EP1543096A1

EP1543096A1 - Alkyl-succinhydrazide additives for lubricants

Info

Publication number: EP1543096A1
Application number: EP02807876A
Authority: EP
Inventors: Theodore E. Nalesnik
Original assignee: Uniroyal Chemical Co Inc
Current assignee: Lanxess Solutions US Inc
Priority date: 2002-09-26
Filing date: 2002-09-26
Publication date: 2005-06-22
Anticipated expiration: 2022-09-26
Also published as: DE60226350T2; CN1272415C; EP1543096B1; JP2005524762A; JP4027934B2; ATE393807T1; WO2004029183A1; CN1606611A; DE60226350D1; AU2002334726A1

Abstract

Disclosed herein is a composition comprising: (A) a lubricant, and; (B) at least one alkyl succinhydrazide compound of the formula: (I); wherein R<1> is selected from the group consisting of linear or branched alkyl, alkenyl, alkaryl, alkyl ether, alkyl ester, and alkylene ester groups; R<2> is selected from the group consisting of hydrogen, linear or branched alkyl, alkenyl, alkyl ether, and alkyl ester groups; and R<3> and R<4> are independently selected from the group consisting of hydrogen, linear or branched alkyl and alkenyl groups, aryl groups, and alkaryl groups.

Description

ALKYL-SUCCINHYDRAZIDE ADDITIVES FOR LUBRICANTS

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention is related to lubricants, especially lubricating oils, and, more

particularly, to a class of ashless and non-phosphorus-containing anti-wear, anti-fatigue, and extreme pressure additives derived f om alkyl-succinhydrazides, i.e., 4-alkyl-l,2-

dihydropyridazine-3,6-diones.

2. Description of Related Art

In developing lubricating oils, there have been many attempts to provide additives that impart anti-fatigue, anti-wear, and extreme pressure properties thereto. Zinc

dialkyldithiophosphates (ZDDP) have been used in formulated oils as anti-wear additives for more than 50 years. However, zinc dialkyldithiophosphates give rise to ash, which

contributes to particulate matter in automotive exhaust emissions, and regulatory agencies are seeking to reduce emissions of zinc into the environment. In addition, phosphorus, also a component of ZDDP, is suspected of limiting the service life of the catalytic converters that

are used on cars to reduce pollution. It is important to limit the particulate matter and

pollution formed during engine use for toxicological and environmental reasons, but it is also

important to maintain undiminished the anti-wear properties of the lubricating oil.

In view of the aforementioned shortcomings of the known zinc and phosphorus- containing additives, efforts have been made to provide lubricating oil additives that contain

neither zinc nor phosphorus or, at least, contain them in substantially reduced amounts. Illustrative of non-zinc, i.e., ashless, non-phosphorus-containing lubricating oil

additives are the reaction products of 2,5-dimercapto-l,3,4-thiadiazoles and unsaturated

mono-, di-, and tri-glycerides disclosed in U.S. Patent No. 5,512,190 and the dialkyl dithiocarbamate-derived organic ethers of U.S. Patent No. 5,514,189.

U.S. Patent No. 5,512,190 discloses an additive that provides anti-wear properties to a

lubricating oil. The additive is the reaction product of 2,5-dimercapto-l,3,4-thiadiazole and a mixture of unsaturated mono-, di-, and triglycerides. Also disclosed is a lubricating oil .

additive with anti-wear properties produced by reacting a mixture of unsaturated mono-, di-,

and triglycerides with diethanolamine to provide an intermediate reaction product and reacting the intermediate reaction product with 2,5-dimercapto-l,3,4 thiadiazole.

U.S. Patent No. 5,514,189 discloses that dialkyl dithiocarbamate-derived organic ethers have been found to be effective anti-wear/antioxidant additives for lubricants and fuels.

U.S. Patent No. 3,284,234 discloses a stabilized cellulosic material which comprises a cellulosic material impregnated with at least 0.1 percent by weight of the cellulosic material

of a hydrazide selected from the group consisting of the following compounds and mixtures

thereof:

(I) RCONHNB,

(II) RCONHNHCOR

(III) R'(CONHNH₂)₂

wherein each R is independently selected from the group consisting of hydrogen and alkyl containing from 1 to 2 carbon atoms and wherein R' is selected from the group consisting of (-CH₂-)_n, wherein n is an integer having a value of 0 to 5 and an alkylene of 2 to 6 carbon atoms interrupted by from 1 to 2 atoms selected from the group consisting of oxygen and sulfur.

U.S. Patent Nos. 5,084,195 and 5,300,243 disclose N-acyl-thiourethane thioureas as anti-wear additives specified for lubricants or hydraulic fluids.

German Patent 1 ,260, 137 discloses ethylene polymers that are said to exhibit reduced

film blocking that are prepared by adding fatty acid hydrazides with more than six carbon

atoms in addition to the usual internal lubricants. Lauroyl hydrazide, palmitoyl hydrazide, and stearoyl hydrazide were specifically used.

Japanese Published Application No. 03140346 discloses rigid vinyl chloride resin

compositions said to have improved processability comprising 100 parts vinyl chloride resins

and 3-20 parts of compounds selected from (R₁CONH)₂(CH₂)_n (wherein Rj is an OH-substituted C_rC₂₃ alkyl and n is 1-10), (R₂CONH)₂(CH₂)_n (wherein R₂ is an OH-substituted C₄-C₂₃ alkyl and n is 1-10), R₃CONHNH₂ (wherein R₃ is an

OH-substituted C₄-C₂₃ alkyl), R₄NHCONHR₅ (wherein R₄ is an OH-substituted alkyl, and R₆NHCONH)₂R₇ (wherein R₆ is an OH-substituted C₇-C₂₃ alkyl and R₇ is a C_rC_]0 alkylene,

phenylene, or phenylene derivative). Stearic acid hydrazide and capric acid hydrazide are

specifically mentioned.

U.S. Appl. No. 09/871,120 filed May 31, 2001, discloses a composition comprising:

(A) a lubricant, and (B) at least one alkyl hydrazide compound of the formula:

3 R,

^^■A AA r R,

H wherein R_j is a hydrocarbon or functionalized hydrocarbon of from 1 to 30 carbon atoms, R₂

and R₃ are independently selected from the group consisting of hydrocarbon or functionalized

hydrocarbons of from 1 to 30 carbon atoms and hydrogen.

The disclosures of the foregoing references are incorporated herein by reference in

their entirety.

SUMMARY OF THE INVENTION

The present invention relates to compounds of the formula

wherein R_j is a linear or branched alkyl, alkenyl, alkaryl, alkyl ether, or alkyl ester group, preferably of

from 1 to 30 carbon atoms;

R₂ is hydrogen, a linear or branched alkyl, alkenyl, allcyl ether, or alkyl ester group, preferably

of from 1 to 30 carbon atoms; and

R₃ and R₄ can be the same or different while being hydrogen or a linear or branched alkyl,

aryl, alkenyl, or alkaryl group, preferably of from 1 to 30 carbon atoms.

The alkyl-succinhydrazide compounds of this invention are useful as ashless, non- phosphorus, non-sulfur-containing anti-fatigue, anti-wear, extreme pressure, anti-corrosion additives for lubricating oils. The present invention also relates to lubricating oil compositions comprising a

lubricating oil and a functional property-improving amount of at least one alkyl-

succinhydrazide compound of the above formula. More particularly, the present invention is

directed to a composition comprising:

(A) a lubricant, and

(B) at least one alkyl succinhydrazide compound of the formula:

wherein:

R_j is selected from the group consisting of linear or branched alkyl, alkenyl, alkaryl, alkyl

ether, alkyl ester, and alkylene ester groups;

R₂ is selected from the group consisting of hydrogen, linear or branched alkyl, alkenyl, alkyl

ether, and alkyl ester groups; and

R₃ and R₄ are independently selected from the group consisting of hydrogen, linear or

branched alkyl and alkenyl groups, aryl groups, and alkaryl groups.

Preferably, the alkyl-succinhydrazide is present in the compositions of the present

invention in a concentration in the range of from about 0.01 to about 10 wt%. DESCRIPTION OF THE PREFERRED EMBODIMENTS

The alkyl-succinhydrazide compounds of the present invention are compounds of the formula:

wherein:

Rj is selected from the group consisting of linear or branched alkyl, alkenyl, alkaryl, alkyl ether, and alkyl ester groups;

R₂ is selected from the group consisting of hydrogen, linear or branched alkyl, alkenyl, alkyl ether, and alkyl ester groups; and

branched alkyl and alkenyl groups, aryl groups, and alkaryl groups.

In the above structural formula, where Rj, R₂, R₃ and/or R₄ comprise an alkyl or

alkenyl moiety, such moiety can be a straight or branched hydrocarbon chain, fully saturated or partially unsaturated, preferably having from 1 to 30 carbon atoms, more preferably 1 to

22, most preferably 1 to 18 carbon atoms, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,

heptadecyl, octadecyl, oleyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tefradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl,

tetracosenyl, pentacosenyl, triacontenyl, and the like, and isomers and mixtures thereof.

Additionally, R_j andR₂ can be a linear or branched, saturated or partially unsaturated hydrocarbon chain, as described above, within which may be ester or oxygen ether groups,

and R₃ and/or R₄ can be alkaryl groups, such as nonylphenyl, dodecylphenyl, and the like.

The use of the alkyl-succinhydrazide compounds of this invention can improve the

anti-fatigue, anti-wear, and extreme pressure properties of a lubricant.

General Synthesis of Additives of this Invention The general process for preparing the alkyl succinhydrazides of the present invention involves charging an alkyl succinic anhydride to a reaction vessel with a solvent that boils

above 80° C and is capable of azeotroping off the water by-product. This solvent should also

be unreactive with all the reactants and the product. Examples of solvent are hydrocarbons,

such as heptane, decane, and dodecanes, and aromatic solvents, such as toluene, tetralins, and

xylenes. The hydrazine hydrate is added slowly to the reaction vessel with the initial reaction temperature at room temperature or about 20° C. After the hydrazine addition is complete,

the reaction media temperature may exotherm about 20 to 30° C, depending on the amount of

solvent present and hydrazine used. The temperature of the reaction media is then raised to reftux to complete the reaction and remove the water by-product. The solvent is then

removed under reduced pressure or under vacuum to yield the final product. This product may be polish filtered if necessary. When preparing products based on mono alkyl or unsymmetrical hydrazines, such as methyl and phenyl hydrazine, a minor amount of possible side product may also be a hydrazine succinimide of the structure:

wherein R_l5 R₂, and R₃ are as described above. It is believed that this material, present in the

product as a minor component, may also exhibit anti-wear properties in lubricant fluids

Use with Other Additives The alkyl-succinhydrazide additives of this invention can be used as either a partial or

complete replacement for the zinc dialkyldithiophosphates currently used. They can also be used in combination with other additives typically found in lubricating oils, as well as with

other ashless, anti-wear additives. These alkyl-succinhydrazides may also display synergistic

effects with these other typical additives to improve oil performance properties. The additives typically found in lubricating oils are, for example, dispersants, detergents,

corrosion/rust inhibitors, antioxidants, anti-wear agents, anti-foamants, friction modifiers,

seal swell agents, demulsifiers, VI improvers, pour point depressants, and the like. See, for example, U.S. Patent No. 5,498,809 for a description of useful lubricating oil composition

additives, the disclosure of which is incorporated herein by reference in its entirety.

Examples of dispersants include polyisobutylene succinimides, polyisobutylene succinate esters, Mannich Base ashless dispersants, and the like. Examples of detergents include alkyl metallic phenates, alkyl metallic sulfurized phenates, alkyl metallic sulfonates, alkyl metallic salicylates, and the like. Examples of antioxidants include alkylated diphenylamines, N- alkylated phenylenediamines, hindered phenolics, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, oil soluble copper and molybdenum compounds,

and the like. Examples of anti-wear additives that can be used in combination with the

additives of the present invention include organo borates, organo phosphites, organic sulfur-containing compounds, zinc dialkyldithiophosphates, zinc diaryldithiophosphates,

phosphosulfurized hydrocarbons, and the like. The following are exemplary of such additives

and are commercially available from The Lubrizol Corporation: Lubrizol 677A, Lubrizol

1095, Lubrizol 1097, Lubrizol 1360, Lubrizol 1395, Lubrizol 5139, and Lubrizol 5604,

among others. Examples of friction modifiers include fatty acid esters and amides, organo sulfurized and unsulfurized molybdenum compounds, molybdenum dialkylthiocarbamates (molybdenum monomers, dimers, and trimers), molybdenum dialkyl dithiophosphates, and the like. An example of an anti-foamant is polysiloxane, and the like. An example of a rust

inhibitor is a polyoxyalkylene polyol, and the like. Examples of VI improvers include olefin

copolymers and dispersant olefin copolymers, and the like. An example of a pour point depressant is polymethacrylate, and the like. Representative conventional anti-wear agents that can be used include, for example,

the zinc dialkyl dithiophosphates and the zinc diaryl dithiophosphates.

Suitable phosphates include dihydrocarbyl dithiophosphates, wherein the hydrocarbyl

groups contain an average of at least 3 carbon atoms. Particularly useful are metal salts of at least one dihydrocarbyl dithiophosphoric acid wherein the hydrocarbyl groups contain an average of at least 3 carbon atoms. The acids from which the dihydrocarbyl dithiophosphates can be derived can be illustrated by acids of the formula: -P.

R₅O^A

^"SH

OR,

wherein R₅ and R₆ are the same or different and are alkyl, cycloalkyl, aralkyl, alkaryl or

substituted substantially hydrocarbon radical derivatives of any of the above groups, and wherein the R_s and R₆ groups in the acid each have, on average, at least 3 carbon atoms. By

"substantially hydrocarbon" is meant radicals containing substituent groups (e.g., 1 to 4 substituent groups per radical moiety) such as ether, ester, nitro, or halogen that do not materially affect the hydrocarbon character of the radical.

Specific examples of suitable R₅ and R₆ radicals include isopropyl, isobutyl, n-butyl, sec-butyl, n-hexyl, heptyl, 2-ethylhexyl, diisobutyl, isooctyl, decyl, dodecyl, tetradecyl,

hexadecyl, octadecyl, butylphenyl,o,p-depentylphenyl, octylphenyl, polyisobutene-(molecular

weight 350)-substituted phenyl, tetrapropylene-substituted phenyl, beta-octylbutylnaphthyl,

cyclopentyl, cyclohexyl, phenyl, chlorophenyl, o-dichlorophenyl, bromophenyl, naphthenyl,

2-methylcyclohexyl, benzyl, chlorobenzyl, chloropentyl, dichlorophenyl, nitrophenyl, dichlorodecyl and xenyl radicals. Alkyl radicals having from about 3 to about 30 carbon

atoms and aryl radicals having from about 6 to about 30 carbon atoms are preferred.

Particularly preferred R₅and R₆ radicals are alkyl of from 4 to 18 carbon atoms. The phosphorodithioic acids are readily obtainable by the reaction of phosphorus pentasulfide and an alcohol or phenol. The reaction involves mixing, at a temperature of about 20° C. to 200° C, 4 moles of the alcohol or phenol with one mole of phosphorus pentasulfide. Hydrogen sulfide is liberated as the reaction takes place. Mixtures of alcohols, phenols, or both can be employed, e.g., mixtures of C₃ to C₃₀ alcohols, C₆ to C₃₀ aromatic alcohols, etc.

The metals useful to make the phosphate salts include Group I metals, Group II metals, aluminum, lead, tin, molybdenum, manganese, cobalt, and nickel. Zinc is the

preferred metal. Examples of metal compounds that can be reacted with the acid include

lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylate, sodium phenoxide, potassium oxide, potassium hydroxide, potassium carbonate, potassium methylate, silver

oxide, silver carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate,

magnesium ethylate, magnesium propylate, magnesium phenoxide, calcium oxide, calcium hydroxide, calcium carbonate, calcium methylate, calcium propylate, calcium pentylate, zinc

oxide, zinc hydroxide, zinc carbonate, zinc propylate, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethylate, barium oxide,

barium hydroxide, barium hydrate, barium carbonate, barium ethylate, barium pentylate,

aluminum oxide, aluminum propylate, lead oxide, lead hydroxide, lead carbonate, tin oxide,

tin butylate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentylate, nickel oxide, nickel hydroxide, and nickel carbonate.

In some instances, the incorporation of certain ingredients, particularly carboxylic

acids or metal carboxylates, such as, small amounts of the metal acetate or acetic acid, used in conjunction with the metal reactant will facilitate the reaction and result in an improved product. For example, the use of up to about 5% of zinc acetate in combination with the required amount of zinc oxide facilitates the formation of a zinc phosphorodithioate. The preparation of metal phosphorodithioates is well known in the art and is

described in a large number of issued patents, including U.S. Patent Nos. 3,293,181;

3,397,145; 3,396,109 and 3,442,804, the disclosures of which are hereby incorporated by

reference. Also useful as anti-wear additives are amine derivatives of dithiophosphoric acid

compounds, such as are described in U.S. Patent No. 3,637,499, the disclosure of which is

hereby incorporated by reference in its entirety.

