JPH01207393A - Improved lubricant composition for internal combustion engine - Google Patents

Abstract

PURPOSE: To obtain a lubricant composition which low in sulfated ash which consists of a base oil having lubricating viscosity, an oil-soluble ashless dispersing, a sulfurized alkylphenol and dihydrocarbyl dithiophosphate and shows remarkable reduction of engine carbon deposit.

CONSTITUTION: This composition is obtained by blending a base oil (A) that is used as a major component and has lubricating viscosity, with about ≥3 wt.% of an oil-soluble ashless dispersing (B),about ≥2 wt.% of an oil-soluble sulfurized alkylphenol (C) and a small amount of an oil-soluble metal dihydrocarbyl dithiophosphate (D) represented by the formula (each of R¹ and R² is a (cyclo)alkyl, an aralkyl or an alkaryl group, or the like, wherein the R¹ and R² groups contain carbon atoms of ≥6 on average), and also has a <0.6 wt.% total sulfated ash (SASH) and a weight ratio of SASH to dispersant is 0.01:1 to 0.2:1.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to lubricating oil compositions that exhibit significant reductions in engine carbon deposits. In particular, the present invention is adapted for use in diesel engines and contains ashless dispersants, sulfurized alkylphenols and metal dihydrocarbyl dithiophosphates, and also contains sulfated ash-forming additives at unusually low levels. The present invention relates to a lubricating oil composition with a low total sulfur ash content.

BACKGROUND OF THE INVENTION It is an object of the present invention to provide lubricating oil compositions that exhibit minimal engine deposit improvements and low lubricant consumption rates, particularly in diesel engine vehicles.

Among conventional lubricating oil additives, zinc dihydrocarbyl dithiophosphates perform multiple functions in motor oils: oxidation protection, bearing corrosion protection, and extreme pressure/wear protection for valve systems.

Conventional patent documents include detergents,
Compositions using polyisobutenyl succinimide in combination with zinc dialkyl dithiophosphate used with other conventional additives such as viscosity index improvers, rust inhibitor additives, etc. are exemplified. Typical of these prior art disclosures are US Pat.

Because phosphorus is a catalyst poison in catalytic converters, and because zinc itself provides a source for sulfated ash, the prior art has attempted to reduce or eliminate zinc-phosphorus containing motor oil components. It was done. Examples of prior art directed to the reduction of phosphorus-containing lubricant additives include U.S. Pat.
No. 0, No. 4.350゜420 and No. 4.659.
No. 324 is mentioned.

U.S. Pat. No. 4,147,640 discloses that olefinic hydrocarbons having 6 to 8 carbon atoms and about 1 to S olefinic double bonds are reacted simultaneously with sulfur and hydrogen sulfide, and then the obtained The present invention relates to a lubricating oil having improved antioxidant and antiwear properties obtained by reacting a reactive intermediate with an additional olefinic hydrocarbon. These additives are generally disclosed for use in conjunction with other conventional oil additives such as overbased metal detergents, polyisobutenyl succinimide dispersants, and phenolic antioxidants. Although it is disclosed that the t of zinc additives can be greatly reduced to create "low ash" or "ashless" lubricating oil compositions, the patentee claims that all SAS
(It is clear that he was referring to ash derived from Zn.

U.S. Pat. No. 4,350,420 is directed to low ash, low phosphorous motor oils that have improved oxidative stability as a result of including synergistic amounts of dialkyldiphenylamine antioxidants and sulfurized polyolefins. The synergy between these two additives is disclosed to compensate for the reduced amount of phosphorus in the form of zinc dithiophosphate. Fully formulated motor oil contains 2-10 wt. ashless dispersant, 15-55 wt.
5% by weight nesium or calcium salt detergent (to provide at least 0.1% magnesium or calcium km), (Ls~2.0wt-zinc dialkyldithiophosphate, α2~2.0wt-dialkyldiphenolamine Antioxidant, 0.2-4% by weight sulfurized polyolefin antioxidant, 2-10% by weight primary ethylene propylene VI improver, 2-10% by weight SO secondary VI improver such as methacrylate terpolymer. It is said to contain a lot of oil and a balance of paste oil.

U.S. Pat. No. 4,659,324 discloses that metal dithiophosphate salts are useful as antioxidants but are a source of ash, and also contain at least one fatty acid having 8 to 26 carbon atoms. A group olefinically unsaturated hydrocarbon is reacted simultaneously with sulfur and at least 1s fatty acid ester to form a reaction intermediate, followed by additional sulfur and a dimer of cyclopentadiene or lower C1-C4 alkyl substituted cyclopentadiene. Ashless antioxidants are disclosed that include reaction products made by reacting with dimers. These additives are generally used in lubricating oil compositions in conjunction with other conventional oil additives such as neutral and overbased calcium or magnesium alkaryl sulfonates, dispersants, and phenolic antioxidants. Disclosed. In addition, when using the additive of this invention, the t of the zinc additive can be greatly reduced, resulting in a low ash content.
Alternatively, it is disclosed that "ashless" lubricating oil formulations can be made. Again, the patentee is not all SASH (
It is clear that he was referring to ash derived from Zn.

Metal detergents help control fencing and corrosion, thereby reducing the efficiency of internal combustion engines by minimizing the blockage of constriction openings and the reduction of gaps between moving parts. have been used in motor oils to minimize the negative effects of

U.S. Patent No. 4.089.791 describes the MS11C Last Test (Ruat Te5t) and the L-38 Bearing Weight Loss Test (B
To provide a formulated motor oil that passes , in which at least 50% of the ZDDP compound consists of zinc diallyldithiophosphate). This patent describes three components containing an overbased calcium detergent, ZDDP, trialkanolamine, and unspecified conventional lubricating oil additives to provide viscosity index enhancement, antioxidant properties, dispersibility, and antifoam properties. illustrating an oil formulation of The exemplary formulations each had a SASH level of approximately 0.66 wt- based on the reported Ca and Zn concentrations. No diesel motor oil formulations are exemplified.

U.S. Pat. No. 4,153,562 discloses an antioxidant that is particularly useful for formulated lubricating oils destined for one use (abuse) in automotive crankcase formulations with relatively low ash content. It is related to. Here, such antioxidants are produced by condensation of dithiophosphates of alkylphenol sulfides with unsaturated compounds such as styrene. Antioxidant is approximately 2.65 iF
t% (a,i,) of boron-treated polyisobutenyl succinimide dispersant, overbased magnesium sulfonate as a detergent; C
about 0.10 wt.
13 to 1.25 weight f in lubricating oil compositions containing
Illustrated at the k-level (Example 3).

U.S. Pat. No. 4,159/972 shows that the trend toward unleaded fuel oil and ashless lubricating oil compositions necessitated the search for nonmetallic (ashless) alternatives to metal-organic detergents, and The present invention relates to tetrahydropyrimidyl-substituted compounds disclosed as being useful as ash base and rust inhibitor additives.

Examples of this patent describe various lubricating oil formulations in the Ford V8 Varnish Test (Table ■) and additional formulations (termed "low ash" or "ashless") in the Humidity Cabinet Last Test (Table ■). The performance of each of the following is compared. SA of “low ash” formulations
SH levels are not reported and cannot be determined from the information provided for metal detergent- and ZDDP components.

U.S. Pat. No. 4,165,292 discloses that overbased metal compounds provide effective rust protection in automotive crankcase lubricating oils and that such additives are used in reduced amounts as in ashless oils. It is disclosed that rust formation becomes a serious problem in the absence of overbased additives, such as in low ash oils when present.
Evaluated by ASTM sequence [C engine test]. This patent covers oil-soluble basic organic nitrogen compounds.
and an alkenyl- or alkyl-substituted succinic acid having from 12 to 50 carbon atoms. Basic organic nitrogen compounds and carboxylic acid compounds are required to be used together to obtain the desired antirust properties.

It is disclosed that best results are achieved by using an excess of amine over that required to form a neutral salt of the substituted cono-phosphate present.

U.S. Pat. No. 4,502,970 discloses a lubricating oil dispersant, an overbased metal dispersant, a zinc dialkyldithiophosphate antiwear additive, and a polyisobutenylsuccinic anhydride in the amounts described therein. An improved crankcase lubricating oil composition. 5 in 91.0 wt. of pace oil
weight of polyimbutenyl succinimide dispersant, 50 parts of polyisobutenyl succinic anhydride, 2.0 parts of weight
1? ! Exemplary lubricating oil formulations containing an overbased metal sulfonate or an overbased sulfurized 7-enate detergent and a 1.0 weight-weight zinc dialkyldithiophosphate antiwear additive are disclosed.

European Patent No. 24.146 relates to lubricating oil compositions containing copper antioxidants and 1.0
Weight - of 400 TBN Magnesium Sulfonate (9,
2wt. of magnesium), cL5wt.il:%0
250 TBN calcium phenate (containing 933 wt. calcium), and zinc dialkyldithiophosphate (containing an alkyl group having 4 to 5 carbon atoms) to provide a 1.0 wt.-wt. phosphorus level in the lubricating oil composition. mosquito\
in a lubricating oil composition having a mixed group of phosphorus (P, S, made by reacting a mixture of about 65% isobutyl alcohol and 35% amyl alcohol). Examples include copper antioxidants.

British Patent Publication No. 2.062.672 describes an additive composition comprising a sulfurized alkylphenol and an oil-soluble carboxylic acid dispersant containing hydrocarbon pasting groups having a number average molecular weight of at least 1.300, which (disclosed in combination with forming detergents).

However, it is extremely difficult to translate the development of lubricants intended for use in passenger cars and light trucks into lubricants for use in heavy duty diesel engines.

SAE Technical Paper Series (Tschni)
eal Paper 5eries) paper boiled 8
31720 (1983), R.D. Herkamp conducted an engine test run to determine the relative ability of each push lubricant formulation to control oil consumption in heavy-duty diesel engines. Reports on development research. The authors note that laboratory analysis of crown land deposits from diesel engine pistons indicates the presence of organic binders containing high molecular weight esters, and the authors also note that oxidation products in the oil are present in the deposits. We speculate that it may be a precursor to the binder found in Improved antioxidants are stated to be the key to preventing premature oil loss.

SAE Technical Paper Series Paper Flat 8
! 11722 (1983), Mr. A. A. Sketeritsch discusses the effect of ffs+? The influence of W oil parameters is reported. Over the past 30 years,
Trends in the heavy-duty diesel oil industry have increased sulfated ash levels to 2.4 weight sulfated ash (SASH) levels in 1960.
to the typical American SASH level of α8~1 heavy food, and correspondingly HD oil total base @l1 (T
BN) D2896 values from >20 to typical North American TBN values of >7-10. Also, according to the author, SAS
The significant reduction in H and TBN levels has been attributed to improved performance of ashless components, including ashless diesel detergents and ashless dispersants. In diesel engine tests, approx.
At ~2% SASH levels and approximately 8-17% TBN levels, the level of piston deposits or oil fluid 52f# and SASH
Or no significant correlation was found between TBN levels. We compared the ash-free component treatment level, piston deposits t (92% confidence level) and oil consumption (
98% confidence level). This correlation is stated by the authors to be drawn for diesel fuels with average sulfur levels of less than about 0.5%. It is also stated that ash deposition levels are accelerated in hotter engine parts. The author is 97
We conclude that there is a correlation between oil consumption and piston deposits, particularly topland deposits, at the % confidence level.

