JP6965342B2 - Diesel Lubricants Composition for Ships - Google Patents

Description

Technical Field The present invention generally relates to a lubricating oil composition for a marine diesel internal combustion engine.

Background of the Invention Diesel internal combustion engines (engines) for ships can generally be classified as low speed, medium speed, or high speed engines, and the low speed types are some other, such as the largest deep shaft ships and power generation applications. Used for industrial applications.

Low-speed diesel engines are unique in terms of size and operating method. These engines are fairly large and typically operate at speeds in the range of about 60 to about 200 rpm. A low-speed diesel engine operates on a two-stroke cycle and is typically a direct-coupled and direct-reversing engine with a "crosshead" construction, with one or more stuffing boxes and dividers that separate the power cylinder from the crankcase. Prevents combustion products from entering the crankcase and mixing with crankcase oil. Marine 2-stroke diesel cylinder lubricants must meet performance requirements to meet the stringent operating conditions required for the harsh loads of cylinder liners and the more modern, larger caliber engines operating at high temperatures and powers. Must be. By completely separating the crankcase from the combustion zone, those skilled in the art will use different lubricants, cylinder lubricants and system oils for the combustion chamber and crankcase due to the unique requirements of each type of lubricant. I came to lubricate.

In a two-stroke crosshead engine, the cylinders are lubricated on a total loss basis by separately injecting cylinder oil into each cylinder using a lubricator located around the cylinder liner. Cylinder lubricant is not recirculated and burns with the fuel. The cylinder lubricant must provide a strong film between the piston ring and the cylinder liner for sufficient cylinder wall lubrication to prevent wear, and the lubricant is the hot surface of the piston ring and piston. It needs to be thermally stable so that no deposits form on it, and it needs to be able to neutralize the sulfur-based acidic products of combustion. This neutralization has typically been achieved by including basic species such as metal cleaners. Unfortunately, the basicity of the marine cylinder lubricant can be reduced by the oxidation of the marine cylinder lubricant (due to the heat and oxidative stress the lubricant receives in the engine), thus increasing the lubricant's ability to neutralize. Reduce. Oxidation can be accelerated if the marine cylinder lubricant contains an oxidation catalyst such as a wear metal that is generally known to be present in the lubricant during engine operation. In order to prevent the oxidation and polymerization of the lubricating oil by the metal catalyst, it would be desirable to find a way to prevent the metal ions from fulfilling the function of the oxidation and polymerization catalyst and to sequester or complex the metal ions.

System oil lubricates the crossheads and crankshafts of two-stroke engines. It lubricates the main bearings, crosshead bearings, gears and camshafts, and it cools the piston undercrown and protects the crankcase from corrosion. The system oil needs to be able to prevent rust in the crankcase and corrosion of metal in the bearing body in the presence of contaminated water. The system oil must also provide sufficient dynamic lubrication of the bearings and also need to have a sufficient wear resistant system to provide wear protection to the bearings and gears under extreme pressure conditions. In contrast to cylinder lubricants, system oils are not exposed to the combustion chamber where the fuel is burning and are formulated to last as long as possible to maximize the life of the oil. Therefore, the key performance characteristics of system oils are related to wear protection, oxidation stability, viscosity increase control and precipitate performance.

Medium speed engines are typically operated in the range of about 250 to about 1100 rpm and are operated in four stroke cycles. These engines are typically a trunk piston design. In trunk piston engines, in contrast to crosshead engines, a single lubricating oil is used to lubricate all areas of the engine. Therefore, trunk piston engine oil has unique requirements. Key performance parameters for operating a trunk piston engine include sediment control for piston ring packs and piston cooling gallery, oxidation and viscosity buildup controls, and sludge control. In marine residual fuel operations, these performance parameters are determined almost exclusively by asphaltene contamination from marine residual fuel.

Similar to cylinder lubricants, system and trunk piston engine oils are oxidized in the presence of metal ions. Therefore, interference of such types of oxidation is necessary by sequestering or complexing metal ions.

Recent health and environmental concerns have led to rules that exist in several areas that direct the use of low-sulfur fuels for the operation of marine diesel engines. As a result, manufacturers typically combine poorer quality intermediate or heavy fuels, such as marine residual fuels with high sulfur and high asphaltene content, with high quality distillate fuels and non-residual gaseous. We are designing a marine diesel engine for use with a variety of fuels, including fuels (eg, compressed or liquefied natural gas). In non-residual fuel operations, the fuel does not contain the significant asphaltene present in the fuel and contains much lower sulfur levels. When low-sulfur fuel burns, less acid is formed in the combustion chamber. The requirements for lubricating oils used to operate engines that use low sulfur gaseous and distillate fuels with respect to marine residual fuels are very different. For example, controlling piston deposits in marine engines operating on low sulfur fuels is a particular challenge. It was discovered that even the addition of large amounts of high-soap-containing cleaning agents did not lead to the desired level of piston deposit control. In addition, the basicity of the lubricant can be reduced by oxidation of the marine cylinder lubricant. The reduction in the neutralizing capacity of the lubricant due to oxidation can be particularly problematic for marine lubricants designed for use in marine engines operating on low sulfur fuels.

Lubricating oils for lubricating marine diesel internal combustion engines have an industry requirement of high viscosity due to low operating speeds and high loads, and typically SAE20, SAE30, SAE40, SAE50 or SAE60. Viscosity grade (viscosity grade) high viscosity monograde (ie, one that shows no or little viscosity index improving properties) lubricating oil. Since hydrocracking results in a loss of viscosity of the basestock, marine oils generally cannot simply be blended with hydrocracking basestock, but require the use of significant amounts of brightstock. .. However, due to the presence of oxidatively unstable aromatics, dependence on bright stock is not always desirable. In addition, the utilization of bright stock is declining, resulting in the use of high volumes, such as those for marine engines, and an alternative solution is required to give the lubricating oil the desired viscosity measurement. There is.

Another important performance aspect of marine diesel lubricants is foaming performance. When a large amount of gas is mixed in the liquid, it foams. Foaming is desirable in certain applications such as levitation, cleaning and cleaning, but may not be desirable in lubricant-related applications where foaming can be an obstacle because of the loss of lubrication effect. The viscosity and surface tension of the lubricant contribute to the stability of the foam. Low-viscosity oils produce bubbles with large bubbles, which tend to be of little concern as they break rapidly. However, high-viscosity oils such as oils used as marine lubricants contain fine bubbles and generate stable bubbles that are hard to break. Over time, foaming accelerates the oxidative decomposition of the lubricant, which in addition can affect the oil transport and pumping capacity.

Considering restrictive emission rules that reduce the supply of bright stock and change operating conditions and fuel sources for marine diesel internal combustion engines, the metal ions in the lubricant are complexed or isolated to various BN levels. Provides high detergency performance and oxidative stability and foaming control over, slowing down the rate of loss of basicity (loss of BN) and allowing a reduction in the amount of brightstock used in the lubricating oil composition. And there is a need for marine diesel lubricant technology that meets the requirements for SAE20, SAE30, SAE40, SAE50 or SAE60 monograde lubricant compositions and marine lubricant performance requirements.

Description of the Invention According to one embodiment of the present invention, the following lubricating oil compositions are provided:
Polyisobutyl-substituted hydroxyaromatic compounds, aldehydes, amino acids with (a) major amounts of lubricating viscosity oils; and (b) about 0.1% to about 10% by weight active based on the total weight of the lubricating oil composition. Or an ester derivative thereof, and at least one Mannich reaction product prepared by condensation of an alkali metal base, wherein the polyisobutyl group is derived from polyisobutene containing at least about 70% by weight of the methylvinylidene isomer, and , Polyisobutyl groups having a number average molecular weight of about 400 to about 2500;
Lubricating oil composition containing:
The lubricating oil composition has a TBN of 5 to 200 mg KOH / g, and the lubricating oil composition is SAE J300 revised in January 2015 for SAE20, SAE30, SAE40, SAE50 or SAE60 monograde lubricating oils. The above-mentioned lubricating oil composition, which is a monograde lubricating oil composition that meets the specifications for SAE J300 revised January 2015 requirements.

According to another embodiment of the invention, the following marine diesel cylinder lubricant compositions are provided:
(A) Major amounts of oil with lubricating viscosity; and (b) Polyisobutyl-substituted hydroxy aromatic compounds with about 0.1% to about 10% by weight activity based on the total weight of the marine diesel cylinder lubricating oil composition. From polyisobutene, which is a Mannich reaction product prepared by condensation of an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group contains at least about 70% by weight of the methylvinylidene isomer. Derived and the polyisobutyl group has a number average molecular weight of about 400 to about 2500;
Is a marine diesel cylinder lubricant composition containing:
The marine diesel cylinder lubricant composition has a TBN of 5 to 200 mg KOH / g, and the marine diesel cylinder lubricant composition is 2015 for SAE30, SAE40, SAE50 or SAE60 monograde lubricants. The marine diesel cylinder lubricant composition, which is a monograde lubricant composition that meets the specifications for SAE J300 revised January 2015 requirements.

According to another embodiment of the present invention, the following marine trunk piston engine lubricating oil compositions are provided:
(A) Major amounts of lubricating viscosity oil; and (b) Polyisobutyl-substituted hydroxy aromatics with about 0.1% to about 10% by weight activity based on the total weight of the marine trunk piston engine lubricating oil composition. A polyisobutene in which at least one Mannich reaction product prepared by condensation of a compound, an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group contains at least about 70% by weight of the methylvinylidene isomer. Derived from and having a polyisobutyl group having a number average molecular weight of about 400 to about 2500;
Is a marine trunk piston engine lubricating oil composition containing:
The marine trunk piston engine lubricating oil composition has a TBN of 10 to 80 mg KOH / g, and the marine trunk piston engine lubricating oil composition is for SAE30 or SAE40 monograde lubricating oil January 2015. The marine trunk piston engine lubricating oil composition, which is a monograde lubricating oil composition that meets the specifications for SAE J300 revised January 2015 requirements.

According to another embodiment of the present invention, the following marine system oil lubricant compositions are provided:
Polyisobutyl-substituted hydroxyaromatic compounds, which are (a) major amounts of lubricating viscosity oil; and (b) about 0.1% to about 10% by weight active based on the total weight of the marine system lubricating oil composition. At least one Mannich reaction product prepared by condensation of an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group is derived from polyisobutene containing at least about 70% by weight of the methylvinylidene isomer. And the polyisobutyl group has a number average molecular weight of about 400 to about 2500;
A marine system lubricant composition comprising:
The marine system oil lubricating oil composition has a TBN of 5-40 mg KOH / g, and the marine system oil lubricating oil composition is for SAE20, SAE30 or SAE40 monograde lubricating oil January 2015. The marine system oil lubricating oil composition, which is a monograde lubricating oil composition that meets the specifications for SAE J300 revised January 2015 requirements.

According to another embodiment of the invention, the following marine diesel cylinder lubricant compositions are provided:
(A) Major amounts of oil with lubricating viscosity; and (b) Polyisobutyl-substituted hydroxy aromatic compounds with about 0.1% to about 10% by weight activity based on the total weight of the marine diesel cylinder lubricating oil composition. From polyisobutene, which is a Mannich reaction product prepared by condensation of an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group contains at least about 70% by weight of the methylvinylidene isomer. Derived and the polyisobutyl group has a number average molecular weight of about 400 to about 2500;
Is a marine diesel cylinder lubricant composition containing:
The marine diesel cylinder lubricant composition has a TBN of 5-40 mg KOH / g, and the marine diesel cylinder lubricant composition is 2015 for SAE30, SAE40, SAE50 or SAE60 monograde lubricants. The marine diesel cylinder lubricant composition, which is a monograde lubricant composition that meets the specifications for SAE J300 revised January 2015 requirements.

According to another embodiment of the invention, the following marine diesel cylinder lubricating oil compositions designed for lubrication of marine two-stroke crosshead engines operated on low sulfur fuels are provided:
(A) Major amounts of oil with lubricating viscosity; and (b) Polyisobutyl-substituted hydroxy aromatic compounds with about 0.1% to about 10% by weight activity based on the total weight of the marine diesel cylinder lubricating oil composition. From polyisobutene, which is a Mannich reaction product prepared by condensation of an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group contains at least about 70% by weight of the methylvinylidene isomer. Derived and the polyisobutyl group has a number average molecular weight of about 400 to about 2500;
Is a marine diesel cylinder lubricant composition containing:
The marine diesel cylinder lubricant composition has a TBN of 5-40 mg KOH / g, and the marine diesel cylinder lubricant composition is 2015 for SAE30, SAE40, SAE50 or SAE60 monograde lubricants. The marine diesel cylinder lubricant composition, which is a monograde lubricant composition that meets the specifications for SAE J300 revised January 2015 requirements.

According to another embodiment of the invention, the following marine diesel lubricant compositions are provided:
Polyisobutyl-substituted hydroxyaromatic compounds, which are (a) major amounts of lubricating viscosity oil; and (b) about 0.1% to about 10% by weight active based on the total weight of the marine diesel lubricating oil composition. At least one Mannich reaction product prepared by condensation of an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group is derived from polyisobutene containing at least about 70% by weight of the methylvinylidene isomer. And the polyisobutyl group has a number average molecular weight of about 400 to about 2500;
A marine diesel lubricant composition comprising:
The marine diesel lubricating oil composition has a TBN of 5-40 mg KOH / g, and the marine diesel lubricating oil composition is for SAE20, SAE30, SAE40, SAE50 or SAE60 monograde lubricating oil 2015. The marine diesel lubricating oil composition, which is a monograde lubricating oil composition that meets the specifications for SAE J300 revised January 2015 requirements.

