JP2008144164A - Lubricant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive composition without substantially containing a sulfur compound giving damage to a silver member, and a lubricant composition containing such the additive composition. <P>SOLUTION: This lubricant composition is characterized by containing the additive composition containing the base oil of a major amount, and (i) a triazole compound other than an alkylbis-3-amino-1,2,4-triazole of which aryl part is substituted and (ii) a nitrogen-containing compound expressed by formula [wherein, R<SP>1</SP>, R<SP>2</SP>are each independently selected from at least 1 kind of an aryl part having approximately 6 to approximately 30 number of carbon atoms, H, a halogen, hydroxy, hydrocarbyl, a substituted hydrocarbyl, amino, phosphoro and sulfono] each by small amounts. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

Reference to related applications

  This application is a continuation-in-part of US patent application Ser. No. 11 / 609,084 filed Dec. 11, 2006. This patent application is hereby incorporated by reference in its entirety.

    The present invention relates to additive and lubricant compositions and methods of use thereof. In particular, the invention relates to additive compositions having a synergistic combination comprising (i) a triazole compound and (ii) a nitrogen-containing compound.

  Diesel engines are used in various applications, and lubricant compositions used in diesel engines are known. Among the various types of diesel engines are medium speed diesel engines used for applications requiring thousands of horsepower (eg, 2000-10,000 horsepower). These include stationary marine vessels, small vessels operating on islands and coastal channels, and railroad locomotives, offshore drilling platforms, and a variety of applications including industrial facilities and buildings. Or include a continuous generator propulsion engine. Typically, these engines are run at a speed of about 100 to about 1,200 rpm. As a result of such a supply and demand environment, oxidation of the oil occurs, which may cause corrosion of the metal present in the engine.

  Medium speed diesel engines are typically unique among diesel engines because these engines often have silver components, such as silver bearings. That is, a lubricant composition intended for use in medium speed diesel engines provides stability against oxidation and protects against the formation of sludge and carbonaceous deposits in the engine. In order to prevent the silver bearings from being corroded by additives in the oil or decomposition products that occur during long-term engine operation, they must be formulated with a special silver protectant. Such agents are often referred to as silver lubricants and provide protection against extreme pressure, wear and corrosion.

  A typical engine lubricating composition would comprise an extreme pressure and antiwear agent. The most commonly used extreme pressure and wear protection agents are sulfur-containing compounds such as zinc dialkylthiophosphate (ZDDP). However, certain sulfur-containing compounds are known to be unusable for engines with silver parts because they tend to damage the silver parts. Such a generally accepted tendency is described in Patent Document 1, for example. Accordingly, it is desirable to find an additive composition that can be substantially free of such active sulfur-containing compounds that provide protection against oxidation and in some cases potentially damaging properties. ing.

U.S. Pat. No. 4,428,850.

Disclosure of the present invention

Summary of the Invention According to the present invention, (i) a triazole compound substituted with an aryl moiety but not an alkylbis-3-amino-1,2,4-triazole; (ii)

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
An additive composition comprising a nitrogen-containing compound represented by is provided.

  In one embodiment, a major amount of substrate oil and a minor amount of (i) a triazole compound substituted with an aryl moiety other than alkylbis-3-amino-1,2,4-triazole, and (ii)

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having from about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
A lubricant composition comprising a synergistic additive composition comprising a nitrogen-containing compound represented by is provided.

  In another embodiment, (i) a triazole compound substituted with an aryl moiety other than alkylbis-3-amino-1,2,4-triazole, and (ii) a formula

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
A lubricant composition comprising a synergistic additive composition comprising a nitrogen-containing compound represented by is provided.

  Further, in a method for improving the antioxidant properties of a lubricant composition, the method includes a major amount of substrate oil and a small amount of (i) an aryl moiety other than alkylbis-3-amino-1,2,4-triazole. Substituted triazole compounds, and (ii)

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
There is provided a method comprising providing to a machine a lubricant composition comprising a synergistic additive composition comprising a nitrogen-containing compound represented by:

  Still further, a major amount of substrate oil, and a small amount of (i) a triazole compound substituted with an aryl moiety other than alkylbis-3-amino-1,2,4-triazole, and (ii)

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
There is provided a method of operating a machine comprising adding a lubricant composition comprising a synergistic additive composition comprising a nitrogen-containing compound represented by:

  In addition, in a method of lubricating at least one movable member of a machine, the method includes a major amount of substrate oil, and a minor amount of (i) other than alkylbis-3-amino-1,2,4-triazole, A triazole compound substituted with an aryl moiety, and (ii)

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
There is provided a method comprising contacting a lubricant composition comprising a synergistic additive composition comprising a nitrogen-containing compound represented by at least one movable member.

  Still other objects and advantages of the invention will be set forth in part in the description that follows, and / or can be learned by practice of the invention. The objects and advantages of the invention will be realized by the elements and combinations particularly pointed out in the appended claims.

  It should be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed.

