JPH01501396A - Lubricant compositions containing transition metals for viscosity control - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Lubricant Compositions Containing Transition Metals for Viscosity Control Background of the Invention 1. FIELD OF INDUSTRIAL APPLICATION This invention relates to lubricant compositions, and in particular to the viscosity control of lubricants in diesel engines. 2. BACKGROUND OF THE INVENTION Lubricants, especially diesel engine lubricants used in low speed, high torque operations, suffer from the problem of viscosity build-up over a period of two hours. This increase in viscosity is caused by Initially, the viscosity of the lubricant in the tank increases gradually, and the rate of increase in viscosity increases over time. This appears in the form of being promoted by Eventually, the viscosity increase becomes high enough and oil flow within the engine becomes restricted. The second factor is that the lubricant in the oil storage tank gradually becomes thicker. This means that it cannot be used for lubrication. If the thickened lubricant does not pass through the oil pump inlet, engine damage will result. Such increased viscosity can therefore lead to undesirable engine wear, especially in cold climates. The main prevention technique to avoid damage due to excessive viscosity build-up is to drain a small amount of oil from the oil storage tank and measure the viscosity of the lubricant. Therefore, it becomes a problem to determine the correct interval to check the oil storage tank. sticky As the rate of temperature change increases, the intervals between lubricant viscosity checks must become more frequent to ensure that engine damage is not occurring. Covitch+ by Humphrey and Ripple. The paper entitled ``N2 Thickening in the Mack T-7 Engine'' describes the use of various compounds in diesel lubrication. It is stated that it can be added to lubricants to suppress oil thickening. The paper by Covitch et al. was presented at the SAE Fuels and Lubricants Conference, October 23, 1985, Tulsa, Oklahoma. The paper by Covitch et al. teaches that Reportedly, soot is produced as a product of incomplete combustion in diesel engines and gets into the lubricating oil. The presence of soot in the crank chamber can cause damage to the lubricant. This has led to an increase in viscosity and viscosity. Application of Koch et al. (filed on September 24, 1985, application number; Science No. L-2226B) suggests that various metal complexes of Mannich bases and transition metals may be used in fuels. Koch et al. further suggest that Schiff bases can be included in these compositions. Dorer et al., in a pending application (filed on October 5, 1983; attorney's case docket number L-2161B), disclose that salts containing manganese and salts containing copper that are soluble in hydrocarbons mixture of It points out that substances can be used as fuel additives to lower the combustion temperature of particulates exhausted from diesel engines. Diesel lubricants containing alkali metal salts as additives to minimize undesirable viscosity increases in diesel engines have been developed by Ripple. United States application filed on September 19, 1985, application number; Case reference number L-2238R). The Ripple application further describes dispersants useful in diesel crankcase lubricants. transition fee soluble in hydrocarbons (ash-free dispersants and phenolics) containing antioxidants) are disclosed in Tupa, US Application No. 2176B, filed August 30, 1984. U.S. Pat. However, this composition contains a succinimide dispersant, calcium phenate + and copper, iron as an oxidation catalyst. Contains a kerosene solution of naphthenic acid metal salts containing soot, manganese and lead. In the Hendrickson patent, the object containing the metal was determined by the effectiveness of the dispersant used. Obviously, part of the fruit testing is to rapidly increase the oxidation of the oil. Yan, U.S. Pat. No. 4,529,408 (July 16, 1985), teaches that the combustion of coal can be improved by incorporating several thousand parts of metal into the coal. vinegar In other words, it has been suggested that it can alleviate corrosion caused by ash and reduce dirt and ash slagging. Substances suggested by Yan include manganese dioxide. Includes one selected from the group consisting of iron oxide, manganese nodules, sand and mixtures thereof. Johnson, in U.S. Patent No. 4,411.774 (October 25, 1983), states that waste oil contains soot, lead, copper, and aluminum. Iron, chromium, zinc, magnesium, nickel, barium, sodium, calcium This suggests that various metals are present in percent concentrations, including aluminum, vanadium, molybdenum, boron, and manganese. According to Johnson9, waste oil may also contain silicon, phosphorus, and possibly silver. )1otten, in U.S. Patent No. 4.049.562 (September 20, 1977), states that the antioxidant activity of oil is It is suggested that it can be tested in the presence of solutions containing phthenate. Hotten further states that such a distribution of metals is expected to be found in crankcase oils used from diesel engines. Various transition metals as oxidation inhibitors are described in Black, US Pat. No. 4.122.033 (October 24, 1978). In U.S. Patent No. 3,652,616 (March 28, 1972), Katson describes zinc, manganese, chromium, copper, cobalt and vanadium. Describes fuel and lubricant compositions containing metals such as titanium, molybdenum, silver, cadmium, tungsten or mercury. The use of copper as an antioxidant in lubricants is Coleugh, European Patent Application No. 0024146 (published February 25, 1981). It has been found in the present invention that relatively small amounts of certain transition metals can be used in oil-soluble form in diesel lubricant compositions to substantially reduce viscosity increase and soot associated with viscosity increase (promotion). It's being served. The compositions of the present invention are particularly useful for diesel oils that undergo rapid viscosity increases. Throughout the specification and claims, percentages and ratios are by weight and temperatures are by weight. Temperatures are in degrees Celsius and pressures are in KP, gauge unless otherwise noted. References cited in this application are hereby incorporated by reference to the extent