TW200302270A - Lubricating compositions and concentrates containing an antiwear amount of a thiadiazole - Google Patents

Abstract

This invention relates to lubricating compositions comprising a major amount of an oil of lubricating viscosity and at least about 0.4% by weight of at least one amine free thiadiazole, wherein the lubricating composition is free of organic polysulfides and contains less than about 2% by weight of at least one dispersant. The invention also relates to concentrates and methods of using the lubricating compositions to control micro pitting. The lubricants provide improved performance for both macro and micro pitting, especially micro pitting.

Description

200302270 议, Capsule discussion [Technical Field of the Invention] The present invention relates to a lubricating composition and a concentrate containing amine-free thiadiazole. Thiadiazole systems exist to provide improved surface fatigue properties. Lubricants are typically manual transmission fluids and industrial gear oils. [Prior Art] Background of the Invention Surface fatigue, commonly known as pitting or spalling, is a wear mode in which material is lost as a result of repeated stress cycles on the surface. For years, science has sought to use lubricant additives to control large-scale wear and tear of equipment. Additives with active sulfur and phosphorus have been used to control wear. Wear is typically revealed on the surface of the equipment. Design tests to determine the degree of wear protection provided by the additive. These tests include 4-ball wear test, FZG gear test, etc. There are two main subfamilies of surface fatigue known as micro and large erosion spots. As their name implies, the type of erosion spots is related to the size of the erosion spots. Large pits are usually visible to the naked eye as irregularly shaped holes on the tooth surface. Lesions starting with a diameter grade of 0.5 to 1.0 mm are considered large lesions. Micro-etching is a fatigue phenomenon that can begin at or near the surface of the gear teeth. Cracks usually travel a short distance at the concave corners of the surface before turning or branching back to the surface. Finally, the material is expelled from the surface to form pits. An irregularly shaped cavity in the surface of the material. In the case of gears, the origin of cracks is more likely to start at the surface, because the lubricant film has a low thickness, 200302270, resulting in a high amount of roughness or metal-to-metal contact. For high-speed gears with smooth surface etchants, the film thickness is large and crack formation starting under the surface can account for the majority. In these cases, inclusions or small voids in the material are a source of stress concentration. Microcorrosion is a fatigue phenomenon that occurs in Hertzian contact that operates under elastic hydrodynamic or boundary lubrication conditions and has combined rolling and sliding. In addition to operating conditions (such as load, speed, slip, temperature, and specific film thickness), the chemical composition of the lubricant strongly affects micro-etched spots. Damage can begin during the first 105 to 106 stress cycles and cause many surface cracks. These cracks form micro-etched spots on the concave corners of the surface about 10-20 microns deep, about 25-100 microns long, and 10-20 microns wide. The micro-eroded spot appears to the observer as a matte, matte surface. Micro-etched spots are the better name for this damage modality, but they have also been referred to as grey spots, grey spots, frosting and flaking. Although microuranium lesions usually occur in heavily loaded carburized gears, they also occur in nitrided, hardened, and fully hardened gears. Micro-etching spots can be prevented after commissioning. However, if micro-etched spots continue to progress, it may cause reduced gear tooth accuracy, increased dynamic loading and noise. Finally, it can progress to large pits and gear failure. It would be desirable to have a lubricant that provides improved wear protection, and in particular improved protection against pitting. [Summary of the Invention] The invention relates to a lubricating composition comprising a large amount of oil having a lubricating 200302270 viscosity and at least about 0.4% by weight of at least one amine-free warm diazole, wherein the lubricating composition is free of organic polysulfides and Contains less than about 2% by weight of at least one dispersant. The invention also relates to a concentrate and a method for controlling surface fatigue using a lubricating composition. Lubricants provide improved performance for surface fatigue. [Embodiment] Detailed description of preferred specific examples The term "hydrocarbon group" includes hydrocarbons and essentially hydrocarbon groups. Substantially hydrocarbons describe groups containing heteroatom substituents that do not alter the group's primary hydrocarbon properties. Examples of hydrocarbyl groups include the following: (1) Hydrocarbon substituents, that is, aliphatic (eg, alkyl or alkenyl), cycloaliphatic (eg, cycloalkyl, cycloalkenyl) substituents, via aromatic, Aliphatic and cycloaliphatic substituted aromatic and analogues, as well as cyclic substituents in which the ring is completed via other parts of the molecule (ie, for example, any two of the substituents shown may form an alicyclic group together ); (2) Substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups, which do not change the main hydrocarbon properties of the substituents in the context of the present invention; those skilled in the art will know such groups (For example, halo (especially chloro and fluoro), hydroxyl, fluorenyl, nitro, nitroso, sulfoxy (SUlf0Xy), etc.); (3) heteroatom substituents, that is, when in When having a predominantly hydrocarbon nature in the context of the present invention, it will include substituents other than carbon atoms present in a ring or chain consisting of carbon atoms (eg, alkoxy or alkylthio). Appropriate heteroatoms are readily apparent to those of ordinary skill and include, for example, sulfur, 200302270 oxygen, nitrogen, and such substituents such as, for example, pyridyl, furyl, thienyl, imidazolyl, and the like. Generally, there are no more than about 2 or no more than one hetero-substituent per ten carbon atoms in the hydrocarbyl group. Typically ' there will be no such heteroatom substituents in the hydrocarbyl group. Thus, hydrocarbyl is purely hydrocarbon. The term "organic polysulfide" refers to a sulfide-linked organic compound containing two or more sulfur atoms. The sulfide linkage typically extends between two or more unsaturated compounds (such as olefins). These organic polysulfides have been referred to as polysulfide olefins, and are exemplified by the reaction of olefins with sulfur, sulfur compounds, or combinations thereof to form reaction products containing an average of more than one sulfur atom per olefin. These products are often referred to as polysulfide olefins or polysulfides. Examples of these products are the reaction products of isobutylene, sulfur and hydrogen sulfide under pressure. In the scope of the description and patent application, the term "lubricating composition" refers to a composition of oil and additives having a lubricating viscosity. Weight percentages are based on the total amount of additives and oils with lubricating viscosity. If not explicitly stated, the oil with lubricating viscosity constitutes the balance of the lubricating composition. As described herein, the lubricating composition comprises less than about 2% by weight of at least one dispersant. When the dispersant content exceeds about 2% by weight, the lubricating composition is more sensitive to foaming. Foaming destroys the ability of lubricants to form a protective layer on the surface of equipment such as gears and pinions of manual transmissions or industrial gear accessories. In a specific example, the dispersant is present in an amount of less than about 1.5%, or less than about 1% by weight. In another specific example, the lubricating composition is free of one or all of the dispersants described below. In another specific example, the lubricating composition is free of a dispersant. 200302270 As mentioned above, the lubricating composition contains at least about 0.4% of at least one amine-free thiadiazole. The thiadiazoles are typically oil soluble or oil dispersible. The term "amine-free" refers to thiadiazole derivatives prepared without the use of amines. Amine-free thiadiazoles are those that are not amine salts or amine coupling when added to lubricating oils. The amine-free thiadiazole derivative of the present invention was prepared without using an amine. In a specific example, the lubricating composition comprises at least one thiadiazole compound of at least about 0.6% by weight, or at least about 0.8% by weight or at least about 0.9% by weight. In a specific example, the lubricating composition comprises at least one thiadiazole compound up to about 8% by weight, or up to about 5% by weight, or up to about 3% by weight. In another specific example, thiadiazole provides the sole sulfur to the lubricating composition from the additive. It should be noted that oils with lubricating viscosity may originally contain sulfur. The present invention includes derivatives of thiadiazole. Thiadiazole is a cyclic compound in which the ring contains 2 nitrogen, 2 carbon, and 1 sulfur atom. They are discussed by W. R. Sherman, "Warm Two Sits" by Heterocyclic Compounds, edited by R. C. Elderfield, Volume 7, John Weiss & Sons, New York, pp. 541-426, 1961. The synthesis and properties of many thiadiazoles are disclosed in this reference. Examples of thiadiazoles include 2,5_ substituted 1,3,4-thiadiazole; 3,5_ substituted 1,2,4-thiadiazole; 3,4- substituted 1,2 , 5-thiadiazole; and 4,5-substituted 1,2,3-thiadiazole. The easiest compound to be obtained and particularly effective for the purposes of the present invention is 2,5-substituted 1,3,4-thiadiazole, an example of which is 2,5-diazyl-1,3,4-thiadi The azole, sometimes referred to herein as "DMTD". However, it should be understood that the term DMTD, as used herein, may include any difluorenyl-diazoles or a mixture of two or more difluorenylthiadiazoles. 2,5-Difluorenyl-1,3,4-thiadiazole is conveniently prepared as the reaction of 1 mole of hydrazine or a salt of hydrazine with 2 moles of 200302270 carbon disulfide in an alkaline medium. The product can be recovered by acidification of the reaction mixture. Thiadiazole derivatives include a) mono- or di-substituted hydrocarbylthio or hydrodithio substituted thiadiazoles; b) carboxylic acid esters of DMTD; c) condensation products of halogenated aliphatic monocarboxylic acids and DMTD; d) reaction products of unsaturated cyclic hydrocarbons and unsaturated ketones with DMTD; e) reaction products of aldehydes and alcohols or aromatic hydroxy compounds with DMTD; f) reaction products of aldehydes, thiols and DMTD; and g) two or The above mixture. Compositions a-g are disclosed in U.S. Patent No. 4,612,129 and patent references cited therein. This patent is therefore incorporated by reference. In a specific example, thiadiazole derivatives include mono- or di-substituted thiadiazoles having a hydrocarbon thio group, a hydrocarbon dithio group, or a mixture of these groups. Examples of these thiadiazoles include hydrocarbylthio, fluorenylthiadiazole; bis- (hydrocarbylthio) diadiazole; hydrocarbyldithio, fluorenylthiadiazole; and bis- (hydrocarbyldithio) thiadi Azole. It should be understood that the hydrocarbyl groups on the thiadiazole may be the same or different. Such hydrocarbon groups may be aliphatic or aromatic, and include alkyl, cyclic, alicyclic, aralkyl, aryl, and alkylaryl. In a specific example, the hydrocarbyl group independently contains from 1 to about 30, or from about 2 to about 24, or from about 4 to about 12 carbon atoms. Limitations of scope or proportions may be combined herein and in the scope of the specification and patent application. Examples of special hydrocarbon groups may be alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl or dodecyl, undecyl, dodecyl, hexadecyl And its isomers. The 1,3,4-thiadiazole compounds, or mixtures thereof, intended for use in the present invention are readily available from commercial sources such as Amoco Petroleum Additives, or 11 200302270 can be synthesized in a known manner from hydrazine and carbon disulfide. Particularly effective thiadiazoles include those commercially available under the trade names "Amoco-153" and "Amoco-158" from Amoco Petroleum Additives. 2,5-bis- (hydrocarbon dithio) · ι, 3,4-thiadiazole and its mono-substituted equivalent 2-alkylthio-5-fluorenyl-1,3,4-thiadiazole, in A mixture of two compounds at about 85 percent bis-hydrocarbyl versus 15 percent monohydrocarbyl is commercially available from Ethyl Corporation as Hitec 4313. U.S. Patents 2,719,125; 2,719,126; 2,765,289; 2,749,311; 2,760,933; 2,850,453; 2,910,439; 3,087,937; 3,663,561; 3,862,798; and 3,840,549 can be used as a reference for the preparation of 1,3,4-thiadiazole compounds to be used in the lubricating composition of the present invention detailed steps. These patents are incorporated herein by reference. The steps for preparing these derivatives are disclosed in U.S. Patent No. 2,191,125, and include the reaction of DMTD with an appropriate sulfenyl chloride, or by reacting difluorenylthiadiazole with chlorine and the resulting sulfenyl醯 Chlorine reacts with primary or tertiary thiols. Appropriate sulfenyl chloride which can be used in the first step can be obtained by chlorochlorothiol (RSH or RSH) in carbon tetrachloride. In the second step, DMTD is chlorinated to form the desired disulfenyl chloride, which is then reacted with at least one thiol (RSH and / or RSH). The disclosures of U.S. Patents 2,719,125; 2,719,126; and 3,087,937 are incorporated herein by reference for their disclosure of DMTD derivatives that can be used in the compositions of the present invention. U.S. Patent No. 3,087,932 describes a one-step process for preparing 2,5-bis (hydrocarbon dithio) -1,3,4-diazole. The method includes the reaction of DMTD or its alkali metal or ammonium salt and a thiol in the presence of hydrogen peroxide and a solvent.

