CA2030096A1

CA2030096A1 - Gear oils and additives therefor

Info

Publication number: CA2030096A1
Application number: CA002030096A
Authority: CA
Inventors: Stephen Norman; Gregory S. Conary
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 1989-11-27
Filing date: 1990-11-15
Publication date: 1991-05-28
Also published as: JPH03258898A; EP0430624A1; AU627957B2; AU6683790A

Abstract

GEAR OILS AND ADDITIVES THEREFOR

Abstract of the Disclosure Clean gears in the L-60 Test result from the use of gear oils containing, in combination, (i) a carboxylic derivative such as a succinimide, boronated succinimide, succinic acid ester, boronated succinic acid ester, succinic acid salt, (or any mix-ture of these), in which the succinic moiety is substituted by a group derived from polyalkene having an Mn value of about 500 to about 10,000; and (ii) one or more fully-esterified hydrocarbyl esters of a phosphoric acid or phosphorothioic acid. Preferably there is also present one or more amine salts of one or more long chain monocarboxylic acids or of one or more long chain poly-carboxylic acids or of a mixture of one or more long chain mono-carboxylic acids with one or more long chain polycarboxylic acids.

Description

203009~
Case EI-6087 G~'AR OILS AND_ADDITIVE5 THEREFOR

Technical Field : ' This invention relates to gear oils and gear oil addi-tive formulations having enhanced performance characteristics. ' More particularly this invention relates to gear oil and gear oil 5 additive compositions having enhanced antiwear and extreme pressure properties.

Backaround In order to satisfy the performance criteria imposed upon automotive and industrial gear oils, a large number of addi-lO tives and additive formulations have been proposed for use in gear oils. Generally speaking, most commercially used gear oil additive packages contain, inter alia, one or more phosphorus-containing components, one or more sulfur-containing components, and one or more nitrogen-containing components. Indeed, one or lS more of these additives can contain two, and possibly all three, of the elements P, S and N. But irrespective of the number and chemical composition of the individual additives employed, the commercially-used gear oil additive packages generally have an over-all sulfur-to-phosphorùs weight ratio in the range of about 20 5:1 to about 40:1, and an over-all nitrogen-to-phosphorus weight ratio in the range of about 0.05:1 to about 2:1.

.,.
Among the phosphorus-containing additives proposed for use in gear oils are monoalkyl phosphites and phosphates, dialkyl phosphites and phosphates, trialkyl phosphites and phosphates, 25 monoaryl phosphites and phosphates, diaryl phosphites and phos-2 0 3 0 0 9 6 case EI-6087 phates, triaryl phosphites and phosphates, long chain phosphoric or phosphonic acids and esters, alkyl acid phosphates, alicyclic esters of phosphoric acids, and the like. Included among the sulfur-containing additives proposed for use in gear oils are 5 sulfurized olefins, alkyl polysulfides, sulfurized fatty oils, sulfur chloride treated fatty oils, sulfurized terpenes, metal sulfides, and the like. Nitrogen-containing additives proposed for use in gear oils include substituted imidazolines, fatty amides, long chain amines, long chain imides, aromatic amines, 10 alkenyl succinimides, amine salts of high molecular weight organic acids, alkylamines, polyacrylamides, triazole deriv-atives, and the like. Some of the additives containing at least two of the elements P, S and N in the same molecule proposed for gear oil usage are dithiophosphoric acid esters, zinc dithio-15 phosphates, zinc and lead dithiocarbamates, phosphosulfurizedterpenes, thiadiazoles, amine phosphates, olefin/phosphorus pentasulfide reaction products, and the like.

Unfortunately, during actual service conditions, a number of phosphorus-containing antiwear and extreme pressure 20 additives tend to separate from the gear lubricant in the form of . .
insoluble sludge or other residues. This phenomenon of additive separation from the base oil is generally believed to result from insufficient thermal and/or oxidative stability of the components utilized. Whatever the mechanism, the result is most undesir-.

25 able. A need thus exists for an effective and efficient way of overcoming this adverse problem.
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-- Another problem confronting the art is the tendency of a number of technologicallY-adVanced gear oil packages to yield gear oils which in the standard L-60 Test produce excessive de-30 posits on the gear face- Oftentimes these deposits average as Case EI-6087 much as 0.02 to 0.03 millimeters in thickness on the gear face on completion of the test. For example, ANGLAMOL 6063A, a commer-cial gear oil additive formulation available from The Lubrizol Corporation -- a product believed to contain, inter alia, 5 sulfurized isobutylene, dialkyl polysulfide, and a phosphorus-based antiwear complement, when employed at the recommended dosage level of 6.25 weight percent was found t~ produce black deposits on the L-60 gear face. Likewise, a commercial gear oil formulation available from Ethyl Petroleum Additives, Inc., as 10 HITEC~ 320 additive, when used at the recommended dosage level of 5.25 weight percent also produces black deposits on the gear face in the L-60 test. Elemental analysis of these two products shows the former contains, on a weight basis, 1.4% of P, 27.8% of S, and 0.69% of N. Thus the ANGLANOL 6063A additive formulation 15 has a sulfur:phosphorus weight ratio of about 20:1, and a nitro-gen:phosphorus weight ratio of about 0.5:1. In the HITEC~ 320 additive formulation these ratios are, respectively, 16.3:1 and 0.4:1. Similar considerations apply, both as regards over-all . chemical composition and L-60 gear face performance, to several 20 other commercially available gear oil additive packages.

The formation of such deposits on the gear face in L-60 tests is an undesirable result which has led some consumers to the erroneous belief that the commercial additive package has inadequate thermal stability- Accordingly the industry has been ~-25 revising their additive packages to provide formulations which give relatively clean gear faces in the L-60 test.

The Invention This invention provides gear oil and gear oil additive formulations which exhibit enhanced antiwear and extreme pressure 30 properties during all types of conventional service conditions.
By use of particular combinations of additives, premature thermal ~; - 3 -Case EI-6087 and/or oxidative degradation of the phosphorus antiwear and ex-treme pressure components is inhibited, and moreover, the active phosphorus residues resulting from the use of such components re- .
main dissolved or at least suspended in the gear oil so that they 5 can continue to exert their beneficial effects. In.other words, the phosphorus-containing antiwear and extreme pressure additives employed pursuant to the practice of this invention do not prema-turely precipitate out in the form of sludge or other insoluble residues -- they remain available within the body of the lubri-10 cant to exert their antiwear and extreme pressure functions.

In accordance with one of its embodiments, this inven-tion provides a gear oil composition comprising a major amount of a gear oil base stock containing a sulfur additive complement, a phosphorus additive complement, and a nitrogen additive comple-lS ment, in proportions such that the composition possesses a weight ratio of sulfur to phosphorus in the range of about S:l to about 40:1 and a weight ratio of nitrogen to phosphorus in the range of about 0.05:1 to about 2:1, said gear oil additionally containing a minor effective amount of:

(i) ~.at least one carboxylic derivative composition produced by reacting at least one.substituted succinic acylating agent with a reactant selected from the group consisting of (a) amine having at least one primary or secondary amino group in the molecule, (b) alcohol, (c) reactive metal or reactive metal com-25 pound, and (d) a combination of two or more of any of (a) through (c) the components of (d) being reacted with such substituted suc-cinic ac.ylating agent(s) simultaneously or sequentially in any order, wherein such substituted succinic acylating agent(s) has/
have a substituent group derived from polyalkene having an Mn 30 value of about 500 to about 10,000 (preferably in the range of about 750 to about 5,000), and Case EI-6087 (ii) at least one oil-soluble fully-esterified hydro-carbyl ester of a phosphoric acid or at least one oil-soluble fully-esterified hydrocarbyl ester of a phosphorothioic acid, or a combination of at least one oil-soluble fully-esterified hydro-5 carbyl ester of a phosphoric acid and at least one oil-soluble fully-esterified hydrocarbyl ester of a phosphorothioic acid.
Such gear oil compositions exhibit enhanced antiwear and extreme pressure performance by virtue of the above-referred-to coopera-tion between components (i) and (ii).

In another of its embodiments this invention provides a gear oil additive concentrate which includes a sulfur additive complement, a phosphorus additive complement, and a nitrogen addi-tive complement, in proportions such that the concentrate pos-sesses a weight ratio of sulfur to phosphorus in the range of 15 about 5:1 to about 40:1 and a weight ratio of nitrogen to phos-phorus in the range of about 0.05:1 to about 2:1, said concen-trate additionally containing a minor effective amount of compo-- nents (i) and (ii) as described above.

A further embodiment of this invention involves the 20 additional presence in the above gear oils and gear oil additive concentrates of a third component whereby the resultant gear oil or gear oil additive concentrate exhibits enhanced performance in the L-60 Test. Accordingly, this invention further provides a gear oil composition comprising a major amount of a gear oil base 25 stock and a minor effective amount of:
(i) at least one carboxylic derivative composition pro-duced by reacting at least one substituted succinic acylating agent with a reactant selected from the group consisting of (a) amine having at least one primary or secondary amino group in the 30 molecule, (b) alcohol, (c) reactive metal or reactive metal com-pound, and (d) a combination of two or more of any of (a) through (c) the components of (d) being reacted with such substituted Case EI-6081 succinic acylating agent~s) simultaneously or sequentially in any order, wherein such substituted succinic acylating agent(s) has/
have a substituent group derived from polyalkene having an Mn value of about 500 to about lO,000 (preferably in the range of 5 about 750 to about 5,000);
(ii) at least one oil-soluble fully-esterified hydro-carbyl ester of a phosphoric acid or at least one-oil-soluble fully-esterified hydrocarbyl ester of a phosphorothioic acid, or a combination of at least one oil-soluble fully-esterified hydro-lO carbyl ester of a phosphoric acid and at least one oil-soluble fully-esterified hydrocarbyl ester of a phosphorothioic acid; and (iii) at least one amine salt of one or more long chain (e.g., C8 to C50) monocarboxylic acids or at least one amine salt of one or more long chain (e.g., C8 to C50) polycarbox-15 ylic acids, or a combination of at least one amine salt of one ormore long chain monocarboxylic acids and at least one amine salt of one or more long chain polycarboxylic acids. Such gear oils form little or no deposits on the gear face when the gear oil is subjected to the standard L-60 Test ~formerly the CRC L-60 Test 20 and FTMS 791B Method 2504) as set forth in ASTM Special Technical Publication 512A, Copyright 1986, Library of Congress Catalog No.
86-20566. Thus the compositions of this invention exhibit superior-properties as seen in the L-60 test.

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Without desiring to be bound by theoretical consider-25 ations, it is believed that the succinic derivative (component ti) above) prevents the formation of sludge during the L-60 test and that the amine salt (component (iii) above) forms, because of its polarity, a film on the surfaces of the gear faces in the L-60 test and prevents harder carbonaceous deposits from forming 30 on such surfaces. In addition, the trihydrocarbyl phosphoric species (component (ii) above) imparts an unusually high degree of thermal and/or oxidative stability which greatly reduces the .. . .. .. . ..

- 20~0096 Case EI-6087 tendency of sludge formation involving such trihydrocarbyl phos-phoric species. The overall mechanism allows the active phos-phoric residues to remain dissolved or at least suspended in the gear oil so that they can continue to exert their substantial 5 beneficial effects. Irrespective of the actual mechanism or mechanisms involved, the net result of the use-of these compo-nents in combination is that excellent extreme pressure and anti-wear effects are achieved and, additionally, the gear faces obtained from the L-60 test are clean or essentially clean.

In yet another embodiment of this invention, there are provided gear oil additive concentrates containing components (i), (ii), and (iii) as above described.

The gear oil additive concentrates of this invention are generally employed in suitable lubricant base stocks in amounts 15 ranging from about 1 to about 15~ by weight. For automotive gear oil use, it is preferred to employ the additive concentrates in amounts in the range of about 2.5 to about 15 weight percent and for industrial use, amounts in the range of about 1 to about 4 weight percent.

In the interest of brevity, the above-defined carboxylic derivative compositions are collectively referred to as "succinic derivatives". Likewise, unless otherwise specified, the products formed from reactant (a) or a combination of reactant (a) with one or more of reactants (b) and/or (c) are collectively referred 25 to as "succinimides", a term which is meant to encompass the com-pleted reaction product from the reaction irrespective of whether the product contains amide, amidine, ester, and/or salt linkages in addition to the imide linkage of the type that results from the reaction of a primary amino group and an anhydride moiety.
30 Similarly, the products formed from reactant (b) or a combination 2 0 3 0 0 9 6 Case EI-6087 of reactant tb) with reactant (c) are collectively referred to as "succinic esters", a term which is ~eant to encompass the com-pleted reaction product from the reaction irrespective of whether the product contains salt linkages in addition to the ester link-5 age of the type that results from the reaction of a hydroxylgroup and an anhydride moiety.

The succinimides and succinic esters can, in accordance with still further embodiments of this invention, be chemically modified by boronation, e.g., the succinimide(s) and succinic 10 ester(s) can be reacted with boric acid or liXe boron-containing reactant in order to incorporate a small amount (usually in the range of 0.5 to 2 wt.%) of boron into the chemical structure of the succinimide(s) and/or succinic ester(s). Higher or lower concentrations of boron in such succinimide(s) and/or succinic lS ester(s) are feasible. For the sake of brevity, such boron-containing succinimides and boron-containing succinic esters will be collectively referred to hereinafter as "boronated succini-mides" and "boronated succinic esters", respectively.

