JP2019526698A - Marine diesel cylinder lubricating oil composition - Google Patents

Abstract

Marine diesel cylinder lubricating oil compositions contain a major amount of oil of lubricating viscosity. The lubricating oil composition further comprises a sulfur-free aromatic amine. The marine diesel cylinder lubricating oil composition has a total base number (TBN) of about 5 to about 100 mg KOH / g. Furthermore, the contribution of sulfur-free aromatic amines to the TBN of marine diesel cylinder lubricating oil compositions is greater than about 30%.

Description

  The present invention relates generally to lubricating oil compositions for marine engines designed for use with various fuel sources.

  Diesel engines can generally be categorized as low speed, medium speed, or high speed engines, with the low speed type being the largest deep draft ship and certain other industries such as power generation applications. Used for applications.

  Low speed diesel engines are unique in terms of size and operation. The engines themselves are large and the output of these engines can reach 100,000 brake horsepower, with engine speeds from 60 to about 200 revolutions per minute. A low speed diesel engine operates in a two-stroke cycle and is typically a crossheaded direct and direct reversing engine with one or more stuffing boxes and diaphragms that separate the power cylinder from the crankcase. (Diaphragm), which prevents combustion products from entering the crankcase and mixing with the crankcase oil. Marine two-stroke diesel cylinder lubricants to meet the rigorous operating conditions required for more modern large caliber two-stroke crosshead engines operating at higher power and higher cylinder liner loads and higher temperatures. Must meet performance requirements. By completely separating the crankcase from the combustion zone, those skilled in the art have lubricated the combustion chamber and crankcase with different lubricating oils.

  In large crosshead type diesel engines used in marine applications, the cylinders are separately injected with cylinder oil into each cylinder, often in a quill, using a lubrication device placed around the cylinder liner. Lubricated on the basis of total loss. Oil is distributed to the lubricator using a pump, and in current engine designs, the pump is often driven to apply oil directly to the ring to reduce oil waste.

  The typical use of sulfur-containing fuels for the operation of these engines is a lubricant with high cleanliness and neutralization capability even when the oil is exposed to heat and other stresses for only a short time. Is required. Residual fuels commonly used in these engines contain significant amounts of sulfur and, in the combustion stroke, combine with water to produce sulfuric acid, whose presence can lead to corrosive wear. . In particular, in marine two-stroke engines, the area around the cylinder liner and piston ring can be corroded and worn by acid. It is therefore important that diesel engine lubricants have the ability to withstand such corrosion and wear.

  Accordingly, one of the main functions of marine diesel cylinder lubricants is to neutralize the sulfur-based acidic components of the burned sulfur-containing fuel. This neutralization has typically been accomplished by including in the marine diesel cylinder lubricant a basic species such as an overbased metal detergent. The neutralizing ability of an oil is characterized by its basicity and is measured by its total base number (TBN).

  Recently, regulations that require the use of low-sulfur fuel in the operation of marine diesel engines are currently present in certain areas due to health and environmental concerns. As a result, manufacturers now generally use gas fuels (compressed natural gas or compressed natural gas or heavy fuels, such as marine residue fuels with high sulfur content and higher asphaltene content, for poorer quality medium or heavy fuels. Marine diesel engines are designed for use with a variety of fuels, including liquefied natural gas (LNG), high sulfur distillate with low sulfur and low asphaltene content. In gas or distillate fuel operation, the fuel does not contain a significant amount of asphaltenes in the fuel and contains a much lower level of sulfur. When more refined and less sulfur fuel is burned, the amount of acid formed in the combustion chamber is less. Therefore, compared to marine residue fuels, the requirements for lubricants used in engine operation using gas and low sulfur distillate fuels can be very different.

  TBN is a standard criterion that allows cylinder oil basicity to be adjusted to the sulfur content of the fuel used to allow neutralization of all the sulfur contained in the fuel. . Therefore, the higher the sulfur content of the fuel, the higher the TBN that the marine lubricant must have. This is why lubricating oils with a TBN of 5 to 150 mg KOH / g are found in the marine market. Typically, in marine formulations, basicity is provided by overbased detergents that are overbased using metal carbonates. However, the excess overbased detergent present in marine diesel cylinder lubricants results in a fairly excessive basic fraction and destabilizes the micelles of unused overbased detergent containing insoluble metal salts. Danger arises. This destabilization forms insoluble metal salt deposits in ash formation, covering cylinder walls and other engine parts. In the case of large multi-fuel marine engines, the quality of the exhaust gas strongly depends on the fuel used. In order to comply with strict exhaust gas regulations in coastal waters, among other measures, SCR catalytic converters are used in marine engines to reduce nitrite gas. In an engine containing an excessive amount of ash, ash accumulates on the surface of the SCR catalyst, preventing the exhaust gas from approaching the catalyst surface, which may hinder the catalyst function.

  Therefore, optimization of cylinder lubrication in a low speed two-stroke engine requires selection of a lubricant having a TBN that is compatible with the fuel and engine operating conditions. This optimization reduces the flexibility of engine operation and requires considerable technical expertise in defining the conditions that must be switched from one type of lubricant to another during ship operation. This optimization is difficult. Therefore, to simplify operation, it is desirable to have a single cylinder lubricant for a two-stroke marine engine that can adapt to variations in fuel type and fuel sulfur level.

  The present invention provides a vessel with an ashless base source that can ensure good lubrication of the cylinders of a marine engine and can be adapted to constraints on variations in fuel type and fuel sulfur level. The present invention relates to a diesel cylinder lubricant composition. The present invention further relates to the use of sulfur-free aromatic amines to reduce and / or limit harmful effects and to impart basicity to the lubricant.

  In accordance with one embodiment of the present invention, a marine diesel cylinder lubricant comprising: (a) a major amount of an oil of lubricating viscosity; and (b) a sulfur-free aromatic amine having a total base number of about 100 to 600 mg KOH / g. The marine diesel cylinder lubricating oil composition has a TBN of about 5 to about 100, and the TBN contribution of the sulfur-free aromatic amine to the TBN of the lubricant composition is about A lubricating oil composition is provided that is greater than 30%.

  According to a second embodiment of the present invention, (a) a major amount of oil of lubricating viscosity, (b) a sulfur-free aromatic amine having a total base number of about 100 to 600 mg KOH / g, and (c) one or more A marine diesel cylinder lubricant composition comprising: a polyalkenyl succinimide dispersant, wherein the polyalkenyl substituent is derived from a polyalkene group having a number average molecular weight of about 1500 to about 3000; A lubricant composition, wherein the lubricant composition has a TBN of about 5 to about 100, and further, the TBN contribution of the sulfur-free aromatic amine to the TBN of the lubricant composition is greater than about 30% I will provide a.

  The present invention is a surprising discovery that the lubricant composition of the present invention advantageously improves the oxidation, cleanliness and dispersion performance of marine diesel cylinder lubricating oil compositions used in 2-stroke crosshead marine diesel engines. Based on. A cylinder oil with high oxidative stability in the thin film state rather than in the bulk fluid has a smaller increase in viscosity and exhibits anti-scuffing performance. The present invention further relates to the use of non-sulfur-containing aromatic amines in marine diesel cylinder lubricants in an amount that results in a TBN contribution of greater than about 30%, a reduction in basicity (according to BN) measured according to ASTM D2896. It relates to uses that reduce velocities and provide ashless TBN in lubricant compositions that have a relatively low impact on seal materials that can be used in engine lubrication systems or lubricant handling systems.

Detailed Description of Preferred Embodiments In the present invention, sulfur-free aromatic amines replace ash-containing overbased metal detergents as a BN source for lubricants. Accordingly, the present invention relates to a marine diesel cylinder lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity and (b) a sulfur-free aromatic amine having a total base number of about 100 to 600 mg KOH / g. The marine diesel cylinder lubricant composition has a TBN of about 5 to about 100, and further, the TBN contribution of the sulfur-free aromatic amine to the TBN of the lubricant composition is about 30 % Of the lubricating oil composition.

  In one embodiment of the invention, the TBN provided by the sulfur-free aromatic amine is at least 30%, or at least 35%, or at least 40% of the TBN of the marine diesel cylinder lubricant.

  In one embodiment of the invention, the marine diesel cylinder lubricant comprises a low sulfur fuel comprising less than 1.0 wt% sulfur, or less than 0.5 wt% sulfur, or less than 0.1 wt% sulfur. It is used to lubricate marine 2-stroke engines that are operated in use.

