AU627957B2 - Gear oil and additives therefor - Google Patents

Description

i C. i_ C 62 J, COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION NAME ADDRESS OF APPLICANT:

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Ethyl Petroleum Additives, Inc.

South Fourth Street St. Louis Missouri 63102-1886 United States of America NAME(S) OF INVENTOR(S): Stephen NORMAN Gregory Steven CONARY A A

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C. Q A ADDRESS FOR SERVICE: DAVIES COLLISON Patent Attorneys 1 Little Collins Street, Melbourne, 3000.

COMPLETE SPECIFICATION FOR THE INVENTION ENTITLED: Gear oil and additives therefor The following statement is a full description of this invention, including the best method of performing it known to me/us:- A4

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la- This invention relates to gear oils and gear oil additive formulations having enhanced performance characteristics. More particularly this invention relates to gear oil and gear oil additive compositions 0 having enhanced antiwear and extreme pressure properties.

o a0 In order to satisfy the performance criteria imposed o* upon automotive and industrial gear oils, a large number of additives 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 more of these additives can contain two, and possibly all three, of the elements P, S and N. But irrespective of the a number and chemical composition of the individual additives employed, the commercially-used gear oil additive packages generally have an over-all sulfurto-phosphorus weight ratio in the range of 5:1 to 40:1, and an over-all nitrogen-to-phosphorus weight ratio in the range of 0.05:1 to 2:1.

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F- 2 Among the phosphorus-containing additives proposed for use in gear oils are monoalkyl phosphites and phosphates, dialkyl phosphites and phosphates, trialkyl phosphites and phosphates, monoaryl phosphites and phosphates, diaryl phosphites and phosphates, triaryl phosphites and phosphates, long chain phosphoric or phosphonic acids and esters, alkyl acid phosphates, alicyclic esters of phosphoric acids, and the like.

o Included among the sulfur-containing additives proposed So010 for use in gear oils are 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 o 15 amides, long chain amines, long chain imides, aromatic j 0 amines, alkenyl succinimides, amine salts of high molecular weight organic acids, alkylamines, polyacrylamides, triazole derivatives, and the like. Some of the o 0" additives containing at least two of the elements P, S j 20 and N in the same molecule proposed for gear oil usage are dithiophosphoric acid esters, zinc dithiophosphates, zinc and lead dithiocarbamates, phosphosulfurized terpenes, thiadiazoles, amine phosphates, olefin/phosphorus pentasulfide reaction products, and the like.

Unfortunately, during actual service conditions, a -1~.1-11 3 number of phosphorus-containing antiwear and extreme pressure additives tend to separate froi 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 undesirable. A need thus exists for an effective o ,and efficient way of overcoming this adverse problem.

o *10 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 o eo produce excessive deposits on the gear face. Oftentimes these deposits average as much as 0.02 to 0.03 millimeter in thickness on the gear face on completion of the test.

.44 For example, ANGLAMOL® 6063A, a commercial gear oil additive formulation available from The Lubrizol Corporation a product believed to contain, inter alia, sulfurized isobutylene, dialkyl polysulfide, and a oo ,20 phosphorus-based antiwear complement, when employed at the recommended dosage level of 6.25 weight percent was found to produce black deposits on the L-60 gear face.

Likewise, a commercial gear oil formulation available from Ethyl Petroleum Additives, Inc., as HITEC® 320 additive, when used at the recommended dosage level of ri 4 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 ANGLAMOL® 6063A additive formulation has a sulfur:phosphorus weight ratio of about 20:1, and a nitrogen:phosphorus weight ratio of about 0.5:1. In the HITEC® 320 additive formulation these ratios are, S°o respectively, 16.3:1 and 0.4:1. Similar considerations apply, both as regards over-all chemical composition and 0 oL-60 gear face performance, to several other commercially available gear oil additive packages.

The formation of such deposits on the gear face in 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 revising their additive packages to provide formulations which give relatively clean gear faces in the L-60 test.

20 This invention provides gear oil and gear oil S: additive formulations which exhibit enhanced antiwear and extreme pressure properties during all types of conventional service conditions. By use of particular combinations of additives, premature thermal and/or n I- urera~ s 5 oxidative degradation of the phosphorus antiwear and extreme pressure components is inhibited, and moreover, the active phosphorus residues resulting from the use of such components remain dissolved or at least suspended in the gear oil so that they can continue to exert their beneficial effects. In other words, the phosphoruscontaining antiwear and extreme pressure additives employed pursuant to the practice of this invention do not prematurely precipitate out in the form of sludge or .0 other insoluble residues they remain available within the body of the lubricant to exert their antiwear and extreme pressure functions.

00 o 000 00r 0) o 0 00 0 0c 0 0 og o *000 0 00 0 0a 00 0 P 0 @0 0 O 0 9 O 0 00 00 0 0 0 0 0 0 0* 0 0 (a v In accordance with one of its embodiments, this invention provides a gear oil composition comprising a 15 major amount of a gear oil base stock containing a sulfur additive complement, a phosphorus additive complement, and a nitrogen additive complement, in proportions such that the composition possesses a weight ratio of sulfur to phosphorus in the range of 5:1 to 40:1 and a weight 20 ratio of nitrogen to phosphorus in the range of 0.05:1 to 2:1, said gear oil additionally containing a minor effective amount of: at least one carboxylic derivative composition produced by reacting at least one substituted succinic acylating agent with a reactant selected from the group

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rirru~ur~i~ ;r -u 6 consisting of amine having at least one primary or secondary amino group in the molecule, alcohol, (c) reactive metal or reactive metal compound, and a combination of two or more of any of through the components of 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 *0 from polyalkene having an Mn value of 500 to 10,000 (preferably in the range of 750 to 5,000), and at least one oil-soluble fully-esterified Shydrocarbyl ester of a phosphoric acid or at least one 0 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- O 00 esterified hydrocarbyl ester of a phosphorothioic acid.

Such gear oil compositions exhibit enhanced antiwear and extreme pressure performance by virtue of the aboveo20 referred-to cooperation between components and (ii) 0 o 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 additive complement, in proportions such that the concentrate possesses a weight

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I I~ 7 ratio of sulfur to phosphorus in the range of 5:1 to 40:1 and a weight ratio of nitrogen to phosphorus in the range of 0.05:1 to 2:1, said concentrate additionally containing a minor effective amount of components and (ii) as described above.

A further embodiment of this invention involves the additional presence in the above gear oils and gear oil additive concentrates of a third component whereby the o" resultant gear oil or gear oil additive concentrate :"o0 exhibits enhanced performance in the L-60 Test.

9 S° Accordingly, this invention further provides a gear oil composition comprising a major amount of a gear oil base ^o stock and a minor effective amount of: at least one carboxylic derivative composition produced by reacting at least one substituted succinic acylating agent with a reactant selected from the group 0* consisting of amine having at least one primary or o: secondary amino group in the molecule, alcohol, (c) reactive metal or reactive metal compound, and a o :20 combination of two or more of any of through the 00.0: components of 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 500 to 8 8 10,000 (preferably in the range of 750 to 5,000); (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 fullyesterified hydrocarbyl ester of a phosphorothioic acid; and 1 O0 (iii) at least one amine salt of one or more long S° chain C 8 to C 50 monocarboxylic acids or at least one amine salt of one or more long chain Cg to C 50 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. Such gear oils form little or no deposits on the gear face when the gear oil is subjected 3 to the standard L-60 Test (formerly the CRC L-60 Test and FTMS 791B Method 2504) as set forth in ASTM Special 20 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 test.

Without desiring to be bound by theoretical considerations, it is believed that the succinic derivative 9 0~ 0* 00~ a a a *9 o a 0*00 009 (component 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 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 tendency of sludge

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10 formation involving such trihydrocarbyl phosphoric species. The overall mechanism allows the active phoso phoric residues to remain dissolved or at least suspended in the gear oil so that they can continue to exert their substantial beneficial effects. Irrespective of the actual mechanism or mechanisms involved, the net result of the use of these components in combination is that excellent extreme pressure and antiwear effects are achieved and, additionally, the gear faces obtained from the L-60 test are clean or essentially clean.

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

The gear oil &aditive concentrates of this invention are generally employed in suitable lubricant base stocks in amounts ranging from 1 to 15% by weight. For aaa.

P 0 o a. C 0 0 C ,r 10 ao o o o 0 0 00 0 0 0 0 o o 0 a2 0 0 0 2 0 0 4 automotive gear oil use, it is preferred to employ the additive concentrates in amounts in the range of 2.5 to weight percent and for industrial use, amounts in the range of 1 to 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 or a combination of reactant with one or more of reactants and/or are collectively referred to as "succinimides", a term which is meant to encompass the completed 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. Similarly, the products formed from reactant or a combination of reactant with reactant are collectively referred to as "succinic esters", a term which is meant to encompass the completed reaction product from the reaction irrespective of whether the product contains salt linkages in addition to the ester linkage of the type that results from the reaction of a hydroxyl group and an anhydride moiety.

The succinimides and succinic esters can, in 11 accordance with still further embodiments of this invention, be chemically modified by boronation, e.g., the succinimide(s) and succiuit ester(s) can be reacted with boric acid or like boron-containing reactant in order to incorporate a small amount (usually in the range of 0.5 to 2 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) o and/or succinic ester(s) are feasible. For the sake of So 10 brevity, such boron-containing succinimides and ,boron-containing succinic esters will be collectively So referred to hereinafter as "boronated succinimides" and "boronated succinic esters", respectively.

