JPH01201398A - Improved lubricant composition for fortified fuel economy - Google Patents

Abstract

PURPOSE: To obtain a lubricant composition enhanced in fuel economy per unit weight of an additive by using an oil of lubricating viscosity as the major component and blending specified minor components therein.

CONSTITUTION: This lubricating oil composition is the one contg. an oil of lubricating viscosity as the major component and components shown by (A), (B), (C) and (D) as the minor components, in which the component (A) (l) shown as Ca composes about 0.03 to 0.5 wt.% of the lubricating oil composition, the component (A) (2) shown as Mg composes about 0.01 to 0.25 wt.% of the lubricating oil composition, the component (B) is used by the amt. sufficient for giving about 0.05 to 0.15 wt.% phosphorus in the lubricating oil composition, mixed calcium and magnesium detergent inhibitors are present by the weight ratio of the component A (1):A (2) of about (0.3:1) to (6:1), and mixed di (primary hydrocarbyl) zinc dithiosulfate anti wear agents are present by the weight ratio of the component B (1):B (2) of about (4:1) to (9:1).

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to lubricating oil compositions that exhibit significant improvements in fuel economy. In particular, the present invention relates to lubricating oil compositions containing, in addition to dispersant and antioxidant additives, a small proportion of a mixture of calcium and magnesium sulfonates along with secondary and secondary zinc antiwear agents.

It is an object of the art to provide lubricating oil compositions that exhibit improvements in fuel economy in gasoline and diesel engine vehicles. In order to achieve that immediate purpose,
A new category of additives, commonly referred to as fuel economy additives, have been developed that serve primarily to increase the miles or kilometers obtained for a unit volume of fuel. What are modern lubricant compositions? ! Due to the complex formulation, such additives must be compatible with the other ingredients of such compositions. Also, numerous other functions of conventional lubricant additives such as dispersibility, viscosity stability, corrosion and oxidation protection, etc. must not be adversely affected.

U.S. Pat. No. 2,911,367 is designed to prevent rust and corrosion on metal surfaces exposed to moisture and contains a large proportion of mineral lubricating oils, alkali metal salts, oil-soluble sulfonic acids, metal alkyl thiophosphates, etc. , a partial ester of a fatty acid containing at least 8 carbon atoms with a polyol containing 3 to 6 carbon atoms and 3 to 6 hydroxyl groups per molecule, and a small proportion of ethylene glycol C2 branched alkyl ether, respectively. A mineral oil composition comprising: Metal alkylthiophosphates include magnesium, calcium, zinc, strontium, cadmium and barium thiophosphates, of which zinc dioctyl and zinc octylhexyl dithiophosphates are mentioned as typical examples. Sulfone-1. is about 1 to about 5 on a total composition basis.
The metal alkylthiophosphates used in weight percent amounts and including zinc octylhexyl and zinc dioctyl dithiophosphate listed above preferably account for about 0.1% to about 1% of the total composition.
It is stated to be used in an amount of 5% by weight.

U.S. Pat. No. 3,562,159 discloses that basic oil
carboxylic acid esters of lubricating viscosity as additives, alkylated alkylene polyamines (approximately 5 to 30 parts by weight), basic alkaline earth metal sulfonates (approximately 5 to 15 parts by weight), metals as additives. A synthetic resin I agent comprising a phosphorodithioate (approximately 5 to 70 parts by weight), a basic alkaline earth metal salt of a phosphosulfurized hydrocarbon, an ester of a hydrocarbon-substituted succinic acid, and a basic alkaline earth metal salt of a sulfurized alkylphenol. Regarding.

U.S. Pat. The sulfonate, sulfonate-carboxylate and a high molecular weight aliphatic carboxylic acid or anhydride containing at least 25 aliphatic carbon atoms per carboxy group under the mentioned temperature conditions up to an amount equivalent to its total basicity. selected from the group consisting of carboxylic acid complexes. The metal of the basic metal salt complex can be magnesium or calcium (among other listed metals). Additional additives can be used in combination with the mentioned compositions, including Group I metal phosphorodithioates, such as zinc dicyclohexylphosphorodithioate and zinc dioctylphosphorodithioate.

U.S. Pat. The present invention relates to lubricating oil compositions comprising various aliphatic esters and aliphatic amides and amines. Group I metal salts of dihydrocarbyl dithiophosphoric acids are described as being present in amounts of 0.5 to 1.5% by weight of the functional fluid, and basic sulfurized alkaline earth metal alkyl phenoxides are present in amounts of about 0.0 to 1.5% by weight of the functional fluid. .4 to about 4
It is stated to be present in an amount of % by weight.

No. 4,308,154 is said to be useful as an antioxidant and extreme pressure agent with improved thermal stability in lubricants and functional fluids (such as hydraulic fluids). The present invention relates to mixed metal salts (particularly zinc salts) of dialkylphosphorodithioic acids and carboxylic acids.

It is stated that the mixed metal salts of this invention also include salts of group (1) and group (2) metals.

No. 4,417,990 relates to mixed metal salt/sulfurized phenoxide compositions useful as antioxidants and acupressure agents with improved thermal stability in lubricants and functional fluids and the above. U.S. patent cylinder 4.308.1 listed in
Contains statements related to No. 54.

Various suggestions have been made in the prior art regarding the nature, type and carbon content of the alkyl or aryl groups present in the dialkylphosphorodithioic acid used to prepare the desired metal salt. For example, U.S. Patent No. 2,344.3
No. 93 stated that it had already been recognized that metal dithiophosphates must have one or more long chain alkyl groups in order to be sufficiently soluble in lubricating oils to be of practical value. It is listed. However, the patentee discovered that the zinc salt of cyamylphosphorodithioic acid is oil soluble. US Pat. No. 3,318,808 states that high carbon content alkyl groups (more than 4 carbon atoms) increase oil solubility. (Thus, this patent describes the combination of a C3 or higher alcohol with a lower C3 or higher alcohol and/or a secondary alcohol, and the ratio of alcohols is chosen to balance economy and solubility. .

U.S. Pat. , describes oil-soluble metal phosphorodithioates consisting of salts with strontium, zinc and cadmium. To improve the oil solubility of metal salts,
The metal salt is reacted with up to about 0.75 moles of epoxide.

Another patent relating to the preparation of phosphorodithioates as useful additives in lubricants is a US patent.

? ! No. 31000,822. This patent describes a dialkyl phosphor in which the alkyl group consists of a mixture of a low molecular weight primary aliphatic hydrocarbon group having less than 5 carbon atoms and a high molecular weight primary aliphatic hydrocarbon group having at least 5 carbon atoms. Zinc salts of mixtures of rhodithioic acids are described.

The molar ratio of low molecular weight groups to high molecular weight groups in the zinc salt is 1:1 ~
It is within the range of 3:1.

Various proposals have been made in the prior art to improve the utility of lower alkyl phosphorodithioates, which tend to be oil insoluble. U.S. Patent No. 4,306.98
No. 4 describes a method for making oil-insoluble metal C,-C3 dialkyldithiophosphates oil-soluble by forming a complex between the dithiophosphate and an alkenyl or alkyl mono- or bis-succinimide. It is listed. This combination of additives is used in lubricating oils that can be used for crankcase lubrication of internal combustion engines. Another method proposed for producing amorphous mixtures of basic and mixed basic and neutral zinc dialkyldithiophosphates containing 1 to 13 carbon atoms in the furkyl group is disclosed in U.S. Pat. No. 843.530. The basic or mixed basic and neutral zinc salt mixtures described in this patent contain 4 to 13 different alkyl groups, have an average carbon content of 3.5 to 4.5, and have at least 12 carbon atoms. Contains % zinc.

U.S. Pat. No. 4,466,895 discloses that the alkyl groups each contain from 2 to 4 carbon atoms and at least one alkyl group is a butyl group, and the total number of carbon atoms per phosphorus atom is less than 8. and about 30 to 90 alkyl groups
The mole percent is primary alkyl groups, with about 10 to
70 mol % are secondary alkyl groups, and the metal salt is a zinc, copper or iron salt, a mixture thereof, or a mixture of a calcium salt and one or more of said metal salts, provided that only two alkyl groups When present, one or more dialkylphosphoro groups, with the proviso that about 30 to 80 mole percent of the alkyl groups are n-butyl groups and about 20 to 70 mole percent of the alkyl groups are isopropyl groups. The present invention relates to lubricating oil compositions containing metal salts of dithioic acids. The patentee states that these metal salts are useful as antiwear agents and antioxidants in lubricating oil compositions. The metal salts of lower dialkylphosphorodithioic acids of this patent are exemplified in combination with conventional higher alkyl ZDDPs in a complete formulation that also includes a mixture of basic calcium petroleum sulfonate and basic magnesium petroleum sulfonate. There is.

Zinc dialkyldithiophosphates made from mixed dialkyldithiophosphates have been produced previously. U.S. Pat. No. 3,293,181 discloses a method in which one of the alcohols is isobutyl alcohol and the other alcohol is prepared from a mixture of at least two different branched chain primary alcohols containing at least 6 carbon atoms. Regarding mixed salt.

U.S. Pat. No. 3,397.145 discloses that the alkyl group of the alkylthiophosphoric acid can be straight chain or branched and that the alkyl group has primary, secondary and/or tertiary substituents (
eg the same or different alkyl groups).

U.S. Pat. No. 3,442,804 relates to zinc phosphorodithioates useful in lubricating oil compositions in which the hydrocarbon groups are primary alkyl groups and consist of a mixture of low and high molecular weight groups.

U.S. Pat. No. 4,328,111 discloses an improved overbased sulfone that reacts a basic compound with an acidic compound including an organic carboxylic acid, an organic carboxylic acid anhydride, phosphoric acid, a phosphoric acid ester, a thiophosphoric acid ester, or mixtures thereof. Regarding acid salts and phenoxides.

U.S. Pat. No. 4,614,602 relates to a lubricant composition containing an overbased detergent-dispersant lubricant additive consisting of the reaction product of an alkaline earth metal phenoxide and ammonium alkylbenzene sulfonate; The patentees indicate that it can be used in combination with other conventional lubricant additives, including anti-wear agents such as ZDDP. The alkylbenzene sulfonates may consist of sulfonates derived from alkaline earth metals such as Ca, Mg, Ba oxides or hydroxides, alone or in combination. A typical example as a modifier for reaction with overbased magnesium sulfonate is 2-ethylhexyldithiophosphoric acid.

U.S. Pat. No. 4,326,972 describes improvements in the fuel economy of internal combustion engines through the use of special lubricant compositions in which the wood component is a special sulfide composition and a basic metal sulfonate. ing.

U.S. Pat. No. 4,362,633 relates to lubricating oil additives containing molybdenum-containing aminated sulfurized additives. The patentee discloses the use of such an additive in combination with a mixture comprising overbased calcium phenoxide, overbased magnesium sulfonate and zinc dialkyldithiophosphate.

