JP5755253B2 - Method for improving fuel efficiency of engine oil compositions for large low speed and medium speed engines by reducing traction coefficient - Google Patents

Description

  The present invention relates to the operation of large low speed and medium speed engines using lubricating oil formulations (or formulations).

Diesel engines designed for marine and fixed power applications can be either 2-cycle or 4-cycle with 20 or fewer cylinders and are typically classified as low speed, medium speed or high speed diesel engines. The These engines burn a wide variety of fuels ranging from residual fuel oil or heavy oil to natural gas (diesel compression or spark ignition), marine propulsion, marine assistance (ship power generation), distributed power generation, and combined heat and power (CHP) Is most commonly used for. The lubrication of such an engine can be total loss (i.e., lubricating oil supplied directly to the cylinder by cylinder oil) or recirculation involving a sump. Critical engine component lubrication includes piston rings, cylinder liners, bearings, piston cooling, fuel pumps, engine control hydraulics, and the like. Fuel is typically the primary cost of operating these engines, and the typical 12-cylinder, 90-cm caliber low-speed diesel engine used for ship container transportation is up to about $ 33M annually at today's price of $ 480 / MT. Would burn no heavy oil. Therefore, a fuel efficiency gain as low as 1% would provide ship operators annual savings of up to about $ 330k. In addition, International Marine Organization (International Maritime Organization), U.S. Pat. S. Government agencies, such as Environmental Protection Agency (USA) and California Air Resources Board (California Air Resources Board), are legalizing emissions regulations for these engines. An increase in fuel efficiency will correspondingly reduce emissions (CO ₂ , SO _x , NO _x and particulate matter), which should provide some emission trading value.

Since a lubricant is exposed to a constant high temperature environment, the life of the lubricant is often limited by its oxidative stability. In addition, since the engine operates with high emissions of nitrogen oxides (NO _x ), the lubricating oil life may also be limited by its nitrification resistance. A long-term requirement is that the lubricant must also maintain cleanliness within the high temperature environment of the engine, especially with respect to critical components such as pistons and piston rings. Therefore, it is desirable that these engine oils have good cleanliness quality while promoting long life due to improved resistance to oxidation and nitrification.

U.S. Patent No. 6,057,051 includes a liquid oil-miscible polyisobutylene (PIB) and a detergent, preferably one or more of overbased phenolate, phenylate, salicylate or sulfonate, antioxidant, antiwear agent and dispersant. In marine and stationary low speed diesel engines containing medium heavy Group I or Group II neutral base oils, typically 300-500-600 SUS (KV at 100 ° C. of about 12 mm ² / sec or less) in combination with an additive package It relates to diesel engine cylinder oil with improved cleanliness and load capacity for use and reduced port deposit characteristics. The finished lubricant has a KV (or kinematic viscosity) in the range of 15-25 mm ² / sec at 100 ° C. and a total base number (Total Base Number) in the range of 40-100 mg KOH / g.

  The subject matter of U.S. Pat. No. 6,057,834 is an improved life gas engine oil as evidenced by the increased resistance of the oil to oxidation, nitrification and deposit formation. The gas engine oil of the patent includes a major amount of base oil of lubricating viscosity, at least one alkali or alkaline earth metal salt having a total base number (TBN) of about 250 or less, and a second TBN lower than the aforementioned components. A low ash gas engine oil comprising a small amount of an additive mixture including a mixture of detergents including alkali or alkaline earth metal salts. The TBN of this second alkali or alkaline earth metal salt will typically be less than about half that of the aforementioned components.

  The well-prepared gas engine oil of US Pat. No. 6,053,097 also contains dispersants (about 0.5-8% by volume), phenolic or amine antioxidants (about 0.05-1.5% by volume), triazoles. Anti-wear additives such as metal deactivators (about 0.01 to 0.2% by volume), metal dithiophosphates, metal dithiocarbamates, metal xanthates or tricresyl phosphates (about 0 0.05-1.5% by volume), pour point depressants such as poly (meth) acrylates or alkylaromatic polymers (about 0.05-0.6% by volume), antifoams such as silicone antifoams (about 0.05 to 0.15% by volume) and viscosities such as olefin copolymers, polymethacrylates, styrene-diene block copolymers, and star copolymers. Index improver (about 15 volume% or less, preferably about 10 or less% by volume) containing, other standard additives known to those skilled in the art and typically may contain.

  US Pat. No. 6,053,097 discloses a lubricating oil for natural gas engines comprising a major amount of base oil of lubricating viscosity and a small amount of a mixture of one or more metal salicylate detergents and one or more metal phenolate and / or metal sulfonate detergents. Relates to the composition.

  The lubricating base oil is any natural or synthetic lubricating base oil base stock fraction that typically has a kinematic viscosity of about 5-20 cSt at 100 ° C. In a preferred embodiment, the use of a viscosity index improver allows the elimination of oils having a viscosity of about 20 cSt or more at 100 ° C. from the lubricating oil base oil fraction used to make the formulations of the present invention. Therefore, preferred base oils contain little, if any, heavy fractions; for example, little if any lubricating oil fractions having a viscosity of 20 cSt or higher at 100 ° C.

The lubricating base oil can be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable lubricating base oils include not only hydrocracked base oils produced by hydrocracking (rather than solvent extraction) the aromatic and polar components of crude oil, but also synthetic and slack waxes. The base oil obtained by isomerization is mentioned. Suitable base oils include those of API categories I, II and III, where the saturates level and viscosity index are
Group I—less than 90% and 80-120, respectively;
Group II-> 90% and 80-120, respectively; and Group III-> 90% and> 120, respectively.

  The detergent mixture is used in combination with other metal salts or groups of metal salts (listed below) in an amount sufficient to achieve a lubricant oil of at least 0.65 wt% sulfate ash. A first metal salt or group of metal salts selected from the group consisting of one or more metal sulfonates, salicylates, phenolates and mixtures thereof having a high TBN greater than 150 and greater than or equal to 150; medium TBN greater than about 50 to 150 A second metal salt or group of metal salts selected from the group consisting of one or more metal salicylates, metal sulfonates, metal phenolates and mixtures thereof having a TNF of about 10-50, neutral or low A third metal salt or metal selected from the group consisting of one or more metal sulfonates, metal salicylates and mixtures thereof identified as TBN The total amount of medium plus neutral / low TBN detergent is about 0.7% by volume or more (active ingredient), wherein at least one of the medium or low / neutral TBN detergent is metal Salicylate, preferably at least one of the medium TBN detergents is a metal salicylate. The total amount of high TBN detergent is about 0.3% by volume or more (active ingredient). The mixture contains at least two different types of salts, with neutral or neutral salicylate being an essential component. The volume ratio of high TBN detergent to medium plus neutral / low TBN detergent (based on the active ingredient) is in the range of about 0.15-3.5.

  The detergent mixture is in an amount of no more than about 10% by volume based on (or based on) the active ingredients in the detergent mixture, preferably no more than about 8% by volume based on the active ingredients, more preferably the detergent mixture. It is added to the lubricating oil formulation in an amount of up to 6% by volume based on the active ingredient in it, and most preferably about 1.5-5.0% by volume, based on the active ingredient in the detergent mixture. Preferably, the total amount of metal salicylate used of all TBNs is in the range of 0.5% to 4.5% by volume, based on the active component of the metal salicylate.

Patent Document 4, an ester having a PAO having a viscosity of about 40 cSt (mm ² / sec) ~1000cSt (mm ² / sec) at 100 ° C., for about 2.0 cSt (mm ² / sec) or less viscosity at 100 ° C. A finished automotive gear lubricant and a lubricating oil composition useful for the preparation of gear oil, a blend of PAO and ester, wherein the blend of PAO and ester has a viscosity index greater than or equal to that of PAO, and It relates to fluid. This composition comprises thickeners, antioxidants, inhibitor packages, rust inhibitors, dispersants, detergents, friction modifiers, traction modifiers, demulsifiers, antifoam agents, dyes and antifogging agents. May further be contained.

  U.S. Patent No. 6,099,059 relates to detergent additives for lubricating oil compositions comprising at least two of low, medium and high TBN detergents, preferably calcium salicylate. This detergent is present in a lubricating oil composition comprising one of a Group II base oil, a Group III base oil or a wax isomerate base oil and mixtures thereof and an optional minor amount of a co-base oil. Co-base oils include low and medium and high viscosity oils of polyalphaolefin oligomers, dibasic acid esters, polyol esters, other hydrocarbon oils, supplemental hydrocarbyl aromatics, and the like.

US Pat. No. 6,057,031 shows improved micropitting characteristics, wherein the lubricating oil comprises at least two base oils having a viscosity difference between the first base oil and the second base oil of greater than 96 cSt (mm ² / sec) at 100 ° C. For lubricating oil blends. At least one base oil, less than 6 cSt (mm ² / s) but a polyalphaolefin having a viscosity of 2 cSt (mm ² / s) greater than the second base oil, 100 cSt at 100 ° C. (mm ² / sec) than However, it is a synthetic oil having a viscosity of less than 300 cSt (mm ² / sec). The second base oil can be a high viscosity polyalphaolefin.

Patent Document 7 is directed to a lubricating oil blend including at least two base oils having a viscosity difference between a first base oil and a second base oil of greater than 96 cSt (mm ² / sec) at 100 ° C. Indicates improved exhaust. This blend is less than 10cSt at 100 ℃ (mm ² / s) but 2 cSt (mm ² / s) but 100 cSt (mm ² / s) than at least one of a synthetic PAO and 100 ° C. has a viscosity of greater but 300 cSt (mm ² Second synthetic oil having a viscosity of less than / second). Lubricating oils may contain antiwear agents, antioxidants, antifoaming agents, demulsifiers, detergents, dispersants, metal passivators, friction reducers, rust inhibitor additives and mixtures thereof. it can.

Patent Document 8 is a lubricating oil comprising at least two base oils, wherein the first base oil has a viscosity of greater than 40 cSt (mm ² / sec) at 100 ° C. and a molecular weight distribution as a function of viscosity with an algorithm of less than 10%. (MWD):
MWD = 0.2223 + 1.0232 * log (Kv at 100 ° C. in cSt unit)
And the second base oil has a viscosity of less than 10 cSt (mm ² / sec) at 100 ° C. Preferably, the difference in viscosity between the first base oil and the second base oil is greater than 30 cSt (mm ² / sec) at 100 ° C. Preferably the high viscosity first base stock is a metallocene catalyst PAO base oil. The second base stock should be selected from GTL lubricant, wax derived lubricant, PAO, bright stock, bright stock with PIB, group I base oil, group II base oil, group II base oil and mixtures thereof Can do. The lubricating oil can contain additives including detergents. Preferably the first substrate oil has a viscosity of 300 cSt (mm ² / s) than at 100 ° C., the second substrate oil, at 100 ℃ 1.5cSt (mm ² / sec) ~6cSt (mm ² / Sec) viscosity. Preferably, the difference in viscosity between the first base oil and the second base oil is greater than 96 cSt (mm ² / sec) at 100 ° C.

