CA1312070C - Gear lubricant package containing a synergistic combination of components - Google Patents

Gear lubricant package containing a synergistic combination of components

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Publication number
CA1312070C
CA1312070C CA000565656A CA565656A CA1312070C CA 1312070 C CA1312070 C CA 1312070C CA 000565656 A CA000565656 A CA 000565656A CA 565656 A CA565656 A CA 565656A CA 1312070 C CA1312070 C CA 1312070C
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Prior art keywords
weight
gear lubricant
additive
zinc dithiophosphate
treated
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CA000565656A
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French (fr)
Inventor
Craig Daniel Tipton
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Lubrizol Corp
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Lubrizol Corp
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M167/00Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/02Sulfurised compounds
    • C10M135/04Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • C10M137/10Thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/20Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087Boron oxides, acids or salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26Overbased carboxylic acid salts
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/26Amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/02Groups 1 or 11
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/02Bearings
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00Specific manufacturing methods for lubricant compositions
    • C10N2070/02Concentrating of additives

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Title:

GEAR LUBRICANT PACKAGE CONTAINING A SYNERGISTIC
COMBINATION OF COMPONENTS
ABSTRACT OF THE DISCLOSURE
A number of functional characteristics of a gear lubricant are improved by including within the lubricant an additive package comprised of (a) a treated zinc dithiophosphate and (b) an overbased carboxylate which is preferably borated. The additive preferably includes (c) an alkylamine, (d) a sulfurized olefin and (e) a polymeric foam inhibitor. The components of the package provide an interdependent synergistic improvement of numerous performance characteristics of the gear lubricant such as reducing copper strip corrosion, increasing thermal stability and reducing the amount of rust, and odor. The limited slip or anti-chatter performance of the oil is also improved.

Description

7 ~

Title: GEAR LUBRICANT PACKAGE CONTAINING A SY~ERGISTIC
COMBINATION OF COMPONENTS

FIELD OF THE INVENTION
The present invention relates to the field of lubricants containing additive packages which improve the performance of the lubricants. More speciflcally, the invention relates to additive packages and gear lubricants having therein a combination of components which provide an interdependent synergistic effect on improving numerous characteristics of the gear lubricant. The additive package is comprised of (a) a treated zinc dithiophosphate which is preferably treated with propylene oxide and (b) an overbased carboxylate which is preferably borated. The additive preferably also includes an alkylamine, a sulfurized olefin and a polymeric foam inhibi-tor.

BACI~GROUND OF THE INVENTION
. . _ _ Gear lubrican-t packages are included in gear lubricants in order to improve performance characteristics of -the lubricant. A number of different additive compounds are known to effect the performance charac-teristics of a variety of different types of lubricants.

. :

~ 3~2~7~

However, a given additive compound can have different effects on performance characteristics depending on the type of lubricant it is added to and the other additive compounds present in the lubricant. Therefore, a formulator must consider not only the principle effects of including a given compound but how -the effects of the compound are changed due to the presence of other compounds and the total environment the final product will be used in.
U.S. Patent 3,923,669 discloses antiwear hydraulic oils which include therein zinc dialkyl dithiophosphate antiwear agents. In addition, the additive package includes neutral barium salts of a petroleum sulfonate and a succinic acid based rust inhibitor.
U.S. Patent 3,480,54~ discloses lubricating compositions comprised of a major amount of lubricating oil and an additive package which includes an oil soluble normal alkaline earth metal hydrocarbon sulfonate and an alkaline earth metal polyborate alkaline earth metal carbonate in a colloidal-like dispersion.
U.S. Patent 3,929,650 discloses a particulate dispersion of an alkali metal borate which is prepared by contacting boric acid with an alkaline earth metal carbonate overbased metal sulfonate within an oleophilic liquid reaction medium. The resulting particulate dispersion is included within a lubricant in order to improve the performance characteristics.
U.S. Patent 3,903,003 discloses lubricating oil compositions which are intended for use in connection with internal combustion engines. The lubricating oils include additive packages which comprise an amido amine reaction product formed between certain carbo~cylated hydrogenated polyisoprenes and certain amines, imines and hydroxyl alkyl polyamines. The additive is indicated as being used in connection with a number oE different -types of lubricants including gear lubricants.

-~ ~3~2~7~

U.S. Patent 4,563,302 discloses sulfurized olefins which are utilized in connection with lubricating oils in order to improve the stability of the oil. A specific process for manufacturing such sulfurized olefins is disclosed.