The oil-soluble or oil-dispersible reaction products of DMTD can also be prepared by the reaction of DMTD 12 200302270 with thiols and formic acid. The composition prepared in this way is disclosed in U.S. Patent No. 2,749,311. Any thiol can be used in the reaction, such as aliphatic and aromatic mono- or poly-thiols containing from 1 to about 30 or from about 2 to about 18 carbon atoms. The disclosures of U.S. Patent Nos. 3,087,932 and 2,749,31 1 are hereby incorporated herein by reference for their disclosure of DMTD derivatives that can be used as a component of the composition of the present invention. Those skilled in the art should understand that the reactions described above produce some amounts of mono-hydrocarbyl dithio-thionyl and bis-hydrocarbyl compounds. The ratio of the two can be adjusted by changing the amount of reactants. The preparation of 2-hydrocarbyldithio-5-carbyl-U, 4-thiadiazole is disclosed in U.S. Patent No. 3,663,561, which is hereby incorporated by reference. The composition is prepared by the oxidative coupling of an isomolecular hydrocarbon thiol and DMTD or an alkali metal thiolate thereof. The mono-thiol used in the preparation of these compounds is represented by the formula VSH, where R1 is a hydrocarbon group containing from 1 to about 28 carbon atoms. Peroxides, hypohalides or air or mixtures thereof can be used to promote oxidative coupling. Specific examples of mono-thiols include methyl mercaptan, isopropyl mercaptan, hexyl mercaptan, decyl mercaptan, and long-chain alkyl mercaptan, for example, from polyenes such as propylene polymers described herein And isobutylene polymers, especially polyisobutylene, having from 3 to about 70 propylene or isobutylene units per molecule). The disclosure of U.S. Patent No. 3,663,561 is hereby incorporated by reference for its definition of a DMTD derivative that can be used as a component of the composition of the present invention. The carboxylic acid ester (b) of DMTD is disclosed in U.S. Patent No. 2,76,933. Some esters are made from about 25 to about 130. It is prepared by reacting DMTD with organic acid halide (chloride) at a molar ratio of 1: 2 at a temperature of C. Collier 13 200302270 uses a suitable solvent such as benzene or dioxane 'to assist the reaction. The reaction product was washed with dilute aqueous alkali to remove hydrogen chloride and any unreacted carboxylic acid. The disclosure of U.S. Patent No. 2,760,933 is hereby incorporated herein by reference to its description of various DMTD derivatives that can be used in the compositions of the present invention. The condensation product (c) of an α-halogenated aliphatic monocarboxylic acid with DMTD is disclosed in U.S. Patent No. 2,836,564. Examples of alpha-halogenated aliphatic fatty acids that can be used include alpha-bromo or alpha-chlorocarboxylic acids containing from about 6 to about 30 'or from about 8 to about 24 carbon atoms. Specific examples include α-bromo-lauric acid, α-chloro-lauric acid, α-chloro-stearic acid, and the like. The disclosure of U.S. Patent No. 2,836,564 is hereby incorporated herein by reference to its disclosure of DMTD derivatives that can be used in the compositions of the present invention. The oil-soluble reaction products (d) of unsaturated cyclic hydrocarbons and unsaturated ketones are disclosed in U.S. Pat. Nos. 2,764,547 and 2,799,652, respectively, and the disclosure of these references is therefore made by referring to their disclosure of materials Included in this article. Examples of unsaturated cyclic hydrocarbons described in the '547 patent include styrene, alpha-methylstyrene, pinene, dipentene, cyclopentadiene, and the like. The unsaturated ketones disclosed in U.S. Patent No. 2,799,652 include aliphatic, aromatic or heterocyclic unsaturated ketones containing from about 4 to about 40 carbon atoms and from 1 to 6 double bonds. Examples include oxidized 2,4,6-trimethylbenzene, phorone, isophorone, benzylideneacetophenone, furfural acetone, difuran methylacetone, and the like. U.S. Patent No. 2,850,453 describes a product (e) obtained by reacting DMTD, an aldehyde, and an alcohol or an aromatic hydroxy compound at a molar ratio of 1 ·· 2: 1 to 1: 6: 5. The aldehyde used may be an aliphatic aldehyde containing from 1 to about 20 carbon atoms or an aromatic or heterocyclic aldehyde containing from about 5 to about 30 carbon atoms. Examples of suitable aldehydes include formaldehyde, acetaldehyde, benzaldehyde and the like. The reaction can be carried out by mixing all reactants and heating in the presence or absence of a suitable solvent, (b) by first reacting the aldehyde with an alcohol or an aromatic hydroxy compound, and then reacting the resulting intermediate with thiadiazole, or (C) It is performed by reacting an aldehyde with thiadiazole first, and then reacting the obtained intermediate with a hydroxy compound. The disclosure of US Patent No. 2,850,453 is hereby incorporated by reference. U.S. Patent No. 2,703,784 discloses a product (f) obtained by reacting DMTD with an aldehyde and a thiol. This aldehyde is similar to that disclosed in U.S. Patent No. 2,850,453. The disclosure of this patent is also incorporated herein by reference. The thiol may be one or more of those described herein. In a specific example, the thiol is an aliphatic or aromatic mono- or poly-thiol containing from about 1 to about 30, or from about 2 to about 24 carbon atoms. Examples of suitable mercaptans include ethyl mercaptan, butyl mercaptan, octyl mercaptan, and the like. U.S. Patent No. 3,663,561 describes thiadiazole derivatives prepared by the oxidative coupling of an isomolecular portion of a hydrocarbyl mercaptan with DMTD or its alkali metal thiolate. The mono-thiol used in the preparation of the compound includes those described herein and can be represented by the formula R'SH, where R 'is a hydrocarbon group containing from 1 to about 280 carbon atoms. Peroxide compounds (such as the peroxides described herein), low halides or air, or mixtures thereof can be used to promote oxidative coupling. Specific examples of mono-thiols include methyl mercaptan, isopropyl mercaptan, hexyl mercaptan, decyl mercaptan, and long-chain alkane mercaptans, for example, derived from propylene polymers and isobutylene polymers, especially from polyisobutylene A hydrocarbon, a thiol having from 3 to about 70 propylene or isobutylene units per molecule. The disclosure of U.S. Patent No. 3,663,561 is hereby incorporated by reference. 15 200302270 Dispersant The lubricating composition may also contain at least one dispersant. In a specific example, the dispersant is selected from (a) halogenated nitrogen dispersant '(b) hydrocarbyl-substituted amines, (c) carboxylic acid ester dispersant, "Mannich dispersant'", and mixture. Dispersants are typically present in an amount of from about 0.1% to about 2% by weight, or from about 0.2% to about 1.75% by weight, or from about 0.3% to about 1.4% by weight. In a specific example, the dispersant is present in an amount of less than 2% by weight, or less than 1.5% by weight, or less than 1% by weight. The halogenated nitrogen dispersant includes the product of one or more carboxylic acid halogenating agents such as a hydrocarbyl-substituted carboxylic acid halogenating agent and an amine. In a specific example, the hydrocarbyl system is derived from one or more polyenes. Polyolefins include homopolymers and copolymers of olefins having from 2 to about 40, or from 3 to about 24, or from 4 to about 12 carbon atoms. The olefins may be monoolefins, such as ethylene, propylene, 1-butene, isobutylene, α-olefin, or polyolefin monomers, including diene-based monomers such as 1,3-butadiene and isoprene. Alpha-olefins typically have from about 4 to about 30, or from about 8 to about 18 carbon atoms. These olefins are sometimes referred to as mono-1-enes or terminal olefins. Olefins and isomerized olefins include bustene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene , 1-heptadecene, 1-octadecene, 1-nonadecene, diicosene, 1-icosene, 1-docosaene, 1-tetradecosene, and the like. The commercially available olefin portion "includes c15_18 olefins, c12_16-olefins, c14_16-olefins, C14.ir · hydrocarbons, c16_18-olefins, C16_2Q olefins, c18_24-olefins, c22.28-olefin Polyolefins are prepared by conventional procedures. Polyolefins are described in US Patent Nos. 3,219,666 and 4,234,435 16 200302270, the disclosure of which is hereby incorporated by reference. Examples of polyenes include polypropylenes , Polybutenes, polyisoprene, and polybutadiene. In a specific example, the polyene is a homopolymer, such as polybutene. An example of a polybutene that can be used is about 50% of The polymer is derived from a polymer of isobutene. Polybutenes that can be used include those having a Mw of about 4,000 to about 8,000 or 6,000 to about 7,000. In a specific example, the polyenes are derived from one or more dienes. Two Alkenes include 1,3-pentadiene, isoprene, methyl isoprene, 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 5-sub Ethyl-2-norbornene, 5-methylene-2-norbornene, linear 1,3-conjugated diene (e.g. 1,3-butadiene, 2,3- Methyl-1,3-butadiene and 1,3-hexadiene) and cyclodiene (e.g. cyclopentadiene, dicyclopentadiene, olefin-rich, 1,3-cyclohexadiene, 1 , 3,5-cycloheptatriene and cyclooctatetraene). The polyene may be a homopolymer of a diene, or a co- or terpolymer of a diene with another diene or one or more of the above monoolefins. Polyenes can be hydrogenated. A commercially available polyene derived from at least one diene is LIR-290, a hydrogenated polyisoprene (Mw = 25,000), commercially available from Kuraray Co., Ltd. Polyenes are usually included as From at least about 8 carbon atoms to up to about 300, or from about 30 to up to about 200, or from about 35 to up to about 100 carbon atoms. In a specific example, the polyene is Mn (number average (Molecular weight) is greater than about 400, or greater than about 500. Generally, polyolefins have an η of about 500 to about 5000, or from about 700 to about 2500, or from about 800 to about 2000, or from about 900 to about 1500. Characteristics. In another specific example, the polyolefin has a Mn of up to about 1300, or up to about 1200. 17 200302270 Number average molecular weight of polymer and weight The average molecular weight and total molecular weight distribution are provided by gel permeation chromatography (GPC). For the purposes of the present invention, a series of fractionated polyisobutylenes are used as calibration standards in GPC. Determine the η and Mw of the polymer値 's technology is known and disclosed in many books and papers. For example, the measurement method of Mn and molecular weight distribution of polymers is disclosed in WW Yan, U. Kirkland, and DD Bly, "Modern size exclusion liquid chromatography ", Weiss & Sons, 1979. In another specific example, the polyolefin has an Mn of from about 1300 to up to about 5000, or from about 1500 to up to about 4500, or from about 1700 to up to about 3000. Polyolefins also typically have a Mw / Mn from about 1.5 to about 4, or from about 1.8 to about 3.6, or from about 2.5 to about 3.2. Hydrocarbyl-substituted carboxylic acid hydrating agents are disclosed in U.S. Patent No. 4,234,435, the disclosure of which is hereby incorporated by reference. In another specific example, a halogenating agent is prepared by reacting one or more polyolefins with an excess of maleic anhydride to provide a substituted succinic acid halogenating agent, where each equivalent of a substituent, that is, The number of polyalkenyl succinate groups is at least 1.3. The maximum number usually does not exceed 4.5. A suitable range is from about 1.4 to 3.5 and / or from about 1.4 to about 2.5 succinate groups per equivalent. The carboxylic acid hydrating agent described above is reacted with one or more amines to form a tritiated nitrogen dispersant. The amines may be mono- or polyamines, or a mixture of mono- and polyamines. The amines may be primary, secondary or tertiary amines. Useful amines include those disclosed in U.S. Patent No. 4,234,435, column 21, line 4 to column 27, line 50, which sections are incorporated herein by reference. 18 200302270 Monoamines usually contain from 1 to about 24 carbon atoms, or up to about 12, or up to about 6 carbon atoms. Examples of monoamines include methylamine, ethylamine, propylamine, butylamine, octylamine and dodecylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, methylbutylamine, ethylhexylamine, trimethylamine , Tributylamine, methyldiethylamine, ethyldibutylamine, etc. In a specific example, the amine may be a fatty (C4_3 ()) amine, which includes n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine , Oleamide and so on. Also useful fatty amines include commercial fatty amines such as "Armeen" amines (available from Amak Chemicals of Chicago, Illinois), such as Armeen_C, Armeen-O, Armeen-〇L, Armeen-T, Armeen- HT, Armeen S, and Armeen SD, where the letter designations refer to fatty groups, such as cocoa, oleyl, tallow, or soy. Other useful amines include primary ether amines, such as those represented by the formula R "(ORN) xNH2, where RN is a divalent alkylene group having from about 2 to about 6 carbon atoms, and X is from 1 to about 150 ( Or 1), and R "is a hydrocarbon group of about 5 to about 150 carbon atoms. Examples of ether amines are the SURFAM® amines produced and sold by the Mars Chemical Company of Atlanta, Georgia. Etheramines that can be used are named, for example, SURFAM P14B (decyloxypropylamine), SURFAM P16A (linear C16), and SURFAM P17B (tridecyloxypropylamine). The carbon chain length (ie, C14, etc.) of the above and used SURFAMS below is approximately and includes oxyether linkages. In a specific example, the amine may be hydroxylamine. Typically, hydroxylamines are primary, secondary or tertiary alkanolamines or mixtures thereof. The amines can be shown in Table 19 200302270 as follows: H2) N) R,) OH, and (I ^) 2) N) K,) 〇Η, each of which is independently one having from one to about eight carbon atoms The hydrocarbon group is a hydroxy hydrocarbon group having from one to about eight, or from one to about four carbon atoms, and R ′ is a divalent hydrocarbon group having from about two to about 18, or from two to about four carbon atoms. The group -R "OH in this formula represents a hydroxyhydrocarbyl group. R 'may be acyclic, alicyclic or aromatic group. Typically, R' is an acyclic straight or branched chain alkylene, such as ethylene Groups such as phenylene, propylene, 1,2-butylene, 1,2-octadecyl, etc. Two of the R'l groups exist in the same molecule, and they can be directly carbon-carbon bonds or via Heteroatoms (eg, oxygen, nitrogen, or sulfur) are linked to form a 5-, 6-, 7-, or 8-membered ring structure. Examples of heterocyclic amines include N- (hydroxy lower alkyl) -morpholine, -sulfur Morpholines, -piperidines, -oxazosines, -thiazolidines and the like. However, typically each R] is independently methyl, ethyl, propyl, butyl, pentyl or hexyl. Examples of these alkanolamines include mono-, di-, and triethanolamine, diethylethanolamine, ethylethanolamine, butyldiethanolamine, etc. The hydroxylamines may also be ether N- (hydroxyhydrocarbyl) amines. These are the above Hydroxyl poly (hydrocarbyloxy) analogs (these analogs also include hydroxy-substituted oxyalkylene analogs). The N- (hydroxyhydrocarbyl) amines