JP2011516637A - Improved varnish-resistant lubricating oil composition - Google Patents

Abstract

In one embodiment, an advantageous stick control lubricant is disclosed. The lubricant comprises a large amount of base stock selected from the group consisting of Group II, Group III, GTL and any combination thereof, and a Mannich base dispersant that comprises at least 0.1 and 2.0 weight percent of the lubricant. And a demulsifier comprising a polyol ester and a polyoxyalkylene, wherein the demulsifier comprises at least 0.002 to less than 2.0 weight percent of the lubricating oil, wherein the lubricating oil is at 120 ° C. Dry for 504 hours It has a stick control value of less than 60 using the TOST sludge test. In the second embodiment, a method of sticking control is disclosed. In a third embodiment, an oil formulation method for improving sticking control and emulsion properties is disclosed.
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Description

  Lubricating oil composition technology has become more complex as a result of increasing government and user environmental standards and increasing user performance requirements. Lubricants are typically marketed based on characteristics such as fluid durability, adhesion control, anti-wear protection, filterability, water tolerance, rust / corrosion prevention, and viscosity.

  Sticking or varnish is a serious problem in many hydraulic and sensitive lubrication applications such as gas turbine lubrication. Varnish formation is usually the result of a complex series of events leading to lubricant degradation. There are two common causes of oil degradation. One cause is oxidation at high temperatures that results in the formation of decomposition products containing acids and insoluble particulate matter, referred to as sticking, varnish, sludge. The second cause is thermal decomposition, such as pressure-induced or micro-dieseling that occurs when entrained bubbles are crushed under high pressure.

  Sticking varnish is measured using a modified anhydrous ASTM D943 TOST test, 504 hours 120 ° C. DRY-TOST sludge test. This DRY-TOST test method was developed by Mitsubishi Heavy Industries in order to quickly evaluate the sludge or varnish formation tendency of turbine oil. This Dry-TOST complies with ASTM D943 test with the correction conditions shown in the table below. After the 504 hour test period, the test tube is left at room temperature overnight and then the amount of fixation is measured. The amount of sludge or varnish is equal to the amount of filter residue in which 100 g of oil is filtered through a 1 μm Millipore filter. An amount of sludge less than 100 mg / kg (ppm) is an acceptable result. The table below lists the items and test conditions for this test.

  It is well known that API Group II and III basestock oils and GTL are typically better than API Group I base oils. Group II and III basestocks are better due to the oxidative stability and improved viscosity and temperature characteristics of hydrotreated or hydrocracked basestocks compared to conventional solvent refined basestocks. As a result, many lubricants are formulated with API Group II and III basestocks. A known deficiency of these nonpolar, highly saturated API Group II and III basestocks is their lower ability to solubilize or suspend the lubricant degradation by-products once formed. For this reason, API Group II / III based lubricants are more susceptible to stick formation once oil breakdown begins.

  A number of deficiencies in turbine generator applications have been associated with varnish and sludge formation. Sludge and varnish are insoluble materials that are formed as a result of either a decomposition reaction with oil, contamination of the oil or both. The description typically includes, among other things, base oil properties, additive instability or degradation, bulk oil oxidation, electrostatic discharge, and low conductivity.

  Recently, much attention has been directed to the potential role of fluid charging and electrostatic discharge as a significant contributor to sludge and varnish formation in turbine systems. Electrostatic discharge is a form of localized pyrolysis. Charging occurs in the fluid system as a result of internal molecular friction and the potential between the fluid and the machine surface.

  The magnitude of the electrostatic charge in the oil depends on many factors, and the grounding of the machine itself has little effect on reducing charge propagation. This is because the oil is non-conductive and effectively self-insulates the charged fluid zone from the ground surface. Once charge accumulates in working fluid zones, such as reservoirs and filter housings, subsequent electrostatic discharges can cause localized thermo-oxidized oil degradation.

US Pat. No. 6,080,301 US Pat. No. 6,090,989 US Pat. No. 6,165,949 US Pat. No. 5,275,749 U.S. Pat. No. 4,234,435 US Pat. No. 4,652,416 US Pat. No. 3,576,923

The Encyclopedia of Chemical Technology, 2nd edition, Kirk and Othmer, Vol. 7, pp. 27-39, Interscience Publishers, Division of John Wiley and Sons 65 years. Kirk Othmer's “Encyclopedia of Chemical Technology”, 2nd edition, volume 7, pages 22-37, Interscience Publishers, New York (1965)

  There is a need to find formulations that use API Group II, Group III, and GTL basestocks in formulations that provide advantageous fixation formulation properties. Accordingly, the present invention satisfies that need.

  In one embodiment, an advantageous stick control lubricant is disclosed. The lubricant comprises a large amount of base stock selected from the group consisting of Group II, Group III, GTL and any combination thereof, and Mannich comprising at least 0.1 weight percent and less than 2.0 weight percent of the lubricant. A base dispersant and a demulsifier comprising a polyol ester and a polyoxyalkylene comprising at least 0.002 weight percent to less than 2.0 weight percent of the lubricating oil, wherein the lubricating oil is 504 hours 120 C. Adherence control value of less than 60 using DRY TOST sludge test.