These deposits contribute to two dust phenomena: (1) they reduce the amount of blow pie flowing downward past the top land, thereby causing a reduction in the amount of gas behind the top ring of the piston; Ultimately this results in high oil consumption f1-'e, and (2) bore polishing of the piston cylinder liner is increased due to topland deposits, which flow into the ignition chamber of the cylinder along the polished bore passage. It is believed that oil migration contributes to high oil consumption, thereby causing increased oil consumption. Therefore, this article concluded that the ash content in the oil should be reduced in order to reduce the topland deposits and hence the oil sludge.

This 1983 Sketerich paper shows that the SAS of approximately 1%
reports on the formulation of two test oils containing H'i and having TBN levels of 4 to C10 and 9, respectively, in which an overbased metal detergent was used along with the zinc source prior to each formulation. Contains a hole.

SAE paper A331721 Nos. 4,848-4,869
(1984), J.A. Matsukugrehan published a series of papers investigating the effects of topland deposits, fuel sulfur content, and lubricant viscosity on diesel engine oil consumption and cylinder bore polishing. The results of the BID diesel engine tests are summarized. These authors also showed that excessive topland deposits cause high oil consumption and cylinder bore polishing, but that corrosion in oils with low alkalinity values also causes cylinder bore polishing at high sulfur levels. Also listed.

Therefore, they concluded that the oil should provide sufficient alkalinity to minimize the corrosive aspects of bore polishing. The authors also reported that laboratory 0.01% sulfated ash oil (which was combined with 0.2% fuel sulfur)
VL-Mack TZ 675 (turbocharged) 1
(tested in a 20 hour test) provided minimal topland deposits and extremely low oil consumption. This is said to be due to a "highly effective ashless inhibitor". This latter component was not further specified. Furthermore, from the data provided by the authors in Figure 4 of this paper, it is clear that the ash level There does not appear to be any oil consumption benefit in reducing SASH from 1% to 0.01%, since oil consumption in the engine actually decreases from 1% to 0.01%. This is because it occurs in

This reinforces the authors' view that low but meaningful SASH levels are required to obtain sufficient alkalinity to avoid oil consumption as a result of bore polishing emanating from the corrosive surface of the oil. It is something.

Matsuku-Greehan concluded that deposits on the topland are correlated with oil consumption but not directly related to the sulfated ash content of the lubricating oil, and that these deposits can be controlled by crankcase formulations. He said.

SUMMARY OF THE INVENTION In accordance with the present invention, an oil of lubricating viscosity as a major component and as a minor component (4) at least about 5 parts of at least one ashless dispersant; a sulfurized alkylphenol, and (C) at least 11 metal dihydrocarpyl ditheophosphates, and less than about 0.6% by weight and a SASH:dispersant weight double weight ratio of about (LO1 to about 1 to about 1) A low sulfated ash heavy duty diesel lubricating oil composition is provided.

Surprisingly, the low ash lubricating oil of the present invention provides a significant reduction in crown land deposits in heavy duty diesel engines while maintaining desirable additional performance characteristics over commercially acceptable oils. was found to be achieved. In particular, the present invention surprisingly provides a low ash formulation that passes the modern High Severity Heavy Duty Diesel Lubricant Standard, the American Petroleum Institute CE Standard, implemented in April 1987. Do you get it. Therefore, the present invention is a process for making heavy duty diesel lubricating oils adapted to meet American Petroleum Institute CE standards, which control the metal content of the oil to about 0.6 (4) provide a total sulfated ash (SASH) level of less than 1 weight and a SASH:dispersant weight ratio of cLol:1 to about 0.2:1; an ashless dispersant, (B) an anti-wear sulfurized alkyl phenol arranging agent of at least about 2*, and (C) an anti-wear effective amount of at least one metal salt for dihydrocarbyl dithiophosphorylation, including a nucleic acid each of the hydrocarbyl groups having an average of at least 6 carbon atoms).

Furthermore, the present invention provides at least one tight top land piston.
performance of a heavy-duty diesel lubricating oil adapted for use in a diesel engine with (n) and further adapted to be energized by a normally liquid fuel having a sulfur content of preferably less than 1 part by weight. 1. A method for controlling the metal content of an oil to provide a total sulfated ash (SASH) level in the oil of less than about 0.6 wt.
:1 to about 0.2:1 SASH:dispersant weight; and in the kernel oil, at least about 3 weight percent of the ashless dispersant; an anti-wear agent, and (C) an anti-wear effective amount of at least one metal salt of dihydrocarbyldithiophosphoric acid (
(where each hydrocarbyl group in the nucleic acid has on average at least 6 carbon atoms)? The present invention provides a method for improving the performance of heavy-duty diesel lubricants.

DETAILED DESCRIPTION OF THE INVENTION Component A The ashless nitrogen- or ester-containing dispersants useful in this invention include (1) oil-soluble salts, amides of long chain hydrocarbon substituted mono- and dicarboxylic acids or anhydrides thereof;

imides, oxazolines and esters or mixtures thereof; (11) a long chain aliphatic hydrocarbon to which a polyamine is directly attached; formaldehyde and about 0.5 to 2 moles of polyalkylene polyamine (here,
(i), (11) and (weight) long chain hydrocarbon groups are C
2 to C1, for example, C to Cs Monoolefin polymer having a molecular weight of about 300 to about 5. OOOO number average molecule Jit
- a boron-free material selected from the group consisting of:

A(1) Nitrogen- or ester-containing ashless dispersants are long-chain hydrocarbon-substituted mono- and dicarboxylic acids or anhydrides thereof, where the long-chain hydrocarbon groups are C2-CIO, e.g.
2~C, monoolefin polymer with about 700~s
, o o o), amides, imides, oxazolines and esters, or mixtures thereof.

The long-chain hydrocarbyl-substituted mono- or dicarboxylic acid material, ie, acid, anhydride or ester, used in the dispersant may include a long-chain hydrocarbon, generally a polyolefin, with an average of about [L8 to 2.0, preferably about 1 per mole of polyolefin].
．． Examples include those substituted with 0 to 1.6 mol, for example 1.1 to 1.3 mol of α- or β-unsaturated 04-CIO dicarboxylic acid or anhydride or ester thereof. mosquito\
Examples of dicarboxylic acids, anhydrides and their esters include:
fumaric acid, itaconic acid, maleic acid, maleic anhydride,
These include chlormaleic acid, dimethyl fumarate, chlormaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid.

Preferred olefin polymers for reaction with unsaturated dicarboxylic acids to form the dispersant include a majority of C2 to C1
For example, it is a polymer containing a C, to C5 monoolefin. Such olefins include ethylene, propylene,
Examples include butylene, isobutylene, pentene, octene-1, styrene, and the like. The polymer may be a homopolymer such as polyisobutylene, or a copolymer of two or more of such olefins such as a copolymer of ethylene and propylene, a copolymer of butylene and imbutylene, a copolymer of propylene and isobutylene, etc. It may be a polymer. Other copolymers include those in which a small molar amount of the monomer of the copolymer, for example 1 to 10 molar, is a C4-C18 non-conjugated diolefin, such as a copolymer of imbutylene and butadiene or ethylene. and a copolymer of propylene and 1,4-hexadiene.

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

The olefin polymer used in the dispersant generally has a number average molecular weight within the range of about 700 to about 2,000 s, o o o, and preferably from about 800 to about 4,000. Particularly useful olefin polymers have a number average molecular weight within the range of about 900 to about 2,500 and about one terminal double bond in the polymer chain. A particularly useful starting material for the high-potency dispersants useful in accordance with the present invention is polyisobutylene. The number average molecule of such a polymer -! l can be measured by several known techniques. A convenient method for such measurements is by gel permeation chromatography (GPC), which provides additional molecular weight distribution information. W, W, Yau, J, JA, Kirkland and Day, Day, and Bly each "Y Genshuu Tsuyoshi" left y Yumuzo ↓ 4 Ryu Shise l ± S future S key point Yomu-grap
hy' (John, Willie, & Sons, New York, 1979).

Olefin polymer 04-CIO unsaturated dicarboxylic acid,
Methods of mourning, such as reacting with anhydrides or esters, are known in the art. For example, U.S. Patent No. 4361.67
No. 3 and No. 4401.118, the olefin polymer and dicarboxylic acid material can be simply heated together to effect a thermal "ene" reaction. Alternatively, the olefin polymer can be first halogenated, e.g. chlorine or bromine added to the polyolefin from 60 to 2
For example, 50℃ is about 0.5 to 10 at a temperature of 120 to 160℃.
It is possible to chlorinate or bromine up to about 1 to 8, preferably 5 to 7 percent by weight of chlorine or bromine, based on the weight of the polymer, by passing for a period of time preferably from 1 to 7 hours. The halogenated polymer is then treated with 100 to 250 tons of unsaturated acid or anhydride such that the resulting product contains the desired number of moles of unsaturated acid per mole of halogen specific polymer:
This general type of process is described in U.S. Pat. No. 408-436, U.S. Pat.
No. 172.892, No. 4272,746, etc.

Alternatively, the olefin polymer and unsaturated acid material are mixed and heated while adding chlorine to the hot material.

Methods of this type are described in U.S. Pat. It is disclosed in patent no. 1.440.219.

With the use of halogens, typically about 65 to 95 fi (1%) of the polyolefin, e.g.
Only 75% by weight reacts. Chlorination helps improve reactivity.

For convenience, the functionality ratio of dicarbonyl-forming units to polyolefin (e.g., rl, 8 to 2.0) described above refers to the total amount of polyolefin used to make the product, i.e., the total amount of both reacted and unreacted polyolefins. based on.

The dicarboxylic acid-forming material can also be further reacted with amines, alcohols (including polyols, amino alcohols, etc.) to form other useful dispersants. Thus, if the acid-forming material is If the reaction is to be neutralized, for example, at least 50 of the acid units are generally
A majority of the units are reacted.

Amine compounds useful as nucleophilic reactants in the neutralization of hydrocarbyl-substituted dicarboxylic acid materials have about 2 to 60
Seven and (preferably) polyamines preferably have a total number of carbon atoms of 2 to 40 (e.g. 3 to 20) and a number of nitrogen atoms of about 1 to 12, preferably 5 to 12f, and preferably 3 to 9. Both preferably include polyalkylene polyamines. These amines may be hydrocarbyl amines or contain other groups such as hydroxyl groups,
It may be a hydrocarbyl amine containing an alkoxy group, an amide group, a nitrile group, an imidacillin group, and the like. Hydroxyamines having 1 to 6 hydroxyl groups, preferably 1 to 3 hydroxyl groups, are particularly useful. Preferred amines have the general formula [wherein R, R', R" and R"' are each hydrogen, C1-CXS linear or branched alkyl group,
C1~CSZ alkoxy02~Cs fullkylene i, 0
2-C12 hydroxyaminoalkylene group and C1-c
R'' can further consist of a moiety of the formula (wherein R' is as defined above), and 3 and S' may be the same or different numbers from 2 to 6, preferably from 2 to 4, and t and t' may be the same or different numbers from 0 to 10, preferably from 2 to 7, most preferably about A number from 3 to 7, provided that t
and t' shall not be greater than 15]. To ensure easy reaction, R, R', R" and R"', II%ll'
, and t' are selected in a manner sufficient to provide the compounds of formulas 1 and 2 with typically at least one primary or secondary amine group, preferably at least two primary or secondary amine groups Preferably. This is R1R', RIP
or by selecting at least one of the R″′ groups to be hydrogen, or when R″′ becomes H or when the ■ moiety has a secondary amino group, t in formula (■) becomes at least 1. This can be achieved by The most preferred amines of the above formula are represented by formula (1) and contain at least two primary amine groups and at least one, preferably at least three, secondary amine groups.