A feature of this invention is that the chemical composition of the sulfur- and nitrogen-containing additive complement and, except for component (ii), the chemical composition of additional phosphoruscontaining additive(s) in the gear oil and gear oil d additive formulations can be widely varied and thus is of no concern as regards the practice of this o invention. Likewise, the chemical composition and properties of the other additives employed in the formulations defoamers, demulsifiers, sulfur scavengers, diluents, stabilizers, antioxidants, mntal deactivators, or pour point depressants) form no part of 12 this invention. It is to be noted that when preparing the gear oil additive concentrates, individual components may interact with each other to produce new chemical compounds, as for example, a basic substance reacting with an acidic substance to form a salt or salt-like compound. As long as the concentrete performs the functions of a conventional gear oil additive formulation, the concentrate is suitable for use in the practice of this invention.

o 10 Preferred gear oil additive packages of this Sinvention are soluble in mineral and synthetic base oils S* to the extent of at least 15 weight percent at i The above and other features and embodiments of this invention will become still further apparent from the ensuing description and appended claims.

O Inasmuch as the composition, characteristics, and methods for the preparation of the various additives used S in the production of gear oils are well known to those oe, 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) component above), preferably one or more succinimides or boronated succinimides, iii an amount ranging from 5 to 20 (and preferably from 10 to

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13 weight percent of the total composition. Likewise, the additive concentrates of this invention will contain from 5 to 40 and preferably from 10 to 30 weight percent of one or more oil-soluble fully-esterified hydrocarbyl esters of a phoc£horic 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 component (ii) above). In the embodiments of this invention involving o component (iii) above, the additive concentrate will o additionally contain from 0.5 to 5 weight percent of one or more amine salts of one or more aliphatic carboxylic acids component (iii) above).

By the same token, the finished gear oils of this invention will contain from 0.2 to 2.0, and preferably from 0.5 to 1.5, weight percent of the succinic a 8 derivative(s) succinimide(s) and/or boronated succinimide(s) and/or succinic ester(s) and/or boronated 0A8 succinic ester(s) (or any mixture of any two or more of the foregoing) and from 0.1 to 3.0, and preferably from 0.5 to 2.0 weight percent of component (ii) above, one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphoric acid or one or more T- e- 14 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 fullyesterified hydrocarbyl esters of a phosphorothioic acid).

The finished gear oils of this invention which additionally contain component (iii) above the amine salt(s) of one or more long chain aliphatic acids) will contain from 0.05 to 0.5, and preferably from 0.08 to 0.4 10 weight percent of component (iii). Although components 0 0 and (ii) have been separately used heretofore in gear o4 oils, it is believed that they have not been used in o combination with each other in gear oils, much less in gear oil compositions yielding the superior antiwear and extreme pressure properties which characterize this invention. Likewise, although components and (iii) have been separately used 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 and (iii) nor Scomponents (ii) and (iii) have been used in combination with each other in gear oils much less in gear oil compositions yielding the results obtainable by the practice of this invention.

The additive concentrates of this invention can be F3 15 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 stocks, naphthenic oils, or cylinder oils, including o o D straight run and blended oils. Synthetic base stocks can 0 also be used in the practice of this invention, such as 10 for example poly-alpha-olefin oils (PAO), alkylated 0 to aromatics, polybutenes, diesters, polyol esters, polyglycols, or polyphenyl ethers, and blends thereof.

ono Typical of such oils are blends of poly-alpha-olefins o.'o with synthetic diesters in weight proportions (PAO:ester) ranging from 95:5 to 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 140. Suitable automotive gear S*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 ISO grade 32 to ISO grade 680 and preferably from ISO grade 68 to ISO grade 460.

In order to illustrate the practice of this invention, the following examples are presented. It is -16- Sto 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 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 of 0.05:1 to 2:1. Likewise, the succinimide referred to o in the examples is the product formed from polyisoo 0 butenylsuccinic anhydride and ethyleie polyamine mixture 1" 0 approximating tetraethylenepentamine in composition; the 4 a isobutenyl group being derived from polyisobutene having an Mn of about 1300. The boronated succinimide referred ova to in the examples is the product formed by reacting 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 succinimidcs are generally formed in the presence of a diluent for processing purposes. Thus in 4, the ensuing examples, the proportions of succinimide or boronated succinimide represent the weight percentage of a blend composed of approximately 67% of the active ingredient the succinimide or boronated succinimide), and approximately 33% of a mineral oil diluent.

Further, in the ensuing examples the trihydrocarbyl dithiophosphate represents the following individual 17 esters: the product formed by reacting di(2-ethylhexyl)dithiophosphoric acid with wax olefin, the product obtained by reacting diamyldithiophosphoric acid with alpha-pinene, the product obtained by reacting diethyldithiophosphoric acid with bicycloheptadiene, (d) the product obtained by reacting di(2-ethylhexyl)dithiophosphoric acid with 1-butene, the product obtained S° o by reacting dimethyldithiophosphoric acid with dicyclo- 1 pentadiene, the product obtained by reacting 10 di-2-ethylhexyl dithiophosphoric acid with cyclo- 0 00 o 0 0 octadiene, the product obtained by reacting di-2ethylhexyl dithiophosphoric acid with styrene, the product obtained by reacting a mixed dialkyldithiophosoo phoric acid with dicyclopentadiene, wherein the alkyl groups are isopropyl, isobutyl, and hexyl, the o product obtained by reacting a mixed dialkyldithiophoso phoric acid with dicyclopentadiene, wherein the alkyl Oo o* groups are isopropyl, isobutyl, and 2-ethylhexyl, the product obtained by reacting a mixed dialkyldithiophosphoric acid with dicyclopentadiene, wherein the alkyl groups are amyl, hexyl, and 2-ethylhexyl, the product obtained by reacting a mixed dialkyldithiophosphoric acid with styrene, wherein the alkyl groups are isopropyl, isobutyl, and hexyl, the product obtained by reacting a mixed dialkyldithiophosphoric acid with styrene, where-

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1.,r 18 in the alkyl groups are isopropyl, isobutyl, and 2-ethylhexyl, the product obtained by reacting a mixed dialkyldithiophosphoric acid with styrene, wherein the alkyl groups are amyl, hexyl, and 2-ethylhexyl, (n) the product obtained by reacting di-2-ethylhexyl dithiophosphoric acid with divinylbenzene, and the product obtained by reacting di-2-ethylhexyl dithiophosphoric acid with butadiene.

O 0 a 06 0 a 6oil !0 0 0 0 0 0000 0 4 os 0 0 0 t 0000 15 10 0000 0 i0 00 0 .0000 s ft i e- t 01 4 a *i 0 0 0 0 00I~ 00 0 o EXAMPLE 1 A gear oil additive concentrate of composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Octyl amine salt of lauric acid Sulfurized isobutylene Alkyl phosphite and phosphate Alkyl amine Defoamer and demulsifier Sulfur scavenger Mineral oil diluent this invention is 15.0% 17.0% 40.0% 1.9% 0.9% 1.3% 15.9% 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 straight grades of 75 or lower or SAE cross grades having a light viscosity 1- 19 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 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 r a viscosity index improver, if desired.

4 0 o *o EXAMPLE 2 o 0 The procedure of Example 1 is repeated except that the succinimide is boronated succinimide.

EXAMPLE 3 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.

4i o 15 EXAMPLE 4 Qo e: A gear oil additive concentrate of this invention is composed of the following ingredients: Succinimide 13.3% Trihydrocarbyl dithiophosphate 18.8% Octyl amine salt of stearic acid 1.7% Sulfurized isobutylene 38.7% Alkyl phosphite and phosphate Alkyl amine 2.1% I 20 Defoamer and demulsifier Sulfur scavenger Mineral oil diluent 1.4% 17.5% Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil bzae -stocks. For automotive use, with SAE straight grades of Sa O 75 or lower or SAE cross grades having a light viscosity s poo end of 75W or lower, the formulation is used at a S..o 10 concentration of 9.45%. For automotive use, with SAE e grades heavier than 75, the treat rate is 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 0 0 a viscosity index improver, if desired.

0 a EXAMPLE 6 2 The procedure of Example 4 is repeated except that o the succinimide is boronated succinimide.

EXAMPLE 6 A gear oil additive concentrate of this invention is composed of the following ingredients: Succinimide 16.6% Trihydrocarbyl dithiophosphate 18.8%

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nnm~"~ i 21 Octyl amine salt of stearic acid 3.3% Sulfurized isobutylene 44.2% Alkyl phosphite and phosphate Alkyl amine 2.1% Defoamer and demulsifier Sulfur scavenger 1.4% Mineral oil diluent 7.1% o Gear oils are formed by blending the concentrate in o o, mineral oil base stocks, synthetic base stocks, and 10 combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE straight grades of "n 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 0" 15 grades heavier than 75, the treat rate is For Sindustrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concen- *o tration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

EXAMPLE 7 The procedure of Example 6 is repeated except that the succinimide is boronated succinimide.

EXAMPLE 8 A gear oil additive concentrate of this invention is composed of the following ingredients: 22 Succinimide 16.6% Trihydrocarbyl dithiophosphate 18.8% Octyl amine salt of stearic acid 1.7% Sulfurized isobutylene 44.1% Alkyl phosphite and phosphate Alkyl amine 2.1% Defoamer and demulsifier Sulfur scavenger 1.4% oo Mineral oil diluent 8.8% 0 10 Gear oils are formed by blending the concentrate in Smineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE straight grades of or lower or SAE cross grades having a light viscosity 15 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 For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concen- \:20 tration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

EXAMPLE 9 The procedure of Example 8 is repeated except that the succinimide is boronated succinimide.

ii 00 23 EXAMPLE A gear oil additive concentrate of this invention is formed by blending together the following components in the proportions specified: Succinimide 9.2% Trihydrocarbyl dithiophosphate 12.3% Process oil o °o Anglamol 6063A* 70.0% 0 6 0 o a 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 oil and synthetic oil base S 15 stocks. For automotive use, with SAE straight grades of or lower or SAE cross grades having a light viscosity o end of 75W or lower, the formulat- n is used at a concentration of 13.4%. For automotive use, with SAE So grades heavier than 75, the treat rate is For 0:20 industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of and the finished oil should contain at least 0.3% demulsifier. Any such base stocks may contain a viscosity index improver, if desired.

