JPH02229892A - Improved demulsifying lubricating oil composition - Google Patents

Abstract

In accordance with one aspect, the present invention is directed to a lubricating oil additive mixture comprising (A) a lubricating oil dispersant additive comprising at least one of (1) ashless dispersants and/or (2) polymeric viscosity index improver dispersants, and (B) a demulsifier additive comprising the reaction product of an alkylene oxide and an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol. In a preferred embodiment, the lubricating oil additive mixtures further comprises (C) a compatibilizer additive for the demulsifier, which comprises a glycol ester or a hydroxyamide derivative of a carboxylic acid having a total of from 24 to 90 carbon atoms and at least one carboxylic group per molecule, for enhanced solubility, viz. stability, of the demulsifier in the oil solutions containing such dispersants.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to oily compositions containing a high molecular weight ashless dispersant and a demulsifier having improved demulsifying properties. Such concentrates are useful in oil compositions, including fuel oil and lubricating oil silk formulations.

In one aspect, the present invention provides a lubricating oil dispersant comprising at least one of (A') C1) an ashless dispersant and/or (2) a polymeric viscosity index improver/dispersant;
(B) A lubricating oil additive mixture containing a demulsifier 2=, which is a reaction product of an alkylene oxide and an adduct obtained by reacting a bisepoxide with a polyhydric alcohol. In a preferred embodiment, the lubricating oil additive mixture comprises: to obtain improved solubility or stability of the demulsifier in a solution containing such dispersant;
(C) A compatibilizer for a demulsifier comprising a glycol ester of a carboxylic acid or a hydrocyanide derivative having a total number of carbon atoms of 24 to 90 per molecule and at least one carboxylic acid group.

BACKGROUND OF THE INVENTION Sequence nD is an established AST standard that sets today's standards for crankcase lubricants for gasoline engines.
It is one of the M test methods (^merican So
Society for Testing and MaL
erialsSpecial Technical P
Publication 315H, Partl: 1
September 15, 979). This test method is designed to evaluate the rust prevention properties of lubricating oils and prevent rust from occurring by using a condenser at the crankcase discharge to prevent water vapor from escaping from the combustion gases in the crankcase. creating a sensitive environment.

A by-product of a humid nD environment is the presence of conditions that are extremely sensitive to emulgiline formation. Although the emulsion itself is not necessarily of interest, the condenser tube becomes partially occluded with emulsion, which results in a pressure drop across the condenser and a resulting pressure build-up within the crankcase. The engine manufacturer
Oil that generates emulsions tends to clog PC valves or other pipes connected to the crankcase exhaust system at the site, and also coat other engine internal surfaces such as rocker covers, valve decks, etc. with emulsion. I became interested in it. These concerns are particularly directed to internal combustion engines where crankcase fresh air purge is not used. In such cases, the absence of fresh air purge can cause water accumulation in the crankcase steam. In some engines, the crankcase vapors are sent to an external separator designed to separate the entrained liquid and vapors. The separated liquid is intended to be discharged continuously into the crankcase, and the gas passing through the separator is introduced into the cylinders of the engine and mixed with air (or) fuel (or a mixture thereof) for combustion. It is planned that.

The presence of emulsions in the crankcase and in the entrained steam entering the separator causes blockage of the separator or at least increases the effective pressure drop, reducing its efficiency. In severe cases, this can lead to an undesired increase in crankcase pressures beyond design limits, thus causing oil seepage from the crankcase seals and other problems. In cold climates and in short range or low engine speed conditions, the above problems may become increasingly pronounced.

Crankcase lubricating oils for internal combustion engines are designed to minimize the unavoidable oxidation of oil components, e.g. during engine operation, in order to minimize both the extent of deposits (e.g. varnish) adhering to engine parts and the formation of sludge. It is required to suspend the solids resulting from the process. Because today's engines operate at higher temperatures, and as a result of reduced engine dimensions and higher power demands, today's crankcase lubricant formulations minimize the negative effects on the engine of lubricant oxidation during use. This requires the use of high levels of molecular weight agents (e.g., provided by the use of high molecular weight dispersants or increased levels of low molecular weight dispersants) and the use of other aggressive engine components. Ru.

Therefore, Sequence IID testing suggests strict limits on crankcase pressure, making it extremely important to prevent emulsion formation in today's lubricating oil formulations.

Unfortunately, the essential ingredients needed to keep engines clean and control deposit formation in today's lubricating oil formulations,
Many dispersants and multifunctional viscosity modifiers can be very effective emulsion formers.

Therefore, various lubricating oil demulsifiers have been proposed.

U.S. Pat. No. 3,509,052 discloses alkyl groups of phosphoric acids/xyboly(ethyleneoxy)ethyl mono- and dielters, polyoxyethylated amines, gamma amide and quaternary salts, polyoxyalkylene polyols, and such polyoxyalkylene polyols. Lubricating oil demulsifiers are disclosed that consist of esters of alkylene polyols with lauric acid, stearic acid, cononic acid, and alkyl- or alkenyl-substituted succinic acids (up to 20 carbons in the alkyl or alkenyl group).

U.S. Pat. No. 3,511. No. 11182 relates to a demulsifier for petroleum crudes prepared by adding a higher alkylene oxide, such as butylene oxide or brobylene oxide, to a monovalent, divalent or trivalent compound (e.g. propylene glycol). Ethylene oxide is added to the adduct to form an oxyethylated adduct, where the ratio of primary to secondary hydroxyl groups is controlled.The oxyethylated adduct is then added to the epoxide of the polyphenol. is reacted with diglycidyl ether of bisphenol A.

Demulsification is carried out by adding about 1 part of the demulsifier to the crude oil emulsion and 2,000 to 2,000 parts of the emulsion.
This is accomplished by mixing in a ratio of 1/2 and then leaving the emulsion relatively still while allowing oil and water separation to occur. These demulsifiers are used in conjunction with other demulsifiers from the group such as the petroleum sulfonate type (one example of which is naphthene sulfonic acid), the modified fatty acid type and the amine modified oxyalkylated phenol-formaldehyde type. It has been disclosed that it is possible.

For example, in wells)
The crude oil demulsifiers used hitherto consist of adducts obtained by reacting diglycidyl ether of bisphenol 8 with polypropylene glycol and its broboxylated derivatives.

However, the environment in which demulsifiers are used to break crude oil emulsions and the manner in which such quiescent conditions for emulsion phase separation are induced is similar to the dynamic environment in which crankcase lubricants are used in internal combustion engines. This is in sharp contrast to a variety of other lubricant additives used in crankcase lubricant compositions, as previously described. Primarily among these, the effect of ashless dispersants in crankcase lubricating oils can be offset by demulsifiers.

The current trend toward the use of high molecular weight ashless dispersants in such formulations and additive concentrates therefor has greatly complicated the search for more powerful demulsifiers. In addition, the frequent simultaneous use of high total base metal detergents in such formulations and concentrates requires that the demulsifier be compatible with these compositions, i.e., the demulsifier must be compatible with these compositions. It should not adversely affect the storage stability of the compound.

Therefore, many lubricating oils and fuels contain compounds known as friction modifiers (also referred to as "friction agents"), which reduce the friction of internal engine components and thereby improve fuel economy. are doing. U.S. Patent No. 3,42
9. No. 817 discloses that esters of esters formed by reacting about 2 moles of C2-C5 glyfur with about 1 mole of C,6 dicarboxylic acid dimers of Cla unsaturated fatty acids (e.g., lyluic acid or oleic acid) The present invention relates to improving the lubricity and load carrying capacity of synthetic ester lubricating oils by addition. U.S. Patent No. 3,273,981
It is directed to fuel oils and lubricating oils containing mixtures of dimer acids and polyhydric alcohol partial esters as lubricating oil additives. U.S. Pat. No. 4,459,223 relates to a friction reducing agent for lubricating oils that is the reaction product of a dimeric carboxylic acid (eg, linoleic acid dimer) and a polyhydric alcohol having at least three hydroxy groups. U.S. Pat. No. 4,479,883 discloses that polycarboxylic acids (
For example, the present invention relates to lubricating oil compositions having relatively low levels of phosphorous and improved friction reducing properties through the use of mixtures of glycol or glycerol esters (for example, linoleic acid dimer) and No, Zn or sb dithiocarbamates. U.S. Pat. No. 4,557,846 relates to a lubricating oil friction reducer comprised of an oil-soluble hydroxyamide compound prepared by condensing a dimeric carboxylic acid (eg, linoleic acid dimer) with a hydroxyamine.

U.S. Pat. No. 4,617,026 discloses C1, to C3
. Hydroxyl-containing esters of monocarboxylic acids and hyglycols or trihydric alcohols, where the glycol is
US Pat. No. 4,683,06.
No. 9 is CI@~Ol. This invention relates to a fuel efficiency improver for fuel oil, which is composed of partial glycol esters of fatty acids.

Instability of compositions containing polycarboxylic acid-glycol esters, ashless dispersants and certain metal lubricant additives)
Therefore, the need for stabilization is recognized in the art. U.S. Pat. No. 4,105,571 discloses improved abrasion and wear resistance containing zinc dihydrocarbyl dithiophosphate, an ester with polycarboxylic acid toglycol, and an ashless polymeric dispersant. A storage-stable lubricating oil composition (wherein either the zinc component or the ester component, or both, are predispersed with an ashless dispersant prior to addition to the Lubricant 411 composition). Friction modifying esters are described to include linoleic acid dimers esterified with glyfurs such as diethylene glycol.

U.S. Patent No. 4. No. 388,201 discloses a lubricating oil composition containing a polyolebonic acid glycol friction modifier ester together with a boron-treated or unboronated alkenyl succinimide dispersant containing an oil-soluble hydrocarbyl-substituted mono- or dioxazoline. or a lubricating oil composition stabilized by the addition of a small proportion of a co-dispersant consisting of a lactone oxazoline.

U.S. Pat. No. 4,505,829 discloses a lubricating oil composition containing a polycarboxylic acid monoglycol ester as a friction modifier together with a hydrocarbon-soluble alkenyl succinimide dispersant that reduces the formation of sediment during storage. Lubricating oil compositions with reduced propensity are disclosed.

U.S. Pat.
A storage stable lubricating oil composition comprising an additive combination with an ashless dispersant containing free hydroxyl groups of certain nails.

U.S. Patent No. 4,684,473 discloses that C4 to C.I. This invention relates to the solubilization of oxygenated (hydroxy) esters of dimer acids (including linoleic acid dimer esters of polyhydric alcohols) by incorporating oil-soluble alkanols or oil-soluble alkyl phosphates. It is disclosed that the selection of alcohol chain length is essential.

SUMMARY OF THE INVENTION According to one aspect, the present invention provides a lubricating oil component comprising at least one of (A) (1) an ashless dispersant and/or (2) a polymeric viscosity index improver and dispersant. The present invention relates to a lubricating oil additive mixture comprising a powder and (B) a demulsifier comprising a reaction product of an adduct obtained by reacting an alkylene oxide and a bisepoxide with a polyhydric alcohol.

In a preferred embodiment, the lubricating oil additive mixture contains (C) 24 to 9 per molecule to obtain improved solubility or stability of the demulsifier in oil solutions containing such dispersants.
It further includes a demulsifier compatibilizer consisting of an alcohol ester or hydroxyamide derivative of a carboxylic acid having a total number of carbon atoms of 0 and at least one carboxylic acid group.

According to another aspect of the invention, the above components A, B and C
and further comprising (D) a metal detergent for lubricating oils, the method comprising: (1) pre-preparing an ashless dispersant component A and a metal detergent component D at an elevated temperature. (2) separately premixing components B and C and then mixing the resulting mixtures (1) and (2). It is surprising here that if a mixture of demulsifier B and compatibilizer C is first formed and then added to the preformed mixture of ashless dispersant A and metal detergent D, a different mixing order can be obtained. It has been found that improved storage stability is obtained compared to mixtures of these components made using

The dispersant component A in the urashy silk composition of the present invention can consist of one or more ashless dispersant substances, one or more polymeric viscosity index improvers and dispersants, or mixtures thereof. . Particularly preferred is an ashless dispersant, and an ashless dispersant mixed with a polymer viscosity index (V, I,) improver/dispersant. When a fully formulated lubricating oil is contemplated to contain both an ashless dispersant and Polymer V-1, an improver and dispersant, they are generally introduced into the final oil as separate additive concentrates. .

That is, polymer V, I. This is because improver-dispersants are generally not compatible with concentrates containing ashless dispersants, metal detergents, and many other conventional lubricating oil additives. Therefore, the polymer V,! ．． 1 and proportions of improver and dispersant, unless otherwise specified, refer to additive concentrates (
It should be understood that the present invention is directed to the final, fully formulated lubricating oil composition, rather than to the final fully formulated lubricating oil composition (as described in more detail below).

The ashless dispersant useful as component 8 in the present invention is (1
) long-chain hydrocarbon-substituted mono- and dicarboxylic acids or their anhydrides, oil-soluble salts, amides, imides, oxazolines and esters or mixtures thereof; (11) long-chain aliphatic hydrocarbons to which polyamines are directly attached; iii)
About 1 molar proportion of the long chain hydrocarbon Ffmphenol is combined with about 1 to 2.5 moles of formaldehyde and about 0.5 to 2 moles of formaldehyde.
manninohi condensation product formed by condensation with moles of polyalkylene polyamine, where (i)
, (ii) and (iii) are from the group consisting of C, to CIO, such as polymers of C2 to C5 monoolefins, having a number average molecular weight of at least 900. Consists of a selected nitrogen- or ester-containing dispersant.

The long-chain hydride L7 carbyl-substituted mono- or dicarboxylic acid substance, i.e., acid, anhydride or ester, used in the present invention is typically a long-chain hydrocarbon, generally a polyolefin, typically on average per mole of polyolefin. at least about 0.8, generally from about 1.0 to about 2.0, preferably about 1.0. 05-1.25 e.g. 1.06-1.20
Or 1. 10 ~I. ．． 20 moles of α or β
Examples of such dicarboxylic acids, anhydrides and esters include fumaric acid, itaconic acid, maleic acid, maleic anhydride. , chlormaleic acid, dimethyl fumarate, chlormaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and the like.

Preferred olefin polymers for reacting with unsaturated dicarboxylic acids to form component A-1 ashless dispersants are polymers containing a permolar amount of C, ~ CI0, e.g. 02 ~ C, Mo7/olefin. . Such olefins include ethylene, flobylene, butylene, imbutylene, bentene,
Examples include octene-1 and styrene. The polymer may be a homopolymer such as polyisobutylene, or a copolymer of two or more of such olefins, such as a Jj polymer of ethylene and brobylene, a copolymer of butylene and imbutylene, a copolymer of brobylene and imbutylene, etc. It is good for polymers. Other copolymers include those in which a small mol 1n of the monomers in the copolymer, for example 1 to 10 mol %, are C4-C non-conjugated diolefins, such as copolymers of imbutylene and butadiene or Examples include copolymers of ethylene, brobylene, and 1,4-hexadiene.

In some cases, olefin polymers are fully saturated, such as hydrogen molecules! Ethylene-brobylene copolymers made by Ziegler-Natta synthesis may also be used as regulators.

The olefin polymer used in the Component A-1 ashless dispersant typically has a molecular weight of at least about 900, preferably about L.20
0 to about 5,000, more preferably about 1,5QO to about 4
, 000. Particularly useful olefin polymers have a molecular weight of about 1,500 to about 3,000
and has a number average molecular weight in the range of .about.1 terminal double bonds per polymer chain. A particularly useful starting material for the production of high efficiency ashless dispersants useful in accordance with the present invention is polyisobutylene. The number average molecular weight of darkening polymers can be measured by several known methods. A convenient method for such measurements is by gel permeation chromatography (GPC), which additionally provides molecule 11 distribution information. Regarding GPC, see “Modern Size Exclusion” by W. W. Sew, J. A. Kirkland, and D. D. Bly.
Liquid Chromato-graphy”
(See A Willy Φ and Ban Sons, New York, 1979).

Methods for reacting olefin polymers with 04-C3-C10 unsaturated dicarboxylic acids, anhydrides or esters are known in the art. For example, U.S. Pat.
61,673 and 3,401,118, 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 is added to the polyolefin at 60-250°C e.g.
Chlorinated or brominated to about 1-8 preferably 3-7% by weight of chlorine or bromine based on the weight of the polymer by passing at a temperature of about 0.5-10 hours, preferably 1-7 hours, at a temperature of be able to. The halogenated polymer is then heated normally at 100-250° C. with sufficient unsaturated acid or anhydride such that the resulting product contains the desired number of moles of unsaturated acid per monomer of halogenated polymer. Approximately 180-235°C
The reaction can be carried out for about 0.5 to 10 hours, for example 3 to 8 hours. This general type of method is described in U.S. Pat. Nos. 3,087,436 and 3,172,8
No. 92, No. 3,272, 746, etc.

Alternatively, the olefin polymer and unsaturated acid material are mixed and heated while adding chlorine to the hot material. This type of method is described in U.S. Pat. No. 3,215,707, U.S. Pat.
No. 64, No. 4, 110, 349, No. 4. 2
No. 34,435 and British Patent No. 1,440,21
It is disclosed in No. 9.

The use of halogen typically causes about 65 to 95 weight percent of the polyolefin, such as polyisobutylene, to react with the dicarboxylic acid material. When the thermal reaction is carried out without the use of halogens or catalysts, approximately 50 to 7
Only 5% by weight reacts. Chlorination helps improve reactivity.

For convenience, the functionality ratio of dicarboxylic acid-forming units to polyolefin (e.g., 1.0 to 2.0), etc. described above refers to the total amount of polyolefin used to make the product, i.e., the total amount of reacted polyolefin and unreacted polyolefin. Based on《
.

The dicarboxylic acid-forming materials can also be further reacted with amines, alcohols (including polyols), amino alcohols, etc. to form other useful dispersants. Thus, if acid-forming substances are to be further reacted, e.g. neutralized, generally at least 50 of the acid units are
% to all of the acid units are reacted.

The amine compound useful for neutralizing the hydrocarbyl-substituted dicarboxylic acid substance has about 2 to 60, preferably 2 to 4 amine compounds in the molecule.
0 (e.g. 3-20) total carbon atoms and about 1-1
Includes mono- and polyamines having a number of nitrogen atoms of 2, preferably 3 to 12, most preferably 3 to 9. These amines may be hydrocarbyl amines,
Alternatively, it may be a hydrorubylamine containing other groups such as a hydroxyl group, an alkoxy group, an amide group, a nitrile group, an imidazoline group, etc. Hydroxyamines having 1 to 6 hydroxyl groups, preferably 1 to 3 hydroxyl groups, are particularly useful. Preferable (Ia)
(Ib) [wherein, R'R'
R' and R1 are each hydrogen, C+-C*S linear or branched alkyl group, C, ~Cat alkoxyC, ~C.
alkylene group, Ct-Cl1hydroxyaminoalkylene group and CI-CltalkylaminoC,~C@alkylene group, respectively, and R'' is further of the formula (wherein R' is as defined above). and S and S' are 2 to 6, preferably 2
may be the same or different numbers of ~4 and t and t'
may be the same or different numbers from 0 to 10, preferably 2
-7 Most preferred are aliphatic saturated amines, including those in which t and t' are a number from about 3 to 7, with the proviso that the sum of t and t' is not greater than 15. To ensure facile reaction, R'R'R'R'', s, s't and t' typically contain at least one primary or niamine group in compounds of formula Ia and rb. is preferably selected in a manner sufficient to provide at least two primary or secondary amine groups, which means that at least one of the R', R'R' or R1 groups is hydrogen. or when R′ becomes H or I
This can be achieved by making t in formula ib at least 1 when the c moiety has a secondary amino group. The most preferred amines of the above formula are represented by 1b 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, 14-C24-diaminobutane, 1,6-diaminohexane, polyethylene amines such as diethylenetriamine, triamine, etc. Ethylenetetramine, tetraethylenepentamine, polybropylene amines such as 1,2-brobylenediamine, di(1,2-brobylene)triamine, di(l,3-brobylene)triamine, N. N-dimethyl-1,3-diaminopropane, N,N-di(2-aminoethyl)ethylenediamine, N,N-di(2-hydroxyethyl)-t,a-propylenediamine, 3-dodecyloxybrobylamine , N-dodecyl-1,3-furobandiamine, trishydroxymethylamine/methane (
THAM), diisopropanolamine, diethanolamine, triethanolamine, monodi- and tritallowamine, aminomorpholine such as N-(3-aminobrobyl)morpholine, and the like.

Other useful amine compounds include l4-C24-di(ami/
Alicyclic diamines such as methyl) cyclohexane, heterocyclic nitrogen compounds such as imidazoline, and compounds of the general formula [where pI and p are the same or different and are each an integer of 1 to 4, and n Is n * and ns are the same or different, and each is 1 to 3
N-aminoalkylbiverazine, which is an integer of . Examples of such amines include, but are not limited to, 2-pentadecyl imidazoline, N-(2-aminoethyl)biperazine, and the like.

Commercially available mixtures of amine compounds may also be used with advantage. For example, one method for producing alkylene amines is to react an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia to form a complex mixture of alkylene amines in which pairs of nitrogen atoms are linked by gamma alkylene groups. and thus forming compounds such as diethylenetosamine, triethylenetetramine, tetraethylenepentamine and viverazine 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,""Polyamine400,""Dow Polyamine E-100," and the like.

In addition, as a breeding amine, formula NH. -Alkylenebe 0-Alkylenebe NH. (
m) in which b has a value of about 3 to 70, preferably 10 to 35, and in which C has a value of about 1 to 40, provided that the sum of all C's is about 3 ~70 preferably from about 6 to about 35, and RIV is a polyvalent saturated hydrocarbon group of 4 to C10 carbon atoms, and the number of substituents on the RIV group is from 3 to 6. represented by the value of a']. The alkylene group in either formula (III) or (IV) may be straight chain or branched containing about 2 to 7, preferably about 2 to 4 carbon atoms.

The polyoxyalkylene polyamines of formula (III) or (fV) above, preferably polyoxyalkylene diamines and polyoxyalkylene triamines, have a molecular weight of about 200 to about 4
, 000, preferably within the range of about 400 to about 2,000. Preferred polyoxyalkylene polyamines include polyoxyethylene and polyoxypropylene diamines and polyoxybrobylene 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 name "Diefamine D-230, D-400, D-100".
0, D-2000, T-403'', etc.

The amine is prepared by adding an oil solution containing 5 to 95% by weight of the dicarboxylic acid material to about 100% to 95% by weight until the desired amount of water is removed.
250°C preferably << is generally 1 to 1 at 125 to 175°C
It is readily reacted with dicarboxylic acid materials such as alkenylsuccinic anhydrides by heating for 0 hours, for example 2 to 6 hours.

Preferably, the heating is carried out to promote the formation of an imide or a mixture of imide and amide rather than amide and 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.

Generally Q. l-
1.0 preferably about 0.2-0.6 such as 0.4-0.

Contains 6 moles of dicarboxylic acid moiety! ! (e.g. graftoma, leic anhydride content) is used. For example, a mixture of amides and imides is the product formed by reacting 1 mole of olefin with enough maleic anhydride to add 1.6 moles of succinic anhydride groups per mole of olefin. Preferably, about 0.8 moles of pentamine (having 2 primary amino groups and 5 equivalents of nitrogen per molecule) are used for the conversion. That is, preferably pentamine is used at about 0.4 moles per m of nitrogen of the amine (i.e., sufficient m).

Nitrogen-containing ashless dispersants are described in U.S. Pat. No. 3,087. 9
3Ci and 3,254,025, as generally taught in US Pat. No. 3,254,025. This comprises combining the selected acyl nitrogen dispersant with a boron compound selected from the group consisting of boron oxide, boron halides, boron acids, and esters of boron acids at a rate of about 0.1 atomic atoms per mole of said acylated nitrogen compound. of boron in an amount that provides about 20 atomic proportions of boron per atomic proportion of nitrogen in the acylated nitrogen compound. Advantageously, the combined dispersants of the present invention contain about 0.05 to 2.0% by weight based on the total weight of the boronated acyl nitrogen compound, e.g.
Contains ~0.7% by weight boron. Boron (this is
Dehydrated boric acid polymers (mainly (HBO-)
s)) is believed to bind to the dispersant imide and diimide as an amine salt, such as a metaporate salt of the diimide.

The treatment may be applied to the acyl nitrogen compound at a concentration of about 0.05 to 4, e.g.
~3% by weight (based on the weight of the acyl nitrogen compound) of a boron compound, preferably boric acid, which is usually added as a slurry) is added and with stirring about 13% by weight (based on the weight of the acyl nitrogen compound)
This is easily carried out by heating at 5-190°C, e.g. 140-170°C, for 1-5 hours followed by nitrogen stripping in that temperature range. Alternatively, boron treatment can be carried out by adding boric acid to a hot reaction mixture of dicarboxylic acid material and amine while removing water.

Tris(hydroxymethyl)aminomethane (THAM)
British Patent No. 984,4
Amide, imide or ester type additives can be formed as taught in US Pat.
, 102. No. 798, No. 4,116,876 and No. 4. 1.13, 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 monohydric and polyhydric alcohols, or aromatic compounds such as phenols and naphthols. The polyhydric alcohol is i.t. Preferred hydroxy compounds and preferably contain from 2 to about 10 hydroxy groups, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol
cole, dibropylene glycol, and other alkylene glycols where the hyanolykylene group contains from 2 to about 8 carbon atoms. Other useful polyhydric alcohols include glycerol, monooleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, diventaerythritol, and the like.

Mata, ester component IM agent is allyl anoleco-nole,
It can also be derived from unsaturated alcohols such as cinnamyl alcohol, fluorochlorinated alcohol, 1-synthelic san-3-ol, and hyoleinol alcohol. Still other groups G'1 of alcohols which can be used to form the esters of the present invention include oxyalkylenes having +ft or more oxyalkylenes, aminoanolekylenes, or oxyalkylenes having an oxyarylene group (aminoarylene, oxyarylene, oxyarylene), Includes ether alcohols and aminoanorecols, including aminoalkylene- and hyaminoarylene-substituted anolecoles.These include Cel!.o-golve, Carbitol, N.N, N', N'
-tetrahydroxytrimethylene diamine, and 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 diesterols or acidic esters of succinic acid, ie partially esterified conic acid, as well as partially esterified polyhydric alcohols or phenolic free alcohols or esters having phenolic hydroxyl groups. Similarly, mixtures of the esters illustrated in , L 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. 022. Also, the ester dispersant can be boron-treated in the same manner as the nitrogen-containing dispersants described above.

Hydroxylamines that can be reacted with the long chain hydrocarbon-substituted dicanolebonic acid materials described above to form dispersants include 2-amino-1-butanol, 2-amino-2
-Methyl-1-brono{nonole, p-(β-hydroxyethyl)aniline, 2-amino-1-probanol,
3-Amino-1-probanol, 2-amino-2-methynole-1,3-brobanediol, 2-amino-2-ethyl,3-brobanediol, N-(.β-hydroxybuchivir)-1J'-( β-amino/ethyl) biverazine, tris(hydroxymethyl)aminomethane (
Torino, also known as methylolaminomethane),
2-amino-1-butanol, ethanolamine, /
3 (β-hydroxyethoxy)ethynoleamine and the like. Mixtures of these or similar amines can also be used. The above description of nucleophilic reactants suitable for reaction with hydrocarbyl-substituted dicarboxylic acids or anhydrides includes amines, alcohols, and compounds with mixed amine and hydroxy-containing reactive functional groups, ie amino alcohols.

A preferred group of ashless dispersants are substituted with succinic anhydride groups and polyethylene amines such as tetraethylene pentamine, pentaethylene hexamine, polyoxyethylene and polyoxybrobylene amines such as boroxybrobylene diamine, trismethylol aminomethane. and pentaerythritol and combinations thereof. 1
One particularly preferred dispersant combination is U.S. Pat.
No. 804,763, (A) a polyisobutylene substituted with succinic anhydride groups; (B) a hydroxy compound reacted therewith, such as pentaerythritol; and CC) a polyoxyalkylene polyamine, such as polyoxybrobylamine. (D) a polyethylene diamine and a tetraethylene pentamine, the combination comprising
It includes about 0.3 to about 2 moles of each of (B) and (D) and about 0.3 to about 2 moles of (C) per mole. Another preferred dispersant combination is described in U.S. Patent No. 3. No. 632,511, (
A) polyisobutenylsuccinic anhydride and (B) polyalkylene polyamine such as tetraethylenepentamine and (
C) Including combinations with polyhydric alcohols or polyhydroxy-substituted aliphatic primary amines such as pentaerythritol or trismethylolaminomethane.

A-1(ii) U.S. Patent No. 3,275,554
Also useful as ashless nitrogen-containing dispersions in the present invention are dispersants in which nitrogen-containing polyamines are bonded directly to long-chain aliphatic hydrocarbons, as taught in U.S. Pat. The halogen groups of carbonated hydrocarbons are replaced with various alkylene polyamines.

A-1(iii) Another group of nitrogen-containing dispersions that can be used in the present invention are those containing Mannich bases or Mannich condensation products as known in the art. Such Mannich condensation products are generally described, for example, in U.S. Pat.
85, about 1 mole of high molecular weight hydrocarbyl-substituted mono- or polyhydroxybenzene (e.g., having a number average molecular weight greater than or equal to i.
It is prepared by condensation with 2.5 moles of formaldehyde or paraformaldehyde and about 0.5 to 2 moles of polyalkylene polyamine. Such Mannich condensation products can include long chain high molecular weight hydrocarbons on the phenolic group, or as described in US Pat. No. 3, cited above. 442
．． No. 808, it is also possible to react with such hydrocarbon-containing compounds such as polyalkenylsuccinic anhydrides.

A-2 Examples of suitable polymeric viscosity index improvers and dispersants include: (i) vinyl alcohol or C2-C5; Polymers consisting of 04-C4-C24 unsaturated esters of unsaturated mono- or dicarboxylic acids and unsaturated nitrogen-containing monomers having 4 to 20 carbon atoms, (ii) C. ~C4~C
20 ole7ine and unsaturated C4-C24G, . (iii) polymers of ethylene and 03-C4-C20 olefins to which are grafted 04-C4-C20 unsaturated nitrogen-containing monomers or polymers with mono- or dicarboxylic acids; Examples include those obtained by grafting an unsaturated acid onto the backbone, and then reacting the carboxylic acid group with an amine, hydroxyamine, or alcohol.

In these polymers, the ``monohydric or polyhydric'' with respect to the amine, hydroxyamine or alcohol may be as described above for the ashless dispersant compound.

The polymer viscosity index improver and dispersant has a molecular weight of 1,000 to 2,000,000, preferably 5,000 to 250, when measured by gas phase osmotic pressure method, membrane osmotic pressure method, or gel permeation chromatography. 000 most preferably <<> preferably has a number average molecular weight range of 1G,000 to 200,000. The polymers of group (i) also consist of a majority by weight of unsaturated esters and a small amount of nitrogen-containing unsaturated monomers, for example from 0.1 to 40% by weight, preferably from 1 to 20% by weight, based on the total polymer. is preferable. Preferably, the polymers of group (ii) contain from 0.1 to 10 moles of olefin per mole of unsaturated carboxylic acid moiety, preferably <<0.2
~5 moles of C2-C5. It contains aliphatic or aromatic olefin moieties and 50-100% of the acid moieties are neutralized. Preferably, the group (iii) has 25 to 8
0% by weight ethylene and 75-20% by weight C2-C5.

It consists of an ethylene copolymer with mono- and (or) diolefins, and iooi parts of the ethylene copolymer is 0.
．． 1 to 4o preferably <c: (glazed with 1 to 20 parts by weight of unsaturated nitrogen-containing monomer or 0.01 to 5 parts by weight of unsaturated C, -cl. mono- or dicarboxylic acid(
This acid is crafted with more than 50% neutralization).

The unsaturated carboxylic acids used in (i), (11) and (iii) above preferably contain from 3 to 10 and more preferably 3 or 4 carbon atoms and are monocarboxylic acids such as methacrylic acid and acrylic acid. It may be an acid or a dicarboxylic acid such as 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, diamyl fumarate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and mixtures thereof.

Examples of other esters include vinyl alcohol esters of C2-C5 fatty acids or monocarboxylic acids (preferably saturated), such as vinyl acetate, vinyl laurate, vinyl balmitate, vinyl stearate, vinyl oleate, etc. Mixtures may be mentioned.

(2) In order to impart dispersibility to the improver, a polymerizable unsaturated nitrogen-containing monomer can be grafted onto the ester polymer, or the monomer can be copolymerized with the ester. Examples of suitable unsaturated nitrogen-containing monomers include 4
~20 carbon atoms, e.g. p-(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,
Vinylpyridine and vinylalkylpyridine such as 2-butyl-5-vinylpyridine and the like are mentioned.

Also suitable are N-vinyl lactams such as N-vinylpyrrolidone or N-vinylbiveridone.

The vinyl group is preferably unsaturated (CI. = CO-)
, but it is 1-2 such as methyl or ethyl
It may also be monosubstituted with an aliphatic hydrocarbon group of up to 1 carbon atoms.

Vinyl pyrrolidone is preferred, examples include N-vinyl pyrrolidone, N-(1-methylvinyl) pyrrolidone, N-
-vinyl-5-methylpyrrolidone, N-vinyl-3.3
-dimethylpyrrolidone, N-vinyl-5-ethylpyrrolidone, N-vinyl-4-butylpyrrolidone, N-ethyl-3-vinylpyrrolidone, N-butyl-5-vinylpyrrolidone, 3-vinylpyrrolidone, 4-vinylpyrrolidone, 5-vinylpyrrolidone, 5-cyclohexyl-N-vinylpyrrolidone and the like.

Examples of olefins that can be used to make copolymers (ii) and (iii) above include brobylene, -butene, 1-bentene, l-hexene, k-
Examples include monoolefins such as hebutene, 1-decene, 1-dodecene, styrene I, and the like.

Representative examples of diolefins that can be used in (iii) include, but are not limited to, 1.4
-hexadiene, 1,5-hebutadiene, 1,6-octadiene, 5-methyl-1,4-hexadiene, 1.4
-cyclohexadiene, l,5-cyclooctadiene,
Vinylcyclohexane, dicyclobentenyl and 4.4
'-dicyclohexenyl, e.g. tetrahydroindene,
Methyltetrahydroindene, dicyclopentadiene,
Examples include bicyclo(2.2.1)-1-hebuta-2.5-diene, alkenyl, alkyldiene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene.

Typical polymeric viscosity index improvers and dispersants include copolymers of alkyl methacrylate and N-vinylpyrrolidone or dimethylaminoalkyl methacrylate, copolymers of alkyl fumarate-vinyl acetate and N-vinylpyrrolidone. , post-grafted copolymers of ethylene-propylene and active monomers such as maleic anhydride, which can be further reacted with alcohols or alkylene polyamines (e.g., U.S. Pat. No. 4,089,794; No. 4, 160, 739, No. 4, 137, 1
85) or a copolymer of ethylene and brobylene reacted or grafted with a nitrogen compound (
U.S. Patent No. 4,068,056, U.S. Patent No. 4,068
, No. 058, No. 4, 146, 489, No. 4
, 149,984), styrene/maleic anhydride polymers post-reacted with alcohols and amines, ethoxylated derivatives of acrylate polymers (see, e.g., U.S. Pat. No. 3,702,300) ), and U.S. Pat. No. 3,493,5
No. 20, No. 3, 558, 743, No. 3. 6
No. 34, 493, No. 3, 684, 713, No. 3, 933, 781, No. 3. 956,14
No. 9, No. 3, 959, 159, No. 4, 02
9,702 and 4,424,317, Hungarian Patent No. 25, i6, Soviet Patent No. 235,
No. 232 and No. 1,121,268 and British Patent No. 2.1.24,633,
Nitrogen-containing compounds (e.g. polyalkylene polyamines,
Also useful are styrene-isobutylene- and styrene-maleic anhydride copolymers and terpolymers substituted with biperidine, morpholine, hydrazine, etc., as well as mannisohyl base condensation product derivatives. Please refer to these patents if necessary.

Demulsifier Component B The lubricating oil demulsifier of the present invention is obtained by reacting (i) an alkylene oxide with (ii) a diglycidyl ether of bisepoxide, preferably bisphenol A, and a polyhydric alcohol, preferably polyoxyalkylene glycol. It is the water-insoluble, at least partially oil-soluble product of the reaction with the adduct.

In making the demulsifier of the present invention, the first adduct is prepared by reacting a bisepoxide with a polyhydric alcohol.

Bisepoxides are compounds containing at least two oxirane rings, one C-C-. These oxirane rings are linked or bonded by a hydrocarbon moiety or a hydrocarbon moiety containing at least one heteroatom or group. This hydrocarbon portion is generally 1
Contains ~100 carbon atoms. These include alkylene, cycloalkylene, alkenylene, arylene,
Includes aralkenylene and arylene groups. Typical alkylene groups are those containing 1 to about 100 carbon atoms, more typically 1 to about 50 carbon atoms. Alkylene groups may be straight or branched and contain 1 to about 100 carbon atoms, preferably 1 to about 50 carbon atoms.

Typical cycloalkylene groups contain 4 to about 16 ring carbon atoms. The cycloalkylene group includes an alkyl substituent on one or more ring carbon atoms, such as C.
-C. It can contain alkyl. Typical arylene groups contain 6 to 12 ring carbon atoms;
Examples are phenylene, naphthylene and biphenylene. Typical alkylene and aralkylene groups are 7
It preferably contains from 7 to about 50 carbon atoms. The hydrocarbon moiety joining the oxirane ring may contain substituents thereon.

This substituent is one that is substantially inert or non-reactive with the oki/ran ring at ambient conditions. In the present specification and claims, the expression "substantially inert or non-reactive under ambient conditions" means that an atom or group is present in the compositions, additives, compounds, etc. of the invention in relation to its intended use. is meant to be substantially inert to chemical reactions with the oxirane ring at ambient temperatures and pressures so as not to substantially interfere in an adverse manner with the manufacture and/or function of the oxirane. For example, minor amounts of these atoms or groups may undergo minimal reaction with the oxirane ring without interfering with the practice and use of the invention as described herein. In other words, such reactions, although discernable in the art, are not sufficient to prevent a person skilled in the art from making and using the invention for its intended purpose. Suitable substituents include, but are not limited to, alkyl groups, hydroxyl groups, tertiary amide groups, halogens, and the like. When more than one substituent is present, they may be the same or different.

Although many substituents are substantially inert or non-reactive with the oxirane ring and the ambient conditions; It will be understood that under the conditions it will react with the oxirane ring.

Whether these groups are suitable substituents that may be present on the bisepoxide depends in part on their reactivity with the oxirane ring. In general, if they are substantially more reactive with the oxirane ring than with the reactive hydroxy groups, they tend to substantially interfere in a negative manner with the preparation of the demulsifier contemplated by the present invention, and therefore It's inappropriate.

However, if their reactivity with the oxirane ring is lower than or approximately the same as the reactivity of the oxirane ring with reactive hydroxy groups, they are in a negative manner for the preparation of the demulsifiers of the present invention. They do not substantially interfere and may therefore be present on the bisepoxide, especially if the epoxide group is present in excess compared to the substituents. An example of such a reactive but suitable group is a hydroxyl group. Examples of unsuitable substituents are primary amino groups.

A hydrocarbon moiety containing at least one heteroatom or group is a hydrocarbon moiety as defined above that contains at least one heteroatom or group in the chain.

The heteroatom or group is one that is substantially non-reactive with the oxirane ring at ambient conditions. When more than one heteroatom or group is present, they may be the same or different. The heteroatoms or groups are separated from the carbon atoms of the oxirane ring by at least one intervening carbon atom.

These heteroatoms or groups containing hydrocarbon moieties are
It can contain at least one substituent on at least one carbon atom. These substituents are the same as those described above as suitable for hydrocarbon moieties.

Some examples of suitable petero atoms or groups include, but are not limited to, the following:

Oxygen atoms (i.e. 101 or ether bridges in the carbon chain)
: sulfur atom (i.e. -S- or thioether bridge in the carbon chain); carboxyl group (i.e. -a-O-). Ketone group (i.e. -C-). O sulfonyl group (i.e. -S-). As previously described, the bisepoxides of the present invention contain at least two oquinlane rings or epoxide moieties. It is essential that the bisepoxide contains at least two oxirane rings in the same molecule.

Bis-epoxides useful in the present invention are well known in the art and generally available commercially, or can be readily prepared by conventional, well-known methods.

Bisepoxides include those represented by the general formula. In the above formula, R is a divalent hydrocarbon group, a substituted divalent hydrocarbon group, a divalent hydrocarbon group containing at least one heteroatom or group,
and a substituted divalent hydrocarbon group containing at least one heteroatom or group, where R+ and R@ are hydrogen, a monovalent hydrocarbon group, a substituted monovalent hydrocarbon group, at least one heteroatom or a monovalent hydrocarbon group containing at least one
a substituted monovalent hydrocarbon group containing 2 heteroatoms or groups,
and oxirane-containing groups, R8 and R' are hydrogen, a monovalent hydrocarbon group, a substituted monovalent hydrocarbon group,
Monovalent hydrocarbon groups containing at least one heteroatom or group, substituted monovalent hydrocarbon groups containing at least one heteroatom or group, monovalent oxirane-containing groups, divalent hydrocarbon groups and substituted each selected from divalent hydrocarbon groups, with the proviso that R! or if R3 is a divalent hydrocarbon group or a substituted divalent hydrocarbon group, both R'' and R3 are divalent hydrocarbon groups bonded to two carbon atoms of the oxirane ring to form a cyclic structure. or a substituted divalent hydrocarbon group, and R and R are hydrogen, a monovalent hydrocarbon group, a substituted monovalent hydrocarbon group, a monovalent hydrocarbon containing at least one heteroatom or group. groups, substituted monovalent hydrocarbon groups containing at least one heteroatom or group, monovalent oxirane-containing groups,
each selected from a divalent hydrocarbon group and a substituted divalent hydrocarbon group, provided that if R' or R5 is a divalent hydrocarbon group or a substituted divalent hydrocarbon group, then both R4 and R5 are It must be a divalent hydrocarbon group or a substituted divalent hydrocarbon group that combines with two carbon atoms of the oxirane ring to form a cyclic structure.

Monovalent hydrocarbon groups represented by R'-R'' generally contain from 1 to about 100 carbon atoms.

These hydrocarbon groups include alkyl, alkenyl, cycloalkyl, aryl, aralkyl and alkaryl groups. 1 to about 100 alkyl groups, preferably 1
It can contain up to about 50 carbon atoms and can be straight or branched. Alkenyl groups can contain 2 to about 100 carbon atoms, preferably 2 to about 50 carbon atoms, and may be straight or branched. Preferred cycloalkyl groups are those containing about 4 to about 12 ring carbon atoms, such as cyclobutyl, cyclobentyl, cyclohexyl, cyclohebutyl, and the like. These cycloalkyl groups may contain a substituent, preferably an alkyl group, on the ring carbon atom, such as methylcyclohexyl, 1,3-dimethylcyclopentyl, and the like.

Preferred alkenyl groups are those containing 2 to about 30 carbon atoms, such as ethenyl, 1-brobenyl, 2-
Brobenil et al. Preferred aryl groups are from 6 to about 1
those containing two ring carbon atoms, e.g. phenyl,
naphthyl and biphenyl. Preferred aralkyl and alkaryl groups are those containing 7 to about 30 carbon atoms, such as p-+-lyl, 2,6-xylyl, 2
4-C24.6-1-limethylphenyl, 2-isobrobylphenyl, benzyl, 2-phenylethyl, 4-phenylbutyl, and the like. A substituted to valent hydrocarbon group represented by R'-R is a monovalent hydrocarbon group as described above containing at least one substituent. The substituents are those that are substantially non-reactive with the oxirane moiety under ambient conditions. 1
When more than one substituent is present, they may be the same or different.

A monovalent hydrocarbon group containing at least one heteroatom or group is a monovalent hydrocarbon group as defined above containing at least one heteroatom or group in the carbon chain. The heteroatoms or groups are separated from the carbon atoms of the oxirane ring by at least one intervening carbon atom. When more than one heteroatom or group is present, they may be the same or different. The heteroatom or group is one that is substantially non-reactive with the oxirane ring under ambient conditions.

These heteroatoms or groups are as described above.

A substituted monovalent hydrocarbon radical containing at least one heteroatom or group contains at least one heteroatom or group as defined above containing at least one substituent on at least one carbon atom. is a substituted monovalent hydrocarbon group. Substituents are as described above.

The oxirane group represented by Rl to R6 has the formula O [wherein R7 has the same meaning as Rl, and R6 to R"
3 to R3, and R'' has the same meaning as R in formula (2).

The divalent hydrocarbon groups represented by R-R6 and R1-R8 are generally aliphatic alicyclic groups and contain about 1-
Contains about 5 carbon atoms. A preferred divalent hydrocarbon group is an alkylene group. Preferred alkylene groups are those that combine with the two carbon atoms of the gamma xylan ring to form a cyclic structure containing from 4 to about 8 ring carbon atoms.

Thus, for example, if R3 and R4 are both ethylene groups, the cyclic structure formed with the two carbon atoms of the oxirane ring is cyclohexylene oxide,
That is, n.

A divalent substituted hydrocarbon group represented by R1 to RS and R"-R" is a divalent hydrocarbon group as described above containing at least one substituent on at least one carbon atom. Thus, for example, if R3 and R4 are both hydroxy-substituted ethylene groups, the cyclic structure formed with the two carbon atoms of the oxirane ring can be represented by the formula:

The divalent hydrocarbon group represented by R and R1° generally contains 1 to about 100 carbon atoms, preferably 1 to about 50 carbon atoms.
Contains 5 carbon atoms. These may be aliphatic, aromatic or aliphatic monoaromatic.

If they are aliphatic, they may be saturated or unsaturated acyclic or cycloaliphatic. These include alkylene, cycloalkylene, alkenylene, arylene,
Includes aralkylene and alkylene groups. Alkylene groups may be straight or branched. Preferred alkylene groups are those containing 1 to about 50 carbon atoms. Preferred alkenylene groups are those containing 2 to about 50 carbon atoms. Preferred cycloalkylene groups are those containing 4 to about 12 ring carbon atoms. Cycloalkylene groups can contain substituents, preferably alkyl groups, on ring carbon atoms.

It is to be understood that the term "arylene" herein is not intended to limit the divalent aromatic moiety represented by R and R'' to benzene.

Therefore, divalent aromatic moieties include benzene nucleus, pyridine nucleus,
It is to be understood that it may be a single aromatic nucleus, such as a thiophene nucleus, a 1,2,3,4-tetrahydro-naphthalene nucleus, or the like, or a polynuclear aromatic moiety. Such polynuclear moieties are of the condensed type, ie, in which at least one aromatic nucleus is fused at two points to another nucleus, such as found in naphthalene, anthracene, azanaphthalene, etc. good. Such polynuclear aromatic moieties may therefore be of the bridged type, in which at least two nuclei (either mononuclear or polynuclear) are linked to each other via a bridging condensation. Such crosslinks include carbon-carbon single bonds, ether bridges, keto bridges, sulfide bridges, polysulfide bridges of 2 to 6 sulfur atoms, sulfinyl bridges, sulfonyl bridges, methylene bridges, alkylene bridges, di(lower alkyl)methylene bridges. , lower alkylene ether bridges, alkylene keto bridges, lower alkylene sulfur bridges, lower alkylene polysulfide bridges of 2 to 6 carbon atoms, amino bridges, polyamino bridges and hybrid cross-links of such divalent cross-links. can.

When the divalent aromatic moiety Ar is a bridged polynuclear aromatic moiety, it has the general formula -Ar (Lng-Ar) y -, where r is from 1 to about 10, preferably from 1 to about 8, and more preferably from 1 to about 8. is an integer of 1, 2, or 3, Ar is a divalent aromatic moiety as previously described, and each Lng is a carbon-carbon single bond, an ether bridge (e.g., I1ba-0-), a keto bridge (e.g. -C-), 'sulfide bridge (e.g. -S-), polysulfide bridge of 2 to 6 sulfur atoms (e.g. Ss), sulfide=/
L rack! (e.g. +f, -S(0)-), X/I/honyl bridge (e.g. -S(0).-), lower alkylene bridge (e.g. -CI1.-, -CI1.-CI+.-, - C.I.
1. -C■1, etc.), \ di(lower alkyl)methylene bridge (e.g. -CR'
, -), lower alkylene ether bridges (for example, -CH2-0- -CH2-0-CI-b- -CH2 -CH2 -0-), lower alkylene sulfide bridges (for example, one or more 〇1 is substituted by one -S atom), and lower alkylene polysulfide bridges (e.g., one or more 〇1 is substituted with -S, ~.1S)
．． a bridging bond independently selected from the group consisting of (substituted with one group), wherein R is a lower alkyl group].

Examples of such bridging polynuclear aromatic moieties include those of the formula [where R'' and r{+3 are independently selected from hydrogen and an alkyl group, preferably anolekyl group containing from 1 to about 20 carbon atoms, and R I1 is selected from alkylene, alkylidene, cycloalkylene and cycloanolekylidene groups, wherein U and u are independently selected from integers having a value of 1 to 4].

Divalent substituted hydrocarbon radicals represented by R and RIG are divalent hydrocarbon radicals as defined above which contain at least one substituent of the above type. Thus, for example, if the divalent hydrocarbon group is C, alkylene, the corresponding divalent substituted hydrocarbon group, such as a hydroxy substituent, may be: OH CHz Clot C11 C11t CL. A divalent hydrocarbon radical containing at least one heteroatom or group, which may be the same or different when more than one substituent is present, is a divalent hydrocarbon group containing at least one heteroatom or The above-mentioned divalent hydrocarbon group containing a group. These heteroatoms or groups are as described above. Some non-limiting examples of divalent hydrocarbon radicals containing at least one heteroatom or group are provided.

-CH2 -0-CH2 - : CIh -0-CH2-CI710-CH2 - :
-CH2-0-CH2 -CH-CH2 -0-CH2
-Zan H2 l CH2-U-{;M2 薯H H 1-1 Divalent substituted hydrocarbon radicals containing at least one heteroatom or group are the above-mentioned substituents having at least one substituent of the above type. A divalent hydrocarbon group containing at least one heteroatom or group. Some non-limiting examples of divalent substituted hydrocarbon groups containing at least one heteroatom or group are shown below.

OH -CIb -CH2 -0-CH2-CH-CH2-0
-CH2 -CHz -; Also, within the scope of the bisepoxide of the present invention, the formula (■) [wherein R and R1 to R3 are as defined above,
R14 and R l s each have the same meaning as RI, X is an aromatic moiety, and R'' and R'' represent two carbon atoms of the oxirane ring and two adjacent ring carbon atoms of the aromatic moiety X. independently selected from divalent aliphatic acyclic hydrocarbon groups and divalent substituted aliphatic acyclic hydrocarbon groups that combine with atoms to form a cyclic structure, and m and m' are each O or the amount However, the sum of m0m' is at least a quantity, and p is O or a quantity].

The aromatic moiety represented by X is preferably from 6 to
Those containing 12 ring carbon atoms, such as benzene, naphthalene and biphenyl. The aromatic part is 1
It can contain one or more substituents on more than one ring carbon atom. These substituents are such that they are substantially non-reactive with the oxazoline ring at ambient conditions such as temperature and pressure. Examples of these include, for example, alkyl, hydroxyl, nitro, and the like.

Further, within the scope of the bisepoxide of the present invention, formula (■) [wherein R. ．． R'-R'R'' to R I5 and p are as defined above, and R'' is a divalent group bonded to the two carbon atoms of the oxazoline ring to form a cyclic, preferably cycloaliphatic structure. selected from a hydrocarbon group or a substituted divalent hydrocarbon group, respectively.

The divalent hydrocarbon or substituted divalent hydrocarbon group represented by Rl8 may be about 2 to 2 carbon atoms such that it joins with the two carbon atoms of the oxirane ring to form a 4 to about 16 membered ring structure, preferably a cycloaliphatic ring. Preferably, it contains up to about 14 carbon atoms. Preferred divalent hydrocarbon groups are divalent aliphatic hydrocarbon groups, preferably alkylene groups.

The divalent aliphatic hydrocarbon group represented by R'' can contain one or more substituents on one or more ring carbon atoms. Selected from those that are substantially non-reactive.

Preferred bisepoxides of the invention are those in which the oxirane rings, preferably at least one of which is a terminal oxirane ring, are not sterically hindered.

"Not sterically hindered" means that the oxirane ring is 1
containing 1 secondary carbon atom or 2 hydrogen atoms bonded to it, preferably 1 secondary carbon atom and 1 tertiary carbon atom or 1 hydrogen atom bonded to it. It means containing. Thus, for example, an unhindered bisepoxide of formula V is one in which R'R'R' and R@ are hydrogen, preferably R 1 , R 3 and R 4 to R 6 are all hydrogen. It's something like this.

Some examples of the bisepoxides of the present invention are shown below,
It is not limited to these.

H h Bisepoxides useful in the present invention also include epoxy resins. These epoxy resins are well known in the art and generally available commercially. These are, for example, "Textbookor Polymer S" by F.W. Billmeyer Jr.
science' (2nd edition, Wiley Interscience, New York, 1971, pp. 479-480)
, by H. Riichi and K. Neville. “Epoxy resin” (pages 209-271), “Encyclopedia or Pol-y” by H.F. Mark, N.G. Guylord and N.M. Baikars.
tner Science and Technology
gy' (Vat. 6, Interscience Division, Gene Wiley & Sons, New York, 1967), a and U.S. Pat. No. 3,477,
No. 990 and No. 3. No. 408, 422.

Ebogyo resin includes such compounds having one or more terminal epoxy groups. These bisepoxides can be saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic and, if desired, contain halogen atoms, hydroxyl J. (substituted with non-interfering substituents such as ether groups, etc.).

Preferred bisepoxides are glycidyl polyethers of polyhydric phenols and polyhydric alcohols, especially glycidyl polyethers of about 300-3
, 000 and an epoxy equivalent weight (WPE) of about 140 to 2,000. Particularly preferred is a WP of about 140 to 500.
B and 2,2 having an average molecular weight of about 300 to about 900
- diglycidyl polyether of bis(4-hydroxyphenyl)propane.

Other suitable epoxy compounds include those derived from polyhydric phenols and having at least one picinal epoxy group, in which the carbon-to-carbon bond in the six-membered ring is saturated. It will be done. Such epoxy resins can be prepared by at least two well known techniques: (1) by hydrogenation of glycidyl polyethers of polyhydric phenols; or (2) by hydrogenation of suitable catalysts such as Lewis acids, boron trihalides and their complexes. It can be obtained by reaction of hydrogenated polyhydric phenols with shrimp chlorohydrin in the presence of chlorohydrin and subsequent dehydrochlorination in an alkaline medium. Although this manufacturing method does not form part of the present invention, saturated epoxy resins derived by either method are suitable in the compositions of the present invention.

Generally speaking, the first method involves hydrogenating glycidyl polyethers of polyhydric phenols at temperatures below about 50°C in the presence of a catalyst consisting of rhodium and/or ruthenium supported on an inert support. It consists of hydrogenation. This method is disclosed and described in US Pat. No. 3,336,241, issued Aug. 15, 1967.

U.S. Patent No. 3,336. Hydrogenated epoxy compounds prepared by the method disclosed in No. 241 are suitable for use in the compositions of the present invention. therefore,. If necessary, reference is made to that US patent.

The second method is BF. The process consists of condensing hydrogenated polyphenols with shrimp yakuchihydrin, such as shrimp chlorohydrin, in the presence of a suitable catalyst, such as shrimp chlorhydrin, followed by dehydrohalogenation in the presence of caustic. Phenol hydrogenated bisphene/
- When A is the saturated epoxy compound obtained, the resulting saturated epoxy compound is often referred to as "Jepo bovine hydrogenated bisphenol A" or more appropriately "diglycidyl ether of 2,2-bis(4-cyclohexanol)propane". be done.

In any case, it will be understood that the term "saturated epoxy resin" as used herein means a glycidyl ether of a polyhydric phenol in which the aromatic ring structure of the phenol is saturated.

A preferred saturated epoxy resin is disclosed in U.S. Pat. No. 3,336
．． This is a hydrogenated resin produced by the method described in No. 241. More preferred is 2,2-bis(4
-Hydrogenated glycidyl ether of -hydroxyphenyl)propane (sometimes referred to as diglycidyl ether of 2,2-bis(4-cyclohexanol)propane).

One group of useful epoxy resins are those made by condensing shrimp chlorohydrin with bisphere/delta. These have the general structural formula [in the above formula, R I , R s are as defined above and preferably are all hydrogen, and R″0 is an alkyl group, preferably from 1 to about 10 R′+ is selected from an alkyl group, a hydroxyl group, or a halogen group, each containing from 1 to about 10 carbon atoms, and R'+ is selected from an alkyl group, preferably an alkyl group, a hydroxyl group, or a halogen group, each containing from 1 to about 10 carbon atoms. Selected, ■
are each selected from integers having a value of 0 to 4, W are each selected from integers having a value of 0 to 4, and f has a value of at least l and the amount of resin r Although the upper limit of f preferably does not exceed about 10 and more preferably does not exceed about 5, the upper limit of f includes resins represented by f.

Preferred compounds of formula (1) are such that R' to R1' are all hydrogen and V and W are all zero.

An example of a commercially available and useful epoxy resin is Shell Oil Company's "EPON" resin.

As mentioned above, bisepoxides, including epoxy resins, in which two carbon atoms of the oxirane ring are bonded to three hydrogen atoms, such as those in which R to R' in the formula are all hydrogen, are preferred. Preferred bisepoxides of this type are those in which the hydrocarbon moiety bridging the epoxide moieties, such as R in formula (1), contains a polar group or atom. These polar groups or atoms include, but are not limited to, the polar heteroatoms or groups described above. Particularly preferred bisepoxides are those derived from epoxy resins, especially polyhydric phenols.

In preferred compositions of the invention, the epoxy of the polyphenol epoxide is preferably limited to a minimum value of 145 and a maximum value of less than 250. Eboxy equivalent is defined as the number 9 of a substance containing one epoxy group. Thus, a suitable substance is “Epon 82g
It is a commercially available eboxidized dihydroxydiphenyldimethylmethane known as ” and has an average epoxy equivalent weight of 175 to 210. Other similar commercial products are also available and can be used as bisepoxides. Examples of these commercial products are bisepoxides of polynuclear phenols.These products often consist primarily of diglycidyl ether of diphenyldimethylmethane.

Diglycidyl ether of diphenylmonomethylmethane and diglycidyl ether of diphenylmethane can be used as reactants.

The polyhydric alcohol reactant has the formula R''(OH) represents a hydrocarbyl chain containing, and X is 2 to 8
For example, it can be made of at least one substance selected from the group consisting of alcohols, numbering from 1 to 5 (preferably). Preferred polyhydric alcohols have the formula HO-(MO)y (To)q H (XI)
[wherein M and T are the same or different and at least 2
is an alkylene group of carbon atoms, and the sum of y and q is such that the total average molecular weight of the polyoxyalkylene glycol is at least i,000, preferably from 1,000 to
10,000, more preferably 2,000 to 8,000
0001m] within the range of 15 to 250]. Preferably M and T have 3 or 4 carbon atoms, so preferably the polyoxyalkylene glycol consists of polypropylene glycol, polybutylene glycol or block copolymer mixtures thereof.

The selected polyhydric alcohol and bisepoxide reactants are:
About 10:1 to about 20:1, preferably about 14=1 to 18:
A polyhydric alcohol to bisepoxide ffiflt ratio of 1 is contacted for the reaction.

The reaction conditions in forming the first adduct will vary depending on factors such as the polyhydric alcohol and bisepoxide used, the presence of a solvent for the reaction, and other factors. Generally about 110-200°C, preferably about 120-17
Temperatures within the range of 0'C are used.

First A: 1 Reaction for the formation of additives is a hydrocarbon solvent, for example! - Can be carried out in the presence of a reaction solvent such as toluene, xylene, etc. Although the amount of solvent selected is not critical, the solvent, such as toluene, is generally in the range of about 25 to 75 parts of solvent per 3 to 100 parts of first adduct, calculated on a minor basis.

The pressure used in the reaction for forming the first adduct is not particularly critical and may be reduced pressure, atmospheric pressure or superpressure.

The reaction between selected polyhydric alcohols and bisepoxides is
It can be carried out in the presence of a minor reaction catalyst such as a Lewis base such as caustic soda or caustic potash. This catalyst is
About 0.2 to 0 of all components included in the reaction mixture
．． It can be used within the range of 1% sfil.

The desired adduct formed by the reaction of a polyhydric alcohol with a bisepoxide can be illustrated by the following formula, which illustrates the reaction of polypropylene glycol with the diglycidyl ether of bisphenol A.

In the formula, rI has a value sufficient to satisfy the number average molecular weight of polypropylene glycol. For example, r, generally ranges from about 5 to about 120 for polypropylene glycols having a number average molecular weight of about 4,000 to about 7,000.

It will be appreciated that it is not necessary to carry the reaction to completion to form the first adduct, and that the reaction mass may also contain by-products and unreacted starting materials. Examples of by-products are dimers, trimers and higher "congeners" formed by the reaction of selected bis-edoxide molecules with the desired polyhydric alcohol.

The product mixture obtained for the preparation of the first adduct can, if desired, be charged directly to a separate reaction vessel for reaction in a second step together with a selected amount of alkylene oxide, e.g. brobylene oxide. can. Alternatively, the alkylene oxide can be introduced directly into the reaction vessel containing the adduct product mixture.

The number of alkylene oxide reactants for use in the oxyalkylation of the bisepoxide/polyhydric alcohol adduct product mixture thus formed is preferably 2 to 10.
Consisting of alkylene oxides having ~5 carbon atoms. Examples of dark alkylene oxides are ethylene oxide, propylene oxide, ■,2-epoxybutane, 2,
3-Epoxybutane, ■,2-Epoxypentane, 2.
3-Eboxypentane, ■,2-Eboxyhexane, 2
, 3-epoxy to beef san, 34-C24-epoxy to beef san, 1,2-epoxy-3-methylbutane, and the like.

Particularly preferred alkylene oxides are propylene oxide and butylene oxide. Most preferably the alkylene oxide consists of propylene oxide.

The amount of alkylene oxide introduced into the second reaction stage for reaction with the adduct may vary over a wide range, but is preferably from about 0.1 to 20 parts lffiffl of the first adduct product mixture. The weight part is more preferably about 0.
4 to 10 parts by weight, most preferably about 1 to 4 parts by weight, of alkylene oxide are reacted with the adduct product mixture. Preferably, the alkylene oxide charged to this reaction step is less than or equal to about 50% by weight, preferably less than or equal to about 40% by weight, and most preferably less than or equal to about 30% (e.g., from 0 to 20% by weight), as described above. %) of ethylene oxide, and the remainder brobylene oxide and higher epoxide. Contacting the selected alkylene oxide with the first adduct reaction mixture is conducted under conditions for reaction of the alkylene oxide with the hydroxy groups of the first adduct. Conditions effective to accomplish such reactions may vary over a wide range, and typically range from about 110 to 180°C, preferably from 130 to +60'C for this second stage reaction.
A reaction temperature within the range of is used. Although any convenient pressure can be used, ie, subatmospheric, atmospheric or superatmospheric pressure, superatmospheric pressure is typically preferred.

Mixtures of alkylene oxides, such as mixtures of ethylene oxide and higher alkylene oxides such as brobylene oxide or butylene oxide, can be used. Alternatively, different alkylene oxides can be charged in any order, thus forming "blocks" of separately charged alkylene oxides.

The order of such sequential oxyalkylations or the number of repetitions of such oxyalkylations can be varied over a wide range. For example, the first adduct can be oxyethylated and then charged with brobylene oxide to carry out the oxidation, or the first adduct can be first treated with brobylene oxide and then the oxybrobylated adduct can be oxyethylated. Can be done. If such sequential alkylation with ethylene oxide is used, propylene or higher alkylene oxide is used second to ( It is preferably charged at the end (if two alkylation stages are used) or at the end (in the case of three or more alkylation stages).

Preferably, the reaction of the selected bisepoxide with the polyhydric alcohol and the alkoxylation of the resulting adduct is carried out under substantially anhydrous conditions.

The oxyalkylation reaction step can be carried out in the presence of the Lewis base catalyst used to form the first adduct, so it is not necessary to remove the Lewis base catalyst before introducing the alkylene oxide. Similarly, oxyalkylation is
It can be carried out in the presence of the same or different solvent used in the first reaction that formed the first adduct of bisepoxide and polyhydric phenol. If desired, additional reaction solvent (
For example, toluene) can be added. Lewis base catalysts have a substantially neutral pH (e.g., a pH of 5 to 8).
Preferably, it is neutralized (for example by addition of acetic acid or a similar alkanoic acid) to

Preferably, the demulsifier of the present invention contains about 10 to 80% by weight of oxyalkylene units derived from the given alkylene oxide used to oxyalkylate the bisepoxide/polyhydric phenol adduct. Approximately 20-70
At least about 25% by weight, preferably at least 40% by weight of oxyalkylene units derived from alkylene oxides having 3 or more carbon atoms (e.g., propylene oxide, butylene oxide, etc.) used in the oxyalkylation step. contains.

One of the preferred demulsifiers of the present invention is a proboxylated copolymer of diglycidyl ether of bisphenol A and polypropylene glycol, wherein polypropylene glycol has a molecular weight of 2,000 g, coo. , borripropylene glyco, bisphenol A
The weight ratio of 1 to diglycidyl ether is 14:1 to 18:
1 and the weight ratio of brobylene oxide reacted with the first adduct is within the range of about 2.5:1 to 3.5:1).

Compatibilizer C Preferably, the lubricating oil additive mixture of the invention contains at least one carboxylic acid having a total number of 24 to 90 carbon atoms per molecule and at least one carboxylic acid group, such as 2 to 3 carboxylic acid groups. It further includes a compatibilizing effective amount of a species alcohol ester or hydroxyamide derivative. These ester compatibilizers are generally derived from the esterification of monocarboxylic or polycarboxylic acids with monohydric, dihydric or trihydric alcohols such as glycols, glycerol, oxaalkanediols. Therefore, such esters are used in lubricating oils as friction modifiers,
The manufacturing method and structure thereof are disclosed in U.S. Patent No. 3,429,
No. 817, same No. 4. 459, 22: {No. 4
, 479, 883, 4, 617, 026
No. 4, 683. It is described in No. 069. Please refer to these patents if necessary. Hydroxyamide derivatives of such mono- and polycarboxylic acids are
U.S. Pat. No. 4,557. No. 846, using the method disclosed in No. It can be produced by condensation with alcohol).

The carboxylic acid may be an aliphatic saturated or unsaturated acid.
and generally about 24 to 90, preferably about 24 to 6
0 total carbon atoms and at least 1, e.g. about 2-3
preferably has about 2 carboxylic acid groups and at least about 9 carbon atoms between the carboxylic acid groups, preferably about 12 to 42 carbon atoms, particularly 16 to 22 carbon atoms. Contains. Examples of hydroxyamide compatibilizers are:
[wherein Jl is a hydrocarbon group of a dimeric carboxylic acid having a total number of carbon atoms of about 24 to about 90 and containing about 9 to about 42 carbon atoms between the carboxylic acid groups or and 2 is (a) a hydroxy-substituted alkyl group having from about 1 to about 20 carbon atoms or (b) a hydroxy-substituted alkyl group having from about 1 to about 20 carbon atoms; (n'l is an integer from 1 to 50)
is an oxyalkylene group, n4 is 0 or an amount,
n, is 1 or 2, and n8 is 1 or 2]
It is an oil-soluble hydroxyamide compound having the following properties.

A preferred compatibilizer is 2'4~C10-J'-OOC-J-COOH (■
a), and 4~C10-J'-OOC-J-COOJ
'-OH (■a) [where J is a hydrocarbon group of an acid, and J' and J' are a hydrocarbon group of an alkanediol or an oxyalkylene group from an oxaalkanediol, as defined below. This group consists of a dicarboxylic acid ester or diester.

Generally about 1 to 3 moles of glycol, preferably 1 to 2 moles of glycol, are used per mole of acid to provide either a complete ester or a partial ester.

Esters can also be obtained by esterifying mono- or dicarboxylic acids or mixtures of such acids with mixtures of diols, where J is the hydrocarbon group of the dicarboxylic acid and J' and J' are A hydrocarbon group related to diols.

The compatibilizer is typically present in the lubricating oil composition in an amount of about 0.1 to 5 parts by weight, preferably about 0.5 to 1.5 parts by weight, based on the weight of the demulsifier of Component B. used in

Higher amounts of compatibilizer can be used if desired. This is because such polycarboxylic acid glycol esters can also act as friction modifiers in lubricating oil compositions.

Therefore, the compatibilizer is generally about 0. 0005-2
% by weight, preferably about 0.001 to 0.25% by weight, most preferably about 0.001 to 0.25% by weight. (Used in an amount of 105 to 0.1% by weight.

Particularly preferred compatibilizers are dimer acid esters.

"Dimer acid" as used herein refers to CIa-C! ffi Used to represent substituted cyclohexenedicarboxylic acids, such as those obtained by Diels-Alder type reactions of unsaturated fatty acids, which are thermal condensations. Such dimer acids typically contain about 36 carbon atoms. The structure of dimer acid can be generalized as follows.

R23 R26 where R23 depends on the way the condensation of the carboxylic acid was carried out.
! Two of 3~R ta contain carboxyl groups and the other two are hydrocarbon groups. Carboxyl group (CHffi). COOH, -CH=CII(CHx
)ecOOH, (CH,)7COOH, -CH, -CI
{=CH(CI,)? COOH, C11=CIl(C
Ht)7COOH, and the hydrocarbon termini are CL(C11t)*, CIls(CII*)s-, C
L(CLL-, CI.(CI1!).CII=CIi,
C.I. (CH.). It can be represented by CI1=CHCH, first order. A preferred specific example of a linoleic acid dimer has the following formula (CH2)? It can be expressed as COOH (C H2 )5 C H:1.

The term "dimer acid" as used herein also refers to trimer (and higher congeners) such as about 24% by weight
trimer, but more typically includes compounds containing up to about 10% trimer by weight. This is because, as is well known in the art, the demerization reaction provides a compound containing a trimer acid having a molecular weight approximately three times that of the starting fatty acid.

The polycarboxylic or dimer acids described above are esterified with glycols having formulas 4-C10
(R"CHCHtO)x'H (where R1 is H or C
and x1 is from about 1 to 100, preferably from 1 to 25), and ethylene glycol and diethylene glycol are particularly preferred. A preferred embodiment is to form the ester using about 1 to 2 moles of glycol per mole of dimer acid or polycarboxylic acid, such as the ester of diethylene glycol and linoleic acid dimer. Examples of such esters have the formula (X
VI) [wherein D is OH] and X is as defined above].

The preparation of the polycarboxylic acid glycol esters described above and their use as friction-reducing esters (i.e., friction modifiers) are disclosed in U.S. Pat. Please refer to

Metal Detergent Component D Lube oil metal detergents are often referred to as rust inhibitor additives and include metal salts of sulfonic acids, alkylphenols, sulfurized alkylphenols, alkyl salicylates, naphthenates, and other oil-soluble mono- and dicarboxylic acids. Highly basic or overbased metal salts, which are often used as detergents, appear to have a particular tendency to interact with ashless dispersants. Typically, these metal-containing rust inhibitor additives and detergents are present in the lubricating oil in an amount of about 0.01 to 10 weight percent, e.g., 0.1 to 5 weight percent, based on the weight of the total lubricating composition. used in With Marlin Diesel Lubricant,
Typically such metal-containing rust inhibitor additives and detergents are used in amounts up to about 20% by weight.

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 that required for complete neutralization of the sulfonic acid present, and then It is produced by forming a dispersed carbonate complex by reacting excess gold 15% carbon oxide to provide the desired overbasing. The sulfonic acid is typically prepared by distillation and (or) by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from the fractionation of petroleum by extraction, or by the sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from the fractionation of petroleum by extraction; Obtained by alkylation of aromatic hydrocarbons such as those obtained by alkylating naphthalene. The alkylation may be carried out in the presence of a catalyst using an alkylating agent having from about 3 to 30 or more carbon atoms. Can be done.

For example, octalobarafin, polyolefins produced by dehydrogenation of paraffins, polyolefins produced from ethylene, propylene, etc. are all suitable. The alkaryl sulfonates usually contain from about 9 to about 70 or more carbon atoms, preferably from about 16 to about 50 carbon atoms per alkyl-substituted aromatic moiety.

Alkaline earth metal compounds that can be used to neutralize these alkaryl sulfonic acids to provide sulfonate include oxides, hydroxides, r-rukoxides, and carbonates of magnesium, calcium, and barium. Salts, carboxylates, arsenic sulfates, hydrosulfides, nitrates, borates and esters may be mentioned. Examples of these are calcium oxide, calcium hydroxide, magnesium acetate and magnesium borate. As previously mentioned, the alkaline earth metal compound is used in excess of that required for complete neutralization of the alkaryl sulfonic acid. Generally, the amount will be in the range of about 100-220%, but at least 125% of the stoichiometric amount of metal required for complete neutralization.
Preferably, % is used.