Patent Document 9 is a lubricating oil comprising at least two base oils, the molecular weight distribution as a function of viscosity viscosity and at least less than 10% algorithms at least 300cSt first base oil at 100 ° C. (mm 2 ^/ sec) (MWD):
MWD = 0.2223 + 1.0232 * log (KV at 100 ° C. in cSt unit)
And the second base oil has a viscosity of less than 100 cSt (mm ² / sec) at 100 ° C. Preferably, the difference in viscosity between the first base oil and the second base oil is greater than 250 cSt (mm ² / sec) at 100 ° C. Preferably, the first base oil is a metallocene catalyst PAO base oil. The second base stock is GTL base oil, wax-derived base oil, PAO, bright stock, bright stock together with PIB, group I base oil, group II base oil, group III base oil, group V base oil, group VI It can be selected from base oils and mixtures thereof. The lubricating oil can contain additives including detergents.

  Patent Document 10 relates to a long-life gas engine lubricating oil containing a detergent. The lubricating oil comprises a major amount of base oil of lubricating viscosity and a small amount of a mixture of one or more metal sulfonates and / or phenolates and one or more metal salicylate detergents, all the detergents in the mixture being the same Or have substantially the same total base number (TBN).

  The lube base oil is any natural or synthetic lube base oil fraction that typically has a kinematic viscosity at 100 ° C. of about 5-20 cSt. In a preferred embodiment, the use of a viscosity index improver allows for the removal of oils with a viscosity of 20 cSt or higher at 100 ° C. from the lubricating oil base oil fraction used to produce the formulations of the present invention. Therefore, preferred base oils, if any, contain a small amount of heavy fraction; for example, a small amount, if any, of a lubricating oil fraction having a viscosity of 20 cSt or greater at 100 ° C.

The lubricating base oil can be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable base oils include those of API categories I, II and III, where the saturates level and viscosity index are
Group I—less than 90% and 80-120, respectively;
Group II-> 90% and 80-120, respectively; and Group III-> 90% and> 120, respectively.

  Suitable lubricating base oils include not only hydrocracked base oils produced by hydrocracking (rather than solvent extraction) the aromatic and polar components of crude oil, but also synthetic and slack waxes. The base oil obtained by isomerization is mentioned.

  The detergent is a mixture of one or more metal sulfonates and / or metal phenolates and one or more metal salicylates. The metal is any alkali or alkaline earth metal; for example, calcium, barium, sodium, lithium, potassium, magnesium, more preferably calcium, barium and magnesium. It is a feature of the lubricating oil that each of the metal salts used in the mixture has the same or substantially the same TBN as the other metal salts in the mixture.

  The TBN of the salt will vary by no more than about 15%, preferably no more than about 12%, more preferably no more than about 10%.

  The one or more metal sulfonates and / or metal phenolates and the one or more metal salicylates are, for example, 5:95 to 95: 5, preferably 10:90 to 90:10, more preferably 20:80 to 80. : Used in detergents as a mixture in a weight ratio of 20.

  The detergent mixture is added to the lubricating oil formulation in an amount up to about 10% by volume based on the active ingredients in the detergent mixture, and preferably in an amount up to about 8% by volume based on the active ingredients.

  Patent Document 11 is a lubricating oil for a two-stroke crosshead marine diesel engine containing an oil-soluble overbased detergent additive in the form of a base oil and a complex, and has two basic substances for the detergent. The present invention relates to a lubricating oil stabilized with the above surfactant. The two or more surfactants are: (1) sulfurized and / or non-sulfurized phenol and one other surfactant that is not a phenol surfactant; (2) sulfurized and / or non-sulfurized salicylic acid and salicylic acid surfactants One other surfactant that is not; or (3) at least three surfactants that are sulfurized or non-sulfurized phenol, sulfurized or non-sulfurized salicylic acid and one other surfactant that is not a phenol or salicylic acid-based surfactant Or (4) a mixture of at least three surfactants that are sulfurized or non-sulfurized phenol, sulfurized or non-sulfurized salicylic acid, as well as at least one sulfuric acid surfactant.

The base oil is an oil having a lubricating viscosity and may be any oil suitable for system lubrication of a crosshead engine. The lubricating oil may suitably be an animal, vegetable or mineral oil. Suitably the lubricating oil is a petroleum derived lubricating oil, such as a naphthenic, paraffinic or mixed base oil. Alternatively, the lubricating oil may be a synthetic lubricating oil. Suitable synthetic lubricants include synthetic ester lubricants, including diesters such as di-octyl adipate, di-octyl sebacate and tridecyl adipate, or polymeric hydrocarbon lubricants such as liquid polyisobutylene and polyalphaolefins. Can be mentioned. Generally, mineral oil is used. The lubricating oil generally comprises more than 60%, typically more than 70% by weight of the lubricating oil composition, typically at 100 ° C. of 2-40 mm ² / sec, for example 3-15 mm ² / sec. And a viscosity index of 80-100, for example 90-95.

Another class of lubricating oils are hydrocracked oils in which the refining process further cracks intermediate and heavy distillate fractions in the presence of hydrogen at elevated temperatures and pressures. Hydrocracked oils typically have a kinematic viscosity at 100 ° C. of 2-40, such as 3-15 mm ² / sec, and typically a viscosity index in the range of 100-110, such as 105-108. Have.

Bright stock is solvent extracted and degassed from vacuum residue having a kinematic viscosity at 100 ° C. of 28-36 mm ² / sec and less than 30% by weight, based on the weight of the lubricating oil composition, It means a base oil typically used in a proportion of less than 10% by weight, such as preferably less than 20, more preferably less than 15, most preferably less than 5% by weight.

Patent Document 12 describes a cleanliness oil of lubricating viscosity, a dispersant containing at least one calcium salicylate having a TBN in the range of 70 to 245, 0 to 0.2 wt% nitrogen, based on the weight of the oil composition. And a detergent gas fuel engine lubricating oil comprising a small amount of one or more co-additives. The base oil can be any animal, vegetable or mineral oil or synthetic oil. Base oil is used in a proportion of more than 60% by weight of the composition. The oil typically has a viscosity at 100 ° C. of ^{2 to} 40, for example 3 to 15 mm ² / sec and a viscosity index of 80 to 100. Hydrocracked oils having a viscosity of ² to 40 mm ² / sec at 100 ° C. and a viscosity index of 100 to 110 can also be used. Bright stock having a viscosity at 100 <0> C of 28-36 mm < ² > / s can also typically be used at a rate of less than 30% by weight, preferably less than 20, most preferably less than 5% by weight.

  U.S. Pat. No. 6,057,031 includes a boron content greater than 95 ppm, including a major amount of lubricating oil having a viscosity index of 80-120, at least 90% by weight of saturates, 0.03% by weight of sulfur and at least one detergent. Gas engine oil having Metal salicylate is a preferred detergent.

Patent Document 14 describes a high-viscosity synthetic hydrocarbon such as high-viscosity PAO, a liquid hydrogenated polyisoprene, or an ethylene-alphaolefin copolymer having a viscosity of 40 to 1000 cSt (mm ² / sec) at 100 ° C., 1 to 100 ° C. 10 cSt (mm ² / sec) low viscosity synthetic hydrocarbon having a viscosity of a low viscosity esters having a viscosity of 1~10cSt (mm ² / sec) at optionally 100 ° C., and optionally 25 weight% or less The present invention relates to a lubricating oil composition containing an additive package.

US Pat. No. 6,339,051 US Pat. No. 5,726,133 US Pat. No. 6,191,081 US Patent Application Publication No. 2005/0059563 US Patent Application Publication No. 2003/0191032 US Patent Application Publication No. 2006/0276355 US Patent Application Publication No. 2007/0289897 US Patent Application Publication No. 2007/0298990 US Patent Application Publication No. 2008/0207475 US Pat. No. 6,140,281 US Pat. No. 6,645,922 US Pat. No. 6,613,724 US Pat. No. 7,101,830 US Pat. No. 4,956,122

The invention relates to the traction of engine oil used to lubricate an engine where the interface surface (or contact surface) speed reaches about 3 mm / second or more, preferably about 10 mm / second or more, more preferably about 50 mm / second or more. It is directed to a method of improving the fuel economy of large low and medium speed engines by reducing the coefficient.
It has a kinematic viscosity at 100 ° C. of 8-25 mm ² / sec, two different base oils,
The first base oil has a kinematic viscosity of ² to 12 mm ² / sec at 100 ° C., and is a first base oil that is one or more oils selected from a group III base oil and a group IV base oil;
One or more polyisobutylenes (PIB) having a number average molecular weight of at least 800 Mn, preferably about 800 Mn to 6,000 Mn, more preferably about 1,300 Mn to 4,200 Mn, more preferably about 1,300 Mn to 3,000 Mn. An engine oil comprising a lubricating oil comprising a base oil comprising a bimodal blend with a second base oil selected from
Achieved by using as engine oil for lubricating the engine,
Here, the improvement in fuel economy is that the traction coefficient of the engine oil using the bimodal blend is not bimodal, or an engine oil based on one or more group I base oils, or group I This is evidenced by being lower than the traction coefficient of engine oil based on a mixture of base oil and PIB.

Lubricating oil comprising a combination of the first base oil and a second base oil preferably has a kinematic viscosity of 12～21Mm ² / s at 100 ° C. kinematic viscosity 8～25Mm ² / sec, more preferably at 100 ° C..

In a preferred embodiment, the present invention provides:
Having a kinematic viscosity at 100 ° C. in the range of 8-25 mm ² / sec, preferably in the range of 8-22 mm ² / sec, more preferably in the range of 12-21 mm ² / sec,
Two different base oils,
A first base oil that is one or more oils selected from the group consisting of a group III base oil and a group IV base oil having a kinematic viscosity at 100 ° C. of ² to 12 mm ² / sec;
One or more polyisobutylenes (PIBs) having a number average molecular weight of at least 800 Mn, preferably about 800 to 6,000 Mn, more preferably about 1,300 to 4,200 Mn, and even more preferably about 1,300 to 3,000 Mn. A base oil comprising a bimodal blend with a second base oil selected from
And an alkali or alkaline earth metal, preferably an alkaline earth metal, selected from salicylates, sulfonates, carboxylates, phenolates, preferably a mixture of phenolate and salicylate or a mixture of phenolate and carboxylate, Preferably an engine oil containing a lubricating oil containing calcium, a detergent,
By using it as an engine oil for lubricating the engine, a surface speed of about 3 mm / second or more, preferably about 10 mm / second or more, more preferably about 30 mm / second or more, and even more preferably about 100 mm / second or more. A method of improving the fuel economy of large low and medium speed engine oils by reducing the traction coefficient of engine oils, including base oils that operate in the engine that reaches,
The improvement in fuel economy is that the traction coefficient of the engine oil is not bimodal, even when it contains a detergent, or an engine oil or group I base oil based solely on a Group I base stock. It is directed to a method that is demonstrated by being lower than the traction coefficient of engine oils based on mixtures with PIB base oils.