European Patent No. 24,146 relates to a lubricating oil composition containing a copper antioxidant, 1.0% by weight of 400 TBN of magnesium sulfonate (containing 9,2% magnesium), 250 TBN of calcium phenoxide. 0.3% by weight (containing 9.3% by weight of calcium) and an alkyl group or a mixture of such groups having 4 to 5 carbon atoms and about 6% of isobutyl alcohol containing phosphorus P2S5.
In a lubricating oil composition that also contains a zinc dialkyldithiophosphate made by reacting a mixture of 5% and 35% amyl alcohol to provide a phosphorus level of 1.0% by weight in the lubricating oil composition. A copper antioxidant is exemplified.

European Patent Application No. 92.946 relates to a lubricating oil composition with improved fuel economy comprising a glycerin partial ester, an oil-soluble organocopper compound, and an oil-soluble organocopper compound. This patent exemplifies compositions containing such combinations in admixture with basic metal detergents and antiwear agents. This patent states that preferred detergent materials are positive or overbased calcium or magnesium phenoxides, sulfurized phenoxides, and/or sulfonate salts, and further states that antiwear agents generally contain at least 5 carbons in total. It shows that it is an oil-soluble zinc dihydrocarbyl dithiophosphate with atoms.

U.S. Pat. No. 4,394,276 relates to lubricating oils containing sulfur-containing alkenediols for reducing fuel consumption in internal combustion engines. The patentee claims that overbased magnesium hydrocarbyl sulfate 30 mmol/kg, overbased calcium sulfide polypropylene phenoxide 20 mmol/k
FIG.

U.S. Patent Nos. 4.362.636 and 4,404.80
No. 3, No. 4.4951088, No. 4.563.293
No. 1, No. 1, and No. 4.6210,576 also relate to lubricating oil fuel economy additives, each of which similarly exemplifies well-formulated lubricating oils.

U.S. Pat. No. 4,104,180 relates to a method for making overbased carbonates. Example 11 of this patent is a neutral calcium phenoxide], 2% by weight, 1.2% by weight of zinc diaryldithiophosphate and 1% by weight of magnesium sulfonate.
．． A lubricating oil containing 2% by weight is illustrated.

N, E, Galopoulos (N, E, Ga1lopou)
los) et al.
ns+ Vol., pp. 14.1-7 (1971)) describes the effect of alkaline petroleum calcium sulfonate on the aging of a mixture of said calcium sulfonate and zinc dialkylphosphorodithioate and lubricating oil. They studied the interaction between the dispersant and the dispersant and concluded that a chemical reaction appears to occur. No studies of mixtures of alkaline earth metal sulfonates have been reported.

J, A, Mc Geehan
) et al. (SAE Paper) 852
133.19810879-892) studied the effects of zinc dithiophosphate and detergents on engine wear control.

It was concluded that zinc diaryldithiophosphates are less effective than zinc dialkyldithiophosphates in controlling valve wear in gasoline engines. Based on research they conducted with a variety of zinc dialkyldithiophosphate and either calcium or magnesium detergents, the authors found that engine wear control was associated with gasoline engine valve train wear, diesel cylinder poor polishing (
poor polishing) wear and diesel roller follower bronze pin (diesel rol
ler follower br.

concluded that a critical balance of zinc dithiophosphate and detergent type is required for wear control. However, the alkyl forms of these zinc dithiophosphates have not been described and mixtures of calcium and magnesium detergents have not been evaluated.

However, none of the above references describes the benefits obtained by controlling the relative amounts of mixed calcium/magnesium detergents and mixed primary/secondary zinc dithiophosphate antiwear agents.

According to the present invention, an oil of lubricating viscosity as a main component, (A) as a subcomponent (1) at least one calcium overbased detergent inhibitor, and (2) at least one A mixture of (B) a magnesium overbased detergent inhibitor comprising: (1) at least one zinc di-(primary hydrocarbyl) dithiophosphate; and (2) at least one di-(
(C) at least one ashless dispersant; and (D) an antioxidant effective amount of at least one copper carboxylate compound. A fuel economy promoting lubricating oil composition, wherein component (A) (1) designated as Ca constitutes about 0.03-0.5% by weight of the lubricating oil composition, and the component designated as Mg A(2) constitutes about 0.01 to 0.25% by weight of the lubricating oil composition, and component (B) contains about 0% by weight of the lubricating oil composition.
．． Component A (1): A mixed calcium and magnesium detergent inhibitor used in an amount sufficient to provide 0.05 to 0.15% by weight of phosphorus and a mixed calcium and magnesium detergent inhibitor of from about 0.3:1 to about 6=1.
(2) is present in a weight:weight ratio of the mixed zinc di(primary hydrocarbyl) dithiophosphate and zinc di(secondary hydrocarbyl) dithiophosphate antiwear agent from about 0.4+1 to about 9:1;
A lubricating oil composition is provided which is present in a weight to weight ratio of B(1):B(2).

The present invention shows that there is a surprising and significant relationship between the ratio of mixed calcium/magnesium detergent inhibitor and mixed primary/sulfuric zinc antiwear agent in crankcase lubricating oil compositions and improved fuel economy. It is based on the discovery that such mixtures provide a degree of fuel economy per unit weight of additive not previously recognized by the art. Equally important is the fact that other desirable functions and properties of the lubricating oil, such as compatibility, detergency and dispersibility, are not diminished.

DETAILED DESCRIPTION OF THE INVENTION Component A Component A is described in U.S. Pat. No. 2.501.731, 2.6.
No. 16゜904, No. 2.616.905, No. 2.61
No. 6.906, No. 2, No. 616.911, No. 2.616
．． No. 924, No. 2.616.925, No. 2.617.
No. 049, No. 2.777, No. 874, No. 3.027.3
No. 25, No. 3.256.186, No. 3.282.83
No. 5, No. 3.384゜585, No. 3.373.108
No. 3.365.396, No. 3, 342.733, No. 3.320.162, No. 3.312.618,
one or more organic sulfonic acids (generally petroleum sulfonic acids or synthetically produced alkarylsulfonic acids), petroleum naphthenes, as described in subheadings 3.318.809 and 3.562.159; acids, alkylbenzenesulfonic acids, alkylphenols, alkylene-bis-phenols, oil-soluble fatty acids, and mixtures of basic (i.e., overbased) Ca and Mg salts such as salicylic acid. For purposes of illustration, the disclosures of the above patents are incorporated herein to the extent that they describe conjugates useful in the present invention. The most useful products among petroleum sulfonates are those produced by sulfonation of the appropriate petroleum fraction with subsequent removal of the acid sludge and purification. Synthetic alkarylsulfonic acids are typically prepared from alkylated benzenes, such as the Friedel-Krach reaction products of benzene and polymers such as tetrapropylene. Suitable acids may also be obtained by sulfonation of alkylated m8 compounds such as diphenylene oxide thianthrene, phenolthioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, decahydronaphthalene, etc. .

Highly basic Ca and Mg sulfonates are often used as detergents. They usually involve heating a mixture consisting of an oil-soluble sulfonate or an alkarylsulfonic acid with an excess of the alkaline earth metal compound in excess of the amount required for complete neutralization of the sulfonic acid present and then producing the desired It is produced by forming a dispersed carbonate complex by reacting excess metal with carbon dioxide to provide an overbase. Sulfonic acids are typically obtained from the separation of petroleum by distillation and/or extraction or by alkylation of halogen m1 such as benzene, toluene, xylene, naphthalene, diphenyl and chlorobenzene, chlorotoluene and chloronaphthalene. by the sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained by the alkylation of aromatic hydrocarbons. Alkylation is carried out with an alkylating agent having about 3 to 30 or more carbon atoms in the presence of a catalyst. For example, haloparaffins, olefins obtained by dehydrogenation of paraffins, polyolefins made from ethylene, propylene, etc. are all suitable. Alkarylsulfonates usually contain from about 9 to about 70 or more carbon atoms, preferably from about 16 to about 50 carbon atoms per alkyl-substituted aromatic moiety.

Alkaline earth metal compounds used to neutralize these alkarylsulfonic acids to sulfonates include oxides and hydroxides, alkoxides, carbonates, carboxylates of magnesium, calcium and barium; Includes sulfides, hydrosulfides, nitrates, borates and others. Examples are calcium oxide, calcium hydroxide, magnesium acetate and magnesium borate. As mentioned above,
The alkaline earth metal compound is used in excess of the amount required for complete neutralization of the alkarylsulfonic acid.

Generally, the amount will range from about 100 to 220% of the stoichiometric amount of metal required for complete neutralization, although it is preferred to use at least 125%.

US Pat. No. 3,150.0 in which overbasing is achieved by hydrolysis of an alkoxide-carbonate complex with an alkaryl sulfonate in a hydrocarbon solvent-diluent oil.
The preparation of various other basic alkaline earth metal alkarylsulfonates is known, such as No. 88 and No. 3.150.089.

Preferred Mg sulfonate additives have a molecular weight of about 25 to about 3, based on the total weight of the additive system of the invention dispersed in the mineral lubricating oil.
A magnesium alkyl aromatic sulfonate having a total alkali number ranging from about 300 to about 400 with a magnesium sulfonate content ranging from 2% by weight. Preferred calcium sulfonate additives are from about 25 to about 32% based on the total weight of the additive system of the invention dispersed in the mineral lubricating oil.
With a calcium sulfonate content in the range of % by weight about 3
Calcium alkyl aromatic sulfonate having a total alkalinity number ranging from 0.00 to about 400.

As an example of a particularly convenient method of manufacturing the composites used,
An oil-soluble sulfonic acid such as synthetically produced didodecylbenzenesulfonic acid is treated with an excess of lime (e.g. 10 equivalents per equivalent of acid) and an accelerator such as methanol, heptylphenol or mixtures thereof and mineral oil. Mixed with solvent at 50-150°C, the process mixture is then carbonated until a homogeneous mixture is obtained. Complexes of sulfonic acids, carboxylic acids, and mixtures thereof can be obtained by methods such as those described in US Pat. No. 3,312,618. Another example is the production of magnesium sulfonate from neutral magnesium sulfonate, excess magnesium oxide, water and preferably an alcohol such as methanol.

Useful for the preparation of sulfonate carboxylate complexes and carboxylate complexes, i.e. complexes obtained from processes such as those described above in which mixtures of sulfonic acids and carboxylic acids or carboxylic acids alone are used in place of sulfonic acids. Carboxylic acids are oil-soluble acids and primarily contain at least about 12 aliphatic carbon atoms and up to about 24 aliphatic carbon atoms. Examples of these acids include palmitic acid, stearic acid,
myristic acid, oleic acid, linoleic acid, dodecanoic acid,
Contains behenic acid. Cyclic carboxylic acids can also be used. This includes aromatic acids and cycloaliphatic acids. The aromatic acid has a benzenoid structure (i.e., benzene, naphthalene, etc.) and one or more geosolubilizing compounds having a total of at least about 15 to 18 carbon atoms, preferably about 15 to about 200 carbon atoms. It is an acid containing a group.