DESCRIPTION OF THE SPECIFIC EXAMPLES The present invention generally comprises a major amount of substrate oil, and a minor amount of (i) a triazole compound substituted with an aryl moiety other than alkylbis-3-amino-1,2,4-triazole, and (ii) formula

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
To a lubricant composition comprising a synergistic additive composition comprising a nitrogen-containing compound represented by:

  As used herein, the term “major amount” means an amount of 50% by weight or more, such as about 80 to about 98% by weight, based on the total weight of the composition. Further, as used herein, the term “small amount” means an amount less than 50% by weight relative to the total weight of the composition.

  As used herein, the term “aromatic” or “aryl” refers to this type of non-aliphatic hydrocarbyl or heterocyclic moiety, with or without typical substituents, unless otherwise specified. For example, polyunsaturated, typically aromatic, hydrocarbyl cyclic, or heterocyclic substituents, a single ring, or multiple rings fused together or covalently linked to each other (up to Means a substituent which can have three rings). Typical hydrocarbyl aromatic moieties include phenyl, naphthyl, biphenylenyl, phenanthrenyl, phenalenyl, and the like. Such moieties can be optionally substituted with one or more hydrocarbyl substituents. Also included are aryl moieties substituted with other aryl moieties, such as biphenyl. Heterocyclic aryl or aromatic moieties contain carbon atoms in the ring and are further unsaturated with one or more heteroatoms, typically oxygen, nitrogen, sulfur, and / or phosphorus. Means a cyclic moiety such as pyridyl, thienyl, furyl, thiazolyl, pyranyl, pyrrolyl, pyrazolyl, imidazolyl, pyrazinyl, thiazolyl and the like; Such moieties are optionally one or more substituents such as hydroxy, optionally substituted alkyl, optionally substituted lower alkoxy, amino, amide, ester moieties and carbonyl moieties (such as aldehyde or ketone moieties). ).

  As used herein, the term “alkaryl” means a non-aliphatic hydrocarbyl or heterocyclic moiety as described above with or without typical substituents, unless otherwise specified. To do. Typical aryl moieties include phenyl, naphthyl, benzyl and the like. Such moieties are optionally one or more substituents such as hydroxy, optionally substituted alkyl, optionally substituted lower alkoxy, amino, amide, ester moieties and carbonyl moieties (such as aldehyde or ketone moieties). ).

  As used herein, the term “hydrocarbon”, “hydrocarbyl” or “hydrocarbon-based” means that the described moiety has predominantly hydrocarbon character within the context of the present invention. means. These include parts with the properties of pure hydrocarbons. That is, they contain only carbon and hydrogen. They can also include moieties containing substituents or atoms that do not change the main hydrocarbon properties of the moiety. Such substituents can comprise halo-, alkoxy-, nitro-, and the like. These moieties can also contain heteroatoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen, oxygen, and phosphorus. Thus, these moieties can contain non-carbon atoms in an atomic chain or ring composed of carbon atoms while retaining the main hydrocarbon properties within the context of the present invention.

As used herein, the term “synergistic” and its grammatically altered expressions refer to element interactions that, when combined, produce an overall effect that is greater than the sum of the individual elements.

  Triazole compounds suitable for use in the compositions of the present invention can be any triazole substituted with an aryl moiety other than alkylbis-3-amino-1,2,4-triazole. In some embodiments, the triazole compound is a 1,2,3-triazole compound. In other embodiments, the triazole compound is a 1,2,4-triazole compound.

  For example, a triazole compound can be substituted with an aryl moiety, with or without substituents, comprising a single ring or multiple rings, such as covalently linked rings. Non-limiting examples of aryl moieties with substituents comprising covalently linked rings include biphenyl, 1,1'-binaphthyl, p, p'-bitryl, biphenylenyl, and the like. As another example, the aryl moiety can comprise multiple fused rings. Non-limiting examples of aryl moieties that comprise multiple fused rings include naphthyl, anthryl, pyrenyl, phenanthrenyl, phenalenyl, and the like. As another example, the aryl moiety can comprise a single ring linked to a triazole. Non-limiting examples of aryl moieties comprising a single ring linked to a triazole include phenyl and the like. As another example, the aryl moiety can comprise a single ring fused to a triazole. Non-limiting examples of such compounds include benzotriazole. An example of a commercially available triazole compound suitable for use in the present invention is benzotriazole, which is a gray solid with a melting point of 95-99 ° C. and a flash point of 170 ° C., and a solubility in water at 20 ° C. of 25 g. / L. In order to increase the solubility in the composition, the triazole compound can be combined with other additives, reacted and mixed.

  In one embodiment, the triazole compound has the formula (I)

Can be represented by Wherein R ³ is selected from the group consisting of hydrogen and at least one alkyl moiety having from about 1 to about 24 carbon atoms, R ⁴ is hydrogen, at least one alkyl moiety having from about 1 to about 24 carbon atoms, and Selected from the group consisting of hydrocarbyl moieties with substituents. In other embodiments, R ³ and R ⁴ of the triazole compound represented by formula (I) each independently comprise about 1 to about 16 carbon atoms.