applicable to the present invention. and adopt it. SUMMARY OF THE INVENTION The present invention features an oil of lubricating viscosity, a dispersant, and a small amount of oil-soluble or oil-dispersible gold. a lubricant composition containing a compound of the group Manganese, Titanium, Cobalt, in an amount sufficient to suppress soot associated with increased viscosity of the oil; , copper, vanadium nickel, tungsten, molybdenum, and chromium, and mixtures thereof. A further embodiment of the present invention provides a lubricant composition containing a major amount of an oil of lubricating viscosity and an oil-soluble or oil-dispersible metal compound from about 30 to about 500 ppa+ as metal. The metal compound is capable of suppressing soot, which is associated with an increase in the viscosity of this oil when used in diesel engines, and is capable of controlling manganese, titanium, and Cobalt, Chromium, Vanadium, Nickel. Contains a metal selected from the group consisting of tungsten, molybdenum, and mixtures thereof. The present invention further describes a method for suppressing soot associated with increased viscosity of a lubricant in a lubricating system prone to increased soot, the method comprising the step of introducing a metal compound into the lubricant. are doing. Here, the metals include manganese, titanium, cobal), &M, vanadium, nickel, tungsten, chromium, and molybdenum, etc. and mixtures thereof. The amount of the metal compound is sufficient to retard the increase in viscosity. DETAILED DESCRIPTION OF THE INVENTION In principle, the present invention is a composition comprising a polyvalent metal compound and a diesel lubricating oil. Metal compounds include manganese and copper. Nickel, vanadium, titanium, tungsten, cobalt. Includes both organic and inorganic forms of chromium, molybdenum and mixtures thereof. good Preferably, the metal compound includes manganese or titanium. Also useful here metal phenates, metal surichlates, metal phosphonates, metal dithiocals bamates and metal napthanates. nabutane is a preferred type of metal compound. Inorganic compounds include, for example, oxides, hydroxides, and carbonates. organic and Nine inorganic metal compounds are useful in the mixtures of the present invention. The amount of metal used is should be sufficient to retard the viscosity increase between 100 and 150 hours in the T-7 test. Therefore, the slope of viscosity increase should be less than 0.1, preferably less than 0.08, in the interval from 100 hours to 150 hours. Preferred organic compounds useful in metal compounds are convenient salts of at least one organic acid. Mixtures of organic and inorganic metal components are useful, but if the metal compound It is highly desirable to use organometallic compounds to aid in dispersion in lubricants. Yes. Organic acids used in preparing salts of metal compounds include carboxylic acids, especially those having 1 to 30 carbon atoms, such as carboxylic acid salts; sulfonic acids, especially those having 4 to about 30 carbon atoms. A sulfonic acid having an aromatic ring structure (e.g. a benzene ring) substituted with one or more alkyl groups having Phosphoric acids having one or more organic groups having from 1 to about 30 or more carbon atoms in their structure are included. Preferably, the organic acid has an average of at least 7 carbon atoms, 9 conveniently such that the total number of carbon atoms per carboxyl group is from about 4 to about 30, preferably from 6 to 30. It is a mixture of organic acids. Such carboxylic, sulfonic, and phosphoric acids are known in the art. mosquito The carboxylic acid may be a mono- or polycarboxylic acid (in the latter case typically a dicarboxylic acid). - or tricarboxylic acids). Monocarboxylic acids include fatty acids having about 12 to 30 carbon atoms, as well as lower Cx-t acids (acetic acid, propionic acid, etc.) and higher C8° acids (e.g. Contains tannic acid, decanoic acid, etc. Neoacids such as neooctanoic acid and neodecanoic acid are also useful. Fatty acids are often a mixture of straight and branched chain acids. The mixture contains, for example, 5 to about 30 (mol)% straight chain acid and about 70 to about 95 (mol)% branched chain acid. Other commercially available fatty acid mixtures containing much higher proportions of straight chain acids are also useful. Mixtures produced by trimerization of unsaturated fatty acids objects can also be used. Higher carboxylic acids can be obtained by alkylating maleic anhydride or its derivatives. Known dicarboxylic acids prepared accordingly are included. The products of such reactions include hydrocarbon-substituted succinic acid, succinic anhydride, and the like. Low molecular weight dicarboxylic acids2, such as polymethylene crosslinked acids (glutaric acid, adipic acid, etc.), as well as low molecular weight substituted succinic acids, such as tetrapropenylsuccinic acid and its analogues of acids substituted up to about C1°. can be used to prepare the salts of the present invention. High molecular weight substituted succinic anhydrides, succinic acids, and and analogs are described in numerous patents, particularly those dealing with acylated compounds useful as dispersants. A typical high molecular weight acid is one prepared by reacting a poly(isobutyne) moiety having between 30 and 400 carbon atoms (usually 50-250) with maleic anhydride. Such materials are described in the following U.S. patents: No. 3,172.892 to Le 5uer et al., published March 9, 1965; (published November 23, 1965); and Le 5uer et al., No. 3.272. No. 746 (Patent Mill September 13, 1966). Other monocarboxylic acids with similar molecular weights include acrylic acid and its analogs. It can be prepared by alkylation. Mixtures of such acids may also be used. Metal compounds useful in this invention can also be prepared from carboxylic acids and also acidic hydroxy compounds such as alkylated phenols. Such materials are described in U.S. Pat. Typically 9 organic acids used to prepare the salts of the present invention include carboxylic acids, sulfuric acids, It is fonic acid, a mixture thereof, or a compound having both functional groups. Sulfonic acids used to form metal compounds include aliphatic sulfonic acids. Examples of such sulfonic acids are: Mahogany sulfonic acid; Brightstock