24 EXAMPLE 11 The procedure of Example 10 is repeated except that the succinimide is boronated succinimide.

,o s os 0 0 o ni0 o0 0 0* o 0 0 10 0 00 0s 0 0000 0i~0 0 0 15 0 0*o 00 0 EXAMPLE 12 A gear oil additive concentrate of composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Lauryl amine salt of lauric acid Dialkyl polysulfide Alkyl phosphite and phosphate Alkyl amine Defoamer Sulfur scavenger Demulsifier Mineral oil diluent this invention is 12.0% 17.0% 35.0% 1.9% 0.6% 1.3% 0.3% 24.9% 0. Gear oils are formed by blending the concentrate in S* mineral oil base stocks, synthetic base stocks, and r combinations of mineral oil and synthetic oil base S0",20 stocks. For automotive use, with SAE straight grades of 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 For industrial use with ISO viscosity grades 68, 100, 150, j r4 -I-IIIY~~L_ CII- _0 25 220, 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 13 The procedure of Example 12 is repeated except that the succinimide is boronated succinimide.

30 *eo o o 001 O 5 0 O 0 0 0 9 00 o o 0 n P* O 0 0 0 0 0 00 0 10 0 0 0 00 O 09 04 0 0 0 p 4 04 a1 (I EXAMPLE 14 A gear oil additive concentrate of composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Dioctyl amine salt of lauric acid Dialkyl polysulfide Alkyl phosphite and phosphate Alkyl amine Defoamer Sulfur scavenger Demulsifier Mineral oil diluent this invention is 15.0% 17.0% 35.0% 1.9% 0.6% 1.3% 0.3% 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 straight grades of or lower or SAE cross grades having a light viscosity i 26 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 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.

t d EXAMPLE o 4 The procedure of Example 14 is repeated except that 10 the succinimide is boronated succinimide.

4rc4 4 44 o 4 4 1 4 4 44 4 4 EXAMPLE 16 A gear oil additive concentrate of this invention is composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Trioctyl amine salt of lauric acid Dialkyl polysulfide Alkyl phosphite and phosphate Alkyl amine Defoamer Sulfur scavenger Demulsifier Mineral oil diluent 15.0% 15.0% 40.0% 2.2% 0.6% 1.3% 0.3% 15.6% 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 concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is For o, industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a conceno tration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

EXAMPLE 17 o 5 The procedure of Example 16 is repeated except that 15 the succinimide is boronated succinimide.

Sa o 0 S. EXAMPLE 18 i 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 Dialkyl polysulfide 45.0% Alkyl phosphite and phosphate Alkyl amine 2.4% 9, 28 Defoamer Sulfur scavenger Demulsifier Mineral oil diluent 0.6% 1.7% 0.3% 14.5% 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 o o stocks. For automotive use, with SAE straight grades of o o 75 or lower or SAE cross grades having a light viscosity So 10 end of 75W or lower, the formulation is used at a 6090 .o concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is For industrial use with ISO viscosity grades 68, 100, 150, "o 220, 320 and 460, the formulation is used at a concen- 15 tration of 2.15%. Any such base stocks may contain a Sviscosity index improver, if desired.

0 9 0 EXAMPLE 19 t "9 The procedure of Example 18 is repeated except that a 0 the succinimide is boronated succinimide.

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

III

29 Succinimide 15.0% Trihydrocarbyl dithiophosphate 14.0% Decyl amine salt of C 16 dicarboxylic acid Dialkyl polysulfide 45.0% Alkyl phosphite and phosphate Alkyl amine 2.4% Defoamer 0.6% SSulfur scavenger 1.7% S '10 Demulsifier 0.3% o o Mineral oil diluent 10.5% 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 S.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 For industrial use with ISO viscosity grades 68, 100, 150, o 220, 320 and 460, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a viscoi.*.y index improver, if desired.

EXAMPLE 21 The procedure of Example 20 is repeated except that the succinimide is boronated succinimide.

~CLi-- WI* I 30 00 0 .0 10 o 00 t0 0O 0 04 0P a 0 0 Wa EXAMPLE 22 A gear oil additive concentrate of composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Octyl amine salt of octanoic acid Sulfurized isobutylene Alkyl phosphite and phosphate Alkyl amine Defoamer and demulsifier Sulfur scavenger Mineral oil diluent this invention is 15.0% 19.6% 1.4% 41.3% 4.7% 3.9% 1.4% 11.2% 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 straight grades of 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 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.

31- EXAMPLE 23 The procedure of Example 22 is repeated except that the succinimide is boronated succinimide.

EXAMPLE 24 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.

EXAMPLE 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.

S EXAMPLE 26 I A gear oil additive concentrate of this invention is composed of the following ingredients: Succinimide 16.2% Trihydrocarbyl dithiophosphate 19.2% Lauryl amine salt of octanoic acid Sulfurized isobutylene 20.5% Dialkyl polysulfide 20.5% Alkyl phosphite and phosphate Oleylamine 3.9% Defoamer and demulsifier Sulfur scavenger 1.4% Mineral oil diluent 10.3% C 1 -e :e 32 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 concentration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is For industrial use with ISO viscosity grades 68, 100, 150, ,10 220, 320 and 460, the formulation is used at a concen- S- tration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

0EXAMPLE 27 The procedure of Example 26 is repeated except that the succinimide is boronated succinimide, the boronated o,,f succinimide is used in the concentrate at a concentration of 15.5%, and the concentration of the mineral oil So diluent in the concentrate is 11.0%.

EXAMPLE 28 A gear oil additive concentrate of this invention is composed of the following ingredients: Succinimide 12.0% Octyl amine salt of decanoic acid 1.6%

V

33 Sulfurized isobutylene 35.0% Trihydrocarbyl dithiophosphate 17.0% Alkyl phosphite and phosphate Alkyl amine 1.9% Defoamer 0.6% Sulfur scavenger 1.3% Demulsifier 0.3% Mineral oil diluent 25.3% 0 Gear oils are formed by blending the concentrate in 0 0 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 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 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 20 a viscosity index improver, if desired.

EXAMPLE 29 The procedure of Example 28 is repeated except that the succinimide is boronated succinimide.

I

i 34 o o o 0 0 o o 0 00 e «f>9 6 S EXAMPLE 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 Sulfurized isobutylene 35.0% Alkyl phosphite and phosphate 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 base stocks, synthetic base stocks, and 0-0. 0 combinations of mineral oil and synthetic oil base 0 0 stocks. For automotive use, with SAE straight grades of 75 or lower or SAE cross grades having a light viscosity t end of 75W or lower, the formulation is used at a 20 concentration of 9.45%. For automotive use, with SAE o r0 oo grades heavier than 75, the treat rate is 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.

I

I

35 EXAMPLE 31 The procedure of Example 30 is repeated except that the succinimide is boronated succinimide.

EXAMPLE 32 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 Sulfurized isobutylene 35.0% Alkyl phosphite and phosphate Alkyl amine 1.9% Defoamer 0.6% Sulfur scavenger 1.3% 15 Demulsifier 0.3% Mineral oil diluent 18.9% 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 .20 stocks. For automotive use, with SAE straight grades of 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 For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 36 460, the formulation is used at a concentration of 2.15%.

Any such base stocks may contain a viscosity index improver, if desired.

EXAMPLE 33 The procedure of Example 32 is repeated except that the succinimide is boronated succinimide.

0 1 o o 00 00 O 0i 0 00 S 150 o a o 0 0 o a zo 0 o o 0 a 0 0 0 0 U 0 EXAMPLE 34 A gear oil additive concentrate of composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Oleyl amine salts of C 10

C

24 mono- and dicarboxylic acids Sulfurized isobutylene Alkyl phosphite and phosphate Laurylamine Defoamer and demulsifier Sulfur scavenger Mineral oil diluent this invention is 14.2% 15.8% 2.8% 35.0% 1.2% 1.2% 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 or lower or SAE cross grades having a light viscosity u i 37 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 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.

*o 0 +o0 EXAMPLE SThe procedure of Example 34 is repeated except that 10 the succinimide is boronated succinimide, and the oleyl amine salts are replaced by lauryl amine salts.

0 00 0EXAMPLE 36 The procedure of Example 34 is repeated except that the succinimide is boronated succinimide, the oleyl amine 415 salts are replaced by cetyl amine salts of decanoic and octadecanoic acids, and the lauryl amine is replaced by a 50/50 w/w mixture of decanoic acid and octadecanoic acid.

0 EXAMPLE 37 A gear oil additive concentrate of this invention is composed of the following ingredients: Succinimide 12.0% Trihydrocarbyl dithiophosphate 19.0%

V

I 38 Tert-dodecyl amine salt of octanoic acid Sulfurized isobutylene 35.0% Alkyl phosphite and phosphate Alkyl amine 1.9% Defoamer 0.6% Sulfur scavenger 1.3% Demulsifier 0.3% Mineral oil diluent 23.4% 04 4O410 Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and oOO.." combinations of mineral oil and synthetic oil base stocks. For automotive use, with 3AE straight grades of cr 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 For .industrial use with ISO viscosity grades 68, 100, 150, 4O 220, 320 and 460, the formulation is used at a concen- "Ol 20 tration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

EXAMPLE 38 The procedure of Example 37 is repeated except that the succinimide is boronated succinimide.