A feature of this invention is that the chemical compo-20 sition of the sulfur- and nitrogen-containing additive complement -- and, except for component (ii), the chemical composition of additional phosphorus-containing additive(s) -- in the gear oil and gear oil additive formulations can be widely varied and thus is of no concern as regards the practice of this invention.

25 Likewise, the chemical composition and properties of the other _ -additives employed in the formulations (e.g., defoamers, demulsi-fiers, sulfur scavengers, diluents, stabilizers, antioxidants, metal deactivators,`poUr point depressants, etc.) form no part of this invention. It is to be noted that when preparing the gear ~ ~t~
30 oil additive concentrateS, individual components may interact Case EI-6087 with each other to produce new chemical compounds, as for exam-ple, a basic substance reacting with an acidic substance to form a salt or salt-like compound. As long as the concentrate per-forms the functions of a conventional gear oil additive formu-5 lation, the concentrate is suitable for use in the practice ofthis invention.

Preferred gear oil additive packages of this invention are soluble in mineral and synthetic base oils to the extent of at least 15 weight percent at 25-C.

The above and other features and embodiments of this invention will become still further apparent from the ensuing description and appended claims.

Inasmuch as the composition, characteristics, and methods for the preparation of the various additives used in the 15 production of gear oils are well known to those skilled in the . art, a description of such components is relegated to the final portions of this specification. At this juncture suffice it to say that the additive concentrates of this invention will contain succinic derivative(s) (i.e., component (i) above), preferably 20 one or more succinimides or boronated succinimides, in an amount ranging from about S to about 20 (and preferably from about 10 to about 15) weight percent of the total composition. Likewise, the additive concentrates of this invention will contain from about 5 to about 40 and preferably from about 10 to about 30 weight 25 percent of one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphoric acid or one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphorothioic acid, or a combination of one or more oil-soluble fully-esterified hydro-carbyl esters of a phosphoric acid or one or more oil-soluble 30 fully-esterified hydrocarbyl esters of a phosphorothioic acid 20300~6 Case EI-6087 (i.e., component (ii) above). In the embodiments of this invention involving component (iii) above, the additive con-centrate will additionally contain from about 0.5 to about 5 weight percent of one or more amine salts of one or more 5 aliphatic carboxylic acids (i.e., component (iii) above).

By the same token, the finished gear oils of this inven-tion will contain from about 0.2 to about 2.0, and preferably from about 0.5 to about 1.5, weight percent of the succinic deriv-ative(s) -- e.g., succinimide(s) and/or boronated succinimide(s) 10 and/or succinic ester(s) and/or boronated succinic ester(s) (or any mixture of any two or more of the foregoing) -- and from about 0.1 to about 3.0, and preferably from about 0.5 to about 2.0 weight percent of component (ii) above, (i.e., one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphoric 15 acid or one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphorothioic acid, or a combination of one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphoric acid or one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphorothioic acid). The finished gear oils of 20 this invention which additionally contain component (iii) above (i.e., the amine salt(s) of one or more long chain aliphatic acids) will contain from about 0.05 to about 0.5, and preferably from about 0.08 to about 0.4 weight percent of component (iii).
Although components (i) and (ii) have been separately used 25 heretofore in gear oils, it is believed that they have not been used in combination with each other in gear oils, muchless in gear oil compositions yielding the superior antiwear and extreme pressure properties which characterize this invention. Likewise, although components (i) and (iii) have been separately used 30 heretofore in gear oils and although components (ii) and (iii) have been used in combination with each other heretofore in gear oils, it is believed that neither components (i) and (iii) nor 20300~6 Case EI-6087 components (i), (ii) and (iii) have been used in combination with each other in gear oils muchless in gear oil compositions yield-ing the results obtainable by the practice of this invention.

The additive concentrates of this invention can be 5 blended into any of a wide variety of lubricant base stocks when forming the finished lubricants of this invention. -The base oils for such use are generally mineral oil base stocks such as for example conventional and solvent-refined paraffinic neutrals and bright stocks, hydrotreated paraffinic neutrals and bright lO stocks, naphthenic oils, cylinder oils, etc., including straight run and blended oils. Synthetic base stocks can also be used in the practice of this invention, such as ~or example poly-alpha-olefin oils (PA0), alkylated aromatics, polybutenes, diesters, polyol esters, polyglycols, polyphenyl ethers, etc., and blends 15 thereof. Typical of such oils are blends of poly-alpha-olefins with synthetic diesters in weight proportions (PAO:ester) ranging from about 95:5 to about 50:50, typically about 75:25. Generally speaking, the base stocks used in automotive gear oils range in viscosity grades from SAE 50 to 250 and preferably from 70 to 20 140. Suitable automotive gear oils also include cross-grades such as 75W-140, 80W-90, 85W-140, 85W-90, and the like. In general, the base stocks used in industrial gear oils will have a viscosity in the range of from about IS0 grade 32 to IS0 grade 680 and preferably from IS0 grade 68 to IS0 grade 460.

In order to illustrate the practice of this invention, the following examples are presented. It is to be understood and appreciated that these examples are not intended to constitute, nor should they be construed as constituting, limitations on the invention. In these examples, all parts and percentages are by 30 weight, and in each case the compositions have a S:P weight ratio in the range of 5:1 to 40:1 and an N:P weight ratio in the range Case EI-6087 of 0.05:1 to 2:1. Likewise, the succinimide referred to in the examples is the product formed from polyisobutenylsuccinic anhy-. _.
dride and ethylene polyamine mixture approximating tetraethylene-pentamine in composition; the isobutenyl group being derived from 5 polyisobutene having an Mn of about 1300. The boronated succini-mide referred to in the examples is the product formed by react-- ing such succinimide with boric acid at a temperature of above 150-C in quantity sufficient to yield a boron content in the product of about 1.3% by weight. Succinimides and boronated lO succinimides are generally formed in the presence of a diluent for processing purposes. Thus in the ensuing examples, the pro-portions of succinimide or boronated succinimide represent the weight percentage of a blend composed of approximately 67% of the active ingredient (i.e., the succinimide or boronated succini-15 mide), and approximately 33% of a mineral oil diluent. Further, in the ensuing examples the trihydrocarbyl dithiophosphate repre-sents the following individual esters: (a) the product formed by reacting di(2-ethylhexyl)dithiophosphoric acid with wax olefin, . (b) the product obtained by reacting diamyldithiophosphoric acid 20 with alpha-pinene, (c) the product obtained by reacting diethyl-dithiophosphoric acid with bicycloheptadiene, (d) the product obtained by reacting di(2-ethylhexyl)dithiophosphoric acid with l-butene, (e) the product obtained by reacting dimethyldithio-phosphoric acid with dicyclopentadiene, (f) the product obtained 25 by reacting di-2-ethylhexyl dithiophosphoric acid with cyclo-octadiene, (g) the product obtained by reacting di-2-ethylhexyl dithiophosphoric acid with styrene, (h) the product obtained by reacting a mixed dialkyldithiophosphoric acid with dicyclopen-tadiene,-wherein the alkyl groups are isopropyl, isobutyl, and 30 hexyl, (i) the product obtained by reacting a mixed dialkyldi-thiophosphoric acid with dicyclopentadiene, wherein the alkyl groups are isopropyl, isobutyl, and 2-ethylhexyl, (j) the product obtained by reacting a mixed dialkyldithiophosphoric acid with Case EI-6087 dicyclopentadiene~ wherein the alkyl groups are amyl, hexyl, and 2-ethylhexyl, (k) the product obtained by reacting a mixed di-alkyldithiophosphOric acid with styrene, wherein the alkyl groups --are isopropyl, isobutyl, and hexyl, (l) the product obtained by 5 reacting a mixed dialkyldithiophosphoric acid with styrene, where-in the alkyl groups are isopropyl, isobutyl, and 2-ethylhexyl, (m) the product obtained by reacting a mixed dialkyldithiophos-phoric acid with styrene, wherein the alkyl groups are amyl, hexyl, and 2-ethylhexyl, (n) the product obtained by reacting 10 di-2-ethylhexyl dithiophosphoric acid with divinylbenzene, and (o) the product obtained by reacting di-2-ethylhexyl dithiophosphoric acid with butadiene.

A gear oil additive concentrate of this invention is 15 composed of the following ingredients:

Succinimide 15.0%
Trihydrocarbyl dithiophosphate 17.0%
` Octyl amine salt of lauric acid 3.0%
Sulfurized isobutylene40.0%
Alkyl phosphite and phosphate 5.0%
Alkyl amine 1.9%
Defoamer and demulsifiero.g%
Sulfur scavenger 1.3%

Mineral oil diluent 15.9%

25 Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a 30 concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6-5%- For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

Case EI-60~7 The procedure of Example 1 is repeated except that the succinimide is boronated succinimide.

The procedure of Example 1 is repeated except that the additive concentrate contains 12.0~ of the succinimide and 19.2%
of the mineral oil diluent.

A gear oil additive concentrate of this invention is 10 composed of the following ingredients:

Succinimide 13.3%
Trihydrocarbyl dithiophosphate 18.8%
Octyl amine salt of stearic acid 1.7%
Sulfurized isobutylene38.7%
15 Alkyl phosphite and phosphate 5.5%
Alkyl amine 2.1%
Defoamer and demulsifier1.0%
. Sulfur scavenger 1.4%
Mineral oil diluent 17.5%

20 Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower,-the formulation is used at a 25 concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

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- ~ EXAMPLE 5 The procedure of Example 4 is repeated except that the succinimide is boronated succinimide.

Case EI-6087 A gear oil additive ~oncentrate of this invention is composed of the following ingredients:

Succinimide 16.6%
Trihydrocarhyl dithiophosphate 18.8%
Octyl amine salt of stearic acid 3.3%
Sulfurized isobutylene44.2%.
Alkyl phosphite and phosphate 5.5%
Alkyl amine 2.1%
Defoamer and demulsifier1.0%
Sulfur scavenger 1.4~
Mineral oil diluent 7.1%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral 15 oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 7S or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with 20 ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15~. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 6 is repeated except that the 25 succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 16.6%
Trihydrocarbyl dithiophosphate 18.8%
Octyl amine salt of stearic acid 1.7%
Sulfurized isobutylene44.1%
Alkyl phosphite and phosphate 5.5%

2030~96 Case EI-6087 Alkyl amine 2.1%
Defoamer and demulsifier1.0%
Sulfur scavenger 1.4%
Mineral oil diluent 8.8%

5 Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a 10 concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with IS0 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 8 is repeated e~cept that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is 20 formed by blending together the following components in the proportions specified:

Succinimide 9.2%
Trihydrocarbyl dithiophosphate 12.3%
Process oil 8.5%
Anglamol 6063A* 70 0%

* A proprietary gear oil additive formulation commercially available from The Lubrizol Corporation Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral 30 oil and synthetic oil base stocks- For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a ~3~9 6 case EI-6087 concentration of 13.4%. For automotive use, with SAE grades heavier than 75, the treat rate is 8.9%. For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 3.5%, and the finished 5 oil should contain at least 0.3% demulsifier. Any such base stocks may contain a viscosity index improver, if desired.

EXAMPLE_ll The procedure of Example 10 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 12.0%
Trihydrocarbyl dithiophosphate 17.0%
Lauryl amine salt of lauric acid 2.0%
Dialkyl polysulfide 35.0%
Alkyl phosphite and phosphate 5.0%
Alkyl amine 1.9%
Defoamer 0.6%

Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent 24.9%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral 25 oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with 30 ~S0 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

2030096 case EI-6087 The procedure of Example 12 is repeated except that the succinimide is boronated succinimide.

5A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 15.0%
Trihydrocarbyl dithiophosphate 17.0%
Dioctyl amine salt of lauric acid 3.0%
Dialkyl polysulfide 35.0%
Alkyl phosphite and phosphate 5.0%
Alkyl amine 1.9%
Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent 20.9%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
20 straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with ISO viscosity grades 68, lO0, 150, 220, 320 and 460, the 25 formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 14 is repeated except that the succinimide is boronated succinimide. ~ .

case EI-6087 A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 15.0~
Trihydrocarbyl dithiophosphate 15.0%
Trioctyl amine salt of lauric acid 3.0%
Dialkyl polysulfide 40.0%
Alkyl phosphite and phosphate 7.0%
Alkyl amine 2.2%
Defoamer 0.6~
Sulfur scavenger 1.~%
Demulsifier 0.3%
Mineral oil diluent 15.6%

Gear oils are formed by blending the concentrate in mineral oil 15 base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a concentration of 9.45%. For automotive use, with SAE grades 20 heavier than 75, the treat rate is 6.5%. For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 16 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 12.0%
Trihydrocarbyl dithiophosphate 14.0%
Dihexyl amine salt of stearic acid 2.0%

. ,.