According to another embodiment of the invention, the following marine trunk piston engine lubricating oil compositions for lubricating marine engines operated on low sulfur fuels are provided:
(A) Major amounts of lubricating viscosity oil; and (b) Polyisobutyl-substituted hydroxy aromatics with about 0.1% to about 10% by weight activity based on the total weight of the marine trunk piston engine lubricating oil composition. A polyisobutene in which at least one Mannich reaction product prepared by condensation of a compound, an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group contains at least about 70% by weight of the methylvinylidene isomer. Derived from and having a polyisobutyl group having a number average molecular weight of about 400 to about 2500;
Is a marine trunk piston engine lubricating oil composition containing:
The marine trunk piston engine lubricating oil composition has a TBN of 10 to 20 mg KOH / g, and the marine trunk piston engine oil lubricating oil composition is for SAE30 or SAE40 monograde lubricating oil 2015 1 The marine trunk piston engine lubricating oil composition, which is a monograde lubricating oil composition that meets the specifications for SAE J300 revised January 2015 requirements.

Condensation of polyisobutyl-substituted hydroxyaromatic compounds, aldehydes, amino acids and alkali metal bases with an activity of about 0.1% to about 10% by weight based on the total weight of the lubricating oil composition in the marine diesel lubricating composition. In at least one Mannig reaction product prepared by, the polyisobutyl group is derived from polyisobutene containing at least about 70% by weight of the methylvinylidene isomer, and the polyisobutyl group is from about 400 to about 2500. Those having a number average molecular weight of are the performance benefits, such as oil thickening (alternative to bright stock), improved detergency performance, reduced basicity degradation rate, foaming performance, and metal catalytic oxidation of lubricating oils. And it has been found that oxidative stability due to polymerization interference can be achieved.

Detailed description of preferred form "Residual fuel for ships" is the International Organization for Standardization Standard ISO 8217: 2005, "Petroleum products --Fuels (class F) --Specifications of marine fuels," which incorporates the entire content here. Viscosm greater than 14.0 cSt at 50 ° C., such as defined marine residual fuel, at least 2.5 weight (with respect to total fuel weight) of carbon residue as defined by the International Organization for Standardization (ISO) 10370). % (Eg, at least 5% by weight or at least 8% by weight) combustible material in a large marine engine.

“Residual fuel” means a fuel that meets the standards for residual marine fuel as described in ISO 8217: 2010 International Standards. "Low-sulfur marine fuel" is for residual vessels as described in ISO 8217: 2010, further having sulfur of about 1.5% by weight or less, or even about 0.5% by weight or less, with respect to the total weight of the fuel. A fuel that meets fuel standards.

“Distillate fuel” means a fuel that meets the standards for distillate marine fuel as described in ISO 8217: 2010 International Standards. A "low sulfur distillate fuel" is a distillate vessel as described in ISO 8217: 2010 International Standard, further containing no more than about 0.1% by weight or even less than about 0.005% by weight of sulfur with respect to the total weight of the fuel. A fuel that meets the standards for fuel for use.

"Low sulfur fuel" is about 1.5% by weight or less, more than 1.0% by weight, more than 0.5% by weight, or more than 0.1% by weight with respect to the total weight of the fuel. It means having sulfur.

The term "on an active (substance) basis" refers to an additive material that is neither a diluent oil nor a solvent.

The term "Mannich condensation product" as used herein is a condensation reaction of a polyisobutyl-substituted hydroxyaromatic compound with an aldehyde and an amino acid described herein in order to produce a condensation product having the following formula. Refers to the mixture of products obtained by. The formula below is provided only as an example of some of the Mannich condensation products believed to be of the present invention and is intended to exclude other possible Mannich condensation products that can be formed using the methods described herein. is not it.

ここで、Ｒ、Ｒ_１、Ｘ及びＷは、ここで定義されるものである。

Here, R, R ₁ , X and W are defined here.

The term "total base value" or "TBN" or "BN" means the level of alkalinity in an oil sample, which neutralizes corrosive acids according to ASTM Standard No. D2896 or equivalent procedures. Shows the ability of the composition to continue. The test measures changes in electrical conductivity and expresses the results as mg · KOH / g (milligram equivalents of KOH required to neutralize 1 gram of product). Thus, a high TBN represents a strong overbasic product and, as a result, a higher base reserve for neutralizing the acid.

The marine diesel lubricant composition of the present invention can have any TBN suitable for use as a marine lubricant. In some embodiments, the TBN of the marine lubricant composition of the present invention is less than about 200 mg KOH / g. In other embodiments, the TBN of the marine lubricating oil compositions of the present disclosure is about 5 to about 200, or about 5 to about 140, or about 5 to about 100, or about 5 to about 80, or about 5 to 5. About 70, or about 5 to about 50, or about 5 to 40, or about 5 to about 30, or about 5 to 25, or about 8 to about 200, or about 8 to about 140, or about 8 to about 100, Or about 8 to about 80, or 8 to about 40, or about 8 to about 30, or about 10 to about 200, or about 10 to about 140, 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 200, or about 15 to about 140, 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 200, or about 20 to about 140. , 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.

The lubricating oil composition is a SAE20 monograde lubricating oil composition, or a SAE30 monograde lubricating oil composition, or a SAE40 monograde lubricating oil composition, or a SAE50 monograde lubricating oil composition, or a SAE60 monograde lubricating oil composition. There can be. The monograde of the lubricating oil composition is defined according to the SAE J300 standard Rev. January 2015.

The marine diesel lubricating oil composition of the present invention has about 6.9 to about 26.1 cSt at 100 ° C, or about 9.3 to about 21.9 cSt at 100 ° C, or about 9.3 to about 16 at 100 ° C. .3 cSt, or about 12.5 to about 21.9 at 100 ° C, or about 12.5 to about 16.3 cSt at 100 ° C, or about 16.3 to about 21.9 cSt at 100 ° C, or about 100 ° C. It can have a kinematic viscosity in the range of 16.3 to about 26.1 cSt. The kinematic viscosity of the marine diesel lubricating oil composition is measured by ASTM D445.

The marine diesel lubricating oil composition can be a marine diesel cylinder lubricating oil composition. Marine cylinder lubricants are typically manufactured to the SAE30, SAE40, SAE50 or SAE60 standards to provide a sufficiently thick lubricating film at high temperatures on the cylinder liner wall. Typically, marine cylinder lubricants have a base value higher than 5 mg KOH / g as measured by ASTM D2896, and most recently have been blended as high as 200 mg KOH / g. The marine diesel cylinder lubricating oil composition of the present invention has about 9.3 to about 26.1 cSt at 100 ° C, or about 12.5 to about 26.1 cSt at 100 ° C, or about 12.5 to about 12.5 to about 100 ° C. It can have kinematic viscosities in the range of 21.9 cSt, about 16.3 to about 21.9 cSt at 100 ° C, or about 16.3 to about 26.1 cSt at 100 ° C. The marine diesel cylinder lubrication composition of the present invention is about 5 to about 200 mg KOH / g, or about 5 to about 140 mg KOH / g, or about 5 to about 100 mg KOH / g, or about 5 to about 70 mg KOH / g. , Or about 5 to about 40 mg KOH / g, or about 5 to about 30 mg KOH / g, or about 8 to about 200, or about 8 to about 140, or about 8 to about 100, or about 8 to about 80, or 8 to about 40, or about 8 to about 30, or about 10 to about 140 mg KOH / g, or about 10 to about 100 mg KOH / g, or about 10 to about 80 mg KOH / g, or about 10 to about 50 mg KOH / g, or about 10 to about 40 mg KOH / g, or about 15 to about 100 mg KOH / g, or about 15 to about 80 mg KOH / g, or about 15 to about 40 mg KOH / g, or about 20 to about 200 mg KOH / g. g, or about 20 to about 140 mg KOH / g, or about 20 to about 100 mg KOH / g, or about 20 to about 80 mg KOH / g, or about 25 to about 80 mg KOH / g, or about 30 to about 80 mg KOH / g. It can have a base value in the range of g.

The marine diesel lubricating oil composition can be a marine system oil lubricating oil composition. Marine system oils Lubricants are typically manufactured to the SAE20, SAE30 or SAE40 standards. The viscosity for marine system oils is partially set to such relatively low levels. This is because system oils can increase in viscosity during use, and engine designers have set limits on the increase in viscosity to prevent operational problems. The marine system oil lubricating oil composition of the present invention is about 6.9 to about 16.3 cSt at 100 ° C., or about 6.9 to about 12.5 cSt at 100 ° C., or about 6.9 to about 9.3. , Or can have kinematic viscosities in the range of about 9.3 to about 16.5 cSt at 100 ° C., or about 9.3 to about 12.5 cSt at 100 ° C. Typically, marine system oil lubricants have a base value higher than 5 mg KOH / g as measured by ASTM D2896. The marine system oil lubricant composition of the present invention is about 5 to about 40 mg KOH / g, or about 5 to about 30 mg KOH / g, or about 5 to about 25 mg KOH / g, or about 5 to about 15 mg KOH /. It can have a base value in the range of g, or about 10 to about 30 mg KOH / g, or about 8 to about 40, or about 8 to about 30, or about 8 to about 20 mg KOH / g.

The marine diesel lubricating oil composition can be a marine trunk piston engine oil lubricating oil composition. Marine trunk piston engine lubricants are typically manufactured to SAE30 or SAE40 standards. The marine trunk piston engine oil lubricating oil composition of the present invention may have kinematic viscosities in the range of about 9.3 to about 16.3 cSt at 100 ° C. or about 12.5 to about 16.3 cSt at 100 ° C. can. Typically, marine trunk piston engine oil lubricants have a base value greater than about 10 mg KOH / g as measured by ASTM D2896. The marine trunk piston engine oil can have a base value of 10 to about 80 mg KOH / g, for example 10 to about 60 mg KOH / g, 20 to 80 mg KOH / g, or about 20 to about 60 mg KOH / g. ..

The marine diesel lubricating oil composition of the present invention can be prepared by any method known to those skilled in the art for producing a marine diesel lubricating oil composition. The ingredients can be added in any order and in any way. Any suitable mixing or dispersing device can be used to blend, mix or solubilize the ingredients. Blending, mixing or solubilization can be carried out using a blender, stirrer, disperser, mixer, homogenizer, mill or any other mixing or dispersing device known in the art.

The marine diesel lubricant composition of the present invention contains a major amount of oil having a lubricating viscosity. "Major amount" means that the marine diesel lubricant composition is at least about 40% by weight, or at least about 45% by weight, or at least about 50% by weight, based on the total weight of the marine diesel lubricant composition. Alternatively, it means that at least about 55% by weight, or at least about 60% by weight, particularly at least about 70% by weight, of an oil having a lubricating viscosity as described below is preferably contained.

The oil having a lubricating viscosity can be any oil suitable for lubricating a marine diesel engine. The oil having a lubricating viscosity can be a base oil derived from a natural lubricating oil, a synthetic lubricating oil or a mixture thereof. Suitable base oils include basestocks obtained by isomerization of synthetic and slack waxes, as well as hydrocracked basestocks produced by hydrocracking (rather than solvent extraction) of aromatic and polar components of crude oils. included.

Suitable natural oils include, for example, mineral lubricating oils such as liquid petroleum, paraffinic, naphthenic or mixed paraffinic naphthenic solvent-treated or acid-treated mineral lubricating oils, coal or shale-derived oils, animal oils, vegetable oils ( For example, rapeseed oil, paraffin oil and lard oil) and the like are included.

Suitable synthetic lubricants 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 copolymers, chlorinated polybutylene, poly (1- Hexene), poly (1-octene), poly (1-decene) and the like; alkylbenzenes such as dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) -benzene and the like; polyphenyls such as Biphenyl, terphenyl, alkylated polyphenyl and the like; include alkylated diphenyl ether and alkylated diphenyl sulfide and derivatives, analogs and homologs thereof.

Other synthetic lubricants include, but are not limited to, oils made by polymerizing less than five carbon atom olefins such as ethylene, propylene, butylene, isobutene, pentene, and mixtures thereof. Methods of preparing such polymeric oils are well known to those of skill in the art. Additional synthetic hydrocarbon oils include liquid polymers of alpha olefins with appropriate viscosities. Particularly useful synthetic hydrocarbon oils are _{hydrogenated liquid oligomers such as C 6} to C ₁₂ alpha olefins, such as 1-decene trimers.

Other types of synthetic lubricants include, but are not limited to, alkylene oxide polymers, homopolymers in which the terminal hydroxyl groups are modified, for example by esterification or etherification, interpolymers and derivatives thereof. Examples of these oils are oils prepared by polymerization of ethylene oxide or propylene oxide, alkyl and phenyl ethers of these polyoxyalkylene polymers (eg, methylpolypropylene glycol ethers with an average molecular weight of 1,000, molecular weights from 500 to 500. Diphenyl ethers of 1,000 polyethylene glycols, diethyl ethers of polypropylene glycols having a molecular weight of 1,000 to 1,500, etc.) or their mono and polycarboxylic acid esters, such as acetates, mixed C ₃ to C ₈ fatty acid esters, or C ₁₃ oxo acid diester of tetraethylene glycol.