Various other methods for preparing basic alkaline earth metal alkaryl sulfonates are described, for example, in U.S. Pat. No. 3,150. 08
No. 111 and No. 3,150,089, in which overbasing is carried out by hydrolysis of an alkoxide carbonate complex with an alkaryl sulfonate in a hydrocarbon solvent-diluent oil. 1) is achieved.

Preferred alkaline earth sulfonate additives include ore. - Physical Properties Alkyl having a total base number within the range of about 300 to about 400 with a magnesium sulfonate content within the range of about 25 to about 32 weight percent based on the total weight of the additive system dispersed in the lubricating oil. Magnesium aromatic sulfonate.

Neutral metal sulfonates are often used as rust inhibitor additives. Polyvalent metal alkyl salicylates and naphthenic materials are known additives for lubricating oil compositions to improve their high temperature performance and prevent carbonaceous build-up on pistons. (U.S. Patent No. 2,
No. 744, 069). The increase in prebasicity of polyvalent metal alkyl salicylates and naphthenates is due to C, ~C. Alkaline earth metals such as calcium salts of mixtures of alkyl salicylates and phenates (U.S. Pat. No. 2,74
No. 4,069) or a polyvalent metal salt of alkylsalicylic acid. Said acids are obtained by alkylation of phenols followed by phenol conversion, carboxylation and hydrolysis (U.S. Pat. No. 3,704,315) and then converted to overbased salts by commonly known and used techniques. can be converted into Beneficially, the prebasicity of these metal-containing rust protection additives is at a TBN level of about 60-150. Useful polyvalent metal salicylate and naphthenate materials include methylene and sulfur bridged materials readily derived from alkyl-substituted salicylic acids or naphthenic acids, or mixtures of either or both with alkyl-substituted phenols. . Basic sulfurized salicylates and methods for their production are disclosed in U.S. Pat. No. 3,595,79.
It is shown in No. 1. Such substances include the general formula HO
OC-ArR. -Xy(ArR,Oil)n (
X
is an alkyl group having 30 carbon atoms (optimally about 12) and X is sulfur (-Sl or methylene (-
C I+ , yJ: a group 6 alkaline earth metal, especially magnenium, calcium, strontium and barium salts; Can be mentioned.

Preparation of overbased methylene bridged salicylate to phenate salts involves the alkylation of phenol followed by phenolization, carboxylation, hydrolysis, methylene crosslinking with a coupling agent such as an alkylene dihalide followed by carbonation and simultaneous salt formation. It is easily carried out by conventional techniques such as. In the present invention, T B N' of 60 to l5α
Overbased calcium salts of methylene-bridged phenolic salicylic acid with and are extremely useful.

Sulfurized metal phenates can be considered as “metal salts of phenol sulfide” and thus have the general formula (X
IX) (where x = 1 or 2, n = o, 1 or 2), or polymeric forms of such compounds (where R'' is alkyl group, where n and do. Each R'' group can each contain 5 to 40, preferably 8 to 20 carbon atoms.

The metal salt is prepared by reacting the alkylphenol J resnolehydride with a sufficient amount of metal-containing material to impart the desired alkalinity to the sulfurized metal phenate.

Regardless of the method of manufacture, useful sulfurized alkylphenols generally contain from about 2% to about 14%, and preferably from about 4% to about 12%, by weight sulfur, based on the weight of the sulfurized alkylphenol.

The sulfurized alkylphenol contains 70% of the oxides, hydroxides, and complexes to neutralize the phenol and, if desired, overbase the product to the desired alkalinity by procedures well known in the art. It can be converted by reaction with metal-containing substances. A preferred method is a neutralization method using a solution of the metal dissolved in glycol ether.

The lubricating oil dispersant mixtures of the present invention can be formulated into lubricating oils in any convenient manner. These mixtures can thus be added directly to the oil by dispersing or dissolving the desired concentration levels of the ashless dispersant, demulsifier, compatibilizer and metal detergent (if used) respectively in the oil. Can be done. Such incorporation into additional lubricating oils can be carried out at room temperature or elevated temperature. Alternatively, a concentrate is prepared by combining the ashless dispersant, demulsifier, compatibilizer, and metal detergent (if used) with a suitable l41 soluble solvent or base oil, and the concentrate is then lubricated. Oil-based ingredients can be blended to obtain the final formulation. Such dispersant concentrates typically contain from about 3 to about 45% by weight, based on the weight of the concentrate, preferably about 10% by weight.
~35% by weight of ashless dispersant A, typically about 0.01
-3% by weight, preferably about 0.05-0.3% by weight of demulsifier B, typically about 0. 0005-2% by weight, preferably about 0.0005-2% by weight. OQ 1-0.25% by weight most preferably about 0. oos to 0.1% by weight (if present) of compatibilizer C, typically about 2-45% by weight, preferably about 2
~14% by weight of metal detergent D (if present) and typically about 30-90% by weight << is about 40-60% by weight
Contains % by weight of base oil (active ingredient (A.l.
) on the basis of).

Ashless dispersants, metal detergents, demulsifiers and compatibilizers (alone or together with other lubricating oil additives such as anti-wear additives, corrosion inhibitors, antioxidants etc. as described below) )
The additive bag of the invention preferably comprises:
Manufactured by. As disclosed in U.S. Pat. For example, 7
(0-130°C) for a sufficient time and with agitation to bring the components into intimate contact, and then the dispersant/detergent mixture is cooled to below 65°C. The selected demulsifier and compatibilizer are mixed in the selected base oil or solvent for a time and under conditions sufficient to bring these ingredients into intimate contact (e.g., 50-130 ml with stirring).
1 to 5 hours) and then introduced as a mixture into the dispersant/detergent mixture at e.g. 50 to 130°C and stirred for 1 to 5 hours to provide intimate mixing.

The remaining lubricating oil additives can be added (separately or simultaneously) before, during, or after contacting the dispersant/detergent mixture and the demulsifier/compatibilizer mixture.

The lubricant base ingredients for lubricant mixtures are formulated with additional additives therein to form lubricant compositions (i.e., formulations).
adapted to perform selected functions by forming a

Lubricating Oil Compositions The additive mixtures of the present invention have very good demulsifying properties when measured in a variety of environments.

Accordingly, additive mixtures are used by formulating and dissolving them in oily substances such as fuel oils and lubricating oils.

The additive mixture of the present invention can be added to kerosene, diesel fuel, household heating fuel oil, jet fuel, etc. with a boiling point of about 65 to 430.
When used in normally liquid petroleum fuels, such as middle distillate oils, at temperatures of about 0.degree. C., based on the total weight of the composition. oot to about 0.5 preferably 0. Additive concentrations (in the fuel oil) ranging from oos to about 0.15% by weight are commonly used.

The additive mixtures of the present invention have their primary use in lubricating oil compositions using base oils in which the additives are dissolved or dispersed. Such base oils may be of natural or synthetic type.

Suitable base oils for use in preparing the lubricating oil compositions of the present invention include automotive and truck engine,
Included are those commonly used as crankcase lubricants for spark ignition and compression ignition internal combustion engines such as marine and railroad diesel engines. Also, automatic transmission fluid,
The present invention in base oils commonly used in and/or adapted for use as power transmission fluids such as tractor fluids, all-purpose tractor fluids, hydraulic fluids, heavy duty hydraulic fluids, power steering fluids, etc. Beneficial results are also obtained by using additive mixtures of. Gear lubricants, industrial oils, pump wells and other lubricating oil compositions can also benefit from the incorporation of the additive mixtures of the present invention.

These lubricating oil compositions typically contain several different types of additives that provide the required properties in the composition. These types of additives include viscosity index improvers, antioxidants, corrosion inhibitors, detergents, dispersants, pour point depressants, antiwear additives, and the like.

In the preparation of lubricating oil compositions, the additives are preferably introduced in the form of 10 to 80% by weight active ingredient concentrates, such as 20 to 80% by weight, in hydrocarbon oils such as mineral lubricating oils or other suitable solvents. This is a common method. Typically, these concentrates contain final lubricants such as crankcase motor oil:
3 to 10 per part by weight of additive package L when making A
For example, it can be diluted with 5 to 40 parts by weight of 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, metal hydrorubylsulfonates or metal alkyl phenates are commonly used in the form of 40-50% by weight concentrates, for example in lubricating oil fractions.

The mixtures of ashless dispersants and demulsifiers of the present invention, alone or together with compatibilizers and metal detergents (if present), are commonly used in lubricating oils, including natural and synthetic lubricating oils and mixtures thereof. It is used in a mixed state with a lubricating oil base material consisting of viscous oil.

Natural base ura includes animal ura and vegetable oils (e.g. castor ura, lard oil), liquid shiura, and baraffinic, naphthenic and mixed baraffinic-naphthenic hydrorefined, solvent-treated or acid-treated mineral lubrication ura. include. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

Alkylene oxide polymers and copolymers and their derivatives whose terminal hydroxyl groups have been modified by esterification, etherification 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.
methyl polyisopropylene glycol ether with an average molecular weight of 500 to 1,000, diphenyl ether of polyethylene glycol with a molecular weight of 500 to 1,000;
diphenyl ethers of polybrobylene glycol with a molecular weight of from 00 to 1,500), and their mono- and polynonorboxylic acid esters, such as acetate esters of detriethylene glycol, hybrid (]3-C-fatty m-esters and C I3 oxaic acid diester.

Other suitable groups of synthetic lubricating oils include dicarboxylic acids (e.g.
Phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, divic acid, linoleic acid,
malonic acid, alkyl malonic acid, alkenyl malonic acid) and various alcohols (e.g., ethyl alcohol, phthyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glyfur, diethylene glycol monoether, propylene glycol) consists of esters. Specific examples of these esters include:
Dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didenyl phthalate, di-n-hexyl sebacate, di-linoleate Ei1 body of 2-ethynolequinyl diester, 1 mole of senoz+ in 4f2 body
Examples include complex esters formed by reacting cinnic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

Esters useful as synthetic esters include C, to Cz monocarboxylic acids and polyols and polyol ethers such as inobentyl glycol, trimethylolbroban,
Also included are those made from pentaerythritol, cypentaerythritol and tripentaerythritol.

Polyalkyl-polyaryl-polyalkoxy/mono- or polyaryloxysiloxane oils and silicon-containing oils, such as silica lubricants, also constitute other useful groups of synthetic lubricating oils. Examples of these include tetraethyl silicate, tetraisobutylphenyl silicate, tetra(2-ethylhexyl)silicate, tetra(4-methyl-2-ethylhexyl) 1-, tetra(pt-butylphenyl) 1-, Mention may be made of hexa(4-methyl-2-pentoquine) di/loxane, poly(methyl)siloxane and poly(methylphenyl)siloxane. Synthetic lubricating oils include liquid esters of phosphorous-containing acids (eg, tricresyl phosphate, trioctyl phosphate, and diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.

Unrefined, refined, and rerefined kh can be used in the lubricant 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 that are used without further treatment. Refined oils are the same as unrefined oils except that they have 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 purification, solvent extraction, acid or base extraction, filtration, and barcolate extraction. The re-refined oil can be obtained by applying a treatment process similar to that used to obtain viscous oil by tapping refined Al that has already been put into practical use. Such 11S refineries are also known as reclaimed oils or reprocessed Ah, and are sometimes additionally treated by techniques for the removal of spent additives and pore breakdown products.

The ashless dispersant/demulsifier mixtures of the present invention can also be used in combination with viscosity index (Vl) improvers to form multigrade automotive engine lubricating oils. Viscosity modifiers impart high and low temperature usability to a lubricating oil and allow it to remain relatively viscous at elevated temperatures while also exhibiting acceptable viscosity or flow properties at low temperatures. It is. 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-controlling polymers generally have a viscosity of 103 to 10", preferably 10' to 10°, as measured by gel permeation chromatography or osmotic pressure methods, such as 20,
Number from 000 to 250,000 ゝI uniform molecule j:'
I cheat on r.

Examples of suitable hydrocarbon polymers include homopolymers of 0, to C30 e.g. C, to C8 olefins, including both α-olefins and internal olefins, or copolymers of two or more of these monomers. (which may be straight or branched, aliphatic, aromatic, alkyl aromatic, cycloaliphatic, etc.). Often these are ethylene and C,
Copolymers with ~C3o olefins, particularly preferred are copolymers of ethylene and brobylene. Polyisobutylene, homopolymers and copolymers of C6 and higher α-olefins, ataxysoctribrobylene, and hydrogenated polymers, copolymers and terpolymers of styrene such as isobrene and/or Other polymers such as copolymers with butadiene and hydrogenated derivatives thereof can be used.

The polymer can have its molecular weight reduced, for example, by kneading, extrusion, oxidation or thermal aging; it can also be oxidized and contain oxygen.

Preferred hydrocarbon polymers include 15 to 90 weight percent ethylene, preferably 30 to 80 weight percent ethylene and 10 to 8 weight percent ethylene.
5 weight f' 11% preferably 20 to 70% by weight of one or more C, -C ts preferably C, -C1. More preferably, it is an ethylene copolymer containing C, to C8 α-olefin. Although not required, such copolymers preferably have a crystallinity of less than 25% by weight as measured by X-ray and differential scanning calorimetry. Most preferred is a conjugate of ethylene and propylene. Other α-olefins suitable for use in place of brobylene to form copolymers or in combination with ethylene and brobylene to form terpolymers, quaternary polymers, etc. include: 1-Butene, 1-benotene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-
Examples include decene, 4-methyl-l-bentene,
4-methyl-1-hexene, 5-methylbentene = 14
~C24. Also included are branched α-olefins such as 4-dimethyl-1-bentene, 6-methylpentene-1, etc. or mixtures thereof.

Further, terpolymers, quaternary polymers, etc. of ethylene, the C, -, 3α-olefin and non-conjugated diolefin or mixtures of such diolefins can also be used. The amount of non-conjugated diolefin will generally range from about 0.5 to 20 mole percent, preferably from about 1 to about 7 mole percent, based on the total amount of ethylene and alpha-olefin present.

Polyester (1) improvers are generally polymers of esters of ethylenically unsaturated C2-C5 mono- and dicarboxylic acids, such as methacrylic acid, 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 having at least 1 carbon atom, preferably 12 to 20 carbon atoms, such as decyl acrylate, lauryl acrylate, stearyl acrylate, Examples include eicosanyl acrylate, docosanyl acrylate, decyl methacrylate, diamyl fumarate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and mixtures thereof.

Other esters include C2-C, vinyl alcohol esters of fatty acids or monocarboxylic acids (preferably saturated), such as vinyl acetate, vinyl laurate, vinyl balmitate, vinyl stearate, vinyl oleate, etc. Mixtures may be mentioned. Copolymers of vinyl alcohol esters and unsaturated acid esters, such as copolymers of vinyl acetate and dialkyl fumarate, can also be used.

Esters can also be combined with other unsaturated monomers such as olefins,
For example, from 0.2 to 5 moles of C2 to C5 per mole of unsaturated ester or mole of unsaturated acid or anhydride. It can be copolymerized with aliphatic or aromatic olefins.

