or calcium sulfided phenate detergents) are prepared by reacting a phenol or sulfided phenol with an appropriate metal compound, such as an oxide or hydroxide. Sulfided phenols can be prepared by reacting a phenol with sulfur or a sulfur-containing compound, such as hydrogen sulfide, a monohalide of sulfur, or a dihalide of sulfur, to form a product that is typically a mixture of compounds in which two or more phenols are bridged by a sulfur-containing bridge. Further details regarding the general preparation of sulfided phenates can be found, for example, in U.S. Patent Nos. 2,680,096, 3,178,368, and 3,801,507, the contents of which are incorporated herein by reference.

[0116] The sulfur used to form the sulfided compound can have any allotrope of sulfur. The sulfur can be present in the form of molten sulfur or a solid (e.g., a powder or a granule), or in the form of a solid suspension in a compatible hydrocarbon liquid.

[0117] In some embodiments, it is desirable to use calcium hydroxide as the calcium base because it is more convenient to handle compared to, for example, calcium oxide, and also because it is capable of providing excellent results. Other calcium bases, such as calcium alcoholates, can also be used.

[0118] Suitable alkyl phenols that can be used are those in which the alkyl substituent contains a sufficient number of carbon atoms so that the resulting alkyl phenate (e.g., overbased sulfurized alkyl phenate calcium) composition is oil soluble. Oil solubility can be provided by a single long chain alkyl substituent or a combination of alkyl substituents. Typically, the alkyl phenols used are different alkyl phenols such as C 20 to C 24 mixtures of alkyl phenols. In one embodiment, the suitable alkyl phenolic compounds will be derived from isomerized normal alpha olefin alkyl groups having from about 10 to about 40 carbon atoms per molecule, with an isomerization level of the alpha olefin of from about 0.1 to about 0.4. The isomerization level can be determined by the method described in US 11485928, 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 suitable alkyl phenolic compounds will be derived from alkyl groups that are branched olefin propylene oligomers having from about 9 to about 80 carbon atoms or mixtures thereof. In one embodiment, the branched olefin propylene oligomers or mixtures thereof have from about 9 to about 40 carbon atoms. In one embodiment, the branched olefin propylene oligomers or mixtures thereof have from about 9 to about 18 carbon atoms. In one embodiment, the branched olefin propylene oligomers or mixtures thereof have from about 9 to about 12 carbon atoms.

[0119] In one embodiment, the suitable alkyl phenolic compounds include distilled cashew nut shell liquid (CNSL) or hydrogenated distilled CNSL. Distilled CNSL is a mixture of biodegradable meta-hydrocarbyl substituted phenols in which the hydrocarbyl groups are linear and unsaturated, including cardanol. Catalytic hydrogenation of distilled CNSL produces a mixture of meta-hydrocarbyl substituted phenols that is predominantly 3-pentadecylphenol.

[0120] The alkyl phenol can be a para-alkyl phenol, a meta-alkyl phenol, or an ortho-alkyl phenol. In certain embodiments, such as when a high base product is desired, the alkyl phenol is preferably predominantly a para-alkyl phenol, with no more than about 45 mole percent of the alkyl phenol being an ortho-alkyl phenol; and more preferably no more than about 35 mole percent of the alkyl phenol being an ortho-alkyl phenol. Alkyl-hydroxytoluene or xylenol, and other alkyl phenols having one or more alkyl substituents in addition to the at least one long chain alkyl substituent, can also be used. In the case of distilled cashew nut shell liquid, catalytic hydrogenation of distilled CNSL produces a mixture of meta-hydrocarbyl substituted phenols.

[0121] In general, the choice of alkyl phenol can be made in accordance with the properties desired for the marine engine lubricating oil composition, particularly TBN and oil solubility. Additional information regarding the preparation of suitable alkyl phenols can be found, for example, in U.S. Patent Nos. 5,024,773, 5,320,763, 5,318,710, and 5,320,762, all of which are incorporated herein by reference.

[0122] As noted, certain embodiments of the lubricating oil formulation can utilize one or more sulfonate detergents, either alone or in combination with other sulfonates (e.g., combinations of overbased sulfonates and underbased sulfonates) and other detergents. The sulfonates can be prepared from sulfonic acids, which can be obtained by sulfonation of alkyl-substituted aromatic hydrocarbons such as those obtained by fractionation of petroleum or by alkylation of aromatic hydrocarbons. Examples of alkyl-substituted aromatic hydrocarbons that can be sulfonated include those obtained by alkylation of benzene, toluene, xylene, naphthalene, biphenyl, or halogen derivatives thereof. The alkylation can be carried out using alkylating agents having from 3 to greater than 70 carbon atoms in the presence of a catalyst. The alkylaryl sulfonates typically contain from 9 to 80 or more carbon atoms per alkyl-substituted aromatic moiety, preferably from 16 to 60, preferably from 16 to 30, most preferably from 20 to 24 carbon atoms.