Yet another type of synthetic lubricant includes, but is not limited to, dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, malonic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipine. Acids, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc. and various alcohols, such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc. And ester is included. Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl sebacate), di-n-hexyl sebacate, dioctyl sebacate, diisooctyl sebacate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate. , Sebacic acid diecosyl, 2-ethylhexyl diester of linoleic acid dimer, composite ester formed by reaction of 1 mol of sebacic acid with 2 mol of tetraethylene glycol, 2 mol of 2-ethylhexanoic acid and the like. ..

Lubricating viscosity oils can be derived from natural or synthetic unrefined, refined and re-refined oils, or mixtures of any two or more of the above types. Unrefined oils are obtained directly from natural or synthetic sources (eg, coal, shale, or tar sands bitumen) without further refining or processing. Examples of unrefined oils include, but are not limited to, shale oils obtained directly from retort operations, petroleum directly obtained from distillation or esterified oils obtained directly from an esterification process, each of which is subsequently further. Used without processing. Refined oils are similar to unrefined oils, except that they have been 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, hydropurification, dewaxing and the like. The rerefined oil is obtained by processing the used oil in a process similar to the process used to obtain the refined oil. Such rerefined oils, also known as regenerated or reprocessed oils, are often additionally treated by techniques aimed at removing used additives and oil decomposition products.

In addition, the lubricating oil basestock derived from the hydrogenation isomerization of waxes can be used alone or in combination with said natural and / or synthetic basestocks. Such wax isomerized oils are produced by hydrogenation isomerization of natural or synthetic waxes or mixtures thereof on hydrogenation isomerization catalysts. Natural waxes are typically slack waxes recovered by solvent dewaxing of mineral oils. Synthetic wax is typically produced by the Fischer-Tropsch method.

In one embodiment, the lubricating viscosity oil is a Group I basestock (Class I basestock). In general, the base stock of group I for use here, API publications 1509, 16th Edition, Addendum I, 10 May 2009 ^{(API Publication 1509, 16 th Edition} , Addendum I, Oct., 2009) defined in It can be an oil-induced base oil having a lubrication viscosity. The API guidelines define basestock as a lubricant component that can be manufactured using a variety of different processes. Group I base oils (Class I base oils) generally have a saturation content of less than 90% by weight (quantified by ASTM D2007) and / or a total sulfur content of more than 300 ppm (ASTM D2622, ASTM D4294, ASTM D4297 or It means an oil-induced lubricating base oil having a viscosity index (VI) of 80 or more and less than 120 (quantified by ASTM D2270) (quantified by ASTM D3120).

Group I base oils can include light overhead cuts from vacuum distillation columns and heavier side cuts, and also include, for example, light neutral, medium neutral and heavy neutral basestocks. be able to. Further, the petroleum-derived base oil can contain, for example, a residual stock such as bright stock or a bottom fraction. Brightstock is a highly viscous base oil that has traditionally been produced from residual stocks or bottoms and has been highly refined and dewaxed. Brightstock can have kinematic viscosities in the range of about 180 cSt over 40 ° C, or about 250 cSt at 40 ° C, or about 500 to about 1100 cSt at 40 ° C.

In one embodiment, one or more basestocks can be a blend or mixture of two or more, three or more, or even four or more Group I basestocks having different molecular weights and viscosities. , The blend is processed in a manner suitable to produce a base oil having suitable properties (such as the viscosity and TBN values discussed above) for use in marine diesel engines. In one embodiment, one or more basestocks may include ExxonMobil CORE® 100, ExxonMobil CORE® 150, ExxonMobil CORE® 600, ExxonMobil CORE® 2500 or a combination thereof. Contains a mixture.

In another embodiment, the oil with a lubricating viscosity can be a Group II basestock (Class II basestock) as defined in API Publication 1509, 16th Edition, Addendum I, October 2009. Group II basestocks generally have a total sulfur content of 300 ppm (parts per million) or less (quantified by ASTM D2622, ASTM D4294, ASTM D4927 or ASTM D3120) and a saturation content of 90% by weight or more (according to ASTM D2007). Means petroleum-induced lubricating base oil with a quantitative index (VI) of 80 to 120 (quantitated by ASTM D2270).

In another embodiment, the oil with a lubricating viscosity can be a Group III basestock (Class III basestock) as defined in API Publication 1509, 16th Edition, Addendum I, October 2009. Group III basestocks generally have a total sulfur content of 0.03% by weight or less (quantified by ASTM D2270), a saturation content of 90% by weight or more (quantified by ASTM D2007), and a viscosity index (VI). 120 or more (quantified by ASTM D4294, ASTM D4297 or ASTM D3120). In one embodiment, the basestock is a Group III basestock, or a blend of two or more different Group III basestocks.

In general, Group III basestocks derived from petroleum-based oils are highly hydrogenated (hydrorefined) mineral oils. Hydrogenation involves reacting hydrogen with a basestock to be treated to remove heteroatoms from hydrocarbons, reducing olefins and aromatics to alkanes and cycloparakanes, respectively, and very advanced hydrogenation. The chemical treatment involves opening the naphthenic cyclic structure into acyclic normals and isoalkanes (“paraffins”). In one embodiment, Group III base stocks, have at least about 70% paraffinic carbon content (% _{C p),} which is the test method ASTM D3238-95 (2005), "Standard Test Method for Calculation of Carbon Quantified by "Distribution and Structural Group Analysis of Petroleum Oils by the ndM Method". In another embodiment, the Group III basestock has a paraffinic carbon content (% _Cp ) of at least about 72%. In another embodiment, the Group III basestock has a paraffinic carbon content (% _Cp ) of at least about 75%. In another embodiment, the Group III basestock has a paraffinic carbon content (% _Cp ) of at least about 78%. In another embodiment, the Group III basestock has a paraffinic carbon content (% _Cp ) of at least about 80%. In another embodiment, the Group III basestock has a paraffinic carbon content (% _Cp ) 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 quantified by the ASTM D3238-95 (2005). In another embodiment, Group III base stocks have a naphthenic carbon content of less than about 20% (% _{C n).} In another embodiment, Group III base stocks have a naphthenic carbon content of less than about 15% (% _{C n).} In another embodiment, Group III base stocks have a naphthenic carbon content of less than about 10% (% _{C n).}

In one embodiment, the Group III basestock for use here is a Fischer-Tropsch-induced base oil. The term "Fischer-Tropsch induction" means that a product, fraction, or feed is produced from the Fischer-Tropsch process or at some stage by the Fischer-Tropsch process. For example, Fischer-Tropsch base oil can be produced from a process in which the feed is a waxy (wax-like) feed recovered from Fischer-Tropsch synthesis, eg, US Patent Application Publication No. 2004/0159582; 2005/0077208; 2005/01333407; 2005/01333409; 2005/0139513; 2005/0139514; 2005/0241990, each of which is incorporated herein by reference. do. Generally, the process involves a complete or partial hydrogenation isomerization dewaxing step utilizing a catalyst capable of selectively isomerizing paraffin or a binary functional catalyst. Hydrogenation isomerization dewaxing is achieved by contacting a waxy feed with a hydrogenation isomerization catalyst under hydrogenation isomerization conditions in the isomerization zone.

In another embodiment, the oil with a lubricating viscosity can be a Group IV basestock (Type IV basestock) as defined in API Publication 1509, 16th Edition, Addendum I, October 2009. Group IV basestocks, or polyalphaolefins (PAOs), 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., which is precisely mixed according to the desired final basestock viscosity. PAOs are typically hydrogenated after oligomerization to remove the remaining unsaturated material.

As mentioned above, lubricants for use in marine diesel engines typically have kinematic viscosities in the range of 6.9 to 26.1 cSt at 100 ° C. Brightstock can be combined with lower viscosity oils to formulate such lubricants. However, as the supply of brightstock is declining, it is not possible to rely on brightstock to increase the viscosity of marine lubricants to the desired range recommended by the manufacturer. One solution to this problem is to use a thickener such as polyisobutylene (PIB) or a viscosity index improver such as an olefin copolymer to increase the viscosity of marine lubricants. PIB is a material commercially available from several manufacturers. PIBs typically have 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. It is a viscous oil-miscible liquid having a viscosity in the range of (100 ° C.). The amount of PIB added to marine lubricants 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 4 of the final oil. Will be about 12% by weight.

The lubricating oil composition of the present invention is about 0.1% by weight to about 10.0% by weight, or about 0.5% by weight to about 10.0% by weight, or about 10.0% by weight, based on the total weight of the lubricating oil composition. 0.5% to about 8.0% by weight, or about 1.0% to about 10.0% by weight, or about 3.0% to about 10.0% by weight, or about 3.0% by weight ~ About 8.0% by weight, or about 2.5 to about 10.0% by weight, or about 2.5% to about 8.0% by weight of active polyisobutyl substituted hydroxyaromatic compounds, aldehydes, amino acids or The ester derivative, and at least one Mannich reaction product prepared by the condensation of an alkali metal base, in which the polyisobutyl group is derived from polyisobutene containing at least about 70% by weight of the methylvinylidene isomer, and Polyisobutyl groups will further contain those having a number average molecular weight of about 400 to about 2500. In general, the major Mannich condensation products can be represented by the structure of formula I:

（ここで、Ｙ’は−ＣＨＲ’ＯＨであり、Ｒ’は上記で定義されたものであり；及びＲ、Ｘ，及びＷは上記で定義されたもの）か、であり；
Ｚは、ヒドロキシルか、又は、下記の式のヒドロキシフェニル基である：

上記式中、Ｒ、Ｒ_１、Ｙ’、Ｘ，及びＷは、上記で定義されたものであり、
そして、ｎは、０〜２０の整数であり、ただし、ｎ＝０の時、Ｚは下記のものでなければならない：

上記式中、Ｒ、Ｒ_１、Ｙ’、Ｘ，及びＷは、上記で定義されたものである。 In the above formula, each R is independently -CHR'-, and R'is a branched chain or linear alkyl having 1 carbon atom to about 10 carbon atoms, and about 3 carbon atoms. ~ Cycloalkyl with about 10 carbon atoms, about 6 carbon atoms ~ aryl with about 10 carbon atoms, about 7 carbon atoms ~ alkalil with about 20 carbon atoms, or about It is an aralkyl having 7 carbon atoms to about 20 carbon atoms, and R ₁ has a number average molecular weight in the range of about 400 to about 2500 and contains at least about 70% by weight of methylvinylidene isomer. It is a polyisobutyl group derived from polyisobutene.
X is a hydrogen, an alkali metal ion, or an alkyl having 1 to about 6 carbon atoms;
W is − [CHR''] − _m , where each R'' is independently H, an alkyl having one carbon atom to about 15 carbon atoms, or an amino. Has one or more substituents selected from the group consisting of, amide, benzyl, carboxyl, hydroxyl, hydroxyphenyl, imidazolyl, imino, phenyl, sulfide, or thiol and one carbon atom to about 10 carbon atoms. Is it a substituted alkyl; and m is an integer from 1 to 4;
Y is hydrogen, alkyl with one carbon atom to about 10 carbon atoms, -CHR'OH (R'is defined above), or

(Here, Y'is -CHR'OH, R'is as defined above; and R, X, and W are as defined above).
Z is a hydroxyl or a hydroxyphenyl group of the formula below:

In the above formula, R, R ₁ , Y', X, and W are defined above.
And n is an integer from 0 to 20, where when n = 0, Z must be:

In the above formula, R, R ₁ , Y', X, and W are those defined above.

In one embodiment, _{R 1} polyisobutyl group has a number average molecular weight of from about 500 to about 2500. In one embodiment, _{R 1} polyisobutyl group has a number average molecular weight of from about 700 to about 1,500. In one embodiment, _{R 1} polyisobutyl group has a number average molecular weight of from about 700 to about 1,100. In one embodiment, R ₁ polyisobutyl group is derived from polyisobutene containing at least about 70 weight percent methylvinylidene isomer, in one form, R ₁ polyisobutyl group is at least about 90 weight percent methylvinylidene isomer Derived from polyisobutene containing the body.

In the compound of formula I above, X is an alkali metal ion, most preferably sodium or potassium ion. In another embodiment, in the compound of formula I above, X is an alkyl selected from methyl or ethyl. In one form, the marine diesel lubricant composition of the present invention comprises a Mannich reaction product and the alkali metal used in the production of the Mannich product is sodium. In another embodiment, the marine diesel lubricant composition of the present invention comprises a Mannich reaction product and the alkali metal used in the production of the Mannich product is potassium. In another embodiment, the marine diesel lubricating oil composition of the present invention comprises a combination of Mannich reaction products, and the alkali metals used in the production of the Mannich product are potassium and sodium.

In one form, R is CH ₂ , R ₁ is derived from polyisobutene containing a number average molecular weight in the range of about 700 to about 1,100 and at least about 70% by weight of the methylvinylidene isomer, and W is CH. ₂ , X is a sodium ion, and n is 0-20.