U.S. Patent 4,481,122 discloses lubricating compositions which include major amounts of a base oil and a minor amount of an additive which comprises an oil soluble polymer such as polyisobutylene. Specific compounds such as an organo silicone anti foaming agent is also indicated as being included within the lubricating oil.

SUMMARY OF THE INVENTION

The invention provides a gear lubricant additive, comprising: a) from about 0.1% to about 5% by weight of a treated zinc dithiophosphate wherein the zinc dithiophosphate is treated with a compound selected from the group consisting of an alkylene oxide containing 2 to 5 carbon atoms, and ethylene diamine; b) from about 0.1%
to 3% by weight of an overbased carboxylate; c) from about 0.05% to about 1% by weight of an alkylamine; and d) from about 0.5% to about 8% by weight of a sulfurized olefin.

~3~2~7~

In addition, there is provided a gear lubricant comprised of a major amount of an oil of lubricating viscosity and a minor amount of an additive package which is comprised of the above-mentioned components.

In the preferred form, the present invention provides an additive package that can be produced economically and efficiently, improves a number of functional characteristics of gear lubricants, greatly improves copper strip corrosion protection which is advantageous in connection with a gear lubricant oil used in contact with copper containing components, and increases the th~rmal stability of the gear lubricant.

Preferably also, the additive package improves anti-corrosion properties, and anti-chatter properties while reducing the odor relative to conventional gear lubricants, and performance in limited slip axles is significantly improved.

~312~7~

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Before the present gear lubricant additive pacXage and gear lubricant are described, it is to be understood that this invention is not limited to the particular components or amounts as described as such components and amounts may, of course, vary. It is to be understood that the terminology used herein is for the purpose for describing particular embodiments only, it is not intended to be limiting since the scope of the present invention will be limited only by the appended claims.

It must be noted that as used in this specification and the appended claims, the singular forms "a", "an" and "the7' include plural referents unless the context clearly dictates otherwise. Thus, for example reference to "a treated zinc dithiophosphate" includes mixtures of such treated zinc dithiophosphates, reference to "an overbased carboxylate includes reference to mixtures of such carboxylates", and reference to "an alkylamine1' includes mixtures of alkylamines which may vary in small increments over a range in order to provide a statistical mixture of such components. The inclusion of such statistical ~ ! ,J

1 3~ ~7~

mixtures of components which vary in small increments over a range is conventional within the art of lubricant additives in that lubricant additives must be economically and efficiently produced from crude reactant components which themselves are statistical mixtures.
The additive package of the invention must include (a) a treated zinc dithiophosphate and (b) an overbased carboxylate. The package comprised of (a) and (b) is useful as an additive package for its ability to improve the corrosion resistance and anti-wear properties of a gear lubricant oil. The package with (a) and (b) is added to a gear oil containing (c) an alkylamine and (d) a sulfurized oleEin or to a gear oil containing other additive com~onents which act in place of (c) and (d).
The fully formulated gear lubricant of the present invention is necessarily comprised of four components.
Those four components include (a) a treated zinc dithi-ophosphate; (b) an overbased carboxylate which is preferably borated; (c) an alkylamine, and (d) a sul-furized olefin. An optional component which is believed -to further increase the performance characteristics of the gear lubricant is (e) a polymeric foam inhibitor.
By including the additive package within a gear lubricant, a number of functional characteristics of the gear lubricant are improved. More specifically, the components of the additive package provide an interde~
pendent synergistic improvement of numerous performance characteristics such as preventing copper strip corrosion, increasing thermal stability, reducing the amount of rust and odor, and improving limited slip or anti-chatter performance. Each of the specific components of the additive package will now be described in detail in order to describe and disclose a representative number of examples of such components which mi~ht be used in connection with the pxesent invention.

13~ 2~7~

TREATED ZINC DITHIOPHOSPHATE

A number of different types of zinc di-thiophosphate compounds are useful additives as anti-wear agents in various types of lubricants. Zinc dithiophosphates continue to provide one of the most economical sources of anti~wear protection. There are three general types of zinc dithiophosphates from which to select, depending on the specific application. The zincs are classified as either primary, secondary, or aryl, depending on the alcohols from which they are made, although the primary and secondary zincs are commonly referred to as alkyl. If the R-O group in the structure for zinc dithiophosphate (shown below) is derived from a primary alcohol, then the zinc is referred to as primary; likewise, if it is derived from a secondary alcohol, it is referred to as secondary and, if derived from a phenol or an alkylated phenol, it is referred to as aryl.