In the lubricant and additive compositions of the present invention, the triazole compound can be present in any effective amount, which can be readily determined by one of ordinary skill in the art. Furthermore, the triazole compound can be present in an amount having a synergistic effect. In one embodiment, the lubricant composition of the present invention comprises from about 0.01 to about 10 weight percent, such as from about 0.05 to about 0.5 weight percent triazole, based on the total amount of the lubricant composition. Can be made. In other embodiments, the additive composition of the present invention can comprise from about 0.01 to about 3 weight percent based on the total amount of the additive composition.

  The composition of the present invention can also comprise a nitrogen-containing compound. There is no particular restriction as to the type of nitrogen-containing compound that can be used in the composition of the invention. In general, nitrogen-containing compounds suitable for use in the present invention are represented by the following formula (II):

Can be expressed as Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having from about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. It is. For example, R ¹ and R ² of the nitrogen-containing compound can both comprise an aryl moiety having from about 6 to about 30 carbon atoms. Non-limiting examples of aryl moieties include phenyl alkphenyl, benzyl, naphthyl and alkaryl. As another example, R ¹ and R ² each independently comprise an alkaryl, such as alkphenyl or alknaphthyl, wherein the alkyl moiety is from about 4 to about 30, such as from about 4 to about 12 carbon atoms. Is made up of. In yet another example, R ¹ and R ² each independently comprise an aryl moiety with or without substituents. Non-limiting examples of substituents for this aryl moiety can include alkyl moieties comprising from about 1 to about 20 carbon atoms, alkyl groups comprising hydroxy, carboxyl, and nitro moieties. As another example, R ¹ and R ² can each independently be alkyl-substituted benzyl, phenyl or naphthyl.

  Other non-limiting examples of nitrogen-containing compounds suitable for the present invention include: phenylamine; diphenylamine; triphenylamine; various alkylated phenylamines, diphenylamine and triphenylamine; N, N′-bis (4-aminophenyl) -alkylamine; 3-hydroxyphenylamine; N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine; dibutyldiphenylamine; dioctyldiphenylamine; dinonyldiphenylamine; α-naphthylamine; phenyl-β-naphthylamine; diheptyldiphenylamine; and p-coordinated styrenated diphenylamine. Non-limiting examples of suitable nitrogen-containing compounds and methods for their preparation include those described in US Pat. No. 6,218,576. This patent is incorporated herein by reference.

  The nitrogen-containing compound used in the present invention can comprise a structure different from the above formula (I), which shows only one nitrogen atom in the molecule. That is, the nitrogen-containing compound is, for example, a variety of diamines having a secondary nitrogen atom, as well as aryl bonded to one of the nitrogen atoms, as long as at least one nitrogen atom has at least one aryl moiety bonded thereto. Such different structures can be included.

The nitrogen-containing compounds used in the present invention exhibit antioxidant properties in the compositions of the present invention when used alone, but also exhibit synergistic properties in the presence of the triazole compounds described herein. be able to. For example, the protective effect against oxidation provided by a single triazole compound and / or nitrogen-containing compound is significantly enhanced when these materials are present in the lubricant composition of the present invention, thus exhibiting a synergistic effect. This synergistic effect is achieved by the additive composition necessary to obtain the desired level that can protect oxidation compared to that required when either a triazole compound or a nitrogen-containing compound is used alone. The rate of throughput can be reduced. In addition, the nitrogen-containing compound used in the present invention must be soluble in the final lubricant composition.

  The amount of nitrogen-containing compound in the composition of the present invention can vary depending on the particular requirements and application. In one aspect, the nitrogen-containing compound can be present in a synergistic amount. In one embodiment, the lubricant composition of the present invention comprises from about 0.01 to about 10%, such as from about 0.3 to about 3%, by weight of nitrogen-containing compound, based on the total amount of the lubricant composition. Can be made up of. In other embodiments, the additive composition of the present invention can comprise from about 0.07 to about 33% by weight of the nitrogen-containing compound relative to the total amount of the additive composition.

  The compositions described herein include additives such as dispersants, ash-containing detergents, ashless detergents, overbasing detergents, pour point reducing agents, viscosity index modifiers, ash-containing friction modifiers, and ashless friction modifiers. , Nitrogen-containing friction modifiers, nitrogen-free friction modifiers, esterified friction modifiers, extreme pressure agents, antifungal agents, antioxidants, corrosion inhibitors, foam inhibitors, titanium compounds, titanium complexes, organic Soluble molybdenum compounds, organic soluble molybdenum complexes, boron-containing compounds, boron-containing complexes, tungsten-containing compounds, tungsten-containing complexes, and combinations thereof can be included at any time. In one embodiment, the composition can contain various concentrations of at least one titanium-containing compound according to the application needs and requirements. In other embodiments, the composition can include various concentrations of at least one molybdenum-containing compound according to application needs and requirements.