For example, copolymers of styrene and maleic anhydride esterified with alcohols and amines are known, see, for example, US Pat. No. 3,702,300.

Dihydrorubyl dithiophosphate metal salts are often used as antiwear additives, but also provide antioxidant activity. Zinc salts are most commonly used in lubricating oils at levels ranging from 0.1 to 10%, preferably from 0.2 to 2% by weight, based on the total weight of the composition.

These are prepared by first adding dithiophosphoric acid, usually alcohol or phenol, to P,S. and by neutralizing the dithiophosphoric acid with a suitable zinc compound.

It is possible to use mixtures of alcohols, including mixtures of primary and secondary alcohols (although in this case the secondary alcohol generally imparts better wear resistance and the primary alcohol provides improved wear resistance). Mixtures of the two are particularly useful. In general, any basic or neutral zinc compound can be used, but
However, oxides, hydroxides and carbonates are most commonly used. Commercial additives often contain excess zinc due to the use of excess basic zinc compounds in the neutralization reaction.

The zinc dihydrorubyl dithiophosphates useful in the present invention are oil-soluble salts of dihydrocarbyl esters of dithiophosphoric acid and have the following formula (XX) [wherein R'' and R 30 are 1-18 preferably 2 ~
It may be the same or different hydrocarbyl groups containing 12 carbon atoms and can be represented by groups containing groups such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic groups. R1
Particularly preferred as the and R'' groups are alkyl groups of 2 to 8 carbon atoms. Thus, such groups include, for example, ethyl, n-propyl, i-propyl, n-butyl, 1-butyl, dibutyl, amyl, n-hexyl, 1
-Hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclono\xyl, methylcyclobentyl, bropenyl, butenyl, etc. To obtain oil solubility, dithiophosphoric acid The total number of carbon atoms in (ie, R''9 and R30 in formula xX) is about 5 or more.

Antioxidants useful in the present invention include oil-soluble copper compounds. Copper compounds can be formulated in oil to provide copper in an oil-soluble form (eg, an oil-soluble copper compound). "Oil-soluble" means that the compound is oil-soluble under normal mixing conditions in the oil or additive package. The copper compound may be in the form of cuprous or cupric. Copper may be in the form of copper dihydrorubylthio or dithiophosphate (where copper can be used in place of zinc in the above compounds and reactions), It is also possible to react the copper oxides with 1 or 2 mol each of dithiA phosphoric acid. Alternatively, copper can be added as a copper salt of a synthetic or natural carboxylic acid. Examples of this include C4-C20-Cl. such as stearic acid or palmitic acid. Due to the favorable handling and solubility of copper carboxylates, unsaturated acids such as oleic acid or branched or synthetic carboxylic acids such as naphthenic acid with a molecular ffi of 200 to 500 are obtained. preferable. In addition, the general formula (R"R"NCSS)nCu (where, n
is 1 or 2, and preferably 1 to 18 R31 and R33 are the same or different hydrocarbyl groups containing 2 to 12 carbon atoms, alkyl, alkenyl,
Also useful are oil-soluble copper dithiocarbamates (including groups such as aryl, aralkyl, alkaryl, and cycloaliphatic groups). Particularly preferred as R'3' and Rs snow groups are alkyl groups of 2 to 8 carbon atoms. Thus, such groups include, for example, ethyl, n-propyl,
i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, rhoheptyl, n-
It may be octyl, decyl, dodecyl, octadecyl, 2ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclobentyl, flobenyl, butenyl, and the like. To obtain oil solubility, carbon atoms (i.e.
The total number of R-IR3-) is generally about 5 or more. It is also possible to use copper sulfonates, phenates and acetylacetonates.

Examples of useful copper compounds are copper (Cu and/or Cu 2 ) salts of alkenylsuccinic acids or anhydrides. The salt itself may be basic, neutral or acidic.

These can be prepared by reacting (a) any of the substances listed above under ashless dispersants (having at least one free carboxylic acid or anhydride group) with (b) a reactive metal compound. can be formed. Suitable acid (or anhydride) reactive metal compounds include such as cuprous or cupric hydroxides, oxides, acetates, borates, carbonates or basic copper carbonates.

Examples of metal salts of the invention are Cu salts of polyisobutenylsuccinic anhydride (hereinafter referred to as Cu-PIBSA) and Cu salts of polyisobutenylsuccinic acid.

Preferably, the metal selected to be used is in its divalent form, e.g. be. The alkenyl group is about 90
Although it is desirable to have an Mn of 0 to 1,400 and up to 2,5 QO, an M of about 950 is most preferred. Among the dispersants listed above, polyisobutylene succinic acid (PIBSA) is particularly preferred.
It is. These materials can, if desired, be 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 not to allow the reaction to remain at temperatures above about 140° C. for extended periods of time, such as for more than 5 hours, or decomposition of the salt may occur.

Copper antioxidants (e.g., Cu-PIBSA, Cu oleate, or mixtures thereof) are commonly used in the final lubricant or fuel oil composition in an amount of about 50 to 5 QQppec (iri) of metal.

The copper antioxidants used in the present 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 used at high temperatures and in high concentrations. In the user's shop, the copper compound does not interfere with the performance of other ingredients in the lubricating oil composition, and in many cases completely satisfactory results are obtained when the copper compound is the only antioxidant in addition to ZDDP. can be obtained. Copper compounds can be used to replace some or all of the required amount of supplemental antioxidants. Thus, for particularly severe conditions, it may be desirable to include supplemental conventional antioxidants. However, the amount of supplemental antioxidant required is small, much lower than that required in the absence of copper compounds.

Although copper antioxidants can be incorporated into lubricating oil compositions in any effective amount, such active ingredients may be added to the lubricating oil composition in amounts of about 50% of the copper added to the lubricating oil composition based on the weight of the lubricating oil composition.
-500 (preferably 10-200, more preferably l
O~180 most preferably 20~130 (e.g. 90
It is contemplated that the amount of copper antioxidant will be sufficient to provide an amount of ~120) 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. Phosphorous sulfide hydrocarbons are prepared by mixing a suitable hydrocarbon such as terpenes, heavy petroleum distillates or C,~06 olefin polymers such as polyimbutylene with 5-30% by weight of phosphorus sulfides at 65-315°C.
It is produced by reacting at a temperature within the range of . Neutralization of phosphosulfide hydrocarbons is described in U.S. Pat.
No. 9,324.

Antioxidants reduce the tendency of mineral oils to deteriorate during use. This deterioration can be evidenced by oxidation products such as sludge and debris deposited on the metal surface and by an increase in viscosity. Such antioxidants are preferably alkaline earth metal salts of alkylphenol thioesters having C, to C1, alkyl side chains, such as calcium nonylphenol sulfur.
Id, B IJ '7 Mutoctylphenyl sulfide, dioctyl phenylamine, phenyl α-naphthylamine, phosphorus sulfide or sulfurized hydrocarbon, 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. 3,933,659 which discloses fatty acid esters and amides, U.S. Pat. , 176
, 074, U.S. Pat. No. 4,05,571 disclosing glycerol esters of dimerized fatty acids, and U.S. Pat. No. 3,779 disclosing anolecan phosphonates.
, 928, U.S. Pat. No. 3,778,375, S., which discloses reaction products of phosphonates and oleamides.
U.S. Pat.
No. 852,205, U.S. Patent No. 3,879,306 disclosing N-(hydroxyalkyl)alkenyl succinamic acids or succinimides, U.S. Patent No. 3,879,306 disclosing reaction products of di(lower alkyl)phosphites and eboxides. No. 3,932,290, and U.S. Pat.
, 028, 258. If necessary,
Please refer to these documents. The most preferred friction modifiers are succinate esters of hydrocarbyl-substituted succinic acids or anhydrides and thiobisalkanols, or metal salts thereof, as described in US Pat. No. 4,344,853.

Pour point depressants (also known as lube oil flow improvers) are those that reduce the temperature at which a liquid flows or can be poured. Typical additives that beneficially optimize the cold flow properties of the liquid include Cl~
C.I. These are dialkyl fumarate/vinyl acetate copolymers, polymethacrylates, and wax naphthalenes.

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

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 salts of alkyl sulfonic acids. Such antirust compounds are well known and can be prepared by conventional means. Nonionic surfactants useful as antirust additives in the oily compositions of this invention typically owe their surface activity to a number of weak stabilizing groups, such as ether bridges. Nonionic rust inhibitor additives with ether bridges are prepared by treating a reactive hydrogen-containing organic substrate with an excess of lower alkylene oxide (such as ethylene oxide and brobylene oxide) until the desired number of alkoxy groups are placed in the molecule. It can be created by .

Preferred rust inhibitor additives are polyoxyalkylene polyols and their derivatives. This group of substances is commercially available from a variety of sources, such as “Plur” from Y. Andotte Chemicals Corporation.
onic Polyols” “Polyglycol” available from Dow Chemical Foam
112-2'' (liquid triol derived from ethylene oxide and brobylene oxide), as well as ``Te'', which can be obtained manually from Union Carbide Corp.
rgitol” (dodecylphenyl or monophenyl polyethylene glycol ether) and “Ucon”
(borealkylene 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 the alkyl- or alkenyl group contains up to about 20 carbon atoms). be.

Preferred polyols are made as block polymers. Thus, to form a hydrophobic base, the hydroxy-substituted compound Q-(OH)n- (where... is 1 to
6 and Q is the residue of a monohydric or polyhydric alcohol, phenol, naphthol, etc.) is reacted with brobylene oxide. This base is then reacted with ethylene oxide to form a hydrophilic portion, thus resulting in a molecule having both hydrophobic and hydrophilic portions. The relative dimensions of these parts can be adjusted by adjusting the proportions of each reactant, reaction times, etc., as will be apparent to those skilled in the art. Thus, the antirust additive is characterized by hydrophobic and hydrophilic portions present in proportions that make it suitable for use in any lubricating oil composition, regardless of differences in pace and the 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.

Examples of compounds exemplifying Q-(Otl)no include alkylene polyols such as alkylene glycol, alkylene triol, and alkylenetetrol, such as ethylene glycol, propylene glyfur, glycerol, pentaerythritol, sorbitol, mannitol, etc. It will be done. It is also possible to use aromatic hydroxy compounds such as alkylated monohydric and polyhydric phenols such as hebutylphenol, dodecylphenol and the like.

Other suitable demulsifiers include U.S. Pat. No. 3,098
, No. 827 and No. 2,674,619.

Liquid polyols available from Y. Andotte Chemical Corporation under the trade name "Pluronic Polyols" and other similar polyols are particularly well suited as rust inhibitor additives. These “Plur
onic Polyols'' has the formula, 110-(CHtC
HtO)z(CICI-0)z' (CHtCHtO)
z' H (X XI) CH. [In the above formula, z, z′ and 2″′ correspond to an integer greater than 1 such that one -cutcuto group accounts for about 10 to about 40% by weight of the total molecular weight of the glycol. Average molecular weight is about 1,000 to about 5,0
It is 00. These compounds are prepared by first condensing brobylene oxide with brobylene glyfur to form the hydrophobic base HO(-CH-CHt-0)z'-H (X
XI) produced by producing CH3. This condensation product is then treated with ethylene oxide to add hydrophilic moieties to both ends of the molecule. For best results, ethylene oxide units should represent about 10 to about 40 percent by weight of the molecule.

The molecular weight of the polyol is about 2,500 to 4,500 and the ethylene oxide units range from about 10 to about 15
% by weight are particularly preferred.

It has a molecular weight of about 4,000 and about 10% of it is (
CI! ．． CH. Polyols derived from units 0) are particularly good. Also, alkoxylated fatty amines, amides, alcohols, etc. and such alkoxylated fatty acid derivatives as described in U.S. Pat. Alkyl-substituted phenols (mono- and dihebutyl, octyl, nonyl, decyl, undecyl,
Also useful are those treated with dodecyl and tridecyl phenols.

These compositions of the invention may also contain other additives such as those mentioned 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 contain between 5 and
Thiadiazole polysulfides containing 50 carbon atoms, their derivatives and their polymers. Preferred materials are those described in U.S. Pat. Nos. 2,719,125, 2,719,126 and 3. 08? ，
3. such as those described in No. 932; It is a derivative of 4-thiadiazole. Particularly preferred is “A
2,5- available on the market as moco 150'''
It is a bis(t-octadithio)-1.3.4-thiadiazole compound. Other suitable similar materials are described in U.S. Pat.
, [1, 236, 3,904, 537, 4,097, 387, 4,107,
No. 059, No. 4. 13fi, (No. 143, No. 4, 188, 299 and No. 4, 193, 8
It is described in No. 82.

Other suitable additives are thiadiazole thio and polythiosulfenamides such as those described in British Patent No. 1,560,830. When these compounds are included in a lubricating oil composition, they are 0.5% based on the weight of the composition. oi-io preferably 0, [~5.0% by weight
It is preferable to have it present in a burial mound.

Any of these numerous additives can provide multiple benefits, such as those of a dispersant monoxidant. 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 in base oils in amounts effective to provide their normal specific function. Typical effects of such additives in fully formulated oils are illustrated below.

Ashless dispersant (component A) Viscosity index improver (component A) Demulsifier (component B) Compatibilizer (component C) Metal detergent (component D) Viscosity modifier Corrosion inhibitor Antioxidant Pour point depressant Foaming agent Anti-wear additive Friction modifier Mineral base oil 0. 1-8 0. 1-200.
01-2 0. 001-100.0(
11-0.03 0,001-0.30.0
01-0.25 0.0005-20. 0
1-3 0. 01-200. 01
-4 0. 01-120.01-1.
5 0.01-50. 01{. 5
0. 01-50.01-1.5
0.01-50. ooi-0. is 0
．． 001-30.001-1.5 0.00
1-50. Ql-1.5 (1, 01-5
Balance When other additives are used, a concentrated solution of the novel dispersant mixture of the present invention or An additive concentrate (the concentrate when forming an additive mixture is referred to herein as an additive package) containing a dispersion (in the concentrate amounts specified above) is prepared, whereby several It may be desirable, although not necessary, to be able to add additives to the base oil at the same time to form a lubricating oil composition or formulation. Dissolution of additive concentrates into lubricating oils can be facilitated by solvents and by mixing with mild heating, but this is not required.

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 base lubricant. is prescribed. Thus, the dispersant mixtures of the present invention can be combined with other desired additives, in addition to a small amount of base oil or other compatible solvent, in appropriate proportions of additives, typically from about 2.5 to about 90% Weight % preferably from about 15 to about 7
Additive packages can be formed containing active ingredients at a collective content of 5% by weight, 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 stated) refer to the active ingredient (A.I.) content of the additive and/or to the A.I. content of each additive. ! ．． It is based on the total weight of the additive package or formulation, which is the sum of the weight and the weight of the gold 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.