  In the second embodiment, a method for improving sticking control is disclosed. The method comprises a large amount of base stock selected from the group consisting of Group II, Group III, GTL and any combination thereof and a Mannich base comprising at least 0.1 weight percent and less than 2.0 weight percent of the lubricating oil A lubricating oil comprising a dispersant and a demulsifier comprising a polyol ester and a polyoxyalkylene and comprising at least 0.002 weight percent to less than 2.0 weight percent of the lubricating oil, wherein 504 hours 120 A step of obtaining a lubricating oil having a sticking control value of less than 60 using the C DRY TOST sludge test and a step of lubricating with the lubricating oil are included.

  In a third embodiment, a method for formulating a lubricating oil to improve sticking control and emulsion properties is disclosed. The method comprises a large amount of base stock selected from the group consisting of Group II, Group III, GTL and any combination thereof and a Mannich base comprising at least 0.1 weight percent and less than 2.0 weight percent of the lubricating oil Obtaining a dispersant and a demulsifier comprising a polyol ester and a polyoxyalkylene, comprising at least 0.002 weight percent to less than 2.0 weight percent of the lubricating oil; 504 hours at 120 ° C. DRY Blending base stock, demulsifier and dispersant to obtain a stick control value of less than 60 using the TOST sludge test.

  The invention will be described in connection with its preferred embodiments. However, as long as the following description is specific to a particular embodiment or particular use of the invention, this is intended to be exemplary only and should not be construed to limit the scope of the invention. . On the contrary, it is intended to cover all alternatives, modifications and equivalents included within the spirit and scope of the invention as defined by the appended claims.

  In one embodiment, we have a lubricating oil composition comprising either an API Group II or III or GTL basestock or a combination thereof with antioxidants and other additives in a unique Mannich base dispersant / It has been discovered that when formulated with a demulsifier combination, it provides an unexpected improvement in sticking control while maintaining good demulsibility. Surprisingly, not all dispersants provided this cleanliness benefit in this application.

  Although dispersants are known to improve sticking control, they are polar in nature and tend to be emulsifiable, providing poor water separation. An additional benefit in one embodiment of the lubricating oil composition is that the final product also exhibits good demulsification with ASTM D-1401. This method is a rapid test that includes mixing 40 ml of oil and 40 ml of water together at 1500 rpm for 5 minutes using an impeller. The mixture is allowed to stand and the time for water, oil and any emulsion phases to separate is recorded. This test is performed at 54 ° C. (130 ° F.) for viscosities below 90 cSt at 40 ° C. and generally accepted results are up to 30 minutes before 3 ml of emulsion remain.

  Acceptable processing ranges for Mannich base dispersants are at least 0.1 weight percent to less than 2.0 weight percent. A preferred treatment range is at least 0.2 weight percent to less than 0.5 weight percent, and a most preferred treatment range is 0.2 weight percent to less than 0.4 weight percent.

  In a preferred embodiment, we have found that Pluronic L 121 surfactant from BASF is effective at the same concentration as the polyol ester. In the most preferred embodiment, the demulsifier also includes a propylene oxide block copolymer. The preferred concentration of polyol ester and ethylene oxide in the demulsifier is at least 0.001 wt% to 0.1 wt% or less. Most preferably, this concentration should be at least 0.6 wt% to less than 0.05 wt%. In this embodiment, higher ethylene oxide content or higher MW tends to be less effective for demulsibility. The ethylene oxide content in Pluronic L 121 is 10% by weight and the average molecular weight is 4400. In a preferred embodiment, a 25 weight percent ethylene oxide or polyol ester and a molecular weight of 5000 will be the upper limit for accepting ethylene oxide or polyol ester in the demulsifier additive.

  An acceptable processing range for the demulsifier is at least 0.002 weight percent to less than 2.0 weight percent. A preferred treatment range is at least 0.01 weight percent to less than 0.1 weight percent, and a most preferred treatment range is 0.01 weight percent to less than 0.05 weight percent.

  This formulation demonstrates excellent varnish adhesion using a 504 hour 120 ° C. DRY TOST sludge test. Preferably the formulation should have a value of less than 60, more preferably less than 50, most preferably less than 25.

  In another embodiment, we have discovered that the claimed invention provides excellent electrical conductivity (“EC”). The test used was D-4308 at 32 ° F. The liquid hydrocarbon sample is introduced into a clean conductivity cell connected in series with a battery voltage source and a high sensitivity dc ammeter. Conductivity, calculated automatically from the peak current reading dc voltage and cell constant observed using Ohm's law, appears as a digital value in either the manual or automatic mode of meter operation. Low conductivity can result in an accumulated static charge when the machine is shut down or idle. Having a higher conductivity can prevent the phenomenon of electrostatic discharge that has been implicated in one fundamental cause of varnish sticking in gas turbines with microfiltration and operating at high flow rates. . Preferably the conductivity should be at least 50 pS / m, more preferably at least 60 pS / m, most preferably greater than 100 pS / m.