Examples of aromatic acids include stearyl benzoic acid, phenylstearic acid, mono- or poly-wax substituted benzoic acids or naphthoic acids in which the wax group comprises at least about 18 carbon atoms, cetyl hydroxybenzoic acid, and the like. The contemplated cycloaliphatic acids have at least about 12 carbon atoms and usually up to about 30 carbon atoms. Examples of such acids are petroleum naphthenic acid, cetylcyclohexanecarboxylic acid, di-lauryldecahydronaphthalenecarboxylic acid, di-octylcyclopencunecarboxylic acid, and the like. Also contemplated are thiocarboxylic acid analogs of the above acids in which one or both of the oxygen atoms of the carboxyl group are replaced with sulfur.

The sulfonic acid:carboxylic acid ratio in the mixture is at least 1:
1 (on a chemical equivalent basis) and usually less than 5:1;
Preferably it is 1:1 to 2:1.

The terms "basic salt" and "overbased salt" are used to denote metal salts in which the metal is present in stoichiometrically greater amounts than the sulfonic acid groups.

As used herein and in the claims, the term "complex" means a basic metal salt containing a metal in excess of the amount present in the neutral or positive metal salt. do. The "alkalinity value" of the complex is equivalent to KOHOmg when 1 g of complex is determined by titration.
It is a number. A commonly used method for producing basic salts is to add a solution of a positive metal salt of a nucleic acid in mineral oil to a metal such as an oxide, hydroxide, carbonate, hydrogen carbonate or sulfide at a temperature of 5°C or higher. It involves heating with a Japanese additive and filtering the resulting mass. The use of "accelerators" in the neutralization step to aid in the addition of large excess metals is known and preferred for the preparation of such compositions. Examples of compounds useful as accelerators include phenolics such as phenopenaphthonopearkylphenols, thiophenols, sulfurized alkylphenols, and condensation products of formaldehyde and phenolics; methanol, 2-propanol,
Alcohols such as octatool, cellosolve, calpitol, ethylene glycol, stearyl alcohol and cyclohexanol; and amines such as aniline, phenylenediamine, phenothiazine, phenol beta-naphthylamine and dodecylamine.

Usually, the basic composition obtained by the above method is A
Treat with carbon dioxide until the alkalinity number is less than about 50 as measured by STM Method D Method 96 (TBN). In many cases, it is advantageous to prepare the basic product by adding Ca or M, the base, in portions and carrying out the reacidification after addition of each portion. Products with very high metal ratios (above 10) can be obtained in this way. As used herein, the term "metal ratio" refers to the total amount of alkaline earth metal in the sulfonate complex. Means the ratio of equivalents to equivalents of the sulfonate anion in the complex. For example, the orthosulfonate has metal specificity, O
and a calcium sulfonate complex containing twice as much calcium as the normal salt has a metal ratio of 2.0. Compositions suitable for use as component A have metal ratios of at least about 1.1, such as from about 1.1 to about 30, with metal ratios of about 2 to 20 being preferred.

It is often advantageous to react the basic sulfonate and anthranilic acid by heating both at about 140-200°C.

The amount of anthranilic acid used is less than about 1 part (by weight) per 10 parts of sulfonate, preferably less than 1 part (by weight) per 10 parts of sulfonate.
~1 part in 200 parts. The presence of anthranilic acid increases the oxidation- and corrosion-inhibiting effectiveness of the sulfonate.

Basic alkaline earth metal sulfonates are known in the art, and methods for their preparation have been described in many ways, such as in U.S. Pat. described in the patent. Any of the sulfonate salts described in these patents and numerous others are suitable for use in the present invention.

The basic Ca and Mg salts are preferably prepared separately and then mixed in controlled amounts as indicated herein. It is generally convenient to mix such separately prepared detergent inhibitors in the presence of the diluent or solvent used in their manufacture.

The Ca detergent inhibitor composition represents about 0.03 to 0.5% by weight of the lubricating oil composition, designated as Ca, preferably about 0.0%.
4-0.4% by weight, more preferably about 0.05-0.2
It should be used in an amount of % by weight. Mg detergent inhibitors, designated as Mg, represent about 0.01 to 0.0.0% of the lubricating oil composition.
It should be used in an amount of 25% by weight, preferably about 0.01-0.2%, more preferably about 0.02-0.11%. Preferably, the overbased Ca detergent inhibitor and the overbased Mg detergent inhibitor, expressed as their respective metals, are about 0.0 parts Ca detergent inhibitor per part Mg detergent inhibitor.
It is used in an amount of 3 to 6 parts, more preferably about 0.4 to 3 parts, most preferably about 0.8 to 1.2 parts.

Component A includes other alkaline earth and/or alkali metal detergent inhibitors such as basic or neutral Na, K and Li sulfonates, and salicylates, and basic or neutral Ba sulfonates, phenoxides and salicylates). An example of such a mixture as component A is a mixture of overbased Ca sulfonate, overbased Mg sulfonate and overbased Na sulfonate detergent inhibitor.

This component is a mixture of (1) a metal salt of di(primary hydrocarbyl)dithiophosphoric acid and (2) a metal salt of di(secondary hydrocarbyl)dithiophosphoric acid. The acid from which the B-1 metal salt is derived has the formula (1) %Formula %(1) [In the above formula (1), R+ and R2 are the same or different, and are alkyl, cycloalkyl, aralkyl, alquaryl or It is a substantially hydrocarbon group with a similar structure. The acid from which the B-2 metal salt is derived has the formula (II) R'S R'-C)I-0-P-3-H(n')R'
-C)I-[1 [In the above formula (II), R3, R4, R3 and R6 are the same or different and are alkyl, cycloalkyl, alquaryl, aralkyl or a substantially hydrocarbon group of a similar structure ] acid.

"Substantially hydrocarbon" means a group containing substituents such as ether, ester, nitro or halogen that do not significantly affect the hydrocarbon character of the group.

Therefore, the acid of formula (I) is such that each oxygen-bonded carbon is primary, i.e. -C)! , -0. Correspondingly, the acid of formula (n) is seen to contain a disecondary hydrocarbyl substituent in which each oxygen-bonded carbon is secondary, ie, CH-0.

Particular examples of suitable R1-R6 groups include imprinopeisobutyl, n-butyl, 5ec-butyl, n-hexyl, heptyl, 2-ethylhexyl, diisobutyl, isooctyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, Butylphenyl, 0. p-diisotylphenyl, octylphenyl, polyisobutyne-(
Molecular weight 350) -Substituted phenyl, tetrapropylene substituted phenyl, β-octylbutylnaphthyl, cyclopentyl, cyclohexyl, phenyl, chlorophenyl, O-
Dichlorophenyl, bromophenyl, naphthinyl, 2-
Included are methylcyclohexyl, benzyl, chlorobenzyl, chloropentyl, dichlorophenyl, nitrophenyl, dichlorodecyl and xenyl groups. Alkyl groups having about 3 to 30 carbon atoms and aryl groups having about 6 to 30 carbon atoms are preferred. Particularly preferable R1
The ~R& group is an alkyl of 3 to 18 carbons.

Phosphorodithioic acids are easily obtained by reaction of phosphorus pentasulfide with alcohols or phenols.

The reaction involves mixing 4 moles of alcohol or phenol with 1 mole of phosphorous pentasulfide at a temperature of about 20 DEG to 200 DEG C. Hydrogen sulfide is liberated when the reaction occurs.

Metal salts useful in the present invention include salts containing Group I metals, Group I metals, aluminum, lead, tin, molybdenum, manganese, cobalt and nickel.

Zinc is the preferred metal. Examples of metal compounds that can be reacted with acids include lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylade, sodium phenoxide, Potassium, potassium hydroxide, potassium carbonate, potassium methylate, silver oxide, silver carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium ethylate, magnesium ethylate, magnesium phenoxide, calcium oxide, calcium hydroxide, calcium carbonate, Calcium methylate, calcium propylate, calcium pentilade, zinc oxide, zinc hydroxide, zinc carbonate, zinc propylade, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethylate, barium oxide, water Barium oxide, barium hydrate, barium carbonate,
Barium ethylate, barium pentylade, aluminum oxide, aluminum pentylade, lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butylade, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentylade,
Includes nickel oxide, nickel hydroxide and nickel carbonate.

In some cases, the addition of small amounts of certain components, such as metal acetate or acetic acid, along with the metal reactant facilitates the reaction and provides improved products.

For example, the use of up to about 5% zinc acetate in combination with the required amount of zinc oxide facilitates the production of zinc phosphorodithioate.

The preparation of metal phosphorodithioic acids is known in the art and has been published in numerous publications including U.S. Pat. U.S. Pat. No. 5,001,000, the disclosures of which are hereby incorporated by reference to the extent that they describe the preparation of metal salts of organic phosphorodithioic acids useful in the present invention.

The B-1 and B-2 metal salts are preferably prepared separately and then mixed to form the mixed anti-wear component B. Alternatively, a mixture of primary and secondary acids 1 and 2 is charged in situ to form mixed B-1 and B-2 metal salts,
Component B can be produced having the desired ratio of metal salt B-1 equivalents to metal salt B-2 equivalents.

Component B is effective to provide about 0.05-0.15%, preferably 0.107-0.12%, more preferably 0.08-0.11% phosphorus in the lubricating oil composition. should be used in sufficient quantities. Metal salt used B-1
The relative amounts of B-2 and B-2 are critical to the invention. Metal salt B-1 (i.e., the metal salt of di-(primary hydrocarbyl)dithiophosphoric acid of formula I) is metal salt B-2 (i.e., the metal salt of di-(secondary hydrocarbyl)dithiophosphoric acid of formula (n)). About 0.4 to 9, preferably about 0.4 to 9, per part by weight.
It should be used in an amount of 5 to 3, most preferably 0.7 to 1.8 parts by weight.

Ashless, nitrogen- and ester-containing dispersants useful in the present invention include (
i) oil-soluble salts, amides, imides, oxazolines and esters or mixtures thereof of long-chain hydrocarbon-substituted mono- and dicarboxylic acids or anhydrides thereof; (11) long-chain aliphatic hydrocarbons with polyamines directly attached thereto; ii
i) about 1 molar ratio of long-chain hydrocarbon-substituted phenol to about 1
a member selected from the group consisting of Mannich condensation products formed by condensation with ~2.5 moles of formaldehyde and about 0.5 to 2 moles of polyalkylene polyamine;
The long chain hydrocarbon groups in (i), (ii) and (iii) are C2-Cl01, e.g. 02-C, monoolefin polymers having a number average molecular weight of about 300 to about 5000.

C(i) The long chain hydrocarbyl-substituted mono- or dicarboxylic acid material, acid, anhydride or ester used in the dispersant contains an average of at least about 0.8, preferably about 1.0 to 1.8 per mole of polyolefin. , for example 1
．． 1 to 1.6 moles of α- or β-fusogenic C4-C4-
Included are long chain hydrocarbons, generally polyolefins, substituted with C10 dicarboxylic acids, or their anhydrides or esters. Typical examples of such mono- and dicarboxylic acids, anhydrides and esters thereof are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, dimethyl fumarate, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, Such as cinnamic acid.

