JP2014534315A - Lubricant with improved seal compatibility - Google Patents

Abstract

The present invention relates to a lubricating composition, specifically comprising a minimum amount of a specific antioxidant component, the antioxidant component comprising (i) a phenolic antioxidant, (ii) an amine-based oxidation. An antioxidant, or (iii) relates to a gear oil composition comprising a combination thereof, wherein the antioxidant component is present at 1.0% by weight or more in the lubricating composition. Such a composition surprisingly provides good seal compatibility. The present invention comprises an oil of lubricating viscosity and (i) a phenolic antioxidant, (ii) an amine antioxidant, or (iii) an antioxidant component comprising a combination thereof, the antioxidant component Provide an industrial lubricating composition that is present in a lubricating composition at 0.4 wt% or more, and in other embodiments 1.0 wt% or more.

Description

  The present invention relates to a lubricating composition, specifically comprising a minimum amount of a specific antioxidant component, the antioxidant component comprising (i) a phenolic antioxidant, (ii) an amine-based oxidation. An antioxidant, or (iii) relates to a gear oil composition comprising a combination thereof, wherein the antioxidant component is present at 1.0% by weight or more in the lubricating composition. Such compositions surprisingly provide good seal compatibility compared to compositions using other triazoles and / or alternative additives.

  In many industrial applications, in an apparatus that uses a lubricating composition, the lubricating composition contacts the seal. Seals are made of a variety of materials including nitrile-butadiene rubber (NBR) because they are not only fluorinated elastomers, silicones and polycarbonates, but are also relatively inexpensive and highly available. It is essential that the lubricating composition used has a good compatibility with the seal, otherwise the seal will deteriorate over time, become defective, leak and cause maintenance costs. Increases the downtime of the device and increases the risk of damage to the device.

  The seal portion, particularly the seal portion made using NBR, breaks with time even under normal operating conditions. In particular, high temperatures can be very detrimental to certain seals. In other cases, the seals sometimes are some extreme pressure agents such as sulfurized olefins, rust inhibitors such as amine compounds, antiwear agents such as phosphates, phosphites, phosphate esters and phosphate amine salts. May be susceptible to attack by chemical additive components of certain lubricating compositions containing components commonly used in industrial applications. In some cases, even the base oil itself may attack the sealing material containing NBR.

  Can give the equipment the necessary performance and protection, and further protect the seals from attack or degradation, thus reducing the risk of lubricant leakage and downtime and ultimately reducing equipment damage or defects There is a current need for a new industrial lubricating composition.

  Wind turbines are particularly representative of industrial applications that require lubricating compositions with good seal compatibility. Wind turbines as an alternative renewable energy source are of increasing interest because they produce electricity by converting clean wind energy into electrical energy. A gearbox, typically placed between the rotating part of the wind turbine and the generator, requires a lubricant. High torque places a great deal of stress on the gears and bearings in the gearboxes of these wind turbines and places high performance requirements on the lubricating composition. In addition, the gearbox is located in the wind turbine nacelle above the ground, and the unit itself is often remote. Therefore, many gearboxes cannot be approached or approached without great expense and difficulty, so it is desirable to reduce maintenance and increase usable life. Lubricating compositions that provide good lubrication performance while improving seal compatibility are expected to reduce maintenance and downtime caused by seal defects. Accordingly, there is a need for a lubricating composition that improves seal compatibility and provides better lubrication performance in wind turbine and similar applications.

  The present invention comprises an oil of lubricating viscosity and (i) a phenolic antioxidant, (ii) an amine antioxidant, or (iii) an antioxidant component comprising a combination thereof, the antioxidant component Provide an industrial lubricating composition that is present in 0.4% or more, or in other embodiments, 1.0% or more by weight in the lubricating composition.

  The phenolic antioxidant may be present in the lubricating composition at least 0.2 wt% or more, at least 0.4 wt% or more, at least 0.5 wt% or more, or at least 1.0 wt% or more. Well, the amine antioxidant is present in the lubricating composition at least 0.2 wt% or more, at least 0.4 wt% or more, at least 0.5 wt% or more, or at least 1.0 wt% or more. May be.

  The present invention is such that the oil of lubricating viscosity contains a mineral base oil, the oil of lubricating viscosity contains a synthetic base oil, and the oil of lubricating viscosity is a combination of a mineral base oil and a synthetic base oil. A composition as described is provided. In certain embodiments, the oil of lubricating viscosity is substantially free or free of synthetic ester base oil.

  The present invention is a method of lubricating a gear assembly comprising supplying a lubricating composition to the gear assembly, the lubricating composition comprising an oil of lubricating viscosity, (i) a phenolic antioxidant, (ii) And) (iii) an antioxidant component comprising a combination thereof, wherein the antioxidant component is 0.4 wt%, 0.5 wt% or 1. A method is provided that is present at 0% by weight or more. Any antioxidant component described herein may be used in such a manner.

  The present invention also provides for the use of the described antioxidant components in minimum amounts required as seal protectants in lubricating compositions, including lubricating compositions for industrial applications. The present invention more specifically provides wind turbines and other applications that require formulations that are resistant to fatigue or micropitting, as well as applications that have stringent seal compatibility requirements.

  The present invention further provides all the compositions, methods and uses described herein, wherein the specific lubricant comprises a demulsifier, the specific lubricant comprising a demulsifier and a sulfurized olefin. Specific lubricants include combinations of substituted triazoles and substituted thiadiazoles, and certain lubricants are essentially free or completely free of dithiophosphates including zinc dialkyldithiophosphates. The agent is essentially free or completely free of overbased metal-containing detergents, and certain lubricants are essentially free or free of zinc, or any combination thereof It is.

  Various features and embodiments of the invention are described below by way of non-limiting illustrations.

  The present invention comprises an oil of lubricating viscosity and (i) a phenolic antioxidant, (ii) an amine antioxidant, or (iii) an antioxidant component comprising a combination thereof, the antioxidant component Provides an industrial lubricating composition that is present in the lubricating composition at 1.0% by weight or more.

(Oil of lubricating viscosity)
One component of the composition of the present invention is an oil of lubricating viscosity and may be present in a major amount in the lubricating composition or may be present in an amount that produces a concentrate with the concentrate.