sulfonic acid; derived from lubricating oil fractions having a Saybolt viscosity of about 100 seconds (37°C) to about 200 seconds (99°C). petrolatum sulfonic acid; substituted with mono- and polywaxes 9 For example, benzene, naphthalene, phenol, diphenyl ether, naphthalene sulfonic and polysulfonic acids, such as di-sulfide, diphenylamine, thiophene, and α-chloronaphthalene; alkylbenzene sulfonic acids (where (the kill group has about 8 carbon atoms), cetyl phenyl monosulfide sulfonic acid, dicetylthianthenedisulfonic acid, dilauryl β-naphthylsulfonic acid, capril nitronaphthalene sulfonic acid, and e.g. dodecylbenzene (bottoms). Other substituted sulfonic acids such as alkaryl sulfonic acid, such as sulfonic acid. Dodecylbenzene (bottoms) is primarily a mixture of mono- and di-dodecylbenzene. Aliphatic sulfonic acids include paraffin wax sulfonic acid. Unsaturated halaffin wax sulfonic acid, hydroxy-substituted paraffin wax sulfonic acid Fonic acid, hexapropylene sulfonic acid. Tetraamylene sulfonic acid, polyisobutyne sulfonic acid (here, polyisobutyne sulfonic acid Chin has 20-7000 or more carbon atoms), chloro-substituted para Fin wax sulfonic acid. such as nitro-paraffin wax sulfonic acids, and petroleum naphthene sulfonic acids, etc. cetylcyclopentylsulfonic acid. Included are cycloaliphatic sulfonic acids such as laurylcyclohexylsulfonic acid, bis-(di-isobutyl)cyclohexylsulfonic acid, mono- or poly-wax substituted cyclohexylsulfonic acid. Further details regarding the sulfonic acids used herein can be found in the following US patents: Wear. Patent Inventor Patent Mortar 2.616,905 As5eff et al. November 4, 1952 3 + 027 + 325 MCM il fen et al. March 27, 1962 3 + 312.618 Le 5uer et al. April 4, 1967 3.350,308 McMille n et al. October 31, 1967 3+47L403 Le 5uer et al. October 7, 1969 3.488,284 Le 5uer et al. January 6, 1970 3, 595.790 1Jorman et al. July 27, 1971 3.798.012 Le 5uer March 19, 1974 3.829.381 Le 5uer August 13, 1974 4, 100.083 Ripple August 22, 1978 4.326.972 Chamberlin April 27, 1982 Japanese invention useful Salts may be prepared from phosphoric acid. Such phosphoric acids are disclosed in numerous US patents and other publications. An example of the former is Jahnke, US Pat. No. 191.658 (March 4, 1980) discloses phosphates of the linear formula: where 1M is the above metal in a metal compound or mixture thereof; each R1 and and R2 are hydrocarbon groups; each of XI, y, Z, X3 and x4 is oxygen or sulfur; and each of a and b is 0 or 1. Salts prepared from organic acids combine organic salts with metals, especially manganese. For example, it can be prepared by reacting with manganese oxide, manganese hydroxide, manganese carbonate, cupric oxide, cupric hydroxide, and cupric carbonate. A particularly preferred method for obtaining metal compounds is such as overbased salts. The overbased salt contains enough gold to neutralize the acid present. It is an organic acid salt containing more metals than the genus. In other words, the overbased salt Contains more than one equivalent of metal per amount of acid-derived moiety. Such salts are known in the art. For disclosures relating to overbasing, see, for example, the following U.S. patents: Piotroevski et al., No. 3.827,979; As5eff Nos. 2.616.904 and 2.616.905 (Patent Mill November 4, 1952); Norman et al. No. 2.595.790; No. 3,725,441 of Murphy et al., April 3, 1973. For specific disclosure regarding overbased manganese and copper salts of organic acids, see the following U.S. patents: No. 2.695.910 to Aseff et al. No. 4.162.986 (Patent Mill July 31, 1979) and Alkaitis et al. In particular, the present invention can be dissolved in hydrocarbons. Concerning manganese salts of organic acids. A highly overbased manganese metal organic composition. Consists of a complex of manganese oxide-hydroxide-carboxylate. The content of the metal is partly with oxygen in the microcrystalline core of the polynuclear metal oxide, and partly with at least two different monocarboxylic acids, or two examples having at least two carbon atoms. Mixtures of one or more monocarboxylic acids and monosulfonic acids, such as the group of hydroxyl-metal-carboxylate and hydroxyl-metal sulfonate salts. By chemical combination with things. See, e.g., US Pat. The composition of the invention is preferably a hydrocarbon soluble composition. This specification ° “Hydrocarbon soluble” as used in and in the appended claims. The term refers to whether the composition is soluble or stable in common liquid hydrocarbons. This means that it can be dispersed. As used herein and in the appended claims, the term "stably dispersible" refers to a composition that is It also means that it can be dispersed in a lubricant to the extent that it can perform its functions as described above. It is. Thus, 2 for example, if the composition can be suspended in a lubricating oil sufficiently so that the lubricating oil can function as a lubricant. The composition may be soluble in hydrocarbons. The combination of oil, metal compound, and dispersant may be accomplished in any convenient manner. copper When both manganese and manganese are used, the manganese per gram atom of copper in one composition is The proportion of cancer ranges from about 0.05 to about 23 gram atoms, preferably from about 2 to about 23 gram atoms. More preferably from about 4 to about 20 gram atoms. here. Mixtures of manganese and titanium 5 manganese and cobalt and titanium and cobalt are also available. It is for use. The metal molar ratio formulated in the above binary composition is to the first metal of about 15:1 to tit5. Preferably the ratio is about 10:1 to 1:10. The present invention also contemplates the use of other additives. For example, such additives Examples include detergents and dispersants of the ash-forming or non-ash-forming type. Ash-forming detergents are produced by oil-soluble neutral and basic salts of alkali metals or alkaline earth metals with sulfonic acids, carboxylic acids, or organophosphoric acids. It is proved. This organophosphoric acid is formed by at least one direct carbon-phosphorus bond. For example, olefin polymers (e.g. polyisobutyne with a molecular weight of 1000) are characterized by phosphorus trichloride, phosphorus heptachloride, phosphorus trisulfide, phosphorus trichloride and sulfur, white phosphorus and sulfur