[0123] In one embodiment, the lubricating oil formulation can utilize a combination of overbased sulfonates and underbased sulfonates derived from alkylation of toluene.

[0124] The oil-soluble sulfonates or alkylaryl sulfonic acids can be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates, and ethers of metals. The amount of the metal compound is selected taking into account the desired TBN of the final product.

[0125] The detergent can also include "hybrid" or "complex" detergents formed with mixed surfactant systems including phenate and / or sulfonate components, such as phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, sulfonate / phenate / salicylate, as described in U.S. Patents 6,429,178, 6,429,179, 6,153,565. The detergent can also include a methylene-bridged polyphenol composition prepared by reacting a phenol with formaldehyde or a reversible polymer thereof, optionally sulfurizing the methylene-bridged intermediate, and subsequently reacting the intermediate with an excess of a metal base to produce a methylene-bridged polyphenol phenate composition. In one embodiment, the methylene-bridged polyphenol phenate composition can be further reacted with an epoxide. In one embodiment, the methylene-bridged polyphenol phenate composition is not sulfurized.

[0126] In one or more embodiments, the lubricating oil composition includes a phenolic detergent that is a high base number sulfurized calcium phenate detergent. In one or more embodiments, the lubricating oil composition includes a high base number sulfurized calcium phenate detergent having a TBN of less than 250 mg KOH / g. In one or more embodiments, the lubricating oil composition includes a high base number sulfurized calcium phenate detergent that is not derived from tetrapropylene phenol. In one or more embodiments, the lubricating oil composition includes a phenolic detergent that is a high base number sulfurized calcium phenate detergent derived from isomerized normal alpha olefin alkyl groups having from about 10 to about 40 carbon atoms per molecule.

[0127] Generally, the amount of detergent can 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.

[0128] In one or more embodiments, the lubricating oil composition includes a low high base number calcium sulfonate detergent, a medium high base number calcium sulfonate detergent, and / or a high high base number calcium sulfonate detergent, or a combination thereof, present in an amount to provide a sulfonate soap content in the lubricating oil composition of 10 mmol / kg sulfonate soap 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).

[0129] In one or more embodiments, the lubricating oil composition includes a low high base number calcium sulfonate detergent, a medium high base number calcium sulfonate detergent, and / or a high high base number calcium sulfonate detergent, or a combination thereof, wherein the TBN contribution from the sulfonate detergent is greater than about 20%, greater than about 25% (e.g., 25 to 95%, 25 to 90%, 25 to 85%, 25 to 80%, 30 to 80%) of the total detergent BN contribution.

[0130] In one or more embodiments, the lubricating oil composition includes 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 comprises greater than about 20% of the total detergent BN contribution; and further wherein the sulfonate detergent is present in an amount to provide a sulfonate soap content in the lubricating oil composition of 25 mmol / kg to 140 mmol / kg.

[0131] In one or more embodiments, the lubricating oil composition includes 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 comprises 20 to 95% of the total detergent BN contribution; and further wherein the sulfonate detergent is present in an amount to provide a sulfonate soap content in the lubricating oil composition of 25 mmol / kg to 140 mmol / kg.

[0132] In one embodiment, the contribution from the phenate-based detergent can be from one or more phenate-based detergents having similar or different TBN levels. In one embodiment, the sulfonate soap contribution can be from one or more sulfonate detergents having similar or different TBN levels (e.g., a combination of low overbased and high overbased).

[0133] Other additional detergents can 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.

[0134] Ashless dispersant

[0135] Dispersants are additives whose primary role is to keep solid and liquid contaminants in suspension, thereby passivating them and reducing engine deposits, while also reducing sludge deposition. For example, dispersants can keep oil-insoluble materials produced by oxidation during lubricant use in suspension, thereby preventing the flocculation and deposition of sludge on the metal parts of the engine.

[0136] Dispersants are typically "ashless", being non-metallic organic materials that do not form substantial ash on burning, as opposed to materials that contain metals and thus form ash. They comprise a long hydrocarbon chain component with a polar head, the polarity arising from the inclusion of at least one nitrogen, oxygen or phosphorus atom. The hydrocarbon is the lipophilic group that confers oil solubility, having for example 40 to 500 carbon atoms. Ashless dispersants can thus comprise an oil-soluble polymeric backbone.

[0137] A preferred class of olefinic polymers consists of polybutenes, in particular polyisobutylene (PIB) or poly-n-butylene, such as can be prepared by polymerization of C4 refinery streams.

