KR102517043B1 - Marine Diesel Cylinder Lubricant Composition - Google Patents

Abstract

A marine diesel cylinder lubricating oil composition includes a large amount of oil of lubricating viscosity. The lubricating oil composition further includes a non-sulfur containing aromatic amine. The marine diesel cylinder lubricating oil composition has a total number (TBN) of about 5 to about 100 mg KOH/g. In addition, the contribution of non-sulfur containing aromatic amines to TBN of marine diesel cylinder lubricating oil compositions is greater than about 30%.

Description

Marine Diesel Cylinder Lubricant Composition

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

Diesel engines can generally be classified as low speed, medium speed or high speed engines, with the low speed variants being used for maximum deep draft ships and certain other industrial applications such as power generation applications. The way it works is unique. The engine itself is huge, and the output of such an engine can reach as high as 100,000 brake horsepower with an engine speed of 60 to about 200 revolutions per minute. Low-speed diesel engines operate on a two-stroke cycle and include one or more stuffing boxes and a diaphragm that separates the power cylinder from the crankcase and mixes the crankcase oil to prevent combustion products from entering the crankcase. It is a direct-coupled direct-reversing engine of crosshead configuration, having a. Marine two-stroke diesel cylinder lubricants are designed to meet the harsh operating conditions required of more modern larger-bore two-stroke cross-head engines operating at high power, heavy loads and higher cylinder liner temperatures. performance requirements must be met. The complete separation of the crankcase from the combustion zone causes one skilled in the art to lubricate the combustion chamber and crankcase with different lubricating oils.

In large diesel engines of the crosshead type used in the marine sector, the cylinders are lubricated on a total loss basis by cylinder oil injected individually into each cylinder, often into a quill, by lubricators located around the cylinder liner. do. Oil is dispensed to the lubricator by a pump, which in modern engine designs is often operated to apply the oil directly to the rings to reduce oil wastage.

The typical use of sulfur-containing fuels for the operation of these engines creates a need for lubricants with high detergency and neutralizing abilities even when the oil is exposed to heat and other stresses for short periods of time. Residual fuels commonly used in these engines contain significant amounts of sulfur, which, in the course of combustion, combines with water to form sulfuric acid, the presence of which causes corrosive wear. In particular, in the case of marine two-stroke engines, the area around the cylinder liner and piston ring can be corroded and worn by acid. Therefore, it is important for diesel engine lubricating oils to 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 burned sulfur-containing fuel. This neutralization is typically achieved by incorporation into marine diesel cylinder lubricants of basic species such as overbased metallic detergents. The neutralizing ability of an oil is characterized by its basicity and is measured by its Total Base Number (TBN).

Recently, due to health and environmental concerns, there are currently regulations in certain fields mandating the use of low sulfur fuels for the operation of marine diesel engines. As a result, manufacturers now use gaseous fuels (compressed natural gas or liquefied natural gas (LNG)), high-quality distillate fuels with low sulfur and low asphaltenes to lower quality intermediates, or generally high sulfur and higher asphaltenes. Marine diesel engines are being designed for use with a variety of fuels, including heavy fuels such as marine residual fuels. For gaseous or distillate fuel operation, the fuel does not contain significant asphaltenes present in the fuel and contains much lower levels of sulfur. When more refined and lower sulfur fuel is burned, less acid is formed in the combustion chamber. Accordingly, the requirements for the lubricating oil used in the operation of engines using gaseous and low sulfur distillate fuels versus marine residual fuels can be very different.

TBN is a standard criterion that makes it possible to adjust the basicity of cylinder oil to the sulfur content of the fuel used, so that all sulfur contained in the fuel can be neutralized. Therefore, the higher the sulfur content of the fuel, the higher the TBN the marine lubricating oil should be. The reason is that lubricating oils with various TBNs from 5 to 150 mg KOH/g are found on the marine market. Typically in marine formulations, basicity is provided by an overbased detergent that is overbased using a metal carbonate. However, the excess of overbased detergent present in marine diesel cylinder lubricating oil poses a risk of destabilization of micelles of unused overbased detergent containing a significant excess of basic sites and insoluble metal salts. This destabilization results in the formation of deposits of insoluble metal salts that plate out on cylinder walls and other engine components when ash is formed. In the case of large multi-fuel marine engines, the quality of the engine exhaust is highly dependent on the fuel used. In order to comply with severe emission regulations in coastal waters, among other measures, SCR catalytic converters are used as marine engines for the reduction of nitrite gas. Engines containing excessive amounts of ash can result in ash deposits on the surface of the SCR catalyst and potentially block exhaust gas access to the catalyst surface, preventing the catalyst from functioning.

Optimization of cylinder lubrication of a low-speed two-stroke engine, therefore, then requires the selection of a lubricating oil with a TBN suitable for the fuel and operating conditions of the engine. This optimization reduces the flexibility of the engine's operation and requires a considerable degree of technical expertise during vessel operation in defining the conditions under which a switchover from one type of lubricant to another must be carried out. To simplify operation, it would therefore be desirable to have a single cylinder lubricant for a two-stroke marine engine that could accommodate variations in fuel type and fuel sulfur level.

The present invention relates to a marine diesel cylinder lubricant composition having a source of ashless base capable of ensuring good lubrication of the cylinders of a marine engine and accommodating the constraints of fluctuations in fuel type and fuel sulfur level. The invention also relates to the use of non-sulfur aromatic containing amines to provide basicity to lubricating oils while reducing and/or limiting adverse effects.

According to one embodiment of the invention, (a) a major amount of an oil of lubricating viscosity, and (b) containing non-sulfur having a total number of about 100 to 600 mg KOH/g A marine diesel cylinder lubricating oil composition comprising an aromatic amine is provided; wherein the marine diesel cylinder lubricating oil composition has a TBN of from about 5 to about 100; Also, the TBN contribution of the non-sulfur containing aromatic amine to the TBN of the lubricating oil composition is greater than about 30%.

According to a second embodiment of the present invention, (a) a quantity of oil of lubricating viscosity, (b) a non-sulfur containing aromatic amine having a general value of about 100 to 600 mg KOH/g, and (c) at least one A marine diesel cylinder lubricating oil comprising a polyalkenyl succinimide dispersant, wherein the polyalkenyl substituent is derived from a polyalkenyl group having a number average molecular weight of from about 1500 to about 3000; The marine diesel cylinder lubricating oil composition has a TBN of about 5 to about 100; Also, the TBN contribution of the non-sulfur containing aromatic amine to the TBN of the lubricating oil composition is greater than about 30%.