chloride. or by treatment with a phosphating agent such as thiophosphate chloride. most is also commonly used. Salts of such acids include sodium salts, potassium salts, and lithium salts. strontium salts, calcium salts, magnesium salts, strontium salts, and barium salts. The term ``basic salt'' is used to indicate a metal salt in which the metal is present in a stoichiometrically greater amount than the organic acid group. The method described involves heating a mineral oil solution of the acid with a stoichiometric excess of a metal neutralizing agent such as a metal oxide, metal hydroxide, metal carbonate, metal bicarbonate, or metal sulfide at about 50°C. temperature and filtering the resulting mass.Using an "accelerator" in the neutralization step can accelerate the incorporation of large excess metals. Also known as Examples of compounds useful as accelerators include phenol, naphthol, phenols, alkylphenols, thiophenols, and sulfurized alkylphenols. Phenolic substances: and condensates of formaldehyde and phenolic substances; methanol 2-propertool, octyl alcohol, cellosolve, calpitol, ethyl Len glycol. Alcohols such as stearyl alcohol, and cyclohexyl alcohol; and aniline, phenylene diamine. Includes amines such as phenothiazine, phenyl-β-naphthylamine, and dodecylamine. A particularly effective method for preparing basic salts involves mixing an acid with a basic alkaline earth metal neutralizer and at least one alcohol promoter. and carbonating the mixture at elevated temperatures, such as from 60 to 200°C. (Left below) Ash-free detergents and dispersants depend on their composition, but if this dispersant is It is so called despite the fact that burning gives non-volatile substances such as boron oxide or phosphorus pentoxide; however,9 it usually does not contain metals and therefore combustion does not give metal-containing ash. do not have. Many types are known in the art, any of which are suitable for use in the lubricant compositions of the present invention. Examples include: (1) Carboxylic acids (or derivatives thereof) having at least about 30 carbon atoms, preferably at least about 50 carbon atoms, and nitrogen-containing compounds such as amines, phenols, etc. organic hydroxy compounds such as alcohols and alcohols, and/or reaction products with basic inorganic substances. Examples of these "carboxylic dispersants'" are described in British Patent No. 1,306,529 and in a number of US patents, including: Patent Inventor Date of Patent 3,163,603 Le 5uer December 29, 1964 3.184.4 74 3, 215.707 Ren5e November 2, 1965 3, 219.666 Norman et al. November 23, 1965 3.271.310 Le 5uer September 6, 1966 Day 3.272.746 Le 5uer et al. September 13, 1966 3, 281.357 Vogel October 25, 1966 3306.9 08 Le 5uer February 28, 1967 3.311.558 Prlze r et al. 1967.3 April 28, 1967 3.316.177 Dorer April 25, 1967 3,340.281 Brannen September 5, 1967 3.341.542 Le 5uer et al. September 12, 1967 3.346,493 Le 5uer 1967 October 10th 3.351.552 Le 5uer 19 November 7th 1967 3.381,022 Le 5uer April 30th 1968 3,399.141 Clemens August 27th 1968 3+415.75 0 Anzenberger l968 year December 1st 3,433,744 L e 5uer March 18, 1969 3,444,170 Norman et al. 1 May 13, 1969 3.448.048 Le 5uer June 3, 1969 3, 448.049 Preuss et al. June 3, 1969 3, 451, 93 3 Leister June 24, 1969 3.454. 607 Le 5uer July 8, 1969 3, 467, 668 Gruber et al. September 16, 1969 3.501.405 Willette March 17, 1970 3.5 22.179 Le 5uer July 28, 1970 3 .541.012 5 tubebe November 17, 1970 3.542.680 Le 5uer 1 November 24, 1970 3.543.678 3,567,637 5abol March 2, 1971 3,574.101 M urphy April 6, 1971 3, 576, 743 Widmer et al. 197 April 27, 1 3,630.904 Musser et al. December 28, 1971 3.632.510 Le 5uer January 4, 1972 3.632,511 Chien-hlei Liao January 4, 1972 3.697,428 3,725. 441 Murphy April 3, 1973 4, 234.435 Meinhardt November 18, 1980 Re 26.433 Le 5u er August 6, 196B (2) Relatively high molecular weight aliphatic halide or cycloaliphatic halide and , a reaction product with an amine, preferably a polyalkylene polyamine. child These can be characterized as "amine dispersants", examples of which are described in the following U.S. patents: Vander Voort et al. July 8, 1969 3, 5 65.804 Honnen et al. February 23, 1971 (3) Few alkyl groups Reaction products of alkylphenols having at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). These can be characterized as "Mannich dispersants". The materials described in the following U.S. patents are illustrative: Patent Inventor Patent Mortar 2.459.112 0berright January 11, 1949 2.962. 442 “Andress November 29, 1960 2, 984.550 Chamot May 16, 1961 3, 036.003 Verdol May 27, 1962 3.166.516 3, 236.770 Matson February 22, 1966 Day 3, 355.270 Annick November 28, 1967 3, 368.972 0tto 19 February 13, 1968 3, 413.347 Horrel November 26, 1968 3.442,808 Traise May 6, 1969 3,448.047 Traise June 3, 1969 3,454.497 Wittner 19 July 8, 1969 3.459,661 5chloboha+ August 5, 1969 3.461,172 3,493.520 Verdol et al. 1970 February 3, 1970 3,539,633 Piasek et al. November 10, 1970 3,558.743 Verdol et al. January 26, 1971 3,586.629 Otto et al. June 2, 1971 3,591.598 Traise et al. July 6, 1971 3,600.3 72 tldelhofen et al. August 17, 1971 3.634,515 Piasek et al. January 11, 1972 3.649,229 3,697.574 Piasek et al. 1972 October 10th 3, 725.2 77 'piorre1 April 3, 1973 3, 725.480 Traise et al. April 3, 1973 3.726.882 Traise et al. April 10, 1973 3, 980.569 Pindar et al. September 14, 1976 (4) The following carboxylic acid dispersants, amine dispersants, or Mannich dispersants can be used with urea, thiourea, carbon disulfide, and aldehydes. Ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitrile di-epoxides, boron Reaction products obtained by post-treatment with reagents such as elementary compounds and phosphorus compounds. Examples of these types of materials are described in the following US patents: Akisha Patent Mortar 3,036.003 Verdol May 22, 1962 3.087.936 Le 5uer April 30, 1963 3.200,107 Le 5uer August 10, 1965 3.216,936 Le 5uer 1965 November 9, 1966 3.254.025 Le 5uer May 31, 1966 3.256. 