Examples of suitable amine compounds include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminobutane, polyethylene amines such as diethylenetriamine, triethylene Tetramine, tetraethylenepentamine, polypropylene amines such as 1,2-propylene diamine, di(1,2-propylene)triamine, di(1,
S-propylene)triamine, N,N-dimethyl-1,
5-diaminoethane, N,N-di(2-aminoethyl)ethylenediamine, N,N-di(2-hydroxyethyl)-1,5-propylenediamine, 3-dodecyloxytalobylamine, N-dodecyl-1, 3-propanediamine, trishydroxymethylaminomethane (TH
AM), diimpropaturamine, jetanolamine, triethanolamine, mono-, di- and tritallowamine, ami7morpholine such as N-(5-aminopropyl)morpholine and the like.

Other useful amine compounds are cycloaliphatic diamines such as 1,4-di(aminomethyl)cyclohexane, bicyclic nitrogen compounds such as imidacillin, and p! and p3 are the same or different and each is an integer of 1 to 4, and nl, nl and n3
are the same or different, each being an integer from 1 to 3]. Examples of such amines include, but are not limited to, 2-pentadecyl imidacilline, N-(2-aminoethyl)piperazine, and the like.

Commercially available mixtures of amine compounds can also be used with advantage. For example, one method for producing alkylene amines is to react an alkylene civalide (such as ethylene dichloride or propylene dichloride) with ammonia to produce a complex mixture of alkylene amines in which pairs of nitrogen atoms are linked by alkylene groups. and thus forming compounds such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and piperazine isomers. On average about 5 nitrogen atoms per molecule
~7 low cost poly(ethylene amine) compounds are commercially available under trade names such as ``Polyamine H#'', ``Polyamine 400'', 1 Dow Polyamine E-10 (1', etc.).

Useful amines also include those of the formula %(), where m has a value of about 3 to 70, preferably 10 to 35; and the formula %(), where n has a value of about 1 to 70. 40, provided that the total sum of n is from about 3 to about 70, preferably from about 6 to about 35, and R is a polyvalent saturated hydrocarbon group of up to 10 carbon atoms; The number of substituents on the R group is represented by the value of "a" which is a number from 3 to 6]. The alkylene group in either formula (V) or (M) may be straight or branched chain containing about 2 to 7, preferably about 2 to 4 carbon atoms.

The polyoxyalkylene polyamine of the above formula (V) or (M) preferably has a polyoxyalkylene diamine and a polyoxyalkylene triamine having a molecular weight of about 200 to about 4.00.
0 preferably within the range of about 400 to about 2.000. Preferred polyoxyalkylene polyamines include polyoxyethylene and polyoxypropylene diamines and polyoxypropylene triamines having average molecular weights within the range of about 200 to 2.000. Polyoxyalkylene polyamines are commercially available, for example from Jefferson Chemical Company, Inc. under the trade names 1 Chefamine D-230, 1)-400, 1)-1000, D-2.
000, T-4031, etc.

7 mi/l'j, an oil solution containing 5 to 95 wt.
It is readily reacted with dicarboxylic acid substances such as alkenylsuccinic anhydride by heating to 00-250°C, preferably Fi 125-175°C, generally for 1-10 hours, e.g. 2-6 hours. Preferably, the heating is carried out to promote the formation of an imide or a mixture of imide and amide rather than an amide and a salt. The reaction ratio of dicarboxylic acid material to equivalents of amine and other nucleophilic reactants described herein can vary considerably depending on the reactants and the type of bond formed. per equivalent of nucleophilic reactant such as amine, generally cL1 to 1.0, preferably about r
1.2 to 0.6, for example, α4 to α6 mole dicarboxylic moiety included! (e.g., grafted maleic anhydride content). For example, 71 olefins are added to 1 mole of olefin.
Approximately 0.8 mole to convert to a mixture of amide and imide, the product formed by reacting enough maleic anhydride to add 1.6 moles of succinic anhydride groups per mole. Pentamine (having a molecular weight of 92 primary amino groups and 5 equivalents of nitrogen) is preferably used. That is, the pentamine is sufficient to provide about 0.4 moles (i.e., 1 mole) of co-phosphoric anhydride moieties per nitrogen equivalent of the amine. It is used in a variety of scenes.

Nitrogen-containing dispersants can be further processed by boration as taught generally in US Pat. Nos. 087.956 and 3.254.025. This ranges from about 11 atomic percentages of boron per mole of acylated drilling compound to about 2 atomic percentages of boron per atomic percentage of nitrogen in the acylated nitrogen compound.
This is readily accomplished by treating the acyl nitrogen dispersant with a boron compound selected from the group consisting of boron oxides, boron halides, boron acids, and esters of boron acids in an amount to provide up to 0 atomic percentages. Ru.

Advantageously, the dispersants of the combinations of the present invention contain about 105-2.0% by weight of boron, such as α05-0.7% by weight, based on the total weight of the borated acyl nitrogen compound. Dehydrated boric acid polymer (mainly (HBO2)s) in the product
The boron, which is believed to be present as a diimide, is believed to bind to the imide and diimide of the dispersant as an amine salt, such as a metaporate salt of the diimide.

The boron treatment comprises adding about (105 to 4% by weight, based on the weight of the acyl nitrogen compound) of the boron compound, preferably boric acid (based on the weight of the acyl nitrogen compound).
(often added as a slurry) and heating with stirring to about 135 DEG C. to 190 DEG C., e.g. 140 DEG to 170 DEG C., for 1 to 5 hours, followed by nitrogen stripping in that temperature range. Or
Boron treatment can also be carried out by adding boric acid to the hot reaction mixture of dicarboxylic acid material and amine while removing water.

Tris(hydroxymethyl)aminomethane (THAM)
British Patent No. 984.40
Amide, imide or ester type additives can be formed as taught in U.S. Patent No. 4.
No. 102.798, No. 4,114876 and No. 4
．． Oxazoline compounds and borated oxazoline compounds such as those described in No. 11 to No. 639 can be formed.

The ashless dispersant may also be an ester derived from the long chain hydrocarbon-substituted dicarboxylic acid materials mentioned above, as well as hydroxy compounds such as -hydric and polyhydric alcohols, or aromatic compounds such as phenol and naphthol. Polyhydric alcohols are the most preferred hydroxy compounds, and preferably contain from 2 to about 10 hydroxy groups;
For example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, diethylene glycol, and other alkylene glycols where the alkylene group contains from 2 to about 8 carbon atoms. Other useful polyhydric alcohols include glycerol, glycerol oleate, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, dipentaerythritol, etc., or mixtures thereof.

Ester dispersants can also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, glopargyl alcohol, 1-cyclohexan-3-ol and oleyl alcohol. Still other groups of alcohols from which the esters of the invention can be formed include, for example, oxyalkylene-, oxyarylene-, aminoalkylene- and aminoarylene groups having one or more oxyalkylene, aminoalkylene or aminoaryleneoxyarylene groups. Includes ether alcohols and amino alcohols, including substituted alcohols. These include Cellosolve, Carbitol, N, N, N', N'-
Examples are ether alcohols having up to about 150 oxyalkylene groups, where the alkylene group contains from 1 to about 8 carbon atoms.

The ester dispersants may be diesters or dispersible esters of succinic acid, ie partially esterified succinic acid, as well as partially esterified polyhydric alcohols or phenols, ie free alcohols or esters with phenolic hydroxyl groups. Similarly, mixtures of the esters illustrated above are also contemplated within the scope of this invention.

Ester dispersants are described, for example, in U.S. Pat.
It can be manufactured by one of several known methods such as those exemplified in No. 9. Next, the ester dispersant is
It can also be boron treated in the same manner as the nitrogen-containing dispersants described above.

Hydroxyamines that can be reacted with the long chain hydrocarbon-substituted dicarboxylic acid materials described above to form dispersants include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, p- (β-hydroxyethyl)aniline, 2-amino-1-propatur, 3-amino-1-propatur, 2-amino-2-methyl-1,
3-propanediol, 2-amino-2-ethyl-1,
3-propanediol, N-(β-hydroxyglobil), , N/-(β-aminoethyl)piperazine, tris(hydroxymethyl)aminemethane (also known as trismethylolaminomethane), 2-amine-1 −
Examples include butanol, ethanolamine, β-(β-hydroxyethoxy)ethylamine, and the like. Mixtures of these or similar amines can also be used. The above description of nucleophilic reactants suitable for reaction with human locarpyl-substituted dicarbonates or anhydrides includes amines,
Includes alcohols and compounds with mixed amine and hydroxy-containing reactive functional groups, ie amino alcohols.

A preferred group of ashless dispersants are substituted with succinic anhydride groups and polyethylene amines such as tetraethylenepentamine, pentaethylenehexamine, polyoxyethylene and polyoxypropylene amines such as polyoxypropylene diamine, trismethylolaminomethane and pentaeryth. IJ)-ol and combinations thereof. One particularly preferred dispersant combination is (1) polyisobutylene substituted with succinic anhydride groups and (11
) a hydroxy compound reacted therewith, such as pentaerythritol; 1) using about 13 to about 2 moles of (lv) and (lv) and about 1 lL3 to about 2 moles of (lv), respectively. Another preferred dispersant combination is disclosed in U.S. Pat. No. 511, (1) polyisobutenylsuccinic anhydride; (11) polyalkylene polyamines such as tetraethylene pentamine; and (m) polyhydric alcohols or polyhydroxy-substituted aliphatic primary amines such as pentamine. Includes combinations with erythritol or trismethylolaminomethane.

A (weight) Nitrogen-containing polyamines are bonded directly to long chain aliphatic hydrocarbons and the halogen atoms of the halogenated hydrocarbons are bonded to various alkylene polyamines as described in U.S. Pat. in! Replaceable dispersants are also useful as ashless nitrogen-containing dispersants in the present invention.

A (m) Another group of nitrogen-containing dispersants that can be used are those containing Mannetch bases or Mannich condensation products as known in the art.

Such Mannich condensation products generally contain about 1 mole of high molecular weight hydrocarpyl-substituted polymers, as disclosed, for example, in U.S. Pat. or polyhydroxybenzene (e.g. 1.aaaJJ.

about 1 to λ5 moles of formaldehyde or paraformaldehyde and about 0.5 to 2
It is produced by condensation with mol of polyalkylene polyamine. If necessary, please refer to these US patents. Such Mannich condensation products can include long chain high molecular weight hydrocarbons on the phenolic group, or compounds containing such hydrocarbons, such as those described in U.S. Pat. No. 4,442,808, supra. It can be reacted with polyalkenylsuccinic anhydrides.