  Suitable oils include natural and synthetic lubricating oils and mixtures thereof. In fully formulated lubricants, the oil of lubricating viscosity is generally present in a major amount (ie, in an amount greater than 50% by weight). Typically, the oil of lubricating viscosity is present in an amount of 75-95% by weight, many in an amount greater than 80% by weight of the total composition. The base oil component generally constitutes up to 100 parts by weight (pbw) of the total composition, and the pbw range of the other components is given with this base oil 100 pbw in mind. In other embodiments, the pbw range of the various components including the base oil is given such that the sum of the pbw of all components is 100, so the pbw value is equal to the weight percent value. The pbw ranges given for the various components described below may be given in any manner, but in most embodiments, it should be read as equivalent to a weight percent value.

  Oils of lubricating viscosity may include natural and synthetic oils, oils derived from hydrocracking, hydrogenation and hydrofinishing, unrefined oils, refined oils, refined oils or mixtures thereof. Unrefined oils are generally oils obtained directly from natural or synthetic sources with no (or little) further purification processing. Refined oils are similar to unrefined oils, except that they are further processed in one or more refining steps to enhance one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like. Rerefined oils, also known as reclaimed or reprocessed oils, are obtained by a process similar to that used to obtain refined oils and many remove used additives and oil breakdown products It is further processed by a technique aimed at.

  Natural oils useful as oils of lubricating viscosity include animal oils, vegetable oils (eg, castor oil, lard oil), mineral lubricating oils, eg, liquid petroleum, and paraffinic, naphthenic, paraffinic and naphthenic mixed types. Solvent treated or acid treated mineral lubricants and oils derived from coal or shale, or mixtures thereof.

  Synthetic oils of lubricating viscosity include hydrocarbon oils such as polymerized olefins and interpolymerized olefins (eg, polybutylene, polypropylene, propylene isobutylene copolymers); poly (1-hexene), poly (1-octene), poly ( 1-decene) and mixtures thereof; alkyl-benzenes (eg dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) -benzene); polyphenyls (eg biphenyl, terphenyl, alkylated poly) Phenyl); alkylated biphenyl ethers and alkylated biphenyl sulfides, and derivatives, analogs and homologues thereof, or mixtures thereof.

  Other synthetic oils of lubricating viscosity include polyol esters other than hydrocarbyl protected polyoxyalkylene polyols as disclosed herein, dicarboxylic acid esters, liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, phosphorus Acid trioctyl and decanephosphonic acid diethyl ester), or polymeric tetrahydrofuran. Conventional synthetic oils of lubricating viscosity further include oils made by the Fischer-Tropsch reaction and may typically be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil of lubricating viscosity may be prepared by Fischer-Tropsch GTL synthesis procedure and other GTL oils.

  Oils of lubricating viscosity may be further defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five groups of base oils are as follows. Group I (sulfur content> 0.03% by weight, and / or saturates <90% by weight, viscosity index 80-120); Group II (sulfur content ≦ 0.03% by weight and saturates ≧ 90% by weight, Viscosity index 80-120); Group III (sulfur content ≦ 0.03% by weight and saturates ≧ 90% by weight, viscosity index ≧ 120); Group IV (all polyalphaolefins PAO, eg PAO-2, PAO) -4, PAO-5, PAO-6, PAO-7 or PAO-8); and Group V. Oils of lubricating viscosity include API Group I, Group II, Group III, Group IV, Group V oils, or mixtures thereof. In one embodiment, the oil of lubricating viscosity is an API Group I, Group II, Group III, Group IV oil, or a mixture thereof. Alternatively, the oil of lubricating viscosity is often an API Group II, Group III or Group IV oil, or a mixture thereof.

  Oils of various described lubricating viscosities may be used alone or in combination. Oils of lubricating viscosity range from about 70% to about 99% by weight of the lubricant, in another embodiment from about 75% to about 98%, in another embodiment from about 88% to Used in the range of about 97% by weight.

  In certain embodiments, the lubricating oil component of the present invention comprises a Group II or Group III base oil, or a combination thereof. These are classifications established by the API (American Petroleum Institute). Group III oils contain <0.03% sulfur and> 90% saturates and have a viscosity index> 120. Group II oils have a viscosity index of 80-120 and contain <0.03% sulfur and> 90% saturates. This oil can also be derived from the hydroisomerization of waxes such as slack waxes or waxes synthesized by Fischer-Tropsch. Such “GTL” oils are typically characterized as Group III.

  The compositions of the present invention may comprise an amount of a Group I base oil, as well as a Group IV and Group V base oil. Polyalphaolefins are classified as Group IV. Group V includes “everything else”. However, in certain embodiments, the lubricating oil component of the present invention contains no more than 20 wt%, no more than 10 wt%, no more than 5 wt%, or no more than 1 wt% Group I base oil. These limitations may also apply to Group IV or Group V base oils. In other embodiments, the lubricating oil present in the composition of the present invention is at least 60%, 70%, 80%, 90%, or even 95% by weight of Group II and / or Group III. Base oil. In certain embodiments, the lubricating oil present in the composition of the present invention is essentially only a Group II and / or Group III base oil, even in the presence of small amounts of other types of base oils. An amount that is good, but does not significantly affect the overall properties or performance of the composition.

  In certain embodiments, the compositions of the present invention comprise an amount of a Group I and / or Group II base oil. In other embodiments, the composition of the present invention is such that the oil of lubricating viscosity is primarily a Group I and / or Group II base oil, or consists essentially of a Group I and / or Group II base oil. Or a lubricating composition that is exclusively a Group I and / or Group II base oil.

  In certain embodiments, the compositions of the present invention comprise an amount of a Group I base oil. In other embodiments, the composition of the present invention provides that the oil of lubricating viscosity is predominantly a Group I base oil, or is essentially a Group I base oil, or exclusively a Group I base oil. This is a lubricating composition.

  In certain embodiments, the composition of the present invention comprises an amount of a Group II base oil. In other embodiments, the composition of the present invention provides that the oil of lubricating viscosity is predominantly a Group II base oil, or is essentially a Group II base oil, or exclusively a Group II base oil. It is a lubricating composition that is an oil.