  In another embodiment, the formulation should have small amounts of calcium and zinc. Preferred embodiments are less than 5 PPM zinc and less than 5 PPM calcium. More preferred embodiments are zinc below 5 PPM, calcium below 5 PPM and phosphorus below 50 PPM. Even more preferred embodiments are less than 1 PPM zinc, less than 1 PPM calcium and less than 5 PPM phosphorus.

  Skilled formulators in the art will appreciate the benefits of adding additional additives to the formulation with the help of the disclosure herein. Preferably, the formulation is at least one addition selected from the group consisting of antiwear additives, metal passivators, demulsifiers, pour point depressants, rust inhibitors, antifoam agents and any combination thereof. Will contain the agent. Additional information regarding base stocks and additives is provided below. Preferably, calcium-containing additives, such as calcium sulfonate, are not used due to the potential reaction to form calcium carboxylate soaps with commonly used ashless rust inhibitors used in typical formulations. Let's go.

Base stock:
Groups I, II, III, IV and V have developed a broad category of base stocks (API Publication 1509) developed and defined by the American Petroleum Institute to create guidelines for lubricating base stocks. ; Www.API.org). Group I base stocks generally have a viscosity index of about 80-120 and contain greater than about 0.03% sulfur and / or less than about 90% saturates. Group II base stocks generally have a viscosity index of about 80-120 and contain no more than about 0.03% sulfur and no less than about 90% saturates. Group III stocks generally have a viscosity index greater than about 120 and contain no more than about 0.03% sulfur and more than about 90% saturates. Group IV includes polyalphaolefins (PAO). Group V base stocks include base stocks not included in Groups I-IV. Table 2 summarizes the characteristics of each of these five groups.

  In a preferred embodiment, the base stock comprises at least one base stock of synthetic oil, and most preferably comprises at least one base stock of API Group IV polyalphaolefin. Synthetic oils for the purposes of this application are intended to include all oils that are not natural mineral oils. Natural mineral oils are often referred to as API Group I oils.

  Gas to liquid (GTL) base stocks can also be used preferentially with the components of the present invention as part or all of the base stock used to formulate the finished lubricant. We have found an advantageous improvement when the components of the present invention are added to a lubrication system primarily comprising Group II, Group III and / or GTL base stock compared to lower amounts of alternative fluids.

  GTL materials include gaseous carbon-containing compounds, hydrogen-containing compounds, and / or hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylene, butyne, etc. A material derived from one or more of its constituents as raw materials by one or more synthesis, compounding, transformation, rearrangement, and / or decomposition / destruction processes. GTL base stocks and base oils are lubricants generally derived from hydrocarbons, such as waxy synthetic hydrocarbons, which are derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and / or components as raw materials. Viscosity GTL material. GTL basestocks are lubricants that have been separated / fractionated from the GTL material, such as by distillation or thermal diffusion, and then subjected to well-known contact or solvent dewaxing processes to produce reduced / low pour point lubricants Oils boiling in the boiling range; wax isomers, including, for example, hydroisomerized or isodewaxed synthetic hydrocarbons; hydroisomerized or isodewaxed Fischer-Tropsch ( “FT”) materials (ie hydrocarbons, waxy hydrocarbons, waxes and possible similar oxygenates); preferably hydroisomerized or isodewaxed FT hydrocarbons or hydroisomerized or Isodewaxed FT wax, hydroisomerization or isodewaxed synthesis Box, or mixtures thereof.

GTL base stocks derived from GTL materials, particularly hydroisomerized / isodewaxed FT material derived base stocks, and other hydroisomerized / isodewaxed wax derived base stocks at about 100 ° C. has a kinematic viscosity and about 130 or more viscosity index of 4 mm ² / sec, as exemplified by the GTL base stocks induced by F-T wax iso dewaxing, about 2 mm ² / sec to about 50 mm ² / s Typically having a kinematic viscosity at 100 ° C. of from about 3 mm ² / sec to about 50 mm ² / sec, more preferably from about 3.5 mm ² / sec to about 30 mm ² / sec. The terms GTL base oil / base stock and / or wax isomerate base oil / base stock as used herein and in the claims are GTL base stock / base oil or as recovered in the manufacturing process. Individual fractions of wax isomerate base stock / base oil, as well as one or more low viscosity GTL base stocks / base to produce bimodal blends exhibiting viscosities within the above listed ranges Includes a mixture of oil fraction and / or wax isomerate basestock / base oil fraction and one, two or more high viscosity GTL basestock / base oil fractions and / or wax isomerate basestock / base oil fraction Should be understood as. Reference herein to kinematic viscosity relates to the measurements made by ASTM method D445.