[0138] Dispersants include, for example, derivatives of long chain hydrocarbon substituted carboxylic acids, an example being derivatives of high molecular weight hydrocarbyl substituted succinic acids. One class of dispersants of note consists of hydrocarbon substituted succinimides, for example, made by reacting the above acids (or derivatives) with nitrogen containing compounds, advantageously polyalkylene polyamines, such as polyethylene polyamines. A typical commercially available polyisobutenyl succinimide dispersant contains polyisobutylene polymers having a number average molecular weight in the range of 900 to 2500, functionalized with maleic anhydride, and derivatized with polyamines having a molecular weight of 100 to 350.

[0139] Other suitable dispersants include succinates and ester amides, Mannich bases, polyisobutylene succinic acid (PIBSA), and other related components.

[0140] Succinates are formed from the condensation reaction between a hydrocarbon substituted succinic anhydride and an alcohol or polyol. For example, the condensation product of a hydrocarbon substituted succinic anhydride and pentaerythritol is a useful dispersant.

[0141] Succinate-amides are formed from the condensation reaction between a hydrocarbon substituted succinic anhydride and an alkanolamine. Suitable alkanolamines include, for example, ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines, and polyalkenyl polyamines such as polyethylene polyamines. One example is propoxylated hexamethylene diamine.

[0142] Mannich bases are made from the reaction of an alkyl phenol, formaldehyde, and a polyalkylene polyamine. The alkyl phenol can have a molecular weight in the range of 800 to 2500.

[0143] Nitrogen-containing dispersants can be post-treated by conventional methods to improve their properties by reaction with any of a variety of agents. Among these are boron compounds (e.g., boric acid) and cyclic carbonates (e.g., ethylene carbonate).

[0144] 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 from 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 from about 1000 to about 1500. In one embodiment, the dispersant is present in the lubricating composition at from 0.05 to 10.0 wt% (e.g., from 0.1 to 10.0 wt%, from 0.1 to 5.0 wt%, from 0.2 to 10 wt%, or from 0.2 to 5.0 wt%).

[0145] Friction modifier

[0146] Friction modifiers are any material or materials or fluids containing such materials that can change the coefficient of friction of a surface lubricated by any lubricant. Friction modifiers include alkoxylated fatty amines, boroated fatty epoxides, fatty phosphites, fatty epoxides, fatty amines, boroated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, boroated glycerol esters, and fatty imidazolines. As used herein, the term "fatty" means a hydrocarbon chain, typically a straight hydrocarbon chain, having 10 to 22 carbon atoms.

[0147] Other known friction modifiers include oil-soluble organic molybdenum compounds. Such organic molybdenum friction modifiers also provide antioxidant and antiwear properties to the lubricating oil composition. Suitable oil-soluble organic molybdenum compounds have a molybdenum-sulfur core. As examples, dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and mixtures thereof can be mentioned. The molybdenum compound can be dinuclear or trinuclear.

[0148] Corrosion inhibitor

[0149] Corrosion inhibitors protect lubricated metal surfaces from chemical attack by water or other contaminants. Suitable corrosion inhibitors include polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, thiadiazoles, and anionic alkyl sulfonic acids.

[0150] Viscosity modifier

[0151] Viscosity modifiers provide high and low temperature operability to lubricants. These additives increase the viscosity of the oil composition at high temperatures, thereby increasing film thickness, but have limited effect on viscosity at low temperatures.

[0152] Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters, and viscosity index improver dispersants, which can serve as both viscosity index improvers and dispersants. These polymers typically have a molecular weight in the range of 1000 to 1,000,000 (e.g., 2000 to 500,000 or 25,000 to 100,000).

[0153] Examples of suitable viscosity modifiers are polymers and copolymers of methyl acrylate, butadiene, olefins, or alkylated styrene. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (e.g., copolymers of alkyl methacrylates of different chain lengths), some formulations of which can also serve as pour point depressants. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (e.g., copolymers of acrylic acid esters of different chain lengths). Specific examples include styrene-isoprene or styrene-butadiene-based polymers having a molecular weight of 50,000 to 200,000.

[0154] Pour point depressant

[0155] A pour point depressant lowers the minimum temperature at which a fluid will flow or be pourable. Suitable pour point depressants include C8to C18fumaric acid dialkyl ester / vinyl acetate copolymers, polymethylalkyl acrylates, and the like.

[0156] Foam inhibitor

[0157] A foam inhibitor retards the formation of stable foam. Examples of suitable foam inhibitors include polysiloxanes, polyacrylates, and the like.

[0158] Thickener

[0159] A thickening agent can increase the viscosity of the lubricating oil composition to achieve a desired viscosity grade. Any suitable thickening agent can be used, such as bright stock (BS), polyisobutylene (PIB), polymethacrylate (PMA), or olefin copolymer (OCP).