上記式中、Ｒ_１は、約４００〜約２５００の範囲の数平均分子量を有しかつ少なくとも約７０重量％のメチルビニリデン異性体を含有するポリイソブテンから誘導されたポリイソブチル基であり、Ｒ_２は、水素か又は１個の炭素原子〜約１０個の炭素原子を有する低級アルキルであり、そして、Ｒ_３は水素か又は−ＯＨである；
（ｂ）ホルムアルデヒド又は下記の式を有するアルデヒド：

上記式中、Ｒ’は、１個の炭素原子〜約１０個の炭素原子を有する分枝鎖又は直鎖アルキルか、約３個の炭素原子〜約１０個の炭素原子を有するシクロアルキルか、約６個の炭素原子〜約１０個の炭素原子を有するアリールか、約７個の炭素原子〜約２０個の炭素原子を有するアルカリールか、又は約７個の炭素原子〜約２０個の炭素原子を有するアラルキルである；
（ｃ）下記の式を有するアミノ酸又はそのエステル誘導体：

上記式中、Ｗは、−［ＣＨＲ’’］−_ｍであり、ここで、各Ｒ’’は、独立して、Ｈか、１個の炭素原子〜約１５個の炭素原子を有するアルキルか、又は、アミノ、アミド、ベンジル、カルボキシル、ヒドロキシル、ヒドロキシフェニル、イミダゾリル、イミノ、フェニル、スルフィド、又はチオールから成る群から選択される１つ以上の置換基及び１個の炭素原子〜約１０個の炭素原子を有する置換アルキルであり；ｍは、１〜４の整数であり，Ａは、水素か又は１個の炭素原子〜約６個の炭素原子を有するアルキルである；及び
（ｄ）アルカリ金属塩基。 Mannig condensation products for use in the lubricating oil compositions of the present invention can be prepared under reaction conditions by combining polyisobutyl-substituted hydroxy aromatic compounds, aldehydes, amino acids or ester derivatives thereof, and alkali metal bases. Here, the polyisobutyl group has a number average molecular weight of about 400 to about 2500. In one form, the Mannich condensation product is prepared by the Mannich condensation of (a); (b); (c); and (d) below:
(A) Polyisobutyl-substituted hydroxyaromatic compound having the following formula:

In the above formula, R ₁ is a polyisobutyl group derived from polyisobutene having a number average molecular weight in the range of about 400 to about 2500 and containing at least about 70% by weight of the methylvinylidene isomer, and R ₂ is , Hydrogen or a lower alkyl having 1 to about 10 carbon atoms, and R ₃ is hydrogen or -OH;
(B) Formaldehyde or an aldehyde having the following formula:

In the above formula, R'is a branched chain or a linear alkyl having one carbon atom to about 10 carbon atoms, or a cycloalkyl having about 3 carbon atoms to about 10 carbon atoms. Aryl having about 6 carbon atoms to about 10 carbon atoms, Alkalial having about 7 carbon atoms to about 20 carbon atoms, or about 7 carbon atoms to about 20 carbon atoms. Aralkill with atoms;
(C) An amino acid having the following formula or an ester derivative thereof:

In the above formula, W is − [CHR''] − _m , where each R'' is independently H or an alkyl having one carbon atom to about 15 carbon atoms. , Or one or more substituents selected from the group consisting of amino, amide, benzyl, carboxyl, hydroxyl, hydroxyphenyl, imidazolyl, imino, phenyl, sulfide, or thiol and one carbon atom to about 10 It is a substituted alkyl having a carbon atom; m is an integer of 1 to 4, A is hydrogen or an alkyl having 1 carbon atom to about 6 carbon atoms; and (d) alkali metal. base.

Various polyisobutyl-substituted hydroxyaromatic compounds can be used in the preparation of the Mannich condensation products of the present invention. An important feature is that the polyisobutyl substituents are large enough to impart oil solubility to the finished Mannich condensation product. In general, the number of carbon atoms on the polyisobutyl substituent is required to allow for oil solubility of the Mannich condensation product is on the order of approximately about C ₂₀ or higher. This corresponds to a molecular weight in the range of about 400 to about 2500. C ₂₀ or higher alkyl substituent on the phenol ring, to position para to the OH group on the phenol is desirable.

The polyisobutyl-substituted hydroxyaromatic compound is typically a polyisobutyl-substituted phenol, the polyisobutyl moiety being derived from polyisobutene containing at least about 70% by weight of the methylvinylidene isomer, more preferably the polyisobutyl moiety. Is derived from polyisobutene containing at least about 90% by weight of the methylvinylidene isomer. The term "polyisobutyl or polyisobutyl substituent" used herein refers to a polyisobutyl substituent on a hydroxyaromatic ring. Polyisobutyl substituents have a number average molecular weight in the range of about 400 to about 2500. In one form, the polyisobutyl moiety has a number average molecular weight in the range of about 450 to about 2500. In one form, the polyisobutyl moiety has a number average molecular weight in the range of about 700 to about 1500. In one form, the polyisobutyl moiety has a number average molecular weight in the range of about 700 to about 1100.

Disubstituted phenols are also suitable starting materials for the Mannich condensation products of the present invention. Disubstituted phenols are suitable if they are substituted in such a way that an unsubstituted ortho position is present on the phenol ring. Examples of suitable disubstituted phenols, o- cresol derivatives substituted with C ₂₀ or polyisobutyl substituent in the para position, and the like.

ここで、Ｒ_１は、約４００〜約２５００の範囲の数平均分子量を有しかつ少なくとも約７０重量％のメチルビニリデン異性体を含有するポリイソブテンから誘導されたポリイソブチル基であり、Ｙは水素である。 In one form, the polyisobutyl-substituted phenol has the following formula:

Here, R ₁ is a polyisobutyl group derived from polyisobutene having a number average molecular weight in the range of about 400 to about 2500 and containing at least about 70% by weight of the methylvinylidene isomer, and Y is hydrogen. be.

_{Suitable polyisobutene can be prepared using a boron trifluoride (BF 3} ) alkylation catalyst as described in US Pat. Nos. 4,152,499 and 4,605,808, for each of these references. The content is incorporated here by reference. Commercially available polyisobutenes with high alkylvinylidene content include Glissopal® 1000, 1300 and 2300 available from BASF.

The preferred polyisobutyl-substituted phenol for use in the preparation of the Mannich condensation product is a mono-substituted phenol, with the polyisobutyl substituent attached to the para-position of the phenol ring. However, other polyisobutyl-substituted phenols that can undergo the Mannich condensation reaction can also be used for the preparation of the Mannich condensation product according to the present invention.

Solvents can be used to facilitate the reaction and handling of polyisobutyl-substituted phenols in the preparation of the Mannich condensation product. Examples of suitable solvents are hydrocarbon compounds such as heptane, benzene, toluene, chlorobenzene, aromatic solvents, neutral oils with lubricating viscosities, paraffin and naphthene. Examples of other suitable solvents on the market that are aromatic mixtures include Chevron® Aromatic 100N, Neutral Oil, Exxon® 150N, Neutral Oil.

In one form, the Mannich condensation product can first be dissolved in an alkyl-substituted aromatic solvent. Generally, alkyl substituents on aromatic solvents have from about 3 carbon atoms to about 15 carbon atoms. In one form, the alkyl substituents on the aromatic solvent have from about 6 carbon atoms to about 12 carbon atoms.

ここで、Ｒ’は、１個の炭素原子〜約１０個の炭素原子を有する分枝鎖又は直鎖アルキル、約３個の炭素原子〜約１０個の炭素原子を有するシクロアルキル、約６個の炭素原子〜約１０個の炭素原子を有するアリール、約７個の炭素原子〜約２０個の炭素原子を有するアルカリール、又は約７個の炭素原子〜約２０個の炭素原子を有するアラルキルである。 Suitable aldehydes for use in forming the Mannich condensation product include formaldehyde or aldehydes having the formula below:

Here, R'is a branched chain or linear alkyl having 1 carbon atom to about 10 carbon atoms, a cycloalkyl having about 3 carbon atoms to about 10 carbon atoms, and about 6 carbon atoms. With an aryl having about 10 carbon atoms, an alkalil having about 7 carbon atoms to about 20 carbon atoms, or an aralkyl having about 7 carbon atoms to about 20 carbon atoms. be.

Representative aldehydes include, but are not limited to, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, barrelaldehyde, caproaldehyde and heptaldehyde. Aromatic aldehydes such as benzaldehyde and alkylbenzaldehyde, such as paitolaldehyde, are also contemplated for use in the preparation of Mannich condensation products. Formaldehyde-producing reagents such as paraformaldehyde and aqueous formaldehyde solutions such as formalin are also useful. In one preferred form, the aldehyde for use in the preparation of the Mannich condensation product is formaldehyde or formalin. Formaldehyde means all its forms, including gaseous, liquid and solid. Examples of gaseous formaldehyde are the monomer CH ₂ O and a trimer having the following formula, (CH ₂ O) ₃ (trioxane).

Examples of liquid formaldehyde are:
Monomer CH ₂ O in ethyl ether.
_{Monomer CH 2} O in water having the formula HO (-CH ₂ O) _n- H and CH ₂ (H ₂ O) ₂ (methylene glycol).
_{Monomer CH 2} O in methanol having the formula CH ₃ O (-CH ₂ O) _n- H and OHCH ₂ OCH _3.

Formaldehyde solutions are commercially available in various alcohols and waters. In water, it is available as a 37% -50% solution. Formalin is a 37% solution in water. Formaldehyde is also commercially available as linear and cyclic (trioxane) polymers. The linear polymer can be a low molecular weight or high molecular weight polymer.

ここで、Ｗは、−［ＣＨＲ’’］_ｍ−であり、各Ｒ’’は、独立して、Ｈか、１個の炭素原子〜約１５個の炭素原子を有するアルキルか、又は、アミノ、アミド、ベンジル、カルボキシル、ヒドロキシル、ヒドロキシフェニル、イミダゾリル、イミノ、フェニル、スルフィド、又はチオールから成る群から選択される１つ以上の置換基及び１個の炭素原子〜約１０個の炭素原子を有する置換アルキルであり；ｍは１〜４の整数であり；Ａは、水素又は１個の炭素原子〜約６個の炭素原子を有するアルキルである。好ましくは、アルキルは、メチル又はエチルである。 Suitable amino acids or ester derivatives thereof for use in forming the Mannich condensation product include amino acids having the formula:

Here, W is − [CHR''] _m −, and each R'' is independently H, an alkyl having one carbon atom to about 15 carbon atoms, or an amino. Has one or more substituents selected from the group consisting of, amide, benzyl, carboxyl, hydroxyl, hydroxyphenyl, imidazolyl, imino, phenyl, sulfide, or thiol and one carbon atom to about 10 carbon atoms. It is a substituted alkyl; m is an integer of 1 to 4; A is hydrogen or an alkyl having 1 carbon atom to about 6 carbon atoms. Preferably, the alkyl is methyl or ethyl.

In one form, the amino acid is glycine.

ここで、Ｗは上記で定義されたものであり、Ｍはアルカリ金属イオンである。好ましくは、Ｍは、ナトリウムイオン又はカリウムイオンである。より好ましくは、Ｘはナトリウムイオンである。 The term "amino acid salt" used herein refers to a salt of an amino acid having the following formula:

Here, W is defined above and M is an alkali metal ion. Preferably, M is a sodium ion or a potassium ion. More preferably, X is a sodium ion.

Some examples of alpha amino acids intended for use in the preparation of Mannig condensation products are: alanine, arginine, asparagine, aspartic acid, cysteine, cysteine, glutamic acid, glutamine, glycine, histidine, Hydroxylysine, isoleucine, leucine, lysine, methionine, phenylalanine, serine, threonine, tyrosine, and valine.

Suitable alkali metal bases for use in forming Mannig condensation products include alkali metal hydroxides, alkali metal alkoxides and the like. In one form, the alkali metal base is an alkali metal hydroxide selected from the group consisting of sodium hydroxide, lithium hydroxide or potassium hydroxide.

In one form, the amino acid can be added in the form of its alkali metal ionic salt. In one form, the alkali metal ion is a sodium ion or a potassium ion. In one preferred form, the alkali metal ion is a sodium ion.

The reaction to form the Mannich condensation product can be carried out in batch, continuous or semi-continuous mode. Normally, the pressure of this reaction is atmospheric pressure, but the reaction can be carried out under a pressure lower than atmospheric pressure or overpressure, if necessary.

The temperature of this reaction can vary widely. The temperature range of this reaction can be varied from about 10 ° C to about 200 ° C, or from about 50 ° C to about 150 ° C, or from about 70 ° C to about 130 ° C.

The reaction can be carried out in the presence of a diluent or a mixture of diluents. The important thing is to ensure that they are in close contact with each other in order for the reactants to react. This is an important consideration. This is because the starting material for the Mannich condensation product contains a relatively non-polar polyisobutyl-substituted hydroxyl aromatic compound and a relatively polar amino acid or an ester derivative thereof. Therefore, it is necessary to find an appropriate set of diluent or reaction conditions that will dissolve all starting materials.

The diluent for this reaction must be capable of dissolving the starting material for this reaction and allowing the reaction materials to come into contact with each other. A mixture of diluents can be used in this reaction. Useful diluents for this reaction include: water, alcohol (including: methanol, ethanol, isopropanol, 1-propanol, 1-butanol, isobutanol, sec-butanol, butanediol, 2). -Ethylhexanol, 1-pentanol, 1-hexanol, ethylene glycol, etc.), DMSO, NMP, HMPA, cellosolve, diglyme, various ethers (including: diethyl ether, THF, diphenyl ether, dioxane, etc.), aromatic Group diluents (including: toluene, benzene, o-xylene, m-xylene, p-xylene, mesitylen, etc.), esters, alkanes (including: pentane, hexane, heptane, octane, etc.), And various natural and synthetic diluting oils (including: 100 neutral oils, 150 neutral oils, polyalphaolefins, Fisher-Tropsch-induced base oils, etc., and mixtures of these diluents, such as methanol and heptane. A mixture of diluents forming the two phases is a suitable diluent for this reaction.