Component B Component B in the compositions of the invention is at least one sulfurized alkylphenol as an anti-aggressive agent. Sulfurized alkylphenols and methods for their preparation are known in the art and are disclosed, for example, in the following U.S. patents: 2.139.76
6.2.19 El, 82 B, λ230.542.
2.8! 4565, to285854.155F3,
No. 166.4B 44.956 and No. 951°830.

Generally, sulfurized alkylphenols can be prepared by reacting an alkylphenol with a sulfiding agent such as elemental sulfur, halogenated sulfur (e.g., sulfur chloride or sulfur dichloride), mixtures of hydrogen sulfide and sulfur dioxide, and the like. can. Preferred sulfiding agents are sulfur and sulfur halides, especially sulfur chlorides, with sulfur dichloride (SCI) being particularly preferred.

The alkylphenol sulfurized to produce component B generally has at least one aromatic ring attached to the same aromatic ring.
hydroxy groups (e.g. 1 to 5 hydroxy groups)
and a compound containing at least one alkyl group (eg, 1 to 3 alkyl groups). Alkyl groups generally contain about 5 to 100 carbon atoms, preferably about 6 to 20 carbon atoms. Alkylphenols can contain more than one hydroxyl group, as exemplified by alkylresorcinol, hydroquinone, and catechol, or they can contain more than one alkyl group, but usually It contains only one of each. Also within the scope of this invention are compounds in which the alkyl and hydroxy groups are ortho, meta and para to each other, as well as mixtures of compounds in which the alkyl and hydroxy groups are ortho, meta and para to each other. Exemplary alkylphenols include n-7'ropyruphenol, inglovirphenol, n-butylphenol,
t-”jf-ruphenol, hexylphenol, ゛heptylphenol, octylphenol, nonylphenol, n-dodecylphenol, (globentetramer)
gt-converted sphenol octadecylphenol, eicosylphenol, polyamine (molecular weight 1. o o o
) are the phenol, n-dodecylresorcinol and 2,4-di-t-butylphenol. Also included are methylene-bridged alkylphenols of the type that can be made by reaction of an alkylphenol with formaldehyde or a formaldehyde-forming reagent such as trioxane or paraformaldehyde.

Sulfurized alkylphenols are typically produced by reacting an alkylphenol with a sulfiding agent at a temperature within the range of about 100-250<0>C.

The reaction can be carried out in a substantially inert diluent such as toluene, xylene, petroleum naphtha, mineral oil, cellosolve, and the like. If the sulfiding agent is a sulfur halide, especially if no diluent is used, the sulfur halide can be removed by vacuum stripping the reaction mixture or by bubbling it with an inert gas such as nitrogen. It is often preferable to remove sexual substances. If the sulfiding agent is sulfur, it is often advantageous to bubble the sulfided product with an inert gas such as nitrogen or air to remove sulfur oxides, etc.

Component C Component C in the composition of the invention is at least one metal salt of at least one dihydrocarbyl dithiophosphorus rR, in which the hydrocarbyl group contains on average at least 6 carbon atoms. It is an anti-wear additive consisting of

The acid capable of deriving a metal salt has the formula % formula % [wherein R1 and Rz are the same or different alkyl,
is a substituted substantially hydrocarbon group derivative of cycloalkyl, aralkyl, alkaryl or any of the following groups, and R1 and R in the 6-acid group have on average at least 6 carbon atoms. This can be exemplified by the acid of [having].

"Commercial hydrocarbon" means substituents such as ethers, esters, nitro, or halogens (e.g., 1 to 4 substituents per group moiety) that do not substantially affect the hydrocarbon properties of the group. means a group containing

Specific examples of suitable R1 and Rz groups include isopropyl, isopdel, n-butyl, nibutyl, n-hexyl, heptyl, 2-ethylhexyl, diisobutyl,
inoctyl, decyl, dodecyl, tetradodecyl, hexadecyl, octadecyl, butylphenyl, o, p-
Dichlorophenyl, octylphenyl, polyisobutyne (molecular weight 350) substituted phenyl, tetrapropylene substituted phenyl, β-octylbutylnaphthyl, cyclopentyl, cyclohexyl, phenyl, chlorphenyl, o,
p-dichlorophenyl, bromphenyl, naphthinyl,
Mention may be made of the 2-methylcyclohexyl, benzyl, chlorobenzyl, chlorphenyl, dichlorphenyl, nitrophenyl, dichlordecyl and hixenyl groups. Approximately 6~
an alkyl group having 30 carbon atoms, and about 6 to 50
Aryl groups having 5 carbon atoms are preferred. Particularly preferred R1 and Bx groups are alkyl having 6 to 18 carbon atoms.

Dithiophosphoric acid can be easily obtained by reaction of phosphorus pentasulfide with alcohol or phenol.

The reaction involves mixing 4 moles of alcohol or phenol with 1 mole of phosphorous pentasulfide at a temperature of about 20-200°C. Hydrogen sulfide is eliminated as the reaction takes place.

Metal salts useful in the present invention include salts containing Group I metals, Group I metals, aluminum, lead, tin, molybdenum, manganese, cobalt and arsenicel. Examples of metal compounds that can be reacted with acids include lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylade, sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylade, sodium phenoxide, Potassium oxide, 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 propylade, calcium ventilate, zinc oxide, zinc hydroxide, zinc carbonate, zinc propylade, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethylate, barium ferment , barium hydroxide, barium hydrate, barium carbonate, barium ethylate, barium pentilade, aluminum oxide,
Aluminum propylade, lead oxide, aqueous lead, lead carbonate, tin oxide, tin butyrad, cobalt oxide, aqueous copal), charcoal ff cobalt, cobalt henchler), nickel oxide, nickel hydroxide and nickel carbonate. It will be done.

In some cases, the addition of small amounts of certain components, particularly carboxylic acids or metal carboxylates, such as metal acetate or vinegar used together with the metal reactants, can accelerate the reaction and yield improved products. Up to about 5% zinc acetate in combination with the required amount of zinc oxide promotes the formation of zinc dithiophosphate.

The production of metal dithiophosphates is well known in the art and is described, for example, in US Pat. No. 4,273. j81, same No. 3, 397.
No. 145, No. 109 to No. 439, and No. 4442.
The invention is described in nine patent documents including No. 804, so please refer to those US patents if necessary.

Lubricating Oil Compositions The additives of the present invention can be used to prepare lubricating oil compositions such as automatic transmission fluids, heavy duty oils suitable for gasoline and diesel engines, and the like. A universal crankcase oil can also be prepared in which the same lubricating oil composition can be used for both gasoline and diesel engines. These lubricating oil compositions typically
It contains several different types of additives that provide the required properties in the formulation. These U-class additives include viscosity index improvers, antioxidants, corrosion inhibitors, detergents, pour point depressants, and other anti-wear additives, but completely blended oils are The low total SASH requirements of the invention shall be satisfied.

In preparing heavy-duty diesel lubricating oil formulations, the additives may be present in a hydrocarbon oil such as mineral lubricating oil or other suitable solvent from 10 to 80% by weight, such as from 20 to 80% by weight.
It is common practice to introduce the active ingredient in the form of a concentrate. These concentrates are usually added to additive packs in preparing the final lubricant, e.g. crankcase motor oil.
91 parts by weight! 73 to 100, for example 5 to 40 parts by weight, can be diluted with a lubricating oil. Of course, the purpose of the concentrate is to reduce the difficulty and inconvenience in handling the substances and to facilitate their solution or dispersion into the final formulation. Thus, the ashless dispersants of component A are commonly used in the form of 40-50% by weight concentrates, for example in lubricating oil fractions.

Components A, B and ch of the present invention are generally used in admixture with a lubricant paste stock consisting of oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.

Components A, B and C can be incorporated into the lubricating oil in any convenient manner. Thus, these or mixtures can be added directly to the oil by dispersing or dissolving them at the desired concentration levels of the detergent and antiwear additive, respectively, in the oil.

Such incorporation into additional lubricating oils can be carried out at room temperature or elevated temperature. Alternatively, components A, B, and C may be combined with suitable oil-soluble solvents and base oils to form a concentrate, and this concentrate may then be combined with lubricant paste ingredients to form the final formulation, i.e., a fully formulated lubricant composition. can get things.

Such concentrates typically range from about 10% to about 40% by weight, preferably from about 20% to about 35% by weight, based on the weight of the concentrate.
Component A is an ashless dispersant (based on the active ingredients, typically about 10 to 40% by weight, preferably about 15 to 25% by weight) Component B is an antioxidant, typically about 5 to 25% by weight 15% by weight
Component C anti-wear additive, preferably about 7-12% by weight;
and typically about 3θ to 80 degrees, preferably about 40 to
Contains 60 wt.- of base oil.

Further, the fully formulated lubricating oil composition of the present invention comprises (1) 101
to about 0.6 weight percent 5ASI (preferably about 11.1 to about 15% by weight SASH, more preferably about 0.2 to about (1L)
Total sulfated ash value (SASH) of 45% by weight S human SH, and (2) cLO1:1 to about [L2:1 preferably 1 to about 0.
02:1 to α15:1, more preferably about 0.03 to α1
! It is also characterized by the weight 4 SASH to weight % component A ratio. In this specification, 1 total sulfated ash 2 is:
Means the total weight of ash content (based on the metal content of the oil) as measured for a given oil by ASTM D874.

The lubricant paste ingredients for components A, B, and C are typically formulated with additional additives therein to form the lubricant composition (i.e., formulation) to achieve the selected function. adapted to fulfill the purpose.

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

Alkylene oxide polymers and copolymers, and derivatives thereof whose terminal hydroxyl groups have been modified by esterification, etherification, etc., also constitute another group of known synthetic lubricating oils. Examples of these are polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (e.g. methylpolyisopropylene glycol ether with an average molecular te of 1.000) , diphenyl ether of polyethylene glycol with a molecular weight of 500 to 1.000, 1,000
diphenyl ether of polypropylene glycol with a molecule i of ~1.500), as well as their mono- and polycarboxylic acid esters, such as the acetate ester of tetraethylene glycol, the hybrid 03-C8 fatty acid ester and the C13 oxaic acid diester.

Another suitable group of synthetic lubricating oils are dicarboxylic acids (e.g.
Phthalic acid, succinic acid, alkylic acid, alkenyl succinic acid, maleic acid, azelaic acid, speric acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer,
malonic acid, alkylmalonic acid, alkenylmalonic acid> and m) 7#j-ru (e.g.,
Hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, sebacin dispersion (2-ethylhexyl), n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diindecyl azelate, dioctyl heptatalate, Didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid. Examples include complex esters.

Esters useful as synthetic oils are C3-CI! Monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane,
Also included are those made from pentaerythritol, cyhentaerythritol and tripentaerythritol.