[0160] PIB is a commercially available material from multiple manufacturers. Polyisobutylenes are typically viscous, oil miscible liquids having a number average molecular weight of 800 to 5000 (e.g., 1000 to 2500), and a kinematic viscosity at 100°C of 200 to 5000 mm 2 / s (e.g., 200 to 1000 mm 2 / s). The amount of PIB added to the lubricating oil composition is typically 1 to 20 wt.% of the finished oil (e.g., 2 to 15 wt.% or 4 to 12 wt.% based on active ingredient).

[0161] Olefin copolymers will typically be present at 0.1 wt.% or greater of the lubricating oil composition, e.g., 0.1 to 12 wt.% based on active ingredient. In certain embodiments, the OCP is present at 0.2 to 10 wt.%, 0.3 to 9 wt.%, 0.4 to 8 wt.%, or 0.5 to 7 wt.% of the lubricating oil composition based on active ingredient. In still further embodiments, the OCP is present at 0.5 to 12.0 wt.%, 0.5 to 5 wt.%, or 1 to 2 wt.% of the lubricating oil composition based on active ingredient. In yet further embodiments, the OCP is present at 1.0 wt.% or greater of the lubricating oil composition, e.g., 1.0 to 12.0 wt.%, 1.0 wt.% to 5 wt.%, 1.3 wt.% to 4.5 wt.%, 1.5 wt.% to 4.0 wt.%, 2.0 to 12.0 wt.%, or 2.0 wt.% to 3.5 wt.% based on active ingredient.

[0162] In certain embodiments, the olefin copolymer is a copolymer based on ethylene units and alpha olefin (e.g., normal alpha olefin, isomerized alpha olefin) units, such as an ethylene-propylene copolymer composition. Other alpha-olefins suitable for replacing propylene or in combination with ethylene and propylene to form a terpolymer or a tetrapolymer, for example, include: 1 -butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene; and branched 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.

[0163] The following non-limiting examples illustrate the present application. A brief description of the manner in which the examples were prepared is provided.

[0164] Example

[0165] The effect of ammonia fuel and its combustion products on MCL packages was investigated.

[0166] Fresh test oil samples containing MCL additive packages were contaminated with ammonia using an accelerated aging method. The aging method simulated the interaction between marine lubricants and ammonia to evaluate the impact on marine lubricant bench test performance. The nitrogen weight % of the aged test oils was measured to demonstrate the uptake of nitrogen due to ammonia exposure.

[0167] Fresh and aged test oils were evaluated using differential scanning calorimetry (DSC), modified IP-48 (MIP-48), and Komatsu Hot Tube (KHT) bench tests.

[0168] Marine cylinder lubricant

[0169] Marine cylinder lubricants were prepared by blending 15 and 40 BN MCL packages in the form of various types of base oil mixtures.

[0170] Base oil mixture A consisted of a major amount of API Group I 600N base oil and a minor amount of API Group I XOM 2500 bright stock as thickener.

[0171] Base oil mixture B consisted of a major amount of bio-based base oil sold as a Group III+ base oil derived 100% from renewable carbon sources, a sustainable synthetic base oil (SSBO) of vegetable origin with a viscosity of 9.5 cSt at 100°C) and a minor amount of API Group I XOM 2500 bright stock thickener and some high molecular weight polyisobutylene (PIB 2300) to maintain an equivalent amount of bright stock and compensate for the viscosity drop due to the use of a low viscosity SSBO.

[0172] Base oil mixture C consists of a large amount of Chevron RLOP 600R API Group II base oil and a small amount of API Group I XOM 2500BS bright stock as thickener.

[0173] The resulting test oil samples containing the marine additive package and base oil mixtures are summarized below.

[0174] Example 1 (40 BN SAE 50 MCL with KV100°C of 18.5 cSt)

[0175] a) Additive Package 1 - 9.0 wt% oil concentrate of high base sulfated calcium phenate derived from propylene tetramer, TBN of 116 BN (40 wt% diluent oil); 60 mmol / kg sulfonate soap made from a mixture of low and high high base calcium sulfonate detergents; bis succinimide dispersant derived from 1000 MW polyisobutylene; 1.5 wt% antioxidant system with a combination of hindered phenolic and diphenylamine aminic antioxidants. The TBN contribution from the sulfonate detergent is 72% of the total detergent BN.