R - O \ S
/ P- S Zn R O

R-O Derived Erom: Zinc Dithiophoshate Classified as:
. .
R-CH2-OH e-g-25 CH3-(CH2)n-CH2-OH Primary R
R-CH-OH e.g.
3 ~ 2)n IH OH Secondary CH3-(CH2) -CH2 R
~ OH e.g.

3 2)n 2 ~ OEI ~ryl ~3~7~

Each of these zincs usually displays a different combination of performance properties as summarized below:

Performance Type of Zinc D thiophospate Characteristic Primary Secondary Aryl _ _ Wear Protection Average Best Poorest Oxidation Average Best Poorest Inhibition Thermal Average Poorest Best 10 Stability Demulsibility Best Average Poorest Cost Lowest Average Highest NOTE - Variations are present among different compounds in any given class. Further, different sources may rate any given performance characteristics differently.

Based on their relative performance levels, zincs are selected for a particular application. For example~ aryl zincs are used almost exclusivel~ in diesel engine oils because of their excellent thermal stability. Primary zincs find a large application in both engine oils and hydraulic oils. Seconclary zincs are used mostly in hydraulic oils, transmission and gear oils. Primary and secondary zincs have been selec-ted for these applications because of -their rela-tively good anti-wear performance, good anti-oxidan-t quali-ties and low cos-t. Where hydraulic oils are concerned, primary zincs have usually been preferred because they offered the best overall performance for the lowes-t cost.

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In the gear lubricant additive and oil of the present invention zinc dithiophosphate may be present. However, the present invention uses zinc dithiophosphate, preferably secondary zinc dithiophosphates as intermediates by reacting the zinc dithiophosphate with a treating agent selected from alkylene oxides containing 2 to 5 carbon atoms, ethylene diamine and combinations thereof. The invention may include untreated zinc dithiophosphate in combination with those treated with one or more of the above mentioned treating agents. Most preferably the invention includes a propy]ene oxide treated secondary zinc dithiophosphate.
The treated zinc dithiophosphate may be present in the gear oil in an amount in the range of from about 0.1%
to 5% by weight based on the weight of the oil, more preferably about 2.0% to 4.0~ by weight and most preferably about 3.0% by weight. The amount of this component, like the other components can be adjusted by those skilled in the art to obtain the best results in a given environmen-t. This component is present in the fully formulated gear oil in an amount sufficient to act as an EP/antiwear agent in the system. The treatment with a compound like propylene oxide decreases the potential corrosivity of this component as used in a system.

OVERBASED CARBOX~LATES (BORATED) The overbased carboxylate component (b) of the present invention can be in a borated or non-borated form.
However, it is pointed out that -the borated versions are generally preferred. The borated versions of the overbased carboxylate component (b) of the invention are most generally prepared by reacting a boron reactant (preferably boric acid) with an overbased carboxylate.

~ 3 ~ 7 -~

The term "overbased compound" is generally used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The commonly employed methods Eor preparing overbased compounds involves heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing a~ent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50C and filtering the resulting mass.
The use of "promoter" in the neutralization step to aid the incorporation of a large excess of metal is generally found to be useful. A particularly effective method of preparing a basic salt comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter and carbonating the mixture by passing CO2 into the mixture at an elevated temperature between 10C and 200C.
In connection with the present invention the overbased compound is an overbased carboxylate prepared by reacting a stoichiometric excess of a metal neutralizing agent with a carboxylic acid to form a carboxylate which includes a stoichiometric excess of the metal. Accor-dingly, for use in the present invention the anion portion of the overbased component is an ionized carboxylic acid or carboxylate. The cationic portion of the overbased component is typically an ionized alkali metal or alkaline earth metal. The commonly used alkaline metals are lithium, potassium and sodium, with sodium being preferred. The alkaline earth metal components typically utilized are magnesium, calcium, and barium with calcium and magnesium being preferred.
A typical calcium carboxylate can be represented empirically by Ca(RCOO)2 . XCa (OH)2 . YCaCO3 where R
is a hydrocarbyl as defined below and X and Y combined are greater than 1 and vary depending on the degree of overbasing desired. Some typical carboxyllc aclds used ~2~