Preferred olefin polymers for reaction with unsaturated dicarboxylic acids to form dispersants are cz-C4-C10
, for example 02-C, are polymers containing a major molar amount of monoolefins. Such olefins include ethylene, propylene, butylene, isobutylene, pentene, octene-11 styrene, and the like. Polymers include homopolymers such as polyisobutylene, as well as copolymers of ethylene and propylene; butylene and isobutylene; propylene and isobutylene.
It can be a copolymer of more than one species. Other copolymers may include minor molar amounts of copolymer monomers, e.g.
Copolymers in which 10 mole percent is C1 to C18 nonconjugated diolefins are included, such as copolymers of isobutylene and butadiene or copolymers of ethylene, propylene, and 1,4-hexadiene.

In some cases, the olefin polymer can be fully saturated, such as an ethylene-propylene copolymer made by Ziegler-Natsuta synthesis using hydrogen as a modifier to control molecular weight.

The olefin polymer used in the dispersant typically has a
It has a number average molecular weight within the range of 0 to about 51,000, more usually about 900 to about 3,000. Particularly useful olefin polymers have number average molecular weights within the range of about 900 to about 2,500 and have about one terminal double bond per polymer chain. A particularly useful starting material for highly effective dispersant additives is polyisobutylene. The number average molecular weight of such polymers can be determined by several known methods. One convenient method for such measurements is gel permeability chromatography (GPC) (W,W), which additionally provides molecular weight distribution information.

Yau, W., Yau, J., Kirkland, J.

Kirkland) and D. Bly (D, D, B
ly) Author “Modern Size Exclusion Ref.
ExclusionLiquid Chromato
graphy), John Wiley and Sons, New York, 1979].

The olefin is a C1-C4-C10 unsaturated dicarboxylic acid,
Methods of reacting with anhydrides or esters are known in the art. For example, U.S. Pat.
The olefin polymer and the dicarboxylic acid material are simply heated together to cause a thermal "ene" reaction, as described in U.S. Patent No. 401.118. Alternatively, the olefin can be first halogenated, for example with chlorine or bromine in the polyolefin at a temperature of 60 to 250°C, such as 120 to 160°C, for about 0.5 to 10 hours, preferably 1 to 7 hours. The chlorine or bromine can be chlorinated or brominated to about 1 to 8% by weight, preferably 3 to 7% by weight, based on the weight of the polymer, of chlorine or bromine. This halogenated polymer is then treated with sufficient unsaturated acid or anhydride for 1
0.0 to 250°C, usually about 180 to 235°C.
The reaction can be carried out for 5 to 10, for example 3 to 8 hours, and the product thus obtained contains the desired number of moles of unsaturated acid per mole of halogenated polymer. This general type of method is described in U.S. Pat. No. 31,087.436, 3.172.
No. 892, No. 3,272.746, and others.

Alternatively, the olefin polymer and unsaturated acidic material are mixed and chlorine is added to the hot mixture while heating. This type of method is described in U.S. Pat. No. 3.2110707, 3.
No. 231.587, No. 3.912.764, No. 4.1
No. 10.349, No. 4.234.435 and British Patent No. 1.440.219.

Due to the use of halogens, about 65 to 95 weight percent of the polyolefin, such as polyisobutylene, typically reacts with the dicarboxylic acid material. When carrying out the thermal reaction without the use of halogens or catalysts, usually only about 50-75% by weight of polyisobutylene is reacted. Chlorination helps increase reactivity. For convenience, the above functionality ratio of dicarboxylic acid generating units to polyolefin, such as 0.8 to 2.0, is based on the total amount of polyolefin used in the production of the product, i.e. the sum of both reacted and unreacted polyolefins. Based on.

The dicarboxylic acid-generating materials can also be further reacted with polyols, amines, alcohols including amino alcohols, etc. to form other useful dispersant additives. Thus, if the acid generator is to be further reacted, eg, neutralized, a large proportion of the acid units, from 50% to all acid units, will be reacted.

Amine compounds useful as nucleophilic reagents for the neutralization of hydrocarbyl-substituted dicarboxylic acid substances include about 2
~60. Mono- and (preferably) polyamines, preferably of 2 to 40 (e.g. 3 to 20) total carbon atoms and about 1 to 12, preferably 3 to 12, most preferably 3 to 9 nitrogen atoms, most preferably includes polyalkylene polyamines. These amines can be hydrocarbyl amines or can be hydrocarbyl groups containing other groups, such as hydroxy groups, alkoxy groups, amido groups, nitriles, imidacillin groups, and the like.

Hydroxyamines having 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups, are particularly useful. Preferred amines have the general formula [R, R' in the above general formulas (III) and (1'/).

R#, R/// are independently hydrogen, C1-CIX alkoxyC! ~C6 alkylene group, C1~CI! Hydroxyaminoalkylene groups, and C6-Cat alkylamino C2-C.

selected from the group consisting of alkylene groups, and R″′ is of the formula (
V) (where R' is as defined above) and S and S' are from 2 to 6, preferably 2
can be the same or different numbers from 0 to 4, and t and t' can be the same or different and are numbers from 0 to 10, preferably from 2 to 7, most preferably from 3 to 7, with the proviso that t and t' is not greater than 15]. To ensure facile reaction, compounds of formula (I [ R2R', R" p I in a manner sufficient to
It is preferred to choose II, s, sl, and t'. This means that R, R", R" or R"
' is hydrogen, or when R'' is H or when moiety (V) has a secondary amino group, t in 2 (TV) is at least 1. The most preferred amines of the above formula are those of formula (IV), in which at least 2
primary amine groups and at least one, preferably at least three, secondary amine groups.

Non-limiting examples of suitable amine compounds include 4-C10
2-diaminoethane, 1,3-diaminopropane, 1.
4-diaminobutane, 1,6-diamithexane, polyethylene amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1.2
- polypropylene amines, such as propylene diamine;
Di-(l,2-propylene)triamine, di-(1,3
-propylene)triamine, N,N-dimethyl-1,3
-Diaminopropane, N,N-di-(2-aminoethyl)ethylenediamine, N,N-di(2-hydroxyethyl)-1,3-propylenediamine, trishydroxymethylaminoethane (THAM), diisopropanol amine, jetanolamine, triethanolamine,
Included are aminomorpholines such as 7-, di-, and tri-tallow amines, N-(3-aminopropyl)morpholine, and mixtures thereof.

Other useful amine compounds include cycloaliphatic diamines such as 1,4-di(aminomethyl)cyclohexane, and heterocyclic nitrogen compounds such as imidacillin, and the general formula (V
a) (Va) (In the above general formula, pl and p2 are the same or different, each bonito is an integer of 1 to 4, and nl + n2 +
N-aminoalkylpiperazine (n is the same or different and each is an integer of 1 to 3). Non-limiting examples of such amines include 2-pentadecyl imidacilline, N-(2-aminoethyl)piperazine, and the like.

Mixtures of commercially available amine compounds can also be used advantageously. For example, one method for making alkylene amines involves reacting an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia, resulting in a complex alkylene amine mixture in which the nitrogen pair is linked with an alkylene group. , producing compounds such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the isomeric piperazines. Low cost poly(ethyleneamine) compounds with an average of about 5 to 7 nitrogen atoms per molecule include 6-polyamine Hs,
sPolyamine 400”, ″
Dow Polyamine (Dow Polyan+1ne) E
It is commercially available under trade names such as "-100".

Useful amines include those of the formula (Vl) (Vl) [in the above formula (Vl), m is about 3 to 70, preferably 10
~35 (having direct) and formula (■) (■) [In the above formula (■), "n" has a value of about 1 to 40, provided that the sum of all n is about 3 to about 70 , preferably from about 6 to about 35, R is a polyvalent saturated hydrocarbon group of up to 10 carbon atoms, and the number of substituents on the R group is a number from 3 to 6.
0 formula (Vl) or (■) which also includes polyoxyalkylene polyamines such as the amines shown by the value of "a"]
The alkylene in can be straight or branched chain containing about 2 to 7, preferably about 2 to 4 carbon atoms.

The polyoxyethylene polyamine of the above formula (Vl) or (■), preferably polyoxyalkylene diamine and polyoxyalkylene triamine, has a molecular weight of about 200 to about 400
0, preferably in the range of about 400 to about 2000. Preferred polyoxyalkylene polyamines include polyoxyethylene and polyoxypropylene diamines and polyoxypropylene triamines having average molecular weights ranging from about 200 to 2,000.

Polyoxyalkylene polyamines are commercially available, for example from Jefferson Chemical Company (Jef
ferson Chemical Company)
, Inc. from “Jeffamin”
es) D-230, D-400, D-1000,
It can be obtained under trade names such as "D-2000, 7-403".

The amine and the selected dicarboxylic acid material, e.g.
The reaction is facilitated by heating to 25-175°C, generally for 1-10, eg 2-6 hours, until the desired amount of water is removed. This heating is preferably carried out to favor the formation of an imide or a mixture of imide and amide rather than amide and salt. The reaction ratio of equivalents of dicarboxylic acid material to amine and other nucleophilic reagents described herein can vary considerably depending on the reagents and the type of linkage produced. Generally, 0.1 to 1.0, preferably about 0.00, per nucleophile, such as an amine, is used.
Dicarboxylic acid moiety contents (for example grafted maleic anhydride contents) of 2 to 0.6, for example 0.4 to 0.6 mol, are used.

For example, for conversion to a mixture of amide and imide, it is preferred to use about 0.8 moles of pentaamine (having 2 primary amino groups and 5 equivalents of nitrogen per molecule), and the product is 1 mole of olefin and olefin 1
By reacting with enough maleic anhydride to add 1.6 moles of succinic anhydride groups per mole, ie, preferably about 0.6 moles per nitrogen equivalent of amine.
It is produced by using a sufficient amount of pentamine to provide 4 moles (ie 1.6/(0,8X5) moles) of succinic anhydride moieties.

Nitrogen-containing dispersants may be treated with boron (b) as generally described in U.S. Pat.
oration). This means that the selected acyl nitrogen dispersant can range from about 0.1 atomic ratio of boron for each mole of cough acylated nitrogen composition to about 20 atomic ratios of boron for each mole of nitrogen of the acylated nitrogen composition.
This is readily accomplished by treatment with a boron compound selected from the group consisting of boron oxide, boron halides, boric acid, and esters of boric acid, in amounts that provide up to an atomic ratio of boron.

Typically, the dispersants of the combinations of the present invention contain about 0.05 to 2.0% by weight boron, such as 0.05 to 0.7% by weight, based on the total weight of the boron-treated acyl nitrogen compound.

The product contains dehydrated boric acid polymer [mainly (HBO2)3
) is believed to be bound to the dispersant imide and diimide as an amine salt, such as a diimide metaborate.

The treatment is most commonly added as a slurry, about 0.0
5-4, e.g. 1-3% by weight (based on the weight of the acyl nitrogen compound) of the boron compound, preferably boric acid, is added to the acyl nitrogen compound and the temperature is increased to about 135-190°C, e.g.
This is easily accomplished by heating with stirring at 40 to 170°C for 1 to 5 hours, followed by nitrogen stripping in this temperature range. Alternatively, boron treatment can be performed by adding boric acid to a thermal reaction mixture of dicarboxylic acid material and amine while removing water.