[0176] b) Base Oil Mixture A - (78.1 wt% base oil blend) contains 54.7 wt% API Group II 600N base oil and 23.4 wt% API Group I XOM 2500BS bright stock as thickener

[0177] Example 2 (40 BN SAE 50 MCL with KV100°C of 18.5 cSt)

[0178] a) Additive Package 1 - 9.0 wt% oil concentrate of high base sulfated calcium phenate derived from propylene tetramer, TBN of 116 BN (40 wt% diluent oil); 60 mmol / kg sulfonate soap made from a mixture of low and high high base calcium sulfonate detergents; bis succinimide dispersant derived from 1000 MW polyisobutylene; 1.5 wt% antioxidant system with a combination of hindered phenolic and diphenylamine aminic antioxidants. The TBN contribution from the sulfonate detergent is 72% of the total detergent BN.

[0179] b) Base Oil Mixture B - (78.1 wt%) contains 50.2 wt% biobased base oil (100% renewable, plant-derived sustainable synthetic base oil (SSBO) with a viscosity of 9.5 cSt at 100°C), 23.4 wt% API Group I XOM 2500BS bright stock thickener, and 4.5 wt% high molecular weight polyisobutylene (PIB 2300)

[0180] Example 3 (40 BN SAE 50 MCL with KV100°C of 18.5 cSt)

[0181] a) Additive Package 2 - 0.9 wt% of high base sulfurized calcium phenate oil concentrate (derived from propylene tetramer) with a TBN of 260 (40 wt% diluent oil); 9.0 wt% of high base sulfurized calcium phenate oil concentrate (derived from propylene tetramer) with a TBN of 116 BN (40 wt% diluent oil); 70 mmol / kg sulfonate soap made from a mixture of low and high high base calcium sulfonate detergents; bis succinimide dispersant derived from 1000 MW polyisobutylene; 1.5 wt% antioxidant system with a combination of hindered phenolic and diphenylamine aminic antioxidants. The TBN contribution from the sulfonate detergent is 70% of the total detergent BN.

[0182] b) Base Oil Mixture A - (75.8 wt% base oil blend) contains 52.2 wt% API Group I 600N base oil and 23.6 wt% API Group I XOM 2500BS bright stock as a thickener

[0183] Example 4 (40 BN SAE 50 MCL with KV100°C of 18.5 cSt)

[0184] a) Additive Package 2 - 0.9 wt% of high base sulfurized calcium phenate oil concentrate (derived from propylene tetramer) with a TBN of 260 (40 wt% diluent oil); 9.0 wt% of high base sulfurized calcium phenate oil concentrate (derived from propylene tetramer) with a TBN of 116 BN (40 wt% diluent oil); 70 mmol / kg sulfonate soap made from a mixture of low and high high base calcium sulfonate detergents; bis succinimide dispersant derived from 1000 MW polyisobutylene; 1.5 wt% antioxidant system with a combination of hindered phenolic and diphenylamine aminic antioxidants. The TBN contribution from the sulfonate detergent is 70% of the total detergent BN.

[0185] b) Base Oil Mixture B - (75.8 wt%) contains 48.1 wt% biobased base oil (100% renewable, plant-derived sustainable synthetic base oil (SSBO) with a viscosity of 9.5 cSt at 100°C), 23.6 wt% API Group I XOM 2500BS bright stock thickener, and 4.1 wt% high molecular weight polyisobutylene (PIB 2300)

[0186] Example 5 (40 BN SAE 50 MCL with KV100°C of 18.5 cSt)

[0187] a) Additive Package 6 - 2.5 wt% of a highly overbased sulfurized calcium phenate oil concentrate (derived from propylene tetramers), TBN of 260 (40 wt% diluent oil); 14.0 wt% of a highly overbased sulfurized calcium phenate oil concentrate (derived from propylene tetramers), TBN of 116 BN (40 wt% diluent oil); 30 mmol / kg sulfonate soap made from a mixture of low and high overbased calcium sulfonate detergents; bis succinimide dispersant derived from 1000 MW polyisobutylene. The TBN contribution from the sulfonate detergent is 43% of the total detergent BN.

[0188] b) Base Oil Mixture 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 XOM 2500BS bright stock as thickener.

[0189] Example 6 (40 BN SAE 50 MCL with KV 100°C of 18.5 cSt)

[0190] a) Additive Package 7 - 23.5 wt% of a highly overbased sulfurized calcium phenate oil concentrate (derived from C20-24 isomerized olefins), TBN of 95 (20 wt% diluent oil); 27 mmol / kg sulfonate soap made from a mixture of low and high overbased calcium sulfonate detergents; bis succinimide dispersant derived from 1000 MW polyisobutylene. The TBN contribution from the sulfonate detergent is 43% of the total detergent BN.

[0191] b) Base Oil Mixture 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 XOM 2500BS bright stock as thickener.