  In one embodiment, the lubricant composition of the present invention can be substantially free of, for example, free active sulfur. As used herein, the term “active sulfur” refers to sulfur-containing compounds that react substantially with machine components at normal engine operating temperatures in the range of about 100 ° C. to about 400 ° C. to form metal sulfides. Defined. Active sulfur is distinguished from non-active sulfur that does not substantially react at temperatures below 400 ° C, while the latter reacts well at temperatures above 400 ° C to produce metal sulfides, which are under extreme pressure conditions. Protect engine parts. That is, in this case, a boundary condition exists. Due to these boundary conditions and extreme pressure conditions, it is known to those skilled in the art that temperatures well above 400 ° C. occur at various locations in engines that typically operate at low temperatures, eg, below 400 ° C. It will be easily understood. Such boundary zones and extreme pressure zones can occur when certain engine components, such as bearings, are loaded. Non-active sulfur can be used that reacts at these higher temperatures to protect engine components in that case, while not reacting substantially at typical lower engine operating temperatures.

  Thus, compounds containing active sulfur, such as zinc dialkyldithiophosphate (ZDDP), can have a measurable degradation effect on certain machines, such as moderate diesel engines or machines containing silver components. Those skilled in the art will appreciate that non-active sulfur compounds can still protect engine components in these machines. For at least this reason, it is desirable that the intended composition for use in such machines be free of active sulfur compounds. A person skilled in the art can obtain a method for determining the effect of sulfur-containing compounds on a machine part, for example by measuring the amount of silver dissolved in the lubricant and / or the amount of precipitation on the silver part. I can do it. For the purposes of the present invention, the term “substantially free” is defined for concentrations that have substantially no measurable degradation effect.

In certain embodiments, the lubricant composition of the present invention is substantially free of phosphorus-containing compounds. For example, it does not contain at all. In other embodiments, the compositions of the present invention are substantially free of compounds containing boron. It is desirable to remove phosphorus and / or boron containing compounds from the compositions of the present invention so that these elements can be used as indicators of lubricant contamination. For example, railway vehicle engine oils are generally formulated to be free of phosphorus and boron. Periodically check the oil for phosphorus and boron during use. Their presence can indicate that the oil has been contaminated with, for example, ZDDP or, in the case of boron, with a boron-containing coolant. In this way, phosphorus and / or boron acts as a sign indicating lubricant contamination. The term substantially free means that the composition contains only trace amounts of phosphorus and / or boron and the concentration of these elements has no effect on the ability of phosphorus and boron to be used as labels.

  Substrate oils suitable for use in formulating the compositions of the present invention can be selected from synthetic or natural oils or mixtures thereof. Natural oils include animal and vegetable oils (eg castor oil, lard) and other mineral lubricating oils such as liquid petroleum and paraffinic, naphthenic or mixed paraffin-naphthenic solvent treated or acid treated minerals Contains lubricating oil. Oils derived from coal or shale are also suitable. Also suitable are oils derived from the gas-to-liquid process.

  Substrate oil can be present in major amounts. As used herein, “major amount” should be understood to mean at least 50% by weight of the lubricant composition, for example from about 80 to about 98% by weight.

  The substrate oil can have any desired viscosity suitable for the intended purpose. Examples of suitable engine oil kinematic viscosities range from about 2 to about 150 cSt at 100 ° C., and other examples are from about 5 to about 15 cStd. Thus, for example, the substrate oil can be estimated to have a viscosity range of about SAE 15 to about SAE 250, and in other examples to have a viscosity range of about SAE 20W to about SAE 50. Suitable automotive oils also include many grades of oil such as 15W-40, 20W-50, 75W-140, 80W-90, 85W-140, 85W-90.

  Non-limiting synthetic oils are polymerized and copolymerized olefins (eg polybutylene, polypropylene, propylene-isobutylene copolymers, etc.); poly-α-olefins such as poly (1-hexene), poly- (1-octene) ), Poly- (1-decene), etc., and mixtures thereof; alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, di-nonylbenzene, di- (2-ethylhexyl) benzene, etc.); polyphenyls (eg, biphenyl, Terphenyl, alkylated polyphenyl, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs and homologues thereof.

Alkylene oxide polymers and copolymers and their derivatives, in which the terminal hydroxyl moiety is modified by esterification, etherification, etc., constitute another type of known synthetic oil that can be used. Such oils include ethylene oxide or propylene oxide, polyoxyalkylene polymers thereof (eg, methyl-polyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500 to 1000, molecular weight of about 1000 to 1000 1500 in diethyl ether of polypropylene glycol, etc.), or a mono- - and polycarboxylic esters thereof, for example, mixed C _{3 to 8} fatty acid ester or exemplified by the oils produced by the polymerization of C ₁₃ oxo acid diester of tetraethylene glycol, Is done.

Other types of synthetic oils that can be used include dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid And esters of various alcohols (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) included. Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, Examples include dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, complex ester formed by reaction of 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid.

Esters useful as synthetic oils include those made from _C5-12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like. .