Tris(hydroxymethyl)amitumekun (THAM)
British Patent No. 984.409
Amide, imide or ester type additives can be produced as described in US Pat.
．． No. 102.798, No. 4゜116.876 and No. 4
, 113.639, oxazoline compounds and boron-treated oxazoline compounds can be produced.

Ashless dispersants may be esters derived from the long chain hydrocarbon substituted dicarboxylic acid materials mentioned above and from hydroxy compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols. Polyhydric alcohols are the most preferred hydroxy compounds, preferably containing 2 to about 10 hydroxy groups, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and alkylene groups containing 2 to about 8 Other alkylene glycols containing 5 carbon atoms. Other useful polyhydric alcohols include glycerin, monooleate ester of glycerin, monostearate ester of glycerin, monomethyl ether of glycerin, pentaerydrift, dipentaerythritol, and mixtures thereof.

Ester dispersants include allyl alcohol, cinnamyl alcohol, propargyl alcohol, and 1-cyclohexane.
It can also be derived from unsaturated alcohols such as 3-ol and oleyl alcohol. Further groups of alcohols which can provide the esters of the invention include:
For example, oxy-alkylene-, oxy-arylene- with one or more oxy-alkylene, amino-alkylene or amino-arylene, oxy-arylene groups.
, ether alcohols and amino alcohols, including amino-alkylene-1 and amino-arylene-substituted alcohols. These include cellosolve, calpitol, N,N,N',N'-tetrahydroxytrimethylenediamine, and ether alcohols having up to about 150 oxy-alkylene groups, where the alkylene group contains from 1 to about 8 carbon atoms. exemplified by.

Ester dispersants can be di-esters or acid esters of succinic acid, ie, partially esterified succinic acid; and partially esterified polyhydric alcohols or phenols, ie, free alcohols or esters with phenolic hydroxyl groups.

Mixtures of the esters exemplified above are also considered to be within the scope of this invention.

Nisual dispersants are disclosed in, for example, U.S. Patent No. 3.38L022.
It can be manufactured by one of several known methods, as described in No. The ester dispersant can also be treated with boron in the same manner as the nitrogen-containing dispersant described above.

Hydroxyamines that can react with the long chain hydrocarbon-substituted dicarboxylic acid materials to form dispersants include 2-
Amino-1-butanol, 2-amino-2-methyl-1
-Propatur, p-(β-hydroxyethyl)aniline, 2-amino-1-propatur, 3-amino-1-
Propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, N-(β-hydroxypropyl)-N'
-(β-aminoethyl)piperazine, tris(hydroxymethyl)aminomethane (also known as trismethylolaminomethane), 2-amino-1-butanol, ethanolamine, β~(β-hydroxyethoxy)ethylamine, etc. is included. Mixtures of these or similar amines can also be used. The above description of suitable nucleophilic reagents for reaction with hydrocarbyl-substituted dicarboxylic acids or anhydrides includes amines, alcohols,
and compounds with mixed amine and hydroxy-containing reactive functional groups, ie amino alcohols.

One preferred group of ashless dispersants are substituted with succinic anhydride groups and include polyethylene amines such as tetraethylenepentamine, pentaethylene hexazine, polyoxyethylene and polyoxypropylene amines such as polyoxypropylene diamine, trismethylol aminomethane. and dispersants derived from polyisobutylene reacted with pentaerythritol, and combinations thereof.

One particularly preferred dispersant combination is (i) polyisobutyne substituted with succinic anhydride groups and (ii)
) polyisobutyne reacted with hydroxy compounds such as pentaerydrift, (iii) polyoxyalkylene polyamines such as polyoxypropylene diamine, and (iv) polyalkylene polyamines such as polyethylene diamine and tetraethylene pentamine, US Pat. , 804.763, each of (ii) and (iv) for every mole of (i).
3 to about 2 moles and combinations using about 0.3 to about 2 moles of (iii). Another preferred dispersant combination is (i) polyisobutenyl succinic anhydride and (ii) polyalkylene polyamine such as tetraethylene pentamine and (iii) combinations with f-hydric alcohols or polyhydroxy-substituted aliphatic primary amines, such as pentaerydrift or trimethylolaminomethane.

C(ii) Also useful as ashless nitrogen-containing dispersants in the present invention are U.S. Pat.
54 and 3.565.804, in which nitrogen-containing polyamines are directly bonded to long chain aliphatic hydrocarbons.

C(iii) Another group of nitrogen-containing dispersants that can be used are those containing Mannich bases or Mannich condensation products known in the art. Such Mannich condensation products are generally described, for example, in U.S. Pat. No. 3,442,808;
No. 3,649.229 and No. 3,798.165 (
about 1 mole of high molecular weight hydrocarbyl-substituted mono- or polyhydroxybenzenes (e.g., number average greater than 1.000), the disclosures of which are hereby incorporated by reference). molecular weight) with about 1 to 2.5 moles of formaldehyde or paraformaldehyde and about 0.5 to 2 moles of polyalkylene polyamine. Such Mannich condensation products can contain long chain high molecular weight hydrocarbons on the phenolic groups, or compounds containing such hydrocarbons, such as polyamides, as shown in the above-cited US Pat. It can be reacted with alkenylsuccinic anhydride.

Antioxidants useful in the present invention include carboxylic acid copper compounds, which are sources of oil-soluble copper in lubricating oils.

Copper can be mixed into the oil as any suitable oil-soluble carboxylic copper compound. By oil-soluble is meant that the carboxylate compound is at least partially oil-soluble under normal mixing conditions in the oil or additive package.

The copper compound may be of the cuprous or cupric type. Copper can be in the form of dihydrocarbylthio- or dithio-copper phosphate, in which case copper is used in place of zinc in the above compounds and reactions, but with 1 mole of cuprous oxide or Cupric acid can be reacted with 1 or 2 moles of dithiophosphoric acid, respectively. Alternatively, copper can be added as a copper salt of a synthetic or natural carboxylic acid.

Examples of carboxylic acids include C4-C10-C11 fatty acids such as stearic acid or palmitic acid, but also unsaturated acids such as oleic acid or branched chain carboxylic acids such as naphthenic acid with a molecular weight of 200-500 or Synthetic carboxylic acids are preferred due to improved handling and solubility of the resulting copper carboxylates. General formula (RR' NC
55),.

Cu (in the above general formula, R and R' are the same or different and contain 1 to 18, preferably 2 to 12 carbon atoms, and alkinobealkeninopearyl, arualkybealquaryl and alicyclic are the same or different hydrocarbyl radicals.Particularly preferred as R and R' groups are alkyl radicals of 2 to 8 carbon atoms.Thus, R and R' groups are, for example, ethyl, n-propyl, ,
1-bropinopene n-butyl, l-butynope 5ec-butyl, amyl, n-hexynope i-hexynoben n-heptinope n-octinopedecyl, dodecyl, octadecyl, 2-ethylhexyl, phenynohebtylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl etc. In order to obtain oil solubility, the total number of carbon atoms (
That is, R and R') are generally about 5 or more. Copper sulfonates, phenoxides and acetylacetonates can also be used.

Copper antioxidants (eg, copper naphthenate, copper oleate, or mixtures thereof) are generally used in the final lubricating oil or fuel composition in an amount of about 40 to 500 ppm by weight.

The copper antioxidants used in this invention are inexpensive and effective at low concentrations, so they do not add substantially to the cost of the product. The results obtained are often better than those obtained with conventionally used antioxidants which are expensive and used in high concentrations.

In the amounts used, the copper compound does not interfere with the performance of the other components of the lubricating composition. In many cases, completely satisfactory results are obtained when, in addition to the other ingredients, the copper compound is the only antioxidant. Copper compounds can be used to replace some or all of the supplemental antioxidants. Thus, for particularly severe conditions, it may be desirable to include supplemental conventional antioxidants. However, the amount of supplemental antioxidant required is small, much less than the amount required in the absence of the copper compound.

Any effective amount of copper antioxidant can be added to the lubricating oil composition, but such effective amount is about 40 to 500 (more preferably 50 to 200) based on the weight of the lubricating oil composition.
It is intended that the amount of added copper antioxidant be sufficient to provide the lubricating oil composition with an amount of added copper, even more preferably between 80 and 150) ppm. Of course, the preferred amount may depend on the quality of the base stock lubricant, among other factors.

Lubricating Oil Compositions Lubricating oil compositions, such as automatic transmission fluids for gasoline and diesel engines.
nfluid), heavy duty oils, etc. can be produced using the additives of the present invention. Crankcase oils can also be produced in which the same lubricating oil composition can be used in both gasoline and diesel engines. These lubricating oil formulations typically contain several different types of additives that provide the required properties to the formulation. Some of these types of additives include viscosity index improvers, antioxidants, corrosion inhibitors, other detergents, ashless dispersants, pour point depressants, other antiwear agents, and the like.

In the preparation of lubricating oil formulations, from 10 to 80% by weight of a hydrocarbon oil, such as mineral lubricating oil, or other suitable solvent,
It is common practice to introduce additives in the form of, for example, 20 to 80% by weight of active ingredient. Typically, these concentrates are used at a concentration of 3 to 10 parts by weight of additive package in the production of finished lubricants, such as crankcase motor oil.
0, for example 5 to 40 parts by weight of lubricating oil. Of course, the purpose of concentrates is to make handling of the various materials less difficult and cumbersome and to facilitate dissolution and dispersion into the final blend.

The components ACa/Mg hydrocarbyl sulfonate mixtures or Ca/Mg alkyl phenoxides are usually used, for example, in the form of 40-50% by weight concentrates in the lubricating oil fraction.

Components A, B, C and D of the present invention are used in admixture with -a a lubricating oil base stock consisting of oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.

Components A, B, C and D are added to the lubricating oil in any convenient manner. These mixtures can thus be added directly to the oil by dispersing or dissolving them in the oil at the desired concentration levels of each of the detergent inhibitor and antiwear agent. Such mixing into the additional lubricating oil at room temperature or elevated temperature can be performed. Alternatively, the components can be mixed with a suitable oil-soluble solvent and base oil to create a concentrate, which can then be mixed with a lubricating oil base stock to obtain the final formulation.

The lubricating oil base stocks for components A and B are typically adapted to perform specific functions by adding additional additives therein to produce the lubricating oil composition (i.e., formulation). There is.

Natural oils include animal and vegetable oils (eg, castor oil, lard oil), liquid petroleum oils, and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic, and mixed paraffin-naphthenic types. Oils of lubricating viscosity derived from coal and shale are also useful base oils.

Alkylene oxide polymers and interpolymers and their derivatives in which the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another group of known synthetic lubricating oils.

These include polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and ester-ethers of these polyoxyalkylene polymers (e.g. methyl-polyisopropylene glycol ether with an average molecular weight of 1000,
diphenyl ether of polyethylene glycol with a molecular weight of 500 to 1000, diethyl ether of polypropylene glycol with a molecular weight of 1000 to 1500), and their mono- and polycarboxylic acid esters, such as acetate ester of tetraethylene glycol, 7R combined C3-C8 fatty acids esters and CI3 oxoacid diesters.