[0192] Example 7 (15 BN SAE 50 MCL with KV 100°C of 18.5 cSt)

[0193] a) Additive Package 8 - 2.7 wt% of a highly overbased sulfurized calcium phenate oil concentrate (derived from C20-24 isomerized olefins), TBN of 95 (20 wt% diluent oil); 15 mmol / kg sulfonate soap made from a mixture of low and high overbased calcium sulfonate detergents; bis succinimide dispersant derived from 1000 MW polyisobutylene. The TBN contribution from the sulfonate detergent is 81% of the total detergent BN.

[0194] b) Base oil mixture C - 52.4 wt% Chevron RLOP 600R API Group II base oil and 41.4 wt% API Group I XOM 2500BS bright stock as thickener (93.8 wt% base oil blend).

[0195] Example 8 (15BN SAE 50MCL with KV100°C of 18.5 cSt)

[0196] a) Additive package 9 - 8.8 wt% oil concentrate of high base sulfated calcium phenate derived from C20-24 isomerised olefins, TBN of 95 (20 wt% diluent oil); 10 mmol / kg sulfonate soap made from a mixture of low and high high base calcium sulfonate detergents; bis succinimide dispersant derived from 1000 MW polyisobutylene. TBN contribution from sulfonate detergent is 42% of total detergent BN.

[0197] b) Base oil mixture C - 53.0 wt% Chevron RLOP 600R API Group II base oil and 35.9 wt% API Group I XOM 2500BS bright stock as thickener (88.9 wt% base oil blend).

[0198] Comparative Example A (40BN SAE 50MCL with KV100°C of 18.5 cSt)

[0199] a) Additive package 3 (sole phenate) - 14.8 wt% oil concentrate of high base sulfated calcium phenate derived from propylene tetramers, TBN of 260 (40 wt% diluent oil); 1.0 wt% oil concentrate of high base sulfated calcium phenate derived from propylene tetramers, TBN of 116 (40 wt% diluent oil); bis succinimide dispersant derived from 1000 MW polyisobutylene. TBN contribution from sulfonate detergent is 0% of total detergent BN.

[0200] b) Base oil mixture C - 55.2 wt% Chevron RLOP 600R API Group II base oil and 28.6 wt% API Group I XOM 2500BS bright stock as thickener (83.8 wt% base oil blend).

[0201] Comparative Example B (40BN SAE 50MCL with KV100°C of 18.5 cSt)

[0202] a) Additive Package 4 (sole sulfonate) - 50 mmol / kg sulfonate soap made from a mixture of low overbased and high overbased calcium sulfonate detergents; bis succinimide dispersant derived from 1000 MW polyisobutylene. TBN contribution from sulfonate detergent is 100% of total detergent BN.

[0203] b) Base Oil Mixture 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 XOM 2500BS bright stock as thickener.

[0204] Comparative Example C (15 BN SAE 50 MCL with KV100°C of 18.5 cSt)

[0205] a) Additive Package 5 (sole phenate) - 15.6 wt% oil concentrate of high overbased calcium sulfidized phenate (derived from C20-24 isomerized olefins), TBN of 95 (20 wt% dilution oil); bis succinimide dispersant derived from 1000 MW polyisobutylene. TBN contribution from sulfonate detergent is 0% of total detergent BN.

[0206] b) Base Oil Mixture 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 XOM 2500BS bright stock as thickener.

[0207] Aging protocol

[0208] To demonstrate the effects of ammonia fuel and its combustion products, the test oils were aged in an atmosphere of NH3. Subsequent bench testing of the aged products provided insight into the lubricant performance.

[0209] During the aging process, 15 and 40 BN marine cylinder lubricants were aged with gaseous ammonia (NH3) at high temperature (180°C) for extended periods of time. After determining that the nitrogen content in the samples increased by at least about 600 ppm, a series of bench tests were performed.

[0210] "soap" refers to the soap content and refers to the concentration in millimoles / kg of surfactant anions contributed to the formulation by one or more detergents within the composition. For the purposes of the present invention, the surfactant concentration is reported as the number of millimoles of surfactant per kg of additive concentrate. The soap or surfactant content in a detergent additive can be measured by:

[0211] Step 1 : Determine the % calcium by mass as sulfonate soap according to ASTM D4251. The resulting value is [wt% calcium / 100] in the expression below, or in other words, the wt% of calcium as soap in 100 grams of additive concentrate.

[0212] Step 2: Once the % calcium as sulfonate soap is determined, the number of surfactant anions or "soap" is calculated (in mmol / kg) using the following expression:

[0213] [wt% calcium / 100] * [1000 g / Kg] * [1 mole calcium / 40 g calcium] * [2 moles surfactant anion / mole calcium] * [1000 mmole / mole] = mmole surfactant "soap" / kg additive concentrate

[0214] DSC Oxidation Test

[0215] The DSC test is used to evaluate the film oxidation stability of a test oil according to ASTM D-6186. During the test, the heat flow to and from the test oil in the sample cup is compared to the reference cup. The oxidation onset temperature is the temperature at which the test oil begins to oxidize. The oxidation induction time is the time at which the test oil begins to oxidize. A longer oxidation induction time means better performance. The oxidation reaction is exothermic and is clearly shown by the heat flow. The oxidation induction time is calculated in minutes to evaluate the film oxidation stability of the test oil.