  In accordance with one embodiment of the present invention, sulfur-free aromatic amine compounds are known as amine antioxidants and cylinders are lubricated on a full loss basis using cylinder oil, so typically Used in lower concentrations in diesel cylinder lubricants. Examples of amine antioxidants that can be conveniently used include diarylamines, alkylated diphenylamines, phenyl-α-naphthylamines, phenyl-β-naphthylamines and alkylated α-naphthylamines.

  In one particular embodiment, the amine-based antioxidants include linear or branched dialkyldiphenylamines such as p, p′-dinonyl-diphenylamine; p, p′-dioctyl-diphenylamine; p, p′-di -Α-methylbenzyl-diphenylamine; Np-butylphenyl-Np'-octylphenylamine; monoalkyldiphenylamines such as mono-t-butyldiphenylamine and mono-octyldiphenylamine; di- (2,4-diethylphenyl) ) Bis (dialkylphenyl) amines such as amines and di (2-ethyl-4-nonylphenyl) amine; alkylphenyl-1-naphthylamines such as octylphenyl-1-naphthylamine and nt-dodecylphenyl-1-naphthylamine; 1-naphthylamine; phenyl-1-naphth Aryl naphthylamines such as ruamine, phenyl-2-naphthylamine, N-hexylphenyl-2-naphthylamine and N-octylphenyl-2-naphthylamine; N, N′-diisopropyl-p-phenylenediamine and N, N′-diphenyl-p -Phenylenediamine such as phenylenediamine is included.

  In one embodiment, the sulfur-free aromatic amine of the present invention is a diarylamine. In one embodiment, the sulfur-free aromatic amine of the present invention is an alkylated diphenylamine. In one particular embodiment, the sulfur-free aromatic amine of the present invention is a dialkyldiphenylamine.

  The sulfur-free aromatic amines of the present invention are measured according to standard ASTM D-2896 and are typically about 100 to about 600 mg KOH / g, preferably about 100 to about 300 mg KOH / g, on an oil-free active substance basis. Preferably from about 100 to about 200 mg KOH / g, preferably from about 120 to about 500 mg KOH / g, more preferably from about 120 to about 300 mg KOH / g, and even more preferably from about 120 to about 250 mg KOH / g.

  In a preferred embodiment, the one or more sulfur-free aromatic amine compounds are at least 1.0 wt%, at least 1.5 wt%, at least based on the active material, based on the total weight of the lubricating oil composition. 2.0 wt%, at least 2.5 wt%, at least 3.0 wt%, at least 3.5 wt%, at least 4.0 wt%, at least 4.5 wt%, at least 5.0 wt%, or about 1.0 to 25.0 wt%, or about 1.0 to 20.0 wt%, or about 1.0 to 18 wt%, or about 1.0 to 15.0 wt%, or about 1.0 About 12.0 wt%, or about 2.0 to 25.0 wt%, or about 2.0 to 20.0 wt%, or about 2.0 to 18 wt%, or about 2.0 to 15.0 % By weight, or about 2.0 to about 12.0% by weight, 3.0 to 25.0 %, Or about 3.0 to 20.0%, or about 3.0 to 18%, or about 3.0 to 15.0%, or about 3.0 to about 12.0% by weight Present in quantity.

  The lubricant composition of the present invention includes at least one metal-free additive. Metal-free additives are also sometimes referred to as “ashless” because they typically do not produce any sulfated ash when subjected to ASTM D874 conditions.

  As used herein, the term “marine diesel cylinder lubricant” or “marine diesel cylinder lubricant” means a lubricant used to lubricate cylinders of low speed or medium speed two-stroke crosshead marine diesel engines. Then it shall be understood. Marine diesel cylinder lubricant is supplied to the cylinder wall through a number of injection points. Marine diesel cylinder lubricants promote engine cleanliness by forming a membrane between the cylinder liner and the piston ring and holding the partially burned fuel residue in suspension, and For example, acids formed by combustion of sulfur compounds in the fuel can be neutralized.

  “Marine Residual Fuel” refers to International Standardization Organization (ISO) 10370, such as marine residual fuel as defined in International Organization for Standardization ISO 8217: 2005, “Petoleum Products-Fuels (class F) -Specifications of marine fuels”. A large vessel having a carbon residue (at least 5% by weight, or at least 8% by weight) as defined in (for example, at least 5% by weight or at least 8% by weight) of carbon residue, viscosity greater than 14.0 cSt at 50 ° C. Means flammable materials in industrial engines, the entire contents of which are incorporated herein by reference.

  “Residual fuel” means a fuel that conforms to the standard for residual marine fuels defined in the ISO 8217: 2010 international standard. “Low sulfur marine fuel” conforms to the standard for residual marine fuel as specified in the ISO 8217: 2010 standard, plus about 1.5 wt% or less, or even about It means a fuel having 0.5% by weight or less of sulfur.

  “Distillate fuel” means a fuel that complies with the standards for distillate marine fuels defined in the ISO 8217: 2010 international standard. “Low sulfur distillate fuel” conforms to the standard for distillate marine fuel as specified in ISO 8217: 2010 international standard, plus about 0.1 wt% or less, or even more, based on the total weight of fuel By fuel having about 0.005% by weight or less of sulfur.

  Low sulfur gas fuel such as liquid natural gas (LNG) is mainly composed of methane, and the remainder is composed of other hydrocarbons. Methane, which is the main component of LNG, is usually kept in a liquid state.

The term “total base number” or “TBN” refers to the level of alkalinity in an oil sample, which is a composition that continues to neutralize corrosive acids according to ASTM standard number D2896 or equivalent procedures. Demonstrate ability. The test measures the change in electrical conductivity and expresses the result in mg · KOH / g (the number of milligram equivalents of KOH required to neutralize 1 gram of product). Thus, a high TBN represents a strong overbased product and consequently a higher base reserve to neutralize the acid.
The term “on an active substance basis” means an additive material that is neither a diluent oil nor a solvent.

  The marine diesel cylinder lubricant composition of the present invention can have any TBN suitable for use as a marine diesel cylinder lubricant. In some embodiments, the marine diesel cylinder lubricating oil composition of the present invention has a TBN of less than about 100 mg · KOH / g. In other embodiments, the TBN of the marine diesel cylinder lubricating oil composition of the present disclosure has about 5 to about 100, or about 5 to about 80, or about 5 to about 70, or about 5 to about 50, or about 5 to about 40, or about 5 to about 30, or about 5 to about 25, or about 10 to about 100, or about 10 to about 80, or about 10 to about 70, or about 10 to about 50, or about 10 From about 40, or from about 10 to about 30, or from about 10 to about 25, or from about 15 to about 100, or from about 15 to about 80, or from about 15 to about 70, or from about 15 to about 50, or from about 15 In the range of about 40, about 15 to about 30, or about 20 to about 100, or about 20 to about 80, or about 20 to about 70, or about 20 to about 40, or about 20 to about 30 mg KOH / g Can do.

  Due to the low operating speed and high load of marine engines, high viscosity oils (SAE 40, 50, and 60) are typically required. The marine diesel cylinder lubricating oil composition of the present invention has a range of from about 12.5 to about 26.1 cSt, or from about 12.5 to about 21.9, or from about 16.3 to about 21.9 cSt at 100 ° C. Can have kinematic viscosity. The kinematic viscosity of marine diesel cylinder lubricating oil compositions is measured by ASTM D445.

  The marine diesel cylinder lubricating oil composition of the present invention can be prepared by any method known to those skilled in the art of producing marine diesel cylinder lubricating oil compositions. The components can be added in any order and in any manner. Any suitable mixing or dispersing device can be used to blend, mix or dissolve the components. Blending, mixing or dissolving can be performed using a blender, stirrer, disperser, mixer, homogenizer, mill or any other mixing or dispersing device known in the art.

  The marine diesel cylinder lubricant composition of the present invention includes a major amount of oil of lubricating viscosity. “A major amount” means that the marine diesel cylinder lubricant composition is at least about 40 wt%, or at least about 50 wt%, based on the total weight of the marine diesel cylinder lubricant composition, Or at least about 60% by weight, and in particular at least about 70% by weight, means suitably comprising an oil of lubricating viscosity as described below.