Polyalkyl, -, polyaryl, polyalkoxy-
Silicon-containing oils such as polyaryloxysiloxane oils and silicate oils also constitute another useful group of synthetic lubricating oils. Examples of these include tetraethyl silicate, tetraisoglobyl silicate, tetra(2-ethylhexyl)silicate, tetra(4-methyl-2-ethylhexyl)silicate, tetra(p-t-butylphenyl)silicate, hexa(4- Mention may be made of methyl-2-pentoxy)disiloxane, poly(methyl)siloxane and poly(methylphenyl)siloxane. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, and 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 those obtained directly from natural or synthetic sources without further purification treatment. For example, unrefined oils are sierre oils obtained directly from retorting operations, petroleum oils obtained directly from distillation, or ester oils obtained directly from esterification processes and used without further treatment. Refined oil is the same as unrefined oil except that it has been further treated with one or more refining steps to improve one or more properties. Many such purification techniques are known to those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration and percolation. Rerefined oils are obtained by applying treatment processes similar to those used to obtain refined oils to R4 oils already in service. Such rerefined oils are also known as reclaimed oils or reprocessed oils, and are sometimes additionally treated by techniques to remove spent additives and oil breakdown products.

The novel dispersant mixtures of this invention can be used in combination with VI improvers to form multigrade automotive engine oils. Viscosity modifiers impart high and low temperature performance capabilities to a lubricating oil and allow it to remain relatively viscous at elevated temperatures while exhibiting acceptable viscosity and fluidity at low temperatures. It is intended to do so.

Viscosity modifiers are generally high molecular weight hydrocarbon polymers including polyesters. Viscosity modifiers can also be derivatized to include other properties or functions, such as imparting dispersibility. These oil-soluble viscosity-adjusting polymers generally have a molecular weight of 103 to 106, preferably 104, as measured by gel permeation chromatography or osmometry.
~10@ for example with a number average molecular t of 20,000 to 25G,000.

Examples of suitable hydrocarbon polymers include C2 to C30, including alpha-olefins and internal olefins, such as C,-C
, olefins (which may be linear or branched, aliphatic, aromatic, alkyl aromatic, cycloaliphatic, etc.)
and copolymers of two or more of these monomers. Sometimes this involves fl ethylene and C3~03
Among the copolymers with G-olefin, particularly preferred are copolymers of ethylene and propylene. Polyisobutylene, homopolymers and copolymers of C6 and higher α-olefins, atactic polypropylene, hydrogenated polymers of styrene, copolymers of styrene with e.g. isoprene and/or butadiene, and Other polymers can also be used, such as parent polymers as well as their hydrogenated derivatives. The polymer can undergo molecular weight reduction, for example by cross-crossing, extrusion, oxidation or thermal degradation; it can also be oxidized and can contain oxygen. Also, derivatives such as ethylene-propylene copolymers with active monomers such as maleic anhydride (which can be further reacted with alcohols or amines such as alkylene polyamines or hydroxyamines) may also be used. polymers (e.g., U.S. Patent No. 4.
No. 089.794, No. 4゜160.739, No. 4
．． 157.185) or ethylene-propylene copolymers reacted or grafted with nitrogen compounds (U.S. Pat. No. 4.06 Ill, '056;
．． 061% 058, 4.144489 and 4.149.984) are also included.

Preferred hydrocarbon polymers include 15-90% by weight ethylene, preferably 30-80% ethylene and 10-8% by weight ethylene.
5% by weight, preferably 20-70% by weight of one or more C3
~ctm preferably c3~CtS more preferably C3~
It is an ethylene copolymer containing C,α-olefin. Although not required, such copolymers preferably have a degree of crystallinity of 25 weight or less as measured by X-ray and scanning calorimetry. Most preferred are copolymers of ethylene and propylene. Other α-olefins suitable for use in place of propylene to form total copolymers or in combination with ethylene and propylene to form terpolymers, quaternary polymers, etc. include 1-butene; , 1-
Examples include pentane, 1-hexene, 1-butene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene, 4-methyl-1-hexene, 5-
Also included are branched α-olefins such as methylpentene-1,4,4-dimethyl-1-pentene, 6-methylpentene-1, etc., and mixtures thereof.

It is also possible to use terpolymers, quaternary polymers, etc. of ethylene, the C3-C28 α-olefin, and nonconjugated diolefins or mixtures of such diolefins. The amount of non-conjugated diolefin will generally range from about 15 to 20 moles, preferably from about 1 to about 7 moles, based on the total amount of ethylene and alpha-olefins present.

Polyester vI improvers generally include methacrylic acid,
Polymers of esters of ethylenically unsaturated C3-C$ mono- and polycarboxylic acids such as 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 decyl acrylate, lauryl acrylate, stearyl acrylate, acrylic Examples include eicosanyl acid, docosanyl acrylate, decyl methacrylate, cyamyl fumarate, methacrylic lauryl, cetyl methacrylate, methacrylic stearyl, and mixtures thereof.

Examples of other esters include vinyl alcohol esters of C2-C22 fatty acids or monocarboxylic acids (preferably saturated), such as vinyl acetate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, etc., and mixtures thereof. can be mentioned. Further, a copolymer of a vinyl alcohol ester and an unsaturated acid ester, such as a copolymer of vinyl acetate and dialkyl heptamarate, can also be used.

The ester can be further combined with other unsaturated monomers such as olefins, for example, per mole of unsaturated ester! +112 to 5 moles of C
It can be copolymerized with 3 to C20 aliphatic or aromatic olefins, or it can be copolymerized with such olefins per mole of unsaturated acid or anhydride and then esterified. For example, copolymers of styrene and maleic anhydride esterified with alcohols and amines are known, see, for example, US Pat. No. 3,702,300.

Polymerizable unsaturated nitrogen-containing monomers can be grafted onto such ester polymers to impart dispersibility to the VI improver, or monomers attached to the esters can be copolymerized. Examples of suitable unsaturated nitrogen-containing monomers include:
containing 4 to 20 carbon atoms, e.g. p-(
amino-substituted olefins such as (β-diethylaminoethyl) styrene, basic nitrogen-containing heterocyclic compounds having polymerizable ethylenically unsaturated substituents such as 2-vinyl-5-ethylpyridine, 2-methyl-5-vinylpyridine, 2
-Vinylpyridine, 4-vinylpyridine, 3-vinylpyridine, 3-methyl-5-vinylpyridine, 4-methyl-2-vinylpyridine, 4-ethyl-2-vinylpyridine, 2-butyl-5-vinylpyridine, etc. Examples include vinylpyridine and vinylalkylpyridine.

Also suitable are N + , vinyllactams such as N-vinylpyrrolidone or N-vinylpiperidone.

Vinylpyrrolidone is preferred, examples include N-vinylpyrrolidone, N-(1-methylvinyl)pyrrolidone, N-
Vinyl-5-methylpyrrolidone, N-vinyl-313-
These include dimethylpyrrolidone and N-vinyl-5-ethylpyrrolidone.

Metal detergents are generally disclosed in the following U.S. patents: 2,50
1.731.2,61 to 904.2.616.905.
2.61 to 906.2.61 to 911.2,616,9
925.2.617.049.2.7 to 24.2.61
74874.3, 027.525.5.256.186
, &282.835.4384, 585.3,373,
108, to 365.396,! 1.542.735,4
32 to 162; 79. Basic (ie, overbased) alkali or alkaline earth metal salts (or mixtures thereof, such as mixtures of Ca and Mg salts) such as furkylphenols, alkylene bisphenols, and oil-soluble fatty acids. Reference may be made, if necessary, to the above-mentioned US patents as they describe complexes useful in the present invention. Among the petroleum sulfonates, the most useful compounds are those prepared by sulfonation of the appropriate petroleum fraction, followed by removal of the mortar sludge and purification. Synthetic alkaryl sulfonic acids are usually composed of benzene and tetrapropylene, Ct
It is prepared from alkylated benzenes such as 7-Lidell-Crafts reaction products with polymers such as S-C24 hydrocarbon polymers and the like. Second, suitable m can also be obtained by sulfonation of alkylated derivatives of compounds such as triphenylene oxide thianthrene, phenolthioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, decahydronaphthalene, etc. be able to.

Highly basic alkaline earth metal sulfonates are often used as detergents. These typically involve heating a mixture containing an oil-soluble sulfonate or alkaryl sulfonic acid with an alkaline earth metal compound in excess of the amount required to completely neutralize the sulfonic acid present; It is produced by reacting excess metal with carbon dioxide to provide the desired overbasing to form a dispersed carbonate complex. The sulfonic acids are typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from the fractionation of petroleum by distillation and/or extraction, or by the sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from the fractionation of petroleum by distillation and/or extraction, or by the Halogen derivatives are obtained by alkylation of aromatic hydrocarbons such as those obtained by alkylating chlorobenzene, chlorotoluene and chlornaphthalene. Alkylation can be carried out using alkylating agents having from about 3 to 50 or more carbon atoms in the presence of a catalyst. for example,
Haloparaffins, polyolefins produced by dehydrogenation of paraffins, polyolefins produced from ethylene, propylene, etc. are all suitable. The alkaryl sulfonate has an alkyl-substituted aromatic subdivision 9 suitably about 9 to about 70 or more carbon atoms, preferably about 16
Contains ~50 carbon atoms.

Alkaline earth metal compounds that can be used to neutralize these alkaryl sulfonic acids to provide sulfonates include oxides, hydroxides, alkoxides, carbonates, and carboxylic acids of magnesium, calcium, and barium. Salts, sulfides, hydrosulfides, nitrates, borates and esters may be mentioned. Examples of these are calcium oxide, calcium hydroxide, magnesium acetate and magnesium borate. As described above and as follows, the alkaline earth metal compound is used in excess of that required for complete neutralization of the alkaryl sulfonic acid. Generally, the amount is about 1
It is preferred to use at least 125% of the stoichiometric amount of metal required for complete neutralization, although within the range of 0.00 to 220%.

Various other methods of preparing basic alkaline earth metal alkaryl sulfonates are known, for example in U.S. Pat.
Overbasing is accomplished here by hydrolyzing the alkoxide-carbonate complex with an alkaryl sulfonate in a hydrocarbon solvent-diluent oil.

The preferred Mg sulfonate additive is the total weight of this additive system dispersed in the mineral lubricating oil! #, based on about 2
The magnesium alkyl aromatic sulfonate has a total base number within the range of about 300 to about 400 with a magnesium sulfonate content within the range of 5 to about 32 Fts. Preferred Ca sulfonate additives are from about 25 to about 32% based on the total weight of the additive system dispersed in the mineral lubricating oil.
With a calcium sulfonate content of about 250~
Calcium alkyl aromatic sulfonate having a total base number within the range of about 500.

An example of a particularly convenient method of preparing the complexes used is the synthesis of an oil-soluble sulfonic acid, such as didodecylbenzenesulfonic acid, in excess of lime (e.g., 5 to t per fit of acid).
and a promoter such as methanol, heptylphenol or mixtures thereof and a solvent such as mineral oil at 50-150°C and the reaction mass is then carbonated until a homogeneous mass is obtained. Complexes of sulfonic acids, carboxylic acids or mixtures thereof can be obtained by methods such as those described in US Pat. No. 4,312,618. Another example is the production of liquefied magnesium in excess of its positive magnesium salt, magnesium sulfonate, water and preferably an alcohol such as methanol.