Accordingly, the substrate oil that can be used to make the above composition can be selected from any of the substrate oils in Groups I-V defined in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. Such groups of substrate oils are as follows:
Group I contains less than 90% saturation and / or more than 0.03% sulfur and has a viscosity index greater than 80 and less than 120. Group II contains 90% or more of saturation and / or 0.03% or less of sulfur, and has a viscosity index of 80 or more and less than 120. Group III contains 90% or more of saturation and / or 0.03% or less of sulfur and has a viscosity index of 120 or more. Group IV is a poly-α-olefin (PAO). Group V contains all other substrate stocks not included in Group I, II, III or IV.

  The test method used to define the above group is one of ASTM D2007 for saturation, ASTM D2270 for viscosity index, and ASTM D2622, 4294, 4927 and 3120 for sulfur. is there.

  Group IV base stocks, ie, poly-α-olefins (PAO), contain halogenated oligomers of α-olefins, the most important methods of oligomerization being the free radical method, Ziegler catalyst and cationic Friedel-Crafts. This is a method using a catalyst.

  The poly-α-olefin typically has a viscosity in the range of 2-100 cSt at 100 ° C., for example in the range of 4-8 cSt at 100 ° C. For example, these are branched or straight chain α-olefin nonyl oligomers having from 2 to about 30 carbon atoms and non-limiting examples include polypropene, polyisobutene, poly-1-butene, poly-1-hexene, poly -1-octene and poly-1-decene are included. Homopolymers, copolymers, and mixtures thereof are also included.

  With respect to the rest of the above base stocks, a “Group I base stock” also includes one or more of the ones as long as the resulting mixture falls within the range defined above for the Group I base stock. Includes Group I base stocks that can be mixed with base stocks from other groups.

Exemplary base stocks include Group I base stocks and mixtures of Group II base stocks with Group I bright stocks.

  Base stocks suitable for use in the present invention can be made using a variety of different methods including, but not limited to, distillation, solvent purification, hydrogenation, oligomerization, esterification, and repurification. it can.

The substrate oil can be an oil derived from a hydrocarbon synthesized by the Fischer-Tropsch method. Hydrocarbons synthesized by the Fischer-Tropsch process can be made from synthesis gas containing H ₂ and CO using a Fischer-Tropsch catalyst. In order to be useful as a substrate oil, typically such hydrocarbons need to be further processed. Hydrocarbons can be hydroisomerized using, for example, the methods described in US Pat. Nos. 6,103,099 or 6,180,575; US Pat. No. 4,943,672 or No. 096,940 for hydrocracking and hydroisomerization; US Pat. No. 5,882,505 for dewaxing; US Pat. No. 6,013 , 171; 6,080,301; or 6,165,949, can be used for hydroisomerization and dewaxing.

  Natural or synthetic (as well as mixtures of two or more of these) unrefined, refined and re-refined oils of the type described above can be used in the substrate oil. Unrefined oil is obtained directly from natural or synthetic raw materials without further purification. For example, shale oil obtained directly from a dry distillation operation, petroleum oil obtained directly from primary distillation, or ester oil obtained directly from an esterification process and used without further treatment is considered an unrefined oil. Refined oils are similar to unrefined oils, but have been further refined in one or more properties through one or more purification steps. Many such purification methods, such as solvent extraction, secondary distillation, acid or base extraction, filtration, and leaching are known to those skilled in the art. The re-refined oil is obtained by a method similar to the method used to obtain a refined oil when applied to a refined oil that has already been used. Such rerefined oils are also known as reclaimed or reprocessed oils and are often further processed by methods for removing spent additives, contaminants, and oil degradation products. .

  According to various embodiments, a method is provided for improving oxidation protection in a lubricant composition. The term “improving oxidation protection” gives the machine a composition that, for example, reduces the absorption of carbonyl by infrared radiation and / or reduces kinematic viscosity of the composition used in the machine, It should be understood that it means enhancing oxidation protection as compared to compositions without these combinations. Methods for improving oxidation protection include a major amount of substrate oil and a small amount of (i) a triazole compound substituted with an aryl moiety other than alkylbis-3-amino-1,2,4-triazole, and (ii) Formula (II)

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
A lubricant composition comprising a synergistic additive composition comprising a nitrogen-containing compound represented by can be provided to the machine.

   In accordance with various embodiments, a method of lubricating at least one movable member of a machine, wherein the method includes the at least one movable member of the machine with a major amount of substrate oil and a small amount of the synergistic additive. A method is provided comprising the step of contacting with a lubricant composition comprising the composition.

  In another embodiment, a method of operating a machine comprising the step of adding a lubricant composition comprising a major amount of substrate oil and a minor amount of the synergistic additive composition is described. ing.

  The machines in the above method are diesel engine, marine engine, rotary engine, turbine engine, locomotive engine, propulsion engine, aircraft piston engine, stationary power generation engine, continuous power generation engine, and silver member Can be selected from spark-combustion and compression-combustion internal combustion engines, including engines equipped with Further, the at least one movable member can be selected from a gear, a piston, a bearing, a rod, a spring, a camshaft, a crankshaft, a rotor, and the like.

