JP5921574B2 - Composition with improved cleanability for lubrication of steam and gas turbine systems - Google Patents

Description

  The present invention relates to a lubricating composition containing a Group II and / or Group III base oil in one or more of two specific types of antioxidants and one or more of four specific types of dispersants. The use of an additive composition containing a combination of The lubricating composition of the present invention provides improved cleanability of steam turbine systems and gas turbine systems. The invention further relates to a process for producing the novel additive composition and the use of this composition in industrial fluids.

  Varnishes are a well-recognized and well-recognized problem in the lubricant industry and power generation field and gas turbine applications and are of increasing interest. The design of the turbine is to move the system to obtain greater power from smaller equipment, which results in smaller gaps and increased time to waste, and the equipment and lubricants used in its operation. The stress on both becomes greater and the conditions become more severe. The best liquid meets these challenges and leaves no varnish and other deposits in the system. In addition, turbine oils are increasingly blended with Group II and Group III oils instead of Group I base oils.

  These new base oils are much less polar than Group I oils, and additive formulations that work well in Group I base oils will have desirable performance when used in Group II and Group III oils. Often not available. In conjunction with the design and operation changes described above, the additive mixture needs to be adjusted for optimal performance in Group II and / or Group III base oils.

  Group II and Group III oils are more refined than Group I oils. Group I oils tend to be rich in aromatic and unsaturated components, and these species are more susceptible to oxidation than other species found in the oil. In fact, these new groups of oils have been developed in part to try and actually increase oxidative stability. This increased the oxidative stability of the base oil itself as compared to Group I oils, but also reduced its solubility. Along with this decrease in solubility, oxidation by-products derived from the oil itself or other sources and remained dissolved in the liquid derived from Group I are often derived from Group II or Group III. Varnish is generated on the surface of the device.

  In addition, in today's market, many power generation turbines are peaking units, which means that peaking units run only at peak demand. In this type of device, cooling the system lubricant during normal downtime reduces the dissolving capacity and polar material and varnish out of solution and deposit on the metal surface.

  In addition to oxidation and by-products generated by oxidation, electrostatic discharge, microdieseling, incompatibility, and contamination are also major causes of varnish. Incompatibility is particularly problematic for Group II and Group III oils because some of the additives that are compatible with Group I oils are not compatible with Group II and Group III oils.

  In addition, liquids from Group I tend to produce a slow oxidation rate that can be monitored over time, providing the operator with a reliable means of determining the remaining life of the liquid. give. In contrast, the liquids from Group II and Group III deviate from the normal amount of oxidation and become faulty very quickly with few or no indicators in advance. This further complex situation provides reliable performance in these high cost systems and is not likely to cause equipment damage caused by unplanned downtime and wasted lubricants. Further increase the need for liquids derived from.

  The challenge is to formulate a liquid that has the required amount of oxidative stability and is resistant to deposit formation. The main types of additives used to control oxidation are phenols and amines, both of which react at high temperatures to form oxidation products that cause system deposits and varnishes. Thus, it is possible to find an appropriate balance of oxidation inhibitor and dispersant components for a particular application and the base solution involved, significantly increasing the life of the lubricant and thus extending the life and operating time of the device. is important. Dispersants frequently cause emulsification of oil and water, so the choice of the correct dispersant must allow the liquid to maintain the good demulsibility required for proper turbine operation. The emulsified water reduces lubricant film formation and promotes rust and oxidation. The emulsifying liquid is not widely accepted in the market.

  Formulating lubricating compositions for steam and gas turbine systems is complicated by increased use of API Group II and Group III base oils, which increase varnish formation in certain power turbines Have been doing. Turbine lubricants that allow the use of Group II and Group III base oils while providing long service life and avoiding varnish problems that could interrupt the operation of the equipment and cause unplanned hibernation is necessary.

  It is desirable that these lubricating oil compositions can impart an acceptable amount of rust and / or oxidation inhibition without forming undesirable deposits that increase the viscosity of the fluid. Furthermore, in industrial fluids, it is desirable that these lubricating oil compositions control and prevent the formation of deposits and / or sludge that clog the filters.

  The present invention provides lubricating compositions formulated with Group II and Group III base oils for steam and gas turbine systems that provide balanced performance in modern turbine systems. The invention further provides methods for producing such compositions and methods for using the compositions in the operation of steam and gas turbine systems.

  The present invention relates to a lubricating oil comprising (a) an oil of lubricating viscosity comprising a Group II base oil, a Group III base oil or a combination thereof, (b) an antioxidant component, and (c) a dispersant component. A composition is provided. Antioxidant components include (i) alkylated diphenylamines and (ii) substituted hydrocarbyl monosulfides. The dispersant component comprises (i) a polyetheramine, (ii) a borated succinimide dispersant, (iii) a non-borated succinimide dispersant, (iv) a Mannich of dialkylamine, aldehyde, and hydrocarbyl substituted phenol. Including reaction products, or any combination thereof. The composition of the present invention may further comprise one or more additional additives.

  The present invention further provides (i) rust inhibitors, such as amine phosphates, fatty carboxylic acids or esters thereof, esters of nitrogen-containing carboxylic acids, ammonium sulfonates or imidazolines; ) Metal deactivators such as triazoles, tolyltriazoles, thiadiazoles or combinations thereof; (iii) demulsifiers such as polyethers; (iv) antifoaming agents such as acrylate copolymers; or any combination thereof. Further comprising a composition is provided.

  The present invention further provides a composition comprising a substituted hydrocarbyl monosulfide. In other embodiments, the present invention provides compositions that are essentially free or completely free of substituted hydrocarbyl monosulfides.

  The invention includes a dispersant component comprising a mixture of alcohols containing 10 to 18 carbon atoms, a polyetheramine derived from the reaction of an alkylene oxide and an amine; an antioxidant component is 0.865 throughout the composition. Present in an amount of less than parts by weight; the composition does not contain N-alkyl sarcosine; the composition contains less than 0.1 parts by weight of fatty carboxylic acid; Provided is a composition as described above, present in 07-0.4 parts by weight.

  In the present invention, the dispersant component includes a boronated succinimide dispersant derived from polyisobutylene having a number average molecular weight of 500 to 3000 and polyethylene polyamine, and the dispersant component is 0.07 to 0.00 in the entire composition. Provided is a composition as described above, present in an amount of less than 4 parts by weight.

  The invention includes a dispersant component comprising a non-borated succinimide dispersant derived from polyisobutylene having a number average molecular weight of 500 to 3000 and a polyethylene polyamine, wherein the composition comprises less than 0.1 parts by weight of a fatty carboxylic acid. Containing and dispersing component provides a composition as described above, present in an amount of 0.06-0.35 parts by weight throughout the composition.

  The present invention comprises a Mannich reaction product wherein the dispersant component is derived from the reaction of a dialkylamine, formaldehyde, and a polyisobutylene substituted phenol, the polyisobutylene having a number average molecular weight of 500 to 3000; Provided is a composition as described above, present in an amount of 0.07 to 0.44 parts by weight throughout the composition.

  The process of the present invention is that the antioxidant package is in the range of 0.05 to 13 parts by weight of the total composition; the dispersant component is in the range of 0.05 to 10 parts by weight of the total composition; optional The additive of choice, when present, is present in an amount of 0.001 to 10 parts by weight of the total composition; the remaining part is composed of oil of lubricating viscosity.

  The present invention provides a process for producing the lubricating composition described herein comprising the step of mixing together the components described above, which process is further described below.

  The present invention further provides a lubricating oil composition that can prevent deposits and sludge from clogging the filter.

  Various features and embodiments of the invention are described below by way of non-limiting illustration. Unless indicated otherwise, the parts by weight (pbw) values presented herein for the various ingredients described below are based on compositions containing 100 pbw base oil. is there. However, the pbw value may be treated as a percentage by weight based on the total composition in some embodiments.

  The present invention relates to a lubricating oil comprising (a) an oil of lubricating viscosity comprising a Group II base oil, a Group III base oil or a combination thereof, (b) an antioxidant component, and (c) a dispersant component. A composition is provided. Antioxidant components include (i) alkylated diphenylamines and (ii) substituted hydrocarbyl monosulfides. The dispersant component comprises (i) a polyetheramine, (ii) a boronated 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 combination of these is included. The composition of the present invention may further comprise one or more additional additives.

(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 as a lubricating composition or may be present in an amount that produces a concentrate as a 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, greater than 50% by weight). Typically, the oil of lubricating viscosity is present in an amount of 75-95% by weight of the total composition, more frequently more than 80%. The base oil component generally constitutes 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. The pbw ranges presented for the various components described below can take any form.

  The lubricating oil component of the present invention comprises a Group II or Group III base oil, or a combination thereof. There is a classification established by the API (American Petroleum Institute). Group III oils contain less than 0.03% sulfur and more than 90% saturation and have a viscosity index greater than 120. Group II oils have a viscosity index of 80-120 and contain less than 0.03% sulfur and more than 90% saturation. The oil can also be derived from the hydroisomerization of a wax (eg, slack wax or Fischer-Tropsch synthetic wax). Such “GTL (Gas-to-Liquid)” oils are typically characterized as Group III.

  The compositions of the present invention may contain an amount of a Group I base oil, and even a Group IV and Group V base oil. Polyalphaolefins are divided into Group IV categories. Group V includes “all others”. 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 restrictions 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 comprises at least 60 wt%, 70 wt%, 80 wt%, 90 wt%, or 95 wt% Group II and / or Group III base oil. It is. In certain embodiments, the lubricating oil present in the composition of the present invention is essentially only Group II and / or Group III base oils, and minor amounts of other types of base oils may be present. However, the amount is such that it does not significantly affect the overall properties or performance of the composition.

  The oil of lubricating viscosity is 60-99.9%, 88.5-99.6%, 96.9-99.5%, or 98.2-99.4% by weight of the lubricating oil composition. It may exist in a range. The oils having the respective lubricating viscosities mentioned above may be used alone or as a mixture of one or more of these.

(Antioxidant component)
The antioxidant component comprises (i) an alkylated diphenylamine and (ii) a substituted hydrocarbyl monosulfide.