  The oil of lubricating viscosity can be any oil suitable for lubricating large diesel engines including, for example, crosshead engines. The oil of lubricating viscosity can be a base oil derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable base oils include base stocks obtained by isomerization of synthetic waxes and slack waxes, as well as hydrocracking base stocks produced by hydrocracking (rather than solvent extraction) of aromatic and polar components of crude oil. included.

  Suitable natural oils include, for example, mineral lubricants such as liquid petroleum, paraffinic, naphthenic or mixed paraffinic-naphthenic solvent-treated or acid-treated mineral lubricants, oils derived from coal or shale, animal oils Vegetable oils (eg rapeseed oil, castor oil and lard oil) and the like.

  Suitable synthetic lubricating oils include, but are not limited to, hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins such as polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly (1- Hexene), poly (1-octene), poly (1-decene) and the like and mixtures thereof; alkylbenzenes such as dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) -benzene and the like; polyphenyl such as Biphenyl, terphenyl, alkylated polyphenyl and the like; alkylated diphenyl ether and alkylated diphenyl sulfide and derivatives, analogs and homologues thereof are included.

Other synthetic lubricating oils include, but are not limited to, oils obtained by polymerizing olefins of less than 5 carbon atoms, such as ethylene, propylene, butylene, isobutene, pentene, and mixtures thereof. Methods for preparing such polymer oils are well known to those skilled in the art. Additional synthetic hydrocarbon oils include alpha olefin liquid polymers with appropriate viscosity. Especially useful synthetic hydrocarbon oils are, C ₁₂ alpha-olefins from C _6, such as hydrogenated liquid oligomers such as 1-decene trimer.

Another class of synthetic lubricating oils includes, but is not limited to, alkylene oxide polymers, i.e. homopolymers, interpolymers and derivatives thereof in which the terminal hydroxyl groups have been modified, for example by esterification or etherification. Examples of these oils include oils prepared by polymerization of ethylene oxide or propylene oxide, alkyls and phenyl ethers of these polyoxyalkylene polymers (eg, methyl polypropylene glycol ethers having an average molecular weight of 1,000, molecular weights of 500 to 1,000 diethylene ethers of polyethylene glycol, diethyl ether of polypropylene glycol having a molecular weight of 1,000 to 1,500, etc.) or their mono- and polycarboxylic acid esters, such as acetate esters, mixed C ₃ to C ₈ fatty acid esters, or C ₁₃ oxo acid diester of tetraethylene glycol.

  Still other types of synthetic lubricants include, but are not limited to, dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipine. Acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, and various alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc. And esters. Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate , Dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, complex ester formed by reaction of 1 mol sebacic acid with 2 mol tetraethylene glycol, 2 mol 2-ethylhexanoic acid, etc. .

  Oils of lubricating viscosity can be derived from natural or synthetic unrefined, refined and rerefined oils, or mixtures of any two or more of the above types of oils. Unrefined oils are those obtained directly from natural or synthetic sources (eg, coal, shale, or tar sand bitumen) without further purification or processing. Examples of unrefined oils include, but are not limited to, shale oil obtained directly from retorting operations, petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process, each of which is then further Used without processing. Refined oils are similar to unrefined oils, except that they are further processed in one or more refining steps to improve one or more properties. These purification techniques are known to those skilled in the art and include, for example, solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, hydrorefining, dewaxing, and the like. Rerefined oil is obtained by treating spent oil in a process similar to that used to obtain refined oil. Such rerefined oils, also known as reclaimed or reprocessed oils, are often additionally processed by techniques aimed at removing spent additives and oil breakdown products.

  Lubricating oil base stocks derived from wax hydroisomerization can be used alone or in combination with said natural and / or synthetic base stocks. Such wax isomerate oils are produced by hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst. Natural wax is typically slack wax recovered by solvent dewaxing of mineral oil. Synthetic waxes are typically produced by the Fischer-Tropsch process.

  In one embodiment, the oil of lubricating viscosity is a Group I base stock. In general, Group I base stocks for use in the present invention may be petroleum derived base oils of lubricating viscosity as defined in API Publication 1509, 16th Edition, Appendix I, October 2009. The API guidelines define base stock as a lubricant component that can be manufactured using a variety of different processes. Group I base oils generally have a saturate content of less than 90% by weight (measured by ASTM D2007) and / or a total sulfur content greater than 300 ppm (measured by ASTM D2622, ASTM D4294, ASTM D4297 or ASTM D3120), And it means a petroleum-derived lubricating base oil having a viscosity index (VI) of 80 or more and less than 120 (measured by ASTM D2270).

  Group I base oils can include light overhead cuts and heavier side cuts from vacuum distillation columns, including, for example, light neutral, medium neutral, and heavy neutral base stocks Can be made. Further, the petroleum derived base oil can include, for example, residue stock such as bright stock or bottom fraction. Bright stock is a high viscosity base oil that has been traditionally manufactured from residual stock or bottom and has been highly refined and dewaxed. The bright stock can have a kinematic viscosity in the range of about 180 cSt at 40 ° C., or even more than about 250 cSt at 40 ° C., or even from about 500 to about 1100 cSt at 40 ° C.

  In one embodiment, the one or more base stocks can be a blend or mixture of two or more, three or more, or even four or more Group I base stocks having different molecular weights and viscosities, where The blend is processed in a manner suitable for making base oils with suitable properties for use in marine diesel engines (such as the viscosity and TBN values discussed above). In one embodiment, the one or more base stocks include ExxonMobil CORE (registered trademark in any country) 100, ExxonMobil CORE (registered trademark in any country) 150, ExxonMobil CORE (registered trademark in any country). ) 600, ExxonMobil CORE (registered trademark in any country) 2500 or combinations or mixtures thereof.

  In another embodiment, the oil of lubricating viscosity is a Group II base stock as defined in API Publication 1509, 16th Edition, Appendix I, October 2009. Group II base stocks generally have a total sulfur content of 300 ppm (parts per million) or less (measured according to ASTM D2622, ASTM D4294, ASTM D4297, or ASTM D3120) and have a saturated content of 90% by weight (according to ASTM D2007). And a petroleum derived lubricating base oil having a viscosity index (VI) of 80 to 120 (measured according to ASTM D2270).

  In another embodiment, the oil of lubricating viscosity is a Group III base stock as defined in API Publication 1509, 16th Edition, Appendix I, October 2009. Group III base stocks generally have a total sulfur content of 0.03% by weight or less (measured by ASTM D2270), a saturate content of 90% by weight or more (measured by ASTM D2007), and a viscosity index (VI). 120 or more (measured by ASTM D4294, ASTM D4297, or ASTM D3120). In one embodiment, the base stock is a Group III base stock or a blend of two or more different Group III base stocks.

In general, Group III base stocks derived from petroleum-based oils are highly hydrotreated mineral oils. Hydroprocessing involves reacting hydrogen with the base stock to be treated to remove heteroatoms from the hydrocarbon, reducing olefins and aromatics to alkanes and cycloparaffins, respectively, and very advanced hydrogen The saponification treatment includes opening the naphthenic ring structure to acyclic normal and isoalkanes (“paraffins”). In one embodiment, the Group III base stock has a paraffinic carbon content (% C _p ) of at least about 70%, which is a test method ASTM D3238-95 (2005), “Standard Test Method for Calculation of Carbon. It is quantified by “Distribution and Structural Group Analysis of Petroleum Oils by the ndM Method”. In another embodiment, the Group III base stock has a paraffinic carbon content (% C _p ) of at least about 72%. In another embodiment, the Group III base stock has a paraffinic carbon content (% C _p ) of at least about 75%. In another embodiment, the Group III base stock has a paraffinic carbon content (% C _p ) of at least about 78%. In another embodiment, the Group III base stock has a paraffinic carbon content (% C _p ) of at least about 80%. In another embodiment, the Group III base stock has a paraffinic carbon content (% C _p ) of at least about 85%.

In another embodiment, Group III base stocks have a naphthenic carbon content of less than about 25% (% _{C n),} which is measured by ASTM D3238-95 (2005). In another embodiment, the Group III base stock has a naphthenic carbon content (% C _n ) of about 20% or less. In another embodiment, the Group III base stock has a naphthenic carbon content (% C _n ) of about 15% or less. In another embodiment, the Group III base stock has a naphthenic carbon content (% C _n ) of about 10% or less.