The reaction can be carried out by first reacting the hydroxy aromatic compound with an alkali metal base followed by the addition of an amino acid or an ester derivative thereof and an aldehyde, or by reacting the amino acid or an ester derivative thereof with an aldehyde and then. , Hydroxy aromatic compounds, alkali metal bases and the like can also be added.

当該中間体は、最終的には下記の環状構造を形成できる：

Reactions of amino acids such as glycine or ester derivatives thereof, plus aldehydes such as formaldehyde are thought to be able to produce intermediates of the formula below:

The intermediate can eventually form the following cyclic structure:

It is believed that these intermediates can react with hydroxyaromatic compounds and bases to form the Mannich condensation product of the invention.

Alternatively, it is believed that the reaction of hydroxyaromatic compounds with aldehydes can produce intermediates of the formula below:

It is believed that this intermediate can react with amino acids or ester derivatives and bases thereof to form the Mannich condensation product of the present invention.

The reaction time can vary widely depending on the temperature. The reaction time can vary from about 0.1 hour to about 20 hours, or from about 2 hours to about 10 hours, or from about 3 hours to about 7 hours.

The reagent input molar ratio (CMR) can also be varied over a wide range. Table I below gives a list of different formulas that can occur if different input molar ratios are used. At a minimum, the oil-soluble Mannich condensation product should preferably contain one amino acid group linked by one alkali metal and one aldehyde group and at least one polyisobutyl substituted phenolic ring. The input molar ratio of polyisobutyl-substituted phenol / aldehyde / amino acid / base in this molecule, which is also shown in Table I below, is 1.0: 1.0: 1.0: 1.0. Other input molar ratios are also possible, and the use of other input molar ratios can lead to the production of different molecules of different formulas.

In a further embodiment, any of the lubricating oil compositions of the invention discussed herein can further comprise one or more additives other than the Mannich product. Such additives can be detergents or dispersants.

In one embodiment, the marine diesel lubricating oil composition of the present invention is a polyalkene dispersant of one or more polyalkenyl succinimide dispersants, wherein the polyalkenyl substituent has a number average molecular weight of about 900 to about 3000. Further included are dispersants derived from the group. In general, biscus cinimide is a complete reaction product from a reaction between a polyalkenyl-substituted succinic acid or anhydride and one or more polyamine reactants, the product of which is anhydrous with a primary amino group. It is intended to include compounds that may have amide, amidin, and / or salt bonds, in addition to the type of imide bond obtained from the reaction with the physical moiety. Bisuccinimide dispersants are prepared according to methods well known in the art, for example, certain basic types of succinimide and related substances included in the term "succinimide" in the art are, for example, US Pat. No. 2. , 992,708; 3,018,291; 3,024,237; 3,100,673; 3,219,666; 3,172,892; and 3,272,746. Is incorporated herein by reference.

式中、Ｒは、数平均分子量が約９００から約３０００のポリアルケン基から誘導されるポリアルケニル置換基である。一実施形態では、Ｒは、約９００から約２５００の数平均分子量を有するポリアルケン基から誘導されるポリアルケニル置換基である。一実施形態では、Ｒは、約１５００から約３０００の数平均分子量を有するポリブテンから誘導されるポリブテニル置換基である。別の実施形態では、Ｒは、約２０００から約３０００の数平均分子量を有するポリブテンから誘導されるポリブテニル置換基である。別の実施形態では、Ｒは、約１５００から約２５００の数平均分子量を有するポリブテンから誘導されるポリブテニル置換基である。 In one embodiment, one or more polyalkenyl succinimide dispersants can be obtained by reacting the polyalkenyl-substituted succinic anhydride of formula I with a polyamine.

In the formula, R is a polyalkenyl substituent derived from a polyalkene group having a number average molecular weight of about 900 to about 3000. In one embodiment, R is a polyalkenyl substituent derived from a polyalkene group having a number average molecular weight of about 900 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 2000 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.

Preparation of polyalkenyl-substituted succinic anhydride by reaction of polyolefin with maleic anhydride is described, for example, in US Pat. Nos. 3,018,250 and 3,024,195. Such methods include thermal reactions of polyolefins with maleic anhydride, and reactions of halogenated polyolefins such as chlorinated polyolefins with maleic anhydride. Reduction of polyalkenyl-substituted succinic anhydride gives the corresponding alkyl derivative. Alternatively, polyalkenyl-substituted succinic anhydride can be prepared, for example, as described in US Pat. Nos. 4,388,471 and 4,450,281, with reference to the contents herein. Invite to.

Polyalkene groups having a number average molecular weight of about 900 to about 3000 for reaction with maleic anhydride and the like and succinic anhydride are major 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 homopolymer such as polyisobutylene and a copolymer of two or more such olefins such as a copolymer of ethylene and propylene, butylene and isobutylene. Other copolymers, copolymers monomers small amounts (e.g., 1 to 20 mole percent), C ₈ nonconjugated diolefin from C _4, for example, copolymers or ethylene of isobutylene and butadiene, propylene and 1,4-hexadiene copolymers Etc. are included.

A particularly preferred class of polyalkene groups having a number average molecular weight of about 900 to about 3000 includes polybutenes prepared by polymerization of one or more of 1-butene, 2-butene and isobutene. Polybutene containing a substantial proportion of isobutene-derived units is particularly desirable. Polybutenes can contain small amounts of butadiene, which may or may not be bound (incorporated) into the polymer. In most cases, isobutene units make up about 80%, or at least about 90%, of the units in the polymer. These polybutenes are readily available commercially available materials known to those of skill in the art, such as US Pat. Nos. 3,215,707; 3,231,587; 3,515,669; It is described in Nos. 3,579,450 and 3,912,764, the contents of which are incorporated herein by reference.

Polyamines suitable for use in the preparation of non-booxide bissuccinimide dispersants include polyalkylene polyamines. Such polyalkylene polyamines typically contain from about 2 to about 12 nitrogen atoms and from about 2 to 24 carbon atoms. Particularly suitable polyalkylene polyamines are of the formula: H ₂ N- (R ¹ NH) _c H (in the formula, R ¹ is a straight or branched chain alkylene group having 2 or 3 carbon atoms, where 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 polyamines (eg, Dow HPA-X number average molecular weight 275 available from Dow Chemical Company, Midland, Mich.). Is done. Such amines include isomers such as the substituted polyamines mentioned above, including branched chain polyamines and hydrocarbyl substituted polyamines. HPA-X heavy polyamines (“HPA-X”) contain an average of about 6.5 amine nitrogen atoms per molecule. Such heavy polyamines generally give excellent results.

Generally, from a polyalkene group of one or more polyalkenyl biscusinimide dispersants in the marine diesel lubricating oil composition of the present invention, wherein the polyalkenyl substituent has a number average molecular weight of about 900 to about 3000. The induced dispersant concentration is about 0.25% by weight, or about 0.5% by weight, or about 1. Over 0% by weight, or over about 1.2% by weight, or over about 1.5% by weight, or over about 1.8% by weight, or over about 2.0% by weight, or over about 2.5% by weight, Or it is over about 2.8% by weight. In another embodiment, one or more non-booxide polyalkenyl biscusinimide dispersants present in the marine diesel lubricating oil composition of the present invention, wherein the polyalkenyl substituents are from about 900 to about 3000. The amount of dispersant derived from the polyalkene group having a number average molecular weight is about 0.25 to 10% by weight, or about 0. 25 to 8.0% by weight, or about 0.25 to 5.0% by weight, or about 0.25 to 4.0% by weight, or 0.25 to 3.0% by weight, or about 0.5 to 10 %%, or about 0.5 to 8.0% by weight, or about 0.5 to 5.0% by weight, or about 0.5 to 4.0% by weight, or about 0.5 to 3.0% by weight. , Or about 0.5 to 10% by weight, or about 0.5 to 8.0% by weight, or about 1.0 to 5.0% by weight, or about 1.0 to 4.0% by weight, or about 1 .0 to 3.0% by weight, or about 1.5 to 10% by weight, or about 1.5 to 8.0% by weight, or about 1.5 to 5.0% by weight, or about 1.5 to 4 0.0% 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 about 2.0 to 5.0% by weight. , Or can be in the range of about 2.0 to 4.0% by weight.

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

The polyalkenyl succinimide dispersant of this embodiment is post-treated with cyclic carbonate to form a cyclic carbonate post-treated polyalkenyl succinimide dispersant. Cyclic carbonates suitable for use in the present invention include, but are not limited to, 1,3-dioxolane-2-one (ethylene carbonate): 4-methyl-1,3-dioxolane-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 can be prepared from saccharides such as sorbitol, glucose, fructose, galactose and from vicinal diols prepared from C _{1 to C 30 olefins by methods known in the art.}

Polyalkenyl succinimide dispersants can be post-treated with cyclic carbonate according to methods well known in the art. For example, a cyclic carbonate post-treatment polyalkenyl succinimide dispersant comprises charging the bissuccinimide dispersant into a reactor, optionally under a nitrogen purge, and heating at a temperature of about 80 ° C to about 170 ° C. Can be prepared by. Optionally, the diluted oil can be charged into the same reactor under nitrogen purge. Cyclic carbonate is charged into the reactor, optionally under 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 mixture is depressurized for about 0.5 to about 2.0 hours to remove the water formed by the reaction.

In order to impart an auxiliary function, the marine diesel lubricating oil composition of the present invention also contains an additive of a conventional marine diesel lubricating oil composition other than the above-mentioned dispersant, and these additives are added. Can be obtained as a marine diesel lubricating oil composition in which is dispersed or dissolved. For example, marine diesel lubricant compositions include antioxidants, cleaning agents (cleaning agents), anti-wear agents, rust inhibitors, defoaming agents, anti-emulsifiers, metal inactivating agents, friction modifiers, and flow point descent. It can be blended with agents, antifoaming agents, auxiliary 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 the preparation of the marine diesel lubricating oil compositions of the present invention by ordinary blending procedures.

In one embodiment, the marine diesel lubricating oil composition of the present invention is essentially free of thickeners (ie, viscosity index improvers).

The marine diesel lubricating oil composition of the present invention may contain one or more antioxidants capable of reducing or preventing oxidation of the base oil. Non-limiting examples of suitable antioxidants include amine-based antioxidants such as alkyldiphenylamines such as bisnonylated diphenylamines, bisoctylated diphenylamines, and octylated / butylated diphenylamines, phenyl-α-naphthylamines, alkyls or Arylalkyl-substituted phenyl-α-naphthylamines, alkylated p-phenylenediamines, tetramethyldiaminodiphenylamines, 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, etc.), phosphorus-based antioxidants, zinc dithiophosphate, and These combinations are included.

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

The marine diesel lubricating oil composition of the present invention may contain one or more cleaning agents. Metal-containing cleaners or ash-forming cleaners act as both cleaners (cleaners) that reduce or remove deposits (precipitates), as well as acid neutralizers or rust inhibitors, thereby causing wear and corrosion. It is reduced and the engine life is extended. The cleaning agent generally includes a polar head (polar head) having a long hydrophobic tail (hydrophobic tail). The polar head contains a metal salt of an acidic organic compound. Salts can contain substantially stoichiometric amounts of metals, in which case they are usually described as positive or neutral salts. Large amounts of metal bases can be incorporated by reacting excess metal compounds (eg, oxides or hydroxides) with acid gases (eg, carbon dioxide).

Cleaners that can be used include oil-soluble neutral and perbasic sulfonates (sulfonates), phenates, especially of alkaline or alkaline earth metals, such as metals such as barium, sodium, potassium, lithium, calcium, and magnesium. Includes sulfide phenates, thiophosphonates, salicylates and naphthenates and other oil-soluble carboxylates. The most commonly used metals are calcium and magnesium, both of which can be present in the detergent used in the lubricant and are a mixture of calcium and / or magnesium and sodium.

Commercially available products are commonly referred to as neutral or hyperbasic. Hyperbasic metal detergents generally include hydrocarbons, detergent acids (detergent acids), eg: sulfonic acids, carboxylates, etc., metal oxides or hydroxides (eg calcium oxide or calcium hydroxide) and promotes. It is produced by carbonating a mixture of agents (promoters), such as xylene, methanol and water. For example, in carbonation (carbonation), in order to prepare perbasic calcium sulfonate, calcium oxide or calcium hydroxide is reacted with gaseous carbon dioxide to form calcium carbonate (calcium carbonate). Sulfonic acid is neutralized with excess CaO or Ca (OH) ₂ to form sulfonates.

The overbasic detergent can be a hyperbasic salt with low hyperbasicity, eg, less than 100 TBN. In one embodiment, the TBN of the low hyperbasic salt can be from about 5 to about 50. In another embodiment, the TBN of the low hyperbasic salt can be from about 10 to about 30. In yet another embodiment, the TBN of the low hyperbasic salt can be from about 15 to about 20.

The hyperbasic detergent can be a medium hyperbasic, eg, a hyperbasic salt having a TBN of about 100 to about 250. In one embodiment, the TBN of the medium hyperbasic salt can be from about 100 to about 200. In another embodiment, the TBN of the medium hyperbasic salt can be from about 125 to about 175.

The hyperbasic detergent can be a hyperbasic salt that is highly hyperbasic, eg, has a TBN greater than 250. In one embodiment, the TBN of highly hyperbasic salts can be from about 250 to about 550.

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

Alkali-substituted hydroxyaromatic carboxylic acid alkali metal salts or alkaline earth metal salts are derived from alpha olefins having about 10 to about 80 carbon atoms. The olefins used can be straight chain, isomerized straight chain, branched chain or partially branched straight chain. The olefin can be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched chain 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 about 12 to about 30 carbon atoms per molecule. In one embodiment, the normal alpha olefin is isomerized using at least one solid or liquid catalyst.