  The lubricant composition can be any composition effective to lubricate the machine. In one embodiment, the composition is selected from the group consisting of medium speed diesel engine oil, passenger car motor oil, and high power diesel engine oil. In one embodiment, the composition is a medium speed diesel engine oil.

Examples The following examples illustrate the invention and its advantageous properties. In these examples as well as elsewhere in this specification, all percentages are by weight unless otherwise indicated. These examples are presented for purposes of illustration only and are not intended to limit the scope of the invention described herein.

  A lubricant composition substantially free of compounds containing active sulfur, boron and phosphorus was tested for its ability to prevent oxidation. The following examples show the synergism obtained when a triazole compound and a nitrogen-containing compound, such as an arylamine, are formulated in a lubricant composition such as engine oil. These examples also show that this synergy is unique compared to the use of antioxidants alone or in combination.

  In this example, the basic lubricant composition is as follows.

  As shown in Table 2 below, Formulations 2-8 comprise at least one component in addition to the basic composition. The triazole compound is benzotriazole from Afton Chemical Corporation, in which 25% by weight of benzotriazole is primary t-alkylamine (Primene JM-T, Rohm and Haas, Philadelphia, USA) and in solvents It is believed that it is soluble in the base composition of Table 1. The arylamine compound was dialkyldiphenylamine. In order to remove the contribution of the primary t-alkylamine to the oxidative stability of the composition, the primary t-alkylamine was also converted to triazole compound (5), arylamine compound (6), and combinations thereof (8 ).

  The oxidative stability of these eight lubricant compositions was measured by an ethyl oxidation test. Oxygen was bubbled at 300 ° F. into a test tube containing suspended iron, copper, and lead pieces and one of the lubricant compositions in Table 2. Most of the volatiles were retained by the air condenser, but the lubricant composition was collected and analyzed every 24 hours. The degree of inhibition of oxidation of the used lubricant composition was evaluated by a known method for measuring the increase in kinematic viscosity of oil oxidation products and infrared absorption of carbonyl.

  The greater the carbonyl absorption, the less oxidation protection that a particular lubricant composition imparts to the machine. In addition, the greater the kinematic viscosity, the lower the stability of the specific lubricant composition against oxidation. The results are shown in Tables 3 and 4 below.

As shown in Tables 3 and 4, a basic formulation comprising a triazole compound (2), a primary t-alkylamine (3), or a nitrogen-containing compound (4) provides a small amount of oxidation protection. It showed some sex. Nitrogen-containing compound (4) shows the best performance among the three lubricant compositions with a 33% reduction in carbonyl absorption at 48 hours test time, 11% at 72 hours and 7% at 96 hours. did. The increase in viscosity for the triazole compound (2) or primary t-alkylamine (3) was comparable to the base formulation. Nitrogen-containing compound (4) showed a small increase in viscosity at 48 and 72 hours, but a large increase in viscosity at 96 hours. Lubricant composition (6) was equivalent to nitrogen-containing compound alone (4) in both carbonyl absorption and viscosity increase. Lubricant composition (5) had virtually no effect on oxidation, the carbonyl absorption was equal to the base formulation, and the viscosity increase was greater than the base formulation. That is, in the case of triazole compound (2) and primary t-alkylamine (3) alone or in combination, oxidation of the base formulation without active sulfur as indicated by carbonyl absorption or increased viscosity. There was little effect on protection. With or without a primary t-alkylamine, only the nitrogen-containing compound (4) gave some oxidation protection.

  Combining the triazole compound with the nitrogen-containing compound (7) shows a significant synergistic effect as shown by the effects of carbonyl absorption and viscosity increase. In Table 4, the negative carbonyl absorption values obtained throughout the 96 hour test period indicate that no detectable oxidation occurred. As shown in Table 3, a slight decrease in kinematic viscosity over 96 hours demonstrates a small amount of oxidation. In the composition (8) combining the nitrogen-containing compound, the triazole compound, and the primary t-alkylamine (8), the oxidation product was found to be small due to the absorption of carbonyl and the slightly large decrease in viscosity. , Indicating that the primary t-alkylamine has a slight pro-oxidation tendency. Therefore, the synergistic effect can be attributed to the combination (7) of the nitrogen-containing compound and the triazole compound. Primary t-alkylamines play no role in the observed effects on oxidation.

  The basic composition of Table 1 was used again, but with different amounts of triazole compounds and nitrogen-containing compounds as shown in Table 5 below.

  The oxidative stability of these compositions was also measured by the ethyl oxidation test. The degree of oxidation inhibition of these lubricant compositions was evaluated by a method of measuring the kinematic viscosity of the oil oxidation product and the infrared absorption increase of the carbonyl. The results are shown in Table 6 and Table 7 below.