  In one embodiment, the Group III base stock for use in the present invention is a Fischer-Tropsch derived base oil. The term “Fischer-Tropsch induction” means that a product, fraction, or feed originates from a Fischer-Tropsch process or is produced at a stage by a Fischer-Tropsch process. For example, Fischer-Tropsch base oil can be made from a process where the feed is a waxy feed recovered from Fischer-Tropsch synthesis, for example, US Patent Application Publication Nos. 2004/0159582; 2005/0077208. 2005/0133407; 2005/0133409; 2005/0139513; 2005/0139514; 2005/02411990. Each of which is also incorporated herein by reference. In general, the process includes a complete or partial hydroisomerization dewaxing step utilizing a catalyst capable of selectively isomerizing paraffin or a bifunctional catalyst. Hydroisomerization dewaxing is accomplished by contacting the waxy feed with a hydroisomerization catalyst under hydroisomerization conditions in the isomerization zone.

  In another embodiment, the oil of lubricating viscosity is a Group IV base stock as defined in API Publication 1509, 16th Edition, Appendix I, October 2009. Group IV base stocks, or polyalphaolefins (PAO), are typically made by oligomerizing low molecular weight alpha olefins, such as alpha olefins containing at least 6 carbon atoms. In one embodiment, the alpha olefin is an alpha olefin containing 10 carbon atoms. PAO is a mixture of dimers, trimers, tetramers, etc., and is accurately mixed depending on the desired final basestock viscosity. PAO is typically hydrogenated after oligomerization to remove residual unsaturation.

  As noted above, marine cylinder lubricants for use in marine diesel engines typically have a kinematic viscosity in the range of 9.3 to 26.1 cSt at 100 ° C. To formulate such lubricants, bright stock can be combined with low viscosity oils, such as oils having a viscosity of 4 to 6 cSt at 100 ° C. However, since the supply of bright stock is gradually decreasing, it is not possible to rely on bright stock to increase the viscosity of marine cylinder lubricants to the desired range recommended by the manufacturer. One solution to this problem is to use thickening agents such as polyisobutylene (PIB) or viscosity index improvers such as olefin copolymers to increase the viscosity of marine cylinder lubricants. PIB is a material that is commercially available from several manufacturers. PIB typically has a weight average molecular weight in the range of about 1,000 to about 8,000, or about 1,500 to about 6,000, and about 2,000 to about 5,000 or about 6,000 cSt. A viscous oil-miscible liquid having a viscosity in the range of (100 ° C.). The amount of PIB added to the marine cylinder lubricant is typically about 1 to about 20% by weight of the final oil, or about 2 to about 15% by weight of the final oil, or about the final oil. It will be from 4 to about 12% by weight.

  In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention includes one or more polyalkenyl bissuccinimide dispersants, wherein the polyalkenyl substituent has a number average molecular weight of about 1500 to about 3000. Further included are dispersants derived from polyalkene groups. In general, bissuccinimide is a completed reaction product from a reaction between a polyalkenyl-substituted succinic acid or anhydride and one or more polyamine reactants, the product of which is a primary amino group and an anhydride. In addition to imide linkages of the type obtained from reaction with product moieties, it is intended to encompass compounds that may have amide, amidine, and / or salt linkages. Bissuccinimide dispersants are prepared according to methods well known in the art, for example certain basic types of succinimides and related substances encompassed by the term “succinimide” in the art are described, for example, in US Pat. , 992,708; 3,018,291; 3,024,237; 3,100,673; 3,219,666; 3,172,892; and 3, No. 272,746, the contents of which are incorporated herein by reference.

In one embodiment, one or more polyalkenyl bissuccinimide dispersants can be obtained by reacting a polyalkenyl substituted succinic anhydride of formula I with a polyamine.

Wherein R is a polyalkenyl substituent derived from a polyalkene group having a number average molecular weight of about 1500 to about 3000. In one embodiment, R is a polyalkenyl substituent derived from a polyalkene group having a number average molecular weight of about 1500 to about 2500. In one embodiment, R is a polybutenyl substituent derived from a polybutene having a number average molecular weight of about 1500 to about 3000. In another embodiment, R is a polybutenyl substituent derived from a polybutene having a number average molecular weight of about 1500 to about 2500.

  The preparation of polyalkenyl substituted succinic anhydrides by reaction of polyolefins with maleic anhydride is described, for example, in US Pat. Nos. 3,018,250 and 3,024,195. Such methods include the thermal reaction of polyolefins with maleic anhydride and the reaction of halogenated polyolefins such as chlorinated polyolefins with maleic anhydride. Reduction of the polyalkenyl-substituted succinic anhydride provides the corresponding alkyl derivative. Alternatively, polyalkenyl substituted succinic anhydrides can be prepared, for example, as described in US Pat. Nos. 4,388,471 and 4,450,281, the contents of which are hereby incorporated by reference. Incorporated into.

  Advantageously, the size of the polyalkenyl substituent is derived from a polyalkene group having a number average molecular weight of about 1500 to about 3000. In one embodiment, the size of the polyalkenyl substituent is advantageously derived from a polyalkene group having a number average molecular weight of about 1500 to about 2500. In another embodiment, the size of the polyalkenyl substituent is advantageously derived from a polyalkene group having a number average molecular weight of about 2300.

Polyalkene groups having a number average molecular weight of about 1500 to about 3000 for reaction with maleic anhydride and the like and succinic anhydride are predominant amounts of C ₂ to C ₅ monoolefins such as ethylene, propylene, butylene, isobutylene and pentene. It is a polymer containing. The polymer can be a copolymer of two or more such olefins, such as homopolymers such as polyisobutylene, and copolymers of ethylene and propylene, butylene and isobutylene. Other copolymers include small amounts (eg 1 to 20 mole percent) of copolymer monomers such as C ₄ to C ₈ non-conjugated diolefins such as copolymers of isobutylene and butadiene or copolymers of ethylene, propylene and 1,4-hexadiene, etc. Is included.

  A particularly preferred class of polyalkene groups having a number average molecular weight of about 1500 to about 3000 includes polybutenes prepared by the polymerization of one or more of 1-butene, 2-butene and isobutene. Polybutene containing a substantial proportion of units derived from isobutene is particularly desirable. The polybutene can contain a small amount of butadiene, which may or may not be bound in the polymer. In most cases, the isobutene units comprise about 80%, or at least about 90% of the units in the polymer. These polybutenes are readily available commercial materials well known to those skilled in the art, for example, U.S. Pat. Nos. 3,215,707; 3,231,587; 3,515,669; Nos. 3,579,450 and 3,912,764, the contents of which are incorporated herein by reference.

Suitable polyamines for use in preparing non-borated bissuccinimide dispersants include polyalkylene polyamines. Such polyalkylene polyamines typically contain about 2 to about 12 nitrogen atoms and about 2 to 24 carbon atoms. Particularly preferred polyalkylene polyamines are those of the formula: H ₂ N— (R ¹ NH) _c H, where R ¹ is a linear or branched alkylene group having 2 or 3 carbon atoms, and c is 1 to 9). Representative examples of suitable polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, and mixtures thereof. Most preferably, the polyalkylene polyamine is tetraethylenepentamine.

  Examples of suitable polyamines include tetraethylenepentamine, pentaethylenehexamine, and heavy polyamine (eg, Dow HPA-X number average molecular weight 275 available from Dow Chemical Company, Midland, Mich.). . Such amines include isomers such as the above mentioned substituted polyamines, including branched chain polyamines and hydrocarbyl substituted polyamines. HPA-X heavy polyamine ("HPA-X") contains an average of about 6.5 amine nitrogen atoms per molecule. Such heavy polyamines generally provide excellent results.

  Generally, the polyalkenyl-substituted succinic anhydride of formula I reacts with the polyamine at a temperature of about 130 ° C to about 220 ° C, preferably about 145 ° C to about 175 ° C. This reaction can be carried out under an inert atmosphere such as nitrogen or argon. The amount of Formula I anhydride utilized in this reaction can range from about 30 to about 95% by weight, preferably from about 40 to about 60% by weight, based on the total weight of the reaction mixture.