In another embodiment, the present invention provides:
Having a kinematic viscosity in the range of 8-25 mm ² / sec at 100 ° C., preferably 8-22 mm ² / sec, more preferably 12-25 mm ² / sec,
Two different base oils,
The first base oil has a kinematic viscosity of ² to 12 mm ² / sec at 100 ° C., and is a first base oil that is one or more oils selected from a group II base oil, a group III base oil, and a group IV base oil;
One or more polyisobutylenes (PIBs) having a number average molecular weight of at least 800 Mn, preferably about 800-1,600 Mn, more preferably about 1,300-4,200 Mn, and even more preferably about 1,300-3,000 Mn. A bimodal blend with a second base oil selected from
Optionally and preferably one or more alkalis selected from salicylates, sulfonates, carboxylates, phenolates, preferably mixtures of phenolates and salicylates or mixtures of phenolates and carboxylates, more preferably phenolates and salicylates. And / or an engine oil comprising a lubricating oil containing an alkaline earth metal, preferably an alkaline earth metal, more preferably calcium, a detergent,
By using it as an engine oil for lubricating the engine, by reducing the traction coefficient of the engine oil used to lubricate the engine, at least about 60 mm / second or more, preferably at least about 70 mm / second or more A method for improving the fuel economy of large low and medium speed engines that reach surface speeds,
Improved fuel economy means that the traction coefficient of the engine oil is lower than the traction coefficient of non-bimodal engine oil, engine oil based on Group I base oil alone or engine oil based on Group I base oil and PIB mixture Is directed to a method proven by.

In another embodiment, the present invention provides:
Having a kinematic viscosity at 100 ° C. of 8-25 mm ² / sec,
A first base oil selected from the group consisting of a group III base oil and a group IV base oil having a kinematic viscosity at 100 ° C. of 2-12 mm ² / sec;
Selected from polyisobutylene (PIB) having a number average molecular weight of at least 800 Mn, preferably about 800 Mn to 6,000 Mn, more preferably about 1,300 Mn to 4,200 Mn, or preferably about 1,300 Mn to 3,000 Mn Lubricating oil including the second base oil,
By using as engine oil, the surface speed of at least 3 mm / second, preferably at least 10 mm / second, more preferably at least 60 mm / second, by reducing the traction coefficient of the engine oil used to lubricate the engine A method of reaching and improving the fuel economy of large low and medium speed engines lubricated by engine oil,
Improved fuel economy is achieved at 100 ° C., where the engine oil contains a single base oil component of a Group III base oil or a Group IV base oil or is based on one or more Group I base oils or a mixture of Group I base oils and PIBs. It is directed to a method that is demonstrated by having a traction coefficient lower than that of engine oil of the same kinematic viscosity.

  As used herein and in the appended claims, the terms “base oil” and “base oil” are used synonymously and interchangeably.

  “Surface speed” means the speed at which two interface surfaces (or contact surfaces), such as cylinder walls and pistons, or bearing surfaces pass each other during engine operation. This surface velocity is a major factor affecting whether the lubrication regime for the interface surface is boundary, hydrodynamic or mixed (boundary / hydrodynamic).

The effect of a bimodal blend of Group III base oil plus PIB, blended to different final blend kinematic viscosities using different molecular weight PIBs, on the traction coefficient in the absence of any additives Or a control oil containing a blend of Group I base oil and PIB. The effect of a bimodal blend of Group III base oil plus PIB, blended to different final blend kinematic viscosities, on the traction coefficient in the presence of different detergents individually, with Group I base oils containing detergents Shown against a control oil containing a blend with PIB. Cleans the effect of a bimodal blend of Group III base oil or Group II base oil plus different molecular weight PIB, blended to nominally the same final blend kinematic viscosity, on traction coefficient in the presence of different mixtures of detergents Shown against a control oil containing a blend of Group I base oil containing the agent and PIB.

The method of the present invention utilizes a bimodal mixture of base oils. As used herein, bimodal refers to a mixture of at least two base oils each having a different kinematic viscosity at 100 ° C., wherein the difference in kinematic viscosity at 100 ° C. between at least two base oils is at least low. By means a mixture that is the difference between a viscosity base oil and polyisobutylene (PIB) having a number average molecular weight of at least 800 Mn. The mixture of at least two base oils is combined with one or more polyisobutylenes (PIB) having a number average molecular weight of at least 800 Mn, and the base oil is group II, group III and group IV using the API classification. One or more low kinematic base oils having a kinematic viscosity at 100 ° C. of 2-12 cSt (mm ² / sec) selected from the group consisting of base oils. The degree of bimodality of these combinations can be determined by measuring the kinematic viscosity of PIB at 100 ° C. according to ASTM D445. For example, the kinematic viscosity of PIB (1300 MW) at 100 ° C. is about 630 mm ² / sec, and the kinematic viscosity of PIB (2500 MW) at 100 ° C. is about 4,100 mm ² / sec.

  Group III base oils are classified by the American Petroleum Institute (American Petroleum Institute) with oils containing 90% or more of saturates, 0.03% or less of sulfur and a viscosity index of 120 or more. Group III base oils are usually highly hydrocracked to remove impurities, such as vacuum gas oil (or light oil), to remove impurities and to saturate any aromatic compounds that may be present. A process for producing a high paraffinic lubricating base oil with a high viscosity index, a process for subjecting the hydrocracked base oil to a selective catalytic hydrodewaxing process in which normal paraffins are converted to branched paraffins by isomerization, followed by hydrogen It is produced using a three-step process that includes the step of chemical purification to remove any residual aromatics, sulfur, nitrogen or oxygenates.

  Group III base stocks are also (1) one or more gas liquefied (GTL) materials; and (2) hydrodewaxed or hydrogen derived from synthetic waxes, natural waxes or waxy feeds Isomerized / contact (and / or solvent) dewaxed base oil and / or base oil, wherein the waxy feed is a gas oil, slack wax (natural oil, mineral oil or synthetic oil, eg Fischer- Mineral oils and / or non-mineral oily waxy feedstocks and waxy fuel hydrocracker bottoms, waxy raffinates, hydrocracked products, thermal cracked products such as Tropsch (Fischer-Tropsch feedstock) Foot oil or other minerals, waxy base oils such as mineral oil, or coal liquefaction Or even a non-petroleum-derived waxy material such as a linear or branched hydrocarbyl compound having a carbon number of about 20 or more, preferably about 30 or more, and such base oils and recovered from shale oil Non-conventional or unconventional base oils and / or base oils comprising one or a mixture of base oils and / or base oils derived from base oils and / or base oils comprising a mixture of base oils.

  GTL substances are gaseous carbon-containing compounds such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylene and butyne, hydrogen-containing compounds and / or feedstocks. A substance derived from one or more components by one or more synthesis, bonding, transformation, rearrangement, and / or degradation / destructive processes. GTL base oils and / or base oils are generally derived from hydrocarbons; for example, waxy synthetic hydrocarbons derived themselves from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and / or components as feedstocks. It is a GTL substance of lubricating viscosity. GTL base oils and / or base oils include oils boiling in the lube oil boiling range (1) separated / fractionated from synthetic GTL material, such as by distillation, and subsequently reduced / low pour point lubricants To produce a final wax treatment step that includes either or both a catalytic dewaxing process or a solvent dewaxing process; (2) for example hydrodewaxed or hydroisomerized Synthetic wax isomers comprising synthetic contact and / or solvent dewaxed synthetic waxes or waxy hydrocarbons; (3) hydrodewaxed or hydroisomerized contact and / or solvent dewaxing Treated Fischer-Tropsch (FT) material (ie hydrocarbons, waxy hydrocarbons, waxes) And possible similar oxygenates); preferably hydrodewaxed or hydroisomerized / subsequently contacted and / or solvent dewaxed dewaxed FT waxy hydrocarbons, or hydrodewaxing Or hydroisomerized / subsequent contact (and / or solvent) dewaxing dewaxed FT wax, or mixtures thereof.

GTL base oils and / or base oils derived from GTL materials, especially hydrodewaxed or hydroisomerized / subsequently contacted and / or solvent dewaxed waxes or waxy feeds, preferably F- The T-material derived base oil and / or base oil is typically characterized as having a kinematic viscosity at 100 ° C. (ASTM D445) of about 2 mm ² / sec to about 50 mm ² / sec. They are typically further characterized as having a pour point (ASTM D97) of −5 ° C. to about −40 ° C. or less. They are also typically characterized as having a viscosity index (ASTM D2270) of about 80 to about 140 or greater.

  In addition, GTL base oils and / or base oils are typically highly paraffinic (> 90% saturates) and may contain a mixture of monocycloparaffins and multicycloparaffins in combination with acyclic isoparaffins. . The ratio of naphthenic (ie cycloparaffin) content in such combinations varies with the catalyst and temperature used. In addition, GTL base oils and / or base oils typically have very low sulfur and nitrogen contents and generally contain less than about 10 ppm, more typically less than about 5 ppm of each of these elements. The sulfur and nitrogen content of GTL base oils and / or base oils obtained from FT materials, especially FT waxes, is essentially zero. In addition, the absence of phosphorus and aromatic compounds makes this material particularly suitable for formulating low SAP products.

The terms GTL base oil and / or base oil and / or wax isomerate base oil and / or base oil are recovered in the manufacturing process to produce a blend exhibiting a target kinematic viscosity in the range of 2-12 mm ² / sec at 100 ° C. Such materials in a wide viscosity range as such, two or more mixtures of such fractions, and one or two or more low combined with one, two or more higher viscosity fractions It should be understood to include individual fractions of a mixture of viscosity fractions.

  The GTL material from which the GTL base oil and / or base oil is derived is preferably an FT material (ie, hydrocarbon, waxy hydrocarbon, wax).

  In a preferred embodiment, the GTL material from which the GTL base oil and / or base oil is derived is an FT material (ie, hydrocarbon, waxy hydrocarbon, wax). The slurry FT synthesis process uses CO and hydrogen and, in particular, an FT catalyst containing a catalytic cobalt component to provide a high Schultz-Flory kinetic alpha to produce the more desirable higher molecular weight paraffins. May be conveniently used to synthesize raw materials from The process is also well known to those skilled in the art.

  GTL base oil and / or base oil, hydrodewaxed or hydroisomerized / contact (and / or solvent) dewaxed FT material-derived base oil, and wax isomerate or hydrogenation Useful compositions of wax-derived hydrodewaxed or hydroisomerized / contact (and / or solvent) dewaxed base oils, such as dewaxed bodies, are disclosed in, for example, US Patents 6,080,301; 6,090,989, and 6,165,949.

  Base oils and / or base oils derived from waxy feeds that are also suitable for use as Group III base stocks in the present invention are mineral oils, non-mineral oils, non-petroleum, or natural sources such as gas oils, slacks. A feedstock such as one or more of waxes, waxy fuel hydrocracker bottoms, hydrocarbon raffinates, natural waxes, hydrocracked products, pyrolysed products, foot oil, coal liquefied or shale oil, or Other suitable mineral oils, non-mineral oils, non-petroleum, or natural source derived waxy materials, linear or branched hydrocarbyl compounds having about 20 or more carbon atoms, preferably about 30 or more carbon atoms, and such isomers Hydrodewaxing or hydroisomerization of a mixture of / isodewaxed base oil and / or base oil The a / contact (and / or solvent) paraffinic fluids of lubricating viscosity derived from dewaxing treated waxy feedstock.

  Slack wax is a wax recovered from any waxy hydrocarbon oil, including synthetic oils such as FT waxy oil or petroleum, by solvent or auto-cooling dewaxing. The solvent dewaxing treatment uses a cooled solvent such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), a mixture of MEK / MIBK, a mixture of MEK and toluene, and the automatic cooling dewaxing treatment uses propane or butane. Pressurized liquefied low boiling point hydrocarbons such as are used.