Another group of suitable synthetic lubricating oils includes dicarboxylic acids such as phthalic acid, succinic acid, alkylsuccinic acid and alkenylsuccinic acid, maleic acid, azelaic acid, schelic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid. dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid) and various alcohols/l/ (e.g. ehafthyl alcohol, hexyl alcohol/l/, dotesyl alcohol, 2-
Includes esters with ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate. , diacosyl sebacate, 2- of rillulic acid dimer
Included are ethylhexyl diester and complex esters prepared by the reaction of 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

Esters useful as synthetic oils include esters made from 05-CI2 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Also included.

Polyalkyl-, polyaryl-, polyalkoxy-1
Alternatively, silicone-based oils such as polyaryloxysiloxane oils and silicate ester oils constitute another useful group of synthetic lubricants. These include tetraethyl silicate, tetraisopropyl silicate, tetra(2-ethylhexyl) silicate, and tetra(4-methyl-2-ethylhexyl) silicate.
, tetra(p-tert-butylphenyl) silicate, hexa(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxane and poly(methylphenyl)
Contains siloxane. Other synthetic lubricating oils include liquid esters of phosphorous acids (eg, tridecyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.

Unrefined, refined, and rerefined oils can be used in the lubricants of the present invention. Unrefined oils are oils obtained directly from natural or synthetic sources without further purification. For example, shale oil obtained directly from a drying operation, petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment are unrefined oils. Refined oils are similar to unrefined oils except that they have been further treated with one or more refining steps to improve one or more properties.

Many refining techniques are known to those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration and percolation. Such rerefined oils are also known as reclaimed oils or reprocessed oils and are often treated with additional additives by techniques for the removal of used additives and oil breakdown products. will be processed.

The novel detergent inhibitor/antiwear mixtures of this invention can be used in conjunction with viscosity index improvers to produce multigrade automotive engine lubricating oils. Viscosity improvers provide a lubricating oil with high and low temperature workability and allow the lubricating oil to remain relatively viscous at high temperatures and exhibit acceptable viscosity or fluidity at low temperatures.

Viscosity improvers are generally high molecular weight hydrocarbon polymers including polyesters. Viscosity improvers can also be derivatized to include other properties or functions, such as imparting dispersibility. These oil-soluble viscosity-enhancing polymers generally have a molecular weight of 103-106, preferably 104-10G, e.g. 201000-250.0 as measured by gel permeation chromatography or osmometry.
It has a number average molecular weight of 0.00.

Examples of suitable hydrocarbon polymers can be linear or branched, aliphatic, aromatic, alkyl aromatic, cycloaliphatic, etc., and include C2-C10, e.g. - Homopolymers of C8 olefins and copolymers of two or more monomers thereof are included. Often hydrocarbon polymers are ethylene and C4-C
10 olefins, and copolymers of ethylene and propylene are particularly preferred. Polyisobutylenes, homopolymers and copolymers of α-olefins of 06 and above, acidic polypropylenes, styrenes such as isoprene and/or butadiene and their hydrogen P
Other polymers such as hydrogenated polymers and copolymers and terpolymers with the g-form can be used. Polymers have reduced molecular weight and can be oxidized and contain oxygen, for example by mastication, extraction, oxidation or thermal degradation. Maleic anhydride, which can be further reacted with alcohols or amines, such as alkylene polyamines or hydroxyamines, as for example found in U.S. Pat. or post-grafted interpolymers of ethylene-propylene with active monomers such as U.S. Pat. No. 4.0681056, 4.
No. 0681058, No. 4゜146.489 and No. 4,
Also included are derivatized polyols such as copolymers of methylene and propylene reacted or grafted with nitrogen compounds as described in US Pat. No. 149,984.

Preferred hydrocarbon polymers are 15-90% by weight ethylene
, preferably 30-80% by weight and one or more C3-Ct
S, preferably C3-cps, more preferably C1-C
8α-olefin 10-85% by weight, preferably 20-85% by weight
70% by weight of ethylene copolymer. Although not essential, such copolymers have a crystallinity of less than 25% by weight as measured by X-ray and differential scanning calorimetry. Most preferred are copolymers of ethylene and propylene. Other α-olefins suitable for use in place of propylene to form copolymers or in combination with ethylene and propylene to form terpolymers, tetrapolymers, etc. include l-butene, 1-pentene, 1 -Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc., 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methylpentene-1,4,4- Also included are branched alpha-olefins such as di-methyl-1-pentene and 6-methylhebutene-1, and mixtures thereof.

Terpolymers, tetrapolymers, etc. of ethylene, aC3-C2a alpha-olefins, and unconjugated diolefins or mixtures of such diolefins can also be used.

The amount of non-conjugated diolefin is generally about 0.5 to 20 mole percent, based on the total amount of ethylene and α-olefin present;
Preferably it ranges from about 1 to about 7 mole percent.

Polyester viscosity index improvers are generally polymers of esters of ethylenically unsaturated C5-C, mono- and dicarboxylic acids, such as methacrylic acid and acrylic acid, maleic acid, maleic anhydride, fumaric acid, and the like.

Examples of unsaturated esters that can be used include esters of aliphatic saturated monoalcohols of at least 1 carbon atom, preferably 12 to 20 carbon atoms, such as decinoacrylate, lauryl acrylate, stearinopeaglyl acrylate. Included are eicosanyl acrylate, docosaninope acrylate, decyl methacrylate, cyamyl fumarate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and mixtures thereof.

Other esters include vinyl 02-C22 fatty acids or monocarboxylic acids, preferably saturated acids, such as vinyl acetate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, etc. and mixtures thereof. Contains alcohol esters. Copolymers of vinyl alcohol nistert unsaturated acid esters can also be used, such as copolymers of vinyl acetate and dialkyl fumarates.

The ester can be combined with further unsaturated monomers such as olefins, for example from 0.2 to 5 mol of 02-C2° per mole of unsaturated ester or per mole of unsaturated acid or anhydride before carrying out the esterification. It can be copolymerized with aliphatic or aromatic olefins. For example, copolymers of styrene and maleic anhydride esterified with alcohols and amines are known (see, eg, US Pat. No. 3,702,300).

Such an ester polymer can be grafted with a polymerizable nitrogen-containing supermer, or the ester can be copolymerized with the monomer to impart dispersibility to the viscosity index improver. Examples of suitable unsaturated nitrogen-containing monomers include monomers containing from 4 to 20 carbon atoms, such as amine-substituted olefins such as p-(β-diethylamineethyl)styrene; polymerizable ethylenically unsaturated substituents nitrogen-containing heterocyclic compounds supporting , such as 2-vinyl-5-ethylpyridine, 2-
Methyl-5-vinylpyridine, 2-vinylpyridine, 4
-vinyl-pyridine, 3-vinylpyridine, 3-methyl-5-vinylpyridine, 4-methyl-2-vinylpyridine, 4-ethyl-2-vinylpyridine and 2-butyl-
Included are vinylpyridines and vinylalkylpyridines such as 5-vinylpyridine and the like.

N-vinyl lactams such as N-vinylpyrrolidone or N-vinylpiperidone are also suitable.

Vinylpyrrolidone is preferred, N-vinylpyrrolidone,
N~ (1-methylvinyl)pyrrolidone, N-vinyl-
Examples include 5-methylpyrrolidone, N-vinyl-3,3-dimethylpyrrolidone, and N-vinyl-5-ethylpyrrolidone.

Corrosion inhibitors, also known as anticorrosive agents, reduce the deterioration of metal parts that come into contact with lubricating oil compositions.

Examples of corrosion inhibitors are phosphorus sulfide hydrocarbons (phosphosulfide hydrocarbons).
products obtained by reaction of phosphosulfurized hydrocarbons with alkaline earth metal oxides or hydroxides, preferably in the presence of alkylated phenols or alkylphenol thioesters, and preferably also in the presence of carbon dioxide. It is a thing. The phosphorus sulfide hydrocarbon is prepared by combining a suitable hydrocarbon, such as a heavy petroleum fraction of Ct-C6 olefin polymers such as terpenes, polyisobutylene, with 5-30% by weight of phosphorus sulfide, 66
It is produced by reacting at a temperature in the range of ~320°C for ~15 hours. Neutralization of sulfurized hydrocarbons can be carried out by the method described in US Pat. No. 1,969,324.

Antioxidants reduce the deterioration of mineral oils during use.

Deterioration is evidenced by oxidation products such as sludge and face deposits on metal surfaces and increased viscosity. Such antioxidants preferably include alkaline earth metal salts of alkylphenol thioesters with C3-C1□ alkyl side chains, calcium nonylphenol sulfide, barium t-octylphenyl sulfide, dioctyl phenylamine, phenyl alpha naphthylamine, fi
This includes hydrogenated or sulfurized hydrocarbons.

Friction modifiers
serves to impart suitable frictional properties to lubricating oil compositions such as automatic transmission fluids.

Representative examples of suitable friction modifiers include U.S. Pat.
No. 59 (describing fatty acid esters and amides), US Pat. No. 4,176.074 (describing molybdenum complexes of polyisobutenylsuccinic anhydride-amino alcohol), US Pat. describes glycerin esters of quantified fatty acids), U.S. Patent No. 3.779.928
No. 3,7 (describing alkane phosphonates), U.S. Pat.
No. 78.375 (describing the reaction product of phosphonate and oleamide), U.S. Pat. No. 3,852.205 (S-
carboxy-alkylene hydrocarbyl succinimide, S-carboxy-alkylene hydrocarbyl succinimide, and mixtures thereof), U.S. Pat.
No. 879,306 (describing N-(hydroxyalkyl)alkenyl-succinamic acid or succinimide)
, U.S. Pat. No. 3,932,290 [describing reaction products of di-(lower alkyl) phosphites and epoxides], and U.S. Pat. alkylene oxide adducts). The above references are incorporated herein by reference. The most preferred friction modifier is U.S. Pat. No. 4,344.
853, or their metal salts, hydrocarbyl-substituted succinic acids or anhydrides, and thiobisalkanols.

Pour point depressants lower the temperature at which a fluid can flow or be poured. Such depressants are known. Typical of additives that usefully optimize the cold flow properties of fluids are 08-C1
8 dialkyl fumarate ester vinyl acetate copolymer,
polymethacrylate, and waxy naphthalene.

Foam control is provided by foam blowing agents of the polysiloxane type, such as silicone oils and polydimethylsiloxanes.

Organic oil-soluble compounds useful as rust inhibitors in the present invention include nonionic surfactants such as boeoxyalkylene polyols and their esters, and anionic surfactants such as alkyl sulfonic acids. Such rust-inhibiting compounds are known and manufactured in conventional manner. The nonionic surfactants useful as anticorrosive additives in the oil compositions of this invention owe their surface activity to a number of weak solubilizing groups, such as ether linkages. Nonionic rust inhibitors containing ether bonds combine organic substrates containing active hydrogen with lower alkylene oxides (such as ethylene oxide and propylene oxide).
is prepared by alkoxylation with an excess of until the desired number of alkoxy groups are in the molecule.