  Generally, one or more polyalkenyl bis succinimide dispersants in marine diesel cylinder lubricating oil compositions of the present invention, wherein the polyalkenyl substituent has a number average molecular weight of about 1500 to about 3000. The concentration of the dispersant derived from is, based on the total weight of the marine diesel cylinder lubricating oil composition, based on the active material, greater than about 0.25 wt%, or greater than about 0.5 wt%, or about More than 1.0 wt%, or more than about 1.2 wt%, or more than about 1.5 wt%, or more than about 1.8 wt%, or more than about 2.0 wt%, or about 2.5 wt% Or greater than about 2.8% by weight. In another embodiment, one or more non-borated polyalkenyl bissuccinimide dispersant present in the marine diesel cylinder lubricating oil composition of the present invention, wherein the polyalkenyl substituent is from about 1500 to about 3000. The amount of dispersant, derived from polyalkene groups having a number average molecular weight, is about 0.25 to 10% by weight, based on the active material, or about 0, based on the total weight of the marine diesel cylinder lubricating oil composition. .25 to 8.0 wt%, or about 0.25 to 5.0 wt%, or about 0.25 to 4.0 wt%, or 0.25 to 3.0 wt%, or about 0.5 10 wt%, or about 0.5 to 8.0 wt%, or about 0.5 to 5.0 wt%, or about 0.5 to 4.0 wt%, or about 0.5 to 3.0 wt% %, Or about 0.5 to 10% by weight, or 0.5 to 8.0 wt%, or about 1.0 to 5.0 wt%, or about 1.0 to 4.0 wt%, or about 1.0 to 3.0 wt%, or about 1. 5 to 10 wt%, or about 1.5 to 8.0 wt%, or about 1.5 to 5.0 wt%, or about 1.5 to 4.0 wt%, or about 1.5 to 3. 0 wt%, or about 2.0 to 10 wt%, or about 2.0 to 8.0 wt%, or about 2.0 to 5.0 wt%, or about 2.0 to 4.0 wt% It can be a range.

  In another embodiment, the marine diesel cylinder lubricating oil composition of the present invention further comprises a cyclic carbonate post-treated polyalkenyl bissuccinimide dispersant. The polyalkenyl bissuccinimide dispersant of this embodiment can be prepared as described above, i.e. by reaction of a polyalkenyl-substituted succinic anhydride with a polyamine.

  In this embodiment, the polyalkenyl-substituted succinic anhydride can be a polyalkenyl-substituted succinic anhydride when the polyalkenyl substituent is derived from a polyalkene having a number average molecular weight of about 500 to about 5000. In another embodiment, the polyalkenyl-substituted succinic anhydride according to this embodiment is a polyalkenyl-substituted succinic anhydride when the polyalkenyl substituent is derived from a polyalkene having a number average molecular weight of about 700 to about 3000. be able to. In another embodiment, the polyalkenyl-substituted succinic anhydride according to this embodiment is a polyalkenyl-substituted succinic anhydride when the polyalkenyl substituent is derived from a polyalkene having a number average molecular weight of about 1000 to about 3000. be able to. In another embodiment, the polyalkenyl-substituted succinic anhydride according to this embodiment is a polyalkenyl-substituted succinic anhydride when the polyalkenyl substituent is derived from a polyalkene having a number average molecular weight of about 1300 to about 2500 be able to. In another embodiment, the polyalkenyl-substituted succinic anhydride according to this embodiment is a polyalkenyl-substituted succinic anhydride when the polyalkenyl substituent is derived from a polyalkene having a number average molecular weight of about 1000 to about 2500 be able to. In another embodiment, the polyalkenyl substituted succinic anhydride according to this embodiment is a polyalkenyl substituted succinic anhydride when the polyalkenyl substituent is derived from a polyalkene having a number average molecular weight of about 1500 to about 2500. be able to. In another embodiment, the polyalkenyl-substituted succinic anhydride according to this embodiment is a polyalkenyl-substituted succinic anhydride when the polyalkenyl substituent is derived from a polyalkene having a number average molecular weight of about 2000 to about 2500 be able to.

The polyalkenyl bis succinimide dispersant of this embodiment is post-treated with a cyclic carbonate to form a cyclic carbonate post-treated polyalkenyl bis succinimide dispersant. Cyclic carbonates suitable for use in the present invention include, but are not limited to, 1,3-dioxolan-2-one (ethylene carbonate); 4-methyl-1,3-dioxolan-2-one (propylene carbonate). 4-hydroxymethyl-1,3-dioxolan-2-one: 4,5-dimethyl-1,3-dioxolan-2-one; 4-ethyl-1,3-dioxolan-2-one (butylene carbonate) Etc. are included. Other suitable cyclic carbonates may be prepared from saccharides such as sorbitol, glucose, fructose, galactose, and vicinal diols prepared from C ₁ to C ₃₀ olefins by methods known in the art. it can.

  The polyalkenyl bissuccinimide dispersant can be post-treated with cyclic carbonates according to methods well known in the art. For example, a cyclic carbonate post-treated polyalkenyl bis succinimide dispersant may be charged with a bis succinimide dispersant charged to the reactor, optionally under a nitrogen purge, and heated at a temperature of about 80 ° C to about 170 ° C. It can be prepared by a method involving. Optionally, the diluent oil can be charged to the same reactor under a nitrogen purge. Cyclic carbonate is charged to the reactor, optionally under a nitrogen purge. The mixture is heated to a temperature in the range of about 130 ° C. to about 200 ° C. under a nitrogen purge. Optionally, the reaction mixture is evacuated for about 0.5 to about 2.0 hours to remove water formed in the reaction.

  In order to provide an auxiliary function, the marine diesel cylinder lubricating oil composition of the present invention may also contain additives of conventional marine diesel cylinder lubricating oil compositions other than the dispersants described above, and these additions A marine diesel cylinder lubricating oil composition in which the agent is dispersed or dissolved can be obtained. For example, marine diesel cylinder lubricating oil compositions include antioxidants, detergents, antiwear agents, rust inhibitors, defogging agents, demulsifiers, metal deactivators, friction modifiers, pour point depressants, It can be blended with foaming agents, co-solvents, corrosion inhibitors, dyes, extreme pressure agents and the like and mixtures thereof. A variety of additives are known and commercially available. These additives can be utilized in preparing the marine diesel cylinder lubricating oil composition of the present invention by conventional blending procedures.

In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention is essentially free of thickeners (ie, viscosity index improvers).
The marine diesel cylinder lubricating oil composition of the present invention can contain one or more antioxidants that can reduce or prevent oxidation of the base oil. Any antioxidant known to those skilled in the art can be used in the lubricating oil composition. Non-limiting examples of suitable antioxidants include amine-based antioxidants (eg, alkyl diphenylamines such as bisnonylated diphenylamine, bisoctylated diphenylamine, and octylated / butylated diphenylamine, phenyl-α-naphthylamine, alkyl or Arylalkyl-substituted phenyl-α-naphthylamine, alkylated p-phenylenediamine, tetramethyldiaminodiphenylamine, etc.), phenolic antioxidants (eg, 2-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol) 2,4,6-tri-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol), phosphorus antioxidants (for example, phosphorous acid) Salt), dithio Zinc phosphate and combinations thereof are included.

The amount of antioxidant is from about 0.01% to about 10%, from about 0.05% to about 5%, or from about 0.00% by weight based on the total weight of the marine diesel cylinder lubricating oil composition. 1% to about 3% by weight.
In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention is essentially free of ashless sulfur-containing compounds.
In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention is essentially free of phenolic antioxidant compounds.

  The marine diesel cylinder lubricating oil composition of the present invention can contain one or more detergents. Metal-containing detergents or ash-forming detergents function both as detergents that reduce or remove deposits, and acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. The detergent is generally composed of a polar head with a long hydrophobic tail. The polar head is composed of a metal salt of an acidic organic compound. The salt can contain a substantially stoichiometric amount of metal, in which case they are usually described as normal or neutral salts. Large amounts of metal bases can be combined by reacting excess metal compounds (eg, oxides or hydroxides) with acidic gases (eg, carbon dioxide).

  Detergents that can be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphones of metals such as alkali or alkaline earth metals such as barium, sodium, potassium, lithium, calcium and magnesium. Nartes, salicylates and naphthenates and other oil-soluble carboxylates are included. The most commonly used metals are calcium and magnesium (both of which can be present in the detergent used in the lubricant) and mixtures that are calcium and / or magnesium and sodium.