  In certain embodiments, the oil of lubricating viscosity is 60-99.9%, 88.5-99.6%, 96.9-99.5%, or 98.2-99% by weight of the lubricating oil composition. It may be present in the range of 4% by weight. The oils of the respective lubricating viscosities mentioned above may be used alone or as a mixture of one or more of these.

(Antioxidant component)
The present invention requires that the described lubricant composition contain a minimum amount of a particular antioxidant component. The antioxidant component comprises (i) a phenolic antioxidant, (ii) an amine antioxidant, or (iii) a combination thereof. The antioxidant component must be present in the described lubricating composition at a minimum of 0.4 wt%, 0.5 wt%, or at a minimum 1.0 wt% or more.

  Suitable phenolic antioxidants that can be used in the present invention include substituted phenols containing at least one alkyl substituent. In some embodiments, phenolic antioxidants include compounds that do not contain nitrogen and do not contain ash. In certain embodiments, the phenolic antioxidant comprises a substituted phenol comprising at least two branched chain alkyl substituents. In certain embodiments, the phenolic antioxidant comprises a substituted phenol comprising at least two branched alkyl substituents and further comprising an ester-containing substituent.

  The phenolic antioxidant is a sterically hindered phenol containing one alkyl group in the ortho position relative to the hydroxyl group, and two in the ortho position relative to the hydroxyl group (occupying positions 2 and 6 of the phenol ring). It may also contain sterically hindered phenols containing alkyl groups, or mixtures thereof. The alkyl group may contain 1 to 24 carbon atoms, in other cases 3 to 18, 3 to 12 carbon atoms. The alkyl group may be linear, branched (including tertiary alkyl groups), or a mixture thereof. The sterically hindered phenol may also contain one or more additional alkyl groups and / or one or more hydrocarbyl groups, such as propionate groups. Useful sterically hindered phenols include ortho-alkylated phenolic compounds such as 2,6-ditertbutylphenol, 4-methyl-2,6-di-tertbutylphenol, 2,4,6-tritertbutylphenol, 2-tert-butylphenol, 2,6-diisopropylphenol, 2-methyl-6-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4- (N, N-dimethylaminomethyl) -2,6 -Di-tertbutylphenol, 4-ethyl-2,6-di-tertbutylphenol, and analogs and homologues thereof. Mixtures of two or more such mononuclear phenol compounds are also suitable.

によってあらわされてもよく、式中、Ｒ^４は、１個から２４個までの炭素原子を含むアルキル基であり、ａは、１〜５の整数である。ある実施形態では、Ｒ^４は、４〜１８個の炭素原子、または４〜１２個の炭素原子を含む。Ｒ^４は、直鎖または分枝鎖であってもよく、ある実施形態では、分岐している。ａの値は、１〜４、１〜３、または２、または３であってもよい。ある実施形態では、フェノールは、２個または３個のｔ−ブチル基を含むブチル置換フェノールである。ある実施形態では、１個のＲ４基は、環の４位にあり、水素、ヒドロカルビル、例えば、メチル、エチルまたはドデシルである。任意のこれらの実施形態では、ａが２であり、ｔ−ブチル基がフェノールの２位および６位を占めている場合、フェノールは、極めて立体障害性であり、以下の構造を有する。

In one embodiment of the invention, the sterically hindered phenol has the formula:

Wherein R ⁴ is an alkyl group containing from 1 to 24 carbon atoms, and a is an integer of 1-5. In certain embodiments, R ⁴ contains ⁴ to 18 carbon atoms, or 4 to 12 carbon atoms. R ⁴ may be linear or branched and in some embodiments branched. The value of a may be 1-4, 1-3, 2, or 3. In certain embodiments, the phenol is a butyl substituted phenol containing 2 or 3 t-butyl groups. In certain embodiments, one R 4 group is at the 4-position of the ring and is hydrogen, hydrocarbyl, such as methyl, ethyl, or dodecyl. In any of these embodiments, when a is 2 and the t-butyl group occupies positions 2 and 6 of the phenol, the phenol is highly sterically hindered and has the following structure:

によってあらわすことができ、式中、ｔ−アルキル基は、４〜８個の炭素原子を有していてもよく、Ｒ^３は、２〜２２個、２〜８個、２〜６個の炭素原子、またはちょうど４個の炭素原子を含む直鎖または分枝鎖のアルキル基である。Ｒ^３は、望ましくは、２−エチルヘキシル基またはｎ−ブチル基である。障害性のエステル置換フェノール、例えば、式（ＩＩＩ）のエステル置換フェノールは、国際公開第ＷＯ０１／７４９７８号に記載されるように、塩基触媒条件（例えば、ＫＯＨ水溶液）下、２，６−ジアルキルフェノールを、アクリル酸エステルとともに加熱することによって調製することができる。本発明の別の実施形態では、立体障害性フェノールは、アルキルフェノール（例えば、ドデシルフェノール）とイソブチレンとを反応させ、ジ−ｔ−ブチル化アルキルフェノールを含む生成物を形成する、アルキル化反応生成物である。本発明の一実施形態は、１〜２４個の炭素原子を含み、フェノール環の２位および６位を占める２個以上のアルキル置換基を有する立体障害性フェノールである。 In one embodiment of the invention, the sterically hindered phenol has the formula:

Wherein the t-alkyl group may have 4 to 8 carbon atoms, and R ³ is 2 to 22, 2 to 8, 2 to 6 carbons. An atom, or a straight or branched alkyl group containing exactly 4 carbon atoms. R ³ is preferably a 2-ethylhexyl group or an n-butyl group. Obstructive ester-substituted phenols, for example ester-substituted phenols of the formula (III), are prepared as described in WO 01/74978 under 2,6-dialkylphenols under basic catalysis conditions (eg aqueous KOH). Can be prepared by heating with an acrylate ester. In another embodiment of the invention, the sterically hindered phenol is an alkylation reaction product that reacts an alkylphenol (eg, dodecylphenol) with isobutylene to form a product comprising di-t-butylated alkylphenol. is there. One embodiment of the present invention is a sterically hindered phenol containing 1 to 24 carbon atoms and having two or more alkyl substituents occupying positions 2 and 6 of the phenol ring.

  The phenolic antioxidant may also contain sterically hindered phenol oligomers coupled with alkylene or alkylidene. Coupled sterically hindered phenol oligomers are those in which the respective rings are in the 2-position, 4-position and 6-position with an alkyl group (eg methyl or t-butyl group) or arylalkyl group (eg 3,5-di-t It may contain two or more phenol rings occupied by -butyl-4-hydroxybenzyl group). The alkylene coupling group and the alkylidene coupling group may be a methylene group and an ethylidene group, respectively. The alkyl group may have 1 to 24 carbon atoms, and in other cases 3 to 18 or 3 to 12 carbon atoms. The alkyl group may be linear, branched (including tertiary alkyl groups), or a mixture thereof. The coupled sterically hindered phenol oligomer may comprise a mixture of two or more oligomers, each oligomer containing a different number of phenol rings. The coupling of the phenol ring in the oligomer may be the ortho position of the ring, the para position of the ring, or a mixture of the ortho position and the para position of the ring.

によってあらわされてもよいカップリングしたアルキルフェノールであり、式中、各Ｒ^５は、独立して、４〜約８個の炭素原子を含む三級アルキル基であり、Ｘ、ＹおよびＺは、それぞれ、独立して、水素または炭化水素基であり、各Ｒ^６は、独立して、アルキレン基またはアルキリデン基であり、ｎは、０〜約４の範囲の数である。各Ｒ^５基は、三級アルキル基でなければならない。三級アルキル基は、以下の一般的な構造

を有し、式中、Ｊ、ＫおよびＬは、それぞれ、１〜４個の炭素原子を含むアルキル基である。代表的な三級アルキル基は、三級ブチル、三級アミル、三級ヘキシルおよび三級オクチルである。Ｒ^５基は、同じであってもよく、または異なっていてもよい。ある実施形態では、すべてのＲ^５は同じであり、なおさらなる実施形態では、すべて三級ブチル基である。各Ｒ^６は、独立して、二価の基、例えば、アルキレン基またはアルキリデン基である。これらの基は、例えば、種々のヒドロカルビル基、例えば、アルキル基およびアリール基で置換されていてもよい。適切なＲ^６基の代表例は、メチレン、エチレン、プロピレン、フェニル置換メチレン、メチル置換メチレン、メチル置換エチレンなどである。典型的には、各Ｒ^６は、１〜約１０個の炭素原子、または１〜約３個の炭素原子を含む。一実施形態では、Ｒ^６は、フェニル置換メチレンである。別の実施形態では、それぞれがメチレンであり、すなわち、式−ＣＨ_２−の基である。Ｘ、ＹおよびＺは、それぞれ独立して、水素または炭化水素系基である。これらの基は、同じであってもよく、または異なっていてもよい。一実施形態では、Ｘ、ＹおよびＺは、それぞれ独立して、脂肪族炭化水素基である。したがって、これらの基は、それぞれ、少なくとも１個の炭素原子を含むが、１個より多く含んでいてもよい。なおさらなる実施形態では、これらの基は、１〜約５００個の炭素原子、４〜約１００個の炭素原子、または約４〜約３０個の炭素原子を含む。 In one embodiment of the invention, the phenolic antioxidant is of the formula

Wherein each R ⁵ is independently a tertiary alkyl group containing from 4 to about 8 carbon atoms, and X, Y, and Z are each a coupled alkylphenol, which may be represented by , Independently hydrogen or a hydrocarbon group, each R ⁶ is independently an alkylene group or an alkylidene group, and n is a number ranging from 0 to about 4. Each R ⁵ group must be a tertiary alkyl group. Tertiary alkyl groups have the following general structure:

Wherein J, K and L are each an alkyl group containing 1 to 4 carbon atoms. Representative tertiary alkyl groups are tertiary butyl, tertiary amyl, tertiary hexyl and tertiary octyl. The R ⁵ groups may be the same or different. In certain embodiments, all R ⁵ are the same, and in yet further embodiments, all are tertiary butyl groups. Each R ⁶ is independently a divalent group such as an alkylene group or an alkylidene group. These groups may be substituted with, for example, various hydrocarbyl groups such as alkyl groups and aryl groups. Representative examples of suitable R ⁶ groups are methylene, ethylene, propylene, phenyl substituted methylene, methyl substituted methylene, methyl substituted ethylene, and the like. Typically, each R ⁶ contains 1 to about 10 carbon atoms, or 1 to about 3 carbon atoms. In one embodiment, R ⁶ is phenyl substituted methylene. In another embodiment, each is methylene, ie, a group of formula —CH ₂ —. X, Y, and Z are each independently hydrogen or a hydrocarbon group. These groups may be the same or different. In one embodiment, X, Y and Z are each independently an aliphatic hydrocarbon group. Thus, each of these groups contains at least one carbon atom, but may contain more than one. In still further embodiments, these groups contain 1 to about 500 carbon atoms, 4 to about 100 carbon atoms, or about 4 to about 30 carbon atoms.

  In one embodiment of the invention, the phenolic antioxidant is a methylene-coupled oligomer of sterically hindered phenol, such as 4,4′-methylene-bis (6-tert-butyl-2-methylphenol), 4 , 4′-methylene-bis (2-tert-amyl-6-methylphenol), 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-methylene-bis (2, 6-di-tert-butylphenol), and similar compounds. In one embodiment of the invention, a methylene-coupled oligomer of sterically hindered phenol is prepared with 2,2′-methylene-bis (6-) as described in US Pat. No. 6,002,051 for preparation and use. tert-butyl-4-dodecylphenol).

  Suitable amine antioxidants that can be used in the present invention include alkaryl amines, and in certain embodiments, the amine antioxidant is an alkylphenylamine. Suitable examples include bis (4-alkylphenyl) amine.

Amine antioxidants are secondary aromatic amines, typically monoamines, which include one aryl group, two aryl groups, or mixtures thereof. One embodiment of the present invention is a secondary aromatic amine containing one aryl group, such as N-methylaniline. Secondary aromatic amines containing a single aryl group, C ₁ -C ₁₆ alkyl or arylalkyl substituent may have an aryl group. In another embodiment of the present invention, the secondary aromatic amine may be a diarylamine, such as diphenylamine, N-phenyl-1-naphthylamine, or a combination thereof. Diarylamines may contain one, two or more alkyl and / or arylalkyl substituents. The alkyl and arylalkyl substituents may have 1 to 16 carbon atoms, and in other cases may have 3 to 14 and 4 to 12 carbon atoms. The alkyl and arylalkyl substituents may be straight chain, branched chain, or mixtures thereof. In one embodiment of the invention, the diarylamine is of the formula R ⁷ -C ₆ H ₄ -NH-C ₆ H ₄ -R ⁸ (VI)
Wherein R ⁷ and R ⁸ are independently hydrogen or an alkyl group containing 1 to 24 carbon atoms. The diphenylamine of formula (VI) may be a mixture of diphenylamine and monoalkylated diphenylamine and dialkylated diphenylamine. R ⁷ and / or R ⁸ may be an alkyl group containing 4 to 20 carbon atoms. In another embodiment of the invention, the diphenylamine of formula (VI) is prepared by alkylating diphenylamine with nonene using well-known alkylation methods. Alkylated diarylamines are also commercially available.

  The antioxidant component must be present in the composition at least 1.0% by weight. This treat rate is related to the final lubricating composition to be used in the mechanical device, but it is typically added later that can be diluted with oil to produce the final lubricant. It can also be applied to agent packages and concentrates. The weight percentages discussed herein are based on the total lubricating composition. Any diluent that may be present in the antioxidant component is generally not considered when determining the weight percent that the antioxidant component is present in the composition. In addition, any material in the antioxidant component other than the phenolic antioxidants and amine antioxidants described herein is used to determine the weight percent that the antioxidant component is present in the composition. As a result, the weight percent values discussed apply only to phenolic and amine antioxidants.

  Furthermore, it is noted that in certain embodiments, the antioxidant component comprises one or more phenolic antioxidants and no amine antioxidants. In other embodiments, the antioxidant component comprises one or more amine antioxidants and no phenolic antioxidants. In yet other embodiments, the antioxidant component comprises a combination of one or more amine antioxidants and one or more phenolic antioxidants.

  In some embodiments, the phenolic antioxidant is present in the lubricating composition at least 0.5% by weight and the amine antioxidant is present in the lubricating composition at least 0.5% by weight. In some embodiments, the phenolic antioxidant is present in the lubricating composition at least 1.0% by weight or more, and the amine antioxidant is at least 1.0% by weight or greater in the lubricating composition. 5% by weight or more.

(Additional additives)
Optionally, the lubricating compositions of the present invention comprise one or more additional additives, including foam suppressants, demulsifiers, pour point depressants, antioxidants other than those mentioned above, dispersants, metal deactivators. (Eg, copper deactivators), antiwear agents, extreme pressure agents, viscosity modifiers, or mixtures thereof may be selected. Optional additives are 0.0005 to 1.3 wt%, 0.00075 to 0.5 wt%, 0.001 to 0.4 wt%, or 0.0015 to 0 wt% of the lubricating oil composition, respectively. It may be present in the range of 3% by weight. However, certain optional additives, including polymers that adjust viscosity (or may be considered part of the base fluid), up to 30% by weight when considered separate from the base fluid Note that higher amounts may be present, including up to 40% by weight, or up to 50% by weight. Optional additives may be used alone or as a mixture thereof.

  Antifoaming agents (also known as antifoaming agents) are known in the art and include, but are not limited to, organosilicones and non-silicon antifoaming agents. Examples of organosilicones include dimethyl silicone and polysiloxane. Examples of non-silicon antifoaming agents include, but are not limited to, polyethers, polyacrylates and mixtures thereof, and copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate. In certain embodiments, the antifoaming agent is a polyacrylate. Antifoaming agents may be present in the composition at 0.001 to 0.012 pbw, or 0.004 pbw or 0.001 to 0.003 pbw.

  Demulsifiers are known in the art and include, but are not limited to, propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkylamines, aminoalcohols, diamine derivatives, or polyamines reacted in turn with ethylene oxide or substituted ethylene oxide, or these A mixture is mentioned. Examples of demulsifiers include polyethylene glycol, polyethylene oxide, polypropylene oxide, (ethylene oxide-propylene oxide) polymers (including block copolymers of ethylene oxide and propylene oxide), and mixtures thereof. In certain embodiments, the demulsifier is a polyether. The demulsifier may be present in the composition in an amount of 0.002 to 0.012 pbw.

  Pour point depressants are known in the art and include, but are not limited to, maleic anhydride-styrene copolymer esters, polymethacrylates; polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatic compounds; Rate polymers; and terpolymers of dialkyl fumarate, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers, alkylphenol formaldehyde condensation resins, alkyl vinyl ethers, and mixtures thereof.

  The composition of the present invention may also contain a rust inhibitor. Suitable rust inhibitors include hydrocarbyl amine salts of alkyl phosphates, hydrocarbyl amine salts of dialkyldithiophosphates, hydrocarbyl amine salts of hydrocarbyl arene sulfonic acids, fatty carboxylic acids or esters thereof, esters of nitrogen-containing carboxylic acids, ammonium sulfonates , An imidazoline, a mono-thiophosphate or ester, or any combination thereof; or a mixture thereof.

によってあらわされ、式中、Ｒ^２１およびＲ^２２は、独立して、水素、アルキル鎖またはヒドロカルビルであり、ある実施形態では、Ｒ^２１およびＲ^２２の少なくとも１つがヒドロカルビルである。Ｒ^２１およびＲ^２２は、約４〜約３０個、約８〜約２５個、または約８個もしくは約１０個〜約２０個、または１３個〜約１９個の炭素原子を含む。Ｒ^２３、Ｒ^２４およびＲ^２５は、独立して、水素、または約１〜約３０個、他の実施形態では、約４〜約２４個、または約６〜約２０個、ある実施形態では、約８もしくは約１０個〜約１６個の炭素原子を含む分岐したアルキルまたは直鎖アルキル鎖である。Ｒ^２３、Ｒ^２４およびＲ^２５は、独立して、水素、分岐したアルキルまたは直鎖アルキル鎖であり、ある実施形態では、Ｒ^２３、Ｒ^２４およびＲ^２５の少なくとも１つ、または２つが水素であり、さらに、Ｒ^２３、Ｒ^２４およびＲ^２５の少なくとも１つは、少なくとも８個の炭素原子を含むヒドロカルビル基である。 Suitable hydrocarbyl amine salts of the alkyl phosphates of the present invention have the formula

In which R ²¹ and R ²² are independently hydrogen, an alkyl chain or hydrocarbyl, and in certain embodiments, at least one of R ²¹ and R ²² is hydrocarbyl. R ²¹ and R ²² contain about 4 to about 30, about 8 to about 25, or about 8 or about 10 to about 20, or 13 to about 19 carbon atoms. R ²³ , R ²⁴ and R ²⁵ are independently hydrogen, or about 1 to about 30, in other embodiments about 4 to about 24, or about 6 to about 20, in some embodiments Branched alkyl or straight chain alkyl chains containing from about 8 or about 10 to about 16 carbon atoms. R ²³ , R ²⁴ and R ²⁵ are independently hydrogen, branched alkyl or a linear alkyl chain, and in certain embodiments, at least one or two of R ²³ , R ²⁴ and R ²⁵ are hydrogen. And in addition, at least one of R ²³ , R ²⁴ and R ²⁵ is a hydrocarbyl group containing at least 8 carbon atoms.

Suitable alkyl groups for R ²³ , R ²⁴ and R ²⁵ include, but are not limited to, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl, 2-ethyl, Hexyl, ethyl-hexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl, or mixtures thereof.

In one embodiment, the hydrocarbylamine salt of alkyl phosphate is Primene 81R (manufactured and sold by Rohm & Haas), which is a mixture of C ₁₄ -C ₁₈ alkylated phosphoric acid and C ₁₁ -C ₁₄ tertiary alkyl primary amines. It is a reaction product.

によってあらわされ、式中、Ｒ^２６およびＲ^２７は、独立して、分枝鎖または直鎖のアルキル基である。Ｒ^２６およびＲ^２７は、約３〜約３０個、または、約４〜約２５個、または、約５〜約２０個、さらにまたは、約６〜約１９個の炭素原子を含む。Ｒ^２３、Ｒ^２４およびＲ^２５は、上に記載したとおりである。 The hydrocarbylamine salt of dialkyldithiophosphoric acid of the present invention used in a rust preventive package has the following formula:

Where R ²⁶ and R ²⁷ are independently a branched or straight chain alkyl group. R ²⁶ and R ²⁷ contain about 3 to about 30, or about 4 to about 25, or about 5 to about 20, or even about 6 to about 19 carbon atoms. R ²³ , R ²⁴ and R ²⁵ are as described above.

  Examples of hydrocarbylamine salts of dialkyldithiophosphoric acids of the present invention include, but are not limited to, reaction products of diheptyldithiophosphoric acid or dioctyldithiophosphoric acid or dinonyldithiophosphoric acid with ethylenediamine, morpholine or Primene 81R, or mixtures thereof Is mentioned.

によってあらわされ、式中、Ｃｙは、ベンゼン環またはナフタレン環である。Ｒ^２８は、約４〜約３０個、または、約６〜約２５個、または、約８〜約２０個の炭素原子を含むヒドロカルビル基である。ｚは、独立して、１、２、３または４であり、ある実施形態において、ｚは、１または２である。Ｒ^２３、Ｒ^２４およびＲ^２５は、上に記載したとおりである。 Suitable hydrocarbyl amine salts of hydrocarbyl arene sulfonic acids for use in the rust inhibitor package of the present invention are represented by the formula

In the formula, Cy is a benzene ring or a naphthalene ring. R ²⁸ is a hydrocarbyl group containing about 4 to about 30, or about 6 to about 25, or about 8 to about 20 carbon atoms. z is independently 1, 2, 3 or 4, and in some embodiments z is 1 or 2. R ²³ , R ²⁴ and R ²⁵ are as described above.

  Examples of hydrocarbyl amine salts of hydrocarbyl arene sulfonic acids of the present invention include, but are not limited to, ethylenediamine salts of dinonyl naphthalene sulfonic acids.

  Examples of suitable fatty carboxylic acids or esters thereof include glycerol monooleate and oleic acid. Examples of suitable esters of nitrogen-containing carboxylic acids include oleyl sarcosine.

  The rust inhibitor may be present in the range of 0.02 to 0.2 pbw, 0.03 to 0.15 pbw, 0.04 to 0.12 pbw, or 0.05 to 0.1 pbw of the lubricating oil composition. Good. The rust inhibitor of the present invention may be used alone or in a mixture thereof.

  The lubricating composition of the present invention may also contain a metal deactivator. A metal deactivator is used to neutralize the catalytic effect of the metal that promotes the oxidation of the lubricating oil. Suitable metal deactivators include, but are not limited to, triazole, tolyltriazole, thiadiazole, or combinations thereof and derivatives thereof. Examples include derivatives of benzotriazole, benzimidazole, 2-alkyldithiobenzimidazole, 2-alkyldithiobenzothiazole, 2- (N, N′-dialkyldithio-carbamoyl) benzothiazole, 2,5-bis (alkyl- Dithio) -1,3,4-thiadiazole, 2,5-bis (N, N′-dialkyldithiocarbamoyl) -1,3,4-thiadiazole, 2-alkyldithio-5-mercaptothiadiazole, or a mixture thereof. Can be mentioned. You may use these additives for 0.01 to 0.25 weight% of the whole composition.

  In certain embodiments, the metal deactivator is a hydrocarbyl substituted benzotriazole compound. Benzotriazole compounds having hydrocarbyl substitution include benzotriazole in at least one of the 1-position, 2-position, 4-position, 5-position, 6-position or 7-position of the ring. The hydrocarbyl group contains from about 1 to about 30, preferably from about 1 to about 15, more preferably from about 1 to about 7 carbon atoms, and most preferably the metal deactivator alone 5-methylbenzotriazole used, or a mixture thereof.

  The metal deactivator may be present in the range of 0.001 to 0.1 pbw, 0.01 to 0.04 pbw, or 0.015 to 0.03 pbw of the lubricating oil composition. The metal deactivator may be present in the composition in the range of 0.002 pbw or 0.004 pbw to 0.02 pbw. The metal deactivator may be used alone or in a mixture thereof.

  Antioxidants other than those described above, including substituted hydrocarbyl mono-sulfides, may also be present. In certain embodiments, the substituted hydrocarbyl monosulfide includes n-dodecyl-2-hydroxyethyl sulfide, 1- (tert-dodecylthio) -2-propanol, or a combination thereof. In certain embodiments, the substituted hydrocarbyl monosulfide is 1- (tert-dodecylthio) -2-propanol.

  (Ii) a borated succinimide dispersant; (iii) a non-borated succinimide dispersant; (iv) a Mannich reaction product of a dialkylamine, an aldehyde and a hydrocarbyl-substituted phenol; or any of these Dispersants containing combinations of these may also be present. In certain embodiments, the dispersant component is present at 0.05 to 0.5 pbw of the total composition.

  The present invention further provides all the compositions, methods and uses described herein, wherein the specific lubricant comprises a demulsifier, the specific lubricant comprising a combination of the demulsifier and the sulfurized olefin. Specific lubricants include highly sulfurized olefins, such as sulfurized olefins containing at least 20 wt% sulfur, and certain lubricants include highly nonsulfidized olefins, such as less than 20 wt% Essentially free or free of sulfurized olefins containing sulfur, specific lubricants include a combination of substituted triazoles and substituted thiadiazoles, and specific lubricants are essentially free of metal dialkyldithiophosphates. Specific lubricants are essentially free of overbased metal-containing detergents or specific Lubricants, contain no zinc essentially, or completely free, or any combination thereof.

(Industrial use)
The present invention provides a process for preparing a lubricating oil composition. A lubricating oil composition is prepared by a process comprising: (a) mixing and / or dissolving together the above-mentioned components, including a combination of an oil of lubricating viscosity, a substituted triazole, and optionally one or more additional additives. Is done. In some embodiments, until the additive is substantially dissolved or completely dissolved, in some embodiments, at an elevated temperature in the range of 40 ° C. to 110 ° C., or 50 ° C. to 95 ° C., or 55 ° C. to 85 ° C. for 30 seconds to These materials are mixed at a pressure in the range of 24 hours, 2 minutes to 8 hours, or 5 minutes to 4 hours, 700 mmHg to 2000 mmHg, 750 mmHg to 900 mmHg, or 755 mmHg to 800 mmHg.

  The order of addition of the additives is not excessively limited. Optional additives may be mixed simultaneously with the other ingredients, or may be mixed later using any mixing procedure described above.

  In some embodiments, a portion of the oil or similar diluent is present with the above ingredients and this ingredient is mixed into the oil. In other embodiments, a minimum amount of oil or diluent is present, except for the amount inherently present in the additive from the means of producing and preparing them, and after mixing the ingredients, additional groups Add oil. In any case, the described process results in a lubricating composition.

  In certain embodiments, the lubricating oil composition comprises (a) a minimum of oils and / or diluents other than those described above, possibly present in some relatively small amounts, allowing for reasonable handling characteristics. And may be prepared from the concentrate. The resulting concentrate may then be used in the preparation of a lubricating composition by mixing the concentrate with an effective amount of a base oil or a mixture thereof to obtain the final fluid. Optional additives may be added to the concentrate or the resulting final fluid. Examples of these optional additives include those described above. In certain embodiments, these optional additives include a defoamer, a demulsifier, a viscosity modifier, a pour point depressant, or a mixture thereof, about 0 pbw, about 0.01 pbw throughout the composition. , About 0.1 pbw or about 0.25 pbw, or up to about 13 pbw, up to about 10 pbw, up to about 8 pbw, or up to about 6 pbw.

  In certain embodiments, the composition of the present invention has an ISO viscosity grade of 100-1000, or 100-460, or 100 or 150-320. In certain embodiments, the composition of the present invention is not a grease composition or an engine oil composition. Rather, these compositions may be industrial gear oils, wind turbine lubricants, bearing lubricants, and the like, and in some embodiments, automotive gear oils.

(Specific embodiment)
The invention is further illustrated by the following examples describing particularly advantageous embodiments. These examples are presented to illustrate the invention, but are not intended to limit the invention.

  The following example groups are designed to evaluate and compare the following additives. Antioxidant A, alkylated phenol; and Antioxidant B, alkarylamine.

  In order to evaluate the additive, the following example group of examples is tested to assess seal section compatibility. Samples were tested for approval based on the Flender-Siemens specification (FS) for wind turbines using an NBR902 seal, which includes 1000 hours of testing at 130 ° C. for each sample. Based on this specification, ideally, the fluid has a hardness change of 5 points or less (-5 to +5), a volume change rate from 2% decrease to 5% increase (-2% to + 5%), tension decrease rate Of 60% or less (maximum -60%) and the rate of elongation reduction should be 60% or less (maximum -60%). These specifications (especially the Flender-Siemens specifications) are very difficult to meet, but the performance is relatively improved compared to the conventional comparative example, even if it is not clearly passed, It is thought that it has improved remarkably. In fact, samples that meet this specification, except for hardness changes up to +7, volume changes up to + 6%, or elongation changes down to -65%, only one of these areas is out of the normal acceptance range. In this case, it is considered that the specification is satisfied and the test is passed. For one of the scores, this secondary tolerance may pass the result even if the sample does not show a “clear pass” where all the scores are in the ideal range. it can.

However, as is apparent from the results, it is important to consider the relative performance of the examples, not just the failure results. Considering the results of the Flender-Siemens specification (FS) of the Examples group and comparing the relative performance, it helps to consider the degree to which a sample passes or fails. be able to. The following symbols can be used for this purpose, with the best results at the top of the table and the worst results at the bottom of the table.

(Example group 1)
Example groups are prepared with Group I (GI) base oil. In each example, the sample contains the same amount of the same conventional additive package so that it is suitable for use as a lubricant in industrial gear applications. Each sample is top-treated with one of the above-mentioned antioxidants to see the effect of the added material on the performance of the formulation, particularly with respect to seal compatibility.

  The conventional additive package used in each of these examples is referred to as additive package A, which is a metal deactivator, demulsifier, rust inhibitor, antiwear and extreme pressure mixture, antifoam agent, Contains detergents and corrosion inhibitors. None of the additives in additive package A meet the requirements of the antioxidant component of the present invention.

Using the same test method as described above, the sample is tested and the seal fit is evaluated. The results obtained from the tests of Example Group 1 are summarized in the following table.

  This result shows that the inventive examples give improved seal compatibility with the Group I-based formulations over the comparative examples.

(Example group 2)
Example groups are prepared with Group II (GII) base oil. Each example contains the same conventional additive package as described in Example Group 1. Using the same test method described above, the sample is tested to assess seal fit. The results obtained from the tests of Example Group 2 are summarized in the following table.

  This result shows that examples of the present invention provide improved seal compatibility with Group II based formulations. However, as is clear from the results, it is important to consider the relative performance of the examples, not just the pass / fail results.

  Although the present invention has been described, it should be understood that various modifications of the present invention will become apparent to those skilled in the art upon reading this specification. Accordingly, it is to be understood that the invention disclosed herein is intended to embrace such modifications as fall within the scope of the appended claims.

  As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” as used herein is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, these terms refer to groups composed primarily of carbon and hydrogen atoms, which are attached to the rest of the molecule through the carbon atom, primarily detrimental to molecules with hydrocarbon character. It does not exclude the presence of other atoms or other groups in a ratio that is not sufficient. Generally, there are no more than 2 and preferably no more than 1 non-hydrocarbon substituent for every 10 carbon atoms in a hydrocarbyl group, typically a non-hydrocarbon substitution in the hydrocarbyl group The group does not exist. A more detailed definition of the term “hydrocarbyl substituent” or “hydrocarbyl group” is described in US Pat. No. 6,583,092.

  Each document referred to above is incorporated herein by reference. Unless stated otherwise or otherwise stated, it should be understood that any stated quantity specifying the amount of material, reaction conditions, molecular weight, number of carbon atoms, etc. is modified by the term “about”. is there. Unless otherwise indicated, all percentages and formulation values listed herein are on a weight basis. Unless otherwise indicated, each chemical or composition referred to herein includes isomers, by-products, derivatives, and other such materials normally understood to exist in commercial grade. It should be interpreted as a commercial grade material that may be present. However, the amount of each chemical component is present in an amount excluding any solvent or diluent that may normally be present in commercially available materials, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts of each element of the invention can be used together with the ranges or amounts of any other element. As used herein, the expression “consisting essentially of” permits inclusion of substances that do not significantly affect the basic and novel characteristics of the composition under consideration.

Claims (16)

An oil of lubricating viscosity and (i) a phenolic antioxidant, (ii) an amine antioxidant, or (iii) an antioxidant component comprising a combination thereof,
The antioxidant component is present in the lubricating composition at 1.0% by weight or more;
Industrial lubricating composition. The phenolic antioxidant is present in the lubricating composition at least 0.5% by weight or more,
The composition according to claim 1, wherein the amine-based antioxidant is present in the lubricating composition at least 0.5% by weight or more. The composition according to any one of claims 1 to 2, wherein the phenolic antioxidant comprises a substituted phenol comprising at least one alkyl substituent. The composition according to any one of claims 1 to 3, wherein the amine-based antioxidant contains a diarylamine. The composition according to any one of claims 1 to 4, wherein the oil of lubricating viscosity includes a mineral base oil. The composition according to claim 1, wherein the oil having a lubricating viscosity includes a synthetic base oil. Antiwear agent, extreme pressure agent, friction modifier, corrosion inhibitor, rust inhibitor, metal deactivator, boronated dispersant, non-borated dispersant, detergent, antifoaming agent, viscosity index improver, viscosity The composition according to any one of claims 1 to 6, further comprising a regulator, an antioxidant, a pour point depressant, a seal portion swelling agent, or any combination thereof. A method of lubricating an industrial gear assembly comprising the step of supplying a lubricating composition to the industrial gear assembly, comprising:
The lubricating composition comprises an oil of lubricating viscosity and (i) a phenolic antioxidant, (ii) an amine antioxidant, or (iii) an antioxidant component comprising a combination thereof,
The antioxidant component is present in the lubricating composition at 1.0% by weight or more;
Method. The phenolic antioxidant is present in the lubricating composition at least 0.5% by weight or more,
The method of claim 8, wherein the amine-based antioxidant is present in the lubricating composition at least 0.5% by weight or more. The method according to any one of claims 8 to 9, wherein the phenolic antioxidant comprises a substituted phenol comprising at least one alkyl substituent. The method according to any one of claims 8 to 10, wherein the amine-based antioxidant comprises a diarylamine. 12. A method according to any one of claims 8 to 11, wherein the oil of lubricating viscosity comprises a mineral base oil. The method of any one of claims 8 to 11, wherein the oil of lubricating viscosity comprises a synthetic base oil. The lubricating composition is an antiwear agent, extreme pressure agent, friction modifier, corrosion inhibitor, rust inhibitor, metal deactivator, boronated dispersant, non-borated dispersant, detergent, antifoaming agent, 14. The method according to any one of claims 8 to 13, further comprising a viscosity index improver, a viscosity modifier, a further antioxidant, a pour point depressant, a seal swell, or any combination thereof. A method for increasing the seal compatibility of an industrial gear assembly lubricant,
Adding to the lubricating composition an antioxidant component comprising (i) a phenolic antioxidant, (ii) an amine antioxidant, or (iii) a combination thereof,
The antioxidant component is present in the lubricant at 1.0 wt% or more,
Method. Use of an antioxidant component to enhance the seal compatibility of industrial gear assembly lubricants,
The antioxidant component comprises (i) a phenolic antioxidant, (ii) an amine antioxidant, or (iii) a combination thereof;
The antioxidant component is present in the lubricant at 1.0 wt% or more,
use.