Sulfonate carboxylate complexes and carboxylic acids useful for the preparation of carboxylate complexes, i.e. obtainable from processes such as those described above, where instead of sulfonic acid a mixture of sulfonic acids and carboxylic acids or a carboxylic acid alone is used. The oil-soluble acids are primary examples of fatty acids having at least about 12 and no more than about 24 aliphatic carbon atoms. Examples of these acids include palmitic acid, stearic acid, myristic acid, oleic acid, linoleic acid, dobutic acid, behenic acid, and the like. Moreover, cyclic carboxylic acids can also be used. These include aromatic and cycloaliphatic acids. Aromatic acids are those containing a benzenoid structure (i.e., benzene, naphthalene, etc.) and an oil-solubilizing group having a total number of carbon atoms of at least about 15 to 18, preferably about 15 to about 200. Examples of group acids include stearylbenzoic acid, phenylstearic acid, mono- or polywax-substituted benzoic acid or naphthoic acid (wherein the wax group consists of at least 18 carbon atoms), cetylhydroxybenzoic acid, etc. can be mentioned.

Contemplated cycloaliphatic acids have at least 12 and usually up to about 50 carbon atoms. Examples of such substances include petroleum naphthene mash, cetylcyclohexanecarboxylic acid, dilauryldecahydronaphthalenecarboxylic acid, dioctylcyclopentanecarboxylic acid, and the like. Also contemplated are thiocarboxylic acid analogs of the above acids in which one or both of the acid atoms of the carboxyl group are replaced by sulfur.

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

The terms "basic salt" and "overbased group" are used to refer to a metal salt where the metal is present in a stoichiometrically greater amount than the sulfonic acid group.

As used herein, the term "complex" refers to basic metal salts that contain metals in a greater degree than those present in neutral or positive metal salts. The "base number" of a complex is the η number of KO)1 corresponding to 1t of the complex when determined by titration. A commonly used method for preparing basic salts is to prepare a solution of a positive metal salt in mineral oil with an acid and a metal neutralizing agent such as a diluted salt, hydroxide, carbonate, bicarbonate or sulfide at 5°C. It also involves heating at high temperatures and treating the resulting mass. It is known to use promoter #1 in the neutralization step to assist in the incorporation of large excess metals;
and is preferred for the production of such compositions. Examples of compounds useful as accelerators include phenolics such as phenol, naphthol, alkylphenols, thiophenols, sulfurized alkylphenols, and condensation products of formaldehyde and heptenols, methanol, 2-propanol, octatool, Mention may be made of alcohols such as cellosolve, carpitol, ethylene glycol, stearyl alcohol and cyclohexanol, and amines such as aniline, phenylene diamine, phenothiazine, phenol β-naphthylamine and dodecylamine.

Usually, the basic composition obtained according to the above method is AS
It is treated with carbon dioxide until its total base number (TBN) as measured by TM procedure D-2896 is less than about 50. In many cases it is advantageous to form the basic product by adding the Ca or Mg base in portions and carbonating after each portion addition. This process makes it possible to obtain products with very high metal ratios (>10). As used herein, the term "metal ratio" refers to the ratio of the total equivalents of alkaline earth metal in the sulfonate complex to the equivalents of sulfonate anion present in the sulfonate complex. For example, the normal sulfonate has a metal ratio of 1.0, and the calcium sulfonate complex F12 contains twice as much calcium as the normal salt.
．． It has a metal ratio of 0. Overbased metal detergent compositions typically have a metal ratio 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.

Basic sulfonate and anthranilic acid from about 140 to 2
It is often advantageous to react the two by heating at 00°C. The amount of anthranilic acid used is generally less than about 1 part per 10 parts by weight of sulfonate, preferably 1 part per 40 to 200 parts by weight of sulfonate. The presence of anthranilic acid improves the oxidation and corrosion protection efficacy of the sulfonate.

Basic alkali and alkaline earth metal sulfonates are known in the art, and methods for their preparation are described in numerous publications such as U.S. Pat. Described in the patent. Any of the sulfonates described in these patents and numerous others are suitable for use in the present invention.

Metal detergents (eg, basic Ca and Mg salts) are preferably prepared separately and then mixed in controlled amounts as added in the present invention. It is generally convenient to mix such separately manufactured detergents in the presence of the diluent or solvent used in their manufacture.

Antioxidants useful in the present invention include oil-soluble copper compounds. Copper can be incorporated into the oil as any suitable oil-soluble copper compound. "Oil-soluble" means that the compound is oil-soluble under normal mixing conditions in/in the oil or additive package. The copper compound may be in the cupric or cupric form.

Copper may be in the form of copper dihydrocarbyl thio- or dithiophosphate (where copper can be used in place of zinc in the above compounds and reactions), 1 each of copper oxide
It is also possible to react with mol or 2 mol of dithiophosphoric acid.

Alternatively, copper can be added as a copper salt of a synthetic or natural carboxylic acid. This example:
I. Improved handling properties and solubility of copper carboxylates containing C1l fatty acids, but resulting in unsaturated carboxylic acids such as oleic acid or branched carboxylic acids such as naphthenic acids or synthetic carboxylic acids with molecular weights from 200 to 500. Therefore, it is preferable. Also, the general formula (RR'NC85)nCu
(where n is 1 or 2 and R and R' are 1 to
oil-soluble dithiocarbamic acids of the same or different hydrocarbyl groups containing 18, preferably 2 to 12 carbon atoms, including groups such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic groups. Copper is also useful. Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms. Thus, such groups include, for example, ethyl, n-propyl, 1
-propyl, n-butyl, i-butyl, nibutyl, amyl, n-hexyl, i-hexyl, n-heptyl, n
-octyl, decyl, dotecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, futhynyl, and the like. To obtain oil solubility, the total number of carbon atoms (ie, R and R') is generally about 5 or more. Second, copper sulfonates (including the alkaryl sulfonates as described above), heptenanates (ie, salts of optionally sulfurized alkylphenols as described above), and acetylacetonates may also be used.

Examples of useful copper compounds are alkenylsuccinic or anhydrous copper (Cu' and/or Cu'') salts.

The salt itself may be basic, neutral or dispersible. These include (a) reacting any of the following substances (having at least one free carboxylic acid or anhydride group) with a reactive metal compound, as previously described under ashless dispersants; It can be formed by A suitable acid (
(or anhydrides) Reactive metal compounds include such as cupric or cupric hydroxides, oxides, acetates, borates, carbonates or basic copper carbonates.

Examples of metal salts of the present invention are Cu salts of polyisobutenylsuccinic anhydride (hereinafter referred to as Cu-PIBSA) and Cu salts of polyisobutenylsuccinic acid. Preferably,
The metals selected and used are in their divalent form e.g. Cu+
! It is. A preferred substrate has about 70 alkenyl groups.
A polyalkenylsuccinic acid having a molecular weight greater than zero. Alkenyl group is about 900-1.400
And although it is desirable to have an Mn of up to 2.500, a Mn of about 950 is most preferred. Among the dispersants described above, polyisobutylene succinic acid (PIBSA) is particularly preferred. These materials can be desirably dissolved in a solvent such as mineral oil and heated in the presence of an aqueous solution (or slurry) of the metal-containing material. Heating can be carried out at 70 to about 200°C. Temperatures of 110-140°C are quite suitable. Depending on the salt formed, it may be necessary to allow the reaction to remain at temperatures higher than about 140° C. for extended periods of time, for example for no more than 5 hours, otherwise decomposition of the salt may occur.

Copper antioxidants (e.g. Cu-PIBSA, olein r
RCu or mixtures thereof) are generally used in the final lubricating oil or fuel oil composition in an amount of 50 to 500 ppm metal parts (by weight).

The copper antioxidants used in this invention are inexpensive and effective at low concentrations, so they do not substantially add to the cost of the product. The results obtained are often better than those obtained with previously used antioxidants which are expensive and used in high concentrations. In the amounts used, the copper compound does not interfere with the performance of other components in the lubricating oil composition.

Although the copper antioxidant can be incorporated into the lubricating oil composition in any effective amount, such effective amount may be less than the amount of steel added to the lubricating oil composition based on the weight of the lubricating oil composition.
~500 (preferably 10-200, more preferably 10
~180 most preferably 20-130 (e.g. 90-130)
120 )) is sufficient to provide a copper antioxidant in an amount of ppm. Of course, the preferred amount will depend on the nature of the lubricant paste stock, among other factors.

Corrosion inhibitors (also known as anti-corrosion agents) reduce the deterioration of metal components with which the lubricating oil composition comes into contact. Examples of corrosion inhibitors include phosphorus sulfide hydrocarbons and phosphorus sulfide hydrocarbons and alkaline earth metal oxides or hydroxides, preferably in the presence of an alkylated phenol or alkylphenol thioester and preferably in the presence of carbon dioxide. It is a product obtained by reaction. The phosphorus sulfide hydrocarbon can be mixed with a suitable hydrocarbon such as terpenes, heavy petroleum distillates or C2-C6 olefin polymers such as polyisobutylene at about 65-320°C.
It is produced by reacting at a temperature in the range of i to 15 hours. Neutralization of phosphosulfurized hydrocarbons can be carried out in the manner taught in US Pat. No. 1.969.324.

A friend that helps further reduce the tendency of mineral oils to degrade during use (if desired), thereby reducing the formation of oxidation products such as sludge and face-like deposits on metal surfaces and reducing viscosity build-up. In addition to component B, other antioxidants can also be used for this purpose. The other antioxidants are preferably C5 to CI! alkaline earth metal salts of alkylphenol thioesters having alkyl side chains (e.g., calcium nonylphenol sulfide, barium-t-octylphenyl sulfide, etc.),
Diphenylamine, alkyldiphenylamine, dioctyl phenylamine, phenyl-α-naphthylamine (
and its alkylated derivatives), phosphorus sulfurized hydrocarbons, other sulfurized hydrocarbons (for example, sulfurized phenol, sulfurized alkylcatechol, etc.), phenol, hindered phenol, bisphenol, catechol, alkylated catechol, and the like.

Friction modifiers serve to impart appropriate frictional properties to lubricating oil compositions, such as automotive transmission fluids.

Representative examples of suitable friction modifiers include U.S. Pat. No. 4,935,659, which discloses fatty acid esters and amides, and U.S. Pat. No. 4,170, which describes molybdenum complexes of polyisobutenylsuccinic anhydride-amino alkanols. &07
No. 4, U.S. Pat. No. 4,105,571 disclosing the dimerized fatty acid glycerol nisdel; U.S. Pat. No. 3,779,928 disclosing alkane phosphonates, reaction products of phosphonates with oleamide U.S. Pat. U.S. Pat. No. 4,879,506 disclosing alkenyl-succinamide or succinimide
No. 4,932.290, which discloses the reaction product of di(lower alkyl)phosphite and ebokykudo;
and US Pat. No. 402 & 258, which discloses alkylene oxide adducts of phosphosulfurized N-(hydroxyalkyl)alkenyl succinimides. If necessary,
It is dangerous to refer to these documents. The most preferred friction modifiers are succinate esters of hydrocarbyl-substituted cono-phosphoric acids or anhydrides and thiobisalkanols, or metal salts thereof, as described in U.S. %l'F No. 4.344.855. .

Pour point depressants are those that lower the temperature at which a liquid flows or can be poured. Typical of such additives which beneficially optimize the cold flow properties of the liquid are C8-CtS dialkyl fumarate/vinyl acetate copolymers, polymethacrylates and wax naphthalenes.