Commercial products are commonly referred to as neutral or overbased. Overbased metal detergents are generally hydrocarbons, detergent acids, eg: sulfonic acids, carboxylates, etc., metal oxides or hydroxides (eg calcium oxide or calcium hydroxide) and accelerators It is produced by carbonated a mixture of agents such as xylene, methanol and water. For example, in carbonation, to prepare an overbased calcium sulfonate, calcium oxide or calcium hydroxide is reacted with gaseous carbon dioxide to form calcium carbonate. The sulfonic acid is neutralized with excess CaO or Ca (OH) ₂ to form the sulfonate.

  Overbased detergents can be overbased salts with low overbasing, for example having less than 100 BN. In one embodiment, the BN of the low overbased salt can be from about 5 to about 50. In another embodiment, the BN of the low overbased salt can be from about 10 to about 30. In yet another embodiment, the BN of the low overbased salt can be from about 15 to about 20.

  The overbased detergent can be an overbased salt that is moderately overbased, for example having a BN of about 100 to about 250. In one embodiment, the BN of the medium overbased salt can be about 100 to about 200. In another embodiment, the BN of the medium overbased salt can be from about 125 to about 175.

  The overbased detergent can be an overbased salt that is highly overbased, for example having a BN greater than 250. In one embodiment, the BN of the highly overbased salt can be from about 250 to about 550.

  In one embodiment, the detergent can be one or more alkali metal or alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids. Suitable hydroxyaromatic compounds include mononuclear monohydroxy and polyhydroxy aromatic hydrocarbons having 1 to 4, preferably 1 to 3 hydroxyl groups. Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol and the like. A preferred hydroxyaromatic compound is phenol.

  The alkyl-substituted portion of the alkali metal salt or alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is derived from an alpha olefin having from about 10 to about 80 carbon atoms. The olefin used can be linear, isomerized linear, branched or partially branched linear. The olefin can be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a partially branched linear mixture, or any mixture thereof.

  In one embodiment, the mixture of linear olefins that can be used is a mixture of normal alpha olefins selected from olefins having from about 12 to about 30 carbon atoms per molecule. In one embodiment, the normal alpha olefin is isomerized using at least one of a solid catalyst or a liquid catalyst.

  In another embodiment, the olefin is a branched olefinic propylene oligomer or mixture thereof having from about 20 to about 80 carbon atoms, ie, a branched olefin derived from the polymerization of propylene. The olefin may be further substituted with other functional groups such as a hydroxy group, a carboxylic acid group, and a heteroatom. In one embodiment, the branched olefinic propylene oligomer or mixture thereof has about 20 to about 60 carbon atoms. In one embodiment, the branched olefinic propylene oligomer or mixture thereof has about 20 to about 40 carbon atoms.

In one embodiment, at least about an alkyl group contained in an alkali metal salt or alkaline earth metal salt of an alkyl substituted hydroxyaromatic carboxylic acid, such as an alkyl group of an alkaline earth metal salt of an alkyl substituted hydroxybenzoic acid detergent. 75 mole% (e.g., at least about 80 mole%, at least about 85 mole%, at least about 90 mole%, at least about 95 mole%, or at least about 99 mole%) _{is C 20} or greater. In another embodiment, the alkyl alkali metal or alkaline earth metal salt of substituted hydroxyaromatic carboxylic acids, alkyl group of at least 75 mole% to C ₂₀ or more normal alpha - residual olefin - normal alpha containing olefin Alkali metal salt or alkaline earth metal salt of alkyl-substituted hydroxybenzoic acid derived from the group alkyl-substituted hydroxybenzoic acid.

In another embodiment, an alkyl group contained in an alkali metal or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid, such as an alkyl group of an alkyl-substituted hydroxybenzoic acid or an alkaline earth metal salt. At least about 50 mol% (e.g., at least about 60 mol%, at least about 70 mol%, at least about 80 mol%, at least about 85 mol%, at least about 90 mol%, at least about 95 mol%, or at least about 99 mol) %) is from about _{C 14} to about _{C 18.}

  The resulting alkali metal salt or alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid will be a mixture of ortho and para isomers. In one embodiment, the product will contain about 1 to 99% ortho isomer and 99 to 1% para isomer. In another embodiment, the product will contain about 5 to 70% ortho isomer and 95 to 30% para isomer.

  Alkali metal salts or alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids can be neutral or overbased. In general, an overbased alkali metal salt or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is a base source of BN of an alkyl-substituted hydroxyaromatic carboxylic acid alkali metal salt or alkaline earth metal salt. (E.g. lime) and increased by processes such as addition of acidic overbased compounds (e.g. carbon dioxide).

  Sulfonates can typically be prepared from sulfonic acids obtained by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from petroleum fractions or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives. Alkylation can be performed using an alkylating agent having from about 3 to more than 70 carbon atoms in the presence of a catalyst. The alkaryl sulfonate typically contains from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms, per alkyl-substituted aromatic moiety.

  Oil soluble sulfonates or alkaryl sulfonic acids can be neutralized using metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and ethers. The amount of metal compound is selected in view of the desired TBN of the final product, but is typically about 100 to about 220% by weight (preferably at least about 125%) of the stoichiometrically required amount. % By weight).

  In one embodiment, the highly overbased sulfonate detergent provides 50% or less of the total composition TBN. In other embodiments, the highly overbased sulfonate detergent provides no more than 40 percent, 30 percent, 25 percent, 10 percent, or 5 percent of the total composition TBN. In still other embodiments, the composition of the present invention is such that the highly overbased sulfonate detergent provides no more than 0.5% of the total composition TBN, or even 0% of the total composition TBN. It is substantially free of highly overbased sulfonates.

  Sulfuric phenate detergents, phenols and metal salts of sulfurized phenols, are prepared by reaction with suitable metal compounds, such as oxides or hydroxides, and neutral or overbased products are well known in the art. It can be obtained by the method. Sulfurized phenols are prepared by reacting phenol with sulfur or a sulfur-containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, and generally two or more phenols are crosslinked by sulfur-containing crosslinking. A product can be formed which is a mixture of the compounds.

  Further details regarding the general preparation of sulfurized phenates can be found, for example, in US Pat. Nos. 2,680,096; 3,178,368 and 3,801,507, the contents of which are Which is incorporated herein by reference.

  Next, considering in detail the reactants and reagents used in the method of the present invention, all the allotropic forms of sulfur can be used first. Sulfur can be used either as molten sulfur or as a solid (eg, powder or particulate) or as a solid suspension in a compatible hydrocarbon liquid.

  The use of calcium hydroxide as a calcium base is desirable, for example, because of its convenience in handling compared to calcium oxide and also because it provides excellent results. Other calcium bases such as calcium alkoxides can also be used.

Suitable alkylphenols that can be used are those in which the alkyl substituent contains a sufficient number of carbon atoms to impart oil solubility to the resulting overbased calcium sulfide alkyl phenate composition. Oil solubility can be provided by a single long chain alkyl substituent or by a combination of alkyl substituents. Typically, alkyl phenols used in the method of the present invention are different alkylphenols such mixtures to C ₂₄ alkyl phenol from C _20. If a phenate product having a TBN of 275 or less is desired, it is economically advantageous to use 100% polypropenyl substituted phenol because of its commercial availability and generally lower cost. If a higher TBN phenate product is desired, about 25 to about 100 mole percent alkylphenol can have a linear alkyl substituent of about 15 to about 35 carbon atoms, and about 75 to about 0. For mole percent, the alkyl group can be a polypropenyl of 9 to 18 carbon atoms. In one embodiment, for about 35 to 100 mole percent alkylphenol, the alkyl group is linear alkyl of about 15 to about 35 carbon atoms, and for about 65 to 0 mole percent alkylphenol, the alkyl group is about A polypropenyl of 9 to about 18 carbon atoms. The use of predominantly linear alkylphenols generally results in high TBN products characterized by lower viscosities. On the other hand, polypropenyl phenols are generally more economical than linear alkyl phenols, but use more than about 75 mole percent of polypropenyl phenols in the preparation of calcium overbased sulfurized alkyl phenate compositions. This generally results in an undesirably high viscosity product. However, it is acceptable to use a mixture of up to about 75 mole percent polypropenyl phenol of about 9 to about 18 carbon atoms and about 15 to about 35 predominantly linear alkylphenol of about 25 mole percent or more. A more economical product with a good viscosity can be obtained. In one embodiment, suitable alkylphenol compounds include distilled cashew nut shell liquid or hydrogenated distilled cashew nut shell liquid. Distilled CNSL is a mixture of biodegradable meta-hydrocarbyl substituted phenols containing cardanol and the hydrocarbyl group being linear and unsaturated. Catalytic hydrogenation of distilled CNSL provides a mixture of meta-hydrocarbyl substituted phenols enriched primarily in 3-pentadecylphenol.