U 39 44 9 9 4 40 9 4 4* f 0 *44U o o 0 EXAMPLE 39 A gear oil additive concentrate of composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Tert-dodecyl and tert-tetradecyl amine salts of decanoic and dodecanoic acid Sulfurized isobutylene Alkyl phosphite and phosphate Alkyl amine Defoamer Sulfur scavenger Demulsifier Mineral oil diluent this invention is 15.0% 15.0% 40.0% 2.1% 0.6% 1.3% 0.3% 17.7% 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 o 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 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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I

_~e 40 EXAMPLE The procedure of Example 39 is repeated except that the succinimide is boronated succinimide.

.4 4 .04a 4* 4 4 44 10 4 4 494.

4t 444 EXAMPLE 41 A gear oil additive concentrate of composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Alkyl amine salts of C 8

C

30 mono- and dicarboxylic acids Sulfurized isobutylene Alkyl phosphite and phosphate Alkyl amine Defoamer and demulsifier Sulfur scavenger Mineral oil diluent this invention is 12.7% 16.6% 2.6% 35.0% 4.7% 1.9% 1.2% 1.3% 24.0% C'(dar oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base 4 e *20 stocks. For automotive use, with SAE straight grades of 4 4 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 For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 41 460, the formulation is used at a concentration of 2.15%.

Any such base stocks may contain a viscosity index improver, if desired.

EXAMPLE 42 The procedure of Example 41 is repeated except that the succinimide is boronated succinimide.

.1 0 S° EXAMPLE 43 9 4 A gear oil additive concentrate of this invention is :t formed by blending together the following components in the proportions specified: Succinimide Trihydrocarbyl dithiophosphate 11.4% Octyl amine salt of octanoic acid 0.8% Process Oil Anglamol 6004A* 73.3% *A proprietary gear oil additive formulation S commercially available from The Lubrizol Corporation.

9 9 1 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 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a

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42 concentration of 14.57%. For automotive use, with SAE grades heavier than 75, the treat rate is For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of and the finished oil should contain at least 0.3% demulsifier. Any such base stocks may contain a viscosity index improver, if desired.

So o* S°EXAMPLE 44 The procedure of Example 43 is repeated except that o 10 the succinimide is boronated succinimide.

0 f o 0 0 04 04 4 9 04 0 00 EXAMPLE A gear oil additive concentrate of composed of the following ingredients: Succinimide Nonyl amine salt of pentadecanoic acid Sulfurized isobutylene Trihydrocarbyl dithiophosphate Alkyl phosphite and phosphate Alkyl amine Defoamer Sulfur scavenger Demulsifier Mineral oil diluent this invention is 15.0% 45.0% 14.0% 2.4% 0.6% 1.3% 0.3% 12.4% I ~LLX_ _V 43 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 concentration of 9.45%. For automotive use, with SAE o grades heavier than 75, the treat rate is For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concen- S 0 tration 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 3 Q the succinimide is boronated succinimide.

EXAMPLE 47 o A gear oil additive concentrate of this invention is composed of the following ingredients: Succinimide 12.0% Trihydrocarbyl dithiophosphate 15.0% Neopentyl amine salt of decanoic acid Sulfurized isobutylene 40.0% Alkyl phosphite and phosphate 44- Alkyl amine 2.1% Defoamer 0.6% Sulfur scavenger 1.3% j 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 o combinations of mineral oil and synthetic oil base

O

stocks. For automotive use, with SAE straight grades of 10 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 For industrial use with ISO viscosity grades 68, 100, 150, a444 220, 320 and 460, the formulation is used at a concen- S tration of 2.15%. Any such base stocks may contain a viscosity index improver, if desired.

S o o EXAMPLE 48 O 4 X The procedure of Example 47 is repeated except that the succinimide is boronated succinimide.

EXAMPLE 49 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 oleic acid Sulfurized isobutylene 35.0% Alkyl phosphite and phosphate Dialkyl thiophosphate amine salt 5.2% Alkyl amine 1.4% Defoamer 0.6% Sulfur scavenger 1.3% Demulsifier 0.3% o, Mineral oil diluent 22.2% 0 Gear oils are formed by blending the concentrate in S0 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 concentration of 9.45%. For automotive use, with SAE grades o heavier than 75, the treat rate is For industrial 0 o use with ISO viscosity grades 68, 100, 150, 220, 320 and B o 460, the formulation is used at a concentration of 2.15%.

S" Any such base stocks may cfntain a viscosity index improver, if desired.

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

si

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'I

00 o 0tO I pO *9 00 000 46 EXAMPLE 51 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 Sulfurized isobutylene 34.5% Alkyl 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 O"g: combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE straight grades of 0 75 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a cono centration of 9.45%. For automotive use, with SAE grades S" *heavier than 75, the treat rate is 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.

I

:i 47 EXAMPLE 52 The procedure of Example 50 is repeated except that the succinimide is boronated succinimide.

o a oo S0 9 9 a 40 10 9 9 9 0 I EXAMPLE 53 A gear oil additive concentrate of composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Di- and tributyl amine salts of stearic acid Sulfurized isobutylene Alkyl phosphite and phosphate Dialkyl thiophosphate amine salt Alkyl amine Defoamer Sulfur scavenger Demulsifier Mineral oil diluent this invention is 12.4% 16.3% 2.2% 34.5% 1.2% 0.6% 1.3% 0.3% 22.7% t Gear oils are formed by blending the concentrate in :20 mineral oil base stocks, synthetic base stocks, and 0 09 0o," combinations of mineral oil and synthetic oil base stocks. For automotive use, with SAE straight grades of 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 For -r I r 48 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.

EXAMPLE 54 The procedure of Example 53 is repeated except that the succinimide is boronated succinimide.

44 (3 4c 4 44 4 4,4.

o 0 0*44 4 40 *a 0044 4.-4,4 4 4 4s 4 4444 4 04O 4 4 4 4 4~ 4 4 4*a -4 4 4, (3 4 44 EXAMPLE A gear oil additive concentrate of composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Mono- and dihexyl amine salts of stearic acid Sulfurized isobutylene Alkyl phosphite and phosphate Dialkyl thiophosphate amine salt Alkyl amine Defoamer 20 Sulfur scavenger Demulsifier Mineral oil diluent this invention is 15.0% 16.4% 35.7% 6.2% 1.3% 0.6% 1.3% 0.3% 17.7% 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 49 stocks. For automotive use, with SAE straight grades of 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 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 S06 Simprover, if desired.

EXAMPLE 56 The procedure of Example 55 is repeated except that the succinimide is boronated succinimide.

0a 0 a".0 EXAMPLE 57 A gear oil additive concentrate of this invention is 115 composed of the following ingredients: Succinimide 12.8% Trihydrocarbyl dithiophosphate 15.4% "4 2-Ethylhexyl amine salt of isostearic acid 2.2% Sulfurized isobutylene 40.0% Alkyl phosphite and phosphate Dialkyl thiophosphate amine salt 5.6% Alkyl amine 1.3% Defoamer 0.6% Sulfur scavenger 1.2% 44 Demulsifier 0.4% 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 or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a S. concentration of 9.45%. For automotive use, with SAE 4 4 S 10 grades heavier than 75, the treat rate is For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 46C, the formulation is used at a concentration of 2.15%. Any such base stocks may contain a o viscosity index improver, if desired.

EXAMPLE 58 The procedure of Example 57 is repeated except that the succinimide is boronated succinimide.

EXAMPLE 59 A gear oil additive concentrate of this invention is composed of the following ingredients: Succinimide 14.8% Trihydrocarbyl dithiophosphate 15.3% Octyl amine salt of lauric acid

I_

r 5 Defoam 51 Sulfurized isobutylene 59.6% Alkyl phosphite and phosE tte Dialkyl thiophosphate ami ec salt 6.2% Alkyl amine 1.2% Defoamer 0.6% Sulfur scavenger 1.3% Demulsifier 0.3% Mineral oil diluent 15.1% S"o o Gear oils are formed by blending the concentrate in o 10 mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base I stocks. For automotive use, with SAE straight grades of 9 o4 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 sao. heavier than 75, the treat rate is For industrial Go o use with ISO viscosity grades 68, 100, 150, 220, 320 and S460, the formulation is used at a concentration of 2.15%.

0 Any such base stocks may contain a viscosity index 1o 20 improver, if desired.

0 V EXAMPLE The procedure of Example 59 is repeated except that the succinimide is boronated succinimide.

ir nr ;:l~ul~sr^r~ 52

S

,ft

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*ir ll ft ft ft ft ft ft fta ft ft ft*,*p EXAMPLE 61 A gear oil additive concentrate of composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Octyl and decyl amine salts of lauric acid Sulfurized isobutylene Alkyl phosphite and phosphate Dialkyl thiophosphate amine salt Alkyl amine Defoamer Sulfur scavenger Demulsifier Mineral oil diluent this invention is 12.5% 13.2% 2.4% 36.0% 0.9% 0.6% 1.,3% 0.3% 23.3% Gear oils are formed by blending th concentrate in mineral oil base stocks, synthetic base stocks, and combinations of mineral oil and synthetic oil base Sstocks. For automotive use, with SAE straight grades of 75 or 1Ll. r or SAE cross grades having a light viscosity f, end of 75W or lower, the formulation is used at a cono a 4 centration of 9.45%. For automotive use, with SAE grades heavier than 75, the treat rate is 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.

-53- EXAMPLE 62 The procedure of Example 61 is repeated except that the succinimide is boronated succinimide.