The present invention is based on the surprising discovery that the lubricating oil compositions of the present invention advantageously improve the oxidation, detergency and dispersibility performance of marine diesel cylinder lubricating oil compositions used in two-stroke crosshead marine diesel engines. Cylinder oils with high oxidation stability in thin film conditions rather than in bulk fluid will exhibit less viscosity increase and anti-scuffing performance. The present invention also relates to the use of a non-sulfur containing aromatic amine in an amount that provides a TBN contribution of greater than about 30% in a marine diesel cylinder lubricant, such use being based on the rate of reduction in basicity (dissipation rate of BN) as determined by ASTM D2896. ) and relatively little impact on sealing materials that can be used in engine lubrication systems or lubricant handling systems.
Further, the present invention provides a marine diesel cylinder lubricating oil composition comprising (a) a large amount of an oil of lubricating viscosity, and (b) a non-sulfur containing aromatic amine; wherein the non-sulfur containing aromatic amine increases the oxidative stability of the marine diesel cylinder lubricating oil composition as determined by ASTM D-6186 by at least 5% when compared to a marine diesel cylinder lubricating oil composition substantially devoid of non-sulfur containing aromatic amines. wherein the contribution of the non-sulfur containing aromatic amine to the TBN of a marine diesel cylinder lubricating oil composition having increased oxidative stability is greater than 30%, the TBN as determined by ASTM D2896, wherein any wherein the marine diesel cylinder lubricating oil composition is substantially devoid of non-sulfur containing aromatic amines, wherein the marine diesel cylinder lubricating oil composition comprises non-sulfur containing aromatic amines in an amount of less than 0.5% by weight.

In the present invention, non-sulfur containing aromatic amines are a substitute for ash containing overbased metallic detergents as a source of BN for lubricants. Accordingly, the present invention relates to a marine diesel cylinder lubricating oil composition comprising (a) a quantity of oil of lubricating viscosity, and (b) a non-sulfur containing aromatic amine having a general value of about 100 to 600 mg KOH/g; wherein the marine diesel cylinder lubricating oil composition has a TBN of from about 5 to about 100; Also, the TBN contribution of the non-sulfur containing aromatic amine to the TBN of the lubricating oil composition is greater than about 30%.

In one embodiment of the present invention, the TBN provided by the non-sulfur containing aromatic amine represents 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 present invention, a marine diesel cylinder lubricant is used for marine two-strokes operated using low sulfur fuel comprising less than 1.0 wt% sulfur, or less than 0.5 wt% sulfur, or less than 0.1 wt% sulfur. Used for engine lubrication.

According to one embodiment of the present invention, non-sulfur containing aromatic amine compounds are known as aminic antioxidants which are typically used in lower concentrations in marine diesel cylinder lubricants as the cylinders are lubricated on a total loss basis with cylinder oil. there is. Examples of conveniently aminic antioxidants include diarylamine, alkylated diphenylamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine (phenyl-β-naphthylamine) and alkylated α-naphthylamine.

In one particular embodiment, the aminic antioxidant is a straight-chain or branched dialkyldiphenylamine, such as p,p'-dinonyl-diphenylamine; p,p'-dioctyl-diphenylamine (p,p'-dioctyl-diphenylamine); p,p'-di-α-methylbenzyl-diphenylamine (p,p'-di-α-methylbenzyl-diphenylamine); N-p-butylphenyl-N-p'-octylphenylamine (N-p-butylphenyl-N-p'-octylphenylamine); monoalkyldiphenylamines such as mono-t-butyldiphenylamine and mono-octyldiphenylamine; bis(dialkylphenyl) amines such as di-(2,4-diethylphenyl)amine and di(2-ethyl-4- nonylphenyl)amine (di(2-ethyl-4-nonylphenyl)amine); Alkylphenyl-1-naphthylamines such as octylphenyl-1-naphthylamine and n-t-dodecylphenyl-1-naphthylamine 1-naphthylamine); 1-naphthylamine (1-naphthylamine); Arylnaphthylamines such as phenyl-1-naphthylamine, phenyl-2-naphthylamine, N-hexylphenyl-2-naphthylamine (N-hexylphenyl-2-naphthylamine) and N-octylphenyl-2-naphthylamine (N-octylphenyl-2-naphthylamine); phenylenediamine, such as N,N'-diisopropyl-p-phenylenediamine and N,N'-diphenyl-p-phenylene Diamine (N,N'-diphenyl-p-phenylenediamine) is included.

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

The non-sulfur containing aromatic amines of the present invention, on an active, oil free basis, typically contain about 100 to about 600 mg KOH/g, preferably about 100 to about 300 mg KOH/g, preferably about 100 to about 200 mg KOH/g, preferably about 120 to about 500 mg KOH/g, more preferably about 120 to about 300 mg KOH/g, more preferably about 120 to about 250 mg KOH/g, It will have a TBN as measured according to standard ASTM D-2896.

In a preferred embodiment, the at least one non-sulfur containing aromatic amine compound is present in an amount of at least 1.0%, at least 1.5%, at least 2.0%, at least 2.5% by weight, based on the total weight of the lubricating oil composition, based on active agent. 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 to 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 wt% , or about 2.0 to about 12.0%, 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. exists as

The lubricating oil composition of the present invention will include at least one non-metal containing additive. Non-metal containing additives will also be referred to as "ashless" because they will typically not produce any sulfated ash when the conditions of ASTM D 874 are applied.

As used herein, the term “marine diesel cylinder lubricant” or “marine diesel cylinder lubricant” should be understood to mean a lubricant used for lubricating the cylinders of low or medium speed two-stroke crosshead marine diesel engines. Marine diesel cylinder lubricant is supplied to the cylinder wall through multiple injection points. Marine diesel cylinder lubricants can provide a film between the cylinder liner and the piston rings and can keep partially burned fuel residues in suspension, thereby promoting engine cleanliness, and preventing acid formation (e.g., sulfur compounds in the fuel). formed by the combustion of

"Marine residual fuel" means at least 2.5% by weight (eg, at least 5% or at least 8%) by weight (relative to the total weight of the fuel), as defined in International Organization for Standardization (ISO) 10370. Carbon residues, substances combustible in large marine engines, having a viscosity greater than 14.0 cSt at 50°C, e.g., International Organization for Standardization specification ISO 8217:2005, "Petroleum products - Fuels (class F) - Refers to marine fuel residues as defined in "Specifications of marine fuels".

“Residual fuel” refers to fuel that meets the specifications for residual marine fuel set forth in the ISO 8217:2010 international standard. "Low sulfur marine fuel" is also a residual marine fuel described in the ISO 8217:2010 specification having no more than about 1.5% by weight, or even no more than about 0.5% by weight sulfur, based on the total weight of the fuel. Refers to fuels that meet the specifications of

"Distillate fuel" refers to a fuel that meets the specifications for distillate marine fuel set forth in the ISO 8217:2010 international standard. "Low sulfur distillate fuel" is also a distillate vessel described in the ISO 8217:2010 International Standard having less than about 0.1%, or even less than about 0.005% sulfur by weight, based on the total weight of the fuel. Refers to fuels that meet fuel specifications.

Low-sulphur gaseous fuels, such as liquid natural gas (LNG), are composed primarily of methane and the balance of other hydrocarbons. On the other hand, methane, the main component of LNG, is generally kept in a liquid state.

The term "Total Base Number" or "TBN" refers to the alkalinity level in an oil sample, which indicates the ability of a composition to continue neutralizing corrosive acids according to ASTM standard number D2896 or equivalent procedures. The test measures the change in electrical conductivity, and the result is expressed as mg·KOH/g (the number of equivalents of milligrams of KOH required to neutralize one gram of product). Thus, a high TBN indicates a strongly overbased product, resulting in more base retention to neutralize the acid.

The term "on an actives basis" refers to an additive material that is not a diluent oil or solvent.

The marine diesel cylinder lubricating oil composition of the present invention may 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 another embodiment, the marine diesel cylinder lubricating oil composition of the present disclosure has a TBN of from about 5 to about 100, or from about 5 to about 80, or from about 5 to about 70, or from about 5 to about 50, or from about 5 to about 40, or about 5 to about 30, or about 5 to 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 10 to about 40, or 10 to about 30, or about 10 to about 25, or about 15 to about 100, or about 15 to about 80, or about 15 to about 70, or about 15 to about 50, or about 15 to about 40, or 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.

Due to the low operating speeds and high loads in marine engines, high viscosity oils (SAE 40, 50 and 60) are typically required. The marine diesel cylinder lubricating oil composition of the present invention may have a kinematic viscosity at 100°C ranging 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. The dynamic viscosity of marine diesel cylinder lubricating oil compositions is measured by ASTM D445.

The marine diesel cylinder lubricating oil composition of the present invention may be prepared by any method known to those skilled in the art for preparing marine diesel cylinder lubricating oil compositions. The ingredients may be added in any order and in any manner. Any suitable mixing or dispersing equipment may be used for blending, mixing or solubilizing the ingredients. Blending, mixing, or solubilization may be performed using a blender, agitator, disperser, mixer, homogenizer, mill, or any other mixing or dispersing equipment known in the art. can be performed with

The marine diesel cylinder lubricating oil composition of the present invention contains a large amount of oil of lubricating viscosity. "Amount" means that the marine diesel cylinder lubricant composition is at least about 40%, or at least about 50%, or at least about 60%, and particularly at least about 60% by weight, based on the total weight of the marine diesel cylinder lubricant oil composition. 70% by weight of an oil of lubricating viscosity set forth below, as appropriate.

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

Suitable natural oils are mineral lubricating oils, such as liquid petroleum oils, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic type, 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 hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and interpolymerized olefins, such as polybutylene, polypropylene, propylene-isobutylene copolymers. isobutyle copolymer), chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene) (poly(1-decene) and the like and mixtures thereof; alkylbenzenes such as dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)- Benzene (di(2-ethylhexyl)-benzene), etc.; Polyphenyl, such as biphenyl, terphenyl, alkylated polyphenyl, etc.; Alkylated diphenyl ether ) and alkylated diphenyl sulfides and their derivatives, analogs and homologs, etc., but are not limited thereto.

Other synthetic lubricating oils include, but are not limited to, oils prepared by polymerizing olefins of less than 5 carbon atoms, such as ethylene, propylene, butylene, isobuphene, pentene, and mixtures thereof. Methods for preparing such polymeric oils are known to those skilled in the art. Additional synthetic hydrocarbon oils include liquid polymers of alpha olefins of suitable viscosity. Particularly useful synthetic hydrocarbon oils are hydrogenated liquid oligomers of C ₆ to C ₁₂ alpha olefins, such as, for example, 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. it is not going to be These oils include ethylene oxide or propylene oxide, alkyl and phenyl ethers of these polyoxyalkylene polymers (e.g., methyl polypropylene glycol ethers with an average molecular weight of 1,000, diphenyl ethers of polyethylene glycols with a molecular weight of 500 to 1000, 1,000 diethyl ether of polypropylene glycol having a molecular weight of from 1,500, etc.) or mono- and polycarboxylic acid esters thereof, such as, for example, acetic acid esters, mixed C ₃ -C ₈ fatty acid esters, or C of tetraethylene glycol ₁₃ is exemplified by oils produced through the polymerization of oxo acid diesters.

Another class of synthetic lubricants are dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid. (azelaic acid), suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, Alkyl malonic acid, alkenyl malonic acid and the like and various alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, esters with propylene glycol and the like, but are not limited thereto. 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 (dieicosyl sebacate), 2-ethylhexyl diester of linoleic acid dimer, react 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid It includes complex esters formed by

Oils of lubricating viscosity may be derived from natural, synthetic, unrefined, refined and rerefined oils, or mixtures of two or more of any of the types disclosed hereinabove. Crude oils are those obtained directly from natural or synthetic sources (eg, coal, shale, or tar sand bitumen) without further refining or processing. Examples of crude oils include, but are not limited to, shale oil obtained directly from a retorting operation, petroleum oil obtained directly from distillation, or ester oil obtained directly from an esterification process, each of which is It is then used without further treatment. Refined oils are similar to crude oils except that they have been further treated in one or more refining steps to improve one or more properties. Such purification techniques are known to those skilled in the art and include, for example, solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, hydrotreating, dewaxing, and the like. Rerefined oil is obtained by treating spent oil with processes similar to those used to obtain refined oil. These re-refined oils are also known as recycled or reprocessed oils and are often further processed by techniques to remove spent additives and oil breakdown products.

Lubricant base stocks derived from the hydroisomerization of waxes may also be used alone or in combination with the natural and/or synthetic base stocks. These wax isomerate oils are produced by the hydroisomerization of natural or synthetic waxes, or mixtures thereof, over a hydroisomerization catalyst. Natural waxes are typically slack waxes recovered by solvent dewaxing of mineral oils; Synthetic waxes are typically waxes produced by the Fischer-Tropsch process.

In one embodiment, the oil of lubricating viscosity is a Group I basestock. In general, a Group I basestock for use herein can be any petroleum derived base oil of lubricating viscosity, as defined in API Publication 1509, ^16th Edition, Addendum I, Oct., 2009. there is. The API guidelines define base stocks as lubricant ingredients that can be made using a variety of different processes. Group I base oils generally have a saturates content of less than 90% by weight (as determined by ASTM D 2007) and/or 300 (as determined by ASTM D 2622, ASTM D 4294, ASTM D 4297 or ASTM D 3120). Refers to a petroleum derived lubricating base oil having a total sulfur content greater than ppm and having a viscosity index (VI) greater than or equal to 80 and less than 120 (as determined by ASTM D 2270).

Group I base oils may include light overhead cuts and heavier side cuts from the vacuum distillation column, which may also include, for example, Light Neutral, Medium Neutral and Heavy質 Can contain Heavy Neutral base stock. Petroleum derived base oils may also include resid stock, or sub-fractions such as brightstock. Brightstock is a highly refined, dewaxed, high viscosity base oil typically produced from residue stock or bottoms. Brightstock can have a kinematic viscosity greater than about 180 cSt at 40°C, or even greater than about 250 cSt at 40°C, or even in the range of about 500 to about 1100 cSt at 40°C.

In one embodiment, the one or more basestocks may be a blend or mixture of two or more, three or more, or even four or more Group I basestocks of different molecular weights and viscosities, wherein the blend is processed in any suitable manner Produces a base oil with properties suitable for use in marine diesel engines (eg, viscosity and TBN value discussed above). In one embodiment, the one or more basestocks include ExxonMobil CORE ^® 100, ExxonMobil CORE ^® 150, ExxonMobil CORE ^® 600, ExxonMobil CORE ^® 2500, or combinations or mixtures thereof.

In another embodiment, the oil of lubricating viscosity is a Group II basestock as defined in API Publication 1509, ^16th Edition, Addendum I, Oct., 2009. Group II basestocks generally have a total sulfur content of 300 parts per million (ppm) or less (as determined by ASTM D 2622, ASTM D 4294, ASTM D 4927 or ASTM D 3120), (as determined by ASTM D 2007) saturates content greater than or equal to 90% by weight) and a viscosity index (VI) of 80 to 120 (as determined by ASTM D 2270).

In another embodiment, the oil of lubricating viscosity is a Group III basestock as defined in API Publication 1509, ^16th Edition, Addendum I, Oct., 2009. Group A III basestocks generally have a total sulfur content of less than or equal to 0.03 weight percent (as determined by ASTM D 2270), a saturates content of greater than or equal to 90 weight percent (as determined by ASTM D 2007), and (as determined by ASTM D 4294 , as determined by ASTM D 4297 or ASTM D 3120) having a viscosity index (VI) of 120 or greater. In one embodiment, the basestock is a Group III basestock, or a blend of two or more Group III basestocks.

Generally, Group III basestocks derived from petroleum are severely hydrotreated mineral oils. Hydrotreating involves reacting hydrogen with the basestock to be treated to remove heteroatoms from hydrocarbons and reducing olefins and aromatics to alkanes and cycloparaffins, respectively; in very severe hydrotreating, the naphthenic ring structure is reduced to non- Cyclic normal and iso-alkanes ("paraffins") are ring-opened. In one embodiment, at least about 70% paraffinic as determined by test method ASTM D 3238-95 (2005), "Standard Test Method for Calculation of Carbon Distribution and Structural Group Analysis of Petroleum Oils by the ndM Method" It has a carbon content (% C _p ). In another embodiment, the Group III basestock has a paraffinic carbon content (% C _p ) of at least about 72%. In another embodiment, the Group III basestock has a paraffinic carbon content (% C _p ) of at least about 75%. In another embodiment, the Group III basestock has a paraffinic carbon content (% C _p ) of at least about 78%. In another embodiment, the Group III basestock has a paraffinic carbon content (% C _p ) of at least about 80%. In another embodiment, the Group III basestock has a paraffinic carbon content (% C _p ) of at least about 85%.

In another embodiment, the Group III basestock has a naphthenic carbon content (% C _n ) of about 25% or less, as determined by ASTM D 3238-95 (2005). In another embodiment, the Group III basestock has a naphthenic carbon content (% C _n ) of about 20% or less. In another embodiment, the Group III basestock has a naphthenic carbon content (% C _n ) of about 15% or less. In another embodiment, the Group III basestock has a naphthenic carbon content (% C _n ) of about 10% or less.

In one embodiment, the Group III basestock for use herein is a Fischer-Tropsch derived base oil. The term "Fischer-Tropsch derived" means that a product, fraction or feed originates from or is produced in some step by a Fischer-Tropsch process. For example, Fischer-Tropsch base oils can be produced from processes in which the feed is a waxy feed recovered from Fischer-Tropsch synthesis, for example, in US patent applications, each incorporated herein by reference. Publication No. 2004/0159582; 2005/0077208; 2005/0133407; 2005/0133409; 2005/0139513; 2005/0139514; See also 2005/0241990. Generally, the process comprises a full or partial hydroisomerization dewaxing step using a bi-functional catalyst or a catalyst capable of selectively isomerizing paraffins. Hydroisomerization dewaxing is accomplished by contacting a waxy feed with a hydroisomerization catalyst in an isomerization zone under hydroisomerization conditions.

In another embodiment, the oil of lubricating viscosity is a Group IV basestock as defined in API Publication 1509, ^16th Edition, Addendum I, Oct., 2009. Group IV basestocks, or polyalphaolefins (PAOs), are typically prepared by oligomerization of 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. with the exact mixture depending on the desired final basestock viscosity. PAOs are typically hydrogenated after oligomerization to remove any residual unsaturation.

As described above, marine cylinder lubricants for use in marine diesel engines typically have a kinematic viscosity at 100° C. in the range of 9.3 to 26.1 cSt. To formulate such a lubricant, brightstock can be combined with a low viscosity oil, such as an oil having a viscosity of 4 to 6 cSt at 100°C. However, Brightstock's suppliers are declining, so Brightstock cannot be trusted to increase the viscosity of marine cylinder lubricants to the desired range recommended by the manufacturers. One solution to this problem is to use viscosity index improvers such as olefin copolymers or thickeners such as polyisobutylene (PIB) to thicken marine cylinder lubricants. PIB is a commercially available material from several manufacturers. PIB is typically a viscous, oil-miscible liquid having a weight average molecular weight ranging from about 1,000 to about 8,000, or about 1,500 to about 6,000, and a viscosity ranging from about 2,000 to about 5,000 or about 6,000 cSt (100°C). The amount of PIB added to the marine cylinder lubricant is generally from about 1 to about 20% by weight of the finished oil, or from about 2 to about 15% by weight of the finished oil, or from about 4 to about 12% by weight of the finished oil. will be.

In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention comprises at least one polyalkenyl bis-succinimide dispersant wherein the polyalkenyl substituent is derived from a polyalkene group having a number average molecular weight of about 1500 to about 3000. include additional In general, a bis-succinimide is the completed reaction product from the reaction between a polyalkenyl-substituted succinic acid or anhydride and one or more polyamine reactants, wherein the product is of the type resulting from the reaction of a primary amino group with an anhydride moiety. It is intended to include compounds that may have amide, amidine, and/or salt linkages in addition to imide linkages. Bis-succinimide dispersants are prepared according to methods well known in the art, e.g., the specific basic type of succinimide and related materials covered by the technical term "succinimide", for example U.S. Patent No. 2,992,708, incorporated herein by reference; 3,018,291; 3,024,237; 3,100,673; 3,219,666; 3,172,892; and 3,272,746.

In one embodiment, the at least one polyalkenyl bis-succinimide dispersant may be obtained by reacting a polyalkenyl-substituted succinic anhydride of Formula 1:

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

The preparation of polyalkenyl-substituted succinic anhydrides by reaction with polyolefins and maleic anhydrides has been described, for example, in US Pat. Nos. 3,018,250 and 3,024,195. Such methods include thermally reacting polyolefins with maleic anhydride and reacting halogenated polyolefins, such as chlorinated polyolefins, with maleic anhydride. Reduction of polyalkenyl-substituted succinic anhydrides gives the corresponding alkyl derivatives. Alternatively, polyalkenyl substituted succinic anhydrides can be prepared, for example, as described in U.S. Pat. Nos. 4,388,471 and 4,450,281, incorporated herein by reference.

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

A polyalkene group having a number average molecular weight of from about 1500 to about 3000 for reaction with succinic anhydride, such as maleic anhydride, can be prepared with a large amount of C ₂ to C ₅ mono-olefins, such as ethylene, propylene, butylene, isobutylene. and polymers comprising pentene. The polymer may be a copolymer of two or more olefins such as ethylene and propylene, butylene and isobutylene, as well as homopolymers such as polyisobutylene. Other copolymers include those in which small amounts, eg, 1 to 20 mole percent, of the copolymer monomers are C ₄ to C ₈ non-conjugated diolefins, such as copolymers of isobutylene and butadiene, or ethylene, propylene and copolymers of 1,4-hexadiene; and the like.

A particularly preferred class of polyalkene groups having a number average molecular weight of from about 1500 to about 3000 includes polybutenes prepared by polymerization of one or more of 1-butene, 2-butene and isobutene. Polybutenes containing a significant proportion of units derived from isobutene are particularly preferred. Polybutenes may contain small amounts of butadiene, which may or may not be incorporated into the polymer. Most often, isobutene units constitute about 80%, or at least about 90%, of the units in the polymer. Such polybutenes are readily available commercial materials well known to those skilled in the art, such as those disclosed in U.S. Patent Nos. 3,215,707; 3,231,587; 3,515,669; 3,579,450 and 3,912,764.

Polyamines suitable for use in preparing the non-borated bis-succinimide dispersants include polyalkylene polyamines. Such polyalkylene polyamines will typically contain from about 2 to about 12 nitrogen atoms and from about 2 to 24 carbon atoms. Particularly suitable polyalkylene polyamines are those having the formula: H ₂ N-(R ¹ NH) _c -H, wherein R ¹ is a straight or branched chain 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 tetraethylene pentamine, pentaethylene hexamine, and heavy polyamines (e.g., Dow HPA-X having a number average molecular weight of 275, available from The Dow Chemical Company of Midland, Mass.) do. Such amines include the aforementioned substituted polyamines including isomers such as branched chain polyamines and hydrocarbyl-substituted polyamines. HPA-X heavy polyamines ("HPA-X") contain an average of approximately 6.5 amine nitrogen atoms per molecule. Such heavy polyamines generally give good results.

Generally, the polyalkenyl-substituted succinic anhydride of Formula 1 is reacted with the polyamine at a temperature of about 130°C to about 220°C and preferably about 145°C to about 175°C. The reaction may be conducted under an inert atmosphere such as nitrogen or argon. The amount of anhydride of Formula 1 used in the reaction may range from about 30 to about 95 weight percent and preferably from about 40 to about 60 weight percent based on the total weight of the reaction mixture.

Generally, in the marine diesel cylinder lubricating oil composition of the present invention, at least one non-borated polyalkenyl bis-succine wherein the polyalkenyl substituent is derived from a polyalkene group having a number average molecular weight of about 1500 to about 3000 The concentration of the mid-dispersant is greater than about 0.25 weight percent, or greater than about 0.5 weight percent, or greater than about 1.0 weight percent, or greater than about 1.2 weight percent, based on actives, based on the total weight of the marine diesel cylinder lubricating oil composition, or greater than about 1.5%, greater than about 1.8%, or greater than about 2.0%, or greater than about 2.5%, or greater than about 2.8%. In another embodiment, the polyalkenyl substituent is at least one non-borated polyalkenyl derived from a polyalkenyl group having a number average molecular weight of about 1500 to about 3000 present in the marine diesel cylinder lubricating oil composition of the present invention. The amount of the bis-succinimide dispersant is about 0.25 to 10 weight percent, or about 0.25 to 8.0 weight percent, or about 0.25 to 5.0 weight percent, or about 0.25 to 5.0 weight percent, based on the active agent, based on the total weight of the marine diesel cylinder lubricating oil composition. 0.25 to 4.0%, or 0.25 to 3.0%, or about 0.5 to 10%, or about 0.5 to 8.0%, or about 0.5 to 5.0%, or about 0.5 to 4.0%, or about 0.5 to 3.0 wt%, or about 0.5 to 10 wt%, or about 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% by weight, or about 1.5 to 5.0% by weight, or about 1.5 to 4.0% by weight, or about 1.5 to 3.0% by weight, or about 2.0 to 10% by weight, or about 2.0 to 8.0% by weight, or It may range from about 2.0 to 5.0 wt% or about 2.0 to 4.0 wt%.

In another embodiment, the marine diesel cylinder lubricating oil composition of the present invention further comprises a cyclic carbonate post-treated polyalkenyl bis-succinimide dispersant. The polyalkenyl bis-succinimide dispersant of this embodiment may be prepared as described above, namely, by reacting a polyalkenyl-substituted succinic anhydride with a polyamine.

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

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 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); and the like, but are not limited thereto. Other suitable cyclic carbonates can be obtained from sugars such as sorbitol, glucose, fructose, galactose, and the like, and from C ₁ to C by methods known in the art. It can be prepared from vicinal diols made from C ₃₀ olefins.

The polyalkenyl bis-succinimide dispersant may be post-treated with the cyclic carbonate according to methods well known in the art. For example, the cyclic carbonate post-treated polyalkenyl bis-succinimide dispersant can be prepared by charging the bis-succinimide dispersant into a reactor and heating at a temperature of about 80° C. to about 170° C., optionally under a nitrogen purge. It can be manufactured by a process including Optionally, diluent oil may be charged to the same reactor under a nitrogen purge. The cyclic carbonate is charged to the reactor, optionally under a nitrogen purge. This mixture is heated to a temperature in the range of about 130° C. to about 200° C. under a nitrogen purge. Optionally, a vacuum is applied to the mixture for about 0.5 to about 2.0 hours to remove any water formed during the reaction.

The marine diesel cylinder lubricating oil composition of the present invention may also contain conventional marine diesel cylinder lubricating oil composition additives to impart auxiliary functions in addition to the above-mentioned dispersant, thereby providing a marine diesel cylinder lubricating oil composition in which these additives are dispersed or dissolved. there is. For example, marine diesel cylinder lubricating oil compositions include antioxidants, detergents, antiwear agents, rust inhibitors, dehazing agents, demulsifiers, metal deactivators, friction modifiers, pour point depressants, and antifoaming agents. agents), co-solvents, corrosion inhibitors, dyes, extreme pressure agents, etc., and mixtures thereof. A variety of additives are known and commercially available. These additives can be used to prepare 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 may contain one or more antioxidants capable of reducing or preventing oxidation of the base oil. Any antioxidant known to those skilled in the art may be used in the lubricating oil composition. Non-limiting examples of suitable antioxidants include amine-based antioxidants (e.g., alkyl diphenylamines such as bis-nonylated diphenylamine, bis-octylated diphenylamine, and octylated/butylated diphenylamine, phenyl -α-naphthylamine, alkyl or arylalkyl substituted phenyl-α-naphthylamine, alkylated p-phenylene diamine, tetramethyl-diaminodiphenylamine, etc.), phenolic antioxidants (e.g., 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, etc.), phosphorus-based antioxidants, zinc dithiophosphate, and combinations thereof.

The amount of antioxidant may vary from about 0.01% to about 10%, from about 0.05% to about 5%, or from about 0.1% to about 3% by weight, based on the total weight of the marine diesel cylinder lubricating oil composition. can

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 may contain one or more detergents. Metal-containing or ash-forming cleaners function both as cleaners to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally include a polar head with a long hydrophobic tail. Polar heads include metal salts of acidic organic compounds. A salt may contain a substantially stoichiometric amount of a metal, in which case the salt is commonly described as a normal or neutral salt. A large amount of metal base can be incorporated by reacting an excess metal compound (eg oxide or hydroxide) with an acidic gas (eg carbon dioxide).

Detergents that can be used include oil-soluble neutral and overbased sulfonates, phenates, sulfide phenates, cyanoates of metals, especially alkali or alkaline earth metals (eg barium, sodium, potassium, lithium, calcium and magnesium). phosphonates, salicylates, and naphthalene and other oil-soluble carboxylates. The most commonly used metals are calcium and magnesium (both of which may be present in detergents used in lubricants), and mixtures of calcium and/or magnesium and sodium.