in preparing a carboxylate include tall oil fatty acid, oleic acid, linoleic acid, linolenic, and palmitic acids.
The use of overbased calcium carboxylate of these acids are preferred.
After the overbased carbo~ylate component is formed the component may be borated by reacting with a boron reactant which is preferably boric acid. The boric acid is charged into the reaction medium in the desired amount in order to form different types of borates. Dlfferent amounts of H3BO3 may be charged into the system to obtain the desired amount of boron incorporation depending on the desired end results.
The overbased carboxylate component (b) in its borated and non-borated versions may be present in the gear oil in an amount in the range of from about 0.1% to 3%, preferably from about 0.2% to about 1.5% and most preferably about 0.5% by weight based on the weight of the fully formulated gear oil.

AL~YLAMINES

The alkylamine component (c) of the present invention may be a mono, di or polyamine. Further, it may be a primary, second or tertiary amine. However, in connection with the present invention it is preferred if the amine is a diamine compound represented by the general formula (I) RNH(CH2)3N~l2 wherein R is hydrocarbyl. However, R is preferably an alkyl moie-ty containing about 10 to about 20 carbon atoms.
In formula (I) and elsewhere in the disclosure hydrocarbyl means "hydrocarbon-based." As used herein, the term "hydrocarbon based," "hydrocarbon-based substi-tuent" and the like denotes a subs-tituent having a carbon directly a-ttached to the remainder of the molecule and ~ 3 ~

having predominantly hydrocarbyl character within the context of this invention.
Examples of hydrocarbyl substituents which might be useful in connection with the present invention include the following:
(1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclie (e.g., cycloalkyl, cycloalkenyl) substituents, aromatic, aliphatlc and alicyclic-substituted aromatic nuclei and the like as well as cyclic substituents wherein the ring is completed through another portion of the molecule (that is, for example, any two indicated substituents may together form an alicyclic radical);
(2) substituted hydrocarbon substituents, that is, those substituents containing nonhydrocarbon radicals which, in the context of this invention, do not alter the predominantly hydrocarbon substituent; those skilled in the art will be aware of such radicals (e.g., halo (especially chloro and fluoro3, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.);
(3) hereto substituents, that is, substituents which will, while having predominantly hydrocarbyl character within the context of this invention, contain other than carbon present in a ring or ehain otherwise composed of carbon atoms. Suitable heteroatoms will. be apparent to those of ordinary skill in the art and inelude, for example, sulfur, oxygen, nitrogen and sueh substituents as, e.g., pyridyl, furanyl, thiophenyl, imidaæolyl, etc., are exemplary of these hereto substituents.
In general, no more than about three radicals or heteroatoms and preferably no more than one, will be present for each ten carbon atoms in the hydrocarbon-based substituents. Typically, there will be no such radicals or heteroatoms in the hydrocarbon-based substituent and it will, therefore, by purely hydrocarbon.

~312i~

The alkylam:ine component (c) may be present in ~he gear oil in an amount in the range of ~rom about 0.05% to about 1.0% by weight, preferably Q.1% to 0.4~ and most preferably about 0.2% by weight based on the weight of the gear oil as a whole.

S~LFURIZED ~LEFINS

Sulfurized olefins are well-known addi~ives in lubricatiny oil, cutting oil and ~he like. Kimball, U.S.
Patent No. 2,2~9,312, de~cribes such a product. Eby, U.S.
lo Patent No. 2,708,199, ~escribes a similar product in which a sulfur halide is reacted with an olefin using a lower alkanol promoter to obtain an intermediate which is reacted with a~ alkali or alkaline e~rth metal polysulfide. Myers! U.S. Patent No. 3,471,404, describes a product in which sulfur monochloride is reacted with olefin to obtain an int~rmediate which is reacted with sulfur and alkali metal sulfide at a critical ratio of 1.8-2.2 gram moles of metal sulfide per gram mole of sulfur. This material is $hen refluxed for 1-24 hours with aqueous alkali metal hydroxide. In U.S. Patent No.
4,204,969, an effective sulfurized olefin i~ made by reacting a sulfur monochloride with an olefin in the presence of a lower alkanol promoter to obtain an adduct which is reaated with sodium sulfide and sulfur in aqueous al~anol.
A sulfuri2ed olefin having improved solubility especially is a-ole~in oligomer lubricating oil i8 made by reacting a monoolefin with S2C12 or SC12 to obtain an adduct which is reacted with ~odium sulfide, sulfur, al~yl mercaptan and optionally sodium hydrosulfide in an aqueousalcohol reaction medium. Such a process is disclosed in U.S. Patent No. 4,563,302.