  The triazole compounds in Table 2 were tested at a traditional fairly high concentration of 0.375% by weight relative to benzothiazole. As shown in Table 5, the concentration of benzothiazole was determined to determine whether a small amount of triazole compound affected the results as described above when triazole alone and with nitrogen-containing compounds. Tests were also conducted at 0.10 and 0.05 wt%. As shown in Tables 6 and 7, when the triazole compound is used alone in the base formulation, at low concentrations, eg, 0.10 wt% (10) and 0.05 wt% (11) An increase in viscosity equivalent to that of the basic formulation occurred. The carbonyl infrared absorption was comparable for all three triazole concentrations, only about 20% less than the base formulation.

  When the triazole compound is used in two low concentrations, 0.10 wt% (13) and 0.05 wt% (14) with a nitrogen-containing compound, the carbonyl infrared absorption is 90% in 48 and 72 hour tests. The decrease was over 50% at 96 hours. At both low concentrations of the triazole compound, a viscosity drop of over 8% at 72 hours indicated that some oxidation was occurring. Even at the 96 hour test time, at the lowest triazole concentration, 0.05 wt% (14), the increase in viscosity is only 6.6%, which is 88% less than the base formulation, It decreased by 84% compared to (4) when the nitrogen-containing compound was present alone in the basic formulation. Therefore, even when the triazole compound was 0.05% by weight, when used with a nitrogen-containing compound, remarkable oxidation protection was obtained as measured by absorption of carbonyl and change in viscosity.

  In this specification and in the appended claims, items modified by the singular forms "a", "an" and "the" are expressly limited to one reference unless otherwise indicated. Unless otherwise noted, it shall include multiple references. Thus, for example, “an antioxidant” includes two or more antioxidants. As used herein, “include” and grammatical variations thereof are intended to be non-limiting, so when an item is cited in a list, It is not intended to exclude other similar items that may be substituted for or added to the items listed there.

For purposes of this specification and the appended claims, all numerical values, percentages or percentages used in this specification and the appended claims, and other values, unless stated otherwise, are all In the case of, it should be understood that it is modified by the word “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and the appended claims are approximations that can vary depending on the desired properties sought to be obtained by the present invention. It is. At least, and not intended to limit the application of the equivalent principle to the claims, each numerical parameter is interpreted using conventional rounding techniques, taking into account the significant number of reported digits. It must be.

  While specific embodiments have been described above, applicants of the present invention or those skilled in the art may consider alternatives, modifications, variations, improvements, and substantial equivalents that are not foreseen or foreseeable. . Accordingly, the appended claims are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents as filed or as may be modified.

Claims (35)

(I) a triazole compound substituted with an aryl moiety but not an alkylbis-3-amino-1,2,4-triazole; and (ii) a formula (II)

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
A synergistic additive composition comprising a nitrogen-containing compound represented by: The synergistic additive composition of claim 1, wherein R ¹ and R ² are each independently an aryl moiety having from about 6 to about 30 carbon atoms.   The synergistic additive composition of claim 1 wherein the aryl moiety is selected from the group consisting of phenyl, benzyl, naphthyl and alkaryl.   4. The synergistic additive of claim 3 wherein the alkaryl is selected from the group consisting of alkphenyl and alknaphthyl, wherein the alkyl moiety comprises from about 4 to about 30 carbon atoms. Composition.   The synergistic additive composition of claim 4, wherein the alkyl portion of the alkaryl comprises from about 4 to about 12 carbon atoms.   2. A synergistic additive composition according to claim 1, wherein the triazole compound is substituted with an aryl moiety with or without a substituent comprising multiple rings.   The synergistic additive composition of claim 1 wherein the triazole compound is substituted with an aryl moiety with or without a substituent comprising a single ring. Triazole compounds have the formula (I)

Wherein R ³ is selected from the group consisting of hydrogen and at least one alkyl moiety having from about 1 to about 24 carbon atoms, R ⁴ is hydrogen, at least one alkyl moiety having from about 1 to about 24 carbon atoms, And selected from the group consisting of substituted hydrocarbyl moieties,
The additive composition having a synergistic action according to claim 1, wherein The synergistic additive composition according to claim 1, wherein the triazole compound is benzotriazole.   The synergistic additive composition of claim 1, wherein the triazole compound is present in an amount ranging from about 0.01 to about 3 weight percent with respect to the total weight of the additive composition.   2. The synergistic additive composition of claim 1 wherein the nitrogen-containing compound is present in an amount ranging from about 0.07 to about 33% by weight relative to the total weight of the additive composition.   Dispersants, ash-containing detergents, ashless detergents, overbasing detergents, pour point reducing agents, viscosity index modifiers, ash-containing friction modifiers, ashless friction modifiers, nitrogen-containing friction modifiers, nitrogen-free friction modifiers Esterified friction modifiers, extreme pressure agents, antifungal agents, auxiliary antioxidants, corrosion inhibitors, antifoaming agents, titanium compounds, titanium complexes, organic soluble molybdenum compounds, organic soluble molybdenum complexes, The synergistic additive of claim 1, further comprising at least one additive selected from the group consisting of boron-containing compounds, boron-containing complexes, tungsten-containing compounds, and tungsten-containing complexes. Composition.   The synergistic additive composition according to claim 1, further comprising at least one molybdenum compound.   2. A synergistic additive composition according to claim 1, further comprising at least one titanium compound. A major amount of substrate oil; and a small amount of (i) a triazole compound substituted with an aryl moiety other than alkylbis-3-amino-1,2,4-triazole; and (ii) formula (II)