  The alkylphenol can be a para-alkylphenol, a meta-alkylphenol or an orthoalkylphenol. Since p-alkylphenols are believed to facilitate the preparation of highly overbased calcium sulfurized alkylphenates, when overbasing products are desired, the alkylphenols are primarily paraalkylphenols, preferably orthoalkylphenols are about 45 mole percent or less, more preferably, the orthoalkylphenol is about 35 mole percent or less of the alkylphenol. Alkyl-hydroxytoluene or xylene and other alkylphenols having one or more alkyl substituents in addition to at least one long chain alkyl substituent can also be used. In the case of distilled cashew nut shell liquid, catalytic hydrogenation of distilled CNSL provides a mixture of meta-hydrocarbyl substituted phenols.

  In general, the choice of alkylphenol can be based on desirable properties for marine diesel engine lubricating oil compositions, particularly TBN and oil solubility. For example, in the case of an alkyl phenate having a substantially linear alkyl substituent, the viscosity of the alkyl phenate composition is affected by the position of the bond in the alkyl chain to the phenyl ring, for example, a terminal bond versus an intermediate bond. obtain. Further information on this and the selection and preparation of suitable alkylphenols can be found, for example, in US Pat. Nos. 5,024,773; 5,320,763; 5,318,710; and 5,972,972. Each of which is incorporated herein by reference.

  Generally, the amount of detergent is from about 0.001% to about 50% by weight, or from about 0.05% to about 25% by weight, based on the total weight of the marine diesel cylinder lubricating oil composition. Or from about 0.1% to about 20%, or from about 0.01% to about 15% by weight.

The marine diesel cylinder lubricating oil composition of the present invention can contain one or more friction modifiers that can reduce friction between moving parts. Any friction modifier known to those skilled in the art can be used in marine diesel cylinder lubricating oil compositions. Non-limiting examples of suitable friction modifiers include: fatty carboxylic acids; derivatives of aliphatic carboxylic acids (eg, alcohols, esters, borated esters, amides, metal salts, etc.); mono-, di- -Or tri-alkyl substituted phosphoric acid or phosphonic acid; mono-, di- or tri-alkyl substituted phosphoric acid or phosphonic acid derivatives (eg esters, amides, metal salts etc.); mono-, di- or tri-alkyl Substituted amines; mono- or di-alkyl substituted amides and combinations thereof are included. In some embodiments, examples of friction modifiers include, but are not limited to, alkoxylated aliphatic amines; borated aliphatic epoxides; aliphatic phosphites, aliphatic epoxides, aliphatic amines, borated alkoxylated fats. Aliphatic amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters; and aliphatic imidazolines, which are disclosed in US Pat. No. 6,372,696, the contents of which are hereby incorporated by reference. A nitrogen-containing compound selected from the group consisting of C ₄ to C ₇₅ , C ₆ to C ₂₄ , or C ₆ to C ₂₀ fatty acid esters, ammonia and alkanolamines, and the like, and mixtures thereof. A friction modifier obtained from the reaction product of

  The marine diesel cylinder lubricating oil composition of the present invention can contain one or more antiwear agents that can reduce friction and excessive wear. Antiwear agents known to those skilled in the art can be used in the lubricating oil composition. Non-limiting examples of suitable antiwear agents include zinc dithiophosphate, metal dithiophosphate (eg, Pb, Sb, Mo, etc.), metal dithiocarbamate (eg, Zn, Pb, Sb, Mo, etc.) Salt, fatty acid metal (eg Zn, Pb, Sb etc.) salt, boron compound, phosphate ester, phosphite ester, phosphate salt or amine salt of thiophosphate ester, reaction product of dicyclopentadiene and thiophosphate And combinations thereof.

  In certain embodiments, the antiwear agent is or includes a dihydrocarbyl dithiophosphate metal salt, such as, for example, a zinc dialkyldithiophosphate compound. The metal of the dihydrocarbyl dithiophosphate metal salt can be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate metal salt has about 3 to about 22 carbon atoms, about 3 to about 18 carbon atoms, about 3 to about 12 carbon atoms, or about 3 To about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

  The amount of dihydrocarbyl dithiophosphate metal salt, including zinc dialkyldithiophosphate, in the lubricating oil composition disclosed herein is measured by its phosphorus content. In some embodiments, the phosphorus content of the lubricating oil compositions disclosed herein is from about 0.01% to about 0.14% by weight, based on the total weight of the lubricating oil composition.

  The marine diesel cylinder lubricating oil composition of the present invention may contain one or more foam inhibitors or anti-foam inhibitors capable of breaking bubbles in the oil. . Antifoaming agents or antifoaming agents known to those skilled in the art can be used in marine diesel cylinder lubricating oil compositions. Non-limiting examples of suitable foam suppressors or antifoaming agents include silicone oil or polydimethylsiloxane, fluorosilicone, alkoxylated fatty acid, polyether (eg, polyethylene glycol), branched polyvinyl ether, alkyl acrylate Polymers, alkyl methacrylate polymers, polyalkoxyamines and combinations thereof are included.

  The marine diesel cylinder lubricating oil composition of the present invention may contain one or more pour point depressants that can lower the pour point of the marine diesel cylinder lubricating oil composition. Any pour point depressant known to those skilled in the art can be used in marine diesel cylinder lubricating oil compositions. Non-limiting examples of suitable pour point depressants include polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, di (tetra-paraffin phenol) phthalates, condensates of tetraparaffin phenols, chlorinated paraffins and naphthalenes. And their condensates and combinations thereof. In some embodiments, pour point depressants include ethylene-vinyl acetate copolymers, condensates of chlorinated paraffins and phenols, polyalkylstyrenes, and the like.

  In another embodiment, the marine diesel cylinder lubricating oil composition of the present invention includes one or more demulsifiers that can facilitate oil-water separation in lubricating oil compositions exposed to water or steam. It can be included. Any demulsifier known to those skilled in the art can be used in the marine diesel cylinder lubricating oil composition. Non-limiting examples of suitable demulsifiers include anionic surfactants (eg, alkylnaphthalene sulfonates, alkylbenzene sulfonates, etc.), nonionic alkoxylated alkylphenol resins, polymers of alkylene oxides (eg, polyethylene oxide, polypropylene oxide). , Block copolymers such as ethylene oxide, propylene oxide), esters of oil-soluble acids, polyoxyethylene sorbitan esters and combinations thereof.

  The marine diesel cylinder lubricating oil composition of the present invention can contain one or more corrosion inhibitors capable of reducing corrosion. Any corrosion inhibitor known to those skilled in the art can be used in marine diesel cylinder lubricating oil compositions. Non-limiting examples of suitable corrosion inhibitors include dodecyl succinic acid half-esters or amides, phosphate esters, thiophosphates, alkyl imidazolines, sarcosine and combinations thereof.

  The marine diesel cylinder lubricating oil composition of the present invention may contain one or more extreme pressure (EP) agents that can prevent the sliding metal surface from seizing under extreme pressure conditions. Any extreme pressure agent known to those skilled in the art can be used in marine diesel cylinder lubricating oil compositions. Generally, an extreme pressure agent is a compound that can form a surface film that chemically bonds to a metal and prevents welding of concavities and convexities on the opposing metal surface under high load. Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable oils, sulfurized animal or vegetable fatty acid esters, phosphorus trivalent or pentavalent acids, wholly or partially Esterified esters, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, dicyclopentadiene sulfides, sulfurized or cosulfided mixtures of fatty acid esters and monounsaturated olefins, cosulfurized blends of fatty acids, fatty acid esters and alpha olefins Functional group-substituted dihydrocarbyl polysulfides, thio (thia) aldehydes, thio (thia) ketones, epithio compounds, sulfur-containing acetal derivatives, cosulfurized blends of terpenes and acyclic olefins, and polysulfide olefin products, phosphate esters or thiophosphorus Amine salts of acid esters Combinations thereof.