~12~7~

A process Eor making a sulfurized olefin having improved solubility in lubricating oil comprises:
a) reacting a sulfide halide selacted from SC12, S2-C12 and mixtures thereof with an aliphatic monoolefin containing 3-6 carbon atoms to produce an adduct;
b) reac~ing said adduct wi-th sulfur, Na2S, an alkyl mercaptan containing 1-12 carbon atoms and opti~nally NaSH in an aqueous alcohol medium at a temperature of 50 C. up to reflux to form said sulfurized olefin;
c) recoveriny said sulfurized olefin from the aqueous alcohol medium. tSee U.S. Patent No. 4,563,302).
A use~ul product can be obtained using either SC12 or S2C12.
Useful ole~ins are the monoethylenically unsaturated aliphatic hydrocarbons xeferred to as aliphatic monoolefin containing 3 to about 6 carbon atoms. These include 1-butene, 2-butene, isobutene, 1-pentene, 2 pentene, 2-methyl-1-but~ne, 3-methyl-1-butene, 2-methyl-2~butene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 2-methyl-2-pentens, 2-ethyl-2-butene and the like including mixtures thereof.
Preferably the olefins are branched-chain olefin such as isobutane, 2-methyl-1-butene, 2-methyl-2-butene, 2-methyl-2-pentene and the like. More preferably the ethylenic double bond adjoins a tertiary carbon atoms such as isobutylene, the most preferred ole~in.
The sulfurized olefin component (d) may be present in the gear oil in an amount in the range o~ from about 0.5%
to about 8.0% by weight, preferably 3.0% to ~.0% and most preferably about 3.0% by weight based on the weight of the year oiJ as a whol.e.

'I'\

- ~3~2~7~

POLYMERIC FOAM INHIBITORS

Acrylate copolymer foam inhibitors have been found to be useful. A specific foam inhibitor which is commercially available from Monsanto is referred to as defoamer PC-12~4. A specific copolymer defoamer compound is the copolymer of 2-ethylhexylacrylate/ethylacrylate in a weight ratio of 2.5:1. The copolymer is generally present in an amount of ~0% by weight of active chemical in a toluene diluent. The copolymer is made by adding a mixture of monomers together with an initiator in toluene solvent in the proper proportions to a "heel." The reactants are combined together in a polymerization vessel at about 110C. The resulting product is a polymer having a molecular weight in the range of about 40,000 and 90,000 (Mw). ~herein the Mn is in the range of 16,000-25,000. The viscosity at 40C is approximately 15cSt.
A number of different types of foam inhibitors may be found to be useful in connection with the present invention. In general, polymeric foam inhibitors may be added in an amount of from about 0.01 to 1.0%, preferably 0.03 to 0.1 and most preferably about 0.075% by weight based on the weight of the fully formulated gear oil.
The following examples are provided so as to provide those of ordinary skill in the art with a complete disclosure and description how to make the additive packages and gear oils of the invention and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to insure accuracy with respect to numbers used (e.g. amoun-ts, weight ratios, etc.) but some experimental errors and devia-tion should be accounted for. Unless indicated otherwise, parts are parts by weight, -temperature is in degrees C, and pressure is at or near a-tmospheric.

de~ rl<

2 0 ~ ~

An additive concentrate is prepared by combining 3%
propylene oxide treated zinc dithiophosphate, 3% sulfu-rized olefin, 0.2% oleylamine plus 0.5% borated overbased fatty calcium carboxylate and 0.075% commercial polymeric foam inhibitor containing 40% active chemical. The components are added to a diluent oil to provide a 7.0% by weight concentrate.

The procedure of Example 1 is followed except that the 0.5% borated overbased fatty calcium carboxylate is replaced with 1.0% weight overbased fatty calcium carboxylate (non-borated) to make a 7.5% by weight concentrateO

A fully formulated gear oil can be prepared by combining about 92% of a mineral oil or combination of mineral oils such as (75% 600N ~ 25% by weight 150 hright stock) with 7.0% weight concentrate described in Example l above and 1.0% weight polymeric pour point depressant.