In another embodiment, the olefin is a branched chain olefinic propylene oligomer or mixture thereof having about 20 to about 80 carbon atoms, i.e. a branched chain olefin derived from the polymerization of propylene. The olefin may be substituted with other functional groups such as a hydroxy group, a carboxylic acid group, a hetero atom and the like. 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 about the alkyl group contained in the alkali metal salt or alkaline earth metal salt of the alkyl substituted hydroxyaromatic carboxylic acid, such as the alkyl group of the alkaline earth metal salt of the alkyl substituted hydroxybenzoic acid detergent. 75 mol% (eg, 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 C ₂₀ or greater. In another embodiment, the alkali metal salt or alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is a residue of normal alpha olefin containing _{at least 75 mol% of C 20 or more normal α-olefin with an alkyl group.} An alkali metal salt or alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid derived from a certain alkyl-substituted hydroxybenzoic acid.

In another embodiment, an alkyl group contained in an alkali metal salt or alkaline earth metal salt of an alkyl substituted hydroxyaromatic carboxylic acid, such as an alkali metal salt of an alkyl substituted hydroxybenzoic acid or an alkyl group of an alkaline earth metal salt. At least about 50 mol% (eg, 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. %) _Are 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 from 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 hyperbasic. In general, the perbasic alkali metal salt or alkaline earth metal salt of an alkyl-substituted hydroxy aromatic carboxylic acid is a base source of the alkali metal salt of an alkyl-substituted hydroxy aromatic carboxylic acid or TBN of an alkaline earth metal salt. It is increased by a process such as the addition of (eg, lime) and an acidic hyperbasic compound (eg, carbon dioxide).

Sulfonates can typically be prepared from alkyl-substituted aromatic hydrocarbons, such as sulfonic acids obtained by fractional distillation of petroleum or by sulfonates of those obtained by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or halogen derivatives thereof. Alkylation can be carried out in the presence of a catalyst with an alkylating agent having from about 3 to more than 70 carbon atoms. Alkaline sulfonates typically contain 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 alkaline sulfonic acids can be neutralized with metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and ethers. The amount of the metal compound is selected in consideration 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. It is in the range of% by weight).

Phenates sulfide cleaning agents and metal salts of phenol sulfide are prepared by reaction with suitable metal compounds such as oxides or hydroxides, and neutral or hyperbasic products are well known in the art. It can be obtained by the method. Phenol sulfides are prepared by reacting the phenols with sulfur or sulfur-containing compounds such as hydrogen sulfide, sulfur monohalogenates or sulfur dihalogenates, and generally two or more phenols are crosslinked by sulfur-containing cross-linking. A product that is a mixture of the compounds can be formed.

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

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

It is desirable to use calcium hydroxide as the calcium base, for example because of its convenient handling of calcium oxide and also because of its excellent results. Other calcium bases such as calcium alkoxide can also be used.

Suitable alkylphenols that can be used are those that have an alkyl substituent containing a sufficient number of carbon atoms to make the resulting perbasic calcium sulfide alkylphenate composition oil soluble. Oil solubility can be provided by a single long chain alkyl substitution or by a combination of alkyl substituents. Typically, the alkylphenol used in this process will be a mixture of different alkylphenols _{, for example C 20 to} C _{24 alkylphenols.} If a phenate product with 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 mol% of alkylphenols can have about 15 to about 35 carbon atom linear alkyl substituents and about 75 to about 75 to about. At 0 mol%, the alkyl group is a polypropenyl with 9 to 18 carbon atoms. In one form, at about 35 to about 100 mole percent of the alkylphenol, the alkyl group would be a linear alkyl of about 15 to about 35 carbon atoms, and at about 65 to 0 mole percent of the alkylphenol, alkyl. The group would be a polypropenyl with 9 to 18 carbon atoms. The use of large amounts of predominantly linear alkylphenols results in high TBN products, which are generally characterized by lower viscosities. On the other hand, polypropenylphenols are generally more economical than linear alkylphenols, while using more than about 75 mole percent of polypropenylphenols in the preparation of calcium perbasic alkylphenyl sulfide compositions. This generally results in an undesiredly high viscosity product. However, a mixture of about 75 mol% or less of polypropenylphenol with about 9 to about 18 carbon atoms and about 25 mol% or more of mainly linear alkylphenol with about 15 to about 35 carbon atoms is used. It then allows for a more economical product of acceptable viscosity. In one form, suitable alkylphenol compounds include distilled cashew nut oil or hydrodistilled cashew nut oil. Distilled CNSL is a mixture of biodegradable meta-hydrocarbyl-substituted phenols, where the hydrocarbyl group is linear and unsaturated, including cardanol. Contact hydrogenation of distilled CNSL results in a mixture of predominantly 3-pentadecylphenol-rich meta-hydrocarbyl-substituted phenols.

The alkylphenol can be a para-alkylphenol, a meta-alkylphenol or an orthoalkylphenol. Alkylphenols are preferably predominantly paraalkylphenols, as p-alkylphenols are believed to facilitate the preparation of highly hyperbasic calcium sulfide alkylphenates for which a perbasic product is desired. About 45 mol percent or less of the orthoalkylphenol; more preferably, about 35 mol% or less of the alkylphenol is orthoalkylphenol. Alkylhydroxytoluene 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 oil, catalytic hydrogenation of distilled CNSL results in a mixture of meta-hydrocarbyl-substituted phenols.

In general, the choice of alkylphenol can be based on the desired properties for a marine diesel engine lubricating oil composition, especially TBN, and oil solubility. For example, in the case of alkylphenates with substantially linear alkyl substituents, the viscosity of the alkylphenate composition is influenced by the position of the alkyl chain's bond to the phenyl ring, eg, end bond vs. center bond. obtain. The preparation and selection of suitable alkylphenols and additional information relating thereto can be found, for example, in US Pat. Nos. 5,024,773, 5,320,763; 5,318,710; and 5,320,762. , Each of them is incorporated here by reference.

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

The marine diesel lubricating oil composition of the present invention may contain one or more friction modifiers capable of reducing friction between moving parts. Non-limiting examples of suitable friction modifiers are aliphatic carboxylic acids; derivatives of aliphatic carboxylic acids (eg, alcohols, esters, borate 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 derivative of phosphonic acid (eg, ester, amide, metal salt, etc.); mono-, di- or tri-alkyl substituted amine; Includes mono- or di-alkyl substituted amides and combinations thereof. In some embodiments, examples of friction modifiers include, but are not limited to, alkoxylated aliphatic amines; booxide aliphatic epoxides; aliphatic phosphite, aliphatic epoxides, aliphatic amines, booxide alkoxylated fats. Group amines, metal salts of fatty acids, fatty acid amides, glycerol esters, booxide glycerol esters; and aliphatic imidazolines, which are disclosed in US Pat. No. 6,372,696, the contents of which are described herein by reference. Incorporated in the book); _{fatty acid esters of C 4} to C ₇₅ , or C ₆ to C ₂₄ , or C ₆ to C ₂₀ , and nitrogen-containing compounds selected from the group consisting of ammonia, alkanolamines, etc. and mixtures thereof. Includes friction modifiers obtained from the reaction products of.

The marine diesel lubricating oil composition of the present invention may contain one or more wear resistant agents capable of reducing friction and excessive wear. Abrasion resistant agents known to those of skill in the art can be used in the lubricating oil composition. Non-limiting examples of suitable abrasion resistant agents include zinc dithiophosphate, metals of dithiophosphate (eg, Pb, Sb, Mo, etc.), metals of dithiocarbamic acid (eg, Zn, Pb, Sb, Mo, etc.). Reaction formation of salts, metal (eg Zn, Pb, Sb, etc.) salts, boron compounds, phosphate esters, phosphite esters, phosphate esters or amine salts of thiophosphate esters, dicyclopentadiene and thiophosphate. Includes objects and combinations thereof.

In certain embodiments, the abrasion resistant agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as a zinc dialkyldithiophosphate compound. The metal of the dihydrocarbyl dithiophosphate metal salt can be an alkali metal or an 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 carbon atoms. Has about 8 carbon atoms from. In a further embodiment, the alkyl group is straight or branched.

The amount of dihydrocarbyl dithiophosphate metal salt containing a zinc dialkyldithiophosphate salt 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 lubricating oil composition of the present invention may contain one or more defoaming agents or defoaming agents capable of breaking bubbles in the oil. Non-limiting examples of suitable defoaming agents or defoaming agents include silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated fatty acids, polyethers (eg polyethylene glycol), branched polyvinyl ethers, alkyl acrylate polymers. , Alkyl methacrylate polymers, polyalkoxyamines and combinations thereof.

The marine diesel lubricating oil composition of the present invention may contain one or more pour point lowering agents capable of lowering the pour point of the marine diesel lubricating oil composition. Any pour point depressant known to those of skill in the art can be used in marine diesel lubricant compositions. Non-limiting examples of suitable pour point lowering agents include polymethacrylate, alkyl acrylate polymer, alkyl methacrylate polymer, di (tetra-paraffin phenol) phthalate, tetraparaffin phenol condensate, chlorinated paraffin and naphthalene condensation. Includes objects and combinations thereof. In some embodiments, the pour point depressant includes an ethylene-vinyl acetate copolymer, a condensate of chlorinated paraffin with phenol, polyalkyl styrene, and the like.

In another embodiment, the marine diesel lubricating oil compositions of the present invention contain one or more anti-emulsifiers capable of facilitating oil-water separation in lubricating oil compositions exposed to water or steam. Can be made to. Any anti-emulsifier known to those of skill in the art can be used in marine diesel lubricant compositions. Non-limiting examples of suitable anti-emulsifiers include anionic surfactants (eg, alkylnaphthalene sulfonate, alkylbenzene sulfonate, etc.), nonionic alkoxylated alkylphenol resins, alkylene oxide polymers (eg, polyethylene oxide, polypropylene oxide, etc.). , Ethylene oxide, block copolymers such as propylene oxide), oil-soluble acid esters, polyoxyethylene sorbitan esters and combinations thereof.

The marine diesel lubricating oil composition of the present invention may contain one or more corrosion inhibitors capable of reducing corrosion. Any corrosion inhibitor known to those of skill in the art can be used in marine diesel lubricant compositions. Non-limiting examples of suitable corrosion inhibitors include semiesters or amides of dodecylsuccinic acid, phosphate esters, thiophosphates, alkylimidazolines, sarcosins and combinations thereof.

The marine diesel lubricating oil composition of the present invention may contain one or more extreme pressure (EP) agents capable of preventing the sliding metal surface from seizing under extreme pressure conditions. Any extreme pressure agent known to those of skill in the art can be used in marine diesel lubricant compositions. In general, extreme pressure agents are compounds that can chemically bond with a metal to form a surface film that prevents the irregularities on the opposing metal surfaces from welding under high load. Non-limiting examples of suitable extreme pressure agents include sulphurized animal or vegetable fats and oils, sulphurized animal or vegetable fatty acid esters, or trivalent or pentavalent acids of phosphorus, wholly or partially. Esters esterified to, olefin sulfide, dihydrocarbyl polysulfide, deal-alder sulfide adduct, dicyclopentadiene sulfide, sulfide or co-sulfide mixture of fatty acid ester and monounsaturated olefin, co-sulfide blend of fatty acid, fatty acid ester and alpha olefin , Functional group-substituted dihydrocarbyl polysulfides, thiaaldehydes, thiaketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfide blends of terpenes and acyclic olefins, and polysulfide olefin products, amine salts of phosphate or thiophosphates and them. Combinations are included.

The marine diesel lubricating oil composition of the present invention may contain one or more rust preventives (rust preventives) capable of suppressing corrosion of the iron metal surface. Non-limiting examples of suitable rust preventives include nonionic polyoxyalkylene agents such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether. , Polyoxyethylene octylstearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate; stearic acid and other fatty acids; dicarboxylic acid; metal soap; Fatty acid amine salts; metal salts of heavy sulfonic acids; partial carboxylic acid esters of polyhydric alcohols; phosphoric acid esters; (short chain) alkenyl succinic acids; their partial esters and their nitrogen-containing derivatives; synthetic alkalil sulfonates, eg. , Dinonylnaphthalene sulfonic acid metal salt; etc. and mixtures thereof.

The following non-limiting examples are examples of the present invention.

Komatsu Hot Tube (KHT) Test The Komatsu Hot Tube Test is a lubrication industry bench test that measures the degree of thermal and oxidative stability and high temperature detergency of lubricating oil. During the test, a specified amount of test oil is pumped upward through a glass tube placed inside an oven set at a certain temperature. Before the oil enters the glass tube, air is introduced into the oil stream and flows up with the oil. Evaluation of marine trunk piston engine lubricants was performed at temperatures between 300 and 320 ° C. Test results are measured by comparing the amount of lacquer deposited (deposited) on the glass tube after cooling and cleaning with an evaluation scale range of 1.0 (very black) to 10.0 (completely clean). decide. Results are reported in multiples of 0.5. If the glass tube is completely blocked by deposits (sediments), the test results are recorded as "blocks" (blocks). The blockage is a deposit smaller than the result of 1.0, where the lacquer is very thick and dark, but still allows fluid to flow at a completely unsatisfactory rate for a usable oil.