Preferred rust inhibitors are polyoxyalkylene polyols and derivatives thereof. This group of materials is commercially available from a variety of manufacturers, including Wyandotte Chemicals Corporation (Wyan dotte Che+++1ca
ls Corporation; Pluronic Polyols; Dow Chemical Company;
l Co, ) to polyglycol (Polyglycol
l) 112-2 (liquid triol derived from ethylene oxide and propylene oxide); and both Union Carbide Corporation (Union Carbide Corporation)
Carbide Corp, ) to Tajitor (T
ergitol (dodecylphenyl or monophenyl polyethylene glycol ethers) and Ucon (polyalkylene gelylcols and derivatives) are commercially available products suitable as rust inhibitors in the improved compositions of this invention. It's just a little bit of that.

In addition to the polyols themselves, esters of polyols obtained by reacting polyols with various carboxylic acids are also suitable. Acids useful in the preparation of these esters are lauric acid, stearic acid, succinic acid, and alkyl- or alkenyl-substituted succinic acids (alkyl or alkenyl groups containing up to about 20 carbon atoms).

Preferred polyols are made as block polymers. Thus, the hydroxy-substituted compound R-(OH),
(where n is 1-6 and R is the residue of a monohydric or polyhydric alcohol, phenonopenaphthol, etc.) with propylene oxide to generate a hydrophobic base. This base is then reacted with ethylene oxide to provide a hydrophilic moiety, resulting in a molecule with both a hydrophobic and a parent moiety. The relative sizes of these parts are
This can be adjusted by adjusting the ratio of reactants, reaction time, etc., as will be apparent to those skilled in the art. Thus, the hydrophobic and hydrophilic portions are present in a ratio that makes the rust inhibitor suitable for use in any lubricant composition, regardless of base oil differences and the presence of other additives. It is within the skill of the art to produce polyols with molecular characteristics.

If more oil solubility is desired in a given lubricating oil composition, the hydrophobic portion can be increased and/or the hydrophilic portion can be decreased. If greater oil-in-water emulsion breaking ability is desired, the hydrophilic and/or hydrophobic portions can be adjusted to achieve this.

Examples of R-(011)n compounds include alkylene glycols such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, sorbitol, mannitol, etc., alkylene polyols such as alkylene triols, alkylene tetrols. Aromatic hydroxy compounds such as alkylated mono- and polyhydric phenols and naphthols, such as heptylphenol, dodecylphenol, etc., may also be used.

Other suitable demulsifiers include U.S. Pat.
No. 7 and No. 2,674,619.

Liquid polyols commercially available from Wyandotte Chemical Company under the name Pluronic Polyol and other similar polyols are particularly suitable as rust inhibitors. These pluronic polyols correspond to formula (■).

HO-(CH2CH20), (CHHCII20L (
CH2CH20), H(■)CH3 In the above formula (■), x, y and 2 are -CH2Cl120
- is an integer greater than 1 such that the group constitutes about 10 to about 40% by weight of the total molecular weight of the glycol and the average molecular weight of the glycol is from about 1000 to about 5000. These products are made by first condensing propylene oxide with propylene glycol to form the hydrophobic base HO(-C)I-CH20)y-H(IX)L. This condensation product is then treated with ethylene oxide to add hydrophilic moieties to both ends of the molecule. For best results, ethylene oxide units should constitute from about 10 to about 40 percent by weight of the molecule. The molecular weight of the polyol is approximately 2500-45
00 and the ethylene oxide unit is about 10 to 100% of the molecule
Particularly suitable are products which constitute about 15% by weight. Approximately 4
000 and approximately 10% is (C)12cl1
20) Particularly good are the polyols attributed to the unit.

Cs-C16 alkyl substituted phenols (mono- and di-heptyl Also useful are alkoxylated fatty amines, amides, alcohols, and the like, including such alkoxylated fatty acid derivatives treated with phenols (such as octyl, nonyl, decyl, undecyl, and tridecylphenols).

These compositions of the invention may also contain other additives as described above and metal-containing additives such as barium and sodium-containing additives.

The lubricating oil compositions of the present invention may also include copper-lead containing corrosion inhibitors. Typically such compounds are 4-diazole polysulfides containing 5 to 50 carbon atoms, derivatives thereof and polymers thereof. Preferred materials include those described in U.S. Pat.
, 3.4-thiadiazole, and is a derivative of Amoco (A
Compound 2,5 commercially available as moco) 150
-bis(t-octadithio)-1,3,4-thiadiazole is particularly preferred. Other similar materials that are also suitable are U.S. Pat.
No. 37, No. 4.097.387, No. 4,107105
No. 9, No. 4゜136.043, No. 4.188.299
No. 4,193.882.

Other suitable additives include British Patent Specification 1.560.830
Thio- and polythiosulfenamides of thiadiazoles such as those described in No. When these compounds are included in the lubricating oil compositions of the present invention, they are present in an amount of 0.01 to 10, preferably 0.1, based on the weight of the composition.
Preferably present in an amount of ~5.0% by weight.

Some of these numerous additives can provide multiple effects, such as dispersants-antioxidants. This is known and need not be elaborated further here.

When including conventional additives, the composition is typically mixed into the base oil in amounts effective to provide its conventional accessory functions. Representative effective amounts of such additives in fully formulated oils are shown below.

Component A (1) Ca detergent”0.04-0.4 0
．． 03-0.5 component At2+hg? i agent”0.01-0
．． 2 0.01-0.25 Component B Anti-wear agent 0
．． 07-0.12(1) 0.05-0.15(1)
Component C dispersant 0.5-4 0.1-8
Ingredients Antioxidant 50-200ppm Cu ” 4
40-500pp Cu” viscosity improver 0.01
-4 0.01-12 Corrosion inhibitor 0.
01-1.5 0.01-5 Antioxidant
0.01-1.5 0.05-5 Antifoaming agent 0.
001-0.15 0.001-3 Wear modifier
0.01-1.5 0.01-5 mineral oil base
Residues Residue (1) Expressed as weight % phosphorus.

(2) Weight ppm added copper.

Shown as 0 Metal Ca (or Shame).

Most preferably, the lubricating oil compositions of the present invention contain from about 0.05 to 0.2% by weight of component (A) (1), designated as Ca;
Component B1 in an amount sufficient to provide about 0.02-0.11% by weight of component (A)(2), expressed as Mg, about 0.08-0.11% by weight of phosphorus; Contains 3% by weight active ingredient Component C ashless dispersant, and about 80-150 ppm component antioxidant (expressed as ppm of Cu).

When using other additives, an additive which, although not strictly necessary, comprises a concentrated solution or dispersion of the novel detergent inhibitor/antiwear mixture of the present invention (in the concentrate amounts mentioned above) together with said other additives. Preparing a concentrate (referred to herein as an additive package when it constitutes an additive mixture) whereby several additives are added simultaneously to the base oil to produce a lubricating oil composition. It may be desirable to be able to do so. Dissolution of the additive concentrate into the lubricating oil can be facilitated by a solvent and by mixing with gentle heat, but this is not required. Concentrates or additive packages are typically formulated to contain the correct amount of additive to provide the desired concentration in the final formulation when the additive package is mixed with a predetermined amount of base lubricant. It is mixed. Thus, the detergent inhibitor/antiwear mixtures of the present invention are added to small amounts of base oils or other compatible solvents, along with other desired additives, typically from about 2.5 to about 90% by weight, preferably Additive packages can be prepared containing active ingredients in appropriate proportions, with the balance being base oil, with a collective amount of about 15 to about 75 weight percent, and most preferably about 25 to about 60 weight percent, additive.

The final formulation can typically employ about 10% by weight of the additive package, with the balance being base oil.

All weight percentages given herein (unless otherwise specified) refer to the active ingredient (A, I,) content of the additive and (
or) based on the total weight of any additive package or formulation, which is the active ingredient weight of each additive plus the total oil or diluent weight.

The invention will be further understood by reference to the following examples. In the examples, all parts are parts by weight unless otherwise specified, and the examples include preferred embodiments of the invention.

EXAMPLE A set of fully formulated lubricating oils were prepared containing selected detergent inhibitors, zinc dialkyldithiophosphate antiwear agents, ashless dispersants, antioxidants and fuel economy additives. The data obtained are shown in Table I below.

Notes: (1) (wt% Ca). overbased calcium sulfonate,
TBN 400, active ingredient 55% by weight.

(2) (wt% Mg). Magnesium overbased sulfonate, TBN 400, 52% active ingredient by weight.

(3) (wt% phosphorus). Di(primary alkyl) prepared by reacting p2s5 with a mixture of about 65% by weight of isobutyl alcohol and 35% by weight of amyl alcohol, wherein the alkyl group or mixture of groups has 4 to 5 carbon atoms. Zinc dithiophosphate? condensate (75% by weight of active ingredient in dilute mineral oil).

(41 (mffi% phosphorus). P2S, in which the alkyl group or mixture of such groups has about 3 to 6 carbon atoms, isopropyl alcohol (30%) tomethyl tert-
Zinc di(secondary alkyl)dithiophosphate concentrate (71% active ingredient in dilute mineral oil) prepared by reaction with a mixture with butylcarpitol (70%).

(5) Volume %, ashless dispersant I = polyisobutylene with a nitrogen content of about 1.47% by weight, a boron content of about 0.35% by weight (BM from polyisobutylene with a number average molecular weight of about 1300) 1.1 per molecule
Boron-treated polyisobutenyl succinic anhydride having a ratio of succinic anhydride moieties of 50% by weight A containing butenyl succinimide, 1. Dilute mineral oil solution. Ashless Dispersant - Contains about 0.97% by weight nitrogen, about 0.25% by weight boron and about 1.5% by weight per molecule of polyisobutylene (derived from polyisobutylene having a number average molecular weight of about 2200).
derived from polyisobutenyl succinic anhydride having 1 succinic anhydride moiety and an average of about 5 to 7 succinic anhydride moieties per molecule.
5 containing boron-treated polyisobutenyl succinimide aminated with a commercially available polyethylene amine mixture of nitrogen
0% by weight A, 1. Dilute mineral oil solution.

(6) Capacity%. Cupric oleate solution in dilute mineral oil (38% by weight A, 1.).

(7) Capacity%. A solution of glyceryl monooleate in dilute mineral oil (50% by weight A, 1. Total monoglycerides).

(8) 5 Vehicle Equivalents* Data Points Shown in Figure 1 Figure 1 shows the fuel economy data summarized in the examples. Figure 1
The relative ratios of Ca and Mg metal detergents and secondary and secondary ZDDPs of Examples 1-27 are shown schematically relative to the observed fuel economy test data. The percentage is shown, and the y-axis is the 1st 2nd 2nd ZDD
The relative percentage of P is shown. The circled number (e.g. 1.98
/1), where the numerator represents the average resulting fuel economy,
The denominator is for the indicated example or area (A, B,
The number of examples so averaged (as indicated in C, D and E) is indicated.

From the above test, it was found that Area A (Examples 1 and 2.100% Mg
, 100% second ZDDP) fuel economy is 99%
Area C (Example 14-17.50/50
The fuel economy is statistically inferior to that obtained with Ca/Mg, 50/50 1st/2nd ZDDP).