Case EI-6087 Dialkyl polysulfide 45.0%
Alkyl phosphite and phosphate 7.5%
Alkyl amine 2.4%
Defoamer 0.6%
Sulfur scavenger 1.7%
Demulsifier 0.3%
Mineral oil diluent 14.5%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral 10 oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.~%. For industrial use with 15 ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 18 is repeated except that the 20 succinimide is boronated succinimide~

.

A gear oil additive concentrate of this invention is composed of the following ingredients:
;.,.
Succinimide 15.0%
Trihydrocarbyl dithiophosphate 14.0%
Decyl amine salt of C16 dicarboxylic acid - . . 3.0%
Dialkyl polysulfide 45 0%
~, . .
Alkyl phosphite and phosphate 7.5%
Alkyl amine 2.4%
,~! Defoàmer 0~6%
Sulfur scaven~er 1.7%
Demulsifier. 0.3%
Mineral oil diluent 10.5%

2030096 Case EI-6087 Gear oils are formed by blendir.g the concentrate in mineral oil base stocks, synthetic base stoc~s, and combinations of mineral oil and synthetic oil base stoc~s. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades haviny a light 5 viscosity end of 75W or lower, the formulation is used at a concentration of 9.45%. For automotive use, with SA~ grades heavier than 75, the treat rate is 6.5%. For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base 10 stocks may contain a viscosity index improver, if desired.

The procedure of Example 20 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 15.0%
Trihydrocarbyl dithiophosphate 19.6%
Octyl amine salt of octanoic acid 1.4%
Sulfurized isobutylene 41.3%
Alkyl phosphite and phosphate 4./%
Alkyl amine 3.9%
Defoamer and demulsifier 1.5%
Sulfur scavenger 1.4%
Mineral oil diluent 11.2%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, an combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross ~rades having a light 30 visccsity end of 75W Gr lower, the formulation is used at a concentration o~ 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with ISO viscosity grades 68, 100, 150, 220, 820 and 460, the Case EI-6087 formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 22 is repeated except that the 5 succinimide is boronated succinimide.

The procedure of Example 22 is repeated except that the additive concentrate contains 10.0% of the succinimide and 16.2%
of the mineral oil diluent.

The procedure of Example 22 is repeated except that the additive concentrate contains 12.0% of boronated succinimide and 14.2% of the mineral oil diluent.

A gear oil additive concentrate of this invention is composed of the following ingrèdients:

Succinimide 16.2%
Trihydrocarbyl dithiophosphate 19.2%
Lauryl amine salt of octanoic acid 1.5%
Sulfurized isobutylene 20.5%
Dialkyl polysulfide 20.5%
Alkyl phosphite and phosphate 5.0%
Oleylamine 3.9%
Defoamer and demulsifier 1.5%
Sulfur scavenger 1.4%
~- ~Mineral oil diluent 10.3%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic bàse stocks, and combinations of mineral oil and synthetic oil base stocks- For automotive use, with SAE
30 straight grades of 75 or lower or SAE cross grades having a light 2030096 Case EI-6087 viscosity end of 75W or lower, the formulation is used at a concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with ISO viscosity grades 68, lO0, 150, 220, 320 and 460, the 5 formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

EXAMPLE_27 The procedure of Example 26 is repeated except that the succinimide is boronated succinimide, the boronated succinimide 10 is used in the concentrate at a concentration of 15.5%, and the eoncentration of the mineral oil diluent in the concentrate is 11. 0% .

;: EXAMPLE 28 A gear oil additive eoneentrate of this invention is 15 eomposed of the following ingredients:

Suecinimide 12.0%
Oetyl amine salt of deeanoie aeid 1.6%
Sulfurized isobutylene 35.0%
Trihydrocarbyl dithiophosphate 17.0%
Alkyl phosphite and phosphate 5.0%
Alkyl amine 1.9%
Defoamer 0.6%
: Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent25.3%
;
Gear oils are formed by blending the concentrate in mineral oil ; base stoeks, synthetie base stoeks, and combinations of mineral oil and synthetie oil base stoeks- For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light 30 viseosity end of 75W or lower, the formulation is used at a eoncentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6-5%. For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the case EI-6087 formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 28 is repeated except that the 5 succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 15.0%
Trihydrocarbyl dithiophosphate 17.0%
Dibutyl amine salt of decanoic acid 2.0%
Sulfurized isobutylene 35.0%
Alkyl phosphite and phosphate 5.0%
Alkyl amine 1.9%
Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent 21.9%

Gear oils are formed by blending the concentrate in mineral oil 20 base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light ' viscosity end of 75W or lower, the formulation is used at a concentration of 9.45%. For automotive use, with SAE grades 25heavier than 75, the treat rate is 6.5%. For industrial use with IS0 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base ~ ~ stocks may contain a viscosity index improver, if desired.
`' The procedure of Example 30 is repeated except that the succinimide is boronated succinimide.

. . .

Case EI-6087 A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 15.0%
Trihydrocarbyl dithiophosphate 20.0%
Dibutyl amine salt of decanoic acid 2.0%
Sulfurized isobutylene35.0%
Alkyl phosphite and phosphate 5.0%
Alkyl amine 1.9%
10 Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent 18.9%

Gear oils are formed by blending the concentrate in mineral oil 15 base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a con-centration of 9.45%. For automotive use, with SAE grades heavier 20 than 75, the treat rate is 6.5%. For industrial use with IS0 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 32 is repeated except that the succinimide is boronated succinimide.

- A gear oil additive concentrate of this invention is composed of the following ingredients:

30 Succinimide 14.2%
Trihydrocarbyl dithiophosphate 15.8%
Oleyl amine salts of C10 & C24 mono- and dicarboxylic acids 2.8%
Sulfurized isobutylene35 0%

~ 25 -Case EI-6087 Alkyl phosphite and phosphate 4.5%
Laurylamine 2.0%
Defoamer and demulsifier1.2%
Sulfur scavenger 1.2%
Mineral oil diluent 23.3%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light 10 viscosity end of 75W or lower, the formulation is used at a con-centration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with ISO
viscosity grades 68, 100, lS0, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may 15 contain a viscosity index improver, if desired.

The procedure of Example 34 is repeated except that the succinimide is boronated succinimide, and the oleyl amine salts are replaced by lauryl amine salts.

The procedure of Example 34 is repeated except that the succinimide is boronated succinimide, the oleyl amine salts are replaced by cetyl amine salts of decanoic and octadecanoic acids, and the làuryl amine is replaced by a 50/50 w/w mixture of 25 decanoic acid and octadecanoic acid.

A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 12.0%
Trihydrocarbyl dithiophosphate 19.0%
Tert-dodecyl amine salt of octanoic acid ~.5%
.
~ - 26 -Case EI-6087 Sulfurized isobutylene35.0%
Alkyl phosphite and phosphate 5.0%
Alkyl amine 1.9%
Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent 23.4%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral 10 oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a concentration of g.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with 15 IS0 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 37 is repeated except that the 20 succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is composed of the following ingredients: ~

Succinimide 15.0%
Trihydrocarbyl dithiophosphate 15.0%
Tert-dodecyl and tert-tetradecyl amine salts of decanoic and dodecanoic acid 2.0%
Sulfurized isobutylene40 0%
Alkyl phosphite and phosphate 6.0%
Alkyl amine 2.1%
Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0 3%
Mineral oil diluent 17.7%

Case EI-6087 Gear oils are formed by blending the concentrate in mineral oil base stocks, sy~thetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cr~ss grades having a light 5 viscosity end of 7sw or lower, the formulation is used at a con-centration of 9 . 45% . For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with IS0 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may 10 contain a viscosity index improver, if desired.

.

: EXAMPLE 40 The procedure of Example 39 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 12.7%
Trihydrocarbyl dithiophosphate 16.6%
Alkyl amine salts of C8 & C30 mono- and dicarboxylic acids 2.6%
Sulfurized isobutylene 35.0%
Alkyl phosphite and phosphate 4~7%
Alkyl amine 1.9%
Defoamer and demulsifier1~2%
Sulfur scavenger 1.3%
Mineral oil diluent - 24.0%
.. . . .... ...
Gear oils are formed by blending the concentrate in mineral oil base stocks, synthétic base stocks, and combinations of mineral : .. oil and synthetic:oil.base stocks- For automotive use, with SAE
30 straight grades of 75 or lower or SAE cross grad1es having a light viscosity end of 75W or lower, the formulation is used at a con-centration of 9.45~. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with IS0 case EI-6087 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

s The procedure of Example 41 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is formed by blending together the following components in the 10 proportions specified:

Succinimide 8.0%
Trihydrocarbyl dithiophosphate 11.4%
Octyl amine salt of octanoic acid 0.8 Process Oil 6.5~
Anglamol 6004A 73.3%

_ * A proprietary gear oil additive formulation commercially available from The Lubrizol Corporation.
Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral 20 oil and synthetic oil base stocks. For automotive us~, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a ` concentration of 14.57%. For automotive use, with SAE grades heavier than 75, the treat rate is 9.7%. For industrial use with 25 ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 3.8%, and the finished oil should contain at least 0.3% demulsifier. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 43 is repeated except that the succinimide is boronated succinimide.

2 0 3 0 0 9 6 Case EI-6087 A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 15.0% -Nonyl amine salt of pentadecanoic acid 2.0%
Sulfurized isobutylene 45.0%
Trihydrocarbyl dithiophosphate 14.0%
Alkyl phosphite and phosphate 7.0%
10 Alkyl amine 2.4%
Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent 12.4%

15 Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a 20 concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with IS0 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

.
~ EXAMPLE 46 The procedure of Example 45 is repeated except that the succinimide is boronated succinimide.

.. . . .. ..

. . . . . . .

A gear oil additive concentrate of this invention is 30 composed of the following ingredients:

Succinimide 12.0%
Trihydrocarbyl dithiophosphate 15.0%

2~3~i9~
Case EI-6087 Neopentyl amine salt of decanoic acid 1.5%
Sulfurized.isobutylene40.0%
Alkyl phosphite and phosphate 6.0%
Alkyl amine 2.1%
Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0.3,%
Mineral oil diluent 21.2%

10 Gear oils are formed by blending the concentrate in mineral oil ~, base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75w or lower, the formulation is used at a 15 concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is u,sed at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

, The procedure of Example 47 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is 25 composed of the following ingredients:

.. Succinimide 12.0%
Trihydrocarbyl dithiophosphate 17.0%
, Lauryl amine salt of oleic acid 2.0%
Sulfurized isobutylene35.0%
, 30 Alkyl phosphite and phosphate 3.0%
Dialkyl thiophosphate amine salt 5.2%
Alkyl amine 1.4%
` Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent 22.2%

C~se EI-6087 Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light 5 viscosity end of 75W or lower, the formulation is used at a con-centration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with IS0 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.lS%. Any such base stocks may 10 contain a viscosity index improver, if desired.

The procedure of Example 49 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 15.0%
Trihydrocarbyl dithiophosphate 17.0%
Dioctyl amine salt of oleic acid 3.0%
Sulfurized isobutylene34.S%
AlkyI phosphite and phosphate 3.2%
Dialkyl thiophosphate amine salt 5.3%

Alkyl amine 1.4%
Defoamer 0.6%
Sulfur scavenger - 1.3%
Demulsifier 0.3%
Mineral oil diluent 18.4%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral 0 oil and synthetic oil base stocks- For automotive use, with SAE
- . .. . .
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a con-centration of 9.45%. For automotive use, with SAE grades heavier .

2 0 3 0 0 9 6 case EI-6087 than 75, the treat rate is 6.5%. For industrial use with ISO
viscosity grades 68, 105, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 50 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is 10 composed of the following ingredients:

Succinimide 12.4%
Trihydrocarbyl dithiophosphate 16.3%
Di- and tributyl amine salts of stearic acid 2.2%
- 15 Sulfurized isobutylene34 . 5%
Alkyl phosphite and phosphate 2.5%
Dialkyl thiophosphate amine salt 6.0%
. Alkyl amine 1.2%
Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent 22. 7%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral 25 oil and synthetic oil base stocXs. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a concentration of 9. 45% . For automotive use, with SAE grades heavier than 75, the treat rate is 6 5% For industrial use with 30 ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

2 0 3 0 0 9 6 Case EI-6087 The procedure of Example 53 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 15.0%
Trihydrocarbyl dithiophosphate 16.4%
Mono- and dihexyl amine salts of stearic acid 3.0%
Sulfurized isobutylene 35.7%
Alkyl phosphite and phosphate 2 . 5%
Dialkyl thiophosphate amine salt 6.2%
Alkyl amine 1.3%
15 Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent 17.7%

Gear oils are formed by blending the concentrate in mineral oil -20 base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a con-centration of 9.45%. For automotive use, with SAE grades heavier 25 than 75, the treat rate is 6-5%. For industrial use with IS0 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

. .

The procedure of ExampIe 55 is repeated except that the succinimide is boronated succinimide.

... .

2030096 Case EI-6087 A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 12.8%
Trihydrocarbyl dithiophosphate 15.4%
2-Ethylhexyl amine salt of iso-stearic acid 2.2~
Sulfurized isobutylene40.0%
Alkyl phosphite and phosphate 2.5%
10 Dialkyl thiophosphate amine salt 5.6%
Alkyl amine 1.3%
Defoamer 0.6%
Sulfur scavenger 1.2%
Demulsifier 0.4%
15 Mineral oil diluent 18.0%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE .
straight grades of 75 or lower or SAE cross grades having a light 20 viscosity end of 75W or lower, the formulation is used at a concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with IS0 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base 25 stocks may contain a viscosity index improver, if desired.