185 L, e 5uer June 14, 1966 3.278,550 No rman et al. October 11, 1966 3.280.234 3.281,428 Le 5uer October 25, 1966 3.282.9 55 Le 5uer November 1, 1966 3.312.619 Dale April 4, 1967 3,366,569 Norman et al. January 30, 1968 3.367.943 3.373,111 Le 5uer et al. March 12, 1968 Day 3.403.1 02 Le 5uer September 24, 1968 3.442,808 Traise et al. May 6, 1969 3,455.831 3.455,832 3,493.520 Verdol et al. February 1970 3rd 3.502.677 Le 5uer March 24, 1970 3.513.093 Le 5uer May 19, 1970 3, 533.945 Vogel October 13, 1970 3, 539.633 Piasek et al. 1970 November 10th 3+573,010 Mehmedbasich March 30th, 1971 3.579,45 0 Le 5uer May 18th, 1971 3.591.598 Traise July 6th, 1971 3,600.372 3.639.242 Le 5uer February 1, 1972 3.649.229 3.649.659 Otto et al. March 14, 1972 3.658.836 ν1neyard April 25, 1972 3,69L 57d Piasek et al. October 10, 1972 3,702.757 3.703,536 3.704.308 3+ 708,422 Swanson January 2, 1973 (5) Decyl meth Oil-soluble models such as acrylates, vinyl decyl ethers and high molecular weight olefins Interpolymers of heptamer-2 and poly-(oxyethylene)-substituted acrylates with polar substituents such as aminoalkyl acrylates or acrylamide. These can be characterized as “polymeric dispersants”. and examples thereof are disclosed in the following US patents: Patent Inventor Patent 3.329.658 Fields July 4, 1967 3.449,250 3,519.565 Coleman July 7, 1970 3 , 666, 730 Coleman May 30, 1972 3, 687.849 Abbott August 29, 1972 3, 702.300 Coleman November 7, 1972 As previously stated, the compositions of the present invention Useful as an additive to lubricants. Generally, these lubricant compositions contain a major amount of an oil of lubricating viscosity and an amount of a minor component. Contains the manganese compound or other metal compound of the invention. As used herein and in the appended claims, the term "minor amount" means 1. When a composition contains a "minor amount" of a specified substance, such amount is 50% of the composition. is intended to mean less than % by weight. As used herein and in the appended claims, the term "major amount" refers to 9.5% of the composition when such amount is 50% of the composition. is intended to mean more than % by weight. Typically, the amount of metal compound relative to the lubricating oil in the compositions of the present invention is The lubricant composition preferably contains about 30 to 500 ppm, based on the weight of the composition. or 35 to 350 ppm, most preferably about 40 to about 150 ppm of metal. The oil of lubricating viscosity utilized in the preparation of the diesel lubricant of the present invention may be based on natural oils, synthetic oils, or mixtures thereof. Natural oils include liquid petroleum, paraffin type, and naphthene type. Also included are solvent-treated or acid-treated mineral lubricating oils of the mixed paraffin-naphthenic type, as well as animal and vegetable oils (eg, castor oil, lard oil). Oils of lubricating viscosity derived from coal or shale are also useful. Synthetic lubricants include hydrocarbon oils and halide oils such as dipolymerized and interpolymerized olefins. Substituted hydrocarbon oils (e.g. polybutylene, polypropylene, propylene-iso Butylene copolymer. (chlorinated polybutylene, etc.); poly(1-hexene), poly(1-octene), and mixtures thereof; alkylbenzenes (e.g., dodecene), and mixtures thereof; Rubenzene, Tetradecylbenzene, Dinonylbenzene, Di(2-ethylhexyl) polyphenyls (e.g. biphenyl, terphenyl, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides. and its derivatives, analogs and homologues. Alkylene oxide polymers and interpolymers and terminal hydroxy The group is modified by esterification, etherification, etc. Its derivatives are used This constitutes another class of known synthetic lubricating oils. These are ethylene oxide or are oils prepared by polymerization of propylene oxide, these polyoxyalkyl alkyl and aryl ethers of polymers (e.g., an average of about 1000 Methyl polyisopropylene glycol ether with a molecular weight of about 500-1000, diphenyl ether of polyethylene glycol with a molecular weight of about 500-1000. Diethyl ethyl polypropylene glycol having a molecular weight of about 1000-1500 esters), or their mono- and polycarboxylic acid esters, such as Acetate ester of laethylene glycol, mixed C5-C11 fatty acid ester, and is exemplified by CI3 oxoacid diester. Other suitable classes of synthetic lubricating oils that may be used include dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, superic acid, sebacic acid, fumaric acid, adipic acid). , lyluic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.) and various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethyl alcohol, xyl alcohol, ethylene glycol, diethylene glycol, diethylene glycol Contains esters with recall monoester, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylate sebacate), Luhexyl). Di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelaate diisodecyl azelaate, dioctyl phthalate, didecyl phthalate, sepa Diacosyl sinate. These include the 2-ethylhexyl diester of lyric acid dimer, the hybrid ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid, and the like. Esters useful as synthetic oils include C5””’e+z monocarboxylic acids and polyols. esters prepared from neopentyl glycol, trimethylol glycol, Lopan, pentaerythritol, dipentaerythritol, tripentaerythritol These include polyol ethers such as toll. Silicon-based oils such as polyalkyl-, polyaryl-, polyalkoxy-2- or polyaryloxy-siloxane oils and silicate oils include other useful types of synthetic lubricants (e.g., tetraethyl silicate). , Tet Lysopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-hexyl-silicate, tetra-(P-tert-butyl-ph) phenyl) silicate. Hexyl-(4-methyl-2-pentoxy)disiloxane. poly(methyl)siloxane, poly(methylphenyl)siloxane, etc.). other cases Synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, triochytyl phosphate, diethyl ester of decanephosphonic acid, etc.). Contains trahydrofuran. Unrefined oils, refined oils and re-refined oils may include any of the above-disclosed natural or synthetic oils (as well as mixtures of two or more of any of these) in the concentrates of the present invention. Can be used. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly by a retort separation operation, petroleum oil obtained directly by primary distillation, or directly obtained by an esterification process. Unrefined oil is an ester oil that is used without further processing. Ru. The refined oil is further processed in one or more refining stages. Similar to unrefined oil, except that one or more properties are improved. Many Such purification techniques include 2 such as solvent extraction, secondary distillation, hydrogen treatment, and hydrogenation. These methods are known to those skilled in the art as percolation, acid extraction or base extraction, filtration, percolation and the like. Re-refined oils are oils that have already been used to obtain refined oils through a process similar to that used to obtain refined oils. obtained by applying it to refined oil. Such re-refined oil is recycled oil or Also known as reprocessed oil, it often contains additives and oil degradation products used. It is further processed by techniques aimed at removing the components. Most preferably, the oil used herein is an oil derived from 9 petroleum. At the same time, the greatest effect of the various metals used here was observed in oils derived from nine petroleum oils. Served. The effects of soot on lubricants related to viscosity increase and viscosity increase are twofold according to the present invention. This can be delayed by periodically adding small amounts of fresh, metal-treated lubricant. can be set. Thus, by replacing the initially untreated (metallic) lubricant with treated lubricant during an oil change. You can enjoy its benefits. Metal compounds may be added to the crankcase in the presence of diluent oil. In this case, the metal compound is present in an excess of 1 to 25 times the amount normally present in the oil! (Money (as a genus). In this way, the crankcase of a diesel with 20-252 untreated oil can be adjusted to the correct metal compound levels by adding additives as small as If. It is stipulated. In the present invention, the lubricating oil typically comprises about 75% to about 99.5% by weight of the composition, preferably Preferably, it is used in an amount of about 80 to about 99% by weight. Diluent oil (lubricant) present as various additives is contained in the above amount. The dispersants previously discussed are conveniently employed at about 0.05 to about 20%, preferably about 0.1 to about 15% by weight of the composition. The diesel lubricating composition used herein is preferably lead-based. Contains substantially no iron, aluminum or soot in any form. above gold The absence of metals is desirable because they are wear metals or materials that normally form part of the engine. The presence of worn metal when tested by the owner indicates an engine wear problem. Therefore, it is undesirable for wear metals to be contained in lubricants. This is because these substances reduce the reliability of analytical methods used to detect wear. Because it makes you go down. The metals mentioned as undesirable have the potential to act as oxidation catalysts. It also has the ability. This oxidizes the oil and requires an early oil change. The total base number of diesel lubricants is typically between 0 and 25. Preferably it is between 1 and 15. These total base numbers reduce the lubricant's potential for acid accumulation. It shows that it can resist the change. Acid accumulation increases corrosion, and higher base numbers indicate resistance to acid accumulation. In a preferred embodiment, the diesel lubricant of the present invention contains at least one acidic It also contains at least one oil-soluble, neutral or basic alkaline earth metal salt of the organic compound. Such salt compounds are commonly referred to as ash-containing detergents. The acidic organic compound can be at least one sulfuric acid, carboxylic acid, phosphoric acid, phenol, salicylate, or mixtures thereof. Calcium, magnesium and barium are the preferred alkaline earth metals. Salts containing mixtures of ions of two or more of these alkaline earth metals may be used. Useful salts can be neutral or basic. A neutral salt is a salt that exists in the anion of this salt. It contains just enough alkaline earth metal to neutralize the acidic groups present; The basic salt contains an excess of alkaline earth metal cations. The amount of alkaline earth metal contained in the diesel lubricant of the present invention may vary over a wide range. Although variations may occur, useful amounts can be readily determined by one of ordinary skill in the art. This salt functions as a supplementary or additional cleaning agent. In the diesel lubricant of the present invention The amount of alkaline earth metal salt used can range from about 0 to about 5% or more by weight of the composition, preferably or may vary from 0.5 to 4% by weight. The present invention also contemplates the use of other additives in the diesel lubricant compositions of the present invention. These other additives include the usual types of additives like antioxidants, extreme pressure agents, corrosion inhibitors, pour point depressants, color stabilizers, foaming agents, and diesel. Other additive materials are included as known to those skilled in the art of formulating lubricants. If an antioxidant is used, it is preferred that the antioxidant be of the amine type, such as alkylated arylamines. Preferably, the t-butyl group is sterically hindered. Phenolic compounds of 90% are not used in the present invention. If used, such sterically hindered phenolic compounds should be used in conjunction with a second antioxidant. Extreme pressure agents, and corrosion and oxidation inhibitors are exemplified by: chlorinated aliphatic hydrocarbons such as chlorinated wastewater (Cwas); bis(chlorobenzyl)disulfide, dibutyltetrasulfide, sulfurized oleic acid methyl ester, sulfurized alkylphenol. Organic sulfides and sulfides such as sulfurized dipentene and sulfurized terpene phosphorus sulfide hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dibutyl phosphite, diheptyl sulfite. Dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite phenyl, tridecyl phosphite, distearyl phosphite, dimethylnaphthite phosphite oleyl 4-pentylphenyl phosphite, polypropylene (molecule 1500) -W substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite, etc. Phosphorus esters containing phosphite dihydrocarbons and phosphite trihydrocarbons as: Zinc cutyl dithiocarbamate and heptyl phenyl dithiocarbamate metal salts of thiocarbamic acids, such as zinc dicyclohexyldithiophosphate, zinc 2-dioctyldithiophosphate, barium di(heptylphenyl)-dithiophosphate; , cadmium dinonyldithiophosphate, and phosphorus trisulfide and 2 isopropyla It is produced by reaction with an equimolar mixture of