0, ;s 0~ O 0 4 0i 4, 4 0 0 o 4, 4, 0i 0 0 EXAMPLE 63 A gear oil additive concentrate of composed of the following ingredients: Succinimide Trihydrocarbyl dithiophosphate Octyl and dioctyl amine salts of stearic acid Sulfurized isobutylene Alkyl phosphite and phosphate Dialkyl thiophosphate amine salt Alkyl amine Defoamer Sulfur scavenger Demulsifier Mineral oil diluent this invention is 15.0% 13.0% 3.2% 35.4% 1.3% 7.8% 0.9% 0.6% 1.3% 0.3% 21.2% 4, 0 4, 00 0 0 0 I Gear oils are formed by blending the concentrate in :20 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 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 For industrial 54 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.

EXAMPLE 64 The procedure of Example 63 is repeated except that the succinimide is boronated succinimide.

4o 4p 0 4 EXAMPLE A gear oil additive concentrate of this invention is formed by blending together the following components in the proportions specified: .o Succinimide 9.3% Trihydrocarbyl dithiophosphate 12.4% a Process Oil 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 oil base stocks. For automotive use, with SAE straight grades of or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a v r I 55 00 o oio 0 00 o 0 0 00 1 0~ 4 04 0 00040 01 00,00, a0 0 0a 04 2 concentration of 13.3%. For automotive use, with SAE grades heavier than 75, the treat rate is For industrial use with .O viscosity grades 68, 100, 150, 220, 320 and 460, the formulation is used at a concentration of and the finished oil should contain at least 0.3% demulsifier. Any such base stocks may contain a viscosity index improver, if desired.

EXAMPLE 66 The procedure of Example 65 is repeated except that 0 the succinimide is boronated succinimide.

EXAMPLE 67 A gear oil additive concentrate of this invention is formed by blending together the following components in the proportions specified: 5 Succinmnide Trihydrocarbyl dithiophosphate 12.0% Octyl amine salt of octanoic acid 0.9% Process Oil 7.3% Elco 7* 70.8% 0 A proprietary gear oi3 additive formulation commercially available fror. Elco Corporation.

Gear oils are formed by blending the concentrate in mineral oil base stocks, synthetic base stocks, and 56 i combinations of mineral oil and synthetic oil base 4 stocks. For automotive use, with SAE straight grades of or lower or SAE cross grades having a light viscosity end of 75W or lower, the formulation is used at a concentration of 13.8%. For automotive use, with SAE grades heavier than 75, the treat rate is For industrial use with ISO viscosity grades 68, 100, 150, 220, 320 and 9o 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 contain a viscosity index improver, if desired.

EXAMPLE 68 o. The procedure of Example 67 is repeated except that the succinimide is boronated succinimide.

The superlative antiwear and extreme pressure results achievable by the practice of this invention 0 ,ere demonstrated in a series of comparative tests in which a formulation of this invention was compared under S" identical test conditions with six commercially available gear oil additive formulations available from three leading manufacturers of such products. The composition of this invention contained as component a succinimide product formed from polyisobutenylsuccinic anhydride and ethylene polyamine mixture approximating S- 57 i tetraethylenepentamine in composition; the isobutenyl group being derived from polyisobutene having an Mn of about 1300. Component (ii) was O,0-mixed dialkyl-Sdicyclopentadienyl phosphorothioate (alkyl isopropyl 30.1%; isobutyl 37.2%; 2-ethylhexyl The performance criteria used in these tests was the percentage of phosphorus retention in the oil after subjecting the respective gear oils to test conditions normally tending to cause loss of phosphorus content through 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 oO.n industry for determining thermal oxidation stability.

15 The first and foremost of such tests is the standard test. The other two tests used were the Indiana Stirring test and the ZF/Renault/Peugeot test.

a The results of these tests are summarized in the o following tables: k m r I~ 58 PERCENTAGE OF PHOSPHORUS RETENTION AF

T

ER OXIDATION Indi ina ZF/Renault/ Formulation L-60 Stirring Peugeot Used Test Test Test 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 Additive D 15.9 22.6 27.1 Additive E 65.0 85.3 42.9 Additive F 75.6 41.8 50.6 9 9 0 6 004I 9 t o I94 40 Dd 10 0 ft <t s The excellent antiwear and extreme pressure properties of the compositions of this invention was further demonstrated in the standard Mack Spalling Rig 15 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 life of 110 hours, and a GO-G Fail Reference Oil exhibits 20 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 formulation of this invention did not exhibit any failure even after 150,000 cycles, at which point the

L,

I

59 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 o 0 1 placing a sample of gear lubricant in a heated gear box a* 10 in which two spur gears and a test bearing are operating at a predetermined load in the presence of a copper catalyst. According to the test procedure, the temperature of the test lubricant is maintained at 325°F o.p .(162.5°C) while bubbling 0.3 gal/h (l.lL/h) of air $i 15 through oil in the gear box for a test duration of hours of continuous operation.

Having described the basic concepts of this invention, attention will now be focused upon details concerning the additive ingredients.

Component (i) 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 having at least one primary or secondary amino I 60 group in the molecule, alcohol, reactive metal or reactive metal compound, or a combination of two or more of any of through the components 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 t substituent having an Mn value of 500 to 10,000, «o preferably in the range of 750 to 5,000.

For the purposes of this invention, the Mn value for the polyalkene used in forming the substituted succinic acylating agent is determined by gel permeation chromatography in the manner described in U.S. Pat. No.

4,234,435 from Column 7, line 7 through Column 8, line 15 31.

Thus, the substituted succinic acylating agents are those which can be characterized by the presence within their 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 61 i 61 groups are derived is characterized by an Mn (number average molecular weight) value of from 500 to 10,000, and preferably in the range of from 750 to 5,000.

The second group or moiety is the succinic group, a group characterized by the structure QO 0 oo II I I [I S° X C C C C X' Formula I o °10 wherein X and X' are the same or different provided at 9oa9 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 15 esterify alcohols, form amides or amine salts with ammonia or amines, form metal salts with reactive metals S or basically reacting metal compounds, and otherwise functions as a conventional carboxylic acid acylating 4 agent. Transesterification and transamidation reactions are considered, for purposes of this invention, as conventional acylation reactions.

Thus, X and/or X' is usually -OH, -0-hydrocarbyl; where M' represents one equivalent of a metal, ammonium or amine cation, -NH 2 -Cl, -Br, and together, X and X' can be so as to form the anhydride. The 62 specific identity of any X or X' group which is not one of the above is not critical so long 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 o C- C I I

S

0 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 substituent group, all but the .15 said one such valence is usually satisfied by a hydrogen atom.

The succinic groups of the succinic acylating agents will normally correspond to the formula a0 20 11 CH C R i Formula II

CH

2 C R' 0 wherein R and R' are each independently selected from the group consisting of -OH, -Cl, -OR" lower alkyl), and when taken together, R and R' are 0 In the 63 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 Formula III °o0 II II CH C OH CH C CH2 C OH CH2 C 1 o o 0 oL (B) and mixtures of III(A) and III(B). Production of substituted succinic acylating agents wherein the O, succinic groups are the same or different is within 0 0 0ordinary skill of the art and can be accomplished through conventional procedures such as treating the substituted succinic acylating agents themselves (for example, 0 20 hydrolyzing the anhydride to the free acid or converting o 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 derived are homopolymers and interpolymers of polymerizable olefin monomers of 2 to 16 carbon atoms; usually 2 to 6 carbon atoms. The interpolymers are those 64 in which two or more olefin monomers are interpolymerized according to well-known conventional procedures to form polyalkenes having units within their structure derived from each of said two or more olefin monomers. Thus, the polymers used include binary copolymers, terpolymers, o, tetrapolymers, and the like. The polyalkenes from which the substituent groups are derived are often referred to as polyolefin(s) o e «The olefin monomers from which the polyalkenes are *10 derived are polymerizable olefin monomers characterized by the presence of one or more ethylenically unsaturated groups that is, they are mono-olefinic o0 monomers such as ethylene, propylene, 1-butene, 0o00 o 0 isobutene, and 1-octene or polyolefinic monomers (usually 15 diolefinic monomers) such as 1,3-butadiene and isoprene.

oqe0 These olefin monomers are usually polymerizable terminal olefins; that is, olefins characterized by the "0o 0 presence in their structure of the group >C=CH 2 However, polymerizable internal olufin monomers characterized by the presence within their structure of the group I I C- C c 25 can also be used to form the polyalkenes. When inernal can also be used to form the polyalkenes. When internal ii

S-HF

65 olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which are interpolyiners. When a particular polymerizable olefin monomer can be classified as both a terminal olefin and an internal olefin, it is usually categorized as a terminal olefin. An example of such a monomer is o .o 1,3-pentadiene piperylene).

0,o While the polyalkenes from which the substituent 1groups of the succinic acylating agents are derived o0lO generally are hydrocarbon polyalkenes, they can contain non-hydrocarbon groups such as lower alkoxy, lower alkyl mercapto, hydroxy, mercapto, oxo, nitro, halo, cyano, o carboalkoxy 0 00 Q- C 0 alkyl where "alkyl" is usually lower alkyl, namely an alkyl group containing up to about 7 carbon atoms), alkanoyloxy °0 (or carbalkoxy, i.e., 0 alkyl C 0 where "alkyl" is usually lower alkyl), and the like, provided the non-hydrocarbon substituents do not

Y

66 substantially interfere witn 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 total weight of the polyalkenes. Since the polyalkene can contain such non-hydrocarbon substituents, it is apparent that the olefin monomers from which the polyalkenes are made can also contain such substituents. Normally, however, as a matter of practicality and expense, the olefin monomers S 10 and the polyalkenes used are free from non-hydrocarbon groups, except chloro groups which usually facilitate the formation of the substituted succinic acylating agents.