  Slack waxes secured from synthetic waxy oils such as FT waxy oils will usually have zero or no sulfur and / or nitrogen containing compound content. Slack waxes secured from petroleum can contain sulfur and nitrogen containing compounds. Such heteroatom compounds may be hydrotreated (and, for example, by hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) to avoid subsequent poisoning / deactivation of the hydroisomerization catalyst. (Not hydrocracking).

  The process of producing a lubricating base oil from a waxy base stock, such as slack wax, FT wax, or a waxy feedstock, may be characterized as an isomerization process. When slack waxes are used as raw materials, they remove sulfur- and nitrogen-containing compounds (catalysts) that would otherwise deactivate the hydroisomerization or hydrodewaxing treatment catalyst used in the next step. May need to be subjected to a pre-hydrotreatment step under conditions well known to those skilled in the art to reduce or eliminate (to a level that would effectively avoid poisoning or inactivation) There is. As FT waxes are used, such waxes only have a trace (less than about 10 ppm, or more typically less than about 5 ppm to none) sulfur or nitrogen compound content. No pre-treatment is required. However, some hydrodewaxing catalysts supplied with FT wax may benefit from pre-hydrotreating for oxygenate removal, while others may benefit from oxygenate treatment. There is sex. The hydroisomerization or hydrodewaxing process may be performed on a combination of catalysts or on a single catalyst.

  After the required hydrodenitrogenation or hydrodesulfurization, the hydroprocessing used for the production of base oils from such waxy feedstocks is amorphous, such as lube oil hydrocracking (LHDC) catalysts. Quality hydrocracking / hydroisomerization catalysts, eg oxide supports such as alumina, silica, catalysts containing Co, Mo, Ni, W, Mo etc. on silica / alumina, or crystalline hydrocracking / Hydrogen isomerization catalyst, preferably a zeolitic catalyst may be used.

  A hydrocarbon conversion catalyst useful for the conversion of the n-paraffin waxy feedstock disclosed herein to form an isoparaffinic hydrocarbon base oil is disclosed in US Pat. No. 4,906,350. Zeolites such as ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-12, ZSM-38, ZSM-48, Offrelite, ferrierite, zeolite beta, zeolite theta, and zeolite alpha It is a catalyst. These catalysts are used in combination with Group VIII metals, in particular palladium or platinum. Group VIII metals may be incorporated into the zeolite catalyst by conventional techniques, such as ion exchange.

  In one embodiment, the conversion of the waxy feedstock is carried out on a combination of Pt / zeolite beta and Pt / ZSM-23 catalyst in the presence of hydrogen, or on such a catalyst used continuously. It may be broken. In another embodiment, the lube base oil manufacturing process includes hydroisomerization and dewaxing over a single catalyst, such as Pt / ZSM-35. In yet another embodiment, the waxy feedstock is a Group VIII metal supported ZSM-48, preferably a Group VIII noble metal supported ZSM-48, more preferably Pt / ZSM-48, either in one or two stages. Can be fed over a catalyst comprising In all cases, useful hydrocarbon-based oil products can be obtained. Catalyst ZSM-48 is described in US Pat. No. 5,075,269.

  The dewaxing step may be accomplished using one or more of solvent dewaxing, catalytic dewaxing or hydrodewaxing processes, or a combination of such processes in any order, as required. .

  In the solvent dewaxing process, the hydroisomer is contacted with a cooled solvent, such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ME / MIBK mixture, or MEK / toluene mixture, and In addition, it is further cooled to precipitate the higher pour point material as a waxy solid, which is then separated from the solvent-containing lubricating oil fraction that is a raffinate. The raffinate is typically further cooled with a scraping surface cooler to remove more wax solids. Autocooling using low molecular weight hydrocarbons, such as propane, at least a portion of which is flushed to cool the hydroisomer and precipitate the wax, eg, mixed with liquid propane and hydroisomer A dewaxing process can also be used. The wax is separated from the raffinate by filtration, membrane separation or centrifugation. The solvent is then stripped from the raffinate, which is then fractionally distilled to produce a preferred base oil useful in the present invention.

  In the catalytic dewaxing process, the hydroisomer is reacted with hydrogen in the presence of a suitable dewaxing catalyst under conditions effective to lower the pour point of the hydroisomer. Catalytic dewaxing also converts a portion of the hydroisomer to lower boiling material, which is separated from the heavier base oil fraction. This base oil fraction can then be fractionated into two or more base oils. Separation of the lower boiling material may be accomplished either before or during fractionation of the heavy base oil fraction material to the desired base oil.

Any dewaxing catalyst that will lower the pour point of the hydroisomer, and preferably one that provides a large yield of lubricating base oil from the hydroisomer may be used. These include shape-selective molecular sieves that have proven useful for dewaxing petroleum fractions when combined with at least one catalytic metal component, such as ferrierite, mordenite, ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-22, also known as Thetaone or TON, and silicoaluminophosphate, also known as SAPO. Surprisingly, a dewaxing catalyst that has been found to be particularly effective comprises a noble metal, preferably Pt, complexed with H-mordenite. The dewaxing process may be accomplished with a catalyst in a fixed bed, fluidized bed or slurry bed. Typical dewaxing process conditions include a temperature in the range of about 400-600 ° F., a pressure of 500-900 psig, a H ₂ process rate of 1500-3500 SCF / B for the flow-through reactor and 0.1-10, preferably Is 0.2 to 2.0 LHSV. The dewaxing process typically converts 40% by weight or less, preferably 30% by weight or less of the hydroisomerized product having an initial boiling point in the range of 650 to 750 ° F. to a material boiling below the initial boiling point. Done for.

  The first base oil of the bimodal mixture can also be a Group IV base oil identified as a polyalphaolefin for purposes of this specification and the appended claims.

Poly-alpha-olefin (PAO) is generally typically, _{C 2} ~ about _{C 32} alpha-olefins, preferably, for example, 1-octene, 1-decene, a _{C 8} ~ about _{C 16} alpha olefins such as 1-dodecene It comprises, but is not limited to, relatively low molecular weight hydrogenated polymers or oligomers of polyalphaolefins. Preferred polyalphaolefins are poly-1-octene, poly-1-decene and poly-1-dodecene and mixtures thereof and mixed olefin derived polyolefins.

PAO fluids include, for example, Friedel- containing complexes of aluminum trichloride, boron trifluoride or boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate. It may be conveniently prepared by the polymerization of alpha olefins in the presence of a polymerization catalyst such as a Crafts (Friedel-Crafts) catalyst. For example, the methods disclosed by US Pat. No. 4,149,178 or US Pat. No. 3,382,291 may be conveniently used herein. Other descriptions of PAO synthesis can be found in the following US patents: 3,742,082, 3,769,363, 3,876,720, 4,239,930. Specification, 4,367,352 specification, 4,413,156 specification, 4,434,408 specification, 4,910,355 specification, 4,956,122 specification In the description and in 5,068,487. Dimers of C _{14 to} C ₁₈ olefins are described in US Pat. No. 4,218,330.

  PAO useful in the present invention can also be produced by metallocene catalysts. The metallocene catalyst PAO (mPAO) can be a copolymer made from at least two alpha olefins or more with a metallocene catalyst system, or a homopolymer made from a single alpha olefin feedstock.

  The metallocene catalyst is activated or promoted by a non-coordinating anion, such as, for example, methylaluminoxane (MAO) or N, N-dimethylanilinium tetrakis (perfluorophenyl) borate or other equivalent non-coordinating anion. It can be a simple metallocene, a substituted metallocene or a bridged metallocene catalyst. Methods for producing mPAO using mPAO and metallocene catalysis are described in WO 2009/123800, WO 2007/011832, and US Patent Application Publication 2009/0036725.

Copolymer mPAO composition is prepared from at least two alpha olefins C ₃ -C ₃₀ range, they are distributed randomly monomers in the polymer. The average carbon number is preferably at least 4.1. Advantageously, ethylene and propylene, when present in the feed, are present individually in an amount of less than 50% by weight or preferably less than 50% by weight combined. The copolymers of the present invention can be isotactic, atactic, syndiotactic polymers or any other form of suitable stereoregularity.

mPAO are _also prepared from C 3 at least two and 26 following different linear mixed feed linear alpha olefin with an alpha-olefin is selected from _{-C 30} linear alpha olefins (LAO). In a preferred embodiment, the mixed feed LAO is obtained from an ethylene growth process using an aluminum catalyst or a metallocene catalyst. Growth olefins, including most _C 6 _~C 18 LAO. LAO from other processes can also be used.

Homopolymer mPAO _composition, C 3 _{-C 30} range, preferably _C 3 _{-C 16,} and most preferably is manufactured from a single alpha-olefins selected from _C 3 _{-C 14} or _C 3 _{-C 12.} The homopolymer can be an isotactic, atactic, syndiotactic polymer or any other form of suitable stereoregularity. Stereoregularity can be carefully tuned by the selected polymerization catalyst and polymerization reaction conditions or by selected hydrogenation conditions.

The alpha olefin can be selected from any component from a conventional LAO manufacturing facility or from a refinery. It was manufactured alone or from another LAO available from a refinery or chemical plant, including propylene, 1-butene, 1-pentene, etc., or from a dedicated manufacturing facility to produce a homopolymer Can be used with hexene or 1-octene. The alpha olefin can be selected from alpha olefins produced from Fischer-Tropsch synthesis (as reported in US Pat. No. 5,382,739). For example, C _{3 to} C ₁₆ alpha olefins, more preferably linear alpha olefins, are suitable for producing homopolymers. C ₄ - and _C 14 -LAO, _{C 6} - and _{C 16 -LAO, C 8 -,} C 10 -, C 12 -LAO or _{C 8,} - and _{C 14 -LAO, C 6 -,} C 10 -, C ₁₄ -LAO, _{C 4} -, such as and _C 12 -LAO, other combinations are suitable for preparing copolymers.

A mixture of LAO selected from C _{3 to} C ₃₀ LAO or a feed comprising a single LAO selected from C _{3 to} C ₁₆ LAO is suitable for liquid production for use in lubricating oil components or as a functional fluid It is contacted with an activated metallocene catalyst under oligomerization conditions to provide a product. Also included are copolymer compositions made from at least two alpha olefins in the C _{3 to} C ₃₀ range and in which the monomers are randomly distributed throughout the polymer. The phrase “at least two alpha olefins” will be understood to mean “at least two different alpha olefins” (and similarly “at least three alpha olefins” means “at least three different alpha olefins” and the like). To do).

  The resulting product is an essentially random liquid copolymer containing at least two alpha olefins. “Essentially random” means that one skilled in the art would consider the product to be a random copolymer. Similarly, the term “liquid” will be understood by those skilled in the art to mean a liquid under normal conditions of temperature and pressure, such as ambient temperature and pressure.

The process comprises a catalyst system comprising a metallocene compound (Formula 1, below) together with an activator such as a non-coordinating anion (NCA) (Formula 2, below) or methylaluminoxane (MAO) 1111 (Formula 3, below). Is used.

  The term “catalyst system” is defined herein to mean a catalyst precursor / activator pair, such as a metallocene / activator pair. When "catalyst system" is used to describe such a pair prior to activation, it may be an activity together with an activator and, optionally, a coactivator (such as a trialkylaluminum compound). It means a catalyst (pre-catalyst) that has not been converted. When it is used to describe such a pair after activation, it means an activation catalyst and an activator or other charge balance moiety. In addition, the activated “catalyst system” may optionally include co-activators and / or other charge balance moieties. Optionally and often, coactivators such as trialkylaluminum compounds are also used as impurity scavengers.