  GTL base stocks and base oils derived from GTL materials, particularly hydroisomerized / isodewaxed FT material derived base stocks, and wax hydroisomers / Other hydroisomerized / isodewaxed wax-derived base stocks, such as isodewaxates, are about −5 ° C. or less, preferably about −10 ° C. or less, more preferably about −15 ° C. or less, Even more preferably, it is typically further characterized as having a pour point of about −20 ° C. or less, and under some conditions, at a useful pour point of about −30 ° C. to about −40 ° C. or less, about − It may have an advantageous pour point of 25 ° C. or less. If necessary, a separate dewaxing step may be performed to achieve the desired pour point. Reference herein to pour points relates to measurements made by ASTM D97 and similar automated versions.

  GTL base stocks derived from GTL materials, particularly hydroisomerized / iso-dewaxed base stocks from FT materials, and other hydroisomerization / iso-dewaxing base stock components that can be used in the present invention The wax derived base stock is also typically characterized as having a viscosity index of 80 or higher, preferably 100 or higher, more preferably 120 or higher. Further, in certain specific cases, the viscosity index of these base stocks may preferably be 130 or higher, more preferably 135 or higher, and even more preferably 140 or higher. For example, GTL base stocks derived from GTL materials, preferably FT materials, especially FT waxes, generally have a viscosity index of 130 or higher. References herein to viscosity index relate to ASTM method D2270.

  In addition, GTL base stocks are typically highly paraffinic with over 90% saturates and may contain a mixture of monocycloparaffins and multicycloparaffins in combination with acyclic isoparaffins. . The ratio of naphthenic (ie cycloparaffin) content in such combinations varies with the catalyst and temperature used. In addition, GTL base stocks and base oils typically have very low sulfur and nitrogen contents and generally contain less than about 10 ppm, more typically less than about 5 ppm of each of these elements. The sulfur and nitrogen content of the GTL base stock and base oil obtained by hydroisomerization / isodewaxing of FT materials, especially FT waxes, is essentially zero.

  In a preferred embodiment, the GTL base stock comprises a paraffinic material consisting primarily of acyclic isoparaffin and a small amount of cycloparaffin. These GTL base stocks typically have more than 60% by weight acyclic isoparaffin, preferably more than 80% by weight acyclic isoparaffin, more preferably more than 85% by weight acyclic isoparaffin, most preferably more than 90% by weight. A paraffinic material consisting of a non-cyclic isoparaffin.

  Useful of wax-derived hydroisomerized / iso-dewaxed basestocks, such as GTL basestocks, hydroisomerized or iso-dewaxed FT material derived base stocks, and wax isomers / iso-dewaxed bodies Examples of such compositions are listed in Patent Document 1, Patent Document 2 and Patent Document 3, for example.

Additive:
Additives may be selected to modify various properties of the lubricating oil. For gear oils, the additive should provide the following properties: wear resistance protection, rust prevention, micropitting prevention, friction reduction, and improved filterability. Those skilled in the art will recognize a variety of additives that can be selected to achieve advantageous properties, including advantageous properties for gear oil applications.

  In various embodiments, additives well known in the art as functional fluid additives are also required in relatively small amounts; often from less than about 0.001% to about 10-20% or more. It will be understood that it can be incorporated into the functional fluid composition of the present invention. In one embodiment, the at least one oil additive is an antioxidant, stabilizer, antiwear additive, dispersant, detergent, antifoam additive, viscosity index improver, copper passivator, metal desensitizer. It is added from the group consisting of activators, rust inhibitors, corrosion inhibitors, pour point depressants, demulsifiers, antiwear agents, extreme pressure additives and friction modifiers. The additives listed below are non-limiting examples and are not intended to limit the scope of the claims.

  The dispersant should contain an alkenyl or alkyl group R having a Mn value of about 500 to about 5000 and a Mw / Mn ratio of about 1 to about 5. The preferred Mn spacing depends on the chemical nature of the reagent that improves filterability. Suitable polyolefin-based polymers for reaction with maleic anhydride or other acid or acid-forming materials include polymers containing a majority of C2-C5 monoolefins such as ethylene, propylene, butylene, isobutylene and pentene. It is. A very suitable polyolefin polymer is polyisobutene. A preferred succinic anhydride as a reactant is PIBSA, i.e. polyisobutenyl succinic anhydride.

  When the dispersant contains succinimide containing the reaction product of succinic anhydride and polyamine, the alkenyl or alkyl substituent of the succinic anhydride acting as a reactant is preferably polymerized having a Mn value of about 1200 to about 2500. Consists of isobutene. More advantageously, the alkenyl or alkyl substituent of the succinic anhydride that serves as the reactant is in polymerized isobutene having a Mn value of about 2100 to about 2400. If the agent that improves filterability contains an ester of succinic acid including the reaction product of succinic anhydride and an aliphatic polyhydric alcohol, the alkenyl or alkyl substituent of succinic anhydride that acts as a reactant is advantageously It consists of polymerized isobutene having a Mn value of 500-1500. Preferably, polymerized isobutene having a Mn value of 850 to 1200 is used.

  Suitable uses of amides include antiwear agents, extreme pressure additives, friction modifiers or dispersants. The amide utilized in the composition of the present invention may be an amide of mono- or polycarboxylic acids or reactive derivatives thereof. Amides may be characterized by hydrocarbyl groups containing from about 6 to about 90 carbon atoms; each independently, hydrogen or hydrocarbyl, aminohydrocarbyl, provided that both are not hydrogen Hydroxyhydrocarbyl or heterocyclic substituted hydrocarbyl groups; each independently a hydrocarbylene group containing about 10 or fewer carbon atoms; Alk is an alkylene group containing about 10 or fewer carbon atoms is there.

  Amides are derived from monocarboxylic acids where the hydrocarbyl group will be a hydrocarbyl group containing from 6 to about 30 or 38 carbon atoms, and more often from a fatty acid containing from 12 to about 24 carbon atoms. Can be guided.

  Amides are derived from di- or tricarboxylic acids and will contain from 6 to about 90 or more carbon atoms, depending on the type of polycarboxylic acid. For example, when the amide is derived from dimer acid, it contains about 18 to about 44 or more carbon atoms, and amides derived from trimer acid generally contain an average of about 44 to about 90 carbon atoms. I will. Each is independently hydrogen or a hydrocarbyl, aminohydrocarbyl, hydroxyhydrocarbyl or heterocyclic substituted hydrocarbon group containing up to about 10 carbon atoms. It may independently be a heterocyclic substituted hydrocarbyl group in which the heterocyclic substituent is derived from pyrrole, pyrroline, pyrrolidine, morpholine, piperazine, piperidine, pyridine, pipecoline and the like. Specific examples include methyl, ethyl, n-propyl, n-butyl, n-hexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, aminomethyl, aminoethyl, aminopropyl, 2-ethylpyridine, 1-ethylpyrrolidine , 1-ethylpiperidine and the like.

  The alkyl group can be an alkylene group containing from 1 to about 10 carbon atoms. Examples of such alkylene groups include methylene, ethylene, propylene and the like. Also hydrocarbylene groups, especially alkylene groups containing up to about 10 carbon atoms. Examples of such hydrocarbylene groups include methylene, ethylene, propylene and the like. The amide contains at least one morpholinyl group. In one embodiment, the morpholine structure is formed as a result of the condensation of two hydroxy groups attached to a hydrocarbylene group. Typically, amides are prepared by reacting a carboxylic acid or reactive derivative thereof with an amine containing at least one> NH group.

  Aliphatic monoamines include monoaliphatic and dialiphatic substituted amines where the aliphatic group may be saturated or unsaturated and linear or branched. Such amines include, for example, mono- and di-alkyl substituted amines, mono- and dialkenyl substituted amines, and the like. Specific examples of such monoamines include ethylamine, diethylamine, n-butylamine, di-n-butylamine, isobutylamine, cocoamine, stearylamine, oleylamine and the like. An example of an alicyclic substituted aliphatic amine is 2- (cyclohexyl) -ethylamine. Examples of heterocyclic substituted aliphatic amines include 2- (2-aminoethyl) -pyrrole, 2- (2-aminoethyl) -1-methylpyrrole, 2- (2-aminoethyl) -1-methylpyrrolidine and 4- (2-aminoethyl) morpholine, 1- (2-aminoethyl) piperazine, 1- (2-aminoethyl) piperidine, 2- (2-aminoethyl) pyridine, 1- (2-aminoethyl) pyrrolidine, 1- (3-aminopropyl) imidazole, 3- (2-aminopropyl) indole, 4- (3-aminopropyl) morpholine, 1- (3-aminopropyl) -2-pipecoline, 1- (3-aminopropyl ) -2-pyrrolidinone and the like.

  Alicyclic monoamines are those monoamines with one alicyclic substituent bonded directly to the amino nitrogen by a carbon atom in the ring structure. Examples of alicyclic monoamines include cyclohexylamine, cyclopentylamine, cyclohexenylamine, cyclopentenylamine, N-ethyl-cyclohexylamine, dicyclohexylamine and the like. Examples of aliphatic, aromatic, and heterocyclic substituted alicyclic monoamines include propyl substituted cyclohexylamine, phenyl substituted cyclopentylamine, and pyranyl substituted cyclohexylamine.

  Aromatic amines include those monoamines in which the carbon atom of the aromatic ring structure is bonded directly to the amino nitrogen. The aromatic ring will usually be a mononuclear aromatic ring (ie, derived from benzene), but can include fused aromatic rings, particularly those derived from naphthalene. Examples of aromatic monoamines include aniline, di- (para-methylphenyl) amine, naphthylamine, N- (n-butyl) aniline and the like. Examples of aliphatic substituted, alicyclic substituted, and heterocyclic substituted aromatic monoamines are para-ethoxyaniline, para-dodecylaniline, cyclohexyl substituted naphthylamine, phenothiazine, and thienyl substituted aniline.

  Polyamines are aliphatic, cycloaliphatic and aromatic polyamines similar to the monoamines described above, except for the presence of an additional amino nitrogen in their structure. The additional amino nitrogen can be a primary, secondary or tertiary amino nitrogen. Examples of such polyamines include N-amino-propyl-cyclohexylamine, N, N′-di-n-butyl-paraphenylenediamine, bis- (para-aminophenyl) methane, 1,4-diaminocyclohexane, and the like. It is done.

  Possible hydroxy-substituted amines are those having a hydroxy substituent bonded directly to a carbon atom other than the carbonyl carbon atom; that is, they have a hydroxy group that can function as an alcohol. Examples of such hydroxy-substituted amines include ethanolamine, di- (3-hydroxypropyl) amine, 3-hydroxybutylamine, 4-hydroxybutylamine, diethanolamine, di- (2-hydroxyamine, N- (hydroxypropyl) -propyl. Examples include amine, N- (2-methyl) -cyclohexylamine, 3-hydroxycyclopentylparahydroxyaniline, N-hydroxyethylpiperazine and the like.

  In one embodiment, the amine useful in the present invention is hydrogen or an alkylene polyamine comprising a hydrocarbyl, aminohydrocarbyl, hydroxyhydrocarbyl or heterocyclic substituted hydrocarbyl group containing up to about 10 carbon atoms, and Alk is about An alkylene group containing up to 10 carbon atoms, from 2 to about 10. Preferably Alk is ethylene or propylene. Usually a will have an average value of 2 to about 7. Examples of such alkylene polyamines include methylene polyamine, ethylene polyamine, butylene polyamine, propylene polyamine, pentylene polyamine, hexylene polyamine, heptylene polyamine and the like.

  Alkylene polyamines include ethylenediamine, triethylenetetramine, propylenediamine, trimethylenediamine, hexamethylenediamine, decamethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, di (heptamethylene) triamine, tripropylenetetramine, tetra Ethylenepentamine, trimethylenediamine, pentaethylenehexamine, di (trimethylene) triamine and the like are included. Higher homologues such as those obtained by condensing two or more of the alkylene amines exemplified above are useful, as are mixtures of any two or more of the polyamines.

  Ethylene polyamines, such as those described above, are particularly useful for cost and effectiveness reasons. Such polyamines are described in detail under the heading “Diamines and Higher Amines” in Non-Patent Document 1, which is hereby incorporated by reference for disclosure of useful polyamines. Such compounds are most conveniently prepared by reaction of alkylene chloride with ammonia or by reaction of ethyleneimine with a ring-opening reagent such as ammonia. These reactions result in the production of somewhat complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazine.

  Another useful type of polyamine mixture is that resulting from stripping of the polyamine mixture described above. In this case, lower molecular weight polyamines and volatile contaminants are removed from the alkylene polyamine mixture, leaving what is often referred to as “polyamine bottoms” as a residue. In general, the alkylene polyamine bottoms can be characterized as having a material boiling below about 200 ° C. of less than 2% by weight, usually less than 1% by weight. In the case of ethylene polyamine bottoms, which are readily available and found to be very useful, the bottoms are less than about 2% by weight total diethylenetriamine (DETA) or triethylenetetramine (TETA). ). A typical sample of such ethylene polyamine bottoms obtained from Dow Chemical Company (Freeport, Texas) is referred to as “E-100”. Gas chromatographic analysis of such a sample shows that it is about 0.93% (by weight) “light fraction” (most likely DETA), 0.72% TETA, 21.74% tetraethylenepentamine and 76%. It was found to contain 61% pentaethylenehexamine and heavy matter. These alkylene polyamine tower bottoms contain cyclic condensation products such as piperazine and higher analogs such as diethylenetriamine and triethylenetetramine.

  The dispersant comprises a Mannich base which is a condensation reaction product of a high molecular weight phenol, an alkylene polyamine and an aldehyde such as formaldehyde, an olefin polymer which can be reacted with an organic hydroxy compound and / or an amine, and a succinic acylating agent (acid, Selected from succinic acid-based dispersants which are reaction products with acid anhydrides, esters or halides).

  Esters such as reaction products of high molecular weight amides and hydrocarbyl acylating agents with polyhydric aliphatic alcohols (such as glycerol, pentaerythritol or sorbitol).

  Ashless (metal-free) polymeric materials that usually contain an oil-soluble high molecular weight backbone attached to polar functional groups associated with the particles to be dispersed are typically used as dispersants. Zinc acetate capped and optionally treated dispersants, including borated cyclic carbonates, end-capped, polyalkylene maleic anhydride, etc .; range from about 0.1 to 10% to 20% or less or more Some mixtures of the above, at a treatment rate of Commonly used hydrocarbon backbone materials are olefin polymers and copolymers, i.e., ethylene, propylene, butylene, isobutylene, styrene; incorporated into the backbone of the polymer whose molecular weight ranges from 300 to 5000 or less. There may or may not be further functional groups. Polar materials such as amines, alcohols, amides or esters are attached to the main chain by bridges.

  Antioxidants include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4- (2-octyl-3-propane) Acid) sterically hindered alkylphenols such as phenol; N, N-di (alkylphenyl) amine; and alkylated phenylenediamines.

  The antioxidant component is suitably a hindered phenolic oxidation such as butylated hydroxytoluene present in an amount of 0.01 to 5%, preferably 0.4 to 0.8% by weight of the lubricating oil composition. An inhibitor may be used. Alternatively or additionally, component b) may comprise an aromatic amine antioxidant, such as mono-octylphenyl alpha naphthylamine or p, p-dioctyldiphenylamine, used alone or in a mixture. The amine antioxidant component is suitably present in the range of 0.01 to 5% by weight of the lubricating oil composition, more preferably 0.5 to 1.5%.

  Amine-type antioxidants include, for example, monoalkyldiphenylamines such as monooctyldiphenylamine and monononyldiphenylamine; 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine, 4,4 Dialkyldiphenylamines such as' -diheptyldiphenylamine, 4,4'-dioctyldiphenylamine and 4,4'-dinonyldiphenylamine; polyalkyldiphenylamines such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine and tetranonyldiphenylamine; and alpha Naphthylamine, phenyl-alpha-naphthylamine, butylphenyl-alpha-naphthylamine, pliers Phenyl - alpha - naphthylamine, hexylphenyl - alpha - naphthylamine, heptylphenyl - alpha - naphthylamine, octylphenyl - include naphthylamine, such as naphthylamine - alpha - naphthylamine and nonylphenyl - alpha. Of these, dialkyldiphenylamine is preferred. The sulfur-containing antioxidant and the amine-type antioxidant are added to the base oil in an amount of 0.01 to 5% by weight, preferably 0.03 to 3% by weight, based on the total weight of the composition.

  Antioxidants, nitrogen, phosphorus containing organic compounds and some alkylphenols are also used. Two general types of antioxidants are those that react with initiators, peroxy radicals, and hydroperoxides to form inert compounds, and those that decompose these materials to form less reactive compounds. is there. Examples are hindered (alkylated) phenols such as 2,6-di (tertiarybutyl) -4-methylphenol [2,6-di (tertiarybutyl) -p-cresol, DBPC], and aromatic amines, For example, N-phenyl-alpha-naphthalamine. These are used in turbines, circulation, and hydraulic oils intended for extended use at amine / phenolic ratios that are 1:10 to 10: 1 of the preferred mixture.

  Examples of phenol-based antioxidants include 2-t-butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone (trade name “Antage DBH Manufactured by Kawaguchi Chemical Co., Ltd.), 2,6-di-t-butylphenol and 2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-4- 2,6-di-tert-butyl-4-alkylphenols such as ethylphenol; 2,6-di-tert-butyl-4-methoxyphenol and 2,6-di-tert-butyl 2,6-di-tert-butyl-4-alkoxyphenol such as ru-4-ethoxyphenol; 3,5-di-tert-butyl-4-hydroxybenzyl mercaptooctyl acetate; n-octyl-3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Yoshitomi Pharmaceutical Co., Ltd. under the trade name “Yonox SS”), n-dodecyl-3- (3,5-di-t-butyl-4 Alkyl-3- (3,5-di-t-butyl-4-hydroxy) such as -hydroxyphenyl) propionate and 2'-ethylhexyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate Phenyl) propionate; 2,6-di-t-butyl-alpha-dimethylamino-p-cresol; 2,2′-methylenebis (4- Til-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd. under the trade name “Antage W-400”) and 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) (trade name “ 2,2′-methylenebis (4-alkyl-6-tert-butylphenol) compounds such as “Antage W-500” (manufactured by Kawaguchi Chemical Co., Ltd.); 4,4′-butylidenebis (3-methyl-6- t-butyl-phenol) (manufactured by Kawaguchi Chemical Co., Ltd. under the trade name “Antage W-300”), 4,4′-methylenebis (2,6-di-t-butylphenol) (trade name “Ionox 220AH”) Manufactured by Laporte Performance Chemicals), 4,4'-bis 2,6-di-t-butylphenol), 2,2- (di-p-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3,5-di-t-butyl-4-hydroxyphenyl) Propane, 4,4′-cyclohexylidenebis (2,6-di-t-butylphenol), hexamethylene glycol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (commercial product Under the name “Irganox L109”, Ciba Specialty Chemicals Co. Triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] (manufactured by Yoshitomi Pharmaceutical Co., Ltd. under the trade name “Tominox 917”), 2 , 2′-thio [diethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Ciba Specialty Chemicals Co. under the trade name “Irganox L115”), 3,9- Bis {1,1-dimethyl-2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] ethyl} 2,4,8,10-tetraoxaspiro [5,5 ] Undecane (manufactured by Sumitomo Chemical Co., Ltd. under the trade name "Sumilizer GA80") 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane (manufactured by Yoshitomi Pharmaceutical Co., Ltd. under the trade name “Yoshinox 930”), 1,3,5-trimethyl- 2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (manufactured by Ciba Specialty Chemicals Co. under the trade name “Irganox 330”), bis [3,3′- Bis (4′-hydroxy-3′-tert-butylphenyl) butyric acid] glycol ester, 2- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) -methyl-4- (2 ″, 4 "-Di-tert-butyl-3" -hydroxyphenyl) methyl-6-tert-butylphenol and 2,6-bis (2'-hydroxy-3'-t Bisphenols such as butyl-5′-methylbenzyl) -4-methylphenol; and phenol / aldehyde condensates such as condensates of pt-butylphenol and formaldehyde and condensates of pt-butylphenol and acetaldehyde. Can be mentioned.

  Viscosity index improvers and / or pour point depressants include high molecular weight alkyl methacrylates and olefin copolymers such as ethylene-propylene copolymers or polyalkylenes such as styrene-butadiene copolymers or PIB. Viscosity index improvers (VI improvers) are high molecular weight polymer polymers that increase the relative viscosity of oils at higher temperatures than at lower temperatures. The most common VI improvers are methacrylate polymers and copolymers, acrylate polymers, olefin polymers and copolymers, and styrene-butadiene copolymers.

  Other examples of viscosity index improvers include polymethacrylates, polyisobutylenes, alpha-olefin polymers, alpha-olefin copolymers (eg, ethylene-propylene copolymers), polyalkylstyrenes, phenol condensates, naphthalene condensates, styrene butadiene copolymers. Etc. Of these, polymethacrylates having a number average molecular weight of 10,000 to 300,000, and alpha-olefin polymers or alpha-olefin copolymers having a number average molecular weight of 1,000 to 30,000, in particular 1,000 to An ethylene-alpha-olefin copolymer having a number average molecular weight of 10,000 is preferred.

  Viscosity index improvers that can be used include other non-dispersed viscosity index improvers such as polymethacrylates and ethylene / propylene copolymers, olefin copolymers such as styrene / diene copolymers, and materials containing nitrogen-containing monomers. And a dispersible viscosity index improver copolymerized therein. These materials can be added and used individually or in the form of a mixture, conveniently in an amount in the range 0.05 to 20 parts by weight per 100 parts by weight of the base oil.

  Pour point depressants (PPD) include polymethacrylate. Commonly used additives such as alkyl aromatic polymers and polymethacrylates are useful for this purpose; typically the treatment ratio ranges from 0.001% to 1.0%.

  Rust inhibitors include (short chain) alkenyl succinic acids, their partial esters and their nitrogen-containing derivatives. Examples of the rust inhibitor include monocarboxylic acids having 8 to 30 carbon atoms, alkyl or alkenyl succinates or partial esters thereof, hydroxy fatty acids having 12 to 30 carbon atoms, and derivatives thereof. Sarcosine having 24 carbon atoms and their derivatives, amino acids and their derivatives, naphthenic acid and its derivatives, lanolin fatty acids, mercapto fatty acids and paraffin oxides are included.

  Particularly preferred rust inhibitors are shown below. Examples of monocarboxylic acids (C8-C30) are caprylic acid, pelargonic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, serotic acid, montanic acid, melicic acid , Oleic acid, docosanoic acid, erucic acid, eicosenoic acid, beef tallow fatty acid, soybean fatty acid, coconut oil fatty acid, linoleic acid, linolenic acid, tall oil fatty acid, 12-hydroxystearic acid, lauryl sarcosine acid, myristyl sarcosine acid, palmityl sarcosine Acid, stearyl sarcosine acid, oleyl sarcosine acid, alkylated (C8-C20) phenoxyacetic acid, lanolin fatty acid.

  Examples of polybasic carboxylic acids: CAS No. Alkenyl (C10-C100) succinic acid and ester derivatives thereof, dimer acid, N-acyl-N-alkyloxyalkylaspartic acid ester represented by 27859-58-1 (Patent Document 4).

  Examples of alkylamines that function as rust inhibitors or as reaction products with the above carboxylates to provide amides and the like include laurylamine, coconut-amine, n-tridecylamine, myristylamine, n-pentadecylamine, Palmitylamine, n-heptadecylamine, stearylamine, n-nonadecylamine, n-eicosylamine, n-heneicosylamine, n-docosylamine, n-tricosylamine, n-pentacosylamine, oleylamine, tallow-amine , Represented by primary amines such as hydrogenated beef tallow-amine and soy-amine. Examples of secondary amines include dilaurylamine, di-coconut-amine, di-n-tridecylamine, dimyristylamine, di-n-pentadecylamine, dipalmitylamine, di-n-pentadecyl. Amine, distearylamine, di-n-nonadecylamine, di-n-eicosylamine, di-n-heneicosylamine, di-n-docosylamine, di-n-tricosylamine, di-n-pentacosylamine, Examples include dioleylamine, di-tallow-amine, di-hydrogenated tallow-amine and di-soy-amine.

  Examples of the aforementioned N-alkylpolyalkylenediamines include laurylethylenediamine, coconut ethylenediamine, n-tridecylethylenediamine, myristylethylenediamine, n-pentadecylethylenediamine, palmitylethylenediamine, n-heptadecylethylenediamine, stearylethylenediamine, n-nona. Decylethylenediamine, n-eicosylethylenediamine, n-heneicosylethylenediamine, n-docosylethylenediamine, n-tricosylethylenediamine, n-pentacosylethylenediamine, oleylethylenediamine