S Although the polyalkenes may include aromatic groups o (especially phenyl groups and lower alkyl- and-/or lower alkoxy-substituted phenyl groups such as p-tert-butylphenyl) and cycloaliphatic groups such as would be obtained from polymerizable cyclic olefins or cyclo- S* aliphatic substituted-polymerizable acyclic 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 4-tert-butyl-styrene are exceptions to this generalization. Similarly, the olefin monomers from

V

II r~--a~C+~V.II~XIOII~ 67 which the polyalkenes are prepared can contain both aromatic and cycloaliphatic groups.

Generally speaking aliphatic hydrocarbon polyalkenes free from aromatic and cycloaliphatic groups are preferred for use in preparing the substituted succinic acylating agents. Particularly preferred are polyalkenes o which are derived from homopolymers and interpolymers of o O terminal hydrocarbon olefins of 2 to 8 carbon atoms, most especially from 2 to 4 carbon atoms. While interpolymers oa 10 of terminal olefins are usually preferred, interpolymers optionally containing up to about 40% of polymer units derived from internal olefins of up to about 8 carbon 0 o U a.

0 atoms are also preferred. The most preferred polyalkenes are polypropylenes and polyisobutenes.

15 Specific examples of terminal and internal olefin monomers which can be used to prepare the polyalkenes according to conventional, well-known polymerization .o C techniques include ethylene; propylene; 1-butene; 2-butane; isobutene; 1-pentene; 1-hexene; 1-heptene, 2-butene; isobutene; 2-pentene, 1-hexene; 1-heptene; 1-octene; 1-nonene; 1-decene; 2-pentene; propylenetetramer; diisobutylene; isobutylene trimer; 1,2-butadiene; 1,3-butadiene; 1,2-pentadiene; 1,3-pentadiene; 1,4-pentadiene; isoprene; 1,5-hexadiene; 2-chloro-l,3-

V

68 butadiene; 2-methyl-l-heptene; 4-cyclohexyl-l-butene; 3-pentene; 4-octene; 3,3-di-methyl-l-pentene; styrene; 2,4-dichlorostyrene; divinylbenzene; vinyl acetate; allyl alcohol; 1-methyl-vinyl acetate; acrylonitrile; ethyl acrylate; methyl methacrylate; ethyl vinyl ether; and o methyl vinyl ketone. Of these, the hydrocarbon polys, merizable monomers are preferred and of these hydrocarbon o, monomers, the terminal olefin monomers are particularly S' preferred.

s i10 Specific examples of polyalkenes include polypropylenes, polybutenes, ethylene-propylene copolymers, styrene-isobutene copolymers, isobutene-1,3-butadiene copolymers, propene-isoprene copolymers, isobutenechloroprene copolymers, isobutene-4-methyl- styrene copolymers, copolymers of 1-hexene with 1,3-hexadiene, copolymers of 1-octene with 1-hexene, copolymers of 4 t 1-heptene with 1-pentene, copolymers of 3-methyl-l-butene with 1-octene, copolymers of 3,3-dimethyl-l-pentene with 1-hexene, and terpolymers of isobutene, styrene and piperylene. More specific examples of such interpolymers include copolymer of 95% (by weight) of isobutene with (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 69 1-hexene; terpolymer of 60% of isobutene with 20% of 1-pentene and 20% of octene-1; copolymer of 80% of 1-hexene and 20% of 1-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 source of polyalkenes are the polyisobutenes i.g obtained by polymerization of C 4 refinery stream having a butene content of 35 to 75 percent by weight and an 0, isobutene content of 30 to 60 percent by weight using a 10 Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (greater than about 80% of the total repeating units) of "s repeating units of the configuration

SCH

3 .400: CH 2 C

CHH

2 In preparing polyalkenes, conventional techniques 20 known to those skilled in the art include suitably controlling polymerization temperatures, regulating the amount and type of polymerization initiator and/or catalyst, employing chain terminating groups in the polymerization procedure, and the like. Othar conventional techniques such as stripping (including vacuum stripping) a very light end and/or oxidatively or 70 mechanically degrading high molecular weight polyalkene to produce lower molecular 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 of the general formula 0 Sa 0 0 1| [I Formula IV ~l 10 X C CH CH C -X' o r wherein X and X' are as defined hereinbefore. Preferably the maleic and fumaric reactants will be one or more compounds corresponding to the formula O O 15 II II Formula V R C CH CH C R' wherein R and R' are as previously defined herein.

Ordinarily the maleic or fumaric reactants will be maleic e4 4 acid, fumaric acid, maleic anhydride, or a mixture of two c u or more of these. The maleic reactants are usually Spreferred over the fumaric reactants because the former are more readily available and are, in general, more readily reacted with the polyalkenes (or derivatives thereof) to prepare the substituted succinic acylating agents. The most preferred reactants are maleic acid, V 7 71 maleic anhydride, and mixtures of these.

Any of a variety of known procedures can be used to produce the substituted succinic acylating agents. For convenience and brevity, when the term "maleic reactant" is used her2after, the term is generic to the reactants corresponding to Formulas IV and V above including P, mixtures of such reactants.

One procedure for preparing the substituted succinic acylating agents is illustrated, in part, by the two-step 10 procedure described in U.S. Pat. No. 3,21S,666. It involves first chlorinating the polyalkene until there is an average of at least about one chloro group for each molecular weight each Mn) of polyalkene.

Ot Chlorination involves merely contacting the polyalkene with chlorine gas until the desired amount of chlorine is incorporated into the chlorinated polyalkene. Chloria nation is generally carried out at a temperature of 0 a c0 t to 125*C. If desired, a diluent can be used in the chlorination 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 at a temperature usually within the range 72 of 100"C to 2001C. The mole ratio of chlorinated polyalkene to maleic reactant is usually about 1:1. In this connection, a mole of chlorinated polyalkene may be regarded as the the weight of chlorinated polyalkene corresponding to the Mn value of the unchlorinated polyalkene. However, a stoichiometric excess of maleic o a reactant can be used, for example, a mole ratio of 1:2.

o°o° If an average of more than about one chloro group per o o molecule of polyalkene is introduced during the 1 0 chlorination step, then more than one mole of maleic reactant can react per molecule of chlorinated polyalkene. Accordingly, the ratio of chlorinated polyalkene oe.<o' to maleic reactant may be referred to in terms of *o equivalents, an equivalent weight of chlorinated :15 polyalkene being the weight corresponding to the Mn value O.t divided by the average number of chloro groups per molecule of chlorinated polyalkene. The equivalent 4 4.

o O weight of a maleic reactant is its molecular weight.

9 04 Thus, the ratio of chlorinated polyalkene to maleic 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

I

-73 desirable to provide an excess of maleic reactant; for example, an excess of 5% to 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 agent is, optionally, again chlorinated if the p a OO 'o desired number of succinic groups are not present in the a0 a product. If there is present, at the time of this a.o 10 subsequent chlorination, any excess maleic reactant from the second step, the excess will react as additional chlorine is introduced during the subsequent chlorination. Otherwise, additional maleic reactant is a introduced during and/or subsequent to the additional .j 15 chlorination step. This technique can be repeated until the total number of succinic groups per equivalent weight o, of substituent groups reaches the desired level.

Another procedure for preparing substituted succinic 0 0 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 the direct alkylation step is completed, chlorine is introduced into the Ij 74 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 alkylation step is conducted at 0o temperatures of 180"C to 250"C. During the chlorineintroducing stage, a temperature of 160"C to 225'C is 0, employed.

Other known processes for preparing the substituted S succinic acylating agents include the one-step process described in U.S. Pat. Nos. 3,215,707 and 3,231,587.

Basically, this process involves preparing a mixture of o the polyalkene and the maleic reactant in suitable eo 0 proportions and introducing chlorine into the mixture, It 1usually by passing chlorine gas through the mixture with o: aagitation, while maintaining a temperature of at least 0 0 about 140*C.

Usually, where the polyalkene is sufficiently fluid at 140"C and above, there is no need to utilize an additional substantially inert, normally liquid solvent/diluent in the one-step process. However, if a solvent/diluent is employed, it is preferably one that resists chlorination such as the poly- and perchlorinated and/or -fluorinated alkanes, cycloalkanes, and benzenes.

-~e 75 Chlorine may be introduced continuously or intermittently during the one-step process. The rate of introduction of the chlorine is not critical although, for maximum utilization of the chlorine, the rate should be about the same as the rate of consumption of chlorine in the course of the reaction. When the introduction 1 rate of chlorine exceeds the rate of consumption, chlorine is evolved from the reaction mixture. It is often o t p, advantageous to use a closed system, including super- '10 atmospheric pressure, in order to prevent loss of chlorine so as to maximize chlorine utilization.

The minimum temperature at which the reaction in the 00e 0 one-step process takes place at a reasonable rate is o04 about 140°C. Thus, the minimum temperature at which the 15 process is normally carried out is in the neighborhood of 140 0 C. The preferred temperature range is usually SI between 160°C and 220°C. Higher temperatures such as o 4 o0\ a 250°C or even higher may be used but usually with little advantage. In fact, excessively high temperatures may be disadvantageous because of the possibility that thermal degradation of either or both of the reactants 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

C--

76 one mole of chlorine for each mole of maleic reactant to be incorporated into the product. Moreover, for practical reasons, a slight excess, usually in the neighborhood of 5% to 30% by weight of chlorine, is utilized in order to offset any loss of chlorine from the reaction mixture. Larger amounts of excess chlorine may o oo be used.

Further details concerning procedures for producing o >the substituted acylatiig agents have been extensively o 10 described in the patent literature, such as for example in U.S. Pat. No. 4,234,435, and thus further amplification of such procedures herein is deemed unnecessary.

0000 0 O As noted above, the substituted acylating agents are 0o 0 reacted with amine having at least one primary or 15 secondary amino group in the molecule, or alcohol, or 0 a reactive metal or reactive metal compound, or a combination of two or more of through the components of being reacted with the acylating reagents simultaneously or sequentially in any order and/or subcombination.