Commercially available products are generally referred to as neutral or overbased. Overbased metal detergents generally contain hydrocarbons, detergent acids such as sulfonic acids, carboxylates, etc., metal oxides or hydroxides (eg calcium oxide or hydroxide) and accelerators such as xylene, It is prepared by carbonizing a mixture of methanol and water. For example, to make overbased calcium sulfonate, upon carbonization, calcium oxide or calcium hydroxide reacts with gaseous carbon dioxide to form calcium carbonate. Sulfonic acids are neutralized with excess CaO or Ca(OH) ₂ to form sulfonates.

The overbased detergent may be an overbased salt having a low overbased, eg, a BN of less than 100. In one embodiment, the low overbased salt may have a BN of about 5 to about 50. In another embodiment, the overbased salt may have a BN of about 10 to about 30. In another embodiment, the overbased salt may have a BN of about 15 to about 20.

The overbased detergent may be an overbased salt having a moderately overbased BN, e.g., a BN of about 100 to about 250. In one embodiment, the BN of the intermediate overbased salt may be from about 100 to about 200. In another embodiment, the intermediate overbased salt may have a BN of about 125 to about 175.

The overbased detergent may be a highly overbased, eg, overbased salt having a BN greater than 250. In one embodiment, the highly overbased salt may have a BN of 250 to about 550.

In one embodiment, the detergent can be one or more alkali 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.

Alkyl-substituted moieties of alkali or alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids are derived from alpha olefins having from about 10 to about 80 carbon atoms. The olefins used may be linear, isomerized linear, branched or partially branched linear. The olefin may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, or a mixture of partially branched linear olefins or a mixture of any of the foregoing.

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, normal alpha olefins are isomerized using at least one of a solid or 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 chain olefin derived from the polymerization of propylene. Olefins may also be substituted with other functional groups such as hydroxyl groups, carboxylic acid groups, heteroatoms, and the like. In one embodiment, the branched olefinic propylene oligomer or mixture thereof may have from about 20 to about 60 carbon atoms. In one embodiment, the branched olefinic propylene oligomer or mixture thereof may have from about 20 to about 40 carbon atoms.

In one embodiment, at least about 75 mole % (e.g., at least about 80 mole %, at least about 85 mole %, at least about 90 mole %, at least about 90 mole %, at least about 95 mole percent, or at least about 99 mole percent) of the alkyl groups, eg, of the alkaline earth metal salt of the alkyl-substituted hydroxybenzoic acid detergent, are C ₂₀ or greater. In another embodiment, the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is an alkyl-substituted, wherein the alkyl group is a residue of a normal alpha-olefin containing at least 75 mol % of a C ₂₀ or higher normal alpha-olefin. It is an alkali or alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid derived from hydroxybenzoic acid.

In another embodiment, at least about 50 mole % (e.g., at least about 60 mole %, at least about 70 mole %, at least about 80 mole %, 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 %) of the alkyl group, such as an alkyl group of an alkali or alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid, from about C ₁₄ to about It is C ₁₈ .

The resulting alkali or alkaline earth metal salt of an 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% of the ortho isomer and 99 to 1% of the para isomer. In another embodiment, the product will contain about 5-70% ortho and 95-30% para isomer.

Alkali or alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids can be neutral or overbased. Generally, an overbased alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is prepared by combining BN of the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid with a base source (e.g., lime) and an acidic acid. It is increased by a process such as the addition of an overbased compound (eg carbon dioxide).

Sulfonates may be prepared by sulfonation of alkyl substituted aromatic hydrocarbons, such as those obtained by fractionation of petroleum, or from sulfonic acids typically obtained by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or hydrogen derivatives thereof. Alkylation can be carried out using an alkylating agent having from about 3 to more than 70 carbon atoms in the presence of a catalyst. Alkaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms per alkyl substituted aromatic moiety, preferably from about 16 to about 60 carbon atoms.

Oil-soluble sulfonates or alkaryl sulfonic acids can be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and ethers of metals. The amount of metal compound is selected with a view to the desired TBN of the final product, but typically ranges from about 100 to about 220 weight percent (preferably at least about 125 weight percent) of that required stoichiometrically.

In one embodiment, the high overbased sulfonate detergent provides 50 percent or less of the TBN of the total composition. In another embodiment, the high overbased sulfonate detergent provides no more than 40 percent, 30 percent, 25 percent, 10 percent or 5 percent of the TBN of the total composition. In another embodiment, the composition of the present invention comprises a high overbased sulfonate detergent such that the high overbased sulfonate detergent provides less than 0.5 percent of the TBN of the total composition, or even 0 percent of the TBN of the total composition. It contains practically no

Metal salts of phenols and sulfurized phenols are prepared by reaction with suitable metal compounds, such as oxides or hydroxides, and neutral or overbased products can be obtained by methods well known in the art. Sulfurized phenols are prepared by reacting phenol with sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide to form a product which is generally a mixture of compounds in which two or more phenols are bridged by a sulfur containing bridge. can

Additional details regarding the general preparation of sulfurized phenates can be found in, for example, U.S. Patent Nos. 2,680,096; 3,178,368 and 3,801,507, the contents of which are incorporated herein by reference.

Considering now the reactants and reagents used in the process in detail, first all allotropic forms of sulfur can be used. Sulfur can be used as molten sulfur or as a solid (eg, powder or granular) or as a solid suspension in a compatible hydrocarbon liquid.

Preference is given to using calcium hydroxide as the calcium base because of its ease of handling compared to, for example, calcium oxide and also because it gives superior results. Other calcium bases, such as calcium alkoxides, may also be used.

Suitable alkylphenols that may be used are those containing a sufficient number of carbon atoms to impart usefulness to the overbased calcium sulphide alkylphenate composition from which the alkyl substituents are obtained. Oil solubility may be provided by a single long-chain alkyl substituent or by a combination of alkyl substituents. Typically, the alkylphenols used in the process will be a mixture of different alkylphenols, such as C ₂₀ to C ₂₄ alkylphenols. When a phenate product with a TBN of 275 or less is desired, it is economically advantageous to use 100% polypropenyl substituted phenols because of their commercial availability and generally low cost. If a higher TBN phenate product is desired, from about 25 to about 100 mole percent of the alkylphenol may have a straight chain alkyl substituent having from about 15 to about 35 carbon atoms, and from about 75 to about 0 mole percent of the alkyl In phenol, the alkyl group is different from polypropenyl of 9 to 18 carbon atoms. In one embodiment, in about 35 to about 100 mole percent of alkylphenol, the alkyl group will be a straight chain alkyl of about 15 to about 35 carbon atoms, and in about 65 to about 0 mole percent of alkylphenol, the alkyl group is about 9 to about 35 carbon atoms. It will be a polypropenyl of about 18 carbon atoms. The use of increasing amounts of predominately straight chain alkylphenols results in high TBN products which are generally characterized by lower viscosity. On the other hand, while polypropenylphenols are predominantly generally more economical than straight chain alkylphenols, the use of greater than about 75 mole percent polypropenylphenols in the preparation of calcium overbased sulfurized alkylphenate compositions is generally undesirable. It results in a product with high viscosity. However, the use of mixtures of up to about 75 mole percent polypropenylphenols having from about 9 to about 18 carbon atoms and greater than about 25 mole percent predominantly straight-chain alkylphenols having from about 15 to about 35 carbon atoms can provide acceptable viscosities. allows for a more economical product of In one embodiment, suitable alkyl phenolic 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, wherein the hydrocarbyl groups, including cardanol, are linear and unsaturated. Catalytic hydrogenation of distilled CNSL produces a mixture of meta-hydrocarbyl substituted phenols that are predominantly enriched in 3-pentadecylphenol.

Alkylphenols can be para-alkylphenols, meta-alkylphenols or ortho alkylphenols. When an overbased product is desired, the alkylphenol is preferably predominantly para-alkylphenol, as p-alkylphenol is believed to facilitate the preparation of highly overbased calcium sulphide alkylphenates, and the alkylphenol is about up to 45 mole percent is an ortho alkyl phenol; And preferably no more than about 35 mole percent of the alkylphenols are ortho alkylphenols. Alkyl-hydroxy toluene or xylene, and other alkylphenols having one or more alkyl substituents in addition to at least one long chain alkyl substituent may 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.

In general, the choice of alkylphenol may be based on the properties required for the marine diesel engine lubricating oil composition, particularly TBN, and oil solubility. For example, in the case of alkylphenates having substantially straight chain alkyl substituents, the viscosity of the alkylphenate composition can be influenced by the location of attachment on the alkyl chain to the phenyl ring, such as terminal versus intermediate attachment. Additional information regarding this and the selection and preparation of suitable alkyl phenols can be found in, for example, US Pat. Nos. 5,024,773; 5,320,763; 5,318,710; and 5,320,762, each of which is incorporated herein by reference.

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

The marine diesel cylinder lubricating oil composition of the present invention may contain one or more friction modifiers capable of lowering frictional force between moving parts. Any friction modifier known to those skilled in the art may be used in marine diesel cylinder lubricating oil compositions. Non-limiting examples of suitable friction modifiers include fatty carboxylic acids; derivatives of fatty carboxylic acids (eg, alcohols, esters, borated esters, amides, metal salts, etc.); mono-, di- or tri-alkyl substituted phosphoric or phosphonic acids; derivatives (eg, esters, amides, metal salts, etc.) of mono-, di- or tri-alkyl substituted phosphoric or phosphonic acids; mono-, di- or tri-alkyl substituted amines; mono- or di-alkyl substituted amides, and combinations thereof. In some embodiments, examples of friction modifiers include alkoxylated fatty amines; borated fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters; and fatty imidazolines disclosed in U.S. Patent No. 6,372,696, incorporated herein by reference; C ₄ to C ₇₅ , or C ₆ to C ₂₄ , or C ₆ to C _{20 selected from the group consisting of ammonia, alkanolamines, etc., and mixtures thereof,} a friction modifier obtained from the reaction product of a fatty acid ester with a nitrogen-containing compound Including, but not limited to these.

The marine diesel cylinder lubricating oil composition of the present invention may contain one or more antiwear agents capable of reducing friction and excessive wear. Any antiwear agent known to those skilled in the art may be used in the lubricating oil composition. Non-limiting examples of suitable antiwear agents include zinc dithiophosphate, metal (eg, Pb, Sb, Mo, etc.) salts of dithiophosphate, metal (eg, dithiophosphate) of dithiophosphate. Zn, Pb, Sb, Mo, etc.) salts, metal (e.g., Zn, Pb, Sb, etc.) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphate esters or thiophosphate esters, dicyclopentadiene reaction products of ene and thiophosphoric acid, and combinations thereof.

In certain embodiments, the antiwear agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as a zinc dialkyl dithiophosphate compound. The metal of the dihydrocarbyl dithiophosphate metal salt may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is zinc. In another embodiment, the alkyl group of the dihydrocarbyl dithiophosphate metal salt contains from about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. has two carbon atoms. In a further embodiment, the alkyl group is linear or branched.

The amount of dihydrocarbyl dithiophosphate metal salt, including zinc dialkyl dithiophosphate salt, in the lubricating oil composition disclosed herein is measured by its phosphorus content. In some embodiments, the phosphorus content of the lubricating oil composition 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 destroying foam in the oil. Any antifoam or antifoam agent known to those skilled in the art may be used in marine diesel cylinder lubricating oil compositions. Non-limiting examples of suitable antifoam or antifoam agents include silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated aliphatic acids, polyethers (eg polyethylene glycols), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines, and combinations thereof.

The marine diesel cylinder lubricating oil composition of the present invention may contain one or more pour point depressants capable of lowering the pour point of the marine diesel cylinder lubricating oil composition. Any pour point depressant known to those skilled in the art may be used in the marine diesel cylinder lubricating oil composition. Non-limiting examples of suitable pour point depressants include polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, di(tetra-paraffinic phenol)diphthalate, condensates of tetra-paraffinic phenols, condensates of chlorinated paraffins and naphthalenes. water, and combinations thereof. In some embodiments, pour point depressants include ethylene-vinyl acetate copolymers, condensates of chlorinated paraffins and phenols, polyalkyl styrenes, and the like.

In another embodiment, the marine diesel cylinder lubricating oil composition of the present invention may contain one or more demulsifiers capable of promoting oil-water separation in a lubricating oil composition exposed to water or steam. Any demulsifying agent known to those skilled in the art may be used in marine diesel cylinder lubricating oil compositions. Non-limiting examples of suitable demulsifiers include anionic surfactants (e.g., alkyl-naphthalene sulfonates, alkyl benzene sulfonates, etc.), nonionic alkoxylated alkyl phenolic resins, polymers of alkylene oxides (e.g., polyethylene oxide, polypropylene oxide, ethylene oxide, block copolymers of propylene oxide, etc.), esters of fat-soluble acids, polyoxyethylene sorbitan esters, and mixtures thereof.

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

The marine diesel cylinder lubricating oil composition of the present invention may contain one or more extreme pressure (EP) agents capable of preventing sliding metal surfaces from seizing under extreme pressure conditions. Any extreme pressure agent known to those skilled in the art may be used in marine diesel cylinder lubricating oil compositions. In general, extreme pressure agents are compounds that can chemically bond with metals to form a surface film that prevents bonding of asperities on opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents are sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydro Carbyl polysulphides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadienes, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, fatty acids, fatty acid esters and alpha-olefins of co-sulfurized blends, functionally-substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds, sulfur-containing acetal derivatives, terpenes and acyclic olefins. co-sulphurized blends, and polysulfide olefin products, amine salts of phosphoric acid esters or thiophosphoric acid esters, and combinations thereof.

The marine diesel cylinder lubricating oil composition of the present invention may contain at least one rust inhibitor capable of inhibiting corrosion of ferrous metal surfaces. Any rust inhibitor known to those skilled in the art may 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 ethers, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol mono stearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate; stearic acid and other fatty acids; dicarboxylic acids; metal soap; fatty acid amine salts; metal salts of heavy sulfonic acids; partial carboxylic acid esters of polyhydric alcohols; phosphate ester; (short chain) alkenyl succinic acid; partial esters thereof and nitrogen-containing derivatives thereof; synthetic alkarylsulfonates such as metal dinonylnaphthalene sulfonate; and the like and 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 dithiocarbamates, sulfurized oxymolybdenum organophosphorodithioates, oxymolybdenum monoglycerides, oxymolybdenum diethyl amides, amine-molybdenum complexes. compounds, and sulfur-containing molybdenum complex compounds.