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
A lubricant composition comprising a synergistic additive composition comprising a nitrogen-containing compound represented by:   The lubricant composition according to claim 15, wherein the lubricant composition is substantially free of a compound containing boron or phosphorus.   The lubricant composition according to claim 15, wherein the lubricant composition is substantially free of zinc dialkyldithiophosphate.   The lubricant composition of claim 15, wherein the triazole compound is present in an amount ranging from about 0.05 to about 0.5 weight percent based on the total weight of the composition.   The lubricant composition of claim 15, wherein the nitrogen-containing compound is present in an amount ranging from about 0.01 to about 10% by weight relative to the total weight of the composition. The lubricant composition of claim 15, wherein the nitrogen-containing compound is present in an amount ranging from about 0.3 to about 3% by weight relative to the total weight of the composition.   16. The triazole compound is present in an amount of about 0.05% by weight relative to the total weight of the composition, and the nitrogen-containing compound is present in an amount of about 0.3% by weight relative to the total weight of the composition. The lubricant composition as described.   Dispersants, ash-containing detergents, ashless detergents, overbasing detergents, pour point reducing agents, viscosity index modifiers, ash-containing friction modifiers, ashless friction modifiers, nitrogen-containing friction modifiers, nitrogen-free friction modifiers Esterified friction modifiers, extreme pressure agents, antifungal agents, auxiliary antioxidants, corrosion inhibitors, antifoaming agents, titanium compounds, titanium complexes, organic soluble molybdenum compounds, organic soluble molybdenum complexes, The lubricant composition according to claim 15, further comprising at least one additive selected from the group consisting of a boron-containing compound, a boron-containing complex, a tungsten-containing compound, and a tungsten-containing complex.   16. The lubricant composition of claim 15, wherein the lubricant composition is selected from the group consisting of medium speed diesel engine oil, passenger car motor oil, and high power diesel engine oil.   The lubricant composition according to claim 15, further comprising at least one molybdenum compound.   The lubricant composition according to claim 15, further comprising at least one titanium compound. A major amount of substrate oil; and a small amount of (i) a triazole compound substituted with an aryl moiety other than alkylbis-3-amino-1,2,4-triazole; and (ii) formula (II)

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
A lubricant composition comprising a nitrogen-containing compound represented by: In a method for improving the antioxidant properties of a lubricant composition, the method comprises a major amount of substrate oil; and a small amount of (i) an aryl moiety substituted alkylbis-3-amino-1,2,4-triazole , Triazole compounds, and (ii) formula (II)

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having from about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
Providing a machine with a lubricant composition comprising a synergistic additive composition comprising a nitrogen-containing compound represented by:   28. The method of claim 27, wherein the machine is selected from the group consisting of a spark combustion type and a compression-combustion type internal combustion engine.   Engines include diesel engines, marine engines, rotary engines, turbine engines, locomotive engines, propulsion engines, aircraft piston engines, stationary power generation engines, continuous power generation engines, and engines with silver components 30. The method of claim 28, wherein the method is selected from the group consisting of: A major amount of substrate oil; and a small amount of (i) a triazole compound substituted with an aryl moiety other than alkylbis-3-amino-1,2,4-triazole; and (ii) formula (II)

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
A method of operating a machine comprising providing the machine with a lubricant composition comprising a synergistic additive composition comprising a nitrogen-containing compound represented by:   31. The method of claim 30, wherein the machine is selected from the group consisting of spark combustion and compression-combustion internal combustion engines.   Engines include diesel engines, marine engines, rotary engines, turbine engines, locomotive engines, propulsion engines, aircraft piston engines, stationary power generation engines, continuous power generation engines, and engines with silver components 32. The method of claim 31, wherein the method is selected from the group consisting of: In a method of lubricating at least one moving member of a machine, the method includes a major amount of substrate oil; and a small amount of (i) an aryl moiety other than alkylbis-3-amino-1,2,4-triazole is substituted. Triazole compounds, and (ii) formula

Wherein R ¹ and R ² are each independently selected from the group consisting of at least one aryl moiety having about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amide, phosphoro, and sulfono. To be elected,
Contacting the at least one movable member with a lubricant composition comprising a synergistic additive composition comprising a nitrogen-containing compound represented by:   34. The method of claim 33, wherein the machine is selected from the group consisting of a spark combustion type and a compression-combustion type internal combustion engine.   35. The method of claim 34, wherein the at least one movable member is selected from the group consisting of gears, pistons, bearings, rods, springs, camshafts, crankshafts, and rotors.