can be conveniently prepared by one or more The above epoxide is prepared by the reaction of the aforementioned amines and can be represented by the formula: H2N) (R'〇) X) H, HO ^ hNXITCOJH and (R'DJNXR'OUH, where x is a number from about 2 to about 15 &Amp; and R 'are as described above. R' may also be a hydroxyl poly (alkoxy) group. The amines may be hydroxylamines, for example in the formula Rr (N ((R2〇) zH) -R3) aN ((R20) zH)-(R20) zH indicates that its center is usually a hydrocarbon group containing from about 6 to about 30 carbon atoms; each of the core and R3 is independently an alkylene group containing about 5 carbon atoms 20 200302270 high , Or ethyl or propyl; a is zero or one; and z are each independently a number from zero to about 10, provided that at least one z is at least 1. These hydroxylamines can be known by this technique Technically, and many hydroxylamines are commercially available. Hydroxylamines include, for example, a mixture of amines obtained by hydrolysis of fatty oils (eg, tallow oil, semen oils, coconut oil, etc.). Specialty of fatty amines Examples, containing from about 6 to about 30 carbon atoms, including saturated and unsaturated aliphatic amines, such as octylamine, decylamine, laurylamine, stearylamine, oleylamine, dodecylamine Octadecylamine. Available hydroxylamines, where a in the above formula is zero, including 2-hydroxyethyl, hexylamine; 2-hydroxyethyloctylamine; 2-hydroxyethyl, pentaamine; Ethyl, oleylamine; 2-hydroxyethyl, soyamine; bis (2-hydroxyethyl) hexylamine; bis (2-hydroxyethyl) oleylamine; and mixtures thereof. Also included are Comparative members, where at least one z in the above formula is at least 2, for example, 2-hydroxyethoxyethyl, hexylamine. Many hydroxylamines in which a in the above formula is zero are available from Akzona Corporation of Chicago, Illinois. Armak Chemicals Division, trade names "Ethomeen" and "Propomeen". Specific examples of these products include: Ethomeen C / 15, an ethylene oxide condensate of a cocoalkylamine containing about 5 moles of ethylene oxide; Ethomeen C / 20 and C / 25, which are An ethylene oxide condensate obtained from coco alkylamines containing about 10 and 15 moles of ethylene oxide, respectively; Ethomeen 0/12, which is a product containing about 2 moles of ethylene oxide per mole of amine Oleylamine ethylene oxide condensate; Ethomeen S / 15 and S / 20, which are ethylene oxide condensates of stearylamine containing about 5 and 10 mol ethylene oxide per molamine; Ethomeen T / 12, T / 15 and T / 25, which are 21 200302270 an ethylene oxide condensate containing tallow amines of about 2, 5 and 15 moles of ethylene oxide per mole of amine; and Propomeen 0 / 12, which is a condensate of mololeamide and about 2 mol propylene oxide. Examples of commercially available amine amine oxides in which a is 1 in the above formula include Ethoduorneen T / 13 and T / 20, which are N-types containing about 3 and 10 moles of ethylene oxide per mole of diamine, respectively. Ethylene oxide condensate of tallow trimethylene diamine. The amine may also be a polyamine. Polyamines include alkoxydiamines, fatty diamines, alkylene polyamines, hydroxyl-containing polyamines, condensed polyamines, and heterocyclic polyamines. Examples of commercially available alkoxydiamines include amines in which a is 1 in the above formula. Examples of these amines include Ethoduorneen T / 13 and 1720, which are ethylene oxide condensation products of N-tallow trimethylene diamine containing about 3 and 10 moles of ethylene oxide per mole of diamine, respectively. In another specific example, the polyamine is a fatty diamine. Fatty diamines include mono- or dialkyl, symmetric or asymmetric ethylene diamines, propane diamines (1,2, or 1, 3), and analogs of the above-mentioned polyamines. Suitable commercial fatty polyamines are Duorneen C (N-coco-1,3-diaminopropane), Duorneen S (N-soy-1,3-diaminopropane), Duorneen T (N-tallow-1, 3. Diaminopropane), and Durorneen 0 (N-oleyl-1,3-diaminopropane). "Duorneens" are commercially available from Armak Chemical Company of Chicago, Illinois. In another specific example, the amine is an alkylene polyamine. Alkyl polyamines are represented by the formula ΗΙ ^ N- (alkylene-N) η- (Ι ^) 2, where each 1 is independently hydrogen; or an aliphatic or hydroxy-substituted lipid up to about 30 carbon atoms Group groups; η 22 200302270 is a number from 1 to about 10, or from about 2 to about 7, or from about 2 to about 5: and "alkylene" groups have from 1 to about 10, or from About 2 to about 6, or from about 2 to about 4 carbon atoms. In another specific example, R! Has the same meaning as R'S described above. The alkylene polyamines include methylene polyamines, ethylene polyamines, butyl polyamines, propyl polyamines, pentyl polyamines, and the like. Also included are higher analogs and related heterocyclic amines, such as piephrens and N-aminoalkyl-substituted amines. Specific examples of these polyamines are ethylene diamine, triethylene tetramine, gins- (2-aminoethyl) amine, propylene diamine, trimethylene diamine, trimethyl amine Amine, triethylenetetraamine, tetraethylethylenepentamine, hexaethylethylheptamine, pentaethylhexamine, and the like. It is also possible to use higher analogs obtained by condensing two or more of the aforementioned alkyleneamines, such as a mixture of two or more of the aforementioned polyamines. In a specific example, the polyamine is an ethylene polyamine. These polyamines are described in detail in Kirk Othmer's "Encyclopedia of Chemical Technology", 2nd Edition, Volume 7, pages 22-37, under the heading Ethylamine in Interscience Press, New York (1965). Ethylene polyamines are often a complex mixture of polyalkylene polyamines including cyclic condensation products. Other types of polyamine mixtures that can be used are those resulting from the stripping of the above polyamine mixtures, leaving behind what is often referred to as "polyamine column bottoms". In general, the alkylene polyamine column bottoms can be characterized as having less than 2%, usually less than 1% by weight, of substances boiling below about 200 ° C. A typical sample of such ethylenic polyamine column bottoms, obtained from Freeport Chemical Company of Freeport, Texas, named "E-100", has a specific gravity of 1.0168 at 15.6 C, a nitrogen weight percentage of 33.15 and at 40C Viscosity of 121 2003 history of 23 200302270. Gas chromatographic analysis of this type of sample contains approximately 0.93% "light ends" (most likely diethylene triamine), 0.72% triethylene tetramine, 21.74% tetraethylene ethyl pentaamine, and 76.61 % Pentaethylhexylamine and higher analogs. These alkylene polyamine bottoms include cyclic condensation products, such as higher analogs of pepherine and diethylene triamine, triethylene tetramine, and the like. These alkylene polyamine bottoms can be reacted with the amidine alone, or they can be used with other amines, polyamines, or mixtures thereof. Another useful polyamine is a condensation reaction between at least one hydroxyl compound and at least one polyamine reactant containing at least one primary or secondary amine group. Hydroxyl compounds are polyhydric alcohols or polyhydroxyamines. Polyols are described below. In a specific example, the hydroxy compound is a polyhydroxy amine. Polyhydroxyamines include any of the above-mentioned monomers that react with alkylene oxides (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) having from 2 to about 20, or from two to about eight carbon atoms. Amines. Examples of polyhydroxyamines include tri- (hydroxypropyl) amine, p- (hydroxymethyl) aminomethane, 2-amino-2-methyl-1,3-propanediol, N, N, N ', N '-Hydroxy (2-hydroxypropyl) ethylenediamine, and N, N, N', N'-Hydroxy (2-hydroxyethyl) ethylenediamine, or ginsyl (hydroxymethyl) amino Methane (THAM). Polyamines which can react with a polyhydric alcohol or amine to form a condensation product or a condensed amine are as described above. Polyamines that can be used include triethylenetetraamine (TETA), tetraethyleneethylpentamine (TEPA), pentaethyleneethylhexaamine (PEHA), and mixtures of polyamines as described above for "amine bottoms" . The condensation reaction between the polyamine reactant and the hydroxy compound is carried out at a high temperature, usually from about 60 C to about 265 C, or from about 220 C to about 250 C, in the presence of an acid catalyst.

Amine condensates and methods of making same are disclosed in PCT Publication WO 24 200302270 86/05501 and U.S. Patent No. 5,230,714 (Steckel), which are incorporated herein by reference to the disclosed condensates and methods of production. A particularly useful amine condensate is from HPA Taft amine (commercial amine tower substrate available from Union Carbide), typically having 34.1% by weight nitrogen and 12.3% by weight-grade amine, 14.4% by weight secondary amine, and 7.4 Nitrogen distribution of the tertiary amine by weight), and ginseng (hydroxymethyl) aminomethane (THAM). In another specific example, the polyamines are polyoxyene polyamines, such as polyoxyene diamines and polyoxyene triamines, having a range from about 200 to about 4000, or from about 400 to about 2000 The average molecular weight. Polyoxyene polyamines that can be used include polyoxyalkylenes and polyoxypropylenediamines and polyoxypropylenetriamines. Polyoxyene polyamines are commercially available and are available from, for example, Jefferson Chemical Company, trade names "6" £ & 111 丨 1 ^ 0-230, 0-400, 0-1000, D-2000, T-403 and others. " U.S. Patent Nos. 3,804,763 and 3,948,800 are specifically incorporated herein by reference to their disclosure of these polyoxyene polyamines and the tritiated products made therefrom. In another specific example, the polyamine is a hydroxyl-containing polyamine. It is also possible to use hydroxy-containing polyamine analogs of hydroxymonoamines, especially alkoxylated alkylene polyamines, e.g., N, N- (diethanol) ethylenediamines. The polyamines can be produced by reacting one or more of the above-mentioned alkyleneamines with one or more of the above-mentioned alkylene oxides. Similar alkylene oxide-alkanolamine products can also be used, such as the above-mentioned primary, secondary or tertiary alkanolamines with ethylene oxide, propylene oxide or higher epoxides by 1.1 to 1.2 mole ratios The product of the reaction. The reactant ratio and temperature at which the reaction is performed are known to those skilled in the art. Specific examples of hydroxyl-containing polyamines include N- (2-hydroxyethyl 25 200302270) ethylenediamine, N, N, -bis (2-hydroxyethyl) -ethylenediamine, (2 -Hydroxyethyl) nepentine, mono (hydroxypropyl) -substituted tetraethylene pentamine, N- (3-hydroxybutyl) -tetramethylene diamine, etc. It is likewise possible to use higher analogs obtainable by the above-exemplified hydroxyl-containing polyamines via amine groups or via condensation of hydroxyl groups. Higher amines are produced through condensation of amine groups with the removal of ammonia, while higher waters are produced through condensation with hydroxyl groups to produce products containing ether bonds. Mixtures of any two or more of the aforementioned polyamines can also be used. In another specific example, the amine is a heterocyclic amine. Heterocyclic polyamines include aziridines, azetidines, azacyclopentanes, tetra- and dihydropyridines, pyrroles, indidines, benidines, imidazoles, di- Tetrahydroimidazoles, piephins, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-amines Alkylalkylmorphine, N, N'-diaminoalkyltonphine, azyl, azine, azonine, azecines, and four of the above-, Di- and perhydro derivatives and mixtures of two or more of these heterocyclic amines. Usable heterocyclic amines are saturated 5- and 6-membered heterocyclic amines containing only nitrogen, oxygen, and / or sulfur in the heterocyclic ring, in particular the epoxidines, erphines, thiomorpholines, Porphyrins, pyrrolidines, and the like. In particular, pyridine, aminoalkyl-substituted pyridines, stilbene, aminoalkyl-substituted piperphines, morpholine, aminoalkyl-substituted morpholine, pyrrolidine, and aminoalkyl can be used. Substituted pyrrolidines. Usually these aminoalkyl substituents are substituted on the nitrogen atom forming the heterocyclic moiety. Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylethylmorphine, and N, N'-diaminoethylmorphine. Hydroxycyclic amines can also be used. Examples include N- (2-hydroxyethyl) cyclohexylamine, 3-hydroxycyclopentylamine, p-hydroxyaniline, 26 200302270 N-hydroxyethylmorphine, and the like. Tritiated nitrogen dispersants and methods of making them are disclosed in U.S. Patent Nos. 3,219,666; 4,234,435; 4,952,328; 4,938,881; 4,957,649; and 4,904,401. The disclosures of tritiated nitrogen dispersants and other dispersants contained in these patents are hereby incorporated by reference. The dispersant may also be an amine substituted with a hydrocarbon group. These hydrocarbyl-substituted amines are known to those skilled in the art. These amines are disclosed in U.S. Patent Nos. 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433: and 3,822,289. These patents are hereby incorporated herein by reference to their disclosure of hydrocarbylamines and their methods of manufacture. Hydrocarbyl-substituted amines are typically prepared by reacting olefins and olefin polymers (polyenes) with amines (mono- or polyamines). The polyolefin may be any of the above-mentioned polyolefins. The amines may be any of the above-mentioned amines. Examples of hydrocarbyl-substituted amines include poly (propylene) amine: N, N-dimethyl-N-poly (ethylene / propylene) amine, (50:50 monomer molar ratio); polybuteneamine; N , N-bis (hydroxyethyl) -N-polybutenamine; N- (2-hydroxypropyl) -N-polybutenamine; N-polybutene-aniline; N-polybutylmorpholine ; -Poly (butene) ethylenediamine; -poly (propylene) trimethylenediamine; -poly (butylene) diethylenetriamine; N ', N'-poly (butene) tetraethylene Ethylpentamine; N, N-dimethyl-N'-poly (propylene) -1,3-propanediamine and the like. In another specific example, the dispersant may also be a carboxylic acid ester dispersant. The carboxylic acid ester dispersant is prepared by reacting at least one of the above-mentioned hydrocarbyl-substituted carboxylic acid sulfonating agents with at least one organic hydroxyl compound and optionally an amine. In another embodiment, a carboxylic acid ester dispersant is prepared by reacting a halogenating agent with at least one of the aforementioned hydroxylamines. 