The procedure of Example 57 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 14.8%
Trihydrocarbyl dithiophosphate 15.3%

203~096 Case EI-6087 Octyl amine salt of lauric acid 3.0%
Sulfurized isobutylene39.6%
Alkyl phosphite and phosphate 2.6%
Dialkyl thiophosphate amine salt 6.2%
Alkyl amine 1.2%
Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent 15.1%

10 Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a con-15 centration of 9.45%. For automotive use, with SAE grades heavier " than 75, the treat rate is 6.5%. For industrial use with ISOviscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Exampl,e 59 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is 25 composed of the following ingredients:

.
Succinimide 12.5%
Trihydrocarbyl dithiophosphate 13.2%
Octyl and decyl amine salts of lauric acid 2.4%
Sulfurized isobutylene36.0%
Alkyl phosphite and phosphate 1.5%
Dialkyl thiophosphate amine salt 8.0%
Alkyl amine o.g%
Defoamer 0.6%
Sulfur scavenger 1.3%

203009~
case EI-6087 Demulsifier 0.3%
Mineral oil diluent 23.3%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral 5 oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a con-centration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with ISO
10 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 61 is repeated except that the 15 succinimide is boronated succinimide.

,. A gear oil additive concentrate of this invention is composed of the following ingredients:

Succinimide 15.0%

Trihydrocarbyl dithiophosphate 13.0%
Octyl and dioctyl amine salts of stearic acid 3.2%
Sulfurized isobutylene 35.4%
Alkyl phosphite and phosphate 1.3%
Dialkyl thiophosphate amine salt 7.8% .
Alkyl amine 0.9%
Defoamer 0.6%
Sulfur scavenger 1.3%
Demulsifier 0.3%
Mineral oil diluent 21.2%

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks- For automotive use, with SAE

2030096 Case EI-6087 straight grades of 75 or lower or sAE cross grades having a light viscosity end of 7sw or lower, the formulation is used at a con-centration of 9.4S%. For automotive use, with SAE grades heavier than 75, the treat rate is 6.5%. For industrial use with ISO
5 viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

The procedure of Example 63 is repeated except that the 10 succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is formed by blending together the following components in the proportions specified:

Succinimide 9.3%
Trihydrocarbyl dithiophosphate 12.4%
Process Oil ` 8.5%
Mobilad G-201 69.8%
_ * A proprietary gear oil additive formulation commercially available from Mobil Chemical Company.
. , ' ', .
Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oll base stocks. For automotive use, with SAE
straight grades of ?5 or lower or SAE cross grades having a light 25 viscosity end of 75W or lower, the formulation is used at a concentration of 13.3%. For automotive use, with SAE grades heavier than 75, the treat rate is 8.9%. For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the ~.
formulation is used at a concentration of 3.5%, and the finished 30 oil should contain at least 0.3% demulsifier. Any such base stocks may contain a viscosity index improver, if desired.

ca~e EI-6087 The procedure of Example 65 is repeated except that the succinimide is boronated succinimide.

A gear oil additive concentrate of this invention is formed by blending together the following components in the proportions specified:

Succinimide 9.0%
Trihydrocarbyl dithiophosphate 12.0%
10 Octyl amine salt of octanoic acid 0.9%
Process Oil 7.3%
Elco 7 70.8%

* A proprietary gear oil additive formulation commercially available from Elco Corporation.

15 Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE
straight grades of 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a con-20 centration of 13.8%. For automotive use, with SAE grades heavierthan 7S, the treat rate is 9.2%. For industrial use with ISO
viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of 3.6%, and the finished oil should contain at least 0.3% demulsifier. Any such base stocks may 25 contain a viscosity index improver, if desired.

The procedure of Example 67 is repeated except that the succinimide is boronated succinimide.

The superlative antiwear and extreme pressure results Case EI-6087 achievable by the practice of this invention were demonstrated in a series of comparative tests in which a formulatiOn of this in-vention was compared under identical test conditions with six com-mercially available gear oil additive formulations available from three leading manufacturers of such products. The composition of this invention contained as component (i) a succinimide product formed from polyisobutenylsuccinic anhydride and ethylene poly-amine mixture approximating tetraethylenepentamine in composi-tion; the isobutenyl group being derived from polyisobutene hav-ing an Mn of about 1300. Component (ii) was O,O-mixed dialkyl-S-dicyclopentadienyl phosphorothioate (alkyl = isopropyl 30.1%;
isobutyl 37.2%; 2-ethylhexyl 32.7%). The performance criteria used in these tests was the percentage of phosphorus retention in the oil after subjecting the respective gear oils to test condi-tions normally tending to cause loss of phosphorus contentthrough sludge formation due to degradation of the phosphorus antiwear and extreme pressure components of the formulation.

,. To conduct such comparative tests, use was made of three test procedures widely used in the gear additive industry for determining thermal oxidation stability. The first and foremost of such tests is the standard L-60 test. The other two tests used were the Indiana Stirring test and the ZF/Renault/Peugeot test.

The results of these tests are summarized in the following tables:

PERCENTAGE OF PHOSPHORUS RETENTION AFTER OXIDATION

Indiana ZF/Renault/
Formulation L-60 Stirring Peugeot Used Test Test Test 30 This Invention 100 100 100 Additive A 76.5 84.4 85.5 Additive B 31.6 34.2 36.9 Additive C 14.7 38.9 33.0 2 0 3 0 0 9 6 case EI-60s7 Additive D 15.9 22.6 27.1 Additive E 65.0 85.3 42.9 Additive F 75.6 41.8 50.6 The excellent antiwear and extreme pressure properties 5 of the compositions of this invention was further demonstrated in the standard Mack Spalling Rig Test. The B10 Life of the above formulation of this invention in this test was found to be 240 hours. Under the same test conditions, a GO-H Pass Reference Oil gives a B10 Life of 160 hours, a GO-G Pass Reference Oil a slo 10 life of llo hours, and a Go-G Fail Reference Oil exhibits a B10 Life of 85 hours.

A still further demonstration of the remarkable properties of the formulations of this invention involved use of the Mack Transmission Cycling Test. In this test, the above 15 formulation of this invention did not exhibit any failure even after 150,000 cycles, at which point the test was arbitrarily discontinued. Under the same test conditions, a GO-H Pass Reference Oil failed at 66,000 cycles and a GO-H Fail Reference Oil failed at 27,500 cycles.

Preferred gear oil compositions of this invention, when subjected to the standard L-60 test, have also been found to eliminate or essentially eliminate deposit formation on the spur gear faces. This test involves placing a sample of gear lubri-cant in a heated gear box in which two spur gears and a test 25 bearing are operating at a predetermined load in the presence of a copper catalyst- According to the test procedure, the tempera- .
ture of the test lubricant is maintained at 325F ~162.5C) while bubbling 0.3 gal/h (l-lL/h) of air through oil in the gear box for a test duration of 50 hours of continuouS operation.

20~0096 Case EI-6087 Having described the basic concepts of this invention, attention will now be focused upon details concerning the additive ingredients.

Component ~l) The carboxylic derivative compositions used in the practice of this invention are produced by reacting at least one substituted succinic acylating agent with (a) amine ha~ing at least one primary or secondary amino group in the molecule, (b) alcohol, (c) reactive metal or reactive metal compound, or (d) a 10 combination of two or more of any of (a) through (c), the compo-nents of (d) being reacted with such substituted succinic acylating agent(s) simultaneously or sequentially in any order.
The substituted succinic acylating agent contains a substituent group derived from polyalkene, the substituent having an Mn value 15 of about 500 to about 10,000, preferably in the range of about 750 to about 5,000.

,.
For the purposes of this invention, the Mn value for the polyalkene used in forming the sùbstituted succinic acylating agent is determined by gel permeation chromatography in the man-20 ner described in U.S. Pat. No. 4,234,43S from Column 7, line 7through Column 8, line 31, which description is expressly incor-porated herein by reference.

Thus, the substituted succinic acylating agents are those which can be characterized by the presence within their .... . . . . .
25 structure of two groups or moieties- The first group or moiety is a substituent group derived from a polyalkene. The polyalkene from which the substituted groups are derived is characterized by ~, ~,. ~ . . . i -an Mn (number average molecular weight) value of from about 500 to about 10,000, and preferably in the range of from about 750 to 30 about 5,000.

The second group or moiety is the succinic group, a group characterized by the structure O O
Il l l 11 x c f f c x . Formula I

5 wherein X and X' are the same or different provided at least one of X and X' is such that the substituted succinic acylating agent can function as a carboxylic acylating agent. In other words, at least one of X and X' must be such that the substituted acylating agent can esterify alcohols, form amides or amine salts with 10 ammonia or amines, form metal salts with reactive metals or basi-cally reacting metal compounds, and otherwise functions as a conventional carboxylic acid acylating agent. Transesterifi-cation and transamidation reactions are considered, for purposes of this invention, as conventional acylation reactions.

Thus, X and/or X' is usually -OH, -O-hydrocarbyl;

-O M+ where M+ represents one equivalent of a metal, ammonium or amine cation, -NH2, -Cl, -Br, and together, X and X' can be -O-so as to form the anhydride. The specific identify of any X or X' group which is not one of the above is not critical so long 20 as its presence does not prevent the remaining group from entering into acylation reactions. Preferably,however, X and X' are each such that both carboxyl functions of the succinic group can enter into acylation reactions.

One of the unsatisfied valences in the grouping - C - C -of Formula I forms a carbon-to-carbon bond with a carbon atom in the substituent group. While other such unsatisfied valence may be satisfied by a similar bond with the same or different substi-tuent group, all but the said one such valence is usually satis-30 fied by a hydrogen atom.

2~30096 E~-6087 The succinic groups of the succinic acylating agents will normally correspond to the formula O
- CH - c - R
I ~ormula II
CH2 - C - R~

wherein R and R' are each independently selected from the group consisting of -OH, -Cl, -OR" tR" = lower alkyl), and when taken 10 together, R and R' are - o -. In the latter case the succinic group is a succinic anhydride group. All the succinic groups in a particular succinic acylating agent need not be the same, but they can be the same. Preferably, the succinic groups will correspond to o O
Il 11 - CH - C - OH - CH - C
¦ ¦ O Formula III

O O
(A) (B) and mixtures of III(A) and III(B). Production of substituted succinic acylating agents wherein the succinic groups!are the same or different is within ordinary skill of the art and can be ~ . ..
.... . . . .
accomplished through conventional procedures such as treating the 25 substituted succinic acylating agents themselves (for example, hydrolyzing the anhydride to the free acid or converting the free acid to an acid chloride with thionyl chloride) and/or selecting the appropriate maleic or fumaric reactants.

The polyalkenes from which the substituent groups are 30 derived are homopolymers and interpolymers of polymerizable ole-fin monomers of 2 to about 16 carbon atoms; usually 2 to about 6 carbon atoms. The interpolYmers are those in whlch two or more olefin monomers are interpolymerized according to well-known conventional procedures to form polyalkenes having units within 203~9~ EI-6087 their structure derived from each of said two or more olefin mono-mers. Thus, the polymers used include binary copolymers, terpoly-mers, tetrapolymers, and the like. The polyalkenes from which the substituent groups are derived are often referred to as poly-5 olefin(s).

The olefin monomers from which the polyalkenes are derived are polymerizable olefin monomers characterized by the presence of one or more ethylenically unsaturated groups (i.e., >C=C<); that is, they are mono-olefinic monomers such as ethyl-lO ene, propylene, 1-butene, isobutene, and l-octene or polyolefinic monomers (usually diolefinic monomers) such as 1,3-butadiene and isoprene.

These olefin monomers are usually polymerizable terminal olefins; that is, olefins characterized by the presence in their 15 structure of the group >C=CH2. However, polymerizable internal olefin monomers characterized by the presence within their structure of the group -- C C = C -- C --.:
can also be used to form the polyalkenes. When internal olefin 20 monomers are employed, they normally will be employed with termi-nal olefins to produce polyalkenes which are interpolymers. When a particular polymerizable olefin monomer can be classified as both a terminal olefin and an internal olefin, it is usually cate-gorized as a terminal olefin. An example of such a monomer is 25 1,3-pentadiene (i.e., piperylene).

;~ While the polyalkenes from which the substituent groups of the succinic acylating agents are derived generally are hydro-carbon polyalkenes, they can contain non-hydrocarbon groups such as lower alkoxy, lower alkyl mercapto, hydroxy, mercapto, oxo, 2030~96 nitro, halo, cyano, carboalkoxy (i.e., - c - o - alkyl where "alkyl" is usually lower alkyl, namely an alkyl group 5 containing up to about 7 carbon atoms), alkanoyloxy (or carbalkoxy, i.e., o Il i.,; ,~
alkyl - C - O -where "alkyl" is usually lower alkyl), and the like, provided the 10 non-hydrocarbon substituents do not substantially interfere with formation of the substituted succinic acid acylating agents.