The amine, reactant 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 acnp(~ -77primary amino groups in the molecule are generally preferred. Alkylene polyamines having both primary and secondary amino groups in the molecule are particularly preferred, especially where the alkylene polyamines contain at least two primary amino groups and one or more :0 secondary amino groups.

o0 i 0" Alcohols, reactant above, which can be used 0°o include the monohydric and polyhydric alcohols. The S polyhydric alcohols are preferred.

.10 Reactive metals and reactive metal compounds, reactant above, are those which are known to form salts and complexes when reacted with carboxylic acids °oo° and carboxylic acid acylating agents.

o* o Numerous examples of reactants and are 15 set forth in U.S. Pat No. 4,234,435 to which reference may be had for this purpose.

0 Of the various succinic derivatives which may be S used 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 preferred. Such polyamines may be represented by the formula

H

2 N (CH 2 (NH (CH2) n) NH 2 a.

F_

78 wherein n is in the range of 2 to 10 (preferably 2 to 3, and most preferably 2) and m is in the range of 0 to (preferably 0 to Illustrative are ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentamine, pentaethylene hexamine, propylene o diamine (1,3-propanediamine), butylene diamine (1,4-butanediamine), hexamethylene diamine (1,6-hexane- 0diamine), decamethylene diamine (1,10-decanediamine), and Sa. the like. Particularly preferred for use is tetra- '10 ethylene pentamine or a mixture of ethylene polyamines which approximates tetraethylene pentamine such as "DOW E-100" (a commercial mixture available from Dow Chemical Company, Midland, Michigan).

When preparing the boronated succinimides and 15 boronated succinic esters, a succinimide or succinic ester (or mixture thereof) is reacted with one or more Sboron-containing reactants such as boron halides, boron acids, and esters of boron acids. 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, r CLlrr~iinq~ -nr~;lu~i-a~ 79 and boronated succinic esters are available as articles of commerce.

Component (ii) The other component required in the gear oil compositions of this invention is one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphoric acid or one or more oil-soluble fully-esterified hydrocarbyl o esters of a phosphorothioic acid, or a combination of one o o or more oil-soluble fully-esterified hydrocarbyl esters a 9+ 10 of a phosphoric acid and one or more oil-soluble fully-esterified hydrocarbyl esters of a phosphorothioic acid. Such compounds may be represented by the general 0 00 oo w formula: o 0 0 0a X

I]

R X P X R, Formula VI :20 R o 3 "o wherein each of R 1 R2, and R 3 is independently a hydrocarbyl group and each X is independently an oxygen atom or a sulfur atom. Thus when the compound has the formula:

F

4

I

1 I _Y 80

R

I

X P X R 2 Formula VII 0 0 0o 0 o 0a o0 0 S 1i it is a fully-esterified hydrocarbyl ester of a phosphoric acid.

On the other hand, when the compound has the formula: R X P X R

X

Formula VIII 0 0 it is a fully-esterified hydrocarbyl ester of a 00a t 0 I phosphorothioic acid. In the foregoing formulas, the to.. 20 hydrocarbyl groups R 1 Rg, and R, can be any hydrocarbyl group, such as alkyl, cycloalkyl, aryl, cycloalkylalkyl, o aralkyl, alkenyl, or cycloalkenyl. 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 by inert substituents in the sense that the substituents do not interfere with the functioning of component (ii) nor destroy the effectiveness of component of the compositions of this invention. For example, the 81 hydrocarbyl groups of the phosphorus esters may include ether oxygen atoms, thioether sulfur atoms, nitrogen atoms, ester functionality, hydroxyl groups, sulfhydryl groups, and like substituents. 'nus, the fullyesterified phosphate and phosphoricthioate esters used in o. the practice of this invention may include alkoxyalkyl, 0 poly(alkoxy)alkyl, alkylthioalkyl, aryloxyalkyl, o°o Bdialkylaminoalkyl, diarylaminoalkyl, hydroxyalkyl, and Slike inert (innocuous) substituents.

010 A preferred group of compounds for use as component (ii) are the O,0-dihydrocarbyl-S-hydrocarbyl phosphorothiothionates of the general formula: o )j 0 R 0 P O R 2 Formula IX

S

"'0.20 wherein each of R 1

R

2 and R 3 is independently a hydro- 24 3 o carbyl group, especially where R3 is an alicyclic hydrocarbyl group. Particularly preferred are the 0,0-dialkyl-S-hydrocarbyl phosphorothiothionates wherein R3 is an alicyclic group an R 1 and R 2 are alkyl groups each having up to about 18 carbon atoms and most preferably up to about 12 carbon atoms.

I

1- I -r 82 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, 2,767,206, 2,802,856, 3,023,209, o and J. Org. Chem., 1963, 28, 1262-8.

Exemplary compounds suitable for use as component o"o (ii) incade such fully-esterified phosphates and phosphorothioates as fusel oil phosphate, tricresyl 1 ,,ol 0 phosphate, dibutyl phenyl phosphate, tri-2-ethylhexyl phosphate, triisodecyl phosphate, trilauryl phosphate, trioctylphosphorothiothionate, tridecylphosphorodioo0 thiothionate, trilaurylphosphorotrithiothionate, diethyl ao. bicyclo(2.2.1)-hepten-2-yl phosphate, O,0-diethyl 15 S-bicyclo-(2.2. i)-5-hepten-2-yl phosphorothiothionate, diethyl 7, 7-dimethyl-bicyclo(2.2.1)-5-hepten-2-yl o phosphate, the product formed by reaction of dithiophosa a So phoric acid-O,0-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 ester, the product formed by reaction of dithiophosphoric acid-O,0-dibutyl ester with cis-endomethylene-tetrahydrophthalic acid dilauryl ester, the product formed by iI 83 reaction of dithiophosphoric acid-0,0-dimethyl ester with acid butyl ester, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with 2,5-endomethylene-1-methyltetrahydrobenzoic acid decyl ester, the product formed by reaction of dithiophosphoric acid-0,O-dimethyl ester with 2,5-endomethylene-6-methyl-tetrahydrobenzoin acid ethyl ester, the product formed by reaction of dithiophosphoric acid-O,0-diethyl ester with hydrobenzyl alcohol, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with the Diels-Alder adduct of cyclopentadiene and allyl alcohol o'00 (2 mols 1 mol), the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with a2Ql15 methylene-tetrahydrophenyl acetate, the product formed by t reaction of dithiophosphoric acid-O,O-dibutyl ester with i 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-cyclopentadiene adduct of p-benzoquinone, the product formed by reaction of dithiophosphoric acid-0,O-dimethyl ester with the azodicarboxylic acid diethyl ester, the product formed by reaction of dithiophosphoric acid-0,0dimethyl ester with dicyclopentadiene the product formed -I III~1I~--- II~ 84 by reaction of dithiophosphoric acid-O,O-dibutyl ester with dicyclopentadiene, the product formed by reaction of dithiophosphoric acid-O,O-dioctyl ester with dicyclopentadiene, the product formed by reaction of dithiophosphoric acid-O,O-dilauryl ester with dicyclopentadiene, the product formed by reaction of dithiophosphoric acid-O,O-di-2-ethylhexyl ester with wax olefin, the product formed by reaction of dithiophosphoric acid-0,O-di-2-ethylhexyl ester with oleyl alcohol, the product formed by reaction of dithiophosphoric acid-0,0-di-2-ethylhexyl ester with linseed oil, the product formed by reaction of dithiophosphoric acid-O,0-diamyl ester with alpha pinene, the product 0 Sformed by reaction of dithiophosphoric acid-O,O-diphenyl o: 15 ester with alpha pinene, the product formed by reaction of dithiophosphoric acid-O,O-diamyl ter with allo- I ocimene, the product formed by reaction of dithiophosphoric acid-0,0-dioctyl ester with dipentene, and the *0 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 salts of one or more long chain i i I~ 85 monocarboxylic acids, or of one or more long chain polycarboxylic acids, or of a combination of at least one acid of and at least one acid of Generally speaking, these acids contain from 8 to 50 carbon atoms in the molecule and thus the salts are oil-soluble. A o variety of amines can be used in forming such salts, a.o 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, heterocyclic amines, or amines containing various mixtures of acyclic and cyclic groups.

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

15 The amine salts are formed by classical chemical reactions, namely, the reaction of an amine or mixture of amines, with the appropriate acid or mixture of acids.

o Accordingly, further discussion concerning methods for I t the preparation of such materials would be redundant.