Foam control can be provided by polysiloxane type antifoam agents such as silicone oils and polydimethylsiloxanes.

The organic oil-soluble compounds useful as antirust additives in this invention consist of nonionic surfactants such as polyoxyalkylene polyols and their esters and anionic surfactants such as alkylsulfonic acids. Such rust-inhibiting compounds are well known and can be produced by conventional means. Nonionic surfactants useful as antirust additives in the oil compositions of the present invention include:
They usually owe their photoactivity to a number of weak stabilizing groups such as ether bridges. Nonionic rust inhibitor additives with ether bridges are produced by alkoxylating an organic substrate containing reactive hydrogen with an excess of lower alkylene oxide (such as ethylene oxide and propylene oxide) until the desired number of alkoxy groups are placed in the molecule. It can be made by

Preferred antirust additives are polyoxyalkylene polyols and their derivatives. This group of substances is commercially available from a variety of sources, such as “Plu” from Y. Antotte Chemicals Corporation.
ronic Polyols - *Po17glyaol available from Dow Chemical Corporation
112-2' (liquid triol derived from ethylene oxide and propylene oxide) and available from Union Carbide Co., Ltd.
Tergitol” (dodecylphenyl or hamonophenyl polyethylene glycol ether) and @Ucon”
(Polyalkylene glycol and derivatives). These are just a few examples of commercially available products suitable in the improved compositions of this invention.

Besides the polyols themselves, also their esters obtained by reacting polyols with various carboxylic acids are suitable. Acids useful in preparing these esters include lauric acid, stearic acid, succinic acid, and alkyl- or alkenyl-substituted succinic acids (where alkyl-
or an alkenyl group containing up to about 20 carbon atoms).

Preferred polyols are made as block polymers. Thus, to form a hydrophobic paste, a hydroxy-substituted compound R-(O)l)n, where n is 1 to 6 and R is a monohydric or polyhydric alcohol, phenol,
(residues such as naphthol) are reacted with propylene oxide. This base is then reacted with ethylene oxide to form a hydrophilic moiety, thus resulting in a molecule having both hydrophobic and hydrophilic portions. The relative dimensions of these parts are as will be apparent to those skilled in the art.
It can be adjusted by adjusting the ratio of each reactant, reaction time, etc. Thus, the pacing oil is characterized by hydrophobic and hydrophilic portions present in proportions that make the rust inhibitor suitable for use in any lubricating oil composition, regardless of the differences and presence of other additives. It is within the skill in the art to produce polyols having molecules that are

If higher oil solubility is required in a given lubricating oil composition, the hydrophobic portion can be increased and/or the hydrophilic portion can be decreased.

If greater oil/water emulsion breaking ability is required, the hydrophobic and/or hydrophilic portions can be tailored to achieve this.

Exemplary compounds of R-(OH)n1 include alkylene polyols such as alkylene glycol, alkylene triol, alkylene tetrol, etc., such as ethylene glycol, propylene gellicol, glycerol, pentaerythritol, sorbitol, mannitol, and the like. Also, aromatic hydroxy compounds such as alkylated and polyhydric phenols, such as heptylphenol,
Dodecylphenol and the like can also be used.

Other suitable demulsifiers include US@Patent No. 50? a82
No. 7 and No. 2.674.619.

Liquid polyols available from Y. Antotte Chemical Corporation under the trade name @Pluronie Polyolg' and other similar polyols are particularly well suited as rust inhibitor additives. These "'P
luronic Polyolm' is a formula, [in the above formula, ] corresponds to The average molecular #, Fi, of the glycol is about 1.000 to about s, o o o. These compounds are made by first condensing propylene oxide with propylene glycol to produce a hydrophobic paste. This condensation product is then treated with ethylene oxide to add hydrophilic moieties to both ends of the molecule. For best results, the ethylene oxide units should occupy from about 10 to about 40 times the molecule.

Particularly preferred are compounds in which the molecular weight of the polyol is about 4,500 to 4,500 and the ethylene oxide units account for about 10 to about 15 percent by weight of the molecule. Approximately 4.00
has a molecular weight of 0 and approximately 10% of it is (CHzCH2
Polyols derived from units 0) are particularly good. Also, alkoxylated fatty amines, amides, alcohols, etc., as described in U.S. Pat. No. 4,849.501, and such alkoxylated fatty acid derivatives tl-C--C!
- Those treated with alkyl substituted phenols (such as mono- and diheptyl, octyl, nonyl, decyl, undecyl, dodecyl and tridecylphenols) are also useful.

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

The lubricating oil compositions of the present invention may also include copper-lead containing corrosion inhibitors. Typically such compounds will have between 5 and
Thiadiazole polysulfides containing 50 carbon atoms, their derivatives and their polymers. Preferred materials are those described in U.S. Pat. No. 2,719,125;
．． 719.126 and 1,44-thiadiazole, such as those described in No. 4087.932. Particularly preferred is 2,5-bis(t-octadithio)-1,x, commercially available as -Amoeo 150''.

4-thiadiazole compound or “Arnoco 158
2,5-bis(nonyldithio)- available as '
1, 4-thiadiazole compound. Other suitable analogs include U.S. Pat. No. 4,821,236;
No. 4.557, No. 4,091387, No. 4.10
No. 7.059, No. 4,136,043, No. 4.1
813.299 and 4.19 to 882. Esters, condensation products, aldehydes and amines, alcohols or mercaptans, amine salts, reaction products with dithiocarbamates, with halogenated carboxylic acids,
reaction mixture with an ashless dispersant (e.g., US-A-414
It is also possible to use derivatives of thiadiazole mercaptans, such as 0643 and US-A-4136043) and reaction products with halogenated sulfurs and olefins.

Other suitable additives are described in British Patent No. 1.560.8 S
Thio and polythiosulfenamides of thiadiazoles such as those described in No. 0. When these compounds are included in a lubricating oil composition, they are 0.5% based on the weight of the composition. ,01-10 preferably (L1-5.0
Preferably it is present in an amount of % by weight.

Some of these numerous additives can provide multiple benefits, such as dispersant-antioxidant benefits. This method is well known and does not need to be explained in further detail here.

Compositions when containing these conventional additives are typically formulated into the pacing oil in amounts effective to provide their normal specific function. Alternative effective amounts of such additives (as each active ingredient) in a fully formulated oil are illustrated below.

Component A4-73-1° Component B2.2-42-6 Component C1, 0-2Q, 8-5 Viscosity modifier 0-4 0-12 Detergent C1
,01~Q,4Q,01~α6 Corrosion inhibitor 101
~G, 5 0~1.5 Other antioxidants θ~1
．． 5 0-5 pour point depressant α01-1
15G, 01~1.0 antifoaming agent
α001~αo1 α6~C201~Q, 1 Other anti-wear additives α001~1.5 0~5 Friction modifier α01~1.5 0~5 Mineral base oil
Balance When other additives are used, a concentrated solution or dispersion of the novel detergent/antiwear additive mixture of the present invention (as described above) together with one or more of the other additives may be used. An additive concentrate (the concentrate when forming an additive mixture is referred to herein as an additive package) containing (a concentrate amount of In addition, it may be desirable, although not necessary, to be able to form a lubricating oil composition. Dissolution of additive concentrates into lubricating oils can be facilitated by solvents and by mixing with mild heating, but this is not necessary. Concentrates or additive packages typically contain additives in amounts appropriate to provide the desired concentration in the final formulation when the additive package is mixed with a predetermined amount of pace lubricant. is prescribed. Thus, the cleaning agent of the present invention/
The antiwear additive mixture is added to a small amount of base oil or other compatible solvent along with other desired additives to form an appropriate proportion of the additive typically from about 25 to about 90% by weight, preferably about Additive packages can be formed containing the active ingredients in a collective amount of 15% to about 75%, most preferably from about 25% to about 60% by weight, with the balance being base oil.

Typically about 10% by weight of the additive package can be used in the final formulation, with the balance being base oil.

All weight percentages expressed herein (unless otherwise noted) refer to the active ingredient (A, 1.) content of the additive, and (also Fi,) the A, I, weight and total content of each additive. Based on the total weight of the additive package or formulation plus the weight of oil or diluent.

The invention will be better understood by reference to the following examples, which include preferred embodiments of the invention.
Therefore, all parts are parts by weight unless otherwise specified. Based on both PIB.

Examples 1-2 Table IK Series of Completely Formulated SAE 1 with Ingredients Listed
A 5W40 lubricant was prepared.

Yama Soeto Area H 噸 o 馨 °
For the avian formulation of O'Cumm1ns' NTC-4
00 driving test (load = refrigerated trailer, 80. OOO
lb gross vehicle weight, a load factor of approximately 80-, used in the continental United States (excluding Alaska, but mainly extending from Dallas to the northeastern part of the Pacific Ocean), but in this case the rl
, a diesel fuel with a sulfur content of less than 3 times fIt was used.

Also included in the above test were the following commercially available SAE 15W40-lube oils: These formulations include an ashless dispersant, an overbased alkaline earth metal detergent, and a zinc dihydrocarbyl dithiophosphate antiwear additive.

Comparative test oil wt CH SASHυN (1) μm S0iI
C1,010 011D 11
12011E [L72
&9011F 1.
0 100i1G
1.0 8011H1,0
8 01111,08 0il J 0.97011
K 195 14
The results obtained are shown in Table 3.

The data in Table 1 shows that the oil of Example 1 provides excellent roundland cleanliness while not sacrificing any of the residual performance characteristics.

Example 5 The low ash oil of Example 1 was subjected to a series of additional engine tests and the resulting data are summarized in Table II. As can be seen from Table 2, the oil of Example 1 passes all of the American Petroleum Institute CE standard requirements for commercially available heavy-duty diesel lubricating oils.

Table ■ Total bearing weight loss, lE9 5 & 8 50 maximum Passed Katapira-I G/2 (480 hours) TG
F 54 80 Maximum passing WTD 204 3
00 Saiken Mack T-6 Oil consumption, lb/Hp-hr α00049
(10014 Most dog passing total demerit points 649
650 Max Max Proudness, 4
[LOO9α020 maximum ring weight loss, η
507 350 Maximum viscosity increase, eat
4.2 14 Maximum estimated Maek score
112 90 Minimum Mack T-7 Oil consumption -11 See Figure 1---Pass Crown Land Carbon, 4 9.2 2
5 Maximum third land reduction point 12.
1 40 Maximum roller follower pin wear,
(100,000.002% thickest) The low ash oil of the present invention preferably contains less than 1% by weight, preferably less than α5 weight i′-, more preferably less than 0.5 weight percent (for example, from about 0.1 to about 0% by weight).
．． 3 wt.) and most preferably α1 wt.
It is preferably used in heavy duty diesel engines using normally liquid fuels having a sulfur content of, for example, 100-500 ppm. The normally liquid fuel is diesel fuel or ASTM standard D396.
includes hydrocarbonaceous petroleum distillate fuels such as fuel oils as defined by In a compression ignition engine,
Normally liquid fuel compositions containing non-hydrocarbon materials such as alcohols, ethers, organic nitrogen compounds, and the like (eg, methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) can also be used. Corn, alfalfa
Also within the scope of this invention are liquid fuels derived from vegetable or mineral sources such as , Scheno V, and coal. The use of normally liquid fuels that are mixtures of one or more hydrocarbonaceous fuels and one or more non-hydrocarbonaceous substances is also contemplated by the present invention. An example of such a mixture is a combination of diesel fuel and ether. Particularly preferred is A2 diesel fuel.