DSC Oxidation Test According to ASTM D-6186, the DSC test is used to evaluate the thin film oxidation stability of the test oil. The heat flow from and to the test oil in the sample cup is compared to the reference cup during the test. The oxidation start temperature is the temperature at which the test oil starts to oxidize. The oxidation induction time is the time when the test oil starts to oxidize. Higher oxidation induction times mean better performance. The oxidation reaction results in an exothermic reaction that is clearly indicated by the heat flow. The oxidation induction time is calculated to evaluate the thin film oxidation stability of the test oil.

Black Sludge Precipitate (BSD) Test This test is used to assess the ability of marine lubricants to deal with unstable-unburned asphaltene in residual fuel oils. The test measures the tendency of the lubricating oil to cause a precipitate on the test strip by applying oxidative thermal strain to a mixture of heavy fuel oil and lubricant. A sample of the marine lubricant oil composition was mixed with a specific amount of marine residual fuel to form a test mixture. The test mixture is pumped during the test as a thin film onto a metal test strip controlled to a constant time (12 hours) test temperature (200 ° C.). The test oil-fuel mixture is recirculated in the sample vessel. After testing, the test strips are cooled, then washed and dried. The test plate is then weighed. In this method, the weight of the precipitate remaining on the test plate was measured and recorded as a change in the weight of the test plate.

Examples 1 to 4 and Comparative Example A
A differential scanning calorimetry (DSC) test in which Examples 1 to 4 and Comparative Example A are prepared and used to evaluate the thin film oxidation stability of the test oil, and Komatsu hot, which is a measurement of high temperature detergency. It was evaluated using the tube (KHT) test.

Comparative Example A: A fully blended marine cylinder lubricant composition of 5BN, SAE30 viscosity grade was prepared with a majority amount of Class I base oil (at 100 ° C., about 5.14 and 11.8 cSt, respectively). Mixture of XOM Core 150N and XOM Core 600N with kinematic viscosity), high hyperbasic calcium sulfonate cleaning agent, low hyperbasic calcium sulfonate cleaning agent, medium hyperbasic calcium sulfide phenate cleaning agent, amine-based antioxidant, antifoaming agent , And about 2.5 wt% ethylene carbonate post-treatment biscusinimide dispersant derived from 2300 MW PIB.

Example 1: Example 1 is prepared with about 1.0% by weight of the Mannich reaction product (with about 45% by weight of diluted oil, polyisobutylene having a number average molecular weight of 1,000 with more than 70% by weight of methylvinylidene isomers). The cylinder lubricant of Comparative Example A was reproduced, except that it further contained polyisobutyl-substituted phenol, sodium glycine, and formaldehyde reaction products).

Example 2: Example 2 is prepared with polyisobutylene having a number average molecular weight of 1,000 having about 5.0% by weight of the Mannich reaction product (having about 45% by weight diluted oil, having more than 70% by weight of methylvinylidene isomers). The cylinder lubricant of Comparative Example A was reproduced, except that it further contained polyisobutyl-substituted phenol, sodium glycine, and formaldehyde reaction products).

Example 3: A fully blended marine cylinder lubricating oil composition of 15BN, SAE50 viscosity grade is prepared and the majority amount of Class I base oil, XOM Core150N (1.71% by weight), XOM Core2500BS (24. 64% by mass) and XOM Core 600N (41.21% by mass) mixture, high hyperbasic calcium sulfonate cleaning agent, low hyperbasic calcium sulfonate cleaning agent, medium hyperbasic calcium sulfide phenate cleaning agent, amine-based antioxidant , Antifoaming agent, about 0.19 wt% ethylene carbonate post-treatment biscucinimide dispersant derived from 2300 MW PIB, and about 5.0 wt% Mannich reaction product (with about 45 wt% diluted oil, 70 wt). A reaction product of polyisobutyl-substituted phenol, sodium glycine, and formaldehyde prepared with polyisobutylene having a number average molecular weight of 1,000 with more than% methylbinylidene isomer.

Example 4: A fully blended marine cylinder lubricant composition of 25 BN, SAE 50 viscosity grade is prepared and the majority amount of Class I base oil, XOM Core 150N (1.83% by weight), XOM Core 2500BS (23. 15% by mass) and XOM Core 600N (40.35% by mass) mixture, high hyperbasic calcium sulfonate cleaning agent, low hyperbasic calcium sulfonate cleaning agent, medium hyperbasic calcium sulfide phenate cleaning agent, amine-based antioxidant , Antifoaming agent, about 0.19 wt% ethylene carbonate post-treatment biscucinimide dispersant derived from 2300 MW PIB, and about 5.0 wt% Mannich reaction product (with about 45 wt% diluted oil, 70 wt). A reaction product of polyisobutyl-substituted phenol, sodium glycine, and formaldehyde prepared with polyisobutylene having a number average molecular weight of 1,000 with more than% methylbinylidene isomer.

The results of the KHT test and the DSC oxidation test of the MCL compositions of Examples 1 to 4 and Comparative Example A of the present invention are shown in Table 1 below.

The Mannich reaction of polyisobutyl-substituted phenols, sodium glycine, and formaldehyde prepared with polyisobutylene having a number average molecular weight of 1,000 with more than 70% by weight of methylvinylidene isomers, as evidenced by the results illustrated in Table 1. The product-containing marine cylinder lubricant composition is surprisingly better than the test oil, as evidenced by the overall higher oxidation induction time compared to the comparative examples without the Mannich reaction product. It showed good thin film oxidation stability. In addition, a marine cylinder lubricant composition containing a polyisobutyl-substituted phenol, sodium glycine, and the Mannich reaction product of formaldehyde prepared with polyisobutylene having a number average molecular weight of 1,000 with more than 70% by weight of methylvinylidene isomer. The material surprisingly showed better detergency and oxidative stability properties at high temperatures, as evidenced by their overall high evaluation compared to the comparative examples.

Examples 5-6 and Comparative Example B
A differential scanning calorimetry (DSC) test in which Examples 5-6 and Comparative Example B are prepared and used to evaluate the thin film oxidation stability of the test oil, and Komatsu hot, which is a measurement of high temperature detergency. It was evaluated using the tube (KHT) test.

Comparative Example B: A fully blended marine cylinder lubricant composition of 30 BN, SAE 50 viscosity grade was prepared with a majority amount of Class I base oil (at 100 ° C., about 5.14 and 31.3 cSt, respectively). Mixture of XOM Core150N and ESSO Core2500BS Brightstock with kinematic viscosity), highly hyperbasic calcium sulfonate cleaning agent, medium hyperbasic calcium sulfide phenate cleaning agent, medium hyperbasic which is a calcium salt of alkyl-substituted hydroxy aromatic carboxylic acid. Included was a carboxylate cleaner, a defoamer, and an approximately 2.5 wt% ethylene carbonate post-treatment biscucinimide dispersant derived from 2300 MW PIB.

Example 5: Example 5 is prepared with polyisobutylene having a number average molecular weight of 1,000 having about 1.0% by weight of the Mannich reaction product (having about 45% by weight diluted oil, having more than 70% by weight of methylvinylidene isomers). The cylinder lubricant of Comparative Example B was reproduced, except that it further contained polyisobutyl-substituted phenol, sodium glycine, and formaldehyde reaction products).

Example 6: Example 6 is prepared with polyisobutylene having a number average molecular weight of 1,000 having about 5.0% by weight of the Mannich reaction product (having about 45% by weight diluted oil, having more than 70% by weight of methylvinylidene isomers). The cylinder lubricant of Comparative Example B was reproduced, except that it further contained polyisobutyl-substituted phenol, sodium glycine, and formaldehyde reaction products).

The results of the KHT test and the DSC oxidation test of the MCL compositions of Examples 5 and 6 of the present invention and Comparative Example B are shown in Table 2 below.

The Mannich reaction of polyisobutyl-substituted phenols, sodium glycine, and formaldehyde prepared with polyisobutylene having a number average molecular weight of 1,000 with more than 70% by weight of methylvinylidene isomers, as evidenced by the results illustrated in Table 2. The product-containing marine cylinder lubricant composition is surprisingly better than the test oil, as evidenced by the overall higher oxidation induction time compared to the comparative examples without the Mannich reaction product. It showed good thin film oxidation stability. In addition, a marine cylinder lubricant composition containing a polyisobutyl-substituted phenol, sodium glycine, and the Mannich reaction product of formaldehyde prepared with polyisobutylene having a number average molecular weight of 1,000 with more than 70% by weight of methylvinylidene isomer. The product surprisingly exhibited better detergency and oxidative stability properties at high temperatures, as evidenced by a general high rating compared to the comparative examples at a temperature of 325 ° C. This illustrates a test oil with improved detergency performance at higher temperatures.

Example 7: A fully blended trunk piston lubricating oil composition of 30 BN is prepared and a highly hyperbasic calcium carboxylate wash, which is the calcium salt of the majority amount of class I base oil, alkyl-substituted hydroxyaromatic carboxylic acids. Agent, medium hyperbasic calcium carboxylate cleaning agent which is a calcium salt of alkyl-substituted hydroxyaroarocarboxylic acid, secondary zinc dithiophosphate, amine-based antioxidant, foam suppressant, and about 5.0% by weight Mannich. Reaction product of polyisobutyl-substituted phenol, sodium glycine, and formaldehyde prepared with a number average molecular weight of 1,000 polyisobutylene having about 45% by weight of diluted oil and more than 70% by weight of methylvinylidene isomer. Things) included.

Example 8: A fully blended trunk piston lubricating oil composition of 15BN is prepared and a highly hyperbasic calcium carboxylate wash, which is the calcium salt of the majority amount of class I base oil, alkyl substituted hydroxyaromatic carboxylic acid. Agent, medium hyperbasic calcium carboxylate cleaning agent, secondary zinc dithiophosphate, amine-based antioxidant, foam suppressant, and about 5.0% by weight of Mannich reaction product (about 45% by weight diluted oil) , A reaction product of polyisobutyl-substituted phenol, sodium glycine, and formaldehyde prepared with polyisobutylene having a number average molecular weight of 1,000 with more than 70% by weight of methylvinylidene isomer.

Examples 7-8
Examples 7 and 8 are prepared and used with the Black Sludge Precipitate (BSD) test, which is used to assess the detergency of oils, and the Komatsu Hot Tube (KHT) test, which is a measurement of high temperature detergency. And was evaluated. The results are shown in Table 3 below.

The Mannich reaction of polyisobutyl-substituted phenols, sodium glycine, and formaldehyde prepared with polyisobutylene having a number average molecular weight of 1,000 with more than 70% by weight of methylvinylidene isomers, as evidenced by the results illustrated in Table 3. The marine trunk piston lubricant composition containing the product showed good detergency performance, as illustrated in both the KHT and BSD tests.

For the avoidance of doubt, the present invention relates to the subject matter described in paragraphs numbered below.
[Paragraph 1]
Polyisobutyl-substituted hydroxyaromatic compounds, aldehydes, amino acids with (a) major amounts of lubricating viscosity oils; and (b) about 0.1% to about 10% by weight active based on the total weight of the lubricating oil composition. Or an ester derivative thereof, and at least one Mannich reaction product prepared by condensation of an alkali metal base, wherein the polyisobutyl group is derived from polyisobutene containing at least about 70% by weight of the methylvinylidene isomer, and , Polyisobutyl groups having a number average molecular weight of about 400 to about 2500;
A marine diesel lubricant composition comprising:
The lubricating oil composition has a BN of 5 to 200 mg KOH / g, and the marine diesel lubricating oil composition is revised in January 2015 for SAE20, SAE30, SAE40, SAE50 or SAE60 monograde lubricating oils. The marine diesel lubricating oil composition, which is a monograde lubricating oil composition that meets the specifications for SAE J300 revised January 2015 requirements.
[Paragraph 2]
BN is 5 to 150 mg KOH / g, 5 to 100 mg KOH / g, 5 to 75 mg KOH / g, 5 to 70 mg KOH / g, 5 to 60 mg KOH / g, 5 to 50 mg KOH / g, 5 to 40 mg KOH / G, 5 to 35 mg KOH / g, 5 to 30 mg KOH / g, 5 to 25 mg KOH / g, 5 to 20 mg KOH / g, or 5 to 15 mg KOH / g, according to [paragraph 1]. Lubricating oil composition.
[Paragraph 3]
(B) is about 0.5% by weight to about 10% by weight active, about 1% by weight to about 10% by weight active, and about 2% by weight to about 8% by weight based on the total weight of the lubricating oil composition. , A marine diesel lubrication according to [paragraph 1], comprising at least one Mannig reaction product having an activity of about 2% by weight to about 6% by weight, or about 2.5% by weight to about 5.5% by weight. Oil composition.
[Paragraph 4]
The marine diesel lubricating oil composition according to [Paragraph 1], further comprising a cleaning agent selected from sulfonate, phenate, naphthenate, carboxylate, salicylate, or any combination thereof.
[Paragraph 5]
(A) Major amounts of lubricating viscosity oil; and (b) Polyisobutyl-substituted hydroxy aromatics with about 0.1% to about 10% by weight activity based on the total weight of the marine trunk piston engine lubricating oil composition. A polyisobutene in which at least one Mannich reaction product prepared by condensation of a compound, an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group contains at least about 70% by weight of the methylvinylidene isomer. Derived from and having a polyisobutyl group having a number average molecular weight of about 400 to about 2500;
Marine Trunk Piston Engine Oil Lubricating Oil Composition Containing:
The marine trunk piston engine lubricating oil composition has a TBN of 10 to 80 mg KOH / g, and the marine trunk piston engine oil lubricating oil composition is for SAE30 or SAE40 monograde lubricating oil 2015 1 The marine trunk piston engine oil lubricating oil composition, which is a monograde lubricating oil composition that meets the specifications for SAE J300 revised January 2015 requirements.
[Paragraph 6]
BN is 10-75 mg KOH / g, 10-70 mg KOH / g, 10-65 mg KOH / g, 10-60 mg KOH / g, 10-55 mg KOH / g, 10-50 mg KOH / g, 10-45 mg KOH / g, 10-40 mg KOH / g, 10-35 mg KOH / g, 10-30 mg KOH / g, 10-25 mg KOH / g, 10-20 mg KOH / g, or 10-15 mg KOH / g, [paragraph 5]. ] The marine trunk piston engine oil lubricating oil composition.
[Paragraph 7]
(B) is about 0.5% by weight to about 10% by weight active, about 1% by weight to about 10% by weight active, and about 2% by weight to about 8% by weight based on the total weight of the lubricating oil composition. , A marine trunk piston according to [paragraph 5], comprising at least one Mannig reaction product having an activity of about 2% by weight to about 6% by weight, or about 2.5% by weight to about 5.5% by weight. Engine oil Lubricating oil composition.
[Paragraph 8]
The marine trunk piston engine oil lubricant composition according to [paragraph 5], further comprising a cleaning agent selected from sulfonate, phenate, naphthenate, carboxylate, salicylate, or any combination thereof.
[Paragraph 9]
Polyisobutyl-substituted hydroxyaromatic compounds, which are (a) major amounts of lubricating viscosity oil; and (b) about 0.1% to about 10% by weight active based on the total weight of the marine system lubricating oil composition. At least one Mannich reaction product prepared by condensation of an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group is derived from polyisobutene containing at least about 70% by weight of the methylvinylidene isomer. And the polyisobutyl group has a number average molecular weight of about 400 to about 2500;
A marine system lubricant composition comprising:
The marine system oil lubricating oil composition has a TBN of 5-40 mg KOH / g, and the marine system oil lubricating oil composition is for SAE20, SAE30 or SAE40 monograde lubricating oil January 2015. The marine system lubricating oil composition, which is a monograde lubricating oil composition that meets the specifications for SAE J300 revised January 2015 requirements.
[Paragraph 10]
(B) is about 0.5% by weight to about 10% by weight active, about 1% by weight to about 10% by weight active, and about 2% by weight to about 8% by weight based on the total weight of the lubricating oil composition. , A marine system lubrication according to [paragraph 9], comprising at least one Mannig reaction product having an activity of about 2% by weight to about 6% by weight, or about 2.5% by weight to about 5.5% by weight. Oil composition.
[Paragraph 11]
The marine system lubricating oil composition according to [Paragraph 9], further comprising a cleaning agent selected from sulfonate, phenate, naphthenate, carboxylate, salicylate, or any combination thereof.
[Paragraph 12]
(A) Major amounts of oil with lubricating viscosity; and (b) Polyisobutyl-substituted hydroxy aromatic compounds with about 0.1% to about 10% by weight activity based on the total weight of the marine diesel cylinder lubricating oil composition. From polyisobutene, which is a Mannich reaction product prepared by condensation of an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group contains at least about 70% by weight of the methylvinylidene isomer. Derived and the polyisobutyl group has a number average molecular weight of about 400 to about 2500;
Is a marine diesel cylinder lubricant composition containing:
The marine diesel cylinder lubricant composition has a TBN of 5 to 200 mg KOH / g, and the marine diesel cylinder lubricant composition is 2015 for SAE30, SAE40, SAE50 or SAE60 monograde lubricants. The marine diesel cylinder lubricant composition, which is a monograde lubricant composition that meets the specifications for SAE J300 revised January 2015 requirements.
[Paragraph 13]
BN is 5 to 150 mg KOH / g, 5 to 100 mg KOH / g, 5 to 75 mg KOH / g, 5 to 70 mg KOH / g, 5 to 60 mg KOH / g, 5 to 50 mg KOH / g, 5 to 40 mg KOH / G, 5 to 35 mg KOH / g, 5 to 30 mg KOH / g, 5 to 25 mg KOH / g, 5 to 20 mg KOH / g, or 5 to 15 mg KOH / g, according to [paragraph 12]. Cylinder lubricating oil composition.
[Paragraph 14]
The marine diesel cylinder lubricant composition according to [paragraph], further comprising a cleaning agent selected from sulfonate, phenate, naphthenate, carboxylate, salicylate, or any combination thereof.
[Paragraph 15]
(B) is about 0.5% by weight to about 10% by weight active, about 1% by weight to about 10% by weight active, and about 2% by weight to about 8% by weight based on the total weight of the lubricating oil composition. , A marine diesel cylinder according to [paragraph 12], comprising at least one Mannig reaction product having an activity of about 2% by weight to about 6% by weight, or about 2.5% by weight to about 5.5% by weight. Lubricating oil composition.
[Paragraph 16]
(A) Major amounts of oil with lubricating viscosity; and (b) Polyisobutyl-substituted hydroxy aromatic compounds with about 0.1% to about 10% by weight activity based on the total weight of the marine diesel cylinder lubricating oil composition. From polyisobutene, which is a Mannich reaction product prepared by condensation of an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group contains at least about 70% by weight of the methylvinylidene isomer. Derived and the polyisobutyl group has a number average molecular weight of about 400 to about 2500;
Is a marine diesel cylinder lubricant composition containing:
The marine diesel cylinder lubricant composition has a TBN of 5-40 mg KOH / g, and the marine diesel cylinder lubricant composition is 2015 for SAE30, SAE40, SAE50 or SAE60 monograde lubricants. The marine diesel cylinder lubricant composition, which is a monograde lubricant composition that meets the specifications for SAE J300 revised January 2015 requirements.
[Paragraph 17]
(B) is about 0.5% by weight to about 10% by weight active, about 1% by weight to about 10% by weight active, and about 2% by weight to about 8% by weight based on the total weight of the lubricating oil composition. , A marine diesel cylinder according to [paragraph 16], comprising at least one Mannig reaction product having an activity of about 2% by weight to about 6% by weight, or about 2.5% by weight to about 5.5% by weight. Lubricating oil composition.
[Paragraph 18]
The marine diesel cylinder lubricant composition according to [paragraph 16], further comprising a cleaning agent selected from sulfonate, phenate, naphthenate, carboxylate, salicylate, or any combination thereof.

Claims (13)

Polyisobutyl-substituted hydroxy aromatic compounds, aldehydes, amino acids with 1.0% to 5.0% by weight activity based on (a) major amounts of lubricating viscosity oil; and (b) total weight of the lubricating oil composition. Or an ester derivative thereof, and at least one Mannich reaction product prepared by condensation of an alkali metal base, wherein the polyisobutyl group is derived from polyisobutene containing at least 70% by weight of the methylvinylidene isomer, and Polyisobutyl groups having a number average molecular weight of 400-2500;
A marine diesel lubricant composition comprising:
The lubricating oil composition has a BN of 5 to 200 mg KOH / g, and the marine diesel lubricating oil composition is revised in January 2015 for SAE20, SAE30, SAE40, SAE50 or SAE60 monograde lubricating oils. The marine diesel lubricating oil composition, which is a monograde lubricating oil composition that meets the specifications for SAE J300 revised January 2015 requirements. BN is 5 to 150 mg KOH / g, 5 to 100 mg KOH / g, 5 to 75 mg KOH / g, 5 to 70 mg KOH / g, 5 to 60 mg KOH / g, 5 to 50 mg KOH / g, 5 to 40 mg KOH / The marine diesel lubricant according to claim 1, wherein g, 5 to 35 mg KOH / g, 5 to 30 mg KOH / g, 5 to 25 mg KOH / g, 5 to 20 mg KOH / g, or 5 to 15 mg KOH / g. Oil composition. The marine diesel lubricating oil composition according to claim 1 or 2 , further comprising a cleaning agent selected from sulfonate, phenate, naphthenate, carboxylate, salicylate, or any combination thereof. (A) Major amounts of lubricating viscosity oil; and (b) Polyisobutyl-substituted hydroxy aromatics with 1.0% to 5.0% by weight activity based on the total weight of the marine trunk piston engine lubricating oil composition. From polyisobutene in which the polyisobutyl group contains at least 70% by weight of the methylvinylidene isomer, which is the Mannig reaction product prepared by condensation of compounds, aldehydes, amino acids or ester derivatives thereof, and alkali metal bases. Derived and the polyisobutyl group has a number average molecular weight of 400-2500;
Marine Trunk Piston Engine Oil Lubricating Oil Composition Containing:
The marine trunk piston engine lubricating oil composition has a TBN of 10 to 80 mg KOH / g, and the marine trunk piston engine oil lubricating oil composition is for SAE30 or SAE40 monograde lubricating oil 2015 1 The marine trunk piston engine oil lubricating oil composition, which is a monograde lubricating oil composition that meets the specifications for SAE J300 revised January 2015 requirements. BN is 10-75 mg KOH / g, 10-70 mg KOH / g, 10-65 mg KOH / g, 10-60 mg KOH / g, 10-55 mg KOH / g, 10-50 mg KOH / g, 10-45 mg KOH / g, 10-40 mg KOH / g, 10-35 mg KOH / g, 10-30 mg KOH / g, 10-25 mg KOH / g, 10-20 mg KOH / g, or 10-15 mg KOH / g, claim 4 Marine Trunk Piston Engine Oil Lubricating Oil Composition. The marine trunk piston engine oil lubricating oil composition according to claim 4 or 5 , further comprising a cleaning agent selected from sulfonate, phenate, naphthenate, carboxylate, salicylate, or any combination thereof. Polyisobutyl-substituted hydroxyaromatic compounds, 1.0% to 5.0 % by weight based on the total weight of (a) major amounts of lubricating viscosity oils; and (b) marine system lubricating oil compositions. At least one Mannich reaction product prepared by condensation of an aldehyde, an amino acid or an ester derivative thereof, and an alkali metal base, wherein the polyisobutyl group is derived from polyisobutene containing at least 70% by weight of the methylvinylidene isomer. And those in which the polyisobutyl group has a number average molecular weight of 400-2500;
A marine system lubricant composition comprising:
The marine system oil lubricating oil composition has a TBN of 5-40 mg KOH / g, and the marine system oil lubricating oil composition is for SAE20, SAE30 or SAE40 monograde lubricating oil January 2015. The marine system lubricating oil composition, which is a monograde lubricating oil composition that meets the specifications for SAE J300 revised January 2015 requirements. The marine system lubricating oil composition according to claim 7 , further comprising a cleaning agent selected from sulfonate, phenate, naphthenate, carboxylate, salicylate, or any combination thereof. (A) Major amounts of oil with lubricating viscosity; and (b) Polyisobutyl-substituted hydroxy aromatic compounds with 1.0% to 5.0% by weight activity based on the total weight of the marine diesel cylinder lubricating oil composition. , An aldehyde, an amino acid or an ester derivative thereof, and at least one Mannich reaction product prepared by condensation of an alkali metal base, wherein the polyisobutyl group is derived from polyisobutene containing at least 70% by weight of the methylvinylidene isomer. And the polyisobutyl group has a number average molecular weight of 400-2500;
Is a marine diesel cylinder lubricant composition containing:
The marine diesel cylinder lubricant composition has a TBN of 5 to 200 mg KOH / g, and the marine diesel cylinder lubricant composition is 2015 for SAE30, SAE40, SAE50 or SAE60 monograde lubricants. The marine diesel cylinder lubricant composition, which is a monograde lubricant composition that meets the specifications for SAE J300 revised January 2015 requirements. BN is 5 to 150 mg KOH / g, 5 to 100 mg KOH / g, 5 to 75 mg KOH / g, 5 to 70 mg KOH / g, 5 to 60 mg KOH / g, 5 to 50 mg KOH / g, 5 to 40 mg KOH / The marine diesel cylinder according to claim 9 , wherein g, 5 to 35 mg KOH / g, 5 to 30 mg KOH / g, 5 to 25 mg KOH / g, 5 to 20 mg KOH / g, or 5 to 15 mg KOH / g. Lubricating oil composition. The marine diesel cylinder lubricating oil composition according to claim 9 or 10 , further comprising a cleaning agent selected from sulfonate, phenate, naphthenate, carboxylate, salicylate, or any combination thereof. (A) Major amounts of oil with lubricating viscosity; and (b) Polyisobutyl-substituted hydroxy aromatic compounds with 1.0% to 5.0% by weight activity based on the total weight of the marine diesel cylinder lubricating oil composition. , An aldehyde, an amino acid or an ester derivative thereof, and at least one Mannich reaction product prepared by condensation of an alkali metal base, wherein the polyisobutyl group is derived from polyisobutene containing at least 70% by weight of the methylvinylidene isomer. And the polyisobutyl group has a number average molecular weight of 400-2500;
Is a marine diesel cylinder lubricant composition containing:
The marine diesel cylinder lubricant composition has a TBN of 5-40 mg KOH / g, and the marine diesel cylinder lubricant composition is 2015 for SAE30, SAE40, SAE50 or SAE60 monograde lubricants. The marine diesel cylinder lubricant composition, which is a monograde lubricant composition that meets the specifications for SAE J300 revised January 2015 requirements. The marine diesel cylinder lubricant composition according to claim 12 , further comprising a cleaning agent selected from sulfonate, phenate, naphthenate, carboxylate, salicylate, or any combination thereof.