27 200302270 Organic hydroxy compounds include compounds of the general formula R "(〇H) m, where R" is a monovalent or polyvalent organic group connected to a -OH group via a carbon bond, and m is an integer from 1 to about 20, Wherein the hydrocarbyl group contains at least about 8 aliphatic carbon atoms. Hydroxyl compounds can be aliphatic compounds such as units and polyols, or aromatic compounds such as phenols and naphthols. The aromatic hydroxy compounds from which esters can be obtained are exemplified by the following special examples: phenol; 5-naphthol, α-naphthol, cresol, resorcinol, catechol, ρ, ρ'-dihydroxyl Benzene, 2-chlorophenol, 2,4-dibutylphenol, etc. Alcohols from which esters can be obtained generally contain up to about 1 to about 40, or from 2 to about 30, or from 2 to about 10 aliphatic carbon atoms. They can be unit alcohols such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol and the like. In a specific example, the hydroxy compound is a polyol, such as an alkylene polyol. In a specific example, the polyols contain from 2 to about 40 or from 2 to about 20 carbon atoms; and from 2 to about 10 or from 2 to about 6 hydroxyl groups. Polyols include ethylene glycols, including di-, tri-, and tetraethylene glycols; propylene glycols, including di-, tri-, and tetrapropylene glycols; glycerol; butanediol; hexanediol; sorbitol; Arabitol; mannitol; sucrose; fructose; glucose; cyclohexanediol; butaerythritol; and isopentaerythritol, including di- and triisopentaerythritol. Particularly useful polyols include diethylene glycol, triethylene glycol, glycerol, sorbitol, isopentaerythritol, and diisopentaerythritol. Polyols can have a monocarboxylic acid esterification of from 2 to about 30, or from about 8 to about 18 carbon atoms, provided that at least one hydroxyl group remains unesterified. Examples of monocarboxylic acids include acetic acid, propionic acid, butyric acid, and fatty carboxylic acids. The fatty monocarboxylic acids are as described above. Specific examples of these esterified polyols 28 200302270 include sorbitol oleate, including mono- and dioleate, sorbitol stearate, including mono- and diisostearate, glyceryl oleate , Including glycerol mono-, di-, and trioleate and butanyl octanoate. Carboxylate dispersants can be prepared by any of several known methods. A method that is particularly useful because of its convenience and the excellent properties of the esters it produces, include the above-mentioned carboxylic acid hydrating agents and one or more alcohols or phenols at about 0.5 equivalents to about 4 equivalents of hydroxy compounds per equivalent of the halogenating agent. reaction. Esterification usually takes place at temperatures above about 100 ° C, or between 150 ° C and 300 ° C. The water system formed as a by-product is removed by distillation as the esterification proceeds. The preparation of useful carboxylate dispersing esters is disclosed in U.S. Patent Nos. 3,522,179 and 4,234,435, and the disclosures of which are incorporated herein by reference. The ester dispersant may be further reacted with at least one of the aforementioned amines (including at least one of the aforementioned polyamines). The amine is added in an amount sufficient to neutralize any non-esterified carboxyl groups. In a specific example, the nitrogen-containing carboxylic acid ester dispersant is prepared by making about 1.0 to 2.0 equivalents or about 1.0 to 1.8 equivalents of a hydroxy compound and up to about 0.3 equivalents or about 0.02 to about 0.25 equivalents per equivalent of a halogenating agent. Prepared by polyamine reactions. In another specific example, the carboxylic acid sulfonating agent can react with an alcohol and an amine simultaneously. Usually there is at least about 0.01 equivalents of alcohol and at least 0.01 equivalent of amine, however, the combined total equivalents should be at least about 0.5 equivalents per equivalent of the amidine. These nitrogen-containing carboxylic acid ester dispersant compositions are known in the art and the preparation of many of these derivatives is disclosed, for example, in U.S. Patent Nos. 3,957,854 and 4,234,435, which have previously been incorporated herein by reference. In another specific example, the dispersant may also be derived from a Mannich dispersant 29 200302270. Mannich dispersants are generally formed by the reaction of at least one aldehyde, at least one of the amines described above, and at least one alkyl-substituted hydroxyaromatic compound. The reaction can occur from room temperature to 225 ° C, or from 50 ° C to about 200 ° C, or from about 75 ° C to about 150 ° C, and the amount of reagent is such that The ear ratio is in the range from about (1: 1: 1) to about (1: 3: 3). The first reagent is an alkyl-substituted hydroxyaromatic compound. This term includes acids (which are particularly effective), carbon-, oxygen-, sulfur-, and nitrogen-bridged amidines and the like, and phenols (e.g., 4,4'-bis ( Hydroxy) biphenyl), hydroxy compounds derived from fused-cyclic hydrocarbons (eg, naphthol and the like); and polyhydroxy compounds such as catechol, resorcinol and hydroquinone. A mixture of one or more hydroxyaromatic compounds may be used as the first reagent. A hydroxyaromatic compound is one having at least about 6 (usually at least about 30, or from at least 50) carbon atoms and up to about 400 or up to about 300 or up to about 200 of at least one and or no more than two Carbon atom aliphatic or alicyclic group substitution. These groups may be derived from the aforementioned polyolefins. In a specific example, the hydroxyaromatic compound is a phenol substituted with an aliphatic or alicyclic hydrocarbon-based group having a Mn of about 420 to about 10,000. The second reagent is a hydrocarbon-based aldehyde, such as a lower aliphatic aldehyde. Suitable aldehydes include formaldehyde, benzaldehyde, acetaldehyde, butyraldehyde, hydroxybutyraldehyde, and heptaldehyde, and aldehyde precursors that act under reaction conditions such as paraformaldehyde, paraldehyde, formalin, and meat Myristyl alcohol (methal). Formaldehyde and its precursors (eg, paraformaldehyde, trioxane) are particularly effective. A mixture of aldehydes can be used as the second reagent. 30 200302270 The third reagent is any of the amines described above. In a specific example, the 'amine is a polyamine as described above. Mannich dispersants are disclosed in the following patents: U.S. Patent No. 3,980,569; U.S. Patent No. 3,877,899; and U.S. Patent No. 4,454,059 (incorporated herein by reference for their disclosure of Mannich dispersants ). In a specific example, the dispersant is a boron-containing dispersant. The boron-containing dispersant prepared by reacting one or more of the above-mentioned dispersants is a boronizing agent. Boring agents include boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boric acids such as boric acid, tetraboric acid and metaboric acid, boranes, boronamines, and Various esters of boric acid. Borates include lower alkyl (1-7 carbon atoms) esters of boric acid. A particularly effective boron compound is boric acid. The following examples relate to boron-containing dispersants. Example D-1 A mixture of 372 g (6 equivalents of boron) boric acid and 3111 g (6 equivalents of nitrogen) of a tritiated nitrogen composition. By using 1 equivalent of polybutene (Mn 2 85) The acid hydrazone (equivalent to 500 equivalents) was obtained by reacting with 2 equivalents of an ethylideneamine commercial mixture having an average composition equivalent to tetraethyleneethylpentamine, heated at 150 C for 3 hours, and then filtered. The filtrate was found to have a boron content of 1.64% and a nitrogen content of 2.56%. Example D-2 (a) A reaction vessel was charged with 1,000 parts of polybutene (Mη = 1000) substituted succinic anhydride, which had a total acid content of 108 'and 275 g of oil and 139 parts A commercial mixture of polyamines equivalent to 85% E-100 amine bottoms and 15% diethylene 31 200302270 triamine. The reaction mixture was heated to 150 to 160C and the reaction temperature was maintained for four hours. The reaction was purged with nitrogen to remove water. (b) The reaction vessel was charged with 1405 parts of the product of Example D-2a, 229 parts of boric acid, and 398 parts of diluent oil. The mixture was heated to 100 to 150C and maintained at this temperature until the water distillate ceased. The final product contains 2.3% nitrogen, 1.9% boron, 33% 100 neutral mineral oil and 60 total alkali rhenium. Phosphorus antiwear agent The lubricating composition of the present invention may also include at least one phosphorus antiwear / high pressure resistant agent. Phosphorus antiwear / high pressure resistant agents are typically present in an amount of from about 0.01% to about 3% by weight, or from about 0.1% to about 1.25% by weight, or from about 0.2% to about 1% by weight. Examples of phosphorus-containing antiwear / high pressure resistant agents include metal thiophosphates; phosphate esters or salts thereof; phosphorus-containing carboxylic acids, esters, ethers, or amidines; and phosphites. Phosphoric acid includes phosphoric acid, phosphonic acid, phosphinic acid, and thiophosphoric acid, including dithiophosphoric acid and monothiophosphoric acid, thiophosphinic acid, and thiophosphonic acid. In a specific example, the phosphorus-containing anti-wear / high pressure resistant agent is a phosphate ester prepared by reacting one or more phosphoric acid or anhydride with an alcohol containing from one or about 3 carbon atoms. Alcohols typically contain up to about 30, or up to about 24, or up to about 12 carbon atoms. Phosphoric acid or anhydride is usually an inorganic phosphorus reagent, such as phosphorus pentoxide, phosphorus trioxide, phosphorus tetroxide, phosphoric acid, phosphorus halides, lower phosphorus esters, or phosphorus sulfide, including phosphorus pentasulfide and the like. Examples of phosphoric acid or anhydride include phosphorus pentoxide, phosphorus pentasulfide, and phosphorus trichloride. Lower phosphates independently contain from 1 to about 7 carbon atoms in each ester group 32 200302270. The phosphate may be a mono-, di- or triphosphate. Alcohols used to make phosphates generally have from 1 to 30, or from about 2 to 24, or from about 4 to 18 carbon atoms. Examples include butyl, pentyl, 2-ethylhexyl, hexyl, octyl, oleyl and cresols. Examples of commercial alcohols include Alfol 810 (a mixture of primary linear primary alcohols having from 8 to 10 carbon atoms); aluminum alcohol 1218 (a synthetic primary linear alcohol containing 12 to 18 carbon atoms) Mixtures); Alfasol 20+ alcohols (mixtures of C18-C28-grade alcohols with C20 alcohol as measured by GLC (gas-liquid chromatography)); and Alfasol 22+ alcohols (mainly C18-C28-grade alcohols containing C22 alcohols). Alfasols were obtained from Continental Oil Products. Another example of a commercially available alcohol mixture is Adol 60 (about 75% by weight linear C22-grade alcohol, about 15% C2Q-grade alcohol and about 8% C18 and C24 alcohols) and Adol 320 (oleyl alcohol). Adol alcohol is sold by Ashland Chemical. Various mixtures of naturally occurring triglycerides and unit fatty alcohols with chain lengths ranging from about 08 to C18 are available from Procter & Gamble. These mixtures contain various amounts of fatty alcohols mainly containing 12, 14, 16 or 18 carbon atoms. For example, CO-1214 is a fatty alcohol mixture containing 0.5% C1 () alcohol, 66.0% C12 alcohol, 26.0% C14 alcohol, and 6.5% C16 alcohol. Another group of commercial mixtures includes "Neodol" available from Shell Chemical Company product. For example, Neodol 23 is a mixture of C12 and C13 alcohols; Neodol 25 is a mixture of C12 and C15 alcohols; and Neodol 45 is a mixture of C14 to C15 linear alcohols. Neodol 91 is a mixture of C9, C1Q and Cn alcohols. 33 200302270 Fatty diols can also be used and these include the general trade names Adol 114 and Adol 158 available from Ashland Oil. The former is derived from the linear α-olefin fraction, while the latter is derived from the C15-C18 fraction. Examples of usable phosphates include phosphates prepared by reacting phosphoric acid or an acid anhydride with cresol alcohols. An example of these phosphates is tricresyl phosphate. In another specific example, the phosphorus anti-wear / high pressure resistant agent is a phosphorothioate or a salt thereof. Phosphorothioate can be prepared by reacting phosphorous sulfide, such as the above, and alcohol, such as the above. The phosphorothioate can be a mono- or dithiophosphate. Phosphorothioates are also commonly referred to as phosphorothioates. In a specific example, the phosphate is a monothiophosphate or a monothiophosphate. Monothiophosphates can be prepared by reacting a sulfur source with a dialkyl phosphite. The source of sulfur may be, for example, elemental sulfur. The source of sulfur may also be a monosulfide ' such as a sulfur-coupled olefin or a sulfur-coupled dithiophosphate. Elemental sulfur is an effective source of sulfur. The preparation of monothiophosphates is disclosed in U.S. Pat. No. 4,755,31 1 and PCT Publication No. WO87 / 07638, which refers to monothiophosphates, sulfur sources, and production of monothiophosphoric acid by reference The disclosure of ester methods is incorporated herein. Monothiophosphates can also be formed in lubricant blends by adding a dihydrogen phosphite to a lubricating composition containing a source of sulfur, such as a sulfurized olefin. Phosphites can react with sulfur sources under blending conditions (i.e., from about 30 C to about 100 C or higher) to form monothiophosphates. In another specific example, the phosphorus anti-wear / UHV agent is a dithiophosphoric acid or a phosphorodithioic acid. Dithiophosphoric acid 34 200302270 An acid can be represented by the formula (R0) 2PSSH, where each R is independently a hydrocarbon group containing from about 3 to about 30 carbon atoms. R typically contains up to about 18, or up to about 12, or up to about 8 carbon atoms. Examples R include isopropyl, isobutyl, n-butyl, secondary-butyl, various pentyl, n-hexyl, methyl isobutylmethyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, Twenty-two, decyl, twelve and thirteen. Exemplary lower alkylphenyl R groups include butylphenyl, pentylphenyl, heptylphenyl and the like. Examples of mixtures of R groups include: 1-butyl and 1-octyl; 1-pentyl and 2-ethyl-1-hexyl; isobutyl and n-hexyl; isobutyl and isopentyl; 2- Propyl and 2-methyl-4-pentyl: isopropyl and secondary butyl; and isopropyl and isooctyl. In a specific example, the dithiophosphoric acid may be reacted with an epoxide or a glycol. This reaction product can be used alone or further reacted with phosphoric acid, anhydride or lower ester. The epoxide is usually an aliphatic epoxide or styrene oxide. Examples of usable epoxides include ethylene oxide, propylene oxide, butylene oxide, octane oxide, dodecane oxide, styrene oxide, and the like. Propylene oxide is particularly effective. The diol may be an aliphatic diol having from 1 to about 12, or about 2 to about 6, or 2 or 3 carbon atoms, or an aromatic diol. Diols include ethylene glycol, propylene glycol, catechol, resorcinol, and the like. Dithiophosphoric acid, glycols, epoxides, inorganic phosphorus reagents, and reaction methods thereof are disclosed in U.S. Patent No. 3,197,405 and U.S. Patent No. 3,544,465, which are incorporated herein by reference to For reference its reveal. The following examples P-1 and P-2 illustrate the preparation of phosphates that can be used. 35 200302270 Example 1-1 Phosphorus pentoxide (64 g) was added at 58 C to 514 g of 0,0- Di (4-methyl-2-pentyl) phosphoryl disulfate (by bis (4-methyl-2-pentyl) -phosphoryl disulfate with 1.3 mol epoxy at 25 C Prepared by propane reaction). The mixture was heated at 75 ° C for 2.5 hours, mixed with diatomaceous earth and filtered at 70 ° C. The filtrate contained 11.8% by weight of phosphorous, 15.2% by weight of sulfur, and hydrazone (bromophenol blue). Example P-2 A mixture of 667 g of phosphorus pentoxide and 3514 g of diisopropyl phosphodisulfate and 986 g of propylene oxide at 50 ° C. was heated at 85 ° C. for 3 hours