The lubricating oil of the present invention is used in the combustion chamber of a cylinder (generally 11 to 8 or more cylinders per engine) or cylinders (typically 11 to 8 or more cylinders per engine) with a tight top land for vertical circulation and reciprocation. Crankcase of a diesel engine having a cylinder in which the distance between the piston top land and the cylinder wall liner is reduced to minimize the amount of particulate matter produced in It is particularly useful in Such a tight topland can also provide improved fuel economy and increased effective compression ratio in the cylinder. The top land consists of the generally cylindrical area of the piston above the top piston ring groove, and therefore the top land is generally characterized by a circular cross section (along the longitudinal axis of the piston). The outer periphery of the top land may consist of a substantially vertical surface designed to be substantially parallel to the vertical wall of the cylinder liner (such top land is herein referred to as a cylindrical top land). ). Or, preferably, the top land may taper inwardly toward the center of the piston from the next point where the top land adjoins the top piston ring structure and the topmost surface of the piston, i.e., one crown. and the cylinder wall liner (referred to herein as the "topland gap") is:
For cylindrical top lands, preferably about (l Lolo ~
(Within LO301a. For tapered toplands, the lower topland clearance (i.e., the topland clearance at the point where the topland is adjacent to the trap piston ring groove) is preferably about 0.005 to α030b, more preferably The upper top land clearance, i.e., the top land clearance at the piston crown, is preferably about 1010 to about 1010 (for LO45iz, and more preferably about 0.015 to 0.L0501tL).

Although the topland clearance may be smaller than the previously listed dimensions (e.g., less than αOO5ia), such a small distance may be less than the desired distance between the topland portion of the piston and the cylinder wall liner during engine operation. This results in no contact (which is undesirable due to the damage caused to the liner). Generally, the topland height (i.e., the vertical distance from the bottom of the topland to the top of the topland as measured along the cylinder wall liner) ranges from about 0.1 to about t2ifL for a 4-cycle diesel engine. (Generally about (18~1゜2 wind)
And for a 2-cycle diesel engine, it is approximately 0.1~α
It is 5b. The design of diesel engines and pistons with such tight top lands is within the skill of those skilled in the art and does not require further discussion here.

The foregoing description describes the principles, preferred embodiments, and modes of operation of the present invention. However, the present invention is disclosed herein and should not be construed to be limited to the specific form disclosed herein.

This is because they are to be considered illustrative rather than limiting. Numerous changes and modifications will occur to those skilled in the art without departing from the spirit of the invention.

[Brief explanation of the drawing]

FIG. 1 is a plot of oil consumption versus test time for the NTC-400 oil consumption test as summarized in Example 3. FIG, 1 ゜、寥杼弼凉）3の川已1ちつ°－外11强こ■01-3

Claims (28)

[Claims] (1) a majority amount of oil of lubricating viscosity; and (A) at least about 3% by weight of at least one oil-soluble ashless dispersant;
) at least about 2% by weight of at least one oil-soluble sulfurized alkylphenol, and (C) the formula ▲ has a mathematical formula, chemical formula, table, etc. ,
alkyl, cycloalkyl, aralkyl, alkaryl or a substituted substantially hydrocarbon group derivative of said group, and the R^1 and R^2 groups each have an average of at least 6 carbon atoms]; each containing a small amount of a mixture of dihydrocarbyldithiophosphoric acid with at least one oil-soluble metal salt, and with a total sulfated ash (SASH) level of less than 0.6% by weight and from about 0.01:1 to about 0.2:
SASH of 1: A low sulfated ash lubricating oil composition characterized by a dispersant weight:weight ratio. (2) the sulfurized alkylphenol has at least one hydroxy group bonded to the same aromatic ring and at least one
At least one alkylphenol containing about 100 to 25 C_6 to C_2_0 alkyl groups is combined with a sulfurizing agent to
The composition according to claim 1, which is reacted at a temperature of 0°C. (3) R^1 and R^2 groups are each 6 to 18 per group
A composition according to claim 1 consisting of an alkyl having 5 carbon atoms. (4) The metal salt is a group I metal, a group II metal, Al, S
2. The composition according to claim 1, which contains at least one metal selected from the group consisting of n, Pb, Mo, Mn, Co, and Ni. (5) The composition according to claim 4, wherein the metal is zinc. (6) An average of 2 to 6 ashless dispersants per molecule of polyamine
Claim 5 consisting of a polyisobutenyl succinimide of a polyalkylene polyamine having 0 nitrogen atoms, and wherein the polyisobutylene portion is derived from polyisobutylene having a number average molecular weight of about 800 to 3,000. Compositions as described in Section. (7) SASH:dispersant weight:weight ratio is about 0.3:1~
7. A composition according to claim 6, wherein the ratio is 0.2:1. (8) the ashless dispersant is formed by reacting (a) an olefin polymer of C_2 to C_1_0 monoolefins having a number average molecular weight of about 700 to 5,000 and a C_4 to C_1_0 monounsaturated acid material; a hydrocarbyl-substituted C_4-C_1_0 monounsaturated dicarboxylic acid-forming material, on average at least 0.8 per molecule of olefin polymer present in the reaction mixture used to form the first acid-forming material; and (b) a nucleophilic reactant selected from the group consisting of amines, alcohols, amino alcohols and mixtures thereof. Compositions as described. (9) The composition according to claim 8, wherein the nucleophilic reactant is an amine. (10) The composition of claim 9, wherein the amine comprises an amine containing 2 to 60 carbon atoms and 1 to 12 nitrogen atoms per molecule. (11) The amine is a polyalkylene polyamine (here,
the polyalkylene group contains 2 to 40 carbon atoms), and the polyalkylene polyamine contains 2 to 40 carbon atoms per molecule.
11. The composition of claim 10 containing ˜about 9 nitrogen atoms. (12) Claim 1 in which the amine consists of polyethylene polyamine and the reaction product is boron-treated.
Composition according to item 1. (13) the amine has a reactive functional group value of about 3 to about 12, the hydrocarbyl-substituted acid-forming material contains succinic acid moieties, and the amount of succinic acid moieties contained in the olefin polymer per equivalent of amine; 10. The composition of claim 9, wherein about 0.1 to about 1.0 moles are reacted. 14. The composition of claim 13, wherein the reaction product contains about 0.05 to 2.0% by weight boron. (15) A claim in which the nucleophilic reactant has a reactive functionality of at least 3, and at least 2 moles of acid-forming material are present in the reaction mixture per mole of the second nucleophilic reactant. The composition according to item 14. 16. The composition of claim 15, wherein the ashless dispersant is boron-treated and the reaction mixture comprises boric acid. (17) The composition according to claim 16, wherein the first olefin polymer and the second olefin polymer each comprise polyisobutylene. (18) The number average molecular weight of the olefin polymer is about 800 or more
3,000 and the amine comprises a polyalkylene polyamine having an average of about 5 to 7 nitrogen atoms per molecule. (19) SASH level is about 0.2 to about 0.45% by weight
The composition according to claim 18, which is (20) SASH: dispersant ratio of approximately 0.02:1 to 0.1
20. The composition of claim 19, wherein the ratio is 5:1. (21) The composition according to claim 20, which additionally contains a high molecular weight hydrocarbon polymer viscosity index improver. (22) (A) At least one oil-soluble ashless dispersant about 1
(B) about 10-40% by weight of at least one sulfurized alkylphenol; (C) dihydrocarbyl dithiophosphoric acid (wherein the hydrocarbyl group has on average at least 6 carbon atoms); about 5-15% by weight of at least one oil-soluble metal salt, and (D) about 30-80% by weight of a base oil, and at a total sulfated ash level (S
ASH) and an ashless dispersant concentration of about 0.01 to 0.2 parts by weight SASH per part by weight of ashless dispersant. (23) A method of improving the performance of a heavy-duty diesel lubricating oil adapted for use in a diesel engine with a normally liquid fuel having a sulfur content of less than 1% by weight, comprising controlling the metal content of the oil. about 0.0% in the oil.
Total sulfurized ash (SASH) less than 6% by weight and 0.01:
providing a SASH:dispersant weight:weight ratio of 1 to about 0.2:1 and containing in the oil at least about 3% by weight of (A) an ashless dispersant and (B) a sulfurized alkylphenol antioxidant. 2% by weight, and (C) at least one metal salt of dihydrocarbyl dithiophosphoric acid (wherein each of the hydrocarbyl groups in the acid has an average of at least 6 carbon atoms) as an effective anti-wear agent. A method for improving the performance of heavy duty diesel lubricants by applying different amounts. (24) A method for producing heavy-duty diesel lubricating oil adapted to meet American Petroleum Institute CE standards, comprising:
The metal content of the oil is controlled to provide a total sulfated ash (SASH) level in the oil of less than about 0.6% by weight and a SASH:dispersant weight:weight ratio of from 0.01:1 to about 0.2:1. and at least about 3% by weight of (A) an ashless dispersant in the oil.
, (B) at least about 2% by weight of a sulfurized alkylphenol antioxidant, and (C) a dihydrocarbyl dithiophosphoric acid, wherein each of the hydrocarbyl groups in the acid has an average of at least 6 carbon atoms. A method for producing a heavy-duty diesel lubricating oil comprising providing an anti-wear effective amount of at least one metal salt. (25) A method of improving the performance of a heavy duty diesel lubricating oil adapted for use in a diesel engine having at least one tight top land piston, the metal content of the oil to control less than about 0.6% total sulfated ash (SASH) and about 0.01:1 in the oil.
giving a SASH:dispersant weight:weight ratio of ~0.2:1;
and (A) at least about 3% by weight of an ashless dispersant, (B) at least about 2% by weight of a sulfurized alkylphenol antioxidant, and (C) dihydrocarbyl dithiophosphoric acid (wherein the oil contains at least about 3% by weight of an ashless dispersant); each hydrocarbyl group has on average at least 6 carbon atoms)
A method for improving the performance of heavy-duty diesel lubricating oils, which comprises providing a variety of metal salts in amounts effective for wear resistance. 26. The method of claim 25, wherein the diesel engine is adapted for use with normally liquid fuels having a sulfur content of less than 1% by weight. (27) Lubricating Oil In a diesel engine having a crankcase and at least one tight-topland piston, a majority of the oil of lubricating viscosity; and (A) at least about 3% by weight of an ashless dispersant; and (B) at least about 2% by weight of a sulfurized alkylphenol antioxidant and (C) an effective amount of dihydrocarbyl dithiophosphoric acid as an antiwear additive, wherein each of the hydrocarbyl groups in the acid contains an average of at least 6 at least one carbon atom)
Each contains a small amount of a mixture with a metal salt of the species, and 0.
A lubricating oil composition characterized by a total sulfated ash (SASH) level of 0.01 to about 0.6% by weight and a SASH:dispersant weight:weight ratio of 0.01:1 to 0.2:1. A diesel engine characterized by having an effective amount in the crankcase. 28. The method of claim 27, wherein the diesel engine is adapted for use with normally liquid fuels having a sulfur content of less than 1% by weight.