When present, such non-hydrocarbon groups normally will not contribute more than about 10% by weight of the totai weight of the polyalkenes. Since the polyalkene can contain such non-15 hydrocarbon substituents, it is apparent that the olefin monomersfrom which the polyalkenes are made can also contain such substi-~- tuents. Normally, however, as a matter of practicality and expense, the olefin monomers and the polyalkenes used are free from non-hydrocarbon groups, except chloro groups which usually 20 facilitate the formation of the substituted succinic acylating agents.

.
Although the polyalkenes may include aromatic groups (especially phenyl groups and lower alkyl- and-/or lower alkoxy-substituted phenyl groups such as p-tert-butylphenyl and cyclo-25 aliphatic groups such as would be obtained from polymerizablecyclic olefins or cycloaliphatic substituted-polymerizable acy-clic olefins, the polyalkenes usually will be free from such groups. Nevertheless, polyalkenes derived from interpolymers of both 1~3-dienes and styrenes such as 1,3-butadiene and styrene or 2030096 El-6087 4-tert-butyl-styrene are exceptions to this generalization. Simi-larly, the olefin monomers from which the polyalkenes are pre-pared can contain bo~h aromatic and cycloaliphatic groups.

Generally speaking aliphatic hydrocarbon polyalkenes 5 free from aro~atic and cycloaliphatic groups are preferred for use in preparing the substituted succinic acylating agents. Par-ticularly preferred are polyalkenes which are derived from homo-polymers and interpolymers of terminal hydrocarbon olefins of 2 to about 8 carbon atoms, most especially from 2 to 4 carbon lO atoms. While interpolymers of terminal olefins are usually pre-ferred, interpolymers optionally containing up to about 40~ of polymer units derived from internal olefins of up to about 8 car-bon atoms are also preferred. The most preferred polyalkenes are polypropylenes and polyisobutenes.

Specific examples of terminal and internal olefin mono-mers which can be used to prepare the polyalkenes according to 11 conventional, well-known polymerization techniques include l ¦
ethylene; propylene; 1-butene; 2-butene; isobutene; l-pentene; ¦¦
l-hexene; 1-heptene, 2-butene; isobutene; 2-pentene, l-hexene; ¦
20 l-heptene; 1-octene; 1-nonene; 1-decene; 2-pentene; propylene- l tetramer; diisobutylene; isobutylene trimer; 1,2-butadiene; ¦¦
1,3-butadiene; 1,2-pentadiene 1,3-pentadiene; 1,4-pentadiene;
isoprene; 1,5-hexadiene; 2-chloro-1,3-butadiene; 2-methyl-1- ¦ !
heptene; 4-cyclohexyl-1-butene; 3-pentene; 4-octene; 3,3-di- ¦
25 methyl-1-pentene; styrene; 2,4-dichlorostyrene; divinylbenzene;

vinyl acetate; allyl alcohol; 1-methyl-vinyl acetate; acrylo-nitrile; ethyl acrylate; methyl methacrylate; ethyl vinyl ether; l and methyl vinyl ketone. Of these, the hydrocarbon polymerizable ;~ monomers are preferred and of these hydrocarbon monomers, the 30 ter=inal olefln =ono=ere are particularly preferred.

_ 47 _ Specific examples of polyalkenes include polypropylenes, polybutenes, ethylene-propylene copolymers, styrene-isobutene co-polymers, isobutene-1,3-butadiene copolymers, propene-isoprene copolymers, isobutene-chloroprene copolymers, isobutene-4-methyl-5 styrene copolymers, copolymers of l-hexene with 1,3-hexadiene, copolymers of l-octene with l-hexene, copolymers of 1-heptene with l-pentene, copolymers of 3-methyl-1-butene with 1-octene, copolymers of 3,3-dimethyl-1-pentene with l-hexene, and ter-polymers of isobutene, styrene and piperylene. ~ore specific 10 examples of such interpolymers include copolymer of 95% (by weight) of isobutene with 5% (by weight) of styrene; terpolymer of 98% of isobutene with 1~ of piperylene and 1% of chloroprene;
terpolymer of 95% of isobutene with 2% of butene 1 and 3% of 1-hexene; terpolymer of 60~ of isobutene with 20% of l-pentene 15 and 20% of octene-l; copolymer of 80% of l-hexene and 20% of l-heptene; terpolymer of 90% of isobutene with 2% of cyclohexene and 8% of propylene; and copolymer of 80% of ethylene and 20% of propylene. A preferred sour'ce of polyalkenes are the polyiso-butenes obtained by polymerization of C4 refinery stream having 20 a butene content of about 35 to about 75 percent by weight and an isobutene content of about 30 to about 60 percent by weight using a Lewis acid catalyst such as aluminum trichloride or boron tri-fluoride. These polybutenes contain predominantly (greater than about 80% of thé total repeating units) of repeating units of the 25 configuration .. . . . .

'- CH2 i-- C --In preparing polyalkenes, conventional techniques known 30 to those skilled in the art include suitably controlling poly-merization temperatures, regulating the amount and. type of poly-merization initiator and/or catalyst, employing chain terminating groups in the polymerization procedure, and the like. Other con-ventional techniques such as stripping (including vacuum strip-ping) a very light end and/or oxidatively or mechanically degrad-ing high molecular weight polyalkene to produce lower molecular 5 weight polyalkenes can also be used.

In preparing the substituted succinic acylating agents, one or more of the above-described polyalkenes is reacted with one or more maleic or fumaric acidic reactants o~the general formula o o Il ll Formula IV
X - C - CH = CH - C - X' wherein ~ and X' are as defined hereinbefore. Preferably the maleic and fumaric reactants will be one or more compounds cor-15 responding to the formula O O
ll ll Formula V
R - C - CH = CH - C - R' wherein R and R' are as previously defined herein. Ordinarily 20 the maleic or fumaric reactants will be maleic acid, fumaric acid, maleic anhydride, or a mixture of two or more of these.
The maleic reactants are usually preferred over the fumaric reac-i tants because the former are more readily available and are, in general, more readily reacted with the polyalkenes (or deriva-25 tives thereof) to prepare the substituted succinic acylating agents. The most preferred reactants are maleic acid, maleic anhydride, and mixtures of these.

Any of a variety of known procedures can be used to produce the substituted succinic acylating agents. For con-30 venien~e and brevity, when the term "maleic reactant" is usedhereafter, the term is generic to the reactants corresponding to Formulas IV and V above including mixtures of such reactants.

203~096 One procedure for preparing the substituted succinic acylating agents is illustrated, in part, by the two-step procedure described-in U.S. Pat. No. 3,219,666. It involves first chlorinating the polyalkene until there is an average of at 5 least about one chloro group for each molecular weight (i.e., each Mn) of polyalkene. Chlorination involves merely contacting the polyalkene with chlorine gas until the desired amount of chlorine is incorporated into the chlorinated polyalkene. Chlori-nation is generally carried out at a temperature of about 75~C to 10 about 125C. If desired, a diluent can be used in the chlorina-tion procedure. Suitable diluents for this purpose include poly-and perchlorinated and/or fluorinated alkanes and benzenes.

.
The second step in the two-step chlorination procedure is to react the chlorinated polyalkene with the maleic reactant 15 at a temperature usually within the range of about 100-C to about 200 C. The mole ratio of chlorinated polyalkene to maleic reac-tant is usually aboutil:1. In this connection, a mole of chlori-nated polyalkene may be regarded as the the weight of chlorinated polyalkene corresponding to the Mn value of the unchlorinated 20 polyalkene. However, a stoichiometric excess of maleic reactant can be used, for example, a mole ratio of 1:2. If an average of more than about one chloro group per molecule of polyalkene is introduced during the chlorination step, then more than one mole of maleic reactant can react per molecule of chlorinated poly-25 alkene. Accordingly, the ratio of chlorinated polyalkene to ma-leic reactant may be referred to in terms of equivalents, an equi-valent weight of chlorinated polyalkene being the weight corres-ponding to the Mn value divided by the average number of chloro groups per molecule of chlorinated polyalkene. The equivalent 30 weight of a maleic reactant is its mol~ecular weight. Thus, the ratio of chlorinated polyal~ene to mal~eic reactant will normally be such as to provided about one equivalent of maleic reactant for each mole of chlorinated polyalkene up to about one equivalent of maleic reactant for each equivalent of chlorinated polyalkene with the_understanding that it is normally desirable to provide an excess of maleic reactant; for example, an excess 5 of about 5% to about 25% by weight. Unreacted excess maleic reactant may be stripped from the reaction product, usually under vacuum, or reacted during a further stage of the process as explained below.

~.

The resulting polyalkenyl-substituted succinic acylating 10 agent is, optionally, again chlorinated if the desired number of succinic groups are not present in the product. If there is pre-sent, at the time of this subsequent chlorination, any excess maleic reactant from the second step, the excess will react as additional chlorine is introduced during the subsequent chlori-15 nation. Otherwise, additional maleic reactant is introducedduring and/or subsequent to the additional chlorination step.
This technique can be repeated until the total number of succinic groups per equivalent weight of substituent groups reaches the desired level.

Another procedure for preparing substituted succinic acid acylating agents utilizes a process described in U.S. Pat.
No. 3,912,764 and U.K. Pat. No. 1,440,219. According to that process, the polyalkene and the maleic reactant are first reacted by heating them together in a direct alkylation procedure. When 25 the direct alkylation step is completed, chlorine is introduced into the reaction mixture to promote reaction of the remaining unreacted maleic reactants. According to the patents, 0.3 to 2 or more moles of maleic anhydride are used in the reaction for ....
each mole of olefin polymer; i.e., polyalkene. The direct alky-30 lation step is conducted at temperatures of 180C to 250C.

2~3~9~

During the chlorine-introducing stage, a temperature of 160C to 225 c is employed.

Other known processes for preparing the substituted succinic acylating agents include the one-step process described 5 in U.S. Pat. Nos. 3,215,707 and 3,231,587. Basically, this process involves preparing a mixture of the polyalkene and the maleic reactant in suitable proportions and introducing chlorine into the mixture, usually by passing chlorine gas through the mixture with agitation, while maintaining a temperature of at 10 least about 140C.

Usually, where the polyalkene is sufficiently fluid at 140~C and above, there is no need to utilize an additional sub-stantially inert, normally liquid solvent/diluent in the one-step process. However, if a solvent/diluent is employed, it is pre-15 ferably one that resists chlorination such as the poly- and per-chlorinated and/or -fluorinated alkanes, cycloalkanes, and ben-zenes.

Chlorine may be introduced~ continuously or intermittent-ly during the one-step~process. The rate of introduction of the 20 chlorinè is not critical although, for maximum utilization of the chlorine, the rate should be about the same as the rate of con-sumption of chlorine in the course of the reaction. When the in-troduction rate of chlorine exceeds the rate of consumption, chlo-rine is evolved from the reaction mixture. It is often advanta-25 geous to use a closed system, including superatmospheric pres-sure, in order to prévent loss of chlorine so as to maximize chlo-rine utilization. ~ `

~ ~~ The minimum temperature at which the reaction in the one-step process takes place at a reasonable rate is about 30 140~C. Thus, the minimum temperature at which thè process is ~ 52 normally carried out is in the neighborhood of 140C. The pre-ferred temperature range is usually between about 160 C and about 220 C. Higher temperatures such as 250 C or even higher may be used but usually with little advantage. In fact, excessively 5 high temperatures may be disadvantageous because of the possi-bility that thermal degradation of either or both of the reac-tants may occur at excessively high temperatures.

In the one-step process, the molar ratio of maleic reactant to chlorine is such that there is at least about one 10 mole of chlorine for each mole of maleic reactant to be incor-porated into the product. Moreover, for practical reasons, a slight excess, usually in the neighborhood of about 5~ to about 30% by weight of chlorine, is utilized in order to offset any loss of chlorine from the reaction mixture. Larger amounts of 15 excess chlorine may be used.

Further details concerning procedures for producing the substituted acylating agents have been extensively described in the patent literature, such as for example in U.S. Pat. No.
4,234,435, all disclosure of which is incorporated herein, and 20 thus further amplification of such procedures herein is deemed unnecessary.

; As noted above, the substituted acylating agents are reacted with (a) amine having at least one primary or secondary amino group in the molecule, or (b) alcohol, or (c) reactive 25 metal or reactive metal compound, or (d) a combination of two or more of (a) through (c), the components of (d) being reacted with the acylating reagents simultaneously or sequentially in any order and/or subcombination.

The amine, reactant (a) above, can be a monoamine or polyamine, including hydrazine and substituted hydrazines. Such reactants can be used either singly or in various mixtures. Use of polyamines having at least two primary amino groups in the molecule are generally preferred. Alkylene polyamines having s both primary and secondary amino groups in the molecule are par-ticularly preferred, especially where the alkylene polyamines contain at least two primary amino groups and one or more secon-dary amino groups.
.. ,, I .
Alcohols, reactant (bl above, which can be used include 10 the monohydric and polyhydric alcohols. The polyhydric alcohols are preferred.

, .
Reactive metais and reactlve metal compounds, reactant (c) above, are those which are known to form salts and complexes when reacted with carboxylic acids and carboxylic acid acylating 15 agents.