and filtered. The filtrate contained 15.3 % By weight phosphorus, 19.6% by weight sulfur and hydrazone (bromophenol blue) of 126. Acid phosphates can react with ammonia, amine compounds, or metal bases to form ammonium or metal salts. These salts can be formed separately and then phosphoric acid can be formed. Salts of esters are added to the lubricating composition. Alternatively, when an acidic phosphate is mixed with other ingredients to form a fully formulated lubricating composition, the salts may also be formed in situ. The amine salt of the phosphate may be from ammonia or amine ( Including the above unit amines and polyamines). The metal salt of a phosphate is prepared by the reaction of a metal base with a phosphate. The metal base can be any metal compound capable of forming a metal salt. Examples of the metal base include metal oxides, hydrogen Oxides, carbonates, sulfates, borates, or the like. Metals of alkali metals include metals IA, IIA, IB to VIIB, and VIII (CAS version of the Periodic Table of Elements). These metals include alkali metals, alkaline earth metals Transition metal. In a specific example, the metal is a Group IIA metal, such as calcium or magnesium, and a Group IIB metal, such as zinc, or a Group VIIB 36 200302270 metal, such as manganese. In a specific example, the metal is magnesium, Calcium, manganese or zinc. Examples of metal compounds that can react with phosphoric acid include zinc hydroxide, zinc oxide, copper hydroxide, copper oxide, etc. In a specific example, the phosphorus-containing anti-wear / high pressure resistant agent is metal thio Phosphates or metal dithiophosphates. Metal thiophosphates are prepared by methods known in the art. Examples of metal dithiophosphates include zinc isopropylmethylpentyl dithiophosphate, Isopropyl isooctyl zinc dithiophosphate, barium di (nonyl) dithiophosphate, zinc di (cyclohexane) dithiophosphate, zinc di (isobutyl) dithiophosphate, di ( Hexyl) calcium dithiophosphate, zinc isobutyl isoamyl dithiophosphate, and zinc isopropyl secondary-butyl dithiophosphate. Examples of the following examples P-3 to P-6 can be used Preparation of Phosphate Ester Example P-3 A reaction vessel was charged with 217 grams from The filtrate of Example P-1. A commercial aliphatic primary amine (66 g) was added at 25-6 CTC over a period of 20 minutes, which had an average molecular weight of 191, in which the aliphatic group was a trivalent group containing 11 to 14 carbon atoms. A mixture of higher alkyl groups. The resulting product has a phosphorus content of 10.2% by weight, a nitrogen content of 1.5% by weight, and a sulfonium acid of 26.3. Example P-4 Following the procedures of Examples P-1 and P-3, 1320 parts of P The product described in -1 was reacted with 584 parts of P-3 amine. The final product had 8.4% phosphorus and 10% sulfur. Example P-5 The filtrate of Example P-2 (1752) was mixed at 25-82 ° C. G) and 764 g 37 200302270 aliphatic primary amines used in Example P-3. The resulting product had 9.9% phosphorus, 2.7% nitrogen, and 12.6% sulfur. Example P-6 Phosphorus pentoxide (852 g) was added to 2340 g of isooctyl alcohol over a period of 3 hours. The temperature increased from room temperature but remained below 65 ° C. After the addition was complete, the reaction mixture was heated to 90 C and maintained at this temperature for 3 hours. Diatomaceous earth was added to the mixture, and the mixture was filtered. The filtrate had 12.4% phosphorous, 192 acid neutralized europium (bromophenol blue) and 290 acid neutralized europium (phenolphthalein). The upper filtrate was mixed with 200 g of toluene, 130 g of mineral oil, 1 g of acetic acid, 10 g of water and 45 g of zinc oxide. The mixture was heated to 60-70 ° C at a pressure of 30 mmHg. The resulting product mixture was filtered using celite. The filtrate had 8.6% zinc and 7.0% phosphorus. Example P-7 Aluminol 8-10 (2628 parts, 18 moles) was heated to a temperature of about 45 ° C, and then 852 parts (6 moles) of phosphorus pentoxide was added over 45 minutes while maintaining the reaction temperature Between about 45-65 ° C. The mixture was allowed to stir at this temperature for an additional 0.5 hour, after which it was heated at 70C for about 2-3 hours. Primene 81-R (2362 parts, 12.6 mol) was added dropwise to the reaction mixture while the temperature was maintained between about 30-50 ° C. When all the amines have been added, the reaction mixture is filtered through a filter aid and the filtrate is the desired amine salt containing 7.4% phosphorus (theoretical, 7.1%). Example P-8 Phosphorus pentoxide (208 g) was added at 30-60 ° C. to 38 g produced by reacting 280 g of propylene oxide with 1184 g of 0,0-diisobutylphosphodisulfuric acid. 200302270. The addition was performed at a temperature of 50-60 ° C, and then the resulting mixture was heated to 80 ° C and maintained at this temperature for 2 hours. The aliphatic primary amine (384 g) identified in Example B-3 was added to the mixture while maintaining the temperature in the range of 30-60 ° C. The reaction mixture was filtered through celite. The filtrate had 9.3% phosphorus, 11.4% sulfur, 2.5% nitrogen and 6.9 alkali bromide (bromophenol blue indicator). In another specific example, the phosphorus anti-wear / UHV agent is a (a) at least one dithiophosphoric acid and (b) at least one metal salt of an aliphatic or alicyclic carboxylic acid. The dithiophosphoric acid is as described above. The carboxylic acid can be a mono or polycarboxylic acid, and usually contains from 1 to about 3, or exactly one carboxylic acid group. The carboxylic acids that can be used are those having the formula RCOOH, where R is an aliphatic or alicyclic hydrocarbon group, preferably alkyne-unsaturated. R typically contains from about 2 or from about 4 carbon atoms. R typically contains up to about 40, or up to about 24, or up to about 12 carbon atoms. In a specific example, R comprises from about 4, or from about 6 to up to about 12, or up to about 8 carbon atoms. In a specific example, R is an alkyl group. Suitable acids include butyric acid, valeric acid, hexanoic acid, octanoic acid, nonanoic acid, capric acid, dodecanoic acid, octadecanoic acid, and icosanoic acid, and enoic acids such as oleic acid, linoleic acid, and linolenic acid and linoleic acid Acid dimer. A particularly effective carboxylic acid is 2-ethylhexanoic acid.

The metal salt can be prepared by blending only a metal salt of a dithiophosphoric acid and a metal salt of a carboxylic acid in a desired ratio. The equivalent ratio of dithiophosphoric acid to carboxylic acid is from about 0. 5 to about 400 to 1. The ratio can be from 0.5 to about 200 'or up to about 100, or up to about 50, or up to about 20 to 1. In a specific example, the ratio is from 0. 5 to about 4. 5 to 1, or from about 2. 5 to about 4. 25 to 1. For this purpose, the equivalent of dithiophosphoric acid is its molecular weight divided by the number of _PSSH 39 200302270 groups therein, and the equivalent of carboxylic acid is its molecular weight divided by the number of mineral groups therein. The second method for preparing a metal salt that can be used in the present invention is to prepare an acid mixture in a desired ratio, such as described above for the metal salt of an individual metal salt, and then react the acid mixture with one of the above-mentioned metal compounds. When using this preparation method, it is often possible to prepare a salt containing an excess of metal relative to the acid equivalents present; therefore, it is possible to prepare up to 2 equivalents and especially up to about 1. 5 equivalents of metal salt of metal. The metal equivalent for this purpose is its atomic weight divided by its valence. Metal salts are typically prepared at temperatures between about 30 ° C and about 150 ° C, or up to about 125 ° C. U.S. Patent Nos. 4,308,154 and 4,417,990 disclose procedures for preparing these metal salts and disclose many examples of such metal salts. These patents are hereby incorporated herein by reference. In a specific example, the phosphorus-containing anti-wear / UHV agent is phosphorus-containing ammonium. Phosphonamide is prepared by the reaction of one of the above-mentioned phosphoric acid or dithiophosphoric acid with unsaturated amidine. Examples of unsaturated fluorenamine include acrylamide, N, N-methylenebis (acrylamide), methacrylamide, crotylamine, and the like. In a specific example, a composition comprising a dithiocarbamate is obtained from a reaction product of dipentylamine or dibutylamine and carbon disulfide, which forms a dithiocarbamic acid or salt. The reaction product of phosphoric acid and unsaturated amidine can be further reacted with a linking or coupling compound such as formaldehyde or paraformaldehyde. Phosphatamines are known in the art and are disclosed in U.S. Pat. Nos. 4,670,169, 4,770,807, and 4,876,374, which are incorporated herein by reference for their disclosure of these phosphatidines and their preparation. 200302270 In a specific example, the phosphorus antiwear / high pressure resistant agent is a phosphorus-containing carboxylic acid ester. Phosphorus-containing carboxylic acid esters are prepared by the reaction of one of the above-mentioned phosphoric acid (preferably dithiophosphoric acid) and an unsaturated carboxylic acid or ester as described herein. If a carboxylic acid is used, the ester can be formed by the subsequent reaction of a phosphoric acid-unsaturated carboxylic acid adduct with an alcohol (such as described herein). In a specific example, the phosphorus-containing antiwear / high pressure resistant agent is a reaction product of phosphoric acid (preferably dithiophosphoric acid) and vinyl ethers. Vinyl ether is represented by the formula Ri-CHsCH-Ol, where R! Is independently hydrogen or a hydrocarbon group having from 1 to about 30, or up to about 24, or up to about 12 carbon atoms. R2 is a hydrocarbon group with the same definition as I. Examples of vinyl ether include methyl vinyl ether, propyl vinyl ether, 2-ethylhexyl vinyl ether and the like. In a specific example, the phosphorus anti-wear / high pressure resistant agent is a phosphorus-containing carboxylic acid ester containing at least one phosphite. The phosphite may be a di- or trialkyl phosphite. In a specific example, each hydrocarbyl group independently contains from 1 to about 24 carbon atoms, or from 1 to about 18 carbon atoms, or from about 2 to about 8 carbon atoms. Each hydrocarbyl can be independently alkyl, alkenyl or aryl. When the hydrocarbyl group is an aryl group, it contains at least about 6 carbon atoms; or about 6 to about 18 carbon atoms. Examples of the alkyl or alkenyl group include propyl, butyl, hexyl, heptyl, octyl, oleyl, linolenyl, stearyl and the like. Examples of aryl include phenyl, naphthyl, heptylphenol and the like. In a specific example, each hydrocarbon group is independently propyl, butyl, pentyl, hexyl, heptyl, oleyl or phenyl or butyl, oleyl or phenyl and or butyl or oleyl. One method of preparing phosphites includes reacting lower (C1-8) phosphites, and their preparation is known and many phosphites are commercially available. Particularly effective phosphites are 41 200302270 dibutyl hydrogen phosphite, dioleyl phosphite, di (c1418) hydrogen phosphite and triphenyl phosphite. Fatty imidazoline or fatty acid-polyamine reaction product The lubricating composition may also include at least one fatty imidazoline or at least one fatty carboxylic acid and at least one polyamine reaction product. In a specific example, the presence of a reaction product of a fatty imidazoline or fatty carboxylic acid and at least one polyamine can provide a final lubricant from about 0.1. 01% by weight to about 0. 7% by weight, or from about 0. 02% by weight to about 0.4% by weight, or from about 0. 03% by weight to about 0. 2% by weight. Fatty imidazolines have fatty substituents containing from about 8 to about 30, or from about 12 to about 24 carbon atoms. The substituent may be saturated or unsaturated. Saturated substituents are particularly effective. In one aspect, fatty imidazolines can be prepared by reacting fatty carboxylic acids with polyene polyamines, such as discussed above. Fatty carboxylic acids are typically mixtures of straight and branched chain fatty acids containing from about 8 to about 30, or from about 12 to about 24, or from about 16 to about 18 carbon atoms. Carboxylic acids include such polycarboxylic acids or carboxylic acids or anhydrides having from 2 to about 4, preferably 2 carbonyl groups. These polycarboxylic acids include Diels-Al De reaction product. In a specific example, the fatty carboxylic acids are fatty monocarboxylic acids having from about 8 to about 30, or from about 12 to about 24 carbon atoms. Specific examples include, for example, octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid, and peroleic acid. Stearic acid is particularly effective. One or more fatty carboxylic acids are reacted with at least one polyamine. Poly 42 200302270 Amines can be aliphatic, cycloaliphatic, heterocyclic or aromatic. Examples of polyamines include alkylene polyamines and heterocyclic polyamines. Specific examples are described in the effective reaction products of carboxylic acids and polyamines by reacting the above alkylene polyamines with linear acids having a percentage of from 5 to about 30 moles and a branch of about 70 to 95 moles. A fatty acid mixture of fatty acids. Among the commercial mixtures are such known general quotients as isostearic acid. These mixtures are produced as by-products from the dimerization of unsaturated fatty acids as described in U.S. Patent Nos. 2,812,342; and 3,260,671. These patents are hereby incorporated herein by reference to their disclosure of these products and methods of manufacture. Branched-chain fatty acids also include those in which the branched chain is non-alkyl, such as found in phenyl and cyclohexane stearic acid and chlorostearic acid. Branched-chain fatty carboxylic acid / alkylene polyamine products have been widely disclosed in this art. See, for example, U.S. Patent Nos. 3,110,673; 3,251,853; 3,326,801; 3,337,459; 3,405,064; 3,429,674; 3,468,639; and 3,857,791. These patents are hereby incorporated herein by reference to their disclosure of the use of fatty acid / polyamine condensates in lubricating oil formulations. In another embodiment, the reaction product of a fatty carboxylic acid and a polyamine is further reacted with an epoxide. Epoxides are generally lower aliphatic epoxides having from 1 to about 7 carbon atoms, or from 1 to about 5 carbon atoms, or from 2 to about 4 carbon atoms. Examples of these epoxides include ethylene oxide, propylene oxide, butylene oxide, hexane oxide, and octane oxide. Based on the total weight of the reaction product, the epoxide is usually about 0. The amount of the lower epoxide is reacted in an amount of 5 to about 5 wt%. The reaction usually occurs at a temperature above about 100 43 2003 02270 c. The reaction products of fatty acids, polyamines, and epoxides are disclosed in U.S. Patent No. 3,240,575, which therefore refers to carboxylic acids, polyamines, epoxides, and reaction products and methods of making reaction products by reference Teachings are incorporated into this article. The following examples illustrate the reaction products of the fatty carboxylic acids of the present invention and at least one polyamine. Example 1-1 6820 parts of isostearic acid was slowly added over a period of two hours to 1133 parts of commercial diethylene triamine heated at 110-150 ° C. The mixture was held at 150 ° C for one hour and then heated to 180 ° C over another hour. Finally, after 0. The mixture was heated to 205 ° C for 5 hours; after this heating, the mixture was purged with nitrogen to remove volatile materials. Keep the mixture at 205-230 ° C for a total of 11. 