The metallocene is selected from one or more compounds according to Formula 1 above. In Formula 1, M is selected from a Group 4 transition metal, preferably zirconium (Zr), hafnium (Hf) and titanium (Ti), and L1 and L2 are independently substituted or unsubstituted Selected from cyclopentadienyl ("Cp"), indenyl, and fluorenyl, which may be optionally hydrogenated. A, when present, in a preferred embodiment is dialkylsilyl, dialkylmethyl, diphenylsilyl or diphenylmethyl, ethylenyl (—CH ₂ —CH ₂ ), alkyl ethylenyl (—CR ₂ —CR ₂ ) (wherein alkyl are independently, C ₁ -C ₁₆ alkyl radical or a phenyl, tolyl, selected from xylyl radicals can be in the like), and wherein the two X groups, each of Xa and Xb independently, Halide, OR (R is preferably an alkyl group, preferably selected from C ₁ -C ₅ linear or branched alkyl groups), hydrogen, C ₁ -C ₁₆ alkyl or aryl groups, haloalkyl, etc. . In general, relatively more highly substituted metallocenes give higher catalyst productivity and a wider product viscosity range and are therefore more preferred in many cases.

  The polyalphaolefin is preferably 1.8 or less, preferably 1.7 or less, preferably 1.6 or less, preferably 1.5 or less, preferably 1.4 or less, preferably as measured by ASTM D1159. It has a bromine number of 1.3 or less, preferably 1.2 or less, preferably 1.1 or less, preferably 1.0 or less, preferably 0.5 or less, preferably 0.1 or less.

（式中、ｊ、ｋおよびｍはそれぞれ、独立して、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０、２１または２２であり、ｎは、プロトンＮＭＲによって測定されるように１〜３５０（好ましくは１〜３００、好ましくは５〜５０）の整数である）
で表されるモノマー単位を有してもよい。 The m-polyalphaolefins described herein have formula 4: in addition to all ordered 1,2-bonds.

(Wherein j, k and m are each independently 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 and n is an integer from 1 to 350 (preferably 1 to 300, preferably 5 to 50) as measured by proton NMR.
It may have a monomer unit represented by.

  Any of the m-polyalphaolefins (mPAO) described herein are preferably 100,000 or less, preferably 100 to 80,000, preferably 250 to 60,000, preferably 280 to 50,000. , Preferably having a Mw (weight average molecular weight) of 336 to 40,000 g / mol.

  Any of the m-polyalphaolefins (mPAO) described herein are preferably 50,000 or less, preferably 200 to 40,000, preferably 250 to 30,000, preferably 500 to 20,000 g. / Mol Mn (number average molecular weight).

  Any of the m-polyalphaolefins (mPAO) described herein are preferably more than 1 and less than 5, preferably less than 4, preferably less than 3, preferably less than 2.5 (MWD- Mw / Mn). mPAO MWD is always a function of fluid viscosity. Alternatively, any of the polyalphaolefins described herein preferably have a Mw / Mn of 1 to 2.5, alternatively 1 to 3.5, depending on the fluid viscosity.

  The molecular weight distribution (MWD), defined as the ratio of the weight average MW to the number average MW (= Mw / Mn), is described in “Principles of Polymer Systems” (from Ferdinand Rodrigues, McGraw-Hill Book, 1970). 115-144, Chapter 6, The Molecular Weight of Polymers can be measured by gel permeation chromatography (GPC) using polystyrene standards. The GPC solvent was HPLC Grade tetrahydrofuran with no stabilizer at a column temperature of 30 ° C., a flow rate of 1 ml / min, and a sample concentration of 1 wt%, and Column Set is Phenogel 500 A, Linear, 10E6A. .

  Any of the m-polyalphaolefins (mPAO) described herein may have a high end tail with a substantially small portion of the molecular weight distribution. Preferably, the mPAO is 5.0 wt% or less of a polymer having a molecular weight greater than 45,000 daltons. Additionally or alternatively, the amount of mPAO having a molecular weight greater than 45,000 daltons is 1.5 wt% or less, or 0.10 wt% or less. Additionally or alternatively, the amount of mPAO having a molecular weight greater than 60,000 daltons is 0.5% or less, or 0.20% or less, or 0.1% or less. The mass fraction at a molecular weight of 45,000-60,000 can be measured by GPC as described above.

  Any PAO described herein is less than 0 ° C (as measured by ASTM D97), preferably less than -10 ° C, preferably less than 20 ° C, preferably less than -25 ° C, preferably -30 ° C. It may have a pour point of less than, preferably less than -35 ° C, preferably less than -50 ° C, preferably -10 ° C to -80 ° C, preferably -15 ° C to -70 ° C.

  The polyalphaolefin produced using the metallocene catalyst is about 1.5 to about 5,000 cSt, preferably about 2 to about 3,000 cSt, preferably about 3 cSt to about 1,000 cSt, as measured by ASTM D445. More preferably from about 4 cSt to about 1,000 cSt, even more preferably from about 8 cSt to about 500 cSt at 100 ° C.

  PAO useful in the present invention includes those produced by the processes disclosed in US Pat. No. 4,827,064 and US Pat. No. 4,827,073. Manufactured using low valence state chromium catalysts, these PAO materials are highly effective in giving them highly desirable properties to be useful as lubricant base oils and at higher viscosity grades as VI improvers. It is a polymer olefin oligomer characterized by a high viscosity index. They are referred to as high viscosity index PAO or HVI-PAO.

  Various modifications and variations of these HVI-PAO materials are also mentioned in the following US patents: 4,990,709, 5,254,274, 5,132,478. Specification, 4,912,272, 5,264,642, 5,243,114, 5,208,403, 5,057,235 No. 5,104,579, No. 4,943,383, No. 4,906,799. These oligomers can be briefly summarized as being produced by oligomerization of 1-olefins in the presence of a metal oligomerization catalyst that is a supported metal in the low valence state. A preferred catalyst comprises low valence state chromium on a silica support prepared by reduction of chromium using carbon monoxide as a reducing agent. The oligomerization is carried out at a temperature selected depending on the desired viscosity for the resulting oligomer, as described in US Pat. Nos. 4,827,064 and 4,827,073. . Higher viscosity materials are disclosed in US Pat. No. 5,012,020 and US Pat. No. 5,146,021, where oligomerization temperatures below about 90 ° C. are used to produce higher molecular weight oligomers. It may be manufactured as described in the specification. In all cases, the oligomer, after hydrogenation when necessary to reduce residual unsaturation, has a branching index less than 0.19 (US Pat. Nos. 4,827,064 and 4,827, As defined in the '073 specification). In general, HVI-PAO usually has a viscosity in the range of about 12 to 5,000 cSt.

In addition, HVI-PAO generally has the following: C ₃₀ -C ₁₃₀₀ hydrocarbons have a branching ratio of less than 0.19, a weight average molecular weight of 300-45,000, a number average molecular weight of 300-18,000, 1-5 Can be characterized by one or more having a molecular weight distribution of HVI-PAO is a fluid having a viscosity of 100 ° C. in the range of 5 to 5000 mm ² / second or more. Further, 3 mm ² / sec ~5000mm ² / s fluid viscosity at 100 ° C. of has a VI that is calculated by 130 than the ASTM method D2270. Usually they are in the range of 130-350. All fluids have a low pour point below -15 ° C.

HVI-PAO is, C ₆ taken from the group consisting of 1-alkenes of -C _20, it only mixtures of Kano either in the form or a hydrocarbon composition comprising a polymer or oligomer is prepared from 1-alkene Can be further characterized as: Examples of raw materials are 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, etc., or a mixture of C ₆ -C ₁₄ 1-alkene or C ₆ -C ₂₀ 1-alkene, C ₆ and C ₁₂ 1-alkene, C ₆ and C ₁₄ 1-alkene, C ₆ and C ₁₆ 1-alkene, C ₆ and C ₁₈ 1-alkene, C ₈ and C ₁₀ 1-alkene, C It can be a mixture of ₈ and C ₁₂ 1-alkenes, C ₈ , C ₁₀ and C ₁₂ 1-alkenes, and other suitable combinations.

The product is generally, those boiling below 600 ° F, or less than C ₂₀ to any low molecular weight compositions, such as those of carbon number, if they are brought in from or a starting material produced from the polymerization reaction And distilled to remove. This distillation step usually improves the volatility of the finished fluid.

  Fluids produced directly from the polymerization or oligomerization process usually have unsaturated double bonds or have an olefin molecular structure. The amount of double bond or unsaturated or olefinic component is measured by several methods such as bromine number (ASTM D1159), bromine index (ASTM D2710), or other suitable analytical methods such as NMR, IR. be able to. The amount of double bonds or the amount of olefin composition depends on several factors-the degree of polymerization, the amount of hydrogen present in the polymerization process and the amount of other promoters involved in the termination of the polymerization process, or in the process. Depends on other reagents to be used. Typically, the amount of double bonds or the amount of olefin component is reduced by the higher degree of polymerization, the higher amount of hydrogen gas present in the polymerization process, or the higher amount of promoter involved in the termination step.

  In general, it is known that the oxidative stability and light or UV stability of fluids improve when the amount of unsaturated double bonds or olefin content decreases. It is therefore desirable to hydrotreat the polymer if it has a high degree of unsaturation. Typically, bromine number fluids less than 5 as measured by ASTM D1159 are suitable for high quality base oil applications. Of course, the lower the bromine number, the better the lubricating oil quality. Fluids with a bromine number of less than 3 or 2 are common. The most preferred range is less than 1 or less than 0.1. Hydroprocessing methods for reducing the degree of unsaturation are well known in the literature (US Pat. No. 4,827,073, Example 16). In some HVI-PAO products, fluids made directly from polymerization already have a very low degree of unsaturation, such as those with viscosities greater than 150 cSt at 100 ° C. They have a bromine number less than 5 or even lower than 2. In these cases, it can be used as is without hydrotreating, or it can be hydrotreated to further improve the base oil properties.

Regardless of their origin or the process or technique used to produce them, the first low kinematic viscosity fluid is a single oil or mixture of oils that has a low kinematic viscosity in the range of 2-12 mm ² / sec at 100 ° C. It can be used as an oil from a single source or as a mixture of oils, provided that it has.

Thus, a low kinematic viscosity fluid can constitute a single base oil that meets the enumerated kinematic viscosity, or it can be two or more base oils, each individually meeting the enumerated kinematic viscosity limit. Can be configured. Further, the low kinematic viscosity fluid is one under the condition that the resulting blend blend exhibits a target low kinematic viscosity of 2-12 mm ² / sec at 100 ° C. listed as the viscosity range of the first low kinematic viscosity fluid. two or more higher kinematic viscosity base oils, for example, such as 100 ° C. at 100 mm ² / sec base oil of the above kinematic viscosity, base stocks and a combination of kinematic viscosity 12 mm ² / sec than in 100 ° C. One, two or more low-viscosity base oils, for example, a mixture of base oils having a kinematic viscosity in the range of 2-12 mm ² / sec at 100 ° C.