Example

The following implementation is intended for illustrative purposes only and does not limit the scope of the present disclosure in any way.

DSC oxidation test

The DSC oxidation test is used to evaluate the thin film oxidation stability of test oils according to ASTM D-6186. During the test the heat flow from the test oil in the sample cup is compared to a reference cup. The oxidation onset temperature is the temperature at which oxidation of the test oil begins. Oxidation induction time is the time at which oxidation of the test oil begins. A longer oxidation induction time means better performance. The oxidation reaction results in an exothermic reaction which is evident by the heat flow. 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 are 25 BN, SAE 50 containing amounts of Esso 600N Group I base oil, Esso 2500 Brightstock, non-sulfur containing aromatic amine, antifoam and additional additives, as shown in Table 1. Formulated as a fully formulated marine cylinder lubricating oil composition of a viscosity grade. The non-sulfur containing aromatic amine used in this example was a nonyl substituted diphenylamine. This additive, containing 3.5% nitrogen by weight, had a TBN of about 135 mgKOH/g and contained no diluent oil. The test oil was evaluated using the DSC oxidation test. The results are presented in Table 1 below.

As is evident from the results illustrated in Table 1, the marine cylinder lubricating oil composition of Example 1, wherein the TBN contribution of the non-sulfur containing aromatic amine to the TBN of the lubricating oil composition is greater than about 30%, is comparable to that of conventional highly overbased sulfonates. Compared to Comparative Example A, which contains a higher BN contribution from detergent, the test oils exhibit surprisingly better thin film oxidation stability as evidenced by the overall higher oxidation induction time. Cylinder oils with high oxidation stability in thin film conditions rather than in bulk fluid will exhibit less viscosity increase, higher diffusivity and greater anti-scuffing performance.

Claims (15)

As a marine diesel cylinder lubricating oil composition,
(a) a large amount of oil of lubricating viscosity and
(b) a non-sulfur containing aromatic amine;
The marine diesel cylinder lubricating oil composition has a total base number (TBN) of 5 to 100 mg KOH/g determined by ASTM D2896; In addition, the contribution of the non-sulfur containing aromatic amine to the TBN of the marine diesel cylinder lubricating oil composition is greater than 30%,
wherein the non-sulfur containing aromatic amine is selected from diphenylamine, N-phenylnaphthylamine, or dinaphthylamine.
2. The marine diesel cylinder lubricating oil composition according to claim 1, wherein the non-sulfur containing aromatic amine consists essentially of diphenylamine.
The method of claim 2, wherein 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'-di-α-methylbenzyl-diphenylamine; A marine diesel cylinder lubricating oil composition selected from Np-butylphenyl-N-p'-octylphenylamine, or bis(dialkylphenyl) amine.
The method of claim 1, wherein the non-sulfur containing aromatic amine is alkylphenyl-1-naphthylamine, octylphenyl-1-naphthylamine, N-4-dodecylphenyl-1-naphthylamine; Marine diesel cylinder lubricating oil selected from arylnaphthylamine, phenyl-1-naphthylamine, phenyl-2-naphthylamine, N-hexylphenyl-2-naphthylamine or N-octylphenyl-2-naphthylamine composition.
2. The method of claim 1, wherein the contribution of the non-sulfur containing aromatic amine to the TBN of the marine diesel cylinder lubricating oil composition is greater than 32%, greater than 34%, greater than 36%, greater than 38%, greater than 40%, greater than 42%, greater than 44%. greater than, greater than 46%, greater than 48%, greater than 50%, greater than 52%, greater than 54%, greater than 56%, greater than 58%, greater than 60%, greater than 62%, greater than 64%, greater than 66%, greater than 68%; greater than 70%, greater than 72%, greater than 74%, greater than 76%, greater than 78%, greater than 80%, greater than 82%, greater than 84%, greater than 86%, greater than 88%, or greater than 90% marine diesel cylinder lubricating oil composition.
The method of claim 1, wherein the contribution of the non-sulfur containing aromatic amine to the TBN of the marine diesel cylinder lubricating oil composition is 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less , 65% or less, 60% or less, 55% or less, or 50% or less, marine diesel cylinder lubricating oil composition.
The method of claim 1, wherein the contribution of the non-sulfur containing aromatic amine to the TBN of the marine diesel cylinder lubricating oil composition is 30% to 95%, 32% to 85%, 34% to 75%, or 36% to 65%. %, marine diesel cylinder lubricating oil composition.
The marine diesel cylinder lubricating oil composition according to claim 1, further comprising a detergent selected from an alkyl-substituted hydroxyaromatic carboxylate or an alkyl-substituted hydroxyaromatic compound.
The method of claim 1, wherein the non-sulfur containing aromatic amine is between 100 mg KOH/g and 600 mg KOH/g, between 100 mg KOH/g and 300 mg KOH/g, or between 120 mg KOH/g and 250 mg KOH/g. Marine diesel cylinder lubricating oil composition having an overall value of.
The marine diesel cylinder lubricating oil composition according to claim 1, having a TBN of 5 to 70 mg KOH/g or 5 to 40 mg KOH/g.
As a marine diesel cylinder lubricating oil composition,
(a) a quantity of oil of lubricating viscosity, and
(b) a non-sulfur containing aromatic amine;
wherein the non-sulfur containing aromatic amine increases the oxidative stability of the marine diesel cylinder lubricating oil composition as determined by ASTM D-6186 by at least 5% when compared to a marine diesel cylinder lubricating oil composition substantially devoid of non-sulfur containing aromatic amines. present in sufficient quantities to
wherein the contribution of non-sulfur containing aromatic amines to the TBN of marine diesel cylinder lubricating oil compositions with increased oxidative stability is greater than 30%, said TBN as determined by ASTM D2896;
wherein the marine diesel cylinder lubricating oil composition is substantially devoid of any non-sulfur containing aromatic amine, wherein the marine diesel cylinder lubricating oil composition comprises a non-sulfur containing aromatic amine in an amount of less than 0.5% by weight.
12. The marine diesel cylinder lubricating oil composition of claim 11, wherein the amount of non-sulfur containing aromatic amine used increases the oxidative stability by at least 7%, at least 9%, at least 11%, at least 13%, or at least 15%.
12. The marine diesel cylinder lubricating oil composition of claim 11, wherein the marine diesel cylinder lubricating oil composition is substantially devoid of any non-sulfur containing aromatic amine, wherein the non-sulfur containing aromatic amine is present in an amount of less than 0.4 weight percent, less than 0.3 weight percent, or less than 0.2 weight percent. A marine diesel cylinder lubricating oil composition comprising an amine.
12. The method of claim 11, wherein the non-sulfur containing 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, A marine diesel cylinder lubricating oil composition selected from N'-diisopropyl-p-phenylenediamine, or N,N'-diphenyl-p-phenylenediamine. delete