5 hours, then stripped at 230 ° C / 20 Torr to provide the desired tritiated polyamines, containing 6. 2% nitrogen residue. Example 1-2 1000 parts of isostearic acid were added to 205 parts of commercial tetraethylene pentamine which had been heated to about 75 C while flushing with nitrogen, and the temperature of the mixture was maintained at about 75E-110 C. The mixture was then heated to 22 ° C. and maintained at this temperature until the acid pH of the mixture was less than 10. After cooling to about 150 ° C., the mixture was filtered, and the filtrate was about 5. The required tritiated polyamines with a nitrogen content of 9%. Example 1-3 A mixture (565 parts by weight) of a mixture of trialkyleneamine and dialkyleneamine in a weight ratio of 3: 1 was added at 200E to 80 ° C. An equal amount of a mixture of naphthoic acid (1270 parts) with 180 acid sulfonium and oleic acid (1110 parts; the total amount of the two acids used is such that one equivalent is provided for every two equivalents of the amine mixture used). The reaction is exothermic. The mixture was purged with nitrogen while at 4. It was heated to 240 ° C for 5 hours, and then heated at this temperature for 2 hours. The water system was collected as a distillate. Ethylene oxide (140 parts) was added to the above residue at 170E-180 ° C over 2 hours while nitrogen was bubbled through the reaction mixture. The reaction mixture was then purged with nitrogen for 15 minutes and diluted with 940 parts of xylene to a solution containing 25% xylene. The resulting solution has 5. Nitrogen content of 4% and alkali hydrazone at pH 4 of 82, the latter is an indicator of free amine groups. Antifoam In a specific example, the lubricating composition contains at least one antifoam. Mothproofing agents are compositions known in the art such as silicone or fluorosilicone. These mothproofing agents are available from Dow Corning Chemical Company and Union Carbide. Usable anti-rust products are Dow FS-1265, Dow Corning DC-200, Union Carbide UC-L45 and available from Nitro, W.  Va. A polyacrylate antimonitor from Monsanto Polymer Products, known as PC-1244. In addition, siloxane polyether copolymer mothproofing agents are available from Farmington Hills, Mich OE Specialty Products and may also be included. One such substance is sold as SILWET-L-7220. Polyacrylates or acrylic polymers are also known antifoaming agents and are disclosed in U.S. Patent No. 3,166,508 and British Patent Publication GB2,234,978. These references are hereby incorporated by reference. Polyacrylates are commercially available from several manufacturers and are typically used as antiseptics in the form of one or more ethyl acrylate and 2-ethylhexyl acrylate 45 200302270 esters, as well as other monomers such as vinyl acetate. Polymers and copolymers, as known to those skilled in the art. An anti-moth agent that can be used is a copolymer of ethyl acrylate and 2-ethylhexyl acrylate sold by Monsanto. For example, PC-1244 defoamer is used as the polyacrylate. Antiseptics are included in the composition of the present invention in an amount of from about 100 to 2000, or from about 150 to 1500, or from about 200 to 10,000 parts per million, wherein the active ingredient is oil-free Benchmark. Antioxidants In another embodiment, the lubricant may also contain one or more antioxidants. In a specific example, the antioxidant is present in an amount of about 0. 001% by weight to about 5% by weight, or from about 0. 01% by weight to about 2% by weight, or from about 0. 05% to about 1% by weight. The total amount of antioxidant present may generally be about 1. 5% by weight to about 10% by weight, or about 1. 8% by weight to about 8% by weight, or from about 1. 9% by weight up to about 6% by weight. In another specific example, the lubricating composition comprises at least about 1% by weight of an amine antioxidant, a dithiocarbamate antioxidant, or a mixture thereof. In a specific example, the antioxidant is an amine antioxidant or a dithiocarbamate antioxidant. In a specific example, the antioxidant is ashless, that is, it is metal-free. In another specific example, the antioxidant is not a polyol. Amine antioxidants include alkylated aromatic amines and heterocyclic amines. Alkylated aromatic amines include compounds represented by the formula Ad-NRpAr2, wherein Ar1 and Ar2 are independently monocyclic or polycyclic substituted or unsubstituted aryl groups; and h is hydrogen, halogen, 0H, NH2 , SH, No2 or a hydrocarbyl group having from 1 to about 50 carbon 46 200302270 atoms. Aryl is represented by "Ar" and may be monocyclic or polycyclic in other formulas elsewhere in this specification and the scope of the appended patent application. Examples of monocyclic Ar ports include this section 'such as phenyltriyl; i, 2,3-phenyltriyl; 3-methyl-1,2,4-phenyltriyl; 2-methylglacial ethyl-u , 'Benzyltriyl;% propoxy-1,2,4,5-phenyltetrayl; 3-chloro-i, 2,4-phenyltriyl; ι, 2,3,5-phenyltetrayl; 3-cyclohexyl-1,2,4-benzenetriyl; and 3-azocyclopentyl-i, 2,5-benzenetriyl, and pyrimidine moieties such as 3,4,5-nitrogen Heterobenzene; and 6-methyl-3,4,5-azabenzene. The polycyclic group may be one in which an aromatic ring is fused to another aromatic nucleus at two points, such as naphthyl and aryl. Specific examples of fused ring aromatic moiety Ar include: 1,4,8-naphthyl; 1,5,8-naphthyl; 3,6-dimethyl-4,5,8 (1-azo Naphthylnaphthalene) '· 7 · methyl-9-methoxy-1,2,5,9-cyclotetrayl; 3,10-phenanthrene; and 9-methoxy-benzo (phenanthrene) _5 , 6,8,12_base. A polycyclic group may be one in which at least two rings (monocyclic or polycyclic) are connected via a bridge. These bridge linkages may be selected from the group consisting of alkylene linkages, ether linkages, ketone linkages, sulfide linkages, and polysulfide linkages of 2 to about 6 sulfur atoms. When Ar is attached to a polycyclic aromatic moiety, specific examples of octa * include: 3,3,, 4,4,, 5-diphenyltetrayl; bis (3,4-phenylene) ether; 2,3 -Phenylene-2,6-naphthylmethane; and 3-methyl-9-shiman-U, 4,5,8-yl; 2,2-bis (3,4-phenylene) propane; Sulfur-coupled 3-methyl-1,2,4-phenyltriyl (with 1 to about 10 thiomethylphenylene groups); and amino-coupled 3-methyl-1,2,4- Phenyltriyl (with 1 to about 10 amine methylphenylenes). Typical Ar is benzene ring type, lower alkylene bridged biphenyl ring type or naphthalene ring type. In another specific example, the alkylated aromatic amines are represented by the formula Ar-R3, in which the feet 2 and r3 are independently hydrogen or a hydrocarbon group having from 1 to about 50, or from about 4 to about 20 carbon atoms. Examples of aromatic amines include P, P'_di 47 200302270 octyldiphenylamine; octylphenyl-β-naphthylamine; octylphenyl-α-naphthylamine, phenyl_α-naphthylamine; phenyl- β-Celineamine; p-octylphenylnaphthylamine and (octylphenyl-small-octyl-β-naphthylamine and bis (nonylphenyl) amine, with bis (nonylphenyl) amine being preferred. US Patent Nos. 2,558,285; 3,601,632; 3,368,975; and 3,505,225 disclose diarylamines that can be used as antioxidants. These patents are incorporated herein by reference. In another specific example, the antioxidant can be phenothiaphine Phenomenine includes phenothiaphine, substituted phenothiogen, or derivatives, as disclosed in U.S. Patent Nos. 4,785,095 and 5,883,057, the disclosures of which are made by reference to their methods and compounds. The teachings are incorporated herein. In a specific example, a dialkyldiphenyl system is treated with sulfur at a high temperature, such as in the range of 145 ° C to 205 ° C, for a time sufficient to complete the reaction. A catalyst, such as iodine, can be used to Establishing sulfur bridges. Phenothiophine and its various derivatives can be made by phenothiaphine containing free NH groups The compound is converted into the above compound by contact with a thiol of the formula R5SR4OH, wherein R4 is an alkylene, an alkenyl or an aralkyl, or a mixture thereof. A group consisting of alkaryl or aralkyl and mixtures thereof; each of R6 is independently: alkyl, alkenyl, aryl, alkyl, aralkyl, halogen, hydroxy, alkoxy, alkylthio, aryl A thio group or a fused aromatic ring, or a mixture thereof; a and b are each independently 0 or greater. In a specific example, R4 contains from about 2 to about 8, or two or three carbon atoms. R5 is typically Contains from about 3 to about 30, or from about 4 to about 15 carbon atoms. R6 contains from 1 to about 50, or from about 4 to about 30, or from 6 to about 20 carbon atoms. Thio Alcohols can be obtained by the reaction of mercaptans (such as c4_3 () mercaptans) such as hexane 48 200302270 alcohols, octyl mercaptans and dodecane mercaptans with alkylene oxides such as ethylene oxide or propylene oxide under basic conditions Alternatively, a thiol can be obtained by reacting a terminal olefin with a fluorenylethanol under free radical conditions as disclosed herein. In another specific example, the phenol Cultivated derivatives are prepared by reacting the above thiols with an oxidant such as peroxygen in a solvent such as glacial acetic acid or ethanol under an inert gas blanket. Partial oxidation is at about 2 ° C to about 150 ° C This occurs conveniently. In another specific example, the antioxidant (A) is at least one phenol antioxidant. Phenol antioxidants include metal and metal-free hindered phenols. Hindered phenols and phenol sulfides or sulfur couplings can also be used Derivatives of phenols which are alkylated. Hindered phenols are defined as those containing sterically hindered hydroxyls, and these include derivatives of dihydroxyaryl compounds where the hydroxyls are at the 0- or P-position of each other. Phenols may have one or more alkyl groups. In a specific example, the alkyl group is derived from one or more of the above-mentioned polyenes. Such alkyl groups may be derived from polymers of ethylene, propylene, 1-butene, and isobutylene, and propylene tetramers or trimers are particularly useful. Examples of the R2 group include: hexyl, heptyl, octyl, decyl, dodecyl, tripropenyl, tetrapropenyl and the like. Examples of the I, R2 and R3 groups include: propyl, isopropyl, butyl, secondary-butyl, tertiary butyl, heptyl, octyl and nonyl. In another specific example, I and R3 are tertiary, such as tertiary butyl or tertiary-pentyl. Phenolic compounds can be prepared by various techniques. In a specific example, these brewing systems are prepared in a step-by-step manner: first, para-substituted novolak phenols are prepared, and if necessary, the 2- and / or 6-positions The para-substituted phenol is alkylated. When it is necessary to prepare a coupled phenol, the alkylation in the second step is carried out under conditions that give ortho-alkylation with only one hydroxyl group. Examples of usable phenolic substances 49 200302270 Examples include: 2-tertiary-butyl-4-heptylphenol; 2-tertiary-butyl-4-octylphenol; 2-tertiary-butyl-4 -Dodecylphenol; 2,6-di-tertiary-butyl-4-butylphenol; 2,6-di-tertiary-butyl-4-heptylphenol; 2,6-di-tris Higher-butyl-4-dodecylphenol; 2,6-di-tertiary-butyl-tetrapropenol; 2-methyl-6-di-tertiary-butyl-4-heptylphenol; 2,6-di-tertiary-butyl-tripropenylphenol; 2,4-dimethyl-6-tertiary-butylphenol; 2,6-tertiary-butyl-4-ethylphenol; 4-tertiary butyl catechol; 2,4-di-tertiary-butyl-p-cresol; 2,6-di-tertiary-butyl-4-methylphenol; and 2-methyl- 6-di-tertiary-butyl-4-dodecylphenol. Examples of ortho-coupled phenols include 2,2'-bis (6-tertiary-butyl-4-heptylphenol); 2,2, bis (6-tertiary-butyl-4-octyl) Phenol); 2,6-bis- (1'-methylcyclohexane) -4-cresol; and 2,2'-bis (6-tertiary-butyl-4-dodecylphenol) . An alkylene-coupled phenolic compound can be obtained by using a phenolic compound with an aldehyde (typically containing from one to about eight carbon atoms, such as formaldehyde or acetaldehyde), an aldehyde precursor (such as paraformaldehyde or trioxane Cyclohexane) or ketones (such as acetone) from phenol. The alkylene-coupled phenol can be made by 3 to about 2 mols are obtained by reacting with 1 equivalent of aldehyde or ketone. The step of coupling a phenolic compound with an aldehyde and a ketone is known to those skilled in the art. Examples of phenolic compounds include: 2,2, ~ methylenebis (6-tertiary-butyl-4-heptylphenol); 2,2'-methylenebis (6-tertiary-butyl- 4-octylphenol); 2,2'-methylenebis (4-dodecyl-6-tertiary-butanol); 2,2, -methylenebis (4-octyl6-tertiary) -Butylphenol); 2,2, -methylenebis (4-octylphosphonium); 2,2'-methylenebis (4-dodecylphenol); 2,2'-methylenebis ( 4-heptylfluorene); 2,2'-methylenebis (6-tertiary-butyl-4-dodecylphenol); 2,2, -methylenebis (6-tertiary-butyl) 4-tetrapropenylphenol): and 2,2, -methylenebis (6-tertiary-butyl-4-butylphenol). 50 200302270 In another specific example, the antioxidant is a metal-free (or ashless) alkylphenol sulfide or sulfur-coupled phenol. Alkylphenols from which sulfides are prepared may also include phenols of the type discussed above and represented by Formula III, where R3 is hydrogen. For example, alkylphenols that can be converted into alkylphenol sulfides include: 2-tertiary-butyl-4-heptylphenol; 2-tertiary-butyl-4-octylphenol; and 2-tertiary -Butyl-4-dodecylphenol; 2-tertiary-butyl-4-tetrapropenylphenol. The term "alkylphenol sulfide" is meant to include di- (alkylphenol) monosulfides, disulfides, and polysulfides, as well as others by using alkylphenols with sulfur monochloride, sulfur dichloride, or elemental sulfur. The product obtained by the reaction. Monomoleol is typically associated with about 0. 5-1. 5 mol or higher sulfur compounds react. For example, an alkylphenol sulfide can be obtained by mixing a mol alkylphenol and 5-2. 