[0216] Modified Petroleum Institute 48 (MIP-48) Test

[0217] The MIP-48 test measures the degree of stability of a lubricant against oxidation-based viscosity increase. The MIP-48 test consists of a thermal portion and an oxidation portion. The sample is heated for a period of time during both portions of the test. In the thermal portion of the test, nitrogen is passed through the heated oil sample for 24 hours, while during the oxidation portion of the test, air is passed through the heated oil sample for 24 hours. The samples are cooled and the viscosity of both samples is determined. The increase in viscosity of the test oil due to oxidation is determined and corrected for thermal effects. The oxidation-based viscosity increase for each marine lubricating oil composition is calculated by subtracting the kinematic viscosity at 200°C of the sample blown with nitrogen from the kinematic viscosity at 200°C of the sample blown with air, and then dividing the difference by the kinematic viscosity at 200°C of the sample blown with nitrogen. This is done to correct for possible evaporation effects or any other thermal effects during the test, so that the effect of oxidation is the focus. This correction can result in negative values. Test oils that exhibit better stability against oxidation-based viscosity increase will produce lower % absolute values. The results of the MIP-48 test are shown in Table 1 below.

[0218] Komatsu Hot Tube (KHT) Test

[0219] The Komatsu Hot Tube Test is a lubrication industry bench test used to measure high temperature cleanliness as well as thermal and oxidative stability of lubricating oils. During the test, a specified amount of test oil is pumped upward through a glass tube placed inside an oven set to a certain temperature. Air is introduced into the oil stream before it enters the glass tube and flows upward with the oil. The evaluation of marine lubricating oils is conducted at a temperature of 300-320°C. After cooling and washing, the test result is determined by comparing the amount of varnish deposited on the glass test tube to a rating scale ranging from 1.0 (very dark) to 10.0 (very clean). The result is reported in multiples of 0.5. If the glass tube is completely clogged with deposits, the test result is recorded as “clog”. A clog is a deposit that results in a value below 1.0, in which case the varnish is very thick and dark, but still allows liquid flow, although the flow rate is completely unsatisfactory for the available oil.

[0220] The MIP-48 test was used to evaluate the oxidation-based viscosity increase in each of the finished oil lubricants of Examples 1-4, first evaluating fresh oil and then evaluating NH3 aged oil. The results for each example are shown in Table 4 below.

[0221] Table 4

[0222]

[0223] Referring to Table 4, ammonia (NH3) aging at 180°C had only a slight effect on the marine cylinder lubricating compositions of the present application. Each of the ammonia aged test oils exhibited stability against oxidation-based viscosity increase, as seen by the relatively stable % viscosity increase, relative to the fresh test oil before aging. This indicates that the cylinder lubricants of the present application are compatible with ammonia fuel. In some cases, as in Examples 2, 3, and 4, the test results show that the % viscosity increase of the ammonia aged oil is less than the fresh test oil, indicating a directed improvement in stability against oxidation-based viscosity increase. Overall, the % viscosity increase in absolute value is lower for the fresh and aged test oils containing a large amount of SSBO base oil (Examples 2 and 4) compared to the fresh and aged test oils containing a large amount of conventional API Group I base oil, indicating better stability against oxidation-based viscosity increase.

[0224] The MIP-48 test was used to evaluate the oxidation-based viscosity increase in each of the finished oil lubricants of Examples 1-4, first evaluating fresh oil and then evaluating NH3 aged oil. The results for each example are shown in Table 4 below.

[0225] Table 5

[0226]

[0227]

[0228] Referring to Table 5, the viscosity increase % of Examples 5 and 6 are lower, indicating better stability against oxidation-based viscosity increase; longer oxidation induction times and higher KHT ratings, demonstrating improved oxidative stability and deposit performance compared to the comparative example when exposed to ammonia aging.

[0229] The high temperature cleanliness of each of Comparative Example C and Examples 7-8 were evaluated using the KHT test for NH3-based aging Class II finished oil lubricants. The results for each example are shown in Table 6 below.

[0230] Table 6

[0231]

[0232] Referring to Table 6, the 15BN Class II based formulations of Examples 7 and 8 have higher ratings in the KHT test, demonstrating improved deposit performance compared to the comparative example when exposed to ammonia aging.