  The second oil used in the bimodal blend has a number average molecular weight of at least 800 Mn, preferably 800 to 6,000 Mn, more preferably 1,300 to 4,200 Mn, even more preferably 1,300 to 3,000 Mn. A high kinematic viscosity polyisobutylene (PIB) having

The present invention is one or more Group II or Group III base oils, the first having a KV at 100 ° C. of 2-12 mm ² / sec, and the second one or more poly having a number average molecular weight of at least 800 Mn. A lubricant comprising a bimodal blend of two different base oils, isobutylene (PIB), is used to achieve that improvement in fuel economy as evidenced by a reduction in traction coefficient. When using such a bimodal blend of base oils, the traction coefficient of the oil in use at a surface speed as low as 10 mm / sec is not bimodal or is a Group I base oil or Group I base oil It is reduced compared to the use of engine oils based only on plus PIB and even when containing detergents.

  The traction coefficient is an alkali or alkaline earth metal, preferably alkaline earth, selected from the group consisting of salicylates, phenolates, sulfonates or carboxylates, preferably phenolates and salicylate detergents or phenolates and carboxylate detergents. By using the bimodal base oil blends listed above, most preferably in combination with a calcium detergent, even lower surface speeds can be reduced at surface speeds as low as 3 mm / sec. The detergent need not be a single metal salt, by way of example and without limitation, a mixture of metal salts, such as a mixture of sodium and / or lithium and / or calcium and / or magnesium salts Can do.

  The method of reducing the traction coefficient uses an engine lubricating oil composition as described above that contains a bimodal base oil blend as a minimum necessary and essential component. Preferably, the engine lubricant used to achieve the reduction in traction coefficient includes both bimodal base oil blends and detergents as essential components.

  The method comprises a bimodal blend base oil, preferably a bimodal blend base oil and detergent, preferably a mixture of a metal phenolate and a metal salicylate detergent or a phenolate / carboxylate detergent. Engine lubricants containing additional performance additives can be used, provided that they contain. When detergents are used in a bimodal blend, it / they are from 4 to 33%, preferably 8 to 25%, by weight (based on (or based on) the detergent active ingredient) of the lubricating oil Preferably it is present in a total amount ranging from 8 to 20% by weight.

  The detergent used can be neutral / low to high, for example having a total base number (TBN) ranging from 0-40 to 400 or more. The finished lubricating oil will have a TBN of at least 5, preferably 40-100 mg KOH / g, more preferably 40-70 mg KOH / g.

  When a mixture of phenolate and salicylate or a mixture of phenolate and carboxylate detergent is used, the weight ratio of phenolate detergent to salicylate or carboxylate detergent is 95: 5 to 5:95, preferably It can be in the range of 3: 1 to 1: 3.

  Formulated (or formulated) lubricating oils useful in the present invention include dispersants, other detergents, corrosion inhibitors, antioxidants, rust inhibitors, metal deactivators, antiwear and / or extreme pressure additives, Anti-sticking agents, wax modifiers, viscosity index improvers, viscosity modifiers, fluid loss additives, seal compatibility agents, other friction modifiers, lubricants, antifouling agents, color formers, antifoaming agents, demulsifiers May further contain one or more of other commonly used lubricating oil performance additives including, but not limited to, emulsifiers, thickeners, wetting agents, gelling agents, adhesives, colorants, and the like. Good. For a review of many commonly used additives, see Klammann in Lubricants and Related Products, Verlag Chemie, Deerfield Beach, FL; ISBN 0-89573-177-0. M., published by Noyes Data Corporation of Parkridge, NJ (1973). W. See also "Lubricant Additives" by Ranney.

  The type and amount of performance additive used in combination with the present invention in the lubricating oil composition is not limited by the examples provided herein by way of illustration.

Viscosity improvers Viscosity improvers (also known as viscosity index modifiers, and VI improvers) provide high and low temperature operability to lubricating oils. These additives increase the viscosity of the oil composition and increase the film thickness at elevated temperatures while exerting a limited effect on viscosity at low temperatures.

  Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters, and viscosity index improver dispersants that function as both viscosity index improvers and dispersants. The typical molecular weight of these polymers is about 10,000 to 1,000,000, more typically about 20,000 to 500,000, even more typically about 50,000 to 200,000. is there.

  Examples of suitable viscosity improvers are methacrylates, butadiene, olefins, or alkylated styrene polymers and copolymers. Suitable viscosity index improvers are polymethacrylates (eg, copolymers of various chain length alkyl methacrylates), some formulations of which also serve as pour point depressants. Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (eg, copolymers of various chain length acrylates). Specific examples include 50,000-200,000 molecular weight styrene-isoprene or styrene-butadiene based polymers.

  The amount of viscosity modifier is from 0 to 12% by weight, preferably from 0 to 6% by weight, more preferably from 0 to 4% by weight, based on the active ingredient and depending on the specific viscosity modifier used. It may be a range.

Antioxidants Typical antioxidants include phenolic antioxidants, amine antioxidants and oil-soluble copper complexes.

  Examples of phenolic antioxidants include sulfurized and non-sulfurized phenolic antioxidants. As used herein, the term “phenolic type” or “phenolic antioxidant” refers to an aromatic ring that may itself be a single ring, eg, benzyl, or polycyclic, eg, naphthylyl and spiroaromatic compounds. Includes compounds having one or more hydroxyl groups bonded thereto. Thus, “phenolic type” includes phenol itself, catechol, resorcinol, hydroquinone, naphthol, and the like, and their alkyl or alkenyl and sulfurized alkyl or alkenyl derivatives, and such as linked by alkylene, sulfur, or oxygen bridges. Bisphenol type compounds including various biphenol compounds are included. Alkylphenols include mono- and poly-alkyl or alkenyl phenols and their sulfurized derivatives in which the alkyl or alkenyl group contains about 3 to 100 carbons, preferably 4 to 50 carbons. The number of alkyl or alkenyl groups present ranges from 1 to the available unsatisfied valence of the aromatic ring remaining after counting the number of hydroxyl groups attached to the aromatic ring.

からなる群から選択され、
式中、Ｒは、Ｃ_３〜Ｃ_１００アルキルもしくはアルケニル基、硫黄置換アルキルもしくはアルケニル基、好ましくはＣ_４〜Ｃ_５０アルキルもしくはアルケニル基または硫黄置換アルキルもしくはアルケニル基、より好ましくはＣ_３〜Ｃ_１００アルキルまたは硫黄置換アルキル基、最も好ましくはＣ_４〜Ｃ_５０アルキル基であり、Ｒ^ｇは、Ｃ_１〜Ｃ_１００アルキレンまたは硫黄置換アルキレン基、好ましくはＣ_２〜Ｃ_５０アルキレンまたは硫黄置換アルキレン基、より好ましくはＣ_２〜Ｃ_２アルキレンまたは硫黄置換アルキレン基であり、ｙは、少なくとも１からＡｒの利用可能な結合価までであり、ｘは、０からＡｒの利用可能な結合価−ｙまでの範囲であり、ｚは１〜１０の範囲であり、ｎは０〜２０の範囲であり、ｍは０〜４であり、ｐは０または１であり、好ましくはｙは１〜３の範囲であり、ｘは０〜３の範囲であり、ｚは１〜４の範囲であり、ｎは０〜５の範囲であり、ｐは０である。 In general, therefore, phenolic antioxidants have the general formula:
(R) _x -Ar- (OH) _y
Where Ar is

Selected from the group consisting of
Wherein, _R, C _{3 -C 100} alkyl or alkenyl group, a sulfur substituted alkyl or alkenyl group, preferably a _C 4 _{-C 50} alkyl or alkenyl group or sulfur substituted alkyl or alkenyl group, more preferably _C 3 _{-C 100} An alkyl or sulfur substituted alkyl group, most preferably a C _{4 to} C ₅₀ alkyl group, and R ^g is a C _{1 to} C ₁₀₀ alkylene or sulfur substituted alkylene group, preferably a C _{2 to} C ₅₀ alkylene or sulfur substituted alkylene group, more preferably a C ₂ -C ₂ alkylene or sulfur substituted alkylene group, y is from at least 1 to the available valences of Ar, x is from 0 to the available valences -y of Ar Range, z is in the range of 1-10, n is in the range of 0-20, and m is 0. -4, p is 0 or 1, preferably y is in the range of 1-3, x is in the range of 0-3, z is in the range of 1-4, n is 0-5. And p is 0.

Preferred phenolic antioxidant compounds are hindered phenol compounds containing sterically hindered hydroxyl groups, which include their derivatives of dihydroxyalure compounds in which the hydroxyl groups are in the o- or p-position to each other. Typical phenolic antioxidants include hindered phenols substituted with C ₁ + alkyl groups and alkylene-linked derivatives of these hindered phenols. Examples of phenolic materials of this type: 2-t-butyl-4-heptylphenol; 2-t-butyl-4-octylphenol; 2-t-butyl-4-dodecylphenol; 2,6-di-t-butyl- 4-heptylphenol; 2,6-di-tert-butyl-4-dodecylphenol; 2-methyl-6-tert-butyl-4-heptylphenol; 2-methyl-6-tert-butyl-4-dodecylphenol; 2,6-di-t-butyl-4 methylphenol; 2,6-di-t-butyl-4-ethylphenol; and 2,6-di-t-butyl 4 alkoxyphenol.

  Phenolic antioxidants are well known in the lubrication industry and include Ethanox® 4710, Irganox® 1076, Irganox® L1035, Irganox® 1010, Irganox® L109, Commercial examples such as Irganox® L118, Irganox® L135, etc. are familiar to those skilled in the art. The above is presented for illustrative purposes only with respect to the types of phenolic antioxidants that can be used and is not limiting.

（式中、Ｒ^ｚは、水素またはＣ_１〜Ｃ_１４線状もしくはＣ_３〜Ｃ_１４分岐アルキル基、好ましくはＣ_１〜Ｃ_１０線状もしくはＣ_３〜Ｃ_１０分岐アルキル基、より好ましくは線状もしくは分岐Ｃ_６〜Ｃ_８であり、ｎは、１〜５の範囲の整数、好ましくは１である）
で表されるフェニル−α−ナフチルアミンが挙げられる。特定例はＩｒｇａｎｏｘ Ｌ０６である。 Aromatic amine antioxidants include the following molecular structures:

Wherein R ^z is hydrogen or a C ₁ -C ₁₄ linear or C ₃ -C ₁₄ branched alkyl group, preferably a C ₁ -C ₁₀ linear or C ₃ -C ₁₀ branched alkyl group, more preferably a linear a Jo or branched _C 6 -C _8, n is 1-5 integer in the range of, preferably 1)
And phenyl-α-naphthylamine represented by the formula: A specific example is Irganox L06.

Other aromatic amine antioxidants include those of formula R ⁸ R ⁹ R ¹⁰ N [wherein R ⁸ is an aliphatic, aromatic or substituted aromatic group and R ⁹ is aromatic or substituted aromatic. R ¹⁰ is H, alkyl, aryl or R ¹¹ S (O) _x R ¹² (where R ¹¹ is an alkylene, alkenylene, or aralkylene group, R ¹² is a higher alkyl group, Or an alkenyl, aryl, or alkaryl group, where x is 0, 1 or 2).] And other alkylated and non-alkylated aromatic amines. The aliphatic group R ⁸ may contain 1 to about 20 carbon atoms, and preferably contains about 6 to 12 carbon atoms. An aliphatic group is a saturated aliphatic group. Preferably, both R ⁸ and R ⁹ are aromatic or substituted aromatic groups, and the aromatic group may be a condensed ring aromatic group such as naphthyl. The aromatic groups R ⁸ and R ⁹ may be bonded to other groups such as S.