The zinc salts are most commonly used as anti-wear additives in lubricating oil in

amounts of 0.1 to 10, preferably 0.2 to 2, wt. %, based upon the total weight of the lubricating

oil composition. They may be prepared in accordance with known techniques by first forming a dithiophosphoric acid, usually by reaction of an alcohol or a phenol with P₂S₅ and

then neutralizing the dithiophosphoric acid with a suitable zinc compound.

Mixtures of alcohols can be used, including mixtures of primary and secondary

alcohols, secondary generally for imparting improved anti-wear properties and primary for

thermal stability. Mixtures of the two are particularly useful. In general, any basic or neutral

zinc compound could be used, but the oxides, hydroxides, and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc owing to use of an excess of the basic zinc compound in the neutralization reaction.

The zinc dihydrocarbyl dithiophosphates (ZDDP) are oil soluble salts of dihydrocarbyl esters of dithiophosphoric acids and can be represented by the following

formula:

.P. ,Zn

^{^}R.O S^'

OR, wherein R₅ and R₆ are as described in connection with the previous formula.

Especially preferred additives for use in the practice of the present invention include

alkylated diphenylamines, hindered alkylated phenols, hindered alkylated phenolic esters, and

molybdenum dithiocarbamates.

Lubricant Compositions

Compositions, when they contain these additives, are typically blended into the base

oil in amounts such that the additives therein are effective to provide their normal attendant

functions. Representative effective amounts of such additives are illustrated in TABLE 1.

When other additives are employed, it may be desirable, although not necessary, to prepare additive concentrates comprising concentrated solutions or dispersions of the subject

additives of this invention, together with one or more of said other additives (said concentrate when constituting an additive mixture being referred to herein as an additive-package) whereby several additives can be added simultaneously to the base oil to form the lubricating

oil composition. Dissolution of the additive concentrate into the lubricating oil can be facilitated by solvents and/or by mixing accompanied by mild heating, but this is not essential. The concentrate or additive-package will typically be formulated to contain the

additives in proper amounts to provide the desired concentration in the final formulation

when the additive-package is combined with a predetermined amount of base lubricant.

Thus, the subject additives of the present invention can be added to small amounts of base oil

or other compatible solvents along with other desirable additives to form additive-packages

containing active ingredients in collective amounts of, typically, from about 2.5 to about

90 percent, preferably from about 15 to about 75 percent, and more preferably from about 25 percent to about 60 percent by weight additives in the appropriate proportions with the

remainder being base oil. The final formulations can typically employ about 1 to 20 weight

percent of the additive-package with the remainder being base oil.

All of the weight percentages expressed herein (unless otherwise indicated) are based

on the active ingredient (Al) content of the additive, and/or upon the total weight of any

additive-package, or formulation, which will be the sum of the Al weight of each additive

plus the weight of total oil or diluent.

In general, the lubricant compositions of the invention contain the additives in a

concentration ranging from about 0.05 to about 30 weight percent. A concentration range for the additives ranging from about 0.1 to about 10 weight percent based on the total weight of the oil composition is preferred. A more preferred concentration range is from about 0.2 to about 5 weight percent. Oil concentrates of the additives can contain from about 1 to about

75 weight percent of the additive reaction product in a carrier or diluent oil of lubricating oil viscosity. In general, the additives of the present invention are useful in a variety of lubricating

oil base stocks. The lubricating oil base stock is any natural or synthetic lubricating oil base stock fraction having a kinematic viscosity at 100° C of about 2 to about 200 cSt, more

preferably about 3 to about 150 cSt, and most preferably about 3 to about 100 cSt. The

lubricating oil base stock can be derived from natural lubricating oils, synthetic lubricating

oils, or mixtures thereof. Suitable lubricating oil base stocks include base stocks obtained by isomerization of synthetic wax and wax, as well as hydrocrackate base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude. Natural lubricating oils include animal oils, such as, lard oil, vegetable oils (e.g.,

canola oils, castor oils, sunflower oils), petroleum oils, mineral oils, and oils derived from

coal or shale.

Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils, such as,

polymerized and interpolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, homologues, and the

like. Synthetic lubricating oils also include alkylene oxide polymers, interpolymers,

copolymers, and derivatives thereof, wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc.

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic

acids with a variety of alcohols. Esters useful as synthetic oils also include those made from C₅ to C₁₂ monocarboxylic acids and polyols and polyol ethers. Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-

siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils.

Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, poly α-olefins, and the like.

The lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source (e.g.,

coal, shale, or tar and bitumen) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to unrefined oils, except that refined oils have been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, percolation, and the like, all of which are well-known to those skilled in the art. Rerefined oils are

obtained by treating refined oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.

Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks. Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst. Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced by the Fischer-Tropsch process. The resulting isomerate product is typically

subjected to solvent dewaxing and fractionation to recover various fractions having a specific

viscosity range. Wax isomerate is also characterized by possessing very high viscosity indices, generally having a NI of at least 130, preferably at least 135 or higher and, following

dewaxing, a pour point of about -20° C or lower.

The additives of the present invention are especially useful as components in many

different lubricating oil compositions. The additives can be included in a variety of oils with

lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. The additives can be included in crankcase lubricating oils for spark-ignited and

compression-ignited internal combustion engines. The compositions can also be used in gas engine lubricants, turbine lubricants, automatic transmission fluids, gear lubricants,

compressor lubricants, metal-working lubricants, hydraulic fluids, and other lubricating oil

and grease compositions. The additives can also be used in motor fuel compositions.

The advantages and the important features of the present invention will be more

apparent from the following examples.

EXAMPLES Example 1

Preparation of Branched Hexadecenyl Hydrazide Into a 250 mL three-necked round-bottomed flask, equipped with a mechanical stirrer, Dean-Stark water trap, addition funnel, thermocouple to temperature controller, heating mantle, and a nitrogen blanket is charged 75 mL of toluene and 31.8 grams (0.1 mole) of hexadecenyl succinic anhydride. In the addition funnel is charged 5.0 grams (0.1 mole) of

hydrazine monohydrate. The hydrazine is slowly added dropwise to the stirred reaction media at room temperature over a five minute period. The reaction media will exotherm

about 20° C. The temperature is then raised to reflux the toluene to the Dean-Stark trap. The

reaction media are refluxed until 3.7 mL of water is removed and the infrared analysis of a

sampled product shows that all the anhydride has been converted to succinhydrazide. The

reaction media are now cooled to room temperature and placed on a Roto-Evaporator to

remove the toluene solvent. The reaction product is now filtered through a bed of Celite filter-aid to yield 33 grams of a clear yellow liquid.

Example 2

Preparation of Branched N-Methyl Octadecenyl Succinhydrazide

Into a 250 mL three-necked round-bottomed flask, equipped with a mechanical stirrer, Dean-Stark water trap, addition funnel, thermocouple to temperature controller, heating

mantle, and a nitrogen blanket is charged 75 mL of toluene and 17.1 grams (0.05 mole) of octadecenyl succinic anhydride. In the addition funnel is charged 2.3 grams (0.05 mole) of

methylhydrazine. The hydrazine is slowly added dropwise to the stirred reaction media at

room temperature over a five minute period. The reaction media showed little exotherm. The temperature is then raised to reflux the toluene to the Dean-Stark trap. The reaction media are refluxed until water is no longer removed and the infrared analysis of a sampled product shows all the anhydride has been converted to succinhydrazide. The reaction media

are now cooled to room temperature and placed on a Roto-Evaporator to remove the toluene solvent. The reaction product is now filtered through a bed of Celite filter-aid to yield 18.4 grams of a clear yellow liquid. Examples 3-6

Linear dodecenyl succinhydrazide, branched dodecenyl succinhydrazide, N-phenyl

dodecyl succinhydrazide, and branched octadecenyl succinliydrazide are all prepared using the procedures described above.

Example 7

Four-Ball Anti-wear Testing The anti-wear properties of the alkyl-succinhydrazides of the present invention at a level of 1.0 wt% in a fully formulated SAE 5W-20 GF-3 motor oil formulation were

determined in the Four-Ball Wear Test under the ASTM D 4172 test conditions. The fully

formulated lubricating oils tested also contained 1 weight percent cumene hydroperoxide to

help simulate the environment within a running engine. The additives were tested for

effectiveness in a motor oil formulation (See description in Table 2) and compared to

identical formulations with and without any zinc dialkyldithiophosphate. In Table 3, the numerical value of the test results (Average Wear Scar Diameter, mm) decreases with an

increase in effectiveness.