0 mol sulfur dichloride is easily obtained. The reaction mixture is usually maintained at about 100 ° C for about 2-5 hours, after which the resulting sulfide is dried and filtered. When using elemental sulfur, temperatures of about 150-250 ° C or higher are typically used. It is also desirable that the drying operation be performed under nitrogen or a similar inert gas. A particularly useful alkylphenol sulfide is thio-bis (tetrapropenyl phenate). Suitable basic alkylphenol sulfides are disclosed, for example, in U.S. Patent Nos. 3,372,116; 3,410,798; and 4,021,419, which are hereby incorporated by reference. These sulfur-containing phenolic compositions disclosed in U.S. Patent No. 4,021,419 are obtained by vulcanizing a substituted phenol with sulfur or halogenated sulfur, and then vulcanizing the phenol with formaldehyde or an aldehyde precursor (such as paraformaldehyde or trioxane). Hexane)). Alternatively, the substituted phenol may be reacted with formaldehyde or paraformaldehyde before reacting with sulfur or sulfur halide to produce the desired alkylphenol sulfide. Lubricating oils Lubricants and concentrates include lubricating oils. 51 200302270 oils with lubricating viscosity are usually present in large amounts (ie, amounts greater than about 50% by weight). In a specific example, the oil having a lubricating viscosity is present in an amount greater than about 60% by weight, or greater than about 70% by weight, or greater than about 80% by weight of the composition. Lubricating oils include natural or synthetic lubricants and mixtures thereof. Natural oils include animal oils, vegetable oils, mineral lubricants, and mineral oils treated with solvents or acids. Synthetic lubricants include: hydrocarbon oils (polyalphaolefins), halogen-substituted hydrocarbon oils, alkylene oxide polymers, esters of dicarboxylic acids and polyols, esters containing phosphoric acid, polymeric tetrahydrofurans and Silicone based oils. Non-refined, refined and re-refined oils, natural or synthetic, can be used in the composition of the present invention. The description of oils with lubricating viscosity appears in U.S. Patent No. 4,582,618 (column 2, line 37 to column 3, line 63 (inclusive)) by referring to its disclosure of oils with lubricating viscosity Combined in this article. In a specific example, the oil with lubricating viscosity is poly alpha-olefin (PAO). Typically, poly-alpha-olefins are derived from monomers having from about 3 to about 30, or from about 4 to about 20, or from about 6 to about 16 carbon atoms. Examples of PAOs that can be used include those obtained from decene. These PAOs may have viscosities ranging from about 3 to about 150 at TC, or from about 4 to about 100, or from about 4 to about 8 cSt. Examples of PAOs include 4 cSt polyolefin, 6 cSt polyolefin, 40 cSt Polyolefins and 100 cSt poly alpha-olefins. In a specific example, an oil with a lubricating viscosity is selected to provide at least about 3. 5 cSt, or at least about 4. Lubricant composition with 0 cSt dynamic viscosity. In a specific example, the lubricating composition has a SAE gear viscosity grade of at least about SAE 75W. The lubricating composition can also have a so-called multi-52 200302270 rating, for example: 3 people £ 75 ¥ -80,75 stomach-90,75 \ ¥ -90,75 \ ¥ · 140, 80W-90, 80W-140 , 85W-90 or 85W-140. In a specific example, the oil of lubricating viscosity is mineral oil. Mineral oils have less than 9 iodine tincture and / or at least about 45% of saturates present as aliphatic saturates. Iodine is measured in accordance with ASTM D-460. In a specific example, the 'mineral oil has an iodine tincture of less than about 8, or less than about 6, or less than about 4. Saturation is measured by a mass spectrometer. By mass spectrometry, the Group I stock solution has about 70% saturates, the Group II stock solution has about 95% to about 98% saturates, and the Group III stock solution has about 98% to 100% saturates. More than 50% of the Group II stock solution is saturated with cyclic paraffin compounds. The saturates used in the mineral oils of the present invention typically have at least about 45%, or at least about 50%, or at least about 60% aliphatic saturates. These aliphatic saturates are often referred to as paraffin saturates. The cyclic saturates are often referred to as cyclic paraffin saturates. The cyclic saturates constitute the balance of saturates in mineral oils. The inventors have found that mineral oils with a higher proportion of aliphatic saturates have better oxidative and low temperature properties. As used herein, the term "mineral oil" refers to oils of lubricating viscosity derived from crude oil. Crude oil can be subjected to processes such as hydroprocessing, hydrocracking, and isomerization. Hydroprocessing includes methods such as sequential isomerization cracking, isodewaxing, and hydrorefining. These mineral oils are known as Group 3 base oils or base oils. In a specific example, mineral oil has less than 0. 3% or less. 1% sulfur. In another specific example, oils with a lubricating viscosity usually have a viscosity index of 120 or more. Examples of lubricating oils that can be used include HVI and XHVI-based 53 200302270 base oils, these isomerized base oils and UCB0 (non-traditional base oil) base oils. Specific examples of these base oils include: 100N isomerized wax base oil (0. 01% sulfur / 141 VI), 120N isomerized wax base oil (〇. 〇1% sulfur / 149 VI), 170N isomerized wax base oil (o. Qi% sulfur / M] VI) and 250N isomerized rhenium base oil (0. 01% sulfur / 146 VI); refined base oils, such as 250N solvent refined paraffin mineral oil (0. 16% sulfur / 89 VI), 200N solvent refined naphthalene mineral oil vi), 100N solvent refined / hydrotreated paraffin mineral oil (0. 01% sulfur / 98 VI), 240N solvent refined / hydrotreated paraffin mineral oil (0. 01% sulfur / 98 VI), 80N solvent refined / hydrotreated paraffin mineral oil (0. 08% sulfur / 127 VI) and 150N solvent refined / hydrotreated paraffin mineral oil (0. 17% sulfur / 127 VI). Further examples of mineral oils include Group 3 base oils manufactured by Texaco, such as TEXHVI, which includes TEXHVI-lOON (95% saturated, 125 viscosity index and 0. 02% sulfur); TEXHVI-70N (97. 8% saturated, 123 viscosity index and 0. 02% sulfur); Texaco "MOTIVA" TEXHVI 90N_100N (100% saturated, 125 viscosity index and 0. 01% sulfur); and "MOTIVA" TEXHVI 75N (100% saturated, 125 viscosity index and 0.0% sulfur). Examples of usable Group 3 base oils manufactured by Chevron include: UCB 200N (100% saturated, 142 viscosity index and 0. 005% sulfur); UCB〇 100N (100% saturated, 129 viscosity index, and 0. 004% sulfur). Polymers In a specific example, the thickened lubricant will have at least one polymer present. The polymer is generally present in an amount of from about 3% to about 40% by weight, or from about 5% to about 35% by weight, or from about 10% by weight to 54 200302270% to about 30% by weight. Polymers include polyenes or their derivatives, ethylene-α-olefin copolymers, ethylene-propylene polymers, oc-olefin-unsaturated carboxylic acid reagent copolymers, polyacrylates, polymethacrylates, alkenyl aromatic hydrocarbons And conjugated diene hydrogenated homopolymers, and mixtures thereof. Here, and elsewhere in this specification and the scope of the patent application, any member of the higher order (or list) may be excluded from the scope of the patent application. In a specific example, the polymer is characterized by a Mw (weight average molecular weight) of less than about 50,000, or less than about 45,000, or less than about 40,000. In a specific example, the polymer has a Mw of less than about 25,000, or less than about 10,000, or less than about 7,000. Typically polymers have a Mw of at least about 1,000, or at least about 2,000, or at least about 3,000. In a specific example, the polymer is characterized by Mn (number average molecular weight) up to about 6000 or up to about 5000. Generally, polymers are characterized by having an η of from about 800 to about 6000, or from about 900 to about 5000, or from about 1000 to 4000. In another specific example, the polymer has a Mn of from about 1300 to about 5000, or from about 1500 to about 4500, or from about 1700 to about 3000. Polymers usually also have from about 1. 5 to about 8, or from about 1. 8 to about 6. 5, or from about 2 to about 5. Mw / Mn 0 of 5 In a specific example, the polymer may be a higher molecular weight (e.g., greater than 50,000) shear polymer. In this specific example, the high molecular weight polymer is sheared to the desired molecular weight. Shearing can be performed in any suitable instrument, such as extruder, syringe, FZG instrument, etc. The abbreviations Mw and Mη are conventional symbols representing weight average and number average molecular weights, respectively. Gel Permeation Chromatography (GPC) is a method to provide the molecular weight and total molecular weight distribution of polymers 55 200302270. For the purposes of the present invention, a series of fractionated polymers of isobutylene, i.e. polyisobutylene, are used as calibration standards in GPC. Techniques for determining the η and w 値 of polymers are known and described in many books and papers. For example, the method for determining the η and molecular weight distribution of a polymer is disclosed in W. W.  Yan, U.  Kirkland and D. D.  Bly, "Modern size excludes liquid chromatography,"]. Weiss & Sons, 1979. In a specific example, the polymer is one of the polyenes described herein. In another specific example, the polymer is a derivative of polyene. The derivatives are typically prepared by reacting one or more of the above polyenes or their halogenated derivatives with an unsaturated reagent. Halogenated polyolefins are prepared by reacting a polyolefin with a halogen gas such as chlorine. The preparation of these materials is known to those skilled in the art. Unsaturated reagents include unsaturated amines, ethers, and unsaturated carboxylic acid reagents, such as unsaturated acids, esters, and anhydrides. Examples of unsaturated amines include unsaturated amines, unsaturated amines, and nitrogen-containing acrylates and methacrylates. Specific examples of unsaturated amines include: acrylamide, N, NN-methylenebis (acrylamide), methacrylamide, crotylamine, N- (3,6-diazaheptyl) Maleimide, N- (3-dimethylaminopropyl) maleimide, N- (2-methoxyethoxyethyl) maleimide, N-vinylpyrrolidone, 2- or 4-vinylpyridine, dimethylaminoethyl methacrylate and the like. In a specific example, the unsaturated carboxylic acid reagent is an acid, an anhydride, an ester, or a mixture thereof. If an ester is required, it can be prepared by reacting an unsaturated carboxylic acid or anhydride with a polyene or a halogenated derivative thereof, and then reacting the reaction product with an alcohol to form an ester. Unsaturated carboxylic acid reagents include: acrylic acid, methacrylic acid 56 200302270 acid, cinnamic acid, crotonic acid, 2-phenylacrylic acid, maleic acid, maleic anhydride, trans-butenedioic acid, methyl -Trans-butenedioic acid, decomposed aconitic and citraconic acid maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid and citraconic acid, esters and anhydrides, if possible. The esters can be represented by one of the following formulas: (1) 2〇 = 〇: 〇 ^) (: (〇) 〇112, or r2〇- (〇) c-hc = CH-C (0) 〇R2, each Ri and R2 are independently hydrogen or a hydrocarbon group having from 1 to about 30, or to about 12, or to about 8 carbon atoms, and & is hydrogen or an alkyl group having from i to about 6 carbon atoms. In a specific example, R1 is preferably hydrogen or methyl. In another specific example, the core is an alkane having from about 1 to about 30, or from 2 to about 24, or from about 3 to about 18 carbon atoms Or hydroxyalkyl. I may be derived from one or more of the following alcohols. Unsaturated carboxylic acid esters include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, ethyl maleate, butyl maleate, and maleate Acid 2-ethylhexyl ester. The above list includes maleic acid 'fumaric acid, and mono- and diesters that decompose aconitic acid and anhydrides. Polyene derivatives are prepared by methods known in the art. These Hydrocarbyl substituted carboxylic acid Chemical agents are discussed below. U.S. Patent Nos. 3,219,666 and 4,234,435 disclose polyene derivatives and methods of making them 'and are incorporated herein for such disclosure. In another specific example, the polymer is an ethylene-alpha -Olefin copolymer ° Typically, the copolymer is a random copolymer. The copolymer typically has from about 30 mole% to about 80 mole%, or from about 50 mole% to about 75 mole%. Ethylene. Alpha-olefins include butene, pentene, hexene, or more than one of the above-mentioned alpha-olefins of 57 200302270. In ~ specific examples, ^ olefins contain from about 3 to about 20, or from about 4 to About 2 carbon atoms. In a specific example, the ethylene-α-olefin copolymer has from about 10,000 to about 40,000, or from about 15,000 to about 35,000, or Mw from about 20,000 to about 30,000. In another specific embodiment, the ethylene-α-olefin copolymer has from about 8% to about 6000, or from about 150,000 to about 5000, or η from about 20 ° to about 450,000. Examples of ethylene alpha-olefin copolymers include ethylene-butene copolymers and ethylene-octene Dimer. Examples of commercial copolymers include Lucant HC 600 and

Lucant HC 2000 (Mw = 25,000), available from Mitsui Petrochemical Co., Ltd. In another specific example, the polymer is an ethylene propylene polymer. These polymers include ethylene propylene copolymers and ethylene propylene terpolymers. When the ethylene propylene polymer is an ethylene propylene copolymer (EPM, also known as an EPR polymer), it can be used by ethylene and propylene under known conditions (such as Ziegler-Natta reaction conditions) The copolymer compound is formed. In a specific example, the ethylene propylene copolymer comprises from about 40 mole% to about 70 mole%, or from about 50 mole% to about 60 mole%, or about 55 mole%. The amount is derived from ethylene and the remainder is derived from propylene units. The molecular weight distribution may be characterized by polydispersity (Mw / Mn) from about 1.2 to about 4, or from about 1.2 to about 4. In another specific example, Ethylene propylene polymers are terpolymers of ethylene, propylene, and diene monomers. In a specific example, the diene is a conjugated diene. Diene systems are disclosed herein. Terpolymers are similar to ethylene Produced under the conditions of a propylene copolymer. A terpolymer that can be used contains an amount of 58 200302270 from about 10 mole% to about 80 mole%, or from about 25 mole% to about 85 mole%, or about 35 moles Ear mole% to about 60 mole% of ethylene-derived units in quantities from about 15 moles Mol% to about 70 mol%, or from about 30 mol% to about 60 mol%, propylene-derived units and quantities from about 0.5 mol% to about 20 mol%, or from about 1 mol% To about 10 mole%, or about 2 mole% to about 8 mole% of units derived from a diene third monomer. The following table contains examples of ethylene propylene terpolymers. Examples Ethylene Propylene Diene A 42% * 53% 5% 1,5 heptadiene B 48% * 48% 4% dicyclopentadiene C 45% * 45% 10% 5-ethylidene-2-norbornene D 48% * 48 % 4% 1,6 octadiene E 48% * 48% 4% 4 Cyclohexadiene F 50% * 45% 4% 5-Methylene-norbornene * Percent in moles in a specific example The ethylene propylene polymer is a terpolymer of ethylene, propylene, and dicyclopentadiene or ethylidene norbornene. The commercial product is a Trilene elastomer obtained from Uniroyal. The ethylene propylene terpolymer that can be used is Tnlene. CP-40. Ethylene propylene polymers are prepared by methods known to those skilled in the art. U.S. Patent No. 3,691,078 describes ethylene propylene polymers and methods of making them, and is hereby incorporated by reference to these disclosures 59 200302270 In another specific example, the 'polymer is a copolymer of an alpha-olefin and an unsaturated test agent. The olefin may be any of the foregoing discussions and includes, propylene, 1-butene, 2 -Methacrylic, 2-methyl-1-octene and; decene. Unsaturated reagents are as described above. Unsaturated carboxylic acid reagents include acrylates, methacrylates, cis-butenedioates and trans • Butenedioate. Ou olefin-unsaturated carboxylic acid reagent polymers are prepared by methods known to those skilled in the art. Examples of olefin-unsaturated carboxylic acid reagent copolymers include poly (octene-co-propionic acid ethyl ester), poly (decene-co-butyl methacrylate), poly (hexene_co_cis-butane Adipic