Region B (Example 3-13. 100% Mg, 100% No.
ZDDP) fuel economy is statistically inferior to Inventive Region C with 99% confidence.

Region C is also, with 95% confidence, region E (Example 1
8-20, characterized by high Ca/Mg and high 2nd/2nd-ZDDP ratio).

Additional fuel economy single data points are shown in FIG. 1 for Examples 22-27.

Another set of lubricating oil compositions was prepared and subjected to fuel economy testing similar to Examples 1-27. These additional experiments 28-3
7 is shown in Table H below. In these experiments, no glyceryl monooleate friction modifier was included in the formulation.

[Brief explanation of the drawing]

FIG. 1 shows the surprisingly improved fuel economy achieved through the use of the composition of the present invention. FIG. 2 is a schematic diagram of data obtained in Example 1-27. FIG, is an engraving of the drawing (no change in content)

Claims (1)

[Scope of Claims] 1. Oil of lubricating viscosity as a main component and (A) as a subcomponent (1) at least one calcium overbased detergent inhibitor and (2) at least one magnesium overbased (B) a mixture of (1) at least one zinc di-(primary hydrocarbyl) dithiophosphate and (2) at least one zinc di-(secondary hydrocarbyl) dithiophosphate; C) a lubricating oil composition comprising at least one ashless dispersant; and (D) an antioxidant effective amount of at least one copper carboxylate compound, wherein component (A) (1) designated as Ca Component (A)(2), designated as Mg, constitutes about 0.03-0.5% by weight of the lubricating oil composition, and component (A)(2) constitutes about 0.01-0.5% by weight of the lubricating oil composition.
Component (B) constitutes about 0% by weight of the lubricating oil composition.
．． Component A(1):A(2) is used in an amount sufficient to provide 0.05 to 0.15% by weight of phosphorus, and the mixed calcium and magnesium detergent inhibitor is from about 0.3:1 to about 6:1. Component B is present in a weight:weight ratio of from about 0.4:1 to about 9:1 mixed zinc di(primary hydrocarbyl) dithiophosphate and zinc di(secondary hydrocarbyl) dithiophosphate antiwear agent.
A lubricating oil composition present in a weight:weight ratio of (1):B(2). 2. The ashless dispersant (a) has a number average molecular weight of about 700 to 5000;
Hydrocarbyl-substituted C_4-C_ produced by reacting an olefin polymer of 2-C_1_0 monoolefin with a C_4-C_1_0 monounsaturated acid material
1_0 monounsaturated dicarboxylic acid-forming material, wherein the acid-forming material contains an average of at least about 0.8 monounsaturated dicarboxylic acid-forming materials per molecule of the olefin polymer present in the reaction mixture used to form the acid-forming material. A claim consisting of an oil-soluble reaction product of a reaction mixture comprising an acid-generating substance having a dicarboxylic acid-generating moiety and (b) a nucleophile selected from the group consisting of amines, alcohols, amino alcohols, and mixtures thereof. 1
The oil composition described. 3. The composition of claim 2, wherein the nucleophilic reactant in (b) is an amine. 4. Claim 3, wherein the amine is polyethylene polyamine.
Compositions as described. 5. The composition according to claim 2, wherein the nucleophilic reactant in (b) is an alcohol. 6. The composition according to claim 2, wherein the nucleophilic reactant in (b) is an amino alcohol. 7. According to any one of claims 2 to 6, there are about 1.0 to 2.0 dicarboxylic acid generating moieties per molecule of the olefin polymer in the acid generating material of (a). Composition. 8. The olefin polymer is comprised of a polymer of C_2 to C_4 monoolefins having a molecular weight of about 900 to 3000, and the C_4 to C_1_0 monounsaturated acid substance is α
8. The composition according to claim 7, comprising a - or β-unsaturated C_4 to C_1_0 dicarboxylic acid, anhydride or ester. 9. The carboxylic acid copper antioxidant is about 40 to 500 p by weight.
A composition according to claim 1, used in the form of said copper carboxylate in an amount of added copper of pm. 10. The composition of claim 9, comprising 10,50 to 200 ppm of said added copper. 11. The composition of claim 1 or 9, wherein the copper compound is selected from the group consisting of copper salts of C_1_0 to C_1_8 fatty acids and copper salts of naphthenic acids having a molecular weight of about 200 to 500. 12. The lubricating oil composition of claim 1, wherein the calcium detergent inhibitor comprises an overbased calcium sulfonate, phenoxide or salicylate. 13. The lubricating oil composition of claim 1, wherein the magnesium detergent inhibitor comprises an overbased magnesium sulfonate, phenoxide, or salicylate. 14. Calcium detergent inhibitor is indicated as Ca about 0
．． 13. A lubricating oil composition according to claim 1 or 12, wherein the lubricating oil composition is present in the lubricating oil composition in an amount of 0.04 to 0.4% by weight. 15. The lubricating oil composition of claim 14, wherein the magnesium detergent inhibitor is present in the lubricating oil composition in an amount of about 0.01 to 0.2% by weight, expressed as Mg. 16. The calcium detergent inhibitor and the magnesium detergent inhibitor may contain from about 0.4 to 1 part by weight of the calcium detergent inhibitor per 1 part by weight of the magnesium detergent inhibitor expressed as the respective metal.
16. The lubricating oil composition of claim 15, wherein the lubricating oil composition is present in the lubricating oil composition in an amount of 3 parts by weight. 17. Zinc di(primary hydrocarbyl) dithiophosphate has the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R^1 and R^2 are the same or different,
The lubricating oil composition of claim 1, which is derived from a zinc salt of an acid which is alkyl, cycloalkyl, aralkyl, alquaryl or a hydrocarbon group of substantially similar structure. 18. Zinc di(secondary hydrocarbyl) dithiophosphate has the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R^3, R^4, R^5 and R^6 are the same or different and are alkyl 2. A lubricating oil composition according to claim 1, which is derived from the zinc salt of an acid which is substantially a hydrocarbon group of cycloalkyl, alquaryl, aralkyl or similar structure. 19, dithiophosphate mixture B was expressed in phosphorus approximately 0.07
15. The lubricating oil composition of claim 14, wherein the lubricating oil composition is present in the lubricating oil composition in an amount of ~0.12% by weight. 20, dithiophosphate mixture B was expressed in phosphorus approximately 0.08
The lubricating oil composition of claim 1, wherein the lubricating oil composition is present in the lubricating oil composition in an amount of -0.11% by weight. 21. Zinc di(primary hydrocarbyl) dithiophosphate and zinc di(secondary hydrocarbyl) dithiophosphate are about 0.5 to 3 zinc di(primary hydrocarbyl) dithiophosphate per 1 part by weight of zinc di(secondary hydrocarbyl) dithiophosphate. 20. The lubricating oil composition of claim 19, wherein the lubricating oil composition is present in the lubricating oil composition in an amount of parts by weight. 22. A mixture of an oil of lubricating viscosity as the main component and (A) (1) at least one calcium overbased detergent inhibitor and (2) at least one magnesium overbased detergent inhibitor as minor components. wherein the mixed calcium and magnesium detergent inhibitor is present in a weight ratio of Components A(1):A(2) of about 0.3 to about 6:1, and Components (A)(1) as Ca. Component (A) (
2) about 0.01-0.25% by weight expressed as Mg
(B) a mixture of (1) at least one zinc di-(primary hydrocarbyl) dithiophosphate and (2) at least one zinc di-(secondary hydrocarbyl) dithiophosphate; mixed zinc di(primary hydrocarbyl) dithiophosphate and di(
(secondary hydrocarbyl) zinc dithiophosphate antiwear agent is about 0.
about 0.05 to 0.15% by weight (designated as phosphorus) of a mixture present in a weight:weight ratio of B(1):B(2) of from 4:1 to about 9:1; (C) at least 1 Seed oil-soluble ashless dispersant about 0.1-1
and (D) at least one oil-soluble copper carboxylate antioxidant to provide about 40 to 500 ppm by weight of added copper in the form of copper carboxylate. 23. The ashless dispersant (a) has a number average molecular weight of about 900 to 5000;
Hydrocarbyl-substituted C_4-C_ produced by reacting an olefin polymer of 2-C_1_0 monoolefin with a C_4-C_1_0 monounsaturated acid material
1_0 monounsaturated dicarboxylic acid-forming material, wherein the acid-forming material has an average of at least about 0.8 monounsaturated dicarboxylic acid-forming materials per molecule of the olefin polymer present in the reaction mixture used to produce the acid-forming material. A claim consisting of an oil-soluble reaction product of a reaction mixture comprising an acid-generating substance having a dicarboxylic acid-generating moiety and (b) a nucleophile selected from the group consisting of amines, alcohols, amino alcohols, and mixtures thereof. 2
2. The oil composition according to 2. 24. The composition of claim 23, wherein the nucleophilic reactant in (b) is an amine. 25. The composition of claim 24, wherein the amine is a polyethylene polyamine. 26.Claim 2, wherein the nucleophilic reactant in (b) is an alcohol.
3. The composition according to 3. 27. The composition according to claim 23, wherein the nucleophilic reactant in (b) is an amino alcohol. 28. Any one of claims 23-27, wherein there are about 1.0 to 2.0 dicarboxylic acid-generating moieties per molecule of the olefin polymer in the acid-generating material of (a). Composition of. 29. The olefin polymer consists of a polymer of C_2-C_4 monoolefins having a molecular weight of about 900-3000, and the C_4-C_1_0 monounsaturated acid material is an α- or β-unsaturated C_4-C_1_0 dicarboxylic acid, anhydride. or ester. 30. The composition of claim 22, wherein said copper carboxylate antioxidant is used in the form of said copper carboxylate in an amount of added copper of about 40 to 500 ppm by weight. 31. Claim 30 comprising 50 to 200 ppm of said added copper.
Compositions as described. 32. The composition of claim 22 or 30, wherein the copper compound is selected from the group consisting of copper salts of C_1_0-C_1_8 fatty acids and copper salts of naphthenic acids having a molecular weight of about 200-500. 33, a mixture of about 25-85% by weight of a base oil, (A) (1) at least one calcium overbased detergent inhibitor and (2) at least one magnesium overbased detergent inhibitor; (B) ( 1) a mixture of at least one zinc di(primary hydrocarbyl) dithiophosphate and (2) at least one zinc di(secondary hydrocarbyl) dithiophosphate, (C) at least one ashless dispersant, and (D ) an antioxidant effective amount of at least one copper carboxylate compound, wherein component (A) (1), denoted Ca, is present in about 0% of the lubricating oil composition;
．． Component (A) (2), designated as Mg, comprises about 0.01 to 0.25% by weight of the lubricating oil composition.
component (B) constitutes about 0.0% by weight in the lubricating oil composition.
Component A(1):A(2) is used in an amount sufficient to provide 5 to 0.15% by weight of phosphorus, and the mixed calcium and magnesium detergent inhibitor is from about 0.3:1 to about 6:1. Di(primary hydrocarbyl) present and mixed in a weight:weight ratio of
Component B(
1): Concentrate present in the weight:weight ratio of B(2). 34. The concentrate of claim 33, wherein said base oil is present at a concentration of 40 to 75% by weight.