¹ In the case of No anti-wear additive in Table 3, solvent neutral 100 is put in its place at 1.0

weight percent.

Numbers in parentheses are repeat test results.

Example 8 Cameron-Plint TE77 High Frequency Friction Machine Anti-wear Testing

Another test used to determine the anti-wear properties of these products is the

Cameron-Plint Anti-wear test based on a sliding ball on a plate. The specimen parts (6 mm

diameter AISI 52100 steel ball of 800 ± 20 kg/mm² hardness and hardened ground NSOH B01 gauge plate of RC 60/0.4 micron) are rinsed and then sonicated for 15 minutes with

technical grade hexanes. This procedure is repeated with isopropyl alcohol. The specimens are dried with nitrogen and set into the TE77. The oil bath is filled with 10 mL of sample.

The test is run at a 30 Hertz Frequency, 100 Newton Load, 2-35 mm Amplitude. The test

starts with the specimens and oil at room temperature. Immediately, the temperature is ramped over 15 minutes to 50° C, where it dwells for 15 minutes. The temperature is then

ramped over 15 minutes to 100° C, where it dwells for 45 minutes. A third temperature ramp over 15 minutes to 150° C is followed by a final dwell at 150° C for 15 minutes. The total length of the test is 2 hours. At the end of the test, the wear scar diameter on the 6 mm ball is measured using a Leica StereoZoomδ® Stereomicroscope and a Mitutoyo 164 series Digimatic Head. In the Examples below, the fully formulated lubricating oils tested contained 1 wt. % cumene hydroperoxide to help simulate the environment within a running engine. The test additive was blended at 1.0 wt. % in a fully formulated SAE 5W-20 Prototype GF-4 Motor Oil formulation containing no ZDDP. The additives were tested for effectiveness in this motor oil formulation (See description in Table 4) and compared to identical formulations with and without any zinc dialkyldithiophosphate. In Table 4 the numerical value of the test results (Ball Wear Scar Diameter, Plate Scar Width, and Plate Scar Depth) decreases with an increase in effectiveness.

^JIn the case of No anti-wear additive in Table 4, solvent neutral 100 is put in its place at 1.0 weight percent.

In view of the many changes and modifications that can be made without departing from principles underlying the invention, reference should be made to the appended claims for an understanding_, of the scope of the protection to be afforded the invention.

Claims

What is claimed is:

A composition comprising:

(A) a lubricant, and

(B) at least one alkyl succinhydrazide compound of the formula:

wherein:

R_j is selected from the group consisting of linear or branched alkyl, alkenyl, alkaryl, alkyl ether, alkyl ester, and alkylene ester groups;

R₃ and R₄ are independently selected from the group consisting of hydrogen, linear or branched alkyl and alkenyl groups, aryl groups, and alkaryl groups.

2. The composition of claim 1 wherein the lubricant is a lubricating oil.

3. The composition of claim 1 wherein R, is a straight chain hydrocarbon, a branched chain hydrocarbon, a fully saturated hydrocarbon chain, or a partially unsaturated hydrocarbon chain.

4. The composition of claim 1 wherein R, is a hydrocarbon chain of from 1 to 30 carbon atoms.

5. The composition of claim 1 wherein R_! is a linear or branched hexadecylene chain.

6. The composition of claim 1 wherein the alkyl-succinhydrazide is present in a concentration in the range of from about 0.01 to about 10 wt%.

7. The composition of claim 1 wherein R₂, R₃, and R₄ are independently selected from the group consisting of hydrogen, aryl, alkyl, alkaryl, and alkenyl.

8. The composition of claim 11 wherein R₂, R₃, and R₄ are the same.

9. The composition of claim 13 wherein R₂, R₃, and R₄ are hydrogen.

10. The composition of claim 1 further comprising at least one additive selected from the group consisting of dispersants, detergents, corrosion/rust inhibitors, zinc dialkyldithiophosphates, NI improvers, pour point depressants, antioxidants, and friction modifiers.

11. The composition of claim 1 further comprising at least one member selected from the group consisting of zinc dialkyldithiophosphates, zinc diaryldithiophosphates, and mixtures thereof.