  Suitable alkylated diphenylamines for use in the present invention have the following formula:

によってあらわされてもよく、式中、Ｒ^１およびＲ^２は、独立して、水素であるか、または約５〜２０個の炭素原子を含むアルキル基；または１〜２４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り、ｑおよびｒは、それぞれ独立して、０、１、２または３であり、但し、ｑとｒの合計は、少なくとも１である。ある実施形態では、Ｒ^１およびＲ^２は、独立して、水素であるか、または１〜２４個、４〜２０個、５〜１６個、または６〜１２個、または１０個の炭素原子を含むアルキル基である。上述のいずれかの実施形態では、Ｒ^１およびＲ^２は、それぞれ直鎖アルキル基、分岐したアルキル基、またはアリールアルキル基であってもよい。

Wherein R ¹ and R ² are independently hydrogen or an alkyl group containing from about 5 to 20 carbon atoms; or from 1 to 24 carbon atoms A linear or branched alkyl group, and q and r are each independently 0, 1, 2 or 3, provided that the sum of q and r is at least 1. In certain embodiments, R ¹ and R ² are independently hydrogen, or 1-24, 4-20, 5-16, or 6-12, or 10 carbon atoms. Including alkyl group. In any of the above-described embodiments, R ¹ and R ² may each be a linear alkyl group, a branched alkyl group, or an arylalkyl group.

  In certain embodiments, the alkylated diphenylamines of the present invention are bis-nonylated diphenylamine and bis-octylated diphenylamine.

  The alkylated diphenylamine is present in the range of 0.02-4 pbw, 0.03-2.5 pbw, or 0.05-1.5 pbw of the entire lubricating composition. In certain embodiments, the alkylated diphenylamine is from a value of 0.01 pbw, 0.05 pbw, 0.10 pbw, 0.15 pbw, 0.20 pbw, 0.25 pbw, 0.3 pbw, or 0.35 pbw of the total lubricating composition. 1.0 pbw, 0.9 pbw, 0.8 pbw, 0.75 pbw, 0.7 pbw, or 0.6 pbw. In still other embodiments, the alkylated diphenylamine ranges from 0.35 pbw or 0.375 pbw of the total lubricating composition to 0.51 pbw, 0.75 pbw, 0.775 pbw or 0.1 pbw, or 0.375 pbw It may exist in a range. The alkylated diphenylamine may be used alone or in a mixture thereof.

  Substituted hydrocarbyl monosulfides suitable for use in the present invention have the formula

によってあらわされてもよく、式中、Ｒ^３は、約８〜約２０個の炭素原子を含む飽和または不飽和の分枝鎖または直鎖のアルキル基であり；Ｒ^４、Ｒ^５、Ｒ^６、およびＲ^７は、独立して、水素であるか、または約１〜約３個の炭素原子、または１〜２個の炭素原子を含むアルキルである。ある実施形態では、Ｒ^３は、８〜２０個、９〜１７個、１０〜１５個、または１１〜１３個の炭素原子を含む。Ｒ^３は、分枝鎖または直鎖であってもよいが、ある実施形態では、分枝鎖である。

Wherein R ³ is a saturated or unsaturated branched or straight chain alkyl group containing from about 8 to about 20 carbon atoms; R ⁴ , R ⁵ , R ⁶ , And R ⁷ are independently hydrogen or alkyl containing from about 1 to about 3 carbon atoms, or from 1 to 2 carbon atoms. In certain embodiments, R ³ contains 8-20, 9-17, 10-15, or 11-13 carbon atoms. R ³ may be branched or straight chain, but in certain embodiments is branched.

  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.

  The substituted hydrocarbyl monosulfide may be present in an amount ranging from 0.02 to 4 pbw, 0.03 to 2.5 pbw, or 0.05 to 1.5 pbw of the lubricating oil composition. In certain embodiments, the substituted hydrocarbyl monosulfide is from 0.01 pbw, 0.03 pbw, 0.05 pbw, or 0.08 pbw of the total lubricating oil composition to 1.0 pbw, 0.8 pbw, 0.5 pbw, 0.3 pbw. Or it can be present in an amount ranging up to 0.1 pbw. In still other embodiments, the substituted hydrocarbyl monosulfide is present in an amount from 0.08 pbw to 0.1 pbw, or 0.09 pbw of the total lubricating composition. The substituted hydrocarbyl monosulfide may be used alone or in a mixture thereof.

  The antioxidant package is optional and has the following formula:

によってあらわされる立体障害性フェノールを含んでもよく、式中、Ｒ^８およびＲ^９は、独立して、約１〜約２４個、好ましくは約４〜約１８個、最も好ましくは約４〜約１２個の炭素原子を含む分枝鎖または直鎖のアルキル基である。

Wherein R ⁸ and R ⁹ are independently about 1 to about 24, preferably about 4 to about 18, most preferably about 4 to about 12. A branched or straight chain alkyl group containing 1 carbon atom.

R ⁸ and R ⁹ may be either linear or branched and are preferably branched. Preferably, the phenol is substituted with butyl containing two t-butyl groups. When the t-butyl group occupies the 2,6 positions, the phenol is sterically hindered. q is hydrogen or hydrocarbyl. Examples of suitable hydrocarbyl groups include, but are not limited to, 2-ethylhexyl or n-butyl ester, dodecyl or mixtures thereof.

  Other optional sterically hindered phenols suitable for the present invention include the following formulae

によってあらわされるフェノールが挙げられるが、これに限定されない。式中、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５は、直鎖または分枝鎖のいずれかであり、約４〜約１８個、好ましくは約４〜約１２個の炭素原子を含む。好ましくは、フェノールは、ブチルで置換されている。

But is not limited to this. Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ are either linear or branched and are about 4 to about 18, preferably about 4 to about 12 Contains carbon atoms. Preferably the phenol is substituted with butyl.

R ¹⁶ and R ¹⁷ are independently hydrogen, an arylalkyl group or a linear or branched alkyl group. R ¹⁶ and R ¹⁷ are preferably in the para position. The arylalkyl group or alkyl group contains about 1 to about 15, preferably about 1 to about 10, and most preferably about 1 to about 5 carbon atoms. Examples of the bridging group Y include, but are not limited to, —CH ₂ — (methylene bridge) or —CH ₂ OCH ₂ — (ether bridge).

  Examples of methylene-bridged sterically hindered phenols include, but are not limited to, 4,4′-methylenebis (6-tert-butyl o-cresol), 4,4′-methylenebis (2-tert-amyl-o-cresol). ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-methylene-bis (2,6-di-tertbutylphenol) or mixtures thereof.

  In one embodiment, the antioxidant is of the formula

によってあらわされるヒンダードエステル置換フェノールであり、式中、Ｒ^１８、Ｒ^１９およびＲ^２０は、約２〜約２２個、好ましくは約２〜約１８個、さらに好ましくは約４〜約８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。具体的な例としては、限定されないが、アルキル基、例えば、２−エチルヘキシルまたはｎ−ブチルエステル、ドデシルまたはこれらの混合物が挙げられる。

In which R ¹⁸ , R ¹⁹ and R ²⁰ are from about 2 to about 22, preferably from about 2 to about 18, more preferably from about 4 to about 8. A straight-chain or branched alkyl group containing a carbon atom. Specific examples include, but are not limited to, alkyl groups such as 2-ethylhexyl or n-butyl ester, dodecyl or mixtures thereof.

  The sterically hindered phenol is present in the range of 0-13 pbw, 0.02-4 pbw, 0.03-2.5 pbw, or 0.05-1.5 pbw of the lubricating oil composition. Sterically hindered phenols may be used alone or in combination. In certain embodiments, the compositions of the present invention are essentially free or completely free of sterically hindered phenols.

  In certain embodiments, the antioxidant component comprises 0.05 to 13 pbw of the entire composition, regardless of whether it contains one antioxidant or a mixture of two or more antioxidants, or Present in amounts from 0.1 to 0.4 pbw, or 0.05 pbw, 0.1 pbw, 0.2 pbw, or 0.3 pbw to 13 pbw, 0.9 pbw, 0.75 pbw, 0.6 pbw, or 0.5 pbw You may do it. In certain embodiments, the antioxidant component is present in an amount from 0.4 pbw to 0.9 pbw or 0.5 pbw. In other embodiments, the antioxidant component is present in an amount from 0.45 pbw, 0.465 pbw, or 0.60 pbw to 0.87 pbw, 0.865 pbw, 0.70 pbw, or 0.65 pbw.

(Dispersant component)
The dispersant component comprises (i) a polyetheramine; (ii) a boronated succinimide dispersant; (iii) a non-borated succinimide dispersant; (iv) a Mannich reaction product of a dialkylamine, an aldehyde and a hydrocarbyl substituted phenol; Including any combination of In certain embodiments, the dispersant component is present at 0.05 to 0.5 pbw of the total composition.

The polyetheramines of the present invention include compounds that contain two or more consecutive ether groups and at least one primary, secondary, or tertiary amino group, with the amine nitrogen being somewhat basic. The polyether amine of the present invention contains ASTM D1401 (Standard Test Method for Water Separation of Petroleum Oils and Synthetic Fluids) while containing a sufficient number of repeating oxyalkylene units to render the poly (oxyalkylene) amine soluble in the base oil. ) Contain poly (oxyalkylene) amines that allow acceptable performance in testing. In general, poly (oxyalkylene) amines containing at least about 5 oxyalkylene units are suitable for use in the present invention. Poly (oxyalkylene) amines include hydrocarbyl poly (oxyalkylene) amines, hydrocarbyl poly (oxyalkylene) polyamines, and at least poly (oxyalkylene) amine chains and / or poly (oxyalkylene) polyamine chains in the molecule of the derivative. Mention may be made of derivatives of polyhydric alcohols containing two. In one embodiment, a poly (oxyalkylene) amine for use in the present invention is represented by the formula R—O— (AO) _m —R ¹ —N—R ² R ³ , wherein R is 1 A hydrocarbyl group containing ˜50 carbon atoms, or about 8 to about 30 carbon atoms; A is an alkylene group containing 2-18 carbon atoms, or 2-6 carbon atoms; m is a number from 1 to 50; R ¹ is an alkylene group containing 2 to 18 carbon atoms, or 2 to 6 carbon atoms; R ² and R ³ are independently hydrogen , A hydrocarbyl group or — [R ⁴ N (R ⁵ )] _n R ⁶ , wherein R ⁴ is an alkylene group containing 2 to 6 carbon atoms, and R ⁵ and R ⁶ are independently A hydrogen or hydrocarbyl group, and n is a number from 1 to 7.

In another embodiment, the poly (oxyalkylene) amines of the present invention can be represented by the formula RO [CH ₂ CH (CH ₂ CH ₃ ) O] _m CH ₂ CH ₂ CH ₂ NH ₂ , wherein R Is an aliphatic group or alkyl-substituted phenyl group containing 8-30 carbon atoms; m is a number from 12-30. In yet another embodiment, the poly (oxyalkylene) amine of the present invention have the formula _{CH 3 CH (CH 3) [} CH 2 CH (CH 3)] 2 CH (CH 3) CH 2 CH 2 O- [CH 2 CH (CH ₂ CH ₃ ) O] _m CH ₂ CH ₂ CH ₂ NH ₂ , wherein m is a number from about 16 to about 28. The poly (oxyalkylene) amines of the present invention may have a molecular weight of about 300 to about 5,000.

  The polyetheramines of the present invention can be prepared by first condensing an alcohol or alkylphenol with an alkylene oxide, a mixture of alkylene oxides, or several alkylenes in a molar ratio of hydrogen compound to alkylene oxide of 1: 1-50. It can be prepared by condensing the oxide in a continuous manner to form a polyether intermediate. US Pat. Nos. 5,112,364 and 5,264,006 present reaction conditions for preparing polyether intermediates.

Alcohols may be monovalent or polyvalent, straight or branched, saturated or unsaturated, 1 to 50 carbon atoms, or 8 to 30 carbon atoms, or 10 to 16 carbons It may contain atoms. The branched alcohols of the present invention can include Guerbet alcohols as described in US Pat. No. 5,264,006, which generally contains 12 to 40 carbon atoms, It can be represented by the formula R—CH (CH ₂ CH ₂ R) CH ₂ OH, where R is a hydrocarbyl group. In one embodiment, the alkyl group of the alkylphenol may contain 1 to 50 carbon atoms, or 2 to 24 carbon atoms, or 10 to 20 carbon atoms.

  In one embodiment, the alkylene oxide includes 1,2-epoxyalkanes containing 2-18 carbon atoms, or 2-6 carbon atoms. In yet another embodiment, the alkylene oxide may be ethylene oxide, propylene oxide, and butylene oxide. Particularly useful are propylene oxide, butylene oxide, or mixtures thereof. The number of units derived from alkylene oxide in the polyether intermediate may be 1-50, or 12-30, or 16-28.

  The polyether intermediate can be converted to a polyetheramine by several methods. Conversion to polyether amines by reductive amination of polyether intermediates with ammonia, primary amines or polyamines as described in US Pat. Nos. 5,112,364 and 5,752,991. can do. In one embodiment, the polyether intermediate can be converted to a polyetheramine by forming a nitrile by a reaction of adding a polyether to acrylonitrile and then hydrogenating it to form a polyetheramine. US Pat. No. 5,264,006 presents reaction conditions for forming a polyether amine by cyanoethylation of a polyether with acrylonitrile and subsequent hydrogenation. In yet another embodiment, replacing chlorine with ammonia, primary or secondary amines, or polyamines after using a suitable chlorinating agent, as described in US Pat. No. 4,247,301. To convert the polyether intermediate or poly (oxyalkylene) alcohol to the corresponding poly (oxyalkylene) chloride.

  In certain embodiments, the polyetheramines of the present invention are derived from the reaction of a mixture of alcohols, alkoxylates and amines containing 10 to 18 carbon atoms.

  In certain embodiments, the composition of the present invention comprises a polyetheramine dispersant in which the polyetheramine is present in the entire composition in an amount of 0.07 to 0.6 pbw, or 0.09 to 0.5 pbw.

  In addition, in some of these embodiments, (i) the antioxidant component is present in the entire composition in an amount of less than 0.865 pbw; (ii) the composition does not include N-alkyl sarcosine; iii) The composition contains less than 0.15 pbw fatty carboxylic acid; or any combination thereof.

  Another type of dispersant that can be used in the present invention is succinimide. Succinimide dispersants are well known in the field of lubricants and are primarily free of ash-forming metals and usually do not cause any ash-forming metal when added to the lubricant, so sometimes Includes dispersants called “ashless” dispersants. Succinimide dispersants are the reaction product of a hydrocarbyl-substituted succinic acylating agent and an amine having at least one hydrogen bonded to a nitrogen atom. The term “succinic acylating agent” refers to a hydrocarbon-substituted succinic acid or a compound that produces succinic acid (this term also includes succinic acid itself). Such materials typically include hydrocarbyl substituted succinic acids, anhydrides, esters (including half esters), and halides.

  Succinic acid-based dispersants have a wide range of chemical structures, and typically include the following structures.

上の構造において、各Ｒ^１は、独立してヒドロカルビル基であり、複数のスクシンイミド基に結合していてもよく、典型的には、数平均分子量（Ｍｎ）が５００または７００から１０，０００のポリオレフィンから誘導される基である。典型的には、ヒドロカルビル基は、アルキル基であり、Ｍｎが５００または７００から５０００、または１５００または２０００から５０００のポリイソブチレンから誘導されるポリイソブチレン基であることが多い。これに代わる表現として、Ｒ^１基は、４０〜５００個の炭素原子、または少なくとも５０〜３００個の炭素原子を含んでいてもよく、例えば、脂肪族炭素原子である。Ｒ^２は、アルキレン基であり、一般的にはエチレン（Ｃ_２Ｈ_４）基である。このような分子は、一般的には、アルケニルアシル化剤とポリアミンとの反応から誘導され、上に示す単純なイミド構造以外に、種々のアミドおよび四級アンモニウム塩など、２つの部分の間の多様な結合が可能である。スクシンイミド分散剤は、米国特許第４，２３４，４３５号、第３，１７２，８９２号、第６，１６５，２３５号により完全に記載されている。

In the above structure, each R ¹ is independently a hydrocarbyl group and may be bonded to a plurality of succinimide groups, typically having a number average molecular weight (Mn) of 500 or 700 to 10,000. A group derived from a polyolefin. Typically, the hydrocarbyl group is an alkyl group, often a polyisobutylene group derived from a polyisobutylene having an Mn of 500 or 700 to 5000, or 1500 or 2000 to 5000. As an alternative expression, the R ¹ group may contain 40 to 500 carbon atoms, or at least 50 to 300 carbon atoms, for example an aliphatic carbon atom. R ² is an alkylene group, generally an ethylene (C ₂ H ₄ ) group. Such molecules are generally derived from the reaction of an alkenyl acylating agent with a polyamine, and in addition to the simple imide structure shown above, between the two moieties such as various amides and quaternary ammonium salts. Various combinations are possible. Succinimide dispersants are more fully described in US Pat. Nos. 4,234,435, 3,172,892, and 6,165,235.

  The polyalkenes from which the substituents are derived are typically homopolymers and interpolymers of polymerizable olefin monomers containing 2 to 16 carbon atoms, usually 2 to 6 carbon atoms.

The olefin monomer from which the polyalkene is derived is a polymerizable olefin monomer characterized by the presence of one or more ethylenically unsaturated groups (i.e.> C = C <), i.e. monoolefinic monomers, e.g. , Ethylene, propylene, 1-butene, isobutene, and 1-octene, or polyolefinic monomers (usually diolefinic monomers) such as 1,3-butadiene and isoprene. These olefin monomers are usually terminal polymerizable olefins, ie olefins characterized by the presence of> C═CH ₂ groups in the structure. The polyolefin may contain relatively small amounts of non-hydrocarbon substituents, provided that such substituents do not substantially interfere with the formation of the substituted succinic acylating agent. Each R ¹ group may contain one or more reactive groups (ie, a succinic group).

The amine that reacts with the succinic acylating agent to form the carboxylic dispersant composition may be a monoamine or a polyamine. In any case, the amine is characterized by the formula R ⁴ R ⁵ NH, wherein R ⁴ and R ⁵ are each independently hydrogen, hydrocarbon group, amino-substituted hydrocarbon group, hydroxy A substituted hydrocarbon group, an alkoxy-substituted hydrocarbon group, an amino group, a carbamyl group, a thiocarbamyl group, a guanyl group, or an acylimidoyl group, provided that R ⁴ and R ⁵ are one or less hydrogen. Thus, in all cases, these amines will be characterized by the presence of at least one HN <group in the structure. Thus, an amine has at least one primary amino group (ie, H ₂ N—) or secondary amino (ie, H—N <) group. Examples of monoamines include ethylamine, diethylamine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, and Octadecylamine is mentioned.

  The polyamines from which the dispersant is derived mainly include alkylene amines, and for the most part, the following formula

を構成するアルキレンアミンが挙げられ、式中、ｔは、典型的には１０未満の整数であり、Ａは、水素であるか、または典型的には３０個までの炭素原子を含むヒドロカルビル基であり、アルキレン基は、典型的には、８個未満の炭素原子を含むアルキレン基である。アルキレンアミンとしては、主に、エチレンアミン、ヘキシレンアミン、ヘプチレンアミン、オクチレンアミン、他のポリメチレンアミンが挙げられる。これらのアミンは、特に、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、プロピレンジアミン、デカメチレンジアミン、オクタメチレンジアミン、ジ（ヘプタメチレン）トリアミン、トリプロピレンテトラミン、テトラエチレンペンタミン、トリメチレンジアミン、ペンタエチレンヘキサミン、ジ（−トリメチレン）トリアミンによって例示される。上述のアルキレンアミンを２つ以上縮合させて得られるより高級な同族体も同様に有用である。テトラエチレンペンタミンが特に有用である。

Where t is an integer less than 10 and A is hydrogen or a hydrocarbyl group typically containing up to 30 carbon atoms. Yes, an alkylene group is typically an alkylene group containing less than 8 carbon atoms. Examples of alkylene amines include ethylene amine, hexylene amine, heptylene amine, octylene amine, and other polymethylene amines. These amines are in particular ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, decamethylenediamine, octamethylenediamine, di (heptamethylene) triamine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, Illustrated by di (-trimethylene) triamine. Higher homologues obtained by condensing two or more of the above-mentioned alkylene amines are also useful. Tetraethylenepentamine is particularly useful.

  Ethyleneamine (also called polyethylene polyamine) is particularly useful. These amines are described in Encyclopedia of Chemical Technology, Kirk and Othmer, Vol. 5, pp. 898-905, Interscience Publishers, New York (1950), the heading “Ethylene Amines” is described in some detail.

  Also useful are hydroxyalkyl substituted alkylene amines (ie, alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atom). Examples of such amines include N- (2-hydroxyethyl) ethylenediamine, N, N′-bis (2-hydroxyethyl) -ethylenediamine, 1- (2-hydroxyethyl) piperazine, monohydroxypropyl) -piperazine , Di-hydroxypropyl substituted tetraethylenepentamine, N- (3-hydroxypropyl) -tetra-methylenediamine, and 2-heptadecyl-1- (2-hydroxyethyl) -imidazoline.

  Higher homologues obtained by condensing the above-mentioned alkylene amines or hydroxyalkyl-substituted alkylene amines through amino radicals or hydroxy radicals are also useful. Condensed polyamines are formed by a condensation reaction between at least one hydroxy compound and at least one polyamine reactant containing at least a primary or secondary amino group and are described in US Pat. No. 5,230,714 (Steckel). ).

  Succinimide dispersants are usually referred to as such because they typically contain primarily nitrogen in the form of imide functional groups, but may also be in the form of amine salts, amides, imidazolines and mixtures thereof. To prepare the succinimide dispersant, the one or more compounds that produce succinic acid and the one or more amines are optionally liquid, substantially liquid, typically while removing water. In the presence of an active organic liquid solvent / diluent, it is generally heated at a high temperature (typically 100 ° C. to 300 ° C.) ranging from 80 ° C. to the decomposition point of the mixture or product.

  The succinic acylating agent and amine (or organic hydroxy compound, or mixture thereof) are typically at least 0.5 equivalents of amine (or, depending on the circumstances, for one equivalent of acid-generating compound) The reaction is carried out in an amount sufficient to form a hydroxy compound. Generally, the maximum amount of amine present is about 2 moles of amine per equivalent of succinic acylating agent. For purposes of the present invention, the equivalent of amine is the amount of amine corresponding to the total weight of the amine divided by the total number of nitrogen atoms present. The number of equivalents of the compound that produces succinic acid depends on the number of succinic groups present in the compound, and generally there are two equivalents of the acylating reagent for each succinic group of the acylating reagent. Further details and examples of procedures for preparing the succinimide detergents of the present invention are described, for example, in US Pat. Nos. 3,172,892; 3,219,666; 3,272,746; , 234, 435; 6,440,905, 6,165,235.

  In certain embodiments, the composition of the present invention comprises a non-borated succinimide dispersant derived from a polyisobutylene having a number average molecular weight of 500 to 3000 and a polyethylene polyamine.

  In such embodiments, the non-borated succinimide dispersant is from 0.06 to 0.35 pbw, or 0.05 pbw, 0.06 pbw, 0.055 pbw, 0.065 pbw, or 0.057 pbw throughout the composition, It may be present in an amount up to 0.5 pbw, 0.35 pbw, 0.33 pbw, 0.325 pbw, or 0.285 pbw. In certain embodiments, the non-borated succinimide dispersant is present from 0.057 to 0.285 pbw. In other embodiments, the non-borated succinimide dispersant is present from 0.057 to 0.325 pbw.

  In some of these embodiments, the composition contains less than 0.1 pbw fatty carboxylic acid.

  In certain embodiments, the above succinimide dispersant may be borated. Boronated dispersants are well known materials and can be prepared by treating one or more of the dispersants described above with a boring agent (eg, boric acid). Typical conditions include heating the dispersant with boric acid at 100-150 ° C. Alternatively, the dispersant may be treated by reaction with maleic anhydride as described in PCT application US99 / 23940 filed October 13, 1999.

  In certain embodiments, the compositions of the present invention comprise a boronated succinimide dispersant derived from polyisobutylene having a number average molecular weight of 500 to 3000 and a polyethylene polyamine.

  In such embodiments, the boronated succinimide dispersant is from 0.07 to 0.4 pbw, or 0.05 pbw, 0.07 pbw, or 0.067 pbw throughout the composition, 0.5 pbw, 0.4 pbw, 0 It may be present in an amount up to .35 pbw, or 0.335 pbw.

  In some of these embodiments, the composition contains less than 0.1 pbw fatty carboxylic acid.

  The dispersant of the present invention may be a Mannich dispersant. Mannich dispersants are reaction products of hydrocarbyl-substituted phenols, aldehydes, and amines or ammonia, but in the present invention are generally dialkylamines. The hydrocarbyl substituent of the hydrocarbyl-substituted phenol contains 10 to 400 carbon atoms, in other cases 30 to 180 carbon atoms, in further cases 10 or 40 to 110 carbon atoms. Also good. The hydrocarbyl substituent may be derived from an olefin or a polyolefin. Useful olefins include α-olefins (eg, 1-decene), which are commercially available.

Polyolefins that can form hydrocarbyl substituents can be prepared by polymerizing olefin monomers by well-known polymerization methods, which are also commercially available. Olefin monomers include monoolefins (including monoolefins containing 2 to 10 carbon atoms), such as ethylene, propylene, 1-butene, isobutylene, and 1-decene. An especially useful monoolefin source is a _{C 4} refinery stream having a butene content and 30 to 60 wt% isobutene content of 35 to 75 wt%. Useful olefin monomers also include diolefins such as isoprene and 1,3-butadiene. The olefin monomer can also include a mixture of two or more monoolefins, a mixture of two or more diolefins, or a mixture of one or more monoolefins and one or more diolefins. Useful polyolefins include polyisobutylene having a number average molecular weight of 140 to 5000, in other cases 400 to 2500, and in further cases 140 or 500 to 1500. The polyisobutylene may have a vinylidene double bond content of 5 to 69%, 50 to 69% in the second case, and 50 to 95% in the third case. The polyolefin may be a homopolymer prepared from a single olefin monomer or a copolymer prepared from a mixture of two or more olefin monomers. Also possible as a hydrocarbyl substituent source is a mixture of two or more homopolymers, a mixture of two or more copolymers, or a mixture of one or more homopolymers and one or more copolymers.

  Hydrocarbyl substituted phenols can be prepared by alkylating phenol with the olefins or polyolefins described above (eg, polyisobutylene or polypropylene) using well-known alkylation methods.

  The aldehyde used to form the Mannich dispersant may contain 1 to 10 carbon atoms and is generally formaldehyde or a reactive equivalent thereof (eg formalin or paraformaldehyde).

  The amine used to form the Mannich dispersant may be a monoamine or a polyamine (including alkanolamines containing one or more hydroxyl groups). Useful amines include ethanolamine, diethanolamine, methylamine, dimethylamine, ethylenediamine, dimethylaminopropylamine, diethylenetriamine and 2- (2-aminoethylamino) ethanol. Mannich dispersants can be prepared by reacting hydrocarbyl substituted phenols, aldehydes, and amines as described in US Pat. No. 5,697,988. In one embodiment of the invention, the Mannich reaction product is prepared from an alkylphenol derived from polyisobutylene, formaldehyde, and an amine (which is a primary monoamine, secondary monoamine, or alkylene diamine, particularly ethylene diamine or dimethyl amine). The In some embodiments, Mannich is prepared from a dialkylamine or dialkenylamine.

  The Mannich reaction product of the present invention is prepared by reacting alkyl-substituted hydroxyaromatic compounds, aldehydes and polyamines by well-known methods, including those described in US Pat. No. 5,876,468. Can do.

  The Mannich reaction product generally contains hydrocarbyl-substituted hydroxyaromatic compounds, aldehydes and amines while removing water in the presence of a solvent or diluent as described in US Pat. No. 5,876,468. It can be prepared by well-known methods including reacting at a temperature of 50-200 ° C.

  In certain embodiments, the composition of the present invention contains a Mannich reaction product derived from the reaction of a dialkylamine, formaldehyde, and a polyisobutylene substituted phenol, the polyisobutylene having a number average molecular weight of 500-3000. Mannich dispersant is present in the entire composition in an amount from 0.07 to 0.44 pbw, 0.05 pbw, 0.07 pbw, or 0.088 pbw to 0.5 pbw, 0.45 pbw, or 0.44 pbw. May be.

(Additional additives)
Optionally, the lubricating composition of the present invention comprises one or more additional additives, wherein the additional additives are selected from the group comprising foam suppressants, demulsifiers, pour point depressants, or mixtures thereof. Also good. Optional additives are present in the range of 0.0005 to 1.3 pbw, 0.00075 to 0.5 pbw, 0.001 to 0.4 pbw, or 0.0015 to 0.3 pbw of the lubricating oil composition. Optional additives may be used alone or in mixtures thereof.

  Antifoaming agents (also known as foam inhibitors) are known in the art and include, but are not limited to, organic silicones and non-silicon foam inhibitors. Examples of organosilicones include dimethyl silicone and polysiloxane. Examples of non-silicon foam inhibitors include, but are not limited to, poly (ethyl acrylate), poly (2-ethylhexyl acrylate), ethyl acrylate, 2-ethylhexyl acrylate, and optionally a copolymer of vinyl acetate, Polyvinyl acetate, polyether, polyacrylate, and mixtures thereof are included. In certain embodiments, the antifoaming agent is a polyacrylate. Antifoaming agents may be present in the composition from 0.001 to 0.012 or 0.004 pbw, or 0.001 to 0.003 pbw.

  Demulsifiers are known in the art and include, but are not limited to, derivatives of propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkylamines, amino alcohols, diamines or polyamines that are continuously reacted with ethylene oxide or substituted ethylene oxide, or These mixtures are mentioned. Examples of demulsifiers include polyethylene glycol, polyethylene oxide, polypropylene oxide, (ethylene oxide-propylene oxide) polymers, 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; carboxylic acids And vinyl polymers; and dialkyl fumarate, terpolymers of fatty acid vinyl esters, 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 dialkyldithiophosphoric acids, hydrocarbyl amine salts of hydrocarbyl aryl sulfonic acids, fatty carboxylic acids or esters thereof, esters of nitrogen-containing carboxylic acids, ammonium sulfonates , Imidazoline, or any combination thereof, or a mixture thereof.

  Suitable hydrocarbyl amine salts of the alkyl phosphates of the present invention have the formula

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、好ましくは、Ｒ^２１およびＲ^２２の少なくとも１つは、ヒドロカルビルである。Ｒ^２１およびＲ^２２は、約４〜約３０個、好ましくは約８〜約２５個、さらに好ましくは約１０〜約２０個、最も好ましくは約１３〜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、アルキル、約１〜約３０個、好ましくは約４〜約２４個、さらになお好ましくは約６〜約２０個、最も好ましくは約１０〜約１６個の炭素原子を含む分枝鎖または直鎖のアルキル鎖である。Ｒ^２３、Ｒ^２４、およびＲ^２５は、独立して、水素、アルキル、分枝鎖または直鎖のアルキル鎖であり、好ましくは、Ｒ^２３、Ｒ^２４、およびＲ^２５のうち、少なくとも１つ、最も好ましくは、Ｒ^２３、Ｒ^２４、およびＲ^２５のうち２つが水素である。

Where R ²¹ and R ²² are independently hydrogen, an alkyl chain or hydrocarbyl, and preferably at least one of R ²¹ and R ²² is hydrocarbyl. R ²¹ and R ²² contain from about 4 to about 30, preferably from about 8 to about 25, more preferably from about 10 to about 20, and most preferably from about 13 to about 19 carbon atoms. R ²³ , R ²⁴ , and R ²⁵ are independently hydrogen, alkyl, about 1 to about 30, preferably about 4 to about 24, still more preferably about 6 to about 20, most preferably about A branched or straight alkyl chain containing from 10 to about 16 carbon atoms. R ²³ , R ²⁴ , and R ²⁵ are independently hydrogen, alkyl, a branched or straight alkyl chain, and preferably at least one of R ²³ , R ²⁴ , and R ²⁵ , Most preferably, two of R ²³ , R ²⁴ , and R ²⁵ are hydrogen.

Examples of 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, 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. The reaction product of

  The hydrocarbylamine salt of a dialkyldithiophosphate of the present invention for use in a rust inhibitor package has the following formula:

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、好ましくは約４〜約２５個、さらに好ましくは約５〜約２０個、最も好ましくは、約６〜約１９個の炭素原子を含む。Ｒ^２３、Ｒ^２４、およびＲ^２５は、上に記載した通りである。

Where R ²⁶ and R ²⁷ are independently a branched or straight chain alkyl group. R ²⁶ and R ²⁷ contain from about 3 to about 30, preferably from about 4 to about 25, more preferably from about 5 to about 20, and most preferably from 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 heptylated or octylated or nonylated dithiophosphoric acid with ethylenediamine, morpholine, or Primene 81R, or mixtures thereof ( More than one).

  Suitable hydrocarbyl amine salts of hydrocarbyl aryl sulfonic acids for use in the rust inhibitor package of the present invention are represented by the formula

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、好ましくは約６〜約２５個、さらに好ましくは約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、最も好ましくは、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。

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

  Examples of hydrocarbyl amine salts of hydrocarbyl aryl sulfonic acids of the present invention include, but are not limited to, ethylenediamine salts of dinonylnaphthalene sulfonic acid.

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

  The rust inhibitor may be present in the range of 0.02-0.2 pbw, 0.03-0.15 pbw, 0.04-0.12 pbw, or 0.05-0.1 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 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, a derivative of 2-alkyldithio-5-mercaptothiadiazole, or a mixture thereof. Can be mentioned.

  In certain embodiments, the metal deactivator is a hydrocarbyl substituted benzotriazole compound. Examples of the benzotriazole compound having hydrocarbyl substitution include at least one of benzotriazoles having a substituent at the 1-position, 2-position, 4-position, 5-position, 6-position or 7-position. 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 is used alone or as these 5-methylbenzotriazole used in the mixture.

  In certain embodiments, the lubricating composition of the present invention comprises a substituted triazole, and the substituted triazole may be a substituted benzotriazole. In some of these embodiments, the hydrocarbyl group attached to any of the nitrogen atoms of the triazole ring does not contain an oxygen atom.

  In certain embodiments, the substituted triazole has one hydrocarbyl group attached to the nitrogen atom of the triazole ring. In certain embodiments, the substituted triazole comprises an aryl group bonded to the nitrogen atom of the triazole ring and a hydrocarbyl group bonded to the nitrogen atom of the triazole ring.

  In certain embodiments, the substituted triazole has the following formula:

によってあらわされてもよく、またはこれらの組み合わせであり、式中、式Ｘおよび式ＸＩの両方について、ｎは、０〜４の整数であり；−Ｒはヒドロカルビル基であり；−Ｙは、−Ｒ^１または−（Ｒ^２）_ｍ−ＮＲ^３Ｒ^３であり、−Ｒ^１はヒドロカルビル基であり、−Ｒ^２−はヒドロカルビレン基であり、ｍは、０または１または２であり、各−Ｒ^３は、独立して、水素またはヒドロカルビル基であるが、但し、−Ｒ^１、−Ｒ^２−、−Ｒ^３は合わせて７または９から４０個までの炭素原子を含む。ある実施形態では、本発明の置換トリアゾールは、式（Ｘ）によってあらわされる。

Or a combination thereof, wherein for both Formula X and Formula XI, n is an integer from 0 to 4; -R is a hydrocarbyl group; -Y is- R ¹ or — (R ² ) _m —NR ³ R ³ , —R ¹ is a hydrocarbyl group, —R ² — is a hydrocarbylene group, m is 0 or 1 or 2, -R ³ is independently hydrogen or a hydrocarbyl group, provided ^{that, -R 1, -R 2 -,} - R 3 contains a carbon atom from a total of 7 or 9 to 40. In certain embodiments, the substituted triazoles of the present invention are represented by formula (X).

In certain embodiments, n may be from 0 or 1 to 4, 3, 2 or 1; R may be a hydrocarbyl group, 1 to 50 carbon atoms, or 1 or 2 May contain from 1 to 40, 30, 20, 18, or 8 carbon atoms, and in certain embodiments, contains 1 or 2 carbon atoms; in Y, m is 0 or 1 or 2, in some embodiments 1 or 2; R ¹ may be a hydrocarbyl group, from ¹ , 6, 10 or 12 up to 40, 30, 20 or 18 R ² may be a hydrocarbylene group and may be from 1, 6, 10 or 12 to 40, 30, 20, 18 or 8 carbon atoms. Or 1 to 8 carbon atoms, in certain embodiments, 1 It may contain carbon atoms; ^{R 3} may be hydrogen or a hydrocarbyl group, a carbon atom of the 1, 6, 10 or 12, 40,30,20,18 one or up to 8, Or may contain 1 to 8 carbon atoms, and in certain embodiments 8 carbon atoms, provided that Y contains 8 to 40 carbon atoms.

In certain embodiments, —Y is —R ¹ , —R ² —NHH, —R ² —NHR ³ , —R ² —NR ³ R ³ , and the various R groups are six total Y groups. Or, as long as it contains 7 or 9 to 40 carbon atoms, it may have any of the definitions presented above.

  In certain embodiments, all of the hydrocarbyl groups described above do not contain an oxygen atom. In certain embodiments, all of the hydrocarbyl groups described above are purely alkyl groups, except that they contain no heteroatoms and there is one nitrogen atom in the Y group.

  The substituted triazoles of the present invention may be prepared by condensing a basic triazole with an aldehyde and an amine via an acidic -NH group. In certain embodiments, the substituted triazole is a reaction product of a triazole, an aldehyde, and an amine. Suitable triazoles that can be used to prepare the substituted triazoles of the present invention include benzotriazoles, while suitable aldehydes include reactive equivalents such as formaldehyde and formalin, while suitable Examples of such amines include primary amines and secondary amines. In certain embodiments, the amine is a secondary amine and further is a branched amine. In a further embodiment, the amine is a β-branched amine, for example bis-2-ethylhexylamine.

  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 an amount from 0.002 or 0.004 pbw to 0.02 pbw. The metal deactivator may be used alone or in a mixture thereof.

(Industrial use)
The present invention further provides a process for preparing a lubricating oil composition. The lubricating oil composition comprises (a) an antioxidant component comprising a combination of an alkylated diphenylamine and a substituted hydrocarbyl monosulfide and a polyetheramine, boronated succinimide dispersant, non-borated succinimide dispersant, or dialkylamine, aldehyde and It is prepared by mixing and / or dissolving the dispersant component comprising at least one of the Mannich reaction products of the hydrocarbyl-substituted phenol. Optionally, one or more additional additives may be mixed into the oil. Until the additive is substantially or completely dissolved, in some embodiments, at an elevated temperature of 40 ° C to 110 ° C, or 50 ° C to 95 ° C, or 55 ° C to 85 ° C, 30 seconds to 24 hours, 2 minutes to 8 hours. Mix the materials at a pressure of 700 mmHg to 2000 mmHg, 750 mmHg to 900 mmHg, or 755 mmHg to 800 mmHg for a time, or 5 minutes to 4 hours.

  The order in which the additives are added is not so strictly 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 ingredients, and the ingredients are mixed into the oil. In other embodiments, there is a minimum amount of oil or diluent in addition to the amount inherent in the additive from the manufacturing and preparation means, and additional base oil is added after the ingredients are mixed. In certain events, the process described above results in a lubricating composition.

  In certain embodiments, the lubricating oil composition comprises (a) all of the above components, and any mineral oil present, and / or any optional relatively small amount that allows for reasonable handling. It may be prepared from a concentrate comprising a step of mixing with a diluent. The resulting concentrate may then be used in the preparation of a lubricating composition by mixing the concentrate with an effective amount of base oil or a mixture thereof to obtain the final fluid. Optional additives may be added to the concentrate or the resulting final fluid. These optional additives include any of those described above. In certain embodiments, these optional additives include foam suppressants, demulsifiers, viscosity modifiers, pour point depressants, or mixtures thereof, with about 0, 0.01, It may be added to be present in the range from 0.1 or 0.25 pbw, or up to about 13, 10, 8 or 6 pbw.

  The compositions of the present invention may be used as industrial fluids, hydraulic fluids, turbine oils and circulating oils and combinations thereof. In certain embodiments, the composition is used in steam turbine systems and gas turbine systems. The use of a lubricating oil composition in such a system may prevent the formation of deposits and sludge that clog the filters in the turbine, or at least one improvement selected from rust control, oxidation control and mixtures thereof. Characteristics may be given. The present invention further provides a lubricating oil composition that is substantially non-reactive with zinc and / or calcium and can prevent the formation of sludge and particulate matter that accumulates and clogs fine filters. To do.

  The present invention further provides a method of lubricating a steam turbine or gas turbine comprising the step of supplying any of the lubricating compositions described above to the steam turbine or gas turbine.

  The present invention further provides a method for improving the cleanability of a steam turbine or gas turbine comprising the step of supplying any of the lubricating compositions described herein to the steam turbine and gas turbine. When the turbine is operated with the lubricating composition described above, improved cleaning compared to systems operated with conventional lubricants, particularly lubricants formulated in Group II and Group III oils Produces sex.

(Specific embodiment)
The invention is further illustrated by the following examples describing particularly advantageous embodiments. While these examples are given to illustrate the present invention, these examples are not intended to limit the present invention.

(Comparative example group)
In order to better show the effect of the composition of the present invention, three comparative examples are prepared. Then, these comparative examples are included in each Example shown below. Other additives are also present in various formulations when used with any of the following examples. While showing the differences between the example formulations, it is considered to be insignificant for the test results and / or specific details are not expected to affect the results between samples, so complete Details of the formulation are not presented.

  Comparative Examples 1, 2, and 3 are prepared in a Group III base oil blend, respectively. Unless otherwise indicated, the same Group III base oil blends are used in the preparation of all examples described herein. All formulations presented below are based on 100 pbw base oil. Comparative Examples 1, 2, and 3 also include polyether demulsifiers, antiwear agents, antifoaming agents, and metal deactivators. Comparative Examples 1 and 2 contain the same polyether demulsifier, while Comparative Example 3 contains a different polyether demulsifier. Comparative Example 1 contains no dispersant and contains 0.375 pbw alkylated diphenylamine antioxidant and 0.09 pbw substituted hydrocarbyl monosulfide. Comparative Example 2 contains no dispersant and contains 0.51 pbw alkylated diphenylamine antioxidant, 0.09 pbw substituted hydrocarbyl monosulfide, and 0.12 pbw sterically hindered phenol antioxidant. Comparative Example 3 contains no dispersant and contains 0.775 pbw alkylated diphenylamine antioxidant and 0.09 pbw substituted hydrocarbyl monosulfide. For the comparative examples, formulation details and test results obtained are included in the table summarized below for each example group.

(Example group 1)
Examples are prepared such that the formulation includes a polyetheramine dispersant. The following table summarizes these formulations, including those of the comparative examples described above. Except for the differences noted in the tables and annotations, the listed example formulations are substantially equivalent. The value in the table is pbw.

１ −比較例１は、従来の量のポリエーテル解乳化剤、摩耗防止剤、消泡剤、金属不活性化剤も含み、以下、添加剤パッケージＩと呼ばれる。
２ −比較例２は、添加剤パッケージＩも含む。
３ −比較例３は、添加剤パッケージＩと同じ添加剤を同じ量で含むが、但し、具体的なポリエーテル解乳化剤は他の実施例で使用するものと異なる。この添加剤群は、以下、添加剤パッケージＩＩと呼ばれる。
４ −実施例１−Ａは、添加剤パッケージＩも含む。
５ −実施例１−Ｂは、添加剤パッケージＩも含む。
６ −実施例１−Ｃは、添加剤パッケージＩも含む。
７ −実施例１−Ｄは、添加剤パッケージＩも含む。
８ −実施例１−Ｅは、添加剤パッケージＩＩも含む。

1—Comparative Example 1 also includes conventional amounts of polyether demulsifiers, antiwear agents, antifoaming agents, metal deactivators and is hereinafter referred to as additive package I.
2—Comparative Example 2 also includes additive package I.
3—Comparative Example 3 contains the same additives in the same amount as Additive Package I, except that the specific polyether demulsifiers are different from those used in the other examples. This group of additives is hereinafter referred to as additive package II.
4- Example 1-A also includes additive package I.
5- Example 1-B also includes additive package I.
6-Example 1-C also includes additive package I.
7-Example 1-D also includes additive package I.
8-Example 1-E also includes additive package II.

９ −実施例１−Ｆは、上の表１−１に定義されるように、添加剤パッケージＩＩも含む。
１０ −実施例１−Ｇは、添加剤パッケージＩＩのポリエーテル解乳化剤および金属不活性化剤を含むが、摩耗防止剤または消泡剤は含まない。この添加剤群は、以下、添加剤パッケージＩＩＩと呼ばれる。この実施例は、脂肪カルボン酸も含む。
１１ −実施例１−Ｈは、添加剤パッケージＩＩＩと、脂肪カルボン酸エステルも含む。
１２ −実施例１−Ｉは、添加剤パッケージＩＩＩと、サルコシン腐食阻害剤も含む。
１３ −実施例１−Ｊは、添加剤パッケージＩＩＩと、脂肪カルボン酸エステルも含む。
１４ −実施例１−Ｋは、添加剤パッケージＩＩＩと、サルコシン腐食阻害剤も含む。
１５ −実施例１−Ｌは、添加剤パッケージＩＩＩと、脂肪カルボン酸も含むが、実施例１−Ｇで使用する量よりも少ない。
１６ −実施例１−Ｍは、添加剤パッケージＩも含む。

9-Example 1-F also includes Additive Package II as defined in Table 1-1 above.
10-Example 1-G contains the polyether demulsifier and metal deactivator of Additive Package II but no antiwear or antifoam agent. This group of additives is hereinafter referred to as additive package III. This example also includes a fatty carboxylic acid.
11-Example 1-H also includes additive package III and a fatty carboxylic acid ester.
12-Example 1-1 also includes additive package III and a sarcosine corrosion inhibitor.
13-Example 1-J also includes additive package III and a fatty carboxylic acid ester.
14-Example 1-K also includes additive package III and a sarcosine corrosion inhibitor.
15-Example 1-L also contains additive package III and fatty carboxylic acid, but less than the amount used in Example 1-G.
16-Example 1-M also includes additive package I.

These examples are evaluated using ASTM D1401 to evaluate the water separation performance and internal thermal stability test of each sample.

  In the case of ASTM D1401, the test procedure includes a sample containing about 40 ml of the composition of the present invention and about 40 ml of distilled water, and the sample is stirred at about 54 ° C. for about 5 minutes in a graduated cylinder. The resulting mixture is then left for about 30 minutes to allow some separation of water and the composition of the present invention. The amount of separation is measured every 5 minutes after the test. The reported results are based on XYZ, where X indicates the amount of separated oil, Y indicates the amount of separated water, and Z is the oil remaining in the emulsion. And the amount of water. The shorter the time it takes for the sample to reach the reported 40-40-0 or nearly equivalent result, the better the performance.

  The thermal stability test used in this test was conducted in an example formulation sample so that a standard sized copper and steel rod was ground and weighed and then brought into contact with each other at its midpoint. (Creates X). The soaked bar is then held at 135 ° C. ± 1 ° C. for 168 hours. The bars are then ranked for corrosion and weighed. The results reported for this test are: copper rod corrosion grade ranking, steel rod corrosion grade ranking, 100 mL of oil filtered, and filter pad containing accumulated deposits cleaned. The amount of sludge produced, as determined by weighing the dried filter paper and then reporting in mg per 100 ml. Corrosion rank ranking is performed from 1 to 10, where 1 is a newly polished bar and 10 is a heavily corroded bar. The lower the degree of corrosion ranking and the less reported sludge, the better the sample performance.

  The results of this test are presented in the table below. If no results are listed for a particular sample, it indicates that the sample was not tested by the above method.

１７ −Ｄ１４０１法を用い、実施例１−Ｂを３回試験した。ある場合には、サンプルは、３０分で４０−４０−０のランク分けに達しなかった。ある場合には、１５分でサンプルは４０−４０−０のランク分けに達した。ある場合には、サンプルは、１０分で４０−４０−０のランク分けに達した。上の表には真ん中の値を報告し、これがサンプルの性能の公正な表示であると予想される。

Example 1-B was tested three times using the 17-D1401 method. In some cases, the sample did not reach a 40-40-0 ranking in 30 minutes. In some cases, in 15 minutes the sample reached a 40-40-0 ranking. In some cases, the sample reached a 40-40-0 ranking in 10 minutes. The table above reports the middle value, which is expected to be a fair indication of sample performance.

この結果は、許容され得る水分離性も維持しつつ、本発明の組成物が、改良された熱安定性による保護を与えることを示す。ある実施形態では、本発明は、改良された熱安定性と水分離性の両方を与える。

This result shows that the composition of the present invention provides improved thermal stability protection while maintaining acceptable water separation. In certain embodiments, the present invention provides both improved thermal stability and water separation.

(Example group 2)
Examples are prepared such that the formulation includes a boronated succinimide dispersant. The following table summarizes these formulations, including those of the comparative examples described above. Except for the differences noted in the tables and annotations, the listed example formulations are substantially equivalent. The value in the table is pbw.

１ −上の比較例１の詳細を参照。
２ −上の比較例２の詳細を参照。
３ −上の比較例３の詳細を参照。
４ −実施例２−Ａは、上に定義するように、添加剤パッケージＩも含む。
５ −実施例２−Ｂは、添加剤パッケージＩも含む。
６ −実施例２−Ｃは、添加剤パッケージＩと、脂肪カルボン酸も含む。
７ −実施例２−Ｄは、添加剤パッケージＩと、脂肪カルボン酸エステルも含む。
８ −実施例２−Ｅは、添加剤パッケージＩと、サルコシン腐食阻害剤も含む。

1—See details of Comparative Example 1 above.
2—See details of Comparative Example 2 above.
3—See details of comparative example 3 above.
4—Example 2-A also includes additive package I as defined above.
5-Example 2-B also includes additive package I.
6-Example 2-C also includes additive package I and fatty carboxylic acid.
7-Example 2-D also includes additive package I and a fatty carboxylic acid ester.
8-Example 2-E also includes additive package I and a sarcosine corrosion inhibitor.

９ −実施例２−Ｆは、添加剤パッケージＩも含む。
１０ −実施例２−Ｇは、添加剤パッケージＩも含むが、但し、このパッケージ中の金属不活性化剤の量は減らされている。
１１ −実施例２−Ｈは、実施例２−Ｇと同じ添加剤パッケージを含む。

9-Example 2-F also includes additive package I.
10-Example 2-G also includes additive package I, except that the amount of metal deactivator in this package is reduced.
11-Example 2-H includes the same additive package as Example 2-G.

  As described in the above section, ASTM D1401 is used to evaluate these examples to evaluate the water separation performance and internal thermal stability test of each sample. The results of this test are presented in the table below. If no results are listed for a particular sample, it indicates that the sample was not tested by the above method.

この結果は、許容され得る水分離性も維持しつつ、本発明の組成物が、改良された熱安定性による保護を与えることを示す。ある実施形態では、本発明は、改良された熱安定性と水分離性の両方を与える。

This result shows that the composition of the present invention provides improved thermal stability protection while maintaining acceptable water separation. In certain embodiments, the present invention provides both improved thermal stability and water separation.

(Example group 3)
Examples are prepared such that the formulation includes a non-borated succinimide dispersant. The following table summarizes these formulations, including those of the comparative examples described above. Except for the differences noted in the tables and annotations, the listed example formulations are substantially equivalent. The value in the table is pbw.