1 3 ~

A fully formulated gear oil can be prepared by adding to a mineral oil of lubricating viscosity, such as bright stock, about 0.1% to 5% of propylene oxide treated zinc dithiophosphate, about 0.1% to about 3.0% of overbased carboxylate which is preferably borated, about 0.05% to about 1.0% of an alkylamine, about 0.56 to about 8.0% of a sulfurized olefin, and about 0.01% to about 1.0% of a polymeric foam inhibitor.

Prepare a fully formulated gear oil by adding to a bright stock mineral oil 3.0 parts by weight of a pxopylene oxide treated zinc dithiophosphate, 0.5 parts by weight of a borated overbased magnesium carboxylate, 0.2 parts by weight of an alkylamine, and 3 parts by weight of a sulfurized olefin. The resulting fully formulated gear oil should contain 6.7 parts by weight of additive components with the remaining 93.3 parts by weight being bright stock mineral oil.

Add about 0.075 parts by weight of a polyrneric foam inhibitor~ to the fully formulated ~ear lubricant of Example 5.

312~7~

Prepare a gear lubricant additive package by combining together about 0.05 to 5.0 parts by weight of a propylene oxide treated zinc dithiophosphate and about 0.1 to about 3.0 parts by weight of an overbased carboxylate which is preferably borated. The additive components may be added to a small amount of mineral oil to act as a diluent oil. The additive is useful as an additive for combining with oils which contain an alkylamine and a sulfurized olefin and/or other components which provide the interaction and properties of the combination of the alkylamine and sulfurized olefin.

The present invention may be sold by itself or in concentrates, in combination with any other known additive which includes, but is not limited to dispersants, detergents, antioxidants, antiwear agents, extreme pressure agents, emulsifiers, demulsifiers, friction modifiers, anti-rus-t agents, corrosion inhibitors, ; viscosity improvers, dyes, and solvents to improve handleability which may include alkyl and/or aryl hydrocarbons. These additives may be present in various amounts depending on the needs of the final product.
The concentrate might contain 0.01 to 90% by weight of the additive package. The additive package may be present in a final product, blend or concentrate in (in a minor amount i.e., up to 50~ by weight) any amount effective to improve the performance of characteristics of a gear oil but it is preferably present in gear oils in the form of mineral oils of lubricating viscosity in an amount of from about 1% to about 10~, preferably about 2%
to about 8%, most preferably about 6.775% by weight by based on the weight of the fully formulated gear oil;
where the individual components are present in amounts as ~3~07~

follows: (a) ahout 3.0% (b) about 0.5% (c) about 0.2% (d) about 3.0% and (e) about 0.075%. The amounts of the additive package and individual components in the gear oil will be varied by those skilled in the art to obtain optimal performance. E`or example, smaller amounts of additive (1-3%) are generally used with industrial gear oils.
The instant invention is shown and described herein in what is considered to be the most practical and preferred embodiments. It is recognized, however, that departures may be made therefrom which are within the scope of the invention, and that obvious modifications will occur to one skilled in the art upon reading this disclosure.

Claims (17)