Example "221"2 A series of test lubricating oil compositions or other test materials were prepared containing ashless dispersants, metal detergents, viscosity modifiers, and demulsifiers of the present invention. These are listed in Tables ■ and ■ below.

The indicated compositions were tested in a shortened version of the sequence nD test (referred to as I[D Screener) to determine the crankcase pressure developed. In this test, “Ol
dsmobilevs” engine using AST
M-Sequence IID operations were conducted for 12 hours, and the engine was carefully flushed without reconfiguration between experiments. Crankcase pressure was monitored for 12 hours to obtain an integral (cumulative) crankcase pressure value. The data obtained are summarized in Table 3. Thus, this test can be used to predict the tendency of lubricating oils to form emulsions and develop crankcase pressures in sequence nD tests.

Table I: Formulation Ashless Dispersant Day'3.0 Metal Detergent TS+ 0.74 Demulsifier
(See table ■)
The remainder (1) boron-treated polyimbutenyl of polyethylene polyamine (PIB un=2200) (2) overbased magnesium sulfonate detergent (TB
N=400) (3) Solvent (approximately 130) 2x also containing copper antioxidant, zinc dialkyldithiophosphate antiwear additive and ethylene-brobylene copolymer viscosity index improver
-Tol 5 Mineral base oil Table I1 Monolytic emulsifier (1) Polybrobylene glycol, average molecular fit=5
0Go (2) EO = ethylene oxide; Po-propylene oxide; weight ratio based on ethylene oxide and propylene oxide reacted with polybrobylene glycol/diglycidyl ether of bisphenol A adduct (“adduct”) (3) Charged alkylene oxide and the alkylene oxide:adduct ratio table III based on the weight of the adduct. In comparison, and compared to the much higher crankcase pressure generated by the control example without demulsifier (Comparative Example C), Examples 4-
11 shows the surprisingly reduced crankcase pressure obtained from the use of the demulsifier of the present invention in No. 11. The propoxylated demulsifiers of Examples 1-2 produced particularly reduced crankcase pressures and were superior in this respect to the demulsifier of Example 3, which contained equal weights of oxyalkylene units derived from ethylene oxide and propylene oxide. . Comparative Example B illustrates the criticality of the alkoxylation step in producing the demulsifiers of the present invention.

Without wishing to be bound by any theory, the alkoxylation step involves chain-extending the bis-epoxide/polyhydric alcohol adduct by addition of an oxyalkylene moiety to the chain end and converting the bis-epoxide to an epoxy It is believed that the hydroxyl groups in the adduct formed by ring opening of the groups, some of which are not further reacted during the adduct preparation step, are alkoxylated.

Examples 12-18 In a separate series of tests, crankcase lubricant additive packages were prepared having the following ingredients listed in Table 1. Each additive vanocage was stored at 66°C and observed for the onset of haze development, which is an indication of the stability of the additive package.

The data obtained are summarized in Table V below.

Table ■ Additive Concentrate Ashless Dispersant (1) Metal Detergent (2) Demulsifier Compatibilizer (3) Base Oil (4) (See Table V) 0, Q. 5, 1.0 Remainder (I) Polyisobutenyl (P
IB Mn=2200) Succinimide (2) Overbased Mg Sulfonate Detergent (TBN=400) (3)
Data for Solvent (approx. 150) Neutral Mineral Oil Base Oil l1k■ Also Containing Copper Antioxidant, Zinc Dialkyldithioposphate Antiwear Additive, Ethylene Propylene Copolymer Viscosity Index Improver and Supplementary Nonylphenol Sulfide Antioxidant exemplifies the improved additive package stability observed with the use of the demulsifiers and compatibilizers of the present invention. Substantial improvement in haze reduction was achieved when the proboxylated demulsifier of Example 2 at a weight ratio of brobylene oxide to adduct of 0.61 was combined with the compatibilizer of the present invention. In Example 12, clouding was observed after 5 days, whereas in the additive package of Example 13, no clouding appeared even after 96 days of storage at 66°C. Example l5 to example l
Also by comparing the additive packages of Examples 17 and 1 (where no compatibilizer was used)
8 (using various amounts of compatibilizer) with the additive package of Example 16, with a P○ to adduct ratio of 3:1. Similar improvements in haze development are obtained when emulsifiers are used in conjunction with the compatibilizer 11 of the present invention.

Examples 19-24 In separate experiments, 1 o part of 3150N lubricant, 55
1 part ashless dispersant (polyisobutenyl succinimide of a polyethylene polyamine having about 7 carbon atoms and 5 to 6 nitrogen atoms per polyamine molecule) and 11 parts metal detergent (overbased Mg sulfonate, TBN= 400
A series of lubricating oil concentrates ("Additive Packages") were prepared by mixing (1) for 3 hours at a temperature of 100°C. An aliquot of each mixture was then taken and observed to be clean without any visible haze or sediment.

The temperature of each mixture was cooled to 75°C and then the next additional ingredient was introduced. In this case, the ingredients listed are in a respective mixture of a zinc dialkyl dithiophosphate i wear additive, a nonylphenol sulfide antioxidant, and a copper antioxidant to form a partial adpack (95.3 parts). used at the same concentration.

A predetermined amount of the demulsifier and compatibilizer of the present invention was introduced into each partial add pack (at 75° C.) along with enough lubricating oil to fill the balance of 100 parts by weight of lubricating oil concentrate. The mixing order of these additional ingredients was changed as follows.

Left Hiro A. The additional required base oil, the demulsifier of Example I and the indicated compatibilizer are introduced separately into the partially admixture with stirring at 75 DEG C. for 1.5 hours.

Method B-1: Additional required base oil, demulsifier of Example 1 and compatibilizer 1 are first premixed together at 75° C. for 1 hour, and the resulting premix is mixed in a partial add-back for 7 hours.
The mixture is introduced with stirring for a further 1.5 hours at 5°C.

Method B-2: The additional required base oil, the demulsifier of Example I and the compatibilizer ■ are first mixed together at 75° C. for 1 hour, and the resulting premix is mixed into a partial A-F hack. ℃
Then introduce with mixing for an additional 1.5 hours.

Each lubricating oil concentrate was then observed for appearance and each aliquot was stored for an extended period of time at either 54°C or 66°C to observe its appearance and to check for other signs of clouding onset or instability of the mixture. I checked the symptoms. The results obtained are shown in Table 3 below.

The above data demonstrate the improved storage stability obtained by premixing the demulsifiers and compatibilizers of the present invention prior to contacting the demulsifiers with the remaining components of the additive package. The results are shown in comparison with the case where the same amounts of demulsifier and compatibilizer were used instead. Example 22
The storage stability achieved by premixing the demulsifier and the lyluic acid dimer glycol ester additive in Example 19 (compared to the results achieved without such premixing in Example 19) was as previously described. This is particularly surprising in light of the prior art knowledge that instability problems have previously been observed when using such strong esters as friction modifiers.

Storage stability was also improved by premixing the demulsifier with a high concentration of linonylic acid dimer glycol ester additive in Example 23 and by premixing the same high concentration of glycerol monooleate additive in Example 24. was obtained (compared to the result obtained without such premixing in Example 2l).

In the above description, the principles, preferred embodiments, and modes of operation of the invention have been described. However, this invention should not be construed as limited to the particular embodiments disclosed herein. This is because they are to be considered illustrative rather than restrictive. For those skilled in the art:
This is because numerous changes and modifications can be made without departing from the spirit of the invention.

Claims (22)

[Claims] (1) (A) (I) (i) oil-soluble salts, amides, imides, oxazolines and esters of long-chain hydrocarbon-substituted mono- and dicarboxylic acids or their anhydrides, or mixtures thereof; (ii) polyamines directly by condensing the attached long chain aliphatic hydrocarbon and (iii) about 1 molar proportion of the long chain hydrocarbon substituted phenol with about 1 to 2.5 moles of formaldehyde and about 0.5 to 2 moles of polyalkylene polyamine. The Mannich condensation products formed, where the long chain hydrocarbon groups in (i), (ii) or (iii) are polymers of C_2-C_1_0 e.g. C_2-C_5 monoolefins with a number average of at least about 900 (II) (i) vinyl alcohol or C_3 to C_1_0
C_4 to C_2_ of unsaturated mono- or dicarboxylic acids
A polymer consisting of a 4-unsaturated ester and an unsaturated nitrogen-containing monomer having 4 to 20 carbon atoms, (ii) C_2~
Polymers of C_2_0 olefins and unsaturated C_3-C_1_0 mono- or dicarboxylic acids, neutralized with amines, hydroxyamines or alcohols, and (i
ii) A polymer of ethylene and a C_3-C_2_0 olefin is grafted with a C_4-C_2_0 unsaturated nitrogen-containing monomer or the polymer backbone is grafted with an unsaturated acid and the carboxylic acid group is grafted with an amine, hydroxyamine or At least one member selected from the group consisting of a polymer viscosity index improver/dispersant including one further reacted by reacting with an alcohol, and (III) a mixture of the above (I) and (II). and (B) a demulsifier consisting of a reaction product of an adduct obtained by reacting a bisepoxide with a polyhydric alcohol and an alkylene oxide. Oil-soluble mixture. (2) The oil-soluble mixture according to claim 1, wherein the bisepoxide is diglycidyl ether of bisphenol A. (3) The oil-soluble mixture according to claim 2, wherein the demulsifier is a propoxylated derivative of the adduct. (4) The oil-soluble mixture of claim 3, wherein the demulsifier contains about 10 to 80% by weight of oxyalkylated units derived from propylene oxide. (5) The oil-soluble mixture according to claim 1, wherein the polyhydric alcohol is polyoxyalkylene glycol. (6) About 1,000 polyoxyalkylene glycols
An oil-soluble mixture according to claim 5 having a number average molecular weight of -10,000. (7) The oil-soluble mixture according to claim 6, wherein the polyoxyalkylene glycol is polypropylene glycol. (8) Polypropylene glycol is about 2,000 to 8,
8. The oil-soluble mixture according to claim 7, having a number average molecular weight of 0.000. (9) The ashless dispersant is a hydrocarbyl-substituted C_4~ formed by reacting (a) an olefin polymer of a C_2-C_1_0 monoolefin having a number average molecular weight of at least about 900 and a C_4-C_1_0 monounsaturated acid material; C_1_0 monounsaturated dicarboxylic acid-forming material, which forms an average of at least about 0.8 dicarboxylic acids per olefin polymer molecule present in the reaction mixture used to form the acid-forming material. and (b) a nucleophilic reactant selected from the group consisting of amines, alcohols, amino alcohols and mixtures thereof. blend. (10) the nucleophilic reactant comprises a polyalkylene polyamine, where the alkylene group contains from 2 to 40 carbon atoms, and the polyalkylene polyamine contains from 2 to about 9 nitrogen atoms per molecule; The oil-soluble mixture according to claim 9, comprising: (11) Olefin polymer is approximately 1,500 to 3,000
11. The oil-soluble mixture of claim 10, wherein the monounsaturated acid material comprises maleic anhydride. (12) The oil-soluble mixture has added at least one metal detergent consisting of at least one magnesium or calcium salt of a substance selected from the group consisting of sulfonic acids, alkylphenols, sulfurized alkylphenols, alkylsalicylates, and naphthenates. The oil-soluble mixture according to claim 1, which contains: (13) at least one compatibilizer consisting of a glycol ester or hydroxyamide derivative of a mono- or polycarboxylic acid having a total number of 24 to 90 carbon atoms per molecule and at least about 1 carboxylic acid group; 13. The oil-soluble mixture according to claim 12, additionally containing a compatibilizing amount. (14) The oil-soluble mixture according to claim 13, wherein the polycarboxylic acid glycol ester has about 2 to 3 carboxylic acid groups per molecule. (15) The compatibilizer has the formula HO-J'-OOC-J-COOH or HO-J'-OOC-J-COOJ''-OH [wherein J
has a total number of carbon atoms of about 24 to 90 per molecule and about 2 to
J 15. The oil-soluble mixture according to claim 14, comprising at least one partial ester or diester of the formula ' and J'' being the same or different and each consisting of an alkanediol or an oxyalkylene hydrocarbon group. 16. The oil-soluble mixture of claim 13, wherein the compatibilizer is used in an amount of about 0.1 to 5 parts by weight based on the total weight of demulsifier in the oil-soluble mixture. (17) The oil-soluble mixture according to claim 13, wherein the compatibilizer comprises at least one dimer acid ester friction-reducing ester. (18) The oil-soluble mixture according to claim 13, wherein the compatibilizer comprises at least one ester of substituted cyclohexenedicarboxylic acid formed by Diels-Alder thermal condensation of C_1_8 to C_2_2 unsaturated fatty acids. (19) The oil-soluble mixture according to claim 13, wherein the compatibilizer is a glycol ester. (20) The oil-soluble mixture according to claim 19, wherein the unsaturated fatty acid is oleic acid, linoleic acid, or a mixture thereof. (21) The compatibilizer has the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, D is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and X' is an integer from 1 to 100] 20. The oil-soluble mixture according to claim 19, comprising an ester of. (22) providing a first additive mixture comprising (i) at least one ashless dispersant lubricant additive and at least one metal detergent; (ii) at least one demulsifier and at least one metal detergent; an improved oil additive useful as an oil additive comprising providing a second additive mixture comprising a compatibilizer and mixing the first and second additive mixtures to produce an improved storage stable concentrate; A method for producing a storage-stable concentrate, wherein (A) the lubricating oil dispersant comprises (i) oil-soluble salts of long-chain hydrocarbon-substituted mono- and dicarboxylic acids or anhydrides thereof, amides, imides, oxazolines, and ester or mixture thereof, (ii) a long chain aliphatic hydrocarbon to which a polyamine is directly attached, and (iii) approximately 1 molar proportion of a long chain hydrocarbon-substituted phenol, together with about 1 to 2.5 moles of formaldehyde and about 0.5 mole of formaldehyde. 5 to 2 moles of at least one substance selected from the group consisting of polyalkylene polyamines, in which case (i), (ii) or (iii)
The long chain hydrocarbon groups in C_2 to C_1_0, e.g. C
a polymer of _2 to C_5 monoolefins having a number average molecular weight of at least about 900, and wherein the dispersant is sufficient to provide a dispersant concentration of about 3 to 45% by weight in the concentrate. (B) the demulsifier comprises the reaction product of an adduct obtained by reacting a bisepoxide with a polyhydric alcohol and an alkylene oxide; (C) the compatibilizer has a total number of carbon atoms of 24 to 90 and at least about 1 per molecule; a glycol ester or hydroxyamide derivative of a mono- or polycarboxylic acid having carboxylic acid groups, and the compatibilizer provides a compatibilizer concentration of about 0.0005 to 2% by weight in the concentrate. and (D) the metal detergent material consists of a calcium salt or from the group consisting of sulfonic acids, alkylphenols, sulfurized alkylphenols, alkyl salicylates, and naphthenates; used in an amount sufficient to provide a detergent concentration of about 2 to 45% by weight.