Numerous examples of reactants (a), (b), and (c) are set forth in U.S. Pat No. 4,234,435 to which reference may be had flor this purpose, and which disclosure is incorporated herein in toto.

...,,,, . ... , I .
of the various succinic derivatives which may be jused in the practice~of this invention, those formed by reaction between an alkenyl succinic acid or alkenyl succinic anhydride and an alkylene polyamine or mixture of alkylene polyamines are pre~
ferred. Such polyamines may be represented by the formula .. . :
~ ~2N~C~21n~NH~C* )n)mN~2 ~ , wherein n is in the range of 2 to about 10 (preferably 2 to 3, and most preferably 2~ and m is in the range of'0 to 10, ,~ ~
~ 54 -. .

203~096 (preferably o to about 6). Illustrative are ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pent-amine, pentaethylene hexamine, propylene diamine (1,3-propane-diamine), butylene diamine (1,4-butanediamine), hexamethylene 5 diamine (1,6-hexanediamine), decamethylene diamine (1,10-decane-diamine), and the like. Particularly preferred for use is tetra-ethylene pentamine or a mixture of ethylene polyamines which approximates tetraethylene pentamine such as "DOW E-lO0" (a commercial mixture available from Dow Chemical Company, Midland, lO Michigan)-When preparing the boronated succinimides and boronatedsuccinic esters, a succinimide or succinic ester (or mixture thereof) is reacted with one or more boron-containing reactants such as boron halides, boron acids, and esters of boron acids.
lS Boric acid is commonly used for this purpose. The procedures employed in producing boronated succinimides and boronated succinic esters are well documented in the patent literature.

~, .
As those skilled in the art can appreciate, various succinimides, succinic esters, boronated succinimides, and 20 boronated succinic esters are available as articles of commerce.

Com~onent (ii) The other component required in the gear oil composi-tions of this invention is one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphoric acid or one or more 25 oil-soluble fully-esterified hydrocarbyl esters of a phosphoro-thioic acid, or a combination of one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphoric acid and one or more oil-soluble fully-esterified hydrocarbyl esters of a phos-phorothioic acid. Such compounds may be represented by the gen-30 eral formula:

203~0g6 Rl X - I - X - R2 Formula VI

5 wherein each of Rl, R2, and R3 is independently a hydro-carbyl group and each X is independently an oxygen atom or a sulfur atom. Thus when the co~pound has the formula:

Rl - X - P - X - R ~ormula VII

it is a fully-esterified hydrocarbyl ester of a phosphoric acid.
on the other hand, when the compound h~as the formula:
S

Rl - X ~ P - X - R ~ormula VIII

it is a fully-esterified hydrocarbyl estjer of a phosphorothioic acid. In the foregoing formulas, the hydrocarbyl groups Rl, 20 R2, and R3 can be any hydrocarbyl group, such as alkyl, cycloalkyl, aryl, cycloalkylalkyl, aralkyl, alkenyl, cycloal-kenyl, etc. Such hydrocarbyl groups may each contain up to 50 or more carbon atoms, although ordinarily they will contain up to about 24 carbon atoms. The hydrocarbyl groups may be substituted 25 by inert substituents in the sense that the substituents do not interfere with the functioning of component (ii~ nor destroy the effectiveness of component ~i) of the compositions of this inven-tion. For example, the hydrocarbyl groups of the phosphorus esters may include ether oxygen atoms, thioether sulfur atoms, 30 nitrogen atoms, ester functionality, hydroxyl groups, sulfhydryl groups, and like substituents. Thus, the fully-esterified phos-phate and phosphoricthioate esters used in the practice of this invention may include alkoxyalkyl, poly(alkoxy)alkyl, alkylthio-I~=

alkyl, aryloxyalkyl, dialkylaminoalkyl, diarylaminoalkyl, hydroxy-alkyl, and like inert (innocuous) substituents.

A preferred group of compounds for use as component (ii) are the O,O-dihydrocarbyl-S-hydrocarbyl phosphorothiothionates of 5 the general formula:

S
Rl - ~ I ~ R2 Formula IX
Sl3 10 wherein each of Rl, R2, and R3 is independently a hydro-carbyl group, especially where R3 is an alicyclic hydrocarbyl group. Particularly preferred are the O,O-dialkyl-S-hydrocarbyl phosphorothiothionates wherein R3 is an alicyclic group an Rl and R2 are alkyl groups each having up to about 18 carbon atoms 15 and most preferably up to about 12 carbon atoms.

Various phosphoric and phosphorothioic esters of the type depicted in formulas VI, VII, VIII, and IX above and methods for their preparation have been reported in the literature. See for example, U.S. Pat. Nos. 2,528,732, 2,561,773, 2,665,295, 20 2,767,206, 2,802,856, 3,023,209, and J. Ora. Chem., 1963, 28, 1262-8.

Exemplary compounds suitable for use as component (ii) include such fully-esterified phosphates and phosphorothioates as fusel oil phosphate, tricresyl phosphate, dibutyl phenyl phos-25 phate, tri-2-ethylhexyl phosphate, triisodecyl phosphate, tri-lauryl phosphate, trioctylphosphorothiothionate, tridecylphos-phorodithiothionate, trilaurylphosphorotrithiothionate, diethyl bicyclo(2.2.1)-hepten-2-yl phosphate, O,O-diethyl S-bicyclo-(2.2.l)-5-hepten-2-yl phosphorothiothionate, diethyl 7,7-di-30 methyl-bicyclo(2.2.1)-5-hePten-2-yl phosphate, the product formed 2û30096 by reaction of dithiophosphoric acid-O,O-dimethyl ester with cis-endomethylene-tetrahydrophthalic acid dimethyl ester, the product formed by reaction of dithiophosphoric acid-0,0-dimethyl ester with cis-endomethylene-tetrahydrophthalic acid dibutyl 5 ester, the product formed by reaction of dithiophosphoric acid-O,o-dibutyl ester with cis-endomethylene-tetrahydrophthalic acid dilauryl ester, the product formed by reaction of dithio-phosphoric acid-Q,0-dimethyl ester with 2,5-endomethylene-l-methyl-tetrahydrobenzoic acid butyl ester, the product formed 10 by reaction of dithiophosphoric acid-O,O-dimethyl ester with 2,5-endomethylene-1-methyl-tetrahydrobenzoic acid decyl ester, the product formed by reaction of dithiophosphoric acid-O,0-di-methyl ester with 2,5-endomethylene-6-methyl-tetrahydrobenzoin acid ethyl ester, the product formed by reaction of dithio-15 phosphoric acid-O,0-diethyl ester with 2,5-endomethylene-tetrahydrobenzyl alcohol, the product formed by reaction of dithiophosphoric acid-0,0-dimethyl ester with the Diels-Alder adduct of cyclopentadiene and allyl alcohol (2 mols : 1 mol), the product formed by reaction of dithiophosphoric acid-0,0-dimethyl 20 ester with 2,5-endomethylene-tetrahydrophenyl acetate, the pro-duct formed by reaction of dithiophosphoric acid-0,0-dibutyl ester with the Diels-Alder adduct of cyclopentadiene and vinyl acetate (2 mols : 1 mol), the product formed by reaction of dithiophosphoric acid-0,0-dimethyl ester with the bis-cyclo-25 pentadiene adduct of p-benzoquinone, the product formed by reac-tion of dithiophosphoric acid-O,O-dimethyl ester with the azodi-carboxylic acid diethyl ester, the product formed by reaction of dithiophosphoric acid-0,0-dimethyl ester with dicyclopentadiene, `~the product formed by reaction of dithiophosphoric acid-O,o-:~30 dibutyl ester with dicyclopentadiene, the product formed by reaction of dithiophosphoric acid-O,0-dioctyl ester with dicyclo-pentadiene, the product formed by reaction of dithiophosphoric .acid-0,0-dilauryl ester with dicyclopentadiene, the product ~ 0 0 ~ 6 EI-6087 formed by reaction of dithiophosphoric acid-O,o-~i-2-ethylhexyl ester with wax olefin, the product formed by reaction of dithio-phosphoric acid-O,0-di-2-ethylhexyl ester with oleyl alcohol, the product formed by reaction of dithiophosphoric acid-O,O-di-2-5 ethylhexyl ester with linseed oil, the product formed by reactionof dithiophosphoric acid-0,0-diamyl ester with alpha pinene, the product formed by reaction of dithiophosphoric acid-O,0-diphenyl ester with alpha pinene, the product formed by reaction of dithiophosphoric acid-0,0-diamyl ester with allo-ocimene, the 10 product formed by reaction of dithiophosphoric acid-O,O-dioctyl ester with dipentene, and the like.

Component (iii) '!"

As noted above, an optional, but preferred component for use in the compositions of this invention is one or more of amine 15 salts of (1) one or more long chain monocarboxylic acids, or of (2) one or more long chain polycarboxylic acids, or of (3) a combination of at least one acid of (1) and at least one acid of (2). Generally speaking, these acids contain from about 8 to about 50 carbon atoms in the molecule and thus the salts are 20 oil-soluble. A variety of amines can be used in forming such salts, including primary, secondary and tertiary amines, and the amines can be monoamines, or polyamines. Further, the amines may be cyclic or acyclic aliphatic amines, aromatic amines, hetero-cyclic amines, or amines containing various mixtures of acyclic 25 and cyclic groups.

Preferred amine salts include the alkyl amine salts of alkanoic acid and the alkyl amines salts of alkanedioic acids.

The amine salts are formed by classical chemical reac-tions, namely, the reaction of an amine or mixture of amines, with'the appropriate acid or mixture of acids. AccordinglY, fur-ther discussion concerning methods for the preparation of such materials would be redundant.

Among the amine salts of long-chain acids that may be 5 used are the following: lauryl ammonium laurate (i.e. thé lauryl amine salt of lauric acid), stearyl ammonium laurate, cyclohexyl ammonium laurate, octyl ammonium laurate, pyridine laurate, ani-line laurate, lauryl ammonium stearate, stearyl ammonium stear-ate, cyclohexyl ammonium stearate, octylammonium stëarate, pyri-10 dine stearate, aniline stearate, lauryl ammonium octanoate,stearyl ammonium octanoate, cyclohexyl ammonium octanoate, octyl ammonium octanoate, pyridine octanoate, aniline octanoate, nonyl ammonium laurate, nonyl ammonium stearate, nonyl ammonium octa-noate, lauryl ammonium nonanoate, stearyl'ammonium nonanoate, 15 cyclohexyl ammonium nonanoate, octyl ammonium nonanoate, pyridine nonanoate, aniline nonanoate, nonyl ammonium nonanoate, lauryl ammonium decanoate, stearyl ammonium decanoate, cyclohexyl ammo-nium decanoate, octyl ammonium deconoate, pyridine decanoate, aniline decanoate, decyl ammonium laurate, decyl ammonium stear-20 ate, decyl ammonium octanoate, decyl ammonium nonanoate, decyl ammonium decanoate, bis octyl amine salt of suberic acid, bis cyclohexyl amine salt of suberic acid, bis lauryl amine salt of suberic acid, bis stearyl amine salt of suberic acid, bis octyl amine salt of sebacic acid, bis cyclohexyl amine salt of sebacic' 25 acid, bis lauryl amine salt of sebacic acid, bis stearyl amine ~salt of sebacic acid, the tert-dodecyl and tert-tetradecyl pri-mary amine salts of octanoic acid, the tert-decyl and tert-dodecyl primary amine salts of octanoic acid, the tert-dodecyl and tert-tetradecyl primary amine salts of lauric acid, the 30 tert-decyl and tert-dodecyl primary amine salts of lauric acid, the tert-dodecyl and tert-tetradecyl primary amine salts of stearic acid, the tert-decyl and tert-dodecyl primary amine salts of stearic acid, the hexyl amine salt of C24-dicarboxylic acid, the octyl amine salt of C28-dicarboxylic acid, the octyl amine salt of C30-dicarboxylic acid, the decyl amine salt of C30-dicarboxylic acid, the octyl amine salt of C32-dicarboxylic S acid, the bis lauryldimethyl amine salt of traumatic acid, di-ethyl ammonium laurate, dioctyl ammonium laurate, dicyclohexyl ammonium laurate, diethyl ammonium octanoate, dioctyl ammonium octanoate, dicyclohexyl ammonium octanoate, diethyl ammonium stearate, dioctyl ammonium stearate, diethyl ammonium stearate, 10 dibutyl ammonium stearate, dicyclopentyl ammonium stearate, dipropyl ammonium benzoate, didecyl ammonium benzoate, dimethyl-cyclohexyl ammonium benzoate, triethyl ammonium laurate, triethyl ammonium octanoate, triethyl ammonium stearate, triethyl ammonium benzoate, trioctyl ammonium laurate, trioctyl ammonium octanoate, 15 trioctyl ammonium stearate, trioctyl ammonium benzoate, and the like. It will be understood of course that the amine salt of the monocarboxylic and/or polycarboxylic acid used should be suffi-ciently soluble in the base oil used as to provide homogeneous solution at the concentration employed.