[0233] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit can be combined with any upper limit to recite additional ranges not explicitly recited, and ranges from any lower limit can be combined with any other lower limit to recite additional ranges not explicitly recited, and likewise, ranges from any upper limit can be combined with any other upper limit to recite additional ranges not explicitly recited. Additionally, each numerical range is intended to include each and every value and sub-range within the range. Accordingly, any numerical range disclosed herein is intended to include each and every value and sub-range within the range. Additionally, any reference cited herein is incorporated by reference in its entirety.

[0234] Also, "comprising" is to be interpreted as synonymous with the term "including". Likewise, whenever a composition, an element or a group of elements is preceded by the transitional phrase "comprising," it is understood that we also contemplate the same composition, element or group of elements preceded by the transitional phrases "consisting essentially of," "consisting of," "selected from the group consisting of," or "is" for the same composition, element or group of elements alternatively predicated by the transitional phrases "consisting essentially of," "consisting of," "selected from the group consisting of," or "is."

[0235] As used herein, the terms "a" and "an" are understood to encompass the plural as well as the singular.

[0236] Various terms have been defined above. To the extent a term used in a claim is not defined above, such term is intended to be given the broadest definition possible under the circumstances in light of the disclosure herein and the skill in the art. Additionally, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0237] The foregoing description of the present disclosure illustrates and describes the present disclosure. Additionally, the disclosure shows and describes only the preferred embodiments, but as aforementioned, it is to be understood that the 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 as 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 can be devised without departing from the basic scope thereof, and the scope of such disclosure is determined by the claims that follow.

[0238] It is to be understood that the combining, subsetting, grouping, and the like of disclosed elements (e.g., the combining of components in a composition, or the combining of steps in a method) while possibly not explicitly disclosed do contemplate each and every combination and permutation of the various individual and collective elements, as well as the specific mention of each of the different individual and collective combinations and permutations.

[0239] The embodiments described hereinabove are further intended to explain known preferred embodiments of the application and to enable others skilled in the art to utilize the application in such or other embodiments and with various modifications as are suited to the particular use or environment with the overall scope of the use being analogous to the concepts described herein. Accordingly, the specification is not intended to limit the application to the form or forms disclosed herein. Additionally, the appended claims are intended to be construed and limited only on their legal equivalents.

Claims

1. A marine cylinder lubricating oil composition for a non-carbon based fuel driven marine engine comprising: (a) a major amount of an oil of lubricating viscosity; and (b) a mixture of a high base number phenolic detergent and a high base number calcium sulfonate detergent; and wherein the marine cylinder lubricating oil composition has a TBN of less than 200 mg KOH / g, and further wherein the marine engine lubricating oil composition is a single grade lubricating oil composition meeting the requirements of SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60 single grade lubricating oil of the SAE J300 specification revised January 2015.

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

3. 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 having a viscosity index of greater than or equal to 120.

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

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

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

7. The marine cylinder lubricating oil composition of claim 1, wherein the phenolic detergent is a high base number calcium sulfide phenate.

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

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

10. A method of lubricating a marine two-stroke engine operating on ammonia fuel, the method comprising lubricating the engine with a lubricating oil composition comprising: (a) a major amount of an oil of lubricating viscosity; and (b) a mixture of a high base number phenolic detergent and a high base number calcium sulfonate detergent; and wherein the marine cylinder lubricating oil composition has a TBN of less than 200 mg KOH / g, and further wherein the marine engine lubricating oil composition is a single grade lubricating oil composition meeting the requirements of SAE 40, SAE 50, or SAE 60 single grade lubricating oil of the SAE J300 specification revised January 2015.

11. The method of claim 10, 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 having a viscosity index of greater than or equal to 120.

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

16. The marine cylinder lubricating oil composition of claim 10, wherein the phenolic detergent is a high base calcium sulfide phenate.

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

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

19. A method of improving or maintaining deposit control performance and / or oxidation stability of an ammonia-fueled marine engine, the method comprising: lubricating the engine with a lubricating oil composition comprising: (a) a major amount of an oil of lubricating viscosity; and (b) a mixture of a high base phenolic detergent and a high base calcium sulfonate detergent; and wherein the marine cylinder lubricating oil composition has a TBN of less than 200 mg KOH / g, and further wherein the marine engine lubricating oil composition is a single grade lubricating oil composition meeting the requirements of the January 2015 revised SAE J300 specification for SAE 40, SAE 50, or SAE 60 single grade lubricating oils.

20. The method of claim 19, 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 having a viscosity index of greater than or equal to 120.

21. 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% sulfur.

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

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

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

25. The marine cylinder lubricating oil composition of claim 19, wherein the phenolic detergent is a high base calcium sulfide phenate.

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

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

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