alcohol and n-hexyl alcohol. Group metal dithiophosphates, such as zinc salts of dithiophosphates. Many of the supplementary extreme pressure agents and corrosion-oxidation inhibitors mentioned above. Also useful as an anti-wear agent. Zinc dialkyldithiophosphate compounds are a well-known example. Pour point depressants are often included in the lubricating oils mentioned herein. particularly useful species It is a type of additive. It is known in the art to use such pour point depressants in oil-based compositions to improve the low temperature properties of the oil-based compositions. See, for example, "Additives for Lubricants" by C.V. Smalbeer and RJennedy Smf th, Retius-Hills Company Publishing Co., Ltd. (Liebrand, Ohio, 1967), page 8. Examples of pour point depressants are polymethacrylates; polyacrylates; condensates of haloparaffin waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of vinyl esters and alkyl vinyl ethers of dialkyl fumarate fatty acids. Pour point depressants useful for purposes of the present invention Laxatives, techniques for their preparation, and their uses are described in the following U.S. patents; .498 Re1ff February 27, 1940 2.666.746 2.721,877 2.721.878 3.250,715 Wy+++an May 10, 1966 Antifoam agents reduce or prevent the formation of stable foam. used for Typical foaming agents include silicone or organic polymers. Other soil retaining compositions are described in "Foam Control Agents" by Henry T., K. Erner (Noyes Data Corporation. 1976), pages 125-162. Viscosity improvers typically contain from about 5 to about 15% by weight of the composition. Viscosity improvers are used when the temperature of the lubricant increases. It functions to maintain a more or less constant viscosity. Examples of viscosity improvers are hydrogenated styrene-isoprene copolymers; maleic anhydride-styrene copolymers; olefin copolymers such as ethylene-propylene copolymers; styrene-butadiene copolymers, and polybutadiene. It is a homopolymer such as The invention will be further understood by considering the following examples. These examples are merely intended to illustrate the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the following examples. (Left below) n ■ Soil A fully formulated lubricant composition is prepared containing the following ingredients: Ingredients Part Mineral oil 92.45 Viscosity improver 0.68 Basic alkylated magnesium benzene sulfonate 0.77 Dispersant 3.48 Zinc salt of alkylated dithiophosphoric acid 1.43 Anti-wear detergent 1.11 Silicone antifoam agent 0.001 Antioxidant 0.08 The preparation of Example I was prepared using Mac T-7 The test results gave a slope of 0.018 between the 100 hour and 150 hour runs. Current experience in the Mack T-7 test The overslope value is 0.04 or less. The same formulation without manganese has 0. A test value of 16 was given. Yigou LfLL A fully formulated lubricant composition is prepared containing the following ingredients: Ingredients Part Mineral Oil 92.45 Viscosity Improver 0.68 Basic Alkylated Magnesium Benzene Sulfonate 0.77 Dispersion Agents 3.48 Zinc salts of alkylated dithiophosphoric acids 1.43 Anti-wear detergents 1.11 Silicone antifoam agents 0.001 Antioxidants 0.08 This formulation tested as follows: A value of 035 was given. The gradient gradient value is 0.04. The test slope value in the absence of manganese is 0.16. Example 11 A fully formulated lubricant composition is prepared containing the following ingredients: Ingredient Part Mineral Oil 92.45 Viscosity Improver 0.68 Basic Alkylated Magnesium Benzene Sulfonate 0.77 Dispersion Agents 3.48 Zinc salts of alkylated dithiophosphoric acids 1.43 Anti-wear detergents 1.11 Silicone antifoam agents 0.001 Antioxidants 0.08 Cobalt as naphthenate 50pp111 Formulations containing cobalt are: 0 The cobalt-free preparation gave a slope value of .068 for the Matsuk T-7 test. shows an improvement of over 50% compared to the compound. This lubricant viscosity increase is 58% greater in the 100-150 hour interval in the absence of cobalt. A fully formulated lubricant composition is prepared containing the following ingredients: Ingredients Part Mineral oil 92.45 Viscosity improver 0.68 Basic alkylated magnesium benzene sulfonate 0. 77 Dispersants 3.48 Zinc salts of alkylated dithiophosphoric acids 1.43 Anti-wear detergents 1.11 Silicone antifoam agents 0.001 Antioxidants 0.08 Mack T-7 test results for titanium compounds are: 0.026 The gradient value is vinegar. The viscosity increase over the baseline is 182% without titanium. A fully formulated lubricant composition is prepared containing the following ingredients: Ingredients Part Mineral oil 92.45 Viscosity improver 0.68 Basic alkylated magnesium benzene sulfonate 0.77 Dispersants 3.48 Zinc salts of alkylated dithiophosphoric acids 1.43 Anti-wear detergents 1.11 Silicone antifoam agents 0.001 Antioxidants 0.08 This sample used fll Fnate as 150 ppm+ copper. In a further modification, manganese salicylate is substituted for the copper phenate at 450 ppm manganese. A fully formulated lubricant composition is prepared containing the following ingredients: Ingredient Part Mineral Oil 92.45 Viscosity Improver 0.68 Basic Alkylated Magnesium Benzene Sulfonate 0.77 Dispersant 3.48 Zinc salt of alkylated dithiophosphoric acid 1.43 Anti-wear detergent 1.11 Silicone antifoam agent 0.001 Antioxidant 0.08 1100 pp vanadium as neooctanoate of the manganese compound of Example I Replace with mu. For further modifications, replace the manganese with a similar amount of nickel, using ungsten, molybdenum and chromium. International Search Report lRlfi-mlA Pass-[esN@, pcr/us a77ooo7゜入NN EX To THE INTER,'1ATIONAL 5EARCHREPO RT 0NINTERNA71ONAL APF'LICATION No, P CT/'LJS 87100070 (SA 15900) US-A-365 261628103/ 72 None

Claims (46)