anhydride), poly (octene-co-trans-butenedioic acid methyl ester) and the like. In another specific example, the polymer is a polyacrylate or polymethacrylate. Polyacrylates and polymethacrylates include one or more of the above homopolymers and homopolymers of acrylic or methacrylic acid or esters. Polyacrylates and polymethacrylates include: Aeroyloid 1019 polymer available from Rohm and Haas Corporation 'Garbacryl 6335 available from Society Francaise d'Organo-Sythese (SFOS), available from Lubrizol LZ 7720C and Viscoplex 0-101 polymer available from Rohm Darmstadt. • In another specific example, the polymer is a hydrogenated homopolymer of a vinyl-substituted aromatic compound and a conjugated diene. Homopolymers include diblock, triblock, and random block homopolymers. Vinyl-substituted aromatic compounds typically have from about 8 to about 20, or from about 8 to about 18, or from about 8 to about 12 carbon atoms. Examples of vinyl-substituted aromatics include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tertiary-butylstyrene, and more preferably Styrene. A total of 60 200302270 conjugated diene is as described above. Isoprene and 1,3-butadiene are preferred conjugated dienes. The vinyl-substituted aromatic content of these copolymers ranges from about 20% to about 70% by weight, or from about 40% to about 60% by weight. Therefore, the conjugated diene content is in the range of about 30% by weight to about 80% by weight, or from about 40% by weight to about 60% by weight. These homopolymers are prepared by conventional methods known in the art. These copolymers are usually prepared by anionic polymerization using, for example, an alkali metal hydrocarbon (for example, tertiary-butyllithium) as a polymerization catalyst. Examples of suitable hydrogenated copolymers of vinyl-substituted aromatic compounds and conjugated dienes include Shellvis-40 and Shellvis-50, both of which are hydrogenated styrene-isoprene block copolymers, manufactured by Shell Chemistry . Fluidizing agent The lubricating composition may additionally include at least one fluidizing agent. Typically, the fluidizing agent is present in an amount up to about 30% by weight. Typically, the fluidizing agent is present in an amount of from about 3% to about 30% by weight, or from about 5% to about 28% by weight, from about 10% to about 27% by weight, or from about 15% to about 25% by weight. The amount of fluidizing agent is equal to the total amount of fluidizing agent in the lubricating composition. In a specific example, the fluidizing agent is at least one selected from the group consisting of alkylated aromatic hydrocarbons, naphthalene oils, polyalphaolefins having a dynamic viscosity at 10 ° C. from about 3 to about 20 cSt, carboxylic acid esters, and A member of the group consisting of a mixture of two or more of them. Alkylated aromatics typically include mono- or di- (or mono-) substituted benzenes, where the substituents have from about 8 to about 30, Or from about 10 to 61 200302270 hydrocarbon-based groups of about 14 carbon atoms. Examples are alkylates A-215 (237 molecular weight alkylated benzene) and alkylates A-230 (available from Monsanto) 230 molecular weight alkylated benzene). Naphthalene oils are derived from naphthalene raw materials such as those found in the Louisiana area. The viscosity of naphthalene oils is usually less than 4 centimeters at 40 ° C, and is more often from about 3.0 to about Within the range of 3.8% history. Desired naphthalene oils 10 (TC viscosity is in the range of about 0.8 to about 1.6% history. Poly alpha-olefins (PAO) are described above. Examples of PAOs that can be used include derivatization From one or more of the aforementioned olefins, such as alpha-olefins. These PAOs at 10 CTC may have from about 2 to about 30, or from about 3 to about 20, or from about 3 Viscosity to about 8 cSt. Examples of PAO include 4 cSt poly alpha-olefins, 6 cSt poly alpha-olefins and 8 cSt poly alpha-olefins. Particularly useful PAO series are derived from decene. Carboxylic acid ester streams Chemical agents are the reaction products of dicarboxylic acid esters with alcohols having from about 1 to about 30, or from about 2 to about 18, or from about 3 to about 12 carbon atoms. Alcohols are described below and include methyl groups , Ethyl, propyl, butyl, hexyl, heptyl, octyl, decyl, and dodecyl alcohol. Dicarboxylic acids typically contain from about 4 to about 18, or from about 4 to about 12, or from About 4 to about 8 carbon atoms. Examples of dicarboxylic acids include peptidic acid, succinic acid, alkyl (cv24) succinic acid, azelaic acid, adipic acid, and malonic acid. Particularly useful esters are the dicarboxylic acids of CV12 alcohols. Carboxylic acid esters' such as propyl, butyl, pentyl, hexyl, and octyl alcohol and azelaic acid. In a specific example, the lubricating composition contains less than about 20% by weight, or less than about 15% by weight of carboxylic acid Ester fluidizers. The above mineral oils can be used with commercially available gear and transmission concentrates (for example, sold by Exχ〇η 62 200302270, Lubrizol, Ethyl and Mobil) In this specific example, the commercial concentrates are diluted with base oils to form transmission and gear formulations. The composition can be used in lubricants or concentrates. The concentrate can include the above-mentioned composition and / or be prepared in The other ingredients used in the lubricant are fully formulated. The concentrate also contains a substantially inert organic diluent, including kerosene, mineral distillate, or one or more oils of lubricating viscosity as discussed herein. Composition Any amount effective in the lubricating composition as an anti-wear, anti-weld and / or ultrahigh pressure agent is present in the final product, blend or concentrate. In a specific example, the lubricating composition is free of sulfurized olefins and fatty acids or esters. In another specific example, the lubricating composition is free of overbased metals. In another specific example, the lubricating composition is free of zinc dithiophosphates. In another specific example, lead compounds are not added to the lubricating composition, such as lead naphthalate, lead dithiophosphate, and lead dithiocarbamate. In another specific example, the lubricating composition is free of succinimine derived from olefins or polyolefins and ammonia or mono-amine. In another embodiment, the lubricant composition is free of detergents or overbased metal salts of acidic organic compounds. Other additives The present invention also contemplates the use of other additives with the above composition. These additives include, for example, detergents and dispersants, corrosion and oxidation inhibitors, pour point depressants, extreme pressure agents, anti-wear agents, color stabilizers, and anti-staining agents. Examples of detergents are oil-soluble neutral and basic salts (ie, highly basic salts) of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, phenols, or organic phosphoric acids (such as those described above). Oil-soluble neutral or basic salts of alkali or alkaline earth metal salts may also react with boron compounds. Examples of overbased and boron-containing overbased metal salts that can be used include sodium, calcium, and magnesium overbased and boron-based overbased sulfonates and carboxylates, including the above-mentioned hydrocarbyl-substituted carboxylic acids 醯化 剂。 Chemical agent. Examples of auxiliary ultrahigh pressure agents and corrosion and oxidation inhibitors that can be included in the lubricants of the present invention are: chlorinated aliphatic hydrocarbons such as rhenium chlorides; sulfurized alkyl phenols; phosphorus sulfurized hydrocarbons such as phosphorus sulfide and turpentine Or methyl oleate products; metal thiocarbamates, such as zinc dioctyl dithiocarbamate and barium diheptylphenyl dithiocarbamate, and ashless dithioamines A reaction product of a formate, such as a dithioamino formic acid and an unsaturated acid, ester, anhydride, amidine, ether or amidine. Many of the above-mentioned UHV agents and corrosion and oxidation inhibitors also act as anti-wear agents. Pour point depressants are an additive often included in the lubricants described herein. Examples of pour point depressants that can be used are: polymethacrylates; polyacrylates; polyacrylamides; condensation products of halostone and aromatic compounds; vinyl carboxylate polymers; and dialkyls Fumarate polymers, vinyl esters of fatty acids and alkyl vinyl ethers. The pour point depressant which can be used for the purpose of the present invention, its preparation technology and its use are disclosed in US Patent Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,746; 2,721,877; 2,721,878; And 3,250,715, which are hereby incorporated by reference. It should be understood that any of the aforementioned additives taught as potential ingredients may be limited by the lubricating composition. 64 200302270 The following examples relate to lubricating compositions containing diazoles. Example 1 An industrial gear oil was prepared by blending 0.95 parts of 2,5-bis (tertiary-nonyldithio) 1,3,4-thiadiazole into an industrial gear base oil. Example 2 An industrial gear oil was prepared by dissolving 1.2 parts of 2-fluorenyl-5-tertiary-nonyldithio-1,3,4thiadiazole and 0.02 parts of ethyl acrylate and 2-ethylhexyl acrylate. A 50% solution of an ester copolymer prepared from an ester (100: 40) is prepared by blending industrial gear oil base stock. Example 3 An industrial gear oil was prepared by blending 1.2 parts of the thiadiazole from Example 1, 0.02 parts of the ester copolymer of Example 1, and 0.4 parts of the product of Example P-3. Example 4 An industrial gear oil was prepared as described in Example 3, but the product of Example P-3 was replaced with 1.2 parts of the product of Example P-8. Example 5 An industrial gear oil was prepared as described in Example 2, but 0.05 parts of the product of Examples 1-2 were included in the industrial gear oil. Example 6 An industrial gear oil was prepared as described in Example 4, but 0.05 parts of the product of Examples 1-2 were included in the industrial gear oil. Example 7 An industrial gear oil was prepared as described in Example 6, but also including 0.02 parts of 65 200302270 tolyltriazole. Example 8 An industrial gear oil was prepared as described in Example 7, but using a reaction product of 0.05% part of a dispersant in 40% oil solution (polyisobutylene succinic anhydride (Mη 850) and polyethylene polyamines, and having TBN of 70) and 0.01 part of Pluradyne FL11 (ethylene oxide-propylene oxide copolymer available from BASF). Example 9 A manual transmission fluid system was prepared by mixing 1.1 parts of 2,5-bis (tertiary-nonyldithio) 1,3,4-phazazole into a manual transmission base oil. Example 10 A manual transmission fluid system was prepared by mixing 1.5 parts of 2-fluorenyl-5_tertiary-nonyldithio-1,3,4thiadiazole and 0.01 parts of Dow Corning 200 liquid kerosene solution (30,000 cSt dynamic Viscosity) is prepared by blending with manual transmission base oil.

Example 9A A manual transmission fluid system was incorporated into a manual transmission by incorporating 1.5 parts of 2,5-bis (tertiary-nonyldithio) 1,3,4-_diazole and 0.5 parts of the product of Example P-8. Prepared in base stock.

Example 10B A manual transmission liquid was prepared as described in Example 9, but 0.01 parts of a kerosene solution of Dow Corning 2000 liquid (dynamic viscosity of 30,000 cSt) was also included in the manual transmission liquid. Example 11 A manual transmission fluid system was prepared as described in Example 10, but 0.5% dinonyldiphenylamine was also included in the manual transmission fluid. 66 200302270 Example 12 A manual transmission fluid system was prepared as described in Example 11, but also included L5 parts of benzenesulfonate substituted with overbased calcium (300 TBN, 12% calcium and 40.8% sulfur ash) 42 % Oil solution. Example 13 A manual transmission fluid system was prepared as described in Example 12, but further comprising 1 part of a dispersant (the reaction product of polyisobutenyl succinic anhydride (Mη 1500) and a polyethylene polyamine, and having a TBT of 27). 50% oil solution. While the present invention has been explained in its related preferred specific examples, various modifications will be apparent to those skilled in the art when reading the specification. Therefore, it should be understood that the invention intended to be disclosed herein encompasses such amendments and falls within the scope of additional patent applications.

67

Claims (1)

200302270 Patent application scope 1. A lubricating composition comprising a large amount of oil with lubricating viscosity and at least about 0.4% by weight of at least one amine-free thiadiazole, wherein the lubricating composition contains no organic polysulfide and contains less than about 2% by weight of at least one dispersant. 02. The composition according to item 1 of the patent application scope, further comprising at least one phosphorus antiwear agent. 3. The composition according to item 1 of the scope of patent application, further comprising less than about 1.5% by weight of at least one dispersant and at least one mothproofing agent, and at least one imidazoline or at least one fatty carboxylic acid and at least one polyamine The reaction product, wherein the amine-free thiadiazole is a fluorenylthiadiazole having at least one hydrocarbyl group or a thiothiadiazole or dithiothiadiazole substituted with a dihydrocarbyl group. 4. An industrial gear oil composition comprising a large amount of oil having a lubricating viscosity and at least about 0.4% by weight of at least one amine-free thiadiazole and at least one phosphorus antiwear agent, wherein the lubricant is free of polysulfide compounds. 5. The composition according to item 4 of the scope of the patent application, wherein the composition further comprises at least one dispersant in an amount of less than about 2% by weight. 6. The composition according to item 4 of the patent application, wherein the composition further comprises at least one imidazoline or a reaction product of at least one fatty carboxylic acid and at least one polyamine. 7. A manual transmission composition comprising a large amount of oil with lubricating viscosity and at least about 0.4% of at least one amine-free thiadiazole 'wherein the lubricant is free of organic polysulfides and contains at least one of less than about 2% by weight Dispersant. 8. The composition according to item 7 of the scope of patent application, which further comprises 68 200302270 at least one phosphorus antiwear agent. 9. The composition according to item 7 of the patent application scope, further comprising at least one imidazole or the reaction product of at least one fatty carboxylic acid and at least one polyamine. 10. The composition according to item 7 of the scope of patent application, further comprising an overbased metal salt of at least one acidic organic compound, at least one antioxidant, and at least one mothproofing agent. Pick up, schema (none). 200302270 Lu, (1), the designated representative of the case is: (No) Figure (2), the representative symbols of the representative diagram are briefly explained: 柒, if there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: