EP0308651B1

EP0308651B1 - Jojoba oil and jojoba oil derivative lubricant compositions

Info

Publication number: EP0308651B1
Application number: EP88113441A
Authority: EP
Inventors: Phillip S. Landis; Frank Erickson
Original assignee: International Lubricants Inc
Current assignee: International Lubricants Inc
Priority date: 1987-08-21
Filing date: 1988-08-18
Publication date: 1992-07-29
Anticipated expiration: 2008-08-18
Also published as: EP0308651A3; AU2104688A; DE3873237D1; DE3873237T2; JPH01131300A; AU602422B2; CA1313180C; EP0308651A2; ATE78865T1

Abstract

There is disclosed an improved lubricant base composition for incorporation into a wide variety of lubricating compositions. The improved lubricant base composition comprises at least two ingredients selected from jojoba oil, sulfurized jojoba oil, and a phosphite adduct of jojoba oil.

Description

The present invention relates to a lubricant base composition and lubricant compositions with antifriction properties that contain jojoba oil and jojoba oil derivatives as the active lubricating agents. More specifically, this invention relates to a composition of jojoba oil, a phosphite adduct of jojoba oil and a sulfurized jojoba oil that is used in combination to form the active lubricating agents.
Jojoba oil is a natural mixture of straight-chain, unsaturated, monocarboxylic acid esters comprising primarily C₁₈ to C₂₄ monounsaturated alcohols esterified with C₁₈ to C₂₄ monounsaturated acids. The double bond is located predominantly in the C₉ position in both the alcohol and acid portion of the esters. Jojoba oil is conventionally cold-pressed from the seed of Simmondsia chinensis, a desert shrub native to California, Arizona, and Mexico.
Jojoba oil and many of its derivatives have been disclosed in the literature. Jojoba oil has been used primarily in cosmetics and hair shampoos, but has also been disclosed as useful as a lubricant. Arndt, United States Patent 4,557,841, refers to jojoba oil as a lubricating additive and useful in the range of 0.1% to 10% (w/w) in a motor oil with a standard motor oil formulation. United States Patent 2,921,874 refers to the use of jojoba oil as a cold forming lubricant for use in cold extrusion of metals. Further, United States Patent 4,360,387 refers to the use of isomorphous compositions of trans-isomerates of jojoba oil as useful as food machinery lubricants. United States Patent 3,849,323 refers to blended petroleum products for lubrication containing a natural oil, such as jojoba oil.
There is a largely unfulfilled need for new and improved lubricants and lubricant additive systems to improve the friction properties of lubricants, such as cutting fluids, precoat oils, metal-working oils, automatic transmission fluids (ATFs), gear oils, way oils, and automotive and marine oils. Various jojoba oil derivatives alone have been suggested as lubricating oil compositions. For example, German Patent 3,309,211 refers to the reaction of jojoba oil with P₂S₅ at high temperature and under a nitrogen atmosphere. German Patent 3,327,127 refers to the use of jojoba oil in a sulfochlorinated mixture to improve anticorrosion or anti-wear properties. Miwa et al. ("Extreme-Pressure Lubricant Tests on Jojoba and Sperm Whale Oils," J. Amer. Oil Chemists' Soc. 56:765-70, 1979) refers to lubricant tests on sulfurized jojoba oil as an extreme-pressure additive for motor oils, gear lubricants, and automotive transmission fluids. Miwa et al. found that the sulfurized jojoba oil as an antiwear additive for lubricants was at least equivalent to, and in some cases superior to, sulfurized sperm oil.
The use of jojoba oil as a lubricating derivative or agent in the prior art has been confined to single-agent use, i.e., jojoba oil and sulfurized derivatives of jojoba oil have been used individually as single agents in the art. There remains, however, much room for improvement of lubricating properties for automotive and marine oils, cutting fluids, precoat oils, metal-working oils, ATFs, gear oils, and way lubricants. The present invention represents compositions which are superior to prior art lubricants for use in many well-known applications.
The present invention provides a lubricant base and lubricating compositions containing a mixture of jojoba oil, sulfurized jojoba oil, and a phosphite adduct of jojoba oil. The compositions of the present invention provide superior lubricating characteristics, having antifriction characteristics and antiwear and load-carrying properties that are superior to any one compound alone. Improved antifriction characteristics may result in reduced fuel consumption for internal-combustion engines and lowered operating temperatures when used in engines and other industrial machinery. Further, the present invention provides for cutting fluids, precoat oils, metal-working oils, ATFs, gear oils, way lubricants, greases, aviation oils, textile lubricants, hydraulic oils, circulating oils, steam cylinder oils, spindle oils, fire-resistant fluids, and automotive and marine oils that incorporate the inventive lubricant base as the active lubricating agent.
As noted above, the present invention comprises a lubricant base and a lubricating composition with anti-friction properties, including antiwear and load-carrying properties, consisting of a lubricant base and a base fluid. The lubricant base comprises a mixture of jojoba oil, a phosphite adduct of jojoba oil, and sulfurized jojoba oil. The amounts of ingredients used in the compositions of this invention are based upon the final lubricating composition. The lubricant base can comprise 0.1% to 20% (w/w) jojoba oil, 0.1% to 5% (w/w) sulfurized jojoba oil, and 0.1% to 5% (w/w) of a phosphite adduct of jojoba oil. Another lubricant base combination can comprise 0.1% to 20% (w/w) jojoba oil and 0.1% to 5% (w/w) of a phosphite adduct of jojoba oil.
The lubricant base is mixed with a base fluid to make a lubricating composition with antifriction properties, including antiwear and load-carrying properties. Examples of lubricating compositions include cutting fluids, precoat oils, metal-working oils, ATFs, gear oils, way lubricants, greases, aviation oils, textile lubricants, hydraulic oils, circulating oils, steam cylinder oils, spindle oils, fire-resistant fluids, and automotive and marine oils. Examples of base fluids include hydrocarbon oil; synthetic hydrocarbon; an ester-based lubricant; a mineral oil; a mixture of a mineral oil and an ester-based lubricant; a mixture of mineral oil, synthetic hydrocarbon, and an ester-based lubricant; a mineral oil-based grease; and a synthetic hydrocarbon-based grease. Specifically, the base fluids are:

a. mineral oils, such as paraffinic neutral 100", furfural-refined paraffinic oil, solvent-refined naphthenic oil, and solvent-refined aromatic oil;
b. synthetic hydrocarbon oils, such as hydrogenated or partially hydrogenated polydecene and other olefins, hydrogenated hexene oligomer, hydrogenated octene oligomer, hydrogenated decene oligomer, hydrogenated C₆₋₁₀ oligomer, and hydrogenated C₈₋₁₀ oligomer;
c. ester fluids, such as pentaerythritol esters having the structures:
wherein R is C₄H₉, C₆H₁₃, C₈H₁₇, or mixtures thereof, esters of trimethylolpropane and dipentaerythritol of the structures:
wherein R is defined as above,
di-2-ethylhexyladipate, di-2-ethylhexylsebacate, didecyladipate, and didecylsebacate;
d. dialkylbenzenes, such as didocecylbenzene;
e. polyglycols, such as UCON fluids, polypropyleneglycols of 1000 to 3000 molecular weight and polyethyleneglycols of 1000 to 3000 molecular weight;
f. alkylaromatics; and
g. dicarboxylic acids.

Jojoba oil has the following structural formula:

wherein

j =: 7, 9, 11 or 13
k =: 6, 8, 10 or 12

n =: 1-3

_n

While other phosphite adducts of jojoba oil may be used in the present invention, a preferred phosphite adduct of jojoba oil is formed by the reaction of jojoba oil and a compound of the formula:

wherein R = H, C₁₋₁₂ alkyl, C₁₋₁₂ aryl, C₁₋₁₂ alkaryl, C₁₋₁₂ aralkyl, and cyclo C₁₋₁₂ alkyl. Preferably, R = C₄₋₈ alkyl, C₄₋₈ alkaryl, C₄₋₈ aralkyl, and cyclo C₄₋₈ alkyl. Most preferably, R is n-butyl.
As may be seen from its structural formula, jojoba oil has two carbon-carbon double bonds. Accordingly, the phosphite adduct can be a diadduct or a monoadduct of the jojoba oil. There are thus four examples of the phosphite adduct of jojoba oil when R is butyl as follows:

wherein j and k are defined as above.
The present invention is further illustrated by the following examples.
Examples of the lubricant base and lubricating compositions are provided in the Tables 1 and 2. The attached tables also provide performance results from standard tests, including low-velocity friction apparatus, the 4-ball wear test, and the Falex test. The procedures for each test are as follows.

4-Ball Tests for Assessing Extreme-Pressure Properties

The measurement of friction as related to rolling, drawing, and other metal-working operations depends upon the surface of the tool and workpiece and the viscosity and chemical makeup of the lubricant, as well as the pressure and temperature developed during processing. The 4-ball wear test machine provides, under controlled testing conditions, a procedure for measuring friction. The machine consists of three balls touching each other and clamped together in a horizontal plane. A fourth ball touches three clamped balls by being positioned between the three and is driven by a motor so that it revolves in contact with the clamped balls. The rotation takes place within a reservoir containing a test lubricant. A temperature-measuring device, as well as a heater, provides a method for controlling the temperature of the test fluid. The rotating ball is loaded and then rotated for a specific time at a specific speed. At the conclusion of the test, the scar patterns developed on the balls are measured. Any stains are observed, the diameter of the scar is measured, and the coefficient of friction is calculated by dividing the tangential force by the normal force at the ball surface.

Low-Velocity Friction Apparatus

The low-velocity friction apparatus (LVFA) is used to measure the friction of test lubricants under various loads, temperatures, and sliding speeds. The LVFA consists of a flat steel surface (diameter 3,81 cm (1.5 inches)) which is attached to a drive shaft and rotated over a stationary, raised, narrow ringed steel surface (area 0,52 cm² (0.08 inch²)). Both surfaces are submerged in the test lubricant. Friction between the steel surfaces is measured as a function of the sliding speed at a lubricant temperature of 121°C (250°F). The friction between the rubbing surfaces is measured using a torque arm/strain gauge system. The strain gauge output, which is calibrated to be equal to the coefficient of friction, is fed to the Y-axis of an X-Y plotter. The speed signal from the tachometer-generator is fed to the X-axis.

Falex Test

The Falex test consists of a method for measuring the torque and friction developed during rotation of a pin between two stationary V blocks. The pin as well as the V blocks can be made of various materials. The temperature of the lubricant bath into which the pin and V block are placed may also be varied. The load is applied by a ratchet arrangement. Wear measurements made above the transition pressure, that is, the load at which the lubricant film breaks down, can be a useful parameter if carried out under conditions comparable to actual operations.

The following Tables 1 and 2 illustrate base fluids, jojoba oil in base fluids, jojoba oil with a dibutyl phosphite adduct plus base fluid, a jojoba oil plus dibutyl phosphite adduct and sulfurized jojoba oil plus base fluid for the LVFA test, the Falex wear test, and the 4-ball wear test. The two tables illustrate the improved lubricating properties of the compositions of the present invention.

TABLE 1

Compound	Wt.%	LVFA, % Reduction in Coefficient of Friction
		Sliding Speed 152.4 cm/min (5 ft/min)	Sliding Speed 152.4 cm/min (5 ft/min)
Base Fluid^*	100.0	0	0
Jojoba Oil	2.0	2	2
Base Fluid	98.0
Jojoba Oil	10.0	8	12
Base Fluid	90.0
Jojoba Oil	1.0	21	20
Di-n-butylphosphite Adduct	4.0
Base Fluid	95.0
Jojoba Oil	5.0	24	28
Di-n-butylphosphite Adduct	2.0
Base Fluid	93.0
Jojoba Oil	5.0	15	19
Di-n-butylphosphite Adduct	2.0
Sulfurized Jojoba Oil	1.0
Base Fluid	92.0

^*Base Fluid is 100" Paraffinic Neutral Mineral Oil

TABLE 2

	4-Ball Wear Test Results		Falex Test
	Wear Scar Diameter	Weld Load	0,454 kg (Lbs) to Fail
Base Fluid	0.94	120	750
Base Fluid + 1% Jojoba	0.78	160	-
Base Fluid + 2% Jojoba	0.75	160	2900
Base Fluid + 5% Jojoba	0.72	180	-
Base Fluid + 5% Jojoba	0.68	160	3000
Base Fluid + 2% Jojoba + 5% Sulfurized Jojoba	0.52	240	4500
Base Fluid + 2% Jojoba + 0.5% Phosphite Adduct	0.52	220	4500
Base Fluid + 1% Jojoba + 2% Sulfurized Jojoba + 0.5% Phosphite Adduct	0.45	280	4900
Base Fluid + 1% Sulfurized Jojoba	0.58	220	3500
Base Fluid + 2% Sulfurized Jojoba	0.50	230	4200
Base Fluid + 5% Sulfurized Jojoba	0.51	250	4200
Base Fluid + 10% Sulfurized Jojoba	0.50	280	4500
Base Fluid + 0.5% Jojoba Phosphite Adduct	0.50	230	4200
Base Fluid + 1.5% Jojoba Phosphite Adduct	0.48	250	4200

The lubricant base may be added to different base fluids to obtain a composition having a variety of end-use applications. Examples of end-use applications with different base fluids are listed in Table 3.

TABLE 3

Application	Base Fluid	Viscosity SUS @ (100°F) 37,8°C
Auto Engine Oil	Mineral Oil and/or Ester Fluid and/or Synthetic Hydrocarbon Oils	100-200
Metal-Working Lubricant	Mineral Oils	100-200
Gear Lubricant	Mineral Oils	300-3000
Textile Lubricant	Polyethyleneglycols Polypropyleneglycols	1000-3000
Aviation Oils	Pentaerythritol Esters and Trimethylolpropane Esters	100-150
Grease	Mineral Oil Synthetic Hydrocarbons	100-2000
Hydraulic Oils	Mineral Oils Synthetic Hydrocarbons	100-300
Circulating Oils	Mineral Oils Synthetic Hydrocarbon	900-3000
Gas Engine Oils	Mineral Oils Synthetic Hydrocarbons	350-600
Diesel Engine Oils	Mineral Oils, Esters and Synthetic Hydrocarbons	600-1000
ATFs	Mineral Oils Synthetic Hydrocarbons	140-300
Way Lubricants	Mineral Oils Synthetic Hydrocarbons	150-1000
Steam Cylinder Oils	Mineral Oils	1800-1900
Fire-Resistant Fluids	Mineral Oil (Water)	400-500
Spindle Oils	Mineral Oils	50-130

Claims

A lubricant base constituent comprising a mixture consisting of jojoba oil, a phosphite adduct of jojoba oil, and a sulfurized jojoba oil.
The lubricant base of claim 1, comprising 0.1% to 20% (w/w) jojoba oil, 0.1% to 5% (w/w) sulfurized jojoba oil, and 0.1% to 5% (w/w) of a phosphite adduct of jojoba oil.
The lubricant base of claim 1, comprising 0.1% to 20% (w/w) jojoba oil and 0.1% to 5% (w/w) of a phosphite adduct of jojoba oil.
The lubricant base of claim 1 wherein the phosphite adduct of jojoba oil is a mono- or a diadduct of the reaction product of:
and jojoba oil, wherein R is selected from the group consisting of hydrogen, C₁₋₁₂ alkyl, C₁₋₁₂ aryl, C₁₋₁₂ alkaryl, C₁₋₁₂ aralkyl, and cyclo C₁₋₁₂ alkyl.
The lubricant base of claim 4 wherein R is butyl.
The lubricant base of claim 4 wherein the point of attachment of the phosphite adduct on the jojoba oil moiety is at a carbon-carbon double bond.
The lubricant base of claim 1 and selected from the group consisting of:
A-S_x-A, and combinations of both,
wherein x is 1 to 3 and A is jojoba oil.
A lubricating composition with antifriction properties, including antiwear and load-carrying properties, comprising a base fluid and a lubricant base comprising a mixture of jojoba oil, a phosphite adduct of jojoba oil, and a sulfurized jojoba oil.
The lubricating composition of claim 8 wherein the base fluid is selected from the group consisting of a hydrocarbon oil, a synthetic hydrocarbon, an ester-based lubricant, a mineral oil, a mixture of mineral oil, synthetic hydrocarbon and ester-based lubricant, a mineral oil-based grease, and a synthetic hydrocarbon-based grease.
The lubricating composition of claim 8 wherein the lubricant base constituent comprises 0.1% to 20% (w/w) jojoba oil, 0.1% to 5% (w/w) sulfurized jojoba oil, and 0.1% to 5% (w/w) of a phosphite adduct of jojoba oil.
The lubricating composition of claim 8 wherein the lubricant base constituent comprises 0.1% to 20% (w/w) jojoba oil and 0.1% to 5% (w/w) of a phosphite adduct of jojoba oil.
The lubricating composition of claim 8 wherein the phosphite adduct of jojoba oil is a mono- or a di-adduct of the reaction product of:
and jojoba oil, wherein R is selected from the group consisting of hydrogen, C₁₋₁₂ alkyl, C₁₋₁₂ aryl, C₁₋₁₂ alkaryl, C₁₋₁₂ aralkyl, and cyclo C₁₋₁₂ alkyl.
The lubricating composition of claim 12 wherein R is selected from the group consisting of C₄₋₈ alkyl, C₄₋₈ alkaryl, C₄₋₈ aralkyl, and cyclo C₄₋₈ alkyl.
The lubricating composition of claim 12 wherein R is butyl.
The lubricating composition of claim 12 wherein the point of attachment of the phosphite adduct moiety on the jojoba oil moiety is at a carbon-carbon double bond.