Among the preferred ami-ne salts for use in practice of this invention are the primary amine salts of long chain mono-carboxylic acids in which the amine thereof is a monoalkyl mono-amine, RNH2; the secondary amine salts of long chain monocar-boxylic acids in which the amine thereof is a dialkyl monoamine, 25 R2NH; the tertiary amine salts of long chain monocarboxylic acids in which the amine thereof is a trialkyl monoamine, R3N;

the bis primary amine salts of long chain dicarboxylic acids in . . . . . .
which the amine thereof is a monoalkyl monoamine, RNH2; the bis secondary amine salts of long chain dicarboxylic acids in which 30the amine thereof is a dialkyl monoamine, R2NH; the bis terti-ary amine salts of long chain dicarboxylic acids in which the amine thereof is a trialkyl monoamine, R3N; and mixtures ~3~

thereof. In the foregoing formulae, R is an alkyl group which contains up to about 30 or more carbon atoms, and preferably from about 6 to about 24~carbon atoms.

.. . .
As pointed out above, the other components which may be 5 used in the gear oil formulations of this invention are well known to those skilled in the art, and form no part of this inven-tion. Nevertheless, brief discussions concernin~ a few such com-ponents are set forth below.

Extreme pressure and antiwear aaents - The most common 10 chemical elements found in extreme pressure and antiwear gear oil additives are sulfur, chlorine, phosphorus, lead, zinc, or boron. A number of sulfur-containing additives, phosphorus-containing additives, and sulfur- and phosphorus-containing additives, have been identified at the outset hereinabove. Pre-15 ferred additives of this type include mixtures of alkyl phos-phites and phosphates, sulfurized olefins, sulfurized esters, di-hydrocarbyl polysulfides, and like materials. Typical chlorine-containing additives include chlorinated paraffin wax, trichloro-thioacetals, tris(trichloroethyl)phosphate, metal chlorides, reac-20 tion products between chlorine or chloride anion with compoundscontaining suitable functionality (such as olefins, carboxylic acids, alcohols, etc.), and~like materials. Additives based on lead are normally lead soaps such as lead naphthenate or lead oleate, or lead salts such as lead carbamate. Typical zinc addi-25 tives include zinc dithiophosphates, zinc dithiocarbamates, zincsalts of organic acids, such as zinc acetate, zinc naphthenate, zinc salts of ethylene diamine tetraacetic acid, zinc chelates such as zinc octyl acetoacetate, and the like. Among the boron additi~es which may used are boronated amines, metal borate 30 salts, boronated phosphenes, boronated phosphites, and the like.

20~0096 EI-6087 ~ efoamers - Illustrative materials of this type include silicone oils of suitable viscosity, sodium and potassium salts of oil soluble acids such as potassium oleate, sodium alkylben-zene sulfonates, etc., glycerol monostearate, polyglycol palmi-5 tate, trialkyl monothiophosphates, esters of sulfonated ricin-oleic acid, benzoylacetone, methyl salicylate, glycerol mono-oleate, glycerol dioleate, and the like. Defoamers are generally employed at concentrations of up to about 1% in the additive concentrate .

Demulsifiers - Typical additives which may be employed as demulsifiers in gear oils include alkyl benzene sulfonates, polyethylene oxides, polypropylene oxides, salts and esters of oil soluble acids, and the li~e. Such additives are generally employed at concentration of up to about 3% in the additive 15 Concentrate.

Su~fur soavfn~ers - This class of additivee includes such materials as thiadiazoles, triazoles, and in general, compounds containing moieties reactive to free sulfur under elevated temperature conditions. See for example U.S. Pat. Nos.
20 3,663,561 and 4,097,387. Concentrations of up to about 3% in the concentrate are typical.

A~ idants - Ordinarily, antioxidants that may be employed in gear oil formulations include phenolic compounds, amines, phosphites, and the li~e. Amounts of up to about 5% in I .
25 the concentrate are generally sufficient.

Other commonly used additives or components include anti-rust agents or rust inhibitors, corrosion inhibitors, deter~
gents, dyes, metal deactivators, pour point depressants, and diluents.

!~=

~a o ~ ~ EI-6087 This invention is susceptible to considerable variation within the spirit and scope of the appended claims, the forms presented hereinabove constituting preferred embodiments thereof.

.. . ", . . .

Claims

What is claimed is:

l. A gear-oil composition comprising a major amount of a gear oil base stock containing a sulfur additive complement, a phosphorus additive complement, and a nitrogen additive comple-ment, in proportions such that the composition possesses a weight ratio of sulfur to phosphorus in the range of about 5:1 to about 40:1 and a weight ratio of nitrogen to phosphorus in the range of about 0.05:1 to about 2:1, said base oil additionally containing a minor effective amount of:
(i) at least one carboxylic derivative composition pro-duced by reacting at least one substituted succinic acylating agent with a reactant selected from the group consisting of (a) amine having at least one primary or secondary amino group in the molecule, (b) alcohol, (c) reactive metal or reactive metal com-pound, and (d) a combination of two or more of any of (a) through (c) the components of (d) being reacted with such substituted succinic acylating agent(s) simultaneously or sequentially in any order, wherein such substituted succinic acylating agent(s) has/
have a substituent group derived from polyalkene having an Mn value of about 500 to about 10,000, and (ii) at least one oil-soluble fully-esterified hydro-carbyl ester of a phosphoric acid or at least one oil-soluble fully-esterified hydrocarbyl ester of a phosphorothioic acid, or a combination of at least one oil-soluble fully-esterified hydro-carbyl ester of a phosphoric acid and at least one oil-soluble fully-esterified hydrocarbyl ester of a phosphorothioic acid.
2. A composition as claimed in Claim 1 wherein compo-nent (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides.
3. A composition as claimed in Claim 1 wherein compo-nent (i) is composed predominantly or entirely of a succinic ester or a mixture of succinic esters.
4. A composition as claimed in Claim 1 wherein compo-nent (i) is composed predominantly or entirely of a boronated succinimide or a mixture of boronated succinimides.
5. A composition as claimed in Claim 1 wherein compo-nent (i) is composed predominantly or entirely of a boronated succinic ester or a boronated mixture of succinic esters.
6. A composition as claimed in Claim 1 wherein said substituent group is derived from polyalkene having an Mn value in the range of from about 750 to about 5,000.
7. A composition as claimed in Claim 1 wherein said substituent group is derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000.
8. A composition as claimed in Claim 1 wherein said reactant is composed predominantly or entirely of at least one alkylene polyamine having both primary and secondary amino groups in the molecule.
9. A composition as claimed in Claim 1 wherein said reactant is composed predominantly or entirely of at least one alkylene polyamine represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to about 10 and m is in the range of 0 to 10.
10. A composition as claimed in Claim 1 wherein said reactant is composed predominantly or entirely of at least one alkylene polyamine represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 6.
11. A composition as claimed in Claim 1 wherein said reactant is composed predominantly or entirely of a mixture of alkylene polyamines represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is 2 and m is in the range of 0 to about 10.
12. A composition as claimed in Claim 1 wherein compo-nent (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting alkenyl succinic acid or alkenyl succinic anhydride or a mixture of alkenyl succi-nic acid and alkenyl succinic anhydride with an alkylene poly-amine or a mixture of alkylene polyamines to form a succinimide or a mixture of succinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from polyalkene having an Mn value in the range of from about 750 to about 5,000.
13. A composition as claimed in Claim 1 wherein compo-nent (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhy-dride with an ethylene polyamine or a mixture of ethylene poly-amines to form a succinimide or a mixture of succinimides, the polyisobutenyl group of the succinic acid or of the succinic anhy-dride or of both of the succinic acid and the succinic anhydride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000.
14. A composition as claimed in Claim 1 wherein compo-nent (i) is composed predominantly or entirely of a boronated succinimide or a mixture of boronated succinimides formed by reacting alkenyl succinic acid or alkenyl succinic anhydride or a mixture of alkenyl succinic acid and alkenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being de-rived from polyalkene having an Mn value in the range of from about 750 to about 5,000; and by reacting a succinimide or a mix-ture of succinimides so formed with a boron-containing reactant.
15. A composition as claimed in Claim 1 wherein compo-nent (i) is composed predominantly or entirely of a boronated succinimide or a mixture of boronated succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and poly-isobutenyl succinic anhydride with an ethylene polyamine or a mix-ture of ethylene polyamines to form a succinimide or a mixture of succinimides, the polyisobutenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000; and by react-ing a succinimide or a mixture of succinimides so formed with a boron-containing reactant.
16. A composition as claimed in Claim 1 wherein compo-nent (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid.
17. A composition as claimed in Claim 1 wherein component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group.
18. A composition as claimed in Claim 1 wherein the gear oil base stock additionally contains a minor effective amount of (iii) at least one amine salt of one or more long chain monocarboxylic acids or at least one amine salt of one or more long chain polycarboxylic acids, or a combination of at least one amine salt of one or more long chain monocarboxylic acids and at least one amine salt of one or more long chain polycarboxylic acids.
19. A composition as claimed in Claim 18 wherein compo-nent (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhy-dride with an ethylene polyamine or a mixture of ethylene poly-amines to form a succinimide or a mixture of succinimides, the polyisobutenyl group of the succinic acid or of the succinic anhy-dride or of both of the succinic acid and the succinic anhydride being derived from polyisobutene having an Mn value of about 1,300: and wherein component (iii) includes an alkyl amine salt of an alkanoic acid.
20. A composition as claimed in Claim 18 wherein component (i) is composed predominantly or entirely of a boro-nated succinimide or a mixture of boronated succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl suc-cinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an ethylene polyamine or a mixture of ethylene polyamines to form a succinimide or a mixture of succinimides, the polyisobutenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from polyisobutene having an Mn value of about 1,300; and by reacting a succinimide or a mixture of succinimides so formed with a boron-containing reactant; and wherein component (iii) includes an alkyl amine salt of an alka-noic acid.
21. A composition as claimed in Claim 18 wherein compo-nent (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhy-dride with an ethylene polyamine or a mixture of ethylene poly-amines the polyisobutenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the suc-cinic anhydride being derived from polyisobutene having an Mn value of about 1,300; and wherein component (iii) includes an alkyl amine salt of an alkanedioic acid.
22. A composition as claimed in Claim 18 wherein compo-nent (i) is composed predominantly or entirely of a boronated succinimide or a mixture of boronated succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and poly-isobutenyl succinic anhydride with an ethylene polyamine or a mixture of ethylene polyamines to form a succinimide or a mixture of succinimides, the polyisobutenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from polyisobutene having an Mn value of about 1,300; and by reacting a succinimide or a mixture of succinimides so formed with a boron-containing reactant; and wherein component (iii) includes an alkyl amine salt of an alkane-dioic acid.
23. A composition as claimed in Claim 18 wherein compo-nent (iii) includes an alkyl amine salt of an alkanoic acid, or an alkyl amine salt of an alkanedioic acid, or a combination of an alkyl amine salt of an alkaneoic acid and an alkyl amine salt of alkanedioic acid.
24. A composition as claimed in Claim 18 wherein compo-nent (iii) includes at least one primary amine salt of a long chain monocarboxylic acid in which the amine thereof is a mono-alkyl monoamine, RNH2.
25. A composition as claimed in Claim 18 wherein compo-nent (iii) includes at least one secondary amine salt of a long chain monocarboxylic acid in which the amine thereof is a dialkyl monoamine, R2NH.
26. A composition as claimed in Claim 18 wherein compo-nent (iii) includes at least one tertiary amine salt of a long chain monocarboxylic acid in which the amine thereof is a tri-alkyl monoamine, R3N.
27. A composition as claimed in Claim 18 wherein component (iii) includes at least one bis primary amine salt of a long chain dicarboxylic acid in which the amine thereof is a monoalkyl monoamine, RNH2.
28. A composition as claimed in Claim 18 wherein compo-nent (iii) includes at least one bis secondary amine salt of a long chain dicarboxylic acid in which the amine thereof is a dialkyl monoamine, R2NH.
29. A composition as claimed in Claim 18 wherein said at least one amine salt includes at least one bis tertiary amine salt of a long chain dicarboxylic acid in which the amine thereof is a trialkyl monoamine, R3N.
30. A composition as claimed in Claim 18 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting alkenyl succinic acid or alkenyl succinic anhydride or a mixture of alkenyl succinic acid and alkenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from poly-alkene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;

b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes an alkyl amine salt of a long chain monocarboxylic acid.
31. A composition as claimed in Claim 18 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting alkenyl succinic acid or alkenyl succinic anhydride or a mixture of alkenyl succinic acid and alkenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from poly-alkene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10:
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes an alkyl amine salt of a long chain dicarboxylic acid.
32. A composition as claimed in Claim 18 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting alkenyl succinic acid or alkenyl succinic anhydride or a mixture of alkenyl succinic acid and alkenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from polyalkene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene poly-amines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes an alkyl amine salt of a long chain monocarboxylic acid and an alkyl amine salt of a long chain dicarboxylic acid.
33. A composition as claimed in Claim 30 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
34. A composition as claimed in Claim 31 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
35. A composition as claimed in Claim 32 wherein compo-nent (i) is a boronated succinimide or mixture of boronated succinimides.
36. A composition as claimed in Claim 18 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succin-imides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhy-dride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to .
about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes at least one primary amine salt of a long chain monocarboxylic acid in which the amine thereof is a monoalkyl monoamine, RNH2.
37. A composition as claimed in Claim 18 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succin-imides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhy-dride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes at least one secondary amine salt of a long chain monocarboxylic acid in which the amine thereof is a dialkyl monoamine, R2NH.
38. A composition as claimed in Claim 18 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succin-imides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhy-dride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes at least one tertiary amine salt of a long chain monocarboxylic acid in which the amine thereof is a trialkyl monoamine, R3N.
39. A composition as claimed in Claim 18 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succin-imides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhy-dride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group: and c) component (iii) includes at least one bis primary amine salt of a long chain dicarboxylic acid in which the amine thereof is a monoalkyl monoamine, RNH2.
40. A composition as claimed in Claim 18 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succin-imides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhy-dride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes at least one bis secondary amine salt of a long chain dicarboxylic acid in which the amine thereof is a dialkyl monoamine, R2NH.
41. A composition as claimed in Claim 18 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succin-imides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhy-dride being derived from polyisobutene having an Mn value in the range of from about 750, to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes at least one bis tertiary amine salt of a long chain dicarboxylic acid in which the amine thereof is a trialkyl monoamine, R3N.
42. A composition as claimed in Claim 36 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
43. A composition as claimed in Claim 37 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
44. A composition as claimed in Claim 38 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
45. A composition as claimed in Claim 39 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
46. A composition as claimed in Claim 40 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
47. A composition as claimed in Claim 41 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
48. A gear oil additive concentrate which includes a sulfur additive complement, a phosphorus additive complement, and a nitrogen additive complement, in proportions such that the con-centrate possesses a weight ratio of sulfur to phosphorus in the range of about 5:1 to about 40:1 and a weight ratio of nitrogen to phosphorus in the range of about 0.05:1 to about 2:1, said concentrate additionally containing a minor effective amount of:
(i) at least one carboxylic derivative composition pro-duced by reacting at least one substituted succinic acylating agent with a reactant selected from the group consisting of (a) amine having at least one primary or secondary amino group in the molecule, (b) alcohol, (c) reactive metal or reactive metal com-pound, and (d) a combination of two or more of any of (a) through (c) the components of (d) being reacted with such substituted suc-cinic acylating agent(s) simultaneously or sequentially in any order, wherein such substituted succinic acylating agent(s) has/
have a substituent group derived from polyalkene having an Mn value of about 500 to about 10,000, and (ii) at least one oil-soluble fully-esterified hydrocarbyl ester of a phosphoric acid or at least one oil-soluble fully-esterified hydrocarbyl ester of a phosphorothioic acid, or a combination of at least one oil-soluble fully-esterified hydrocarbyl ester of a phosphoric acid and at least one oil-soluble fully-esterified hydrocarbyl ester of a phosphoro-thioic acid.
49. A composition as claimed in Claim 48 wherein compo-nent (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides.

. .
50. A composition as claimed in Claim 48 wherein compo-nent (i) is composed predominantly or entirely of a succinic ester or a mixture of succinic esters.
51. A composition as claimed in Claim 48 wherein compo-nent (i) is composed predominantly or entirely of a boronated succinimide or a mixture of boronated succinimides.
52. A composition as claimed in Claim 48 wherein compo-nent (i) is composed predominantly or entirely of a boronated succinic ester or a boronated mixture of succinic esters.
53. A composition as claimed in Claim 48 wherein said substituent group is derived from polyalkene having an Mn value in the range of from about 750 to about 5,000.
54. A composition as claimed in Claim 48 wherein said substituent group is derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000.
55. A composition as claimed in Claim 48 wherein said reactant is composed predominantly or entirely of at least one alkylene polyamine having both primary and secondary amino groups in the molecule.
56. A composition as claimed in Claim 48 wherein said reactant is composed predominantly or entirely of at least one alkylene polyamine represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to about 10 and m is in the range of 0 to 10.
57. A composition as claimed in Claim 48 wherein said reactant is composed predominantly or entirely of at least one alkylene polyamine represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 6.
58. A composition as claimed in Claim 48 wherein said reactant is composed predominantly or entirely of a mixture of alkylene polyamines represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is 2 and m is in the range of 0 to about 10.
59. A composition as claimed in Claim 48 wherein compo-nent (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting alkenyl succinic acid or alkenyl succinic anhydride or a mixture of alkenyl suc-cinic acid and alkenyl succinic anhydride with an alkylene poly-amine or a mixture of alkylene polyamines to form a succinimide or a mixture of succinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from polyalkene having an Mn value in the range of from about 750 to about 5,000.
60. A composition as claimed in Claim 48 wherein compo-nent (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhy-dride with an ethylene polyamine or a mixture of ethylene poly-amines to form a succinimide or a mixture of succinimides, the polyisobutenyl group of the succinic acid or of the succinic anhy-dride or of both of the succinic acid and the succinic anhydride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000.
61. A composition as claimed in Claim 48 wherein compo-nent (i) is composed predominantly or entirely of a boronated suc-cinimide or a mixture of boronated succinimides formed by react-ing alkenyl succinic acid or alkenyl succinic anhydride or a mix-ture of alkenyl succinic acid and alkenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from poly-alkene having an Mn value in the range of from about 750 to about 5,000; and by reacting a succinimide or a mixture of succinimides so formed with a boron-containing reactant.
62. A composition as claimed in Claim 48 wherein compo-nent (i) is composed predominantly or entirely of a boronated succinimide or a mixture of boronated succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and poly-isobutenyl succinic anhydride with an ethylene polyamine or a mix-ture of ethylene polyamines to form a succinimide or a mixture of succinimides, the polyisobutenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000; and by react-ing a succinimide or a mixture of succinimides so formed with a boron-containing reactant.
63. A composition as claimed in Claim 48 wherein compo-nent (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid.
64. A composition as claimed in Claim 48 wherein compo-nent (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group.
65. A composition as claimed in Claim 48 wherein the concentrate additionally contains a minor effective amount of (iii) at least one amine salt of one or more long chain mono-carboxylic acids or at least one amine salt of one or more long chain polycarboxylic acids, or a combination of at least one amine salt of one or more long chain monocarboxylic acids and at least one amine salt of one or more long chain polycarboxylic acids.
66. A composition as claimed in Claim 65 wherein compo-nent (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhy-dride with an ethylene polyamine or a mixture of ethylene poly-amines to form a succinimide or a mixture of succinimides, the polyisobutenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhy-dride being derived from polyisobutene having an Mn value of about 1,300; and wherein component (iii) includes an alkyl amine salt of an alkanoic acid.
67. A composition as claimed in Claim 65 wherein compo-nent (i) is composed predominantly or entirely of a boronated suc-cinimide or a mixture of boronated succinimides formed by react-ing polyisobutenyl succinic acid or polyisobutenyl succinic anhy-dride or a mixture of polyisobutenyl succinic acid and polyiso-butenyl succinic anhydride with an ethylene polyamine or a mix-ture of ethylene polyamines to form a succinimide or a mixture of succinimides, the polyisobutenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from polyisobutene having an Mn value of about 1,300; and by reacting a succinimide or a mixture of succinimides so formed with a boron-containing reactant; and wherein component (iii) includes an alkyl amine salt of an alka-noic acid.
68. A composition as claimed in Claim 65 wherein compo-nent (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhy-dride with an ethylene polyamine or a mixture of ethylene poly-amines the polyisobutenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the suc-cinic anhydride being derived from polyisobutene having an Mn value of about 1,300; and wherein component (iii) includes an alkyl amine salt of an alkanedioic acid.
69. A composition as claimed in Claim 65 wherein compo-nent (i) is composed predominantly or entirely of a boronated succinimide or a mixture of boronated succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and poly-isobutenyl succinic anhydride with an ethylene polyamine or a mix-ture of ethylene polyamines to form a succinimide or a mixture of succinimides, the polyisobutenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from polyisobutene having an Mn value of about 1,300; and by reacting a succinimide or a mixture of succinimides so formed with a boron-containing reactant; and wherein component (iii) includes an alkyl amine salt of an alkanedioic acid.
70. A composition as claimed in Claim 65 wherein compo-nent (iii) includes an alkyl amine salt of an alkanoic acid, or an alkyl amine salt of an alkanedioic acid, or a combination of an alkyl amine salt of an alkaneoic acid and an alkyl amine salt of alkanedioic acid.
71. A composition as claimed in Claim 65 wherein compo-nent (iii) includes at least one primary amine salt of a long chain monocarboxylic acid in which the amine thereof is a mono-alkyl monoamine, RNH2.
72. A composition as claimed in Claim 65 wherein compo-nent (iii) includes at least one secondary amine salt of a long chain monocarboxylic acid in which the amine thereof is a dialkyl monoamine, R2NH.
73. A composition as claimed in Claim 65 wherein compo-nent (iii) includes at least one tertiary amine salt of a long chain monocarboxylic acid in which the amine thereof is a tri-alkyl monoamine, R3N.
74. A composition as claimed in Claim 65 wherein compo-nent (iii) includes at least one bis primary amine salt of a long chain dicarboxylic acid in which the amine thereof is a monoalkyl monoamine, RNH2.
75. A composition as claimed in Claim 65 wherein compo-nent (iii) includes at least one bis secondary amine salt of a long chain dicarboxylic acid in which the amine thereof is a di-alkyl monoamine, R2NH.
76. A composition as claimed in Claim 65 wherein compo-nent (iii) includes at least one bis tertiary amine salt of a long chain dicarboxylic acid in which the amine thereof is a tri-alkyl monoamine, R3N.
77. A composition as claimed in Claim 65 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting alkenyl succinic acid or alkenyl succinic anhydride or a mixture of alkenyl succinic acid and alkenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from poly-alkene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes an alkyl amine salt of a long chain monocarboxylic acid.
78. A composition as claimed in Claim 65 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting alkenyl succinic acid or alkenyl succinic anhydride or a mixture of alkenyl succinic acid and alkenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from poly-alkene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes an alkyl amine salt of a long chain dicarboxylic acid.
79. A composition as claimed in Claim 65 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting alkenyl succinic acid or alkenyl succinic anhydride or a mixture of alkenyl succinic acid and alkenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhydride being derived from poly-alkene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10:
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes an alkyl amine salt of a long chain monocarboxylic acid and an alkyl amine salt of a long chain dicarboxylic acid.
80. A composition as claimed in Claim 77 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
81. A composition as claimed in Claim 78 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
82. A composition as claimed in Claim 79 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
83. A composition as claimed in Claim 65 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succin-imides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhy-dride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes at least one primary amine salt of a long chain monocarboxylic acid in which the amine thereof is a monoalkyl monoamine, RNH2.
84. A composition as claimed in Claim 65 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succin-imides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhy-dride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes at least one secondary amine salt of a long chain monocarboxylic acid in which the amine thereof is a dialkyl monoamine, R2NH.
85. A composition as claimed in Claim 65 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of suc-cinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the suc-cinic anhydride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;

b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes at least one tertiary amine salt of a long chain monocarboxylic acid in which the amine there-of is a trialkyl monoamine, R3N.
86. A composition as claimed in Claim 65 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of succin-imides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the succinic anhy-dride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes at least one bis primary amine salt of a long chain dicarboxylic acid in which the amine thereof is a monoalkyl monoamine, RNH2.
87. A composition as claimed in Claim 65 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of suc-cinimides, the alkenyl group of the succinic acid or of the suc-cinic anhydride or of both of the succinic acid and the succinic anhydride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000, the alkylene poly-amine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes at least one bis secondary amine salt of a long chain dicarboxylic acid in which the amine thereof is a dialkyl monoamine, R2NH.
88. A composition as claimed in Claim 65 wherein:
a) component (i) is composed predominantly or entirely of a succinimide or a mixture of succinimides formed by reacting polyisobutenyl succinic acid or polyisobutenyl succinic anhydride or a mixture of polyisobutenyl succinic acid and polyisobutenyl succinic anhydride with an alkylene polyamine or a mixture of alkylene polyamines to form a succinimide or a mixture of suc-cinimides, the alkenyl group of the succinic acid or of the succinic anhydride or of both of the succinic acid and the suc-cinic anhydride being derived from polyisobutene having an Mn value in the range of from about 750 to about 5,000, the alkylene polyamine or mixture of alkylene polyamines being represented by the formula H2N(CH2)n(NH(CH2)n)mNH2 wherein n is in the range of 2 to 3 and m is in the range of 0 to about 10;
b) component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid of the formula wherein each of R1 and R2 is independently an alkyl group and R3 is an alicyclic hydrocarbyl group; and c) component (iii) includes at least one bis tertiary amine salt of a long chain dicarboxylic acid in which the amine thereof is a trialkyl monoamine, R3N.
89. A composition as claimed in Claim 83 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
90. A composition as claimed in Claim 84 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
91. A composition as claimed in Claim 85 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
92. A composition as claimed in Claim 86 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
93. A composition as claimed in Claim 87 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.
94. A composition as claimed in Claim 88 wherein compo-nent (i) is a boronated succinimide or mixture of boronated suc-cinimides.