Among the amine salts of long-chain acids that may be uied are the following: lauryl ammonium laurate (i.e.

the lauryl amine salt of lauric acid); stearyl ammonium laurate, cyclohexyl ammonium laurate, octyl ammonium laurate, pyridine laurate, aniline laurate, lauryl 86 ammonium stearate, stearyl ammonium stearate, cyclohexyl ammonium stearate, octylammonium stearate, pyridine stearate, aniline stearate, lauryl ammo'iium octanoate, stearyl ammonium octanoate, cyclohexyl ammonium octanoate, octyl ammonium octanoate, pyridine octanoate, o aniline octanoate, nonyl ammonium laurate, nonyl ammoniumn stearate, nonyl ammonium octanoate, lauryl ammonium 0 4 nonanoate, stearyl ammonium nonanoate, cyclohexyl 440 ammonium nonanoate, octyl ammonium nonanoate, pyridine nonanoate, aniline nonanoate, nonyl ammonium nonanoate, lauryl ammonium decanoate, stearyl ammonium decanoate, cyclohexyl ammonium decanoate, octyl ammnonium deconoate, 4, 1 4 ~41 4 pyridine decanoate, aniline decarloate, dec-yl ammonium lartdcy moim44aae eclamnu olarate, decyl ammonium steaate, decyl ammonium 0 decanoate, bis octy! amine salt of suberic acid, bis 44 cyclohexyl amine salt of suberic acid, bis lauryl amine 440 salt of suberic acid, bis stearyl amine salt of suberic acid, bis octyl amine salt of sebacic acid, bis cyclohexyl amine salt of sebacic acid, bis lauryl amine salt of sebacic acid, bis stearyl amine salt of sebacic acid, the tert-dodecyl and tert-tetradecyl primary amine salts of octanoic acid, the tert-decyl and tertdodecyl primary amine salts of octanoic acid, the CC- C "l 87 tert-dodecyl and tert-tetradcyl primary amine salts of lauric acid, the 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 C 2 4 -dicarboxylic acid, the octyl amine salt of C 28 -dicarboxylic acid, the i0 0 octyl. amine salt of C -dicarboxylic acid, the decyl amine o 30 00 00 0 salt of C 30 -dicarboxylic acid, the octyl amine salt of 0 00

C

3 -dicarboxylic acid, the bis lauryldimethyl amine salt of traumatic acid, diethyl ammonium laurate, dioctyl 0 0ammonium laurate, dicyclohexyl ammonium laurate, diethyl ammonium octanoate, dioctyl ammonium octanoate, dicyclohexyl ammonium octanoate, diethyl ammonium 000 stearate, dioctyl ammonium stearate, diethyl ammonium 0 stearate, dibutyl ammonium stearate, dicyclopentyl 00..0 ammonium stearate, dipropyl ammonium benzoate, didecyl 0* 0 *ammonium benzoate, dimethylcyclohexyl ammonium benzoate, 00, 0 triethyl ammonium laurate, triethyl ammonium octanoate, 0triethyl ammonium stearate, triethyl ammonium benzoate, trioctyl ammonium laurate, trioctyl ammonium octanoate, 0 trioctyl ammonium stearate, trioctyl ammonium benzoate, trioctyl ammonium laurate, trioctyl ammonium octanoate, 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

V

88 acid used should be sufficiently soluble in the base oil used as to provide homogeneous solution at the concentration employed.

Among the preferred amine salts for use in practice of this invention are the primary amine salts of long chain monocarboxylic acids in which the amine thereof is a monoalkyl monoamine, RNH 2 the secondary amine salts of long chain monocarboxylic acids in which the amine thereof is a dialkyl monoamine, R NH; the tertiary amine oo 10 salts of long chain monocarboxylic acids in which the o°o, amine thereof is a trialkyl monoamine, R 3 N; the bis o primary amine salts of long chain dicarboxylic acids in which the amine thereof is a monoalkyl monoamine, RNH 2 the bis secondary amine salts of long chain dicarboxylic 15 acids in which the amine thereof is a dialkyl monoamine, a 0

R

2 NH; the bis tertiary amine salts of long chain dicarboxylic acids in which the amine thereof is a trialkyl monoamine, R 3 N; and mixtures thereof. In the O foregoing formulae, R is an alkyl group which contains up :20 to about 30 or more carbon atoms, and preferably from 6 to 24 carbon atoms.

As pointed out above, the other components which may be used in the gear oil formulations of this invention are well known to those skilled in the art, and form no

Y

:r 00 O 00 0 O 00 0 0 4 0 00 o CO o 00 0o 0 0000 89 part of this invention. Nevertheless, brief discussions concerning a few such components are set forth below.

Extreme pressure and antiwear agents The most common chemical elements found in extreme pressure and antiwear gear oil additives are sulfur, chlorine, phosphorus, lead, zinc, or boron. A number of sulfurcontaining additives, phosphorus-containing additives, and sulfur- and phosphorus-containing additives, have been identified at the outset hereinabove. Preferred .0 additives of this type include mixtures of alkyl phosphites and phosphates, sulfurized olefins, sulfurized esters, dihydrocarbyl polysulfides, and like materials.

Typical chlorine-containing additives include chlorinated paraffin wax, trichlorothioacetals, tris(trichloroethyl)- .5 phosphate, metal chlorides, reaction products between chlorine or chloride anion with compounds containing suitable functionality (such as olefins, carboxylic acids, or alcohols), and like materials. Additives based on lead are normally lead soaps such as lead naphthenate 0 or lead oleate, or lead salts such as lead carbamate.

Typical zinc additives include zinc dithiophosphates, zinc dithiocarbamates, zinc salts of organic acids, such as zinc acetate, zinc naphthenate, zinc salts of ethylene 0 i 0041 1 O 440 4U 0 0 0 2 j

II

90 diainine tetraacetic acid, zinc chelates such as zinc octyl acetoacetate, and the like. Among the boron additives which may used are boronated amines, metal borate salts, boronated phosphenes, boronated phosphites, and the like.

Defoamers Illustrative materials of this type include silicone oils of suitable viscosity, sodium and potassium salts of oil soluble acids such as potassium oleate, or sodium alkylbenzene sulfonates, glycerol 10 monostearate, polyglycol palmitate, trialkyl monothiophosphates, esters of sulfonated ricin- .9 oleic acid, benzoylacetone, methyl salicylate, glycerol monooleate, glycerol dioleate, and the like. Defoamers are generally employed at concentrations of up to about 15 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 20 like. Such additives are generally employed at concentration of up to about 3% in the additive conc:entrate.

Sulfur scavengers This class of additives includes such materials as thiadiazoles, triazoles, and in general, compounds containing moieties reactive to free 91 o 4 400 o 0 0 0 o 40 S 00Q a sulfur under elevated temperature conditions. See for example U.S. Pat. Nos. 3,663,561 and 4,097,387.

Concentrations of up to about 3% in the concentrate are typical.

Antioxidants Ordinarily, antioxidants that may be employed in gear oil formulations include phenolic compounds, amines, phosphites, and the like. Amounts of up to about 5% in the concentrate are generally sufficient.

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

0 0r 0004r 4 4 99 0 op 0 0 0 0 L0 O 0 9

Claims (9)

1. 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 complement, in proportions such that the composition possesses a weight ratio of sulfur to phosphorus in the range of 5:1 to 40:1 and a weight ratio .o of nitrogen to phosphorus in the range of 0.05:1 to 2:1, Qeor o^ Soc said t~see additionally containing a minor effective a amount of: S0 at least one carboxylic derivative composition i produced by reacting at least one substituted succinic acylating agent with a reactant selected from the group consisting of amine having at least one primary or secondary amino group in the molecule, alcohol, (c) reactive metal or reactive metal compound, and a combination of two or more of any of through the o 0 components of 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 500 to 10,000, and (ii) at least one oil-soluble fully-esterified ,zM 93 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- esterjfied hydrocarbyl ester of a phosphorothioic acid. 44 o a fl« u a 4 004 0 n4 0L.° 10 4 4 4 44 44 4 4 S 4 4 w.4 4 0 I a ol 4 00 4 44 1

2. A composition as claimed in Claim 1 wherein component is composed p;edominantly 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 succiniQ anhydride being derived from polyalkene having an Mn value in the range of from 750 to 5,000.

3. A composition as claimed in Claim 1 wherein component is composed predominantly or entirely of a boronated succinimide or a mixture of boronated succinimides formed by reacting alkenyl succinic acid or -94 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 "o an Mn value in the range of from 750 to 5,000; and by o -reacting a succinimide or a mixture of succinimides so o. 10 formed with a boron-containing reactant.

4. A composition as claimed in any)of claims 1-3 wherein component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid. eone' A composition as claimed in any of claims 1-4 15 wherein the gear oil base stock additionally contains a minor effective amount of (iii) at least one amine salt o a of one or more long chain monocarboxylic acids or at least one amine salt of one or more long chain a* 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. ri I 95

6. 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 concentrate possesses a weight ratio of sulfur to phosphorus in the range of 5:1 to 40:1 and a weight ratio of nitrogen to phosphorus in the range of 0.05:1 to 2:1, said concentrate additionally containing a minor effective amount of: o2 at least one carboxylic derivative composition o 0 o 0 10 produced by reacting at least one substituted succinic o acylating agent with a reactant selected from the group .e consisting of amine having at least one primary or secondary amino group in the molecule, alcohol, (c) reactive metal or reactive metal compound, and a 15 combination of two or more of any of through the o4 components of 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 .a :20 derived from polyalkene having an Mn value of 500 to 4 .4 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 I- r -4 96 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 phosphorothioic acid. 00 o o J.QJ Co4~ 0V415 Ow *d,00 C) C ~ur 6

7. A eemtnpes4e-\as claimed in Claim 6 wherein component 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 750 to 5,000. 0 8. A ,iegabiaB as claimed in Claim 6 wherein 0 a A component 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 'r 97 o 0~f 0 4o o Fl C 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 750 to 5,000; and by reacting a succinimide or a mixture of succinimides so formed with a boron-containing reactant. CX-%Ce-OCr orve-

9. A -cmps i as claimed in any\of claims 6-8 wherein component (ii) is at least one oil-soluble fully-esterified ester of a phosphorothioic acid. Cro-ncia:-r-ce orne-

10. A -eeps in4 as claimed in any\of claims 6-9 wherein the concentrate additionally contains a minor 15 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. 0~00 44 0 44 1 C(il CC .3 CC C 4r Cd C uC C q _i 4, I I -98

11. Gear oil compositions or gear oil additive concentrates substantially as hereinbefore described with reference to the Examples. i a a eo +r a a eo ee r e o 1 a Q e e ff t B a a a DATED this 16th day of June, 1992 15 Ethyl Petroleum Additives, Inc. By Its Patent Attorneys DAVIES COLLISON CAVE r trsar 920616,dble 127,66837,res,98