  The marine diesel cylinder lubricating oil composition of the present invention can contain one or more rust preventives capable of suppressing corrosion of the iron metal surface. Any rust inhibitor known to those skilled in the art can be used in the marine diesel cylinder lubricating oil composition. Non-limiting examples of suitable rust inhibitors include nonionic polyoxyalkylene agents such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether. , Polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate; stearic acid and other fatty acids; dicarboxylic acids; metal soaps; Fatty acid amine salts; metal salts of heavy sulfonic acids; partial carboxylic acid esters of polyhydric alcohols; phosphate esters; (short chain) alkenyl succinic acids; their partial esters and their Nitrogen-containing derivatives, synthetic alkaryl sulphonate, e.g., dinonyl naphthalene sulfonic acid metal salts; includes such well as mixtures thereof.

  The marine diesel cylinder lubricating oil composition of the present invention may contain one or more multifunctional additives. Non-limiting examples of suitable multifunctional additives include sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum organic phosphorodithioate, oxymolybdenum monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum complex, and sulfur. Containing molybdenum complex compounds.

  The following examples are intended for illustrative purposes only and are in no way intended to limit the scope of the present disclosure.

DSC Oxidation Test The DSC oxidation test is used to evaluate the thin film oxidation stability of the test oil according to ASTM D-6186. The heat flow to and from the test oil in the sample cup is compared to the reference cup during the test. The oxidation start temperature is a temperature at which the test oil starts to be oxidized. The oxidation induction time is the time when the test oil starts to oxidize. Longer oxidation induction times mean better properties. The oxidation reaction becomes an exothermic reaction clearly indicated by the heat flow. The oxidation induction time is calculated to evaluate the thin film oxidation stability of the test oil.

Example 1 and Comparative Example A
Example 1 and Comparative Example A were completed with 25 BN, SAE 50 viscosity grade containing major amounts of ESSO 600 N Group I base oil, ESSO 2500 bright stock, sulfur-free aromatic amine, antifoam and additional additives as shown in Table 1. Formulated in a marine cylinder lubricating oil composition. The sulfur-free aromatic amine used in the examples was nonyl substituted diphenylamine. This additive containing 3.5 wt% nitrogen had a TBN of about 135 mg KOH / g and no diluent oil. The test oil was evaluated using the DSC oxidation test. The results are listed in Table 1 below.

As is apparent from the results shown in Table 1, the marine cylinder lubricating oil composition of Example 1 has a sulfur-free aromatic amine contribution to the TBN of TLB of the lubricating oil composition of more than about 30%. Compared to Comparative Example A, which has a higher BN contribution from conventional high overbased sulfonate detergents, it shows surprisingly good thin film oxidative stability of the test oil, which generally indicates longer oxidation It is clear from the induction time. A cylinder oil that is not bulk fluid but has high oxidative stability in the thin film state shows a lower viscosity increase, higher spreadability, and higher anti-scuffing performance.

Claims (15)

A marine diesel cylinder lubricating oil composition comprising:
A marine diesel cylinder lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity, and (b) a sulfur-free aromatic amine, wherein the marine diesel cylinder lubricating oil composition has a total base number (TBN) of about 5 to about 100 mg KOH / g. And further wherein the contribution of the sulfur-free aromatic amine to the TBN of the marine diesel cylinder lubricant composition is greater than about 30%.   The marine diesel cylinder lubricating oil composition of claim 1, wherein the sulfur-free aromatic amine is selected from diphenylamine, N-phenylnaphthylamine, dinaphthylamine, or phenylenediamine.   The marine diesel cylinder lubricating oil composition of claim 1, wherein the sulfur-free aromatic amine consists essentially of diphenylamine.   The diphenylamine is diphenylamine, N-methyldiphenylamine, 4-butyldiphenylamine, 4,4'-dibutyldiphenylamine, 4-hexyldiphenylamine, 4,4'-dihexyldiphenylamine, 4-heptyldiphenylamine, 4,4'-diheptyldiphenylamine 4-octyldiphenylamine, 4,4'-dioctyldiphenylamine, 4-nonyldiphenylamine, 4,4'-dinonyldiphenylamine, or 4-tetradecyldiphenylamine, 4,4'-ditetradecyldiphenylamine, p, p'- The marine vessel according to claim 3, selected from di-α-methylbenzyl-diphenylamine, Np-butylphenyl-Np'-octylphenylamine, or bis (dialkylphenyl) amine. Over diesel cylinder lubricating oil composition.   The sulfur-free aromatic amine is alkylphenyl-1-naphthylamine, octylphenyl-1-naphthylamine, N-4-dodecylphenyl-1-naphthylamine, 1-naphthylamine, arylnaphthylamine, phenyl-1-naphthylamine, phenyl-2 -Naphthylamine, N-hexylphenyl-2-naphthylamine, N-octylphenyl-2-naphthylamine, phenylenediamine, N, N'-diisopropyl-p-phenylenediamine, or N, N'-diphenyl-p-phenylenediamine The marine diesel cylinder lubricating oil composition according to claim 1.   The contribution of the sulfur-free aromatic amine to the TBN of the marine diesel cylinder lubricant composition is greater than about 32%, greater than about 34%, greater than about 36%, greater than about 38%, greater than about 40%, about 40%, > 42%,> 44%,> 46%,> 48%,> 50%,> 52%,> 54%,> 56%,> 58%,> 60%, More than 62%, more than about 64%, more than about 66%, more than about 68%, more than about 70%, more than about 72%, more than about 74%, more than about 76%, more than about 78%, more than about 80%, about The marine diesel cylinder lubricating oil composition of claim 1, wherein it is greater than 82%, greater than about 84%, greater than about 86%, greater than about 88%, or greater than about 90%.   The contribution of the sulfur-free aromatic amine to the TBN of the marine diesel cylinder lubricating oil composition is about 95% or less, about 90% or less, about 85% or less, about 80% or less, about 75% or less, about 75% or less. The marine diesel cylinder lubricating oil composition of claim 1, wherein the composition is 70% or less, about 65% or less, about 60% or less, about 55% or less, or about 50% or less.   The contribution of the sulfur-free aromatic amine to the TBN of the marine diesel cylinder lubricating oil composition is between 30% and 95%, between 32% and 85%, between 34% and 75%. The marine diesel cylinder lubricating oil composition of claim 1, between 36% and 65%.   The marine diesel cylinder lubricating oil composition of claim 1, further comprising a detergent selected from alkyl-substituted hydroxyaromatic carboxylates or alkyl-substituted hydroxyaromatic compounds.   The sulfur-free aromatic amine has a total base number between 100 mg KOH / g and 600 mg KOH / g, between 100 mg KOH / g and 300 mg KOH, or between 120 mg KOH / g and 250 mg KOH / g. The marine diesel cylinder lubricating oil composition described in 1.   The marine diesel cylinder lubricating oil composition of claim 1, having the TBN between 5 and 70 mg KOH / g or between 5 and 40 mg KOH / g. A marine diesel cylinder lubricating oil composition comprising:
(A) a major amount of oil of lubricating viscosity; and (b) a marine diesel cylinder lubrication comprising a sulfur-free aromatic amine, the sulfur-free aromatic amine being substantially deficient in sulfur-free aromatic amines. The lubricating oil composition present in an amount sufficient to increase the oxidative stability of the marine diesel cylinder lubricating oil composition as measured by ASTM D-6186 as compared to an oil composition by at least 5%.   13. The marine diesel cylinder lubricating oil composition of claim 12, wherein the oxidative stability is increased by at least 7%, at least 9%, at least 11%, at least 13%, or at least 15%.   The marine diesel cylinder lubricating oil composition substantially lacking the sulfur-free aromatic amine is less than 0.5 wt%, less than 0.4 wt%, less than 0.3 wt%, or 0.2 wt% The marine diesel cylinder lubricating oil composition of claim 12, comprising a sulfur-free aromatic amine in an amount less than 13. The sulfur-free aromatic amine is alkylphenyl-1-naphthylamine, octylphenyl-1-naphthylamine, N-4-dodecylphenyl-1-naphthylamine, 1-naphthylamine, arylnaphthylamine, phenyl-1-naphthylamine, phenyl-2 -Naphthylamine, N-hexylphenyl-2-naphthylamine, N-octylphenyl-2-naphthylamine, phenylenediamine, N, N'-diisopropyl-p-phenylenediamine, or N, N'-diphenyl-p-phenylenediamine The marine diesel cylinder lubricating oil composition according to claim 12.