[Claims] 1. Contains oil of lubricating viscosity, dispersant and small amounts of oil-soluble or oil-dispersible metal compounds a lubricant composition for use in diesel engines, the amount of the metal compound being This is sufficient to suppress soot, which is associated with an increase in the viscosity of the oil, when The metal compounds include manganese, titanium, cobalt, copper, vanadium, nickel, Selected from the group consisting of tungsten, molybdenum, and chromium, and mixtures thereof. Contains selected metals. 2. The oil of lubricating viscosity is present from about 75% to about 99.5% by weight of the composition. A lubricant composition according to scope 1. 3. the metal compound is present as a metal at about 30 to about 500 ppm of the composition; A lubricant composition according to claim 1. 4. 2. The lubricant composition of claim 1, wherein the total base number is from about 0 to about 25. 5. A lubricant composition according to claim 1, which is substantially lead-free. 6. The lubricant set according to claim 1, wherein the metal compound is a sulfonate. A product. 7. The lubricant set according to claim 1, wherein the metal compound is a carboxylate. A product. 8. The lubricant composition according to claim 1, wherein the metal compound is a phosphate. . 9. The lubricant set according to claim 1, wherein the metal compound is a salicylate. A product. 10. The lubricant set according to claim 1, wherein the metal compound is phenate. A product. 11. Claim 1 comprising a viscosity improver from about 5% to about 15% by weight of the composition. The lubricant composition described in . 12. The metal compound may be manganese, titanium, and cobalt or a mixture thereof. The lubricant according to claim 1, containing a member selected from the group consisting of: Composition. 13. the metal compound is selected from the group consisting of copper and chromium and mixtures thereof; A lubricant composition according to claim 1, comprising a member comprising: 14. the carboxylate salt has about 6 to about 30 carbon atoms per carboxyl group The lubricant composition according to claim 7, wherein the lubricant composition is a fatty acid. 15. The lubrication according to claim 12, wherein the metal compound contains manganese. agent composition. 16. The lubricant according to claim 12, wherein the metal compound contains titanium. Composition. 17. The dispersant is an olefin polymer containing phosphorus, an amine dispersant, a Mannich dispersants, and alkali metal salts and carboxylic acids, sulfonic acids, and organic phosphoric acids. and alkaline earth metal salts according to claim 1. Lubricant composition. 18. Claim 7, wherein the carboxylic acid salt is derived from a branched chain fatty acid. The lubricant composition described. 19. Claims wherein the dispersant is present from about 0.05% to about 20% by weight of the composition. The lubricant composition according to item 17. 20. The lubricant according to claim 1, wherein the metal compound is a naphthenate. Composition. 21. The metal compound is present as a metal at about 35 to about 350 ppm of the composition. , the lubricant composition according to claim 1. 22. A lubricant composition according to claim 1, which also contains a zinc compound. 23. Oil-soluble oil with a lubricating viscosity of the main component amount and about 30 to about 500 ppm as a metal A lubricant composition containing a dispersible or oil-dispersible metal compound, wherein the metal compound is related to the increase in viscosity of this oil when used in diesel engines. It is possible to suppress soot and contains manganese, titanium, cobalt, chromium, and banana. Dium, nickel. A group consisting of tungsten, molybdenum, and mixtures thereof. Contains selected metals. 24. The lubricant composition of claim 23, having a total base number of 0 to about 25. . 25. 24. The lubricant composition according to claim 23, containing a dispersant. 26. The lubrication according to claim 23, wherein the metal compound is a carboxylate. agent composition. 27. The lubricant set according to claim 23, wherein the metal compound is a phosphate. A product. 28. The lubrication according to claim 23, wherein the metal compound is a salicylate. agent composition. 29. The lubricant according to claim 23, wherein the metal compound is phenate. Composition. 30. Claim 23, comprising a viscosity improver from about 5% to about 15% by weight of the composition. The lubricant composition described in Section. 31. The metal compound may be manganese, titanium, and cobalt or a mixture thereof. The lubricant set according to claim 23, containing a metal selected from the group consisting of: A product. 32. the carboxylate salt has about 6 to about 30 carbon atoms per carboxyl group 27. The lubricant composition according to claim 26, wherein the lubricant composition is a fatty acid comprising: 33. The lubrication according to claim 23, wherein the metal compound is a naphthenate. agent composition. 34. 32. The lubricant composition of claim 31, wherein the metal is manganese. 35. Claim 26, wherein said carboxylic acid salt is derived from a branched chain fatty acid. The lubricant composition described. 36. The lubrication according to claim 23, wherein the metal compound is a sulfonate. agent composition. 37. The metal compound is present as a metal at about 35 to about 350 ppm of the composition. , the lubricant composition according to claim 23. 38. Claim 1, wherein said dispersant is present from about 0.1% to about 15% by weight of the composition. The lubricant composition according to item 25. 39. 24. The lubricant composition of claim 23, which is substantially lead-free. 40. 24. A lubricant composition according to claim 23, which also contains a zinc compound. 41. The dispersant is an olefin polymer containing phosphorus, an amine dispersant, a Mannich dispersants, and alkali metal salts and carboxylic acids, sulfonic acids, and organic phosphoric acids. and alkaline earth metal salts according to claim 25. Lubricant composition. 42. Related to increased viscosity of lubricants in lubricating systems where soot tends to increase. A method for suppressing soot, the method comprising the step of introducing a metal compound into a lubricant. The metals include manganese, titanium, cobalt, copper, vanadium, nickel, and tantalum. Selected from the group consisting of ungsten, chromium, and molybdenum, and mixtures thereof and is sufficient to retard the increase in viscosity. 43. The metal compound is present as a metal in about 30 to 500 ppm of the lubricant. 43. The method of claim 42, wherein the method comprises: 44. 43. The method of claim 42, wherein the metal compound contains manganese. . 45. 43. The method of claim 42, wherein the metal compound contains titanium. 46. 43. The method of claim 42, wherein the metal compound contains cobalt. .