１ −上の比較例１の詳細を参照。
２ −上の比較例２の詳細を参照。
３ −上の比較例３の詳細を参照。
４ −実施例３−Ａは、上に定義されるように、添加剤パッケージＩも含む。
５ −実施例３−Ｂは、添加剤パッケージＩも含む。
６ −実施例３−Ｃは、上に定義されるように、添加剤パッケージＩＩも含む。
７ −実施例３−Ｄは、添加剤パッケージＩＩと、脂肪カルボン酸も含む。
８ −実施例３−Ｅは、添加剤パッケージＩと、サルコシン腐食阻害剤も含む。

1—See details of Comparative Example 1 above.
2—See details of Comparative Example 2 above.
3—See details of comparative example 3 above.
4—Example 3-A also includes additive package I as defined above.
5-Example 3-B also includes additive package I.
6-Example 3-C also includes additive package II, as defined above.
7-Example 3-D also includes additive package II and a fatty carboxylic acid.
8-Example 3-E also includes additive package I and a sarcosine corrosion inhibitor.

９ −実施例３−Ｆは、上に定義されるように、添加剤パッケージＩＩのうち、消泡剤、ポリエーテル解乳化剤、および金属不活性化剤も含むが、摩耗防止剤は含まない。この添加剤群は、以下、添加剤パッケージＩＶと呼ばれる。この実施例は、脂肪カルボン酸も含むが、実施例３−Ｄより量が少ない。
１０ −実施例３−Ｇは、添加剤パッケージＩＶを含み、実施例３−Ｄと同じ量で脂肪カルボン酸も含む。
１１ −実施例３−Ｈは、添加剤パッケージＩと、サルコシン腐食阻害剤も含む。
１２ −実施例３−Ｉは、添加剤パッケージＩも含み、非ホウ素化スクシンイミド分散剤は、他の実施例で使用したものよりも分子量が大きい。
１３ −実施例３−Ｊは、添加剤パッケージＩも含み、実施例３−Ｉの分子量がより大きな非ホウ素化スクシンイミド分散剤も含む。

9-Example 3-F also includes antifoaming agent, polyether demulsifier, and metal deactivator of additive package II as defined above, but no antiwear agent. This group of additives is hereinafter referred to as additive package IV. This example also contains a fatty carboxylic acid, but in less amount than Example 3-D.
10-Example 3-G includes additive package IV and also includes fatty carboxylic acid in the same amount as Example 3-D.
11-Example 3-H also includes additive package I and a sarcosine corrosion inhibitor.
12-Example 3-I also includes additive package I, where the non-borated succinimide dispersant has a higher molecular weight than that used in the other examples.
13-Example 3-J also includes additive package I and also includes a non-borated succinimide dispersant with the higher molecular weight of Example 3-I.

  As described in the above section, ASTM D1401 is used to evaluate these examples to evaluate the water separation performance and internal thermal stability test of each sample. The results of this test are presented in the table below. If no results are listed for a particular sample, it indicates that the sample was not tested by the above method.

この結果は、許容され得る水分離性も維持しつつ、本発明の組成物が、改良された熱安定性による保護を与えることを示す。ある実施形態では、本発明は、改良された熱安定性と水分離性の両方を与える。

This result shows that the composition of the present invention provides improved thermal stability protection while maintaining acceptable water separation. In certain embodiments, the present invention provides both improved thermal stability and water separation.

(Example group 4)
Examples are prepared such that the formulation includes a Mannich reaction product of dialkylamine, aldehyde and hydrocarbyl substituted phenol. The following table summarizes these formulations, including those of the comparative examples described above. Except for the differences noted in the tables and annotations, the listed example formulations are substantially equivalent. The value in the table is pbw.

１ −上の比較例１の詳細を参照。
２ −上の比較例２の詳細を参照。
３ −上の比較例３の詳細を参照。
４ −実施例４−Ａは、上に定義されるように、添加剤パッケージＩも含む。
５ −実施例４−Ｂは、添加剤パッケージＩも含む。

1—See details of Comparative Example 1 above.
2—See details of Comparative Example 2 above.
3—See details of comparative example 3 above.
4-Example 4-A also includes additive package I as defined above.
5- Example 4-B also includes additive package I.

  As described in the above section, ASTM D1401 is used to evaluate these examples to evaluate the water separation performance and internal thermal stability test of each sample. The results of this test are presented in the table below. If no results are listed for a particular sample, it indicates that the sample was not tested by the above method.

この結果は、許容され得る水分離性も維持しつつ、本発明の組成物が、改良された熱安定性による保護を与えることを示す。ある実施形態では、本発明は、改良された熱安定性と水分離性の両方を与える。

This result shows that the composition of the present invention provides improved thermal stability protection while maintaining acceptable water separation. In certain embodiments, the present invention provides both improved thermal stability and water separation.

  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 after 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 has its ordinary meaning, which is well known to those skilled in the art. Specifically, these terms are composed primarily of carbon and hydrogen atoms, and are bonded to the rest of the molecule through the carbon atom, which impairs the properties of molecules that have predominantly hydrocarbon character. Refers to a group that does not exclude the presence of other atoms or groups in an insufficient ratio. Generally, there are no more than 2, preferably no more than 1 non-hydrocarbon substituent for every 10 carbon atoms in the hydrocarbyl group. Typically, there are no non-hydrocarbon substituents on the hydrocarbyl group. A more detailed definition of the term “hydrocarbyl substituent” or “hydrocarbyl group” is described in US Pat. No. 6,583,092.

によってあらわされ、式中、Ｒ ^１ およびＲ ^２ は、独立して、水素であるか、または約５〜２０個の炭素原子を含むアルキル基；または１〜２４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り、ｑおよびｒは、それぞれ独立して、０、１、２または３であり、但し、ｑとｒの合計は、少なくとも１である、上記項１に記載の組成物。
（項６）
前記置換ヒドロカルビルモノスルフィドが、以下の式

によってあらわされ、式中、Ｒ ^３ は、約８〜約２０個の炭素原子を含む飽和または不飽和の分枝鎖または直鎖のアルキル基であり；Ｒ ^４ 、Ｒ ^５ 、Ｒ ^６ 、およびＲ ^７ は、独立して、水素であるか、または約１〜約３個の炭素原子を含むアルキルである、上記項１に記載の組成物。
（項７）
前記置換ヒドロカルビルモノスルフィドは、ｎ−ドデシル２−ヒドロキシエチルスルフィド、１−（ｔｅｒｔ−ドデシルチオ）−２−プロパノール、またはこれらの混合物である、上記項６に記載の組成物。
（項８）
前記分散剤成分が、１０〜１８個の炭素原子を含むアルコールの混合物と、アルコキシレートとアミンとの反応から誘導されるポリエーテルアミンを含み；
前記酸化防止成分が、前記組成物全体に０．８６５重量部未満の量で存在し；
前記組成物は、Ｎ−アルキルサルコシンを含まず；
前記組成物が、０．１重量部未満の脂肪カルボン酸を含有し；
前記分散剤成分が、前記組成物全体に０．０７〜０．４重量部の量で存在する、上記項１に記載の組成物。
（項９）
前記分散剤成分は、数平均分子量が５００〜３０００のポリイソブチレンとポリエチレンポリアミンとから誘導されるホウ素化スクシンイミド分散剤を含み、
前記分散剤成分は、前記組成物全体に０．０７から０．４重量部未満の量で存在する、上記項１に記載の組成物。
（項１０）
前記分散剤成分が、数平均分子量が５００〜３０００のポリイソブチレンとポリエチレンポリアミンとから誘導される非ホウ素化スクシンイミド分散剤を含み、
前記組成物が０．１重量部未満の脂肪カルボン酸を含有し、
前記分散剤成分は、前記組成物全体に０．０６〜０．３５重量部の量で存在する、上記項１に記載の組成物。
（項１１）
前記分散剤成分が、ジアルキルアミン、ホルムアルデヒド、およびポリイソブチレン置換フェノールの反応から誘導されるマンニッヒ反応生成物を含み、前記ポリイソブチレンは、数平均分子量が５００〜３０００であり；
前記分散剤成分は、組成物全体に０．０７〜０．４４重量部の量で存在する、上記項１に記載の組成物。
（項１２）
前記金属不活性化剤は、ヒドロカルビル置換ベンゾトリアゾール、５−メチルベンゾトリアゾール、およびこれらの混合物を含む群から選択される、上記項１に記載の潤滑組成物。
（項１３）
前記添加成分（ｂ）〜（ｄ）は、前記組成物全体の約０〜約１３重量部の範囲である、上記項１に記載の組成物。
（項１４）
（Ｉ）
（ａ）グループＩＩ基油、グループＩＩＩ基油またはこれらの組み合わせを含む、潤滑粘度の油と、
（ｂ）
（ｉ）アルキル化ジフェニルアミン、および
（ｉｉ）置換ヒドロカルビルモノスルフィド
を含む酸化防止成分と、
（ｃ）
（ｉ）ポリエーテルアミン、
（ｉｉ）ホウ素化スクシンイミド分散剤、
（ｉｉｉ）非ホウ素化スクシンイミド分散剤、
（ｉｖ）ジアルキルアミン、アルデヒド、ヒドロカルビル置換フェノールのマンニッヒ反応生成物
のうち、少なくとも１つを含む分散剤成分と、
（ｄ）任意選択で、他の添加剤と
を一緒に混合する工程を含む、潤滑油組成物を調製するプロセス。
（項１５）
前記酸化防止剤パッケージが、前記組成物全体の０．０５〜１３重量部の範囲にあり；前記分散剤成分が、前記組成物全体の０．０５〜１０重量部の範囲であり；任意選択の添加剤は、存在する場合、前記組成物全体の０．００１〜１０重量部の量で存在し；残りの部分が潤滑粘度の油で構成される、上記項１４に記載のプロセス。 Each of the documents listed above is incorporated herein by reference. Unless otherwise stated or otherwise explicitly stated, any quantity specifying the amount of material, reaction conditions, molecular weight, number of carbon atoms, etc. in this specification is qualified with the term “about”. Should be understood. 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 should be construed as a commercial grade material, including isomers, by-products, derivatives, and It may include other such materials that are normally understood to be in commercial grade. However, the amount of each chemical component is usually an abundance excluding any solvents or diluents that may be present in commercially available materials, unless otherwise indicated. It is to be understood that the upper and lower limits of values, ranges and ratios set forth herein may be independently combined. Similarly, the range and amount of each element of the invention may be used in combination with the range or amount of any other element. As used herein, the expression “consisting essentially of” permits inclusion of substances that do not have a significant effect on the basic and new characteristics of the composition under consideration.
According to a preferred embodiment of the present invention, for example, the following is provided.
(Claim 1)
A lubricating oil composition comprising:
(A) an oil of lubricating viscosity comprising a Group II base oil, a Group III base oil or a combination thereof;
(B)
(I) alkylated diphenylamine, and
(Ii) substituted hydrocarbyl monosulfides
An antioxidant component comprising,
(C)
(I) polyetheramine,
(Ii) a borated succinimide dispersant,
(Iii) a non-borated succinimide dispersant,
(Iv) Mannich reaction products of dialkylamines, aldehydes, and hydrocarbyl substituted phenols
A dispersant component comprising at least one of
(D) optionally, one or more additional additives
And a lubricating oil composition.
(Section 2)
The composition of claim 1, wherein component (d) comprises a rust inhibitor, a metal deactivator, a demulsifier, an antifoam agent, or a combination thereof.
(Section 3)
Component (b) is present in the entire composition in an amount of 0.1 to 0.9 parts by weight, and Component (c) is present in the entire composition in an amount of 0.05 to 0.5 parts by weight. Item 2. The composition according to Item 1.
(Section 4)
The rust inhibitor comprises an amine phosphate, a fatty carboxylic acid or ester thereof, an ester of a nitrogen-containing carboxylic acid, ammonium sulfonate, imidazoline, or combinations thereof;
The metal deactivator comprises triazole, tolyltriazole, thiadiazole, or combinations thereof;
The demulsifier comprises a polyether;
Item 3. The composition according to Item 2, wherein the antifoaming agent comprises an acrylate copolymer.
(Section 5)
The alkylated diphenylamine has the following formula:

In which R ¹ and R ² are independently hydrogen or an alkyl group containing about 5 to 20 carbon atoms; or a straight chain containing 1 to 24 carbon atoms or Item 2. The composition according to Item 1, wherein each is a branched alkyl group, and q and r are each independently 0, 1, 2, or 3, provided that the sum of q and r is at least 1. object.
(Claim 6)
The substituted hydrocarbyl monosulfide has the following formula:

Wherein R ³ is a saturated or unsaturated branched or straight chain alkyl group containing from about 8 to about 20 carbon atoms; R ⁴ , R ⁵ , R ⁶ , and R Item 7. The composition according to Item 1, wherein ⁷ is independently hydrogen or alkyl containing about 1 to about 3 carbon atoms.
(Claim 7)
Item 7. The composition according to Item 6, wherein the substituted hydrocarbyl monosulfide is n-dodecyl 2-hydroxyethyl sulfide, 1- (tert-dodecylthio) -2-propanol, or a mixture thereof.
(Section 8)
The dispersant component comprises a mixture of alcohols containing 10 to 18 carbon atoms and a polyetheramine derived from the reaction of an alkoxylate and an amine;
The antioxidant component is present in an amount of less than 0.865 parts by weight throughout the composition;
The composition does not comprise N-alkyl sarcosine;
The composition contains less than 0.1 parts by weight of a fatty carboxylic acid;
Item 2. The composition according to Item 1, wherein the dispersant component is present in the entire composition in an amount of 0.07 to 0.4 parts by weight.
(Claim 9)
The dispersant component includes a boronated succinimide dispersant derived from polyisobutylene having a number average molecular weight of 500 to 3000 and polyethylene polyamine,
Item 2. The composition according to Item 1, wherein the dispersant component is present in the entire composition in an amount of 0.07 to less than 0.4 parts by weight.
(Section 10)
The dispersant component comprises a non-borated succinimide dispersant derived from a polyisobutylene having a number average molecular weight of 500 to 3000 and a polyethylene polyamine;
The composition contains less than 0.1 parts by weight of a fatty carboxylic acid;
The composition according to Item 1, wherein the dispersant component is present in the whole composition in an amount of 0.06 to 0.35 parts by weight.
(Item 11)
The dispersant component comprises a Mannich reaction product derived from the reaction of a dialkylamine, formaldehyde, and a polyisobutylene-substituted phenol, the polyisobutylene having a number average molecular weight of 500 to 3000;
Item 2. The composition according to Item 1, wherein the dispersant component is present in the entire composition in an amount of 0.07 to 0.44 parts by weight.
(Clause 12)
The lubricating composition of claim 1, wherein the metal deactivator is selected from the group comprising hydrocarbyl substituted benzotriazole, 5-methylbenzotriazole, and mixtures thereof.
(Section 13)
Item 2. The composition according to Item 1, wherein the additive components (b) to (d) are in the range of about 0 to about 13 parts by weight of the total composition.
(Item 14)
(I)
(A) an oil of lubricating viscosity comprising a Group II base oil, a Group III base oil or a combination thereof;
(B)
(I) alkylated diphenylamine, and
(Ii) substituted hydrocarbyl monosulfides
An antioxidant component comprising,
(C)
(I) polyetheramine,
(Ii) a borated succinimide dispersant,
(Iii) a non-borated succinimide dispersant,
(Iv) Mannich reaction product of dialkylamine, aldehyde, hydrocarbyl substituted phenol
A dispersant component comprising at least one of
(D) optionally with other additives
A process for preparing a lubricating oil composition comprising mixing together.
(Section 15)
The antioxidant package is in the range of 0.05 to 13 parts by weight of the total composition; the dispersant component is in the range of 0.05 to 10 parts by weight of the total composition; optional Item 15. The process of Item 14, wherein the additive, if present, is present in an amount of 0.001 to 10 parts by weight of the total composition; the remaining portion is comprised of oil of lubricating viscosity.

Claims (18)

A lubricating oil composition comprising:
(A) an oil of lubricating viscosity comprising a Group II base oil, a Group III base oil or a combination thereof;
(B)
An antioxidant component comprising (i) an alkylated diphenylamine, and (ii) a substituted hydrocarbyl monosulfide;
(C)
(I) polyetheramine,
(Ii) a borated succinimide dispersant,
(Iii) a non-borated succinimide dispersant,
(Iv) Among the dialkyl amine, aldehyde, and Mannich reaction products of hydrocarbyl-substituted phenols, and a dispersing agent Ingredient containing at least one lubricating oil composition. The composition of claim 1, further comprising:
(D) one or more additional additives
A composition comprising: The composition of claim 2 , wherein component (d) comprises a rust inhibitor, a metal deactivator, a demulsifier, an antifoam agent, or a combination thereof. Component (b) is present in the entire composition in an amount of 0.1 to 0.9 parts by weight, and Component (c) is present in the entire composition in an amount of 0.05 to 0.5 parts by weight. The composition according to claim 1 or 2 . The rust inhibitor comprises an amine phosphate, a fatty carboxylic acid or ester thereof, an ester of a nitrogen-containing carboxylic acid, ammonium sulfonate, imidazoline, or combinations thereof;
The metal deactivator comprises triazole, tolyltriazole, thiadiazole, or combinations thereof;
The demulsifier comprises a polyether;
4. The composition of claim 3 , wherein the antifoam agent comprises an acrylate copolymer. The alkylated diphenylamine has the following formula:

Wherein R ¹ and R ² are independently hydrogen or an alkyl group containing 5 to 20 carbon atoms; or a straight chain or moiety containing 1 to 24 carbon atoms; an alkyl group of Edakusari, q and r are each independently 0, 1, 2 or 3, with the proviso that the sum of q and r is at least 1, according to claim 1 or 2 Composition. The substituted hydrocarbyl monosulfide has the following formula:

Where R ³ is a saturated or unsaturated branched or straight chain alkyl group containing from 8 to 20 carbon atoms; R ⁴ , R ⁵ , R ⁶ , and R ⁷ The composition according to claim 1 or 2 , wherein is independently hydrogen or alkyl containing 1 to 3 carbon atoms. 8. The composition of claim 7 , wherein the substituted hydrocarbyl monosulfide is n-dodecyl 2-hydroxyethyl sulfide, 1- (tert-dodecylthio) -2-propanol, or a mixture thereof. The dispersant component comprises a mixture of alcohols containing 10 to 18 carbon atoms and a polyetheramine derived from the reaction of an alkoxylate and an amine;
The antioxidant component is present in an amount of less than 0.865 parts by weight throughout the composition;
The composition does not comprise N-alkyl sarcosine;
The composition contains less than 0.1 parts by weight of a fatty carboxylic acid;
The composition according to claim 1 or 2 , wherein the dispersant component is present in an amount of 0.07 to 0.4 parts by weight throughout the composition. The dispersant component includes a boronated succinimide dispersant derived from polyisobutylene having a number average molecular weight of 500 to 3000 and polyethylene polyamine,
3. A composition according to claim 1 or 2 , wherein the dispersant component is present in an amount of 0.07 to less than 0.4 parts by weight throughout the composition. The dispersant component comprises a non-borated succinimide dispersant derived from a polyisobutylene having a number average molecular weight of 500 to 3000 and a polyethylene polyamine;
The composition contains less than 0.1 parts by weight of a fatty carboxylic acid;
The composition according to claim 1 or 2 , wherein the dispersant component is present in an amount of 0.06 to 0.35 parts by weight throughout the composition. The dispersant component comprises a Mannich reaction product derived from the reaction of a dialkylamine, formaldehyde, and a polyisobutylene-substituted phenol, the polyisobutylene having a number average molecular weight of 500 to 3000;
The composition according to claim 1 or 2 , wherein the dispersant component is present in an amount of 0.07 to 0.44 parts by weight throughout the composition. The lubricating composition of claim 3 , wherein the metal deactivator is selected from the group comprising hydrocarbyl substituted benzotriazole, 5-methylbenzotriazole, and mixtures thereof. The composition according to claim 2 , wherein the additive components (b) to (d) are in the range of 0 to 13 parts by weight of the entire composition. (I)
(A) an oil of lubricating viscosity comprising a Group II base oil, a Group III base oil or a combination thereof;
(B)
An antioxidant component comprising (i) an alkylated diphenylamine, and (ii) a substituted hydrocarbyl monosulfide;
(C)
(I) polyetheramine,
(Ii) a borated succinimide dispersant,
(Iii) a non-borated succinimide dispersant,
(Iv) a dispersant component comprising at least one of Mannich reaction products of dialkylamine, aldehyde, hydrocarbyl substituted phenol;
The comprising mixing together, a process for preparing a lubricating oil composition. The process according to claim 15, wherein step (I) further comprises:
(D) Other additives
Process, including mixing together. The antioxidant package is in the range of 0.05 to 13 parts by weight of the total composition; the dispersant component is in the range of 0.05 to 10 parts by weight of the total composition; and the remaining portion is constituted by an oil of lubricating viscosity, the process according to claim 1 5. The antioxidant package is in the range of 0.05 to 13 parts by weight of the total composition; the dispersant component is in the range of 0.05 to 10 parts by weight of the total composition; The process according to claim 16, wherein the additive is present in an amount of 0.001 to 10 parts by weight of the total composition; and the remaining part is composed of oil of the lubricating viscosity.