1. A gear lubricant additive, comprising:
a) from about 0.1% to about 5% by weight of a treated zinc dithiophosphate wherein the zinc dithiophosphate is treated with a compound selected form the group consisting of an alkylene oxide containing 2 to 5 carbon atoms, and ethylene diamine;
b) from about 0.1% to 3% by weight of an overbased carboxylate;
c) from about 0.05% to about 1% by weight of an alkylamine; and d) from about 0.5% to about 8% by weight of a sulfurized olefin.
2. The gear lubricant additive of claim 1, wherein the zinc dithiophosphate is treated with propylene oxide and (b) is a calcium carboxylate.
3. The gear lubricant additive of claim 1, wherein the zinc dithiophosphate is treated with ethylene diamine.
4. The gear lubricant additive of claim 2 or 3, wherein the alkylamine is represented by general formula (I):
R?(CH2)3NH2 wherein R is hydrocarbyl.
5. The gear lubricant additive of claim 4, wherein R is an alkyl moiety containing 10 to 20 carbon atoms.
6. The gear lubricant additive of claim 1, 2, 3 or 5 comprising from about 0.01% to 1% by weight of a polymeric foam inhibitor.
7. A gear lubricant, comprising a major amount of an oil of lubricating viscosity:
a) from about 0.1% to about 5% by weight of a treated zinc dithiophosphate wherein the zinc dithiophosphate is treated with a compound selected from the group consisting of an alkylene oxide containing 2 to 5 carbon atoms, and ethylene diamine;
b) from about 0.1% to 3% by weight of an overbased carboxylate;
c) from about 0.05% to about 1% by weight of an alkylamine; and d) from about 0.5% to about 8% by weight of a sulfurized olefin.
8. The gear lubricant as claimed in claim 7, wherein the overbased carboxylate is a calcium carboxylate which is borated.
9. The year lubricant as claimed in claim 7 or 8, where the alkylamine is represented by general formula (I):
R?(CH2)3NH2 wherein R is hydrocarbyl.
10. The gear lubricant as claimed in claim 9, where R is an alkyl moiety containing 10 to 20 carbon atoms.
11. The gear lubricant as claimed in claim 7, 8 or 10, wherein the zinc dithiophosphate is treated with a propylene oxide.
12. The gear lubricant as claimed in claim 7, 8 or 10, wherein the zinc dithiophosphate is treated with ethylene diamine.
13. The gear lubricant as claimed in claim 7, 8 or 10 comprising from about 0.01% to 1% by weight of a polymeric foam inhibitor.
14. A gear lubricant, comprising at least 90% by weight of an oil of lubricating viscosity and about 0.1% to about 10%
by weight of an additive package comprising:
a) from about 0.1% to about 5% by weight of a treated zinc dithiophosphate wherein the zinc dithiophosphate is treated with a compound selected from the group consisting of an alkylene oxide containing 2 -to 5 carbon atoms, and ethylene diamine;
b) from about 0.1% to 3% by weight of an overbased carboxylate;
c) from about 0.05% to about 1% by weight of an alkylamine; and d) from about 0.5% to about 8% by weight of a sulfurized olefin.
15. The gear lubricant as claimed in claim 14, wherein (b) is a calcium carboxylate and the additive package is present in an amount of about 4% to about 8% by weight.
16. The gear lubricant as claimed in claim 14, wherein (b) is a sodium carboxylate and the additive package is present in an amount of about 1-4% by weight.
17. The gear lubricant as claimed in claim 14, 15 or 16 comprising from about 0.01% to 1% by weight of a polymeric foam inhibitor.
CA000565656A 1987-05-07 1988-05-02 Gear lubricant package containing a synergistic combination of components Expired - Fee Related CA1312070C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4775487A 1987-05-07 1987-05-07
US47,754 1987-05-07

Publications (1)

Publication Number Publication Date
CA1312070C true CA1312070C (en) 1992-12-29

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Application Number Title Priority Date Filing Date
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Country Status (7)

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EP (1) EP0313628B1 (en)
JP (1) JPH01503392A (en)
AU (1) AU602773B2 (en)
CA (1) CA1312070C (en)
DE (1) DE3885853T2 (en)
WO (1) WO1988008874A2 (en)
ZA (1) ZA883229B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989009811A1 (en) * 1988-04-08 1989-10-19 The Lubrizol Corporation Borated and non-borated overbased carboxylates as corrosion inhibitors
GB2288815A (en) * 1994-04-08 1995-11-01 Exxon Chemical Patents Inc Lubricating oil anti-wear additives
US20090093384A1 (en) * 2007-10-03 2009-04-09 The Lubrizol Corporation Lubricants That Decrease Micropitting for Industrial Gears
CN113637514A (en) 2013-12-06 2021-11-12 巴斯夫欧洲公司 Composition and method of forming the same
WO2018057675A1 (en) * 2016-09-21 2018-03-29 The Lubrizol Corporation Polyacrylate antifoam components with improved thermal stability

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3190833A (en) * 1961-04-14 1965-06-22 Lubrizol Corp Oxidation-resistant lubricating composition
GB1121713A (en) * 1966-05-31 1968-07-31 Lubrizol Corp Lubricant additive composition
US3813336A (en) * 1970-09-11 1974-05-28 Chevron Res Reaction products of amines and dithiophosphoric acids or salts

Also Published As

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WO1988008874A3 (en) 1988-12-15
JPH01503392A (en) 1989-11-16
DE3885853T2 (en) 1994-03-17
AU1724488A (en) 1988-12-06
DE3885853D1 (en) 1994-01-05
AU602773B2 (en) 1990-10-25
EP0313628A1 (en) 1989-05-03
WO1988008874A2 (en) 1988-11-17
EP0313628B1 (en) 1993-11-24
ZA883229B (en) 1988-11-11

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