  Typical aromatic amine antioxidants have an alkyl substituent of at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. In general, aliphatic groups will not contain more than about 14 carbon atoms. General types of such other additional amine antioxidants that may be present include diphenylamine, phenothiazine, imidodibenzyl and diphenylphenylenediamine. Mixtures of two or more such other additional aromatic amines may also be present. Polymeric amine antioxidants can also be used.

  Another class of antioxidants used in lubricating oil compositions and that may be present in addition to the required phenyl-α-naphthylamine is oil-soluble copper compounds. Any oil-soluble suitable copper compound may be incorporated into the lubricating oil. Examples of suitable copper antioxidants include copper dihydrocarbylthio- or dithio-phosphates and copper salts of carboxylic acids (natural or synthetic). Other suitable copper salts include copper dithiocarbamate, sulfonate, phenolate, and acetylacetonate. Basic, neutral, or acidic copper Cu (I) and / or Cu (II) salts derived from alkenyl succinic acids or acid anhydrides are known to be particularly useful.

  Such antioxidants may be used in amounts of about 0.50 to 5% by weight, preferably about 0.75 to 3% by weight (on an available basis).

Dispersant Oil-insoluble oxidation by-products are produced throughout engine operation. Dispersants help keep these by-products in solution, thus reducing their deposition on the metal surface. The dispersant may be ashless or ash-forming in nature. Preferably, the dispersant is ashless. So-called ashless dispersants are organic substances that form substantially no ash upon combustion. For example, a dispersant containing no metal or no boronated metal is considered ashless. In contrast, the metal-containing detergents discussed above form ash upon combustion.

  Suitable dispersants typically contain polar groups attached to relatively high molecular weight hydrocarbon chains. The polar group typically contains at least one element of nitrogen, oxygen, or phosphorus. A typical hydrocarbon chain contains 50 to 400 carbon atoms.

  A particularly useful class of dispersants are alkenyl succinic acid derivatives, typically prepared by reaction of long chain substituted alkenyl succinic acid compounds, usually substituted succinic anhydrides, with polyhydroxy or polyamino compounds. The long chain groups that make up the lipophilic portion of the molecule that provide solubility in oil are usually polyisobutylene groups. Many examples of this type of dispersant are well known commercially and in the literature.

  Hydrocarbyl-substituted succinic acid compounds are popular dispersants. In particular, succinates, succinate esters, or succinates prepared by reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent with at least one equivalent of an alkylene amine. Ester amides are particularly useful.

  Succinimides are formed by the condensation reaction of alkenyl succinic anhydrides and amines. The molar ratio can vary depending on the polyamine. For example, the molar ratio of alkenyl succinic anhydride to TEPA can vary from about 1: 1 to about 5: 1.

  Succinate esters are formed by the condensation reaction of alkenyl succinic anhydrides with alcohols or polyols. The molar ratio can vary depending on the alcohol or polyol used. For example, the condensation product of alkenyl succinic anhydride and pentaerythritol is a useful dispersant.

  Succinate ester amides are formed by the condensation reaction of alkenyl succinic anhydride and alkanolamine. For example, suitable alkanolamines include polyalkenyl polyamines such as ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines and polyethylene polyamines. An example is propoxylated hexamethylenediamine.

  The molecular weight of the alkenyl succinic anhydride will typically range from 800 to 2,500. The above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid, and boron compounds such as borate esters or highly boronated dispersants. The dispersant can be borated with about 0.1 to about 5 moles of boron per mole of dispersant reaction product.

  The Mannich base dispersant is made from the reaction of alkylphenols, formaldehyde, and amines. Processing aids and catalysts, such as oleic acid and sulfonic acid, can also be part of the reaction mixture. The molecular weight of the alkylphenol is in the range of 800 to 2,500.

Typical high molecular weight fatty acid modified Mannich condensation products can be prepared from high molecular weight alkyl-substituted hydroxyaromatic compounds or HN (R) ₂ group-containing reactants.

Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol, polybutylphenol, and other polyalkylphenols. These polyalkylphenols are phenolic, such as BF ₃ , of high molecular weight polypropylene, polybutylene, and other polyalkylene compounds to provide alkyl substituents on the benzene ring of phenol having an average molecular weight of 600 to 100,000. Can be obtained by alkylation in the presence of an alkylation catalyst.

Examples of HN (R) ₂ group-containing reactants are alkylene polyamines, mainly polyethylene polyamines. Other representative organic compounds containing at least one HN (R) ₂ group suitable for use in the manufacture of Mannich condensation products are well known, mono- and di-aminoalkanes and their substituted analogs Isomers such as ethylamine and diethanolamine; aromatic diamines such as phenylenediamine, diaminonaphthalene; heterocyclic amines such as morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and substituted analogs thereof.

Examples of alkylene polyamine reactants include ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, nonaethylenedecamine, and decaethylene And undecamine as well as mixtures of such amines of the formula H ₂ N— (Z—NH—) _n H as described above with a nitrogen content corresponding to the alkylene polyamines, where Z in the formula is divalent It is ethylene and n is 1-10. Propylene diamine and the corresponding propylene polyamines such as di-, tri-, tetra-, pentapropylene tri-, tetra-, penta- and hexaamine are also suitable reactants. Alkylene polyamines are usually obtained by reaction of ammonia with dihaloalkanes such as dichloroalkanes. Thus, alkylene polyamines obtained from reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloroalkane having 2 to 6 carbon atoms and chlorine on different carbons are suitable alkylene polyamine reactants. .

  Aldehyde reagents useful for the preparation of the polymeric products useful in the present invention include aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol (β-hydroxybutyraldehyde). Formaldehyde or a formaldehyde-forming reactant is preferred.

  Preferred dispersants include boronated and non-borated succinimides, including mono-succinimide, bis-succinimide, and / or their derivatives from mixtures of mono- and bis-succinimide, the hydrocarbyl succinimide is about 500- Derived from hydrocarbylene groups such as polyisobutylene having a Mn of about 5000 or a mixture of such hydrocarbylene groups. Other preferred dispersants include succinic esters and amides, alkylphenol-polyamine linked Mannich adducts, their capped derivatives, and other related components. Such additives may be from about 0.1 to 20%, preferably from about 0.1 to 8%, more preferably from about 1 to 6% (on an available basis) based on the weight of the total lubricating oil. May be used in quantities.

Pour point depressants Conventional pour point depressants (also known as lube oil flow improvers) may also be present. Pour point depressants may be added to lower the minimum temperature at which the fluid will flow or can be poured. Examples of suitable pour point depressants include alkylated naphthalenes, polymethacrylates, polyacrylates, polyacrylamides, condensation products of haloparaffin waxes with aromatic compounds, vinyl carboxylate polymers, and dialkyl fumarate and fatty acids. Examples include terpolymers of vinyl esters and allyl vinyl ethers.

  Such additives are used in an amount of about 0.0 to 0.5 wt%, preferably about 0 to 0.3 wt%, more preferably about 0.001 to 0.1 wt% on an arrival basis. May be.

Corrosion Inhibitor / Metal Deactivator Corrosion inhibitors are used to reduce the degradation of metal parts in contact with the lubricating oil composition. Suitable corrosion inhibitors include aryl thiazines, alkyl substituted dimercaptothiodiazole thiadiazoles and mixtures thereof.

  Such additives are about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight, more preferably about 0.01 to 0.2% by weight, based on the total weight of the lubricating oil composition. It may be used in an amount of% by weight, even more preferably about 0.01 to 0.1% by weight (on an available basis).

Seal compatibility additives Seal compatibility agents help swell elastomer seals by causing chemical reactions in the fluid or physical changes in the elastomer. Suitable seal compatibility agents for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (eg, butylbenzyl phthalate), and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.01 to 3% by weight, preferably about 0.01 to 2% by weight, on an available (or arrival) basis.

Antifoaming agent An antifoaming agent may be advantageously added to the lubricating oil composition. These agents inhibit the formation of stable foam. Silicones and organic polymers are typical antifoaming agents. For example, polysiloxanes, such as silicone oil or polydimethylsiloxane, provide antifoam properties. Antifoaming agents are commercially available and may be used in conventional small amounts along with other additives such as demulsifiers; usually the amount of these additives combined is the lubricating oil composition Less than 1 percent, preferably from 0.001 to about 0.5 wt%, more preferably from about 0.001 to about 0.2 wt%, and even more preferably from about 0.0001 to 0. 0%, based on the total weight of the product. 15% by weight (on arrival basis).

Inhibitors and rust inhibitors Additives (or corrosion inhibitors) are additives that protect the metal surface being lubricated from chemical attack by water or other contaminants. One type of rust inhibitor is a polar compound that preferentially wets the metal surface and protects it with an oil film. Another type of anti-rust additive absorbs water by incorporating it into a water-in-oil emulsion so that only the oil touches the surface. Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface. Examples of suitable additives include zinc dithiophosphate, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight on an arrival basis.

  Antiwear additives can also be advantageously present. Antiwear additives are exemplified by metal dithiophosphates, metal dithiocarbamates, metal dialkyldithiophosphates, metal xanthates where the metal can be zinc or molybdenum. Tricresyl phosphate is another type of antiwear additive. Such an antiwear additive is about 0.05 to 1.5 wt%, preferably about 0.1 to 1.0 wt%, more preferably about 0.2 to 0.5 wt% on an arrival basis. Can be present in quantities.

Comparative Examples and Examples A series of engine oils were evaluated for the effect of base oil composition and detergent type on the traction coefficient. The engine oil was either a commercially available oil, an additive-free base oil or base oil blend, or an additive base oil or base oil blend.

  The traction coefficient was measured using an MTM Traction Rig, which is a fully automatic Mini Traction Machine traction measuring instrument. This rig is manufactured by PCS Instruments and identified as Model MTM. Test specimens and instrument configurations are defined such that realistic pressures, temperatures and speeds can be achieved without the need for very large loads, motors or structures. A small sample (50 ml) of fluid is placed in the test cell and the machine automatically changes with various speeds, slide-to-roll ratios, temperatures and loads to create a comprehensive traction map for the test fluid without any intervention. Operates on. Standard test specimens are polished 19.05 mm spheres and 50.0 mm diameter disks made from AISI 52100 bearing steel. The specimen is designed to be a single use, disposable item. The sphere is loaded with the disc face back, and the sphere and disc are driven independently by a DC servo motor and drive to enable highly accurate speed control, especially at low slide / roll ratios. Each specimen is end-mounted on the shaft in a small stainless steel test fluid bath. Secure the vertical shaft and drive system that supports the disk test specimen. However, the shaft and drive system that supports the ball test specimen is supported in a gimbal arrangement so that it can rotate about two orthogonal axes. One axis is perpendicular to the load application direction and the other is perpendicular to the traction force direction. Drive the sphere and disc in the same direction. Load application and traction force suppression is performed by a high stiffness force transducer properly attached to the gimbal arrangement to minimize overall support system deflection. The output from these force transducers is monitored directly by a personal computer. The traction coefficient is a ratio between the traction force and the applied load. As shown in Figures 1-3, the traction coefficient was measured over various speeds. 1-3, the speed on the x-axis is the entrainment speed, which is half the sum of the sphere and disk speed. These entrainment speeds simulate the range of surface speeds, or at least part of the range of surface speeds, that are reached when the engine is in operation.

  The test results presented herein were generated under the following test conditions:

The lubricating oil is listed in Table 1 .

  Referring to FIG. 1, it can be seen that the blends of Group I oil and PIB (control oils B, D and E) did not show any significant benefit compared to the Group I / Group I base oil blend (control oil A). .

  Blends of Group III oils and PIBs (Oil X1, X2 and X3 are Group I / Group I and Group I / PIB blends in the medium to high speed range (more obvious at 20 mm / sec and above, 30 mm / sec and above) Exceeded considerable profit.

A blend containing higher molecular weight PIB (2500 MW vs. 1300 MW (oil X1 vs. oil X3)) has a higher traction coefficient when blended with a Group III base oil to the same blend kinematic viscosity (about 16 mm ² / sec) Showed a decline.

For blends containing the same molecular weight PIB and the same kinematic viscosity Group III oil (Oil X1 and Oil X2) there is no difference in profit when the kinematic viscosity is 13 mm ² / sec vs. 16 mm ² / sec.

  Referring to FIG. 2, 100% overbased calcium salicylate (oil X6), 100% overbased calcium carboxylate (oil X7) or 100% overbased calcium sulfonate (oil) in Group III / PIB mixed base oil. All blends of 70TBN cylinder oil detergent system consisting of X8) are large over the entire speed range compared to Control Oil C (overbased calcium phenolate / overbased calcium sulfonate in Group I / PIB mixed base oil) It turns out that it provides a profit.

Oil X5 consisting of 100% overbased calcium salicylate in a Group III / PIB mixed base oil blended to 21 mm ² / sec KV at 100 ° C. is low speed (less than 10 mm / sec) and high speed (more than 100 mm / sec) At a medium speed (10-100 mm / sec), showing little or no benefit, suggesting that the preferred upper limit of kinematic viscosity at 100 ° C. is about 20 mm ² / sec.

  Control oil X4 in the Group III / PIB blend (70 base number cylinder oil consisting of 100% overbased calcium phenolate) offers significant benefits in the medium speed (10 mm / sec) and high speed (100 mm / sec) regions However, it provided less benefit in the low speed (less than 10 mm / sec) region.

  Referring to FIG. 3, a mixture of overbased calcium phenolate (a desirable component in these engine oils for other performance reasons) and overbased calcium salicylate (oil X9) or overbased in a Group III / PIB blend. All 70 base number cylinder oils consisting of a mixture of calcium phenolate and overbased calcium carboxylate (Oil X10 and Oil X12) all had Control Oil C (calcium phenolate and sulfone in the Group I / PIB blend) over the entire speed range. A mixture with calcium acid) and control oil F (a mixture of calcium phenolate and calcium salicylate in a Group I / PIB blend), which benefit became more pronounced at speeds of 10 mm / sec and higher I understand that. Oil X13, which contains a mixture of overbased calcium phenolate and calcium salicylate in a Group II / PIB mixture, shows an advantage over Control Oil C and Control Oil F only at higher speeds, above about 60 mm / sec. It was.

  Oils X11, X12 and X13 were all run on a different second MTM machine device under the same test conditions as all other runs. You can see that XII is an outlier. The results for oil X12 and X13 operation on the same second MTM machine are consistent with the other samples evaluated on the first MTM machine device, and thus the results from different devices are substantially similar and comparable. support. The outlier is considered to reflect either the test error or the mixing error.

Comparing oil X12 to oil X10, it can be seen that blends using higher molecular weight PIBs in bimodal blends provide greater traction coefficient benefits under medium to high speeds (10 mm / sec to 100 mm / sec or more).

The main aspects described in this specification are shown below.
1. Having a kinematic viscosity at 100 ° C. of 8-25 mm ² / sec,
Two different base oils,
A first base oil having a kinematic viscosity at 100 ° C. of ² to 12 mm ² / sec and being one or more oils selected from a group III base oil and a group IV base oil;
Second base oil selected from one or more polyisobutylene (PIB) having a number average molecular weight of at least 800 Mn
Lubricating oils including base oils containing bimodal blends with
Large low and medium speed engine fuels that are lubricated by engine oil to reach a surface speed of at least 10 mm / sec by reducing the traction coefficient of the engine oil used to lubricate the engine when used as engine oil A method of improving economy,
The improvement in fuel economy is that traction is lower than the traction coefficient of the engine oil based on one or more Group I base oils or mixtures of Group I base oils and PIBs or non-bimodal engine oils. A method that is verified by having a coefficient.
2. Having a kinematic viscosity at 100 ° C. of 8-25 mm ² / sec,
Two different base oils,
A first base oil having a kinematic viscosity at 100 ° C. of ² to 12 mm ² / sec and being one or more oils selected from a group III base oil and a group IV base oil;
Second base oil selected from one or more polyisobutylene (PIB) having a number average molecular weight of at least 800 Mn
A base oil containing a bimodal blend with
Alkaline and / or alkaline earth metal salicylate, alkali and / or alkaline earth metal phenolate, alkali and / or alkaline earth metal sulfonate, alkali and / or alkaline earth metal carboxylate, alkali and / or alkaline earth metal A detergent present in the range of 4 to 33% by weight, based on an active ingredient selected from a mixture of phenolate and salicylate, or a mixture of alkali and / or alkaline earth metal phenolate and carboxylate
Including lubricating oil,
Large low- and medium-speed engine fuels that are lubricated by engine oil to reach a surface speed of at least 3 mm / sec by reducing the traction coefficient of the engine oil used to lubricate the engine when used as engine oil A method of improving economy,
The increase in fuel economy is based on engine oils that are not bimodal, or engine oils that are not as bimodal as listed, or Group I base oils and PIB base oils, even when containing detergents A method that proves that the engine oil has a lower traction coefficient than the traction coefficient of the engine oil.
3. Having a kinematic viscosity at 100 ° C. of 8-25 mm ² / sec,
Two different base oils,
A first base oil having a kinematic viscosity at 100 ° C. of 2-12 mm ² / sec and one or more oils selected from Group II base oil, Group III base oil and Group IV base oil;
Second base oil selected from one or more polyisobutylene (PIB) having a number average molecular weight of at least 800 Mn
Lubricating oils including base oils containing bimodal blends with
Method for improving the fuel economy of large low and medium speed engines that reach a surface speed of at least 60 mm / sec by reducing the traction coefficient of the engine oil used to lubricate the engine by using as engine oil Because
The improvement in fuel economy is due to the fact that the engine oil is not bimodal engine oil or engine oil based on one or more group I base oils or a mixture of group I base oils and PIBs, and the traction coefficient of the engine oil is A method demonstrated by having a low traction coefficient.
4). 4. The method of claim 3, wherein the lubricating oil further comprises 4 to 33% by weight of one or more alkali and / or alkaline earth metal salicylates, phenolates, sulfonates or carboxylate detergents based on the active ingredient. .
5. 3. The method according to 1 or 2 above , wherein the lubricating oil has a kinematic viscosity at 100 ° C. in the range of 8 to 22 mm ² / sec.
6). 4. The method according to any one of 1 to 3, wherein the PIB has a number average molecular weight in the range of 800 to 6,000 Mn.
7). A process according to claim 2 wherein the detergent is present in an amount ranging from 8 to 25% by weight based on the active ingredient.
8). The method of claim 4, wherein the detergent is present in an amount ranging from 8 to 25% by weight based on the active ingredient.
9. When the detergent is a combination of alkali and / or alkaline earth metal phenolate and salicylate, or a combination of alkali and / or alkaline earth metal phenolate and carboxylate, the phenolate and salicylate or carboxylate The method according to any one of 2, 4, 7 and 8, wherein the weight ratio is from 95: 5 to 5:95.
10. 10. The method according to 9 above, wherein the weight ratio of phenolate to salicylate or carboxylate is in the range of 3: 1 to 1: 3.
11. 4. The method according to any one of 1 to 3 above, wherein the first base oil is a group III base oil.
12 4. The method according to any one of 1 to 3, wherein the first base oil is a group IV base oil.
13. 13. The process according to 12 above, wherein the group IV base oil is PAO produced using a metallocene catalyst.

Claims (10)

Having a kinematic viscosity at 100 ° C. of 8-25 mm ² / sec,
Two different base oils,
A first base oil having a kinematic viscosity at 100 ° C. of ² to 12 mm ² / sec and being one or more oils selected from a group III base oil and a group IV base oil;
A lubricating oil comprising a base oil comprising a bimodal blend with a second base oil selected from one or more polyisobutylenes (PIB) having a number average molecular weight of at least 800 Mn;
Large low and medium speed engine fuels that are lubricated by engine oil to reach a surface speed of at least 10 mm / sec by reducing the traction coefficient of the engine oil used to lubricate the engine when used as engine oil A method of improving economy,
The improvement in fuel economy is that traction is lower than the traction coefficient of the engine oil based on one or more Group I base oils or mixtures of Group I base oils and PIBs or non-bimodal engine oils. A method that is verified by having a coefficient. Having a kinematic viscosity at 100 ° C. of 8-25 mm ² / sec,
Two different base oils,
A first base oil having a kinematic viscosity at 100 ° C. of ² to 12 mm ² / sec and being one or more oils selected from a group III base oil and a group IV base oil;
A base oil comprising a bimodal blend with a second base oil selected from one or more polyisobutylenes (PIB) having a number average molecular weight of at least 800 Mn, and alkali and / or alkaline earth metal salicylates, alkalis and / or alkalis Earth metal phenolate, alkali and / or alkaline earth metal sulfonate, alkali and / or alkaline earth metal carboxylate, alkali and / or a mixture of alkaline earth metal phenolate and salicylate, or alkali and / or alkaline earth A lubricating oil comprising a detergent present in the range of 4 to 33% by weight, based on an active ingredient selected from a mixture of a metallophenolate and a carboxylate,
Large low- and medium-speed engine fuels that are lubricated by engine oil to reach a surface speed of at least 3 mm / sec by reducing the traction coefficient of the engine oil used to lubricate the engine when used as engine oil A method of improving economy,
The increase in fuel economy is based on engine oils that are not bimodal, or engine oils that are not as bimodal as listed, or Group I base oils and PIB base oils, even when containing detergents A method that proves that the engine oil has a lower traction coefficient than the traction coefficient of the engine oil. The method according to claim 1, wherein the lubricating oil has a kinematic viscosity at 100 ° C. in the range of 8 to 22 mm ² / sec. The method according to claim 1 or 2 , wherein the PIB has a number average molecular weight in the range of 800 to 6,000 Mn.   3. A method according to claim 2, wherein the detergent is present in an amount ranging from 8 to 25% by weight based on the active ingredient. When the detergent is a combination of alkali and / or alkaline earth metal phenolate and salicylate, or a combination of alkali and / or alkaline earth metal phenolate and carboxylate, the phenolate and salicylate or carboxylate The method according to claim 2 or 5 , wherein the weight ratio of the catalyst is in the range of 95: 5 to 5:95. 7. The method of claim 6 , wherein the weight ratio of phenolate to salicylate or carboxylate is in the range of 3: 1 to 1: 3. The method according to claim 1 or 2 , wherein the first base oil is a Group III base oil. The method according to claim 1 or 2 , wherein the first base oil is a group IV base oil. The process according to claim 9 , wherein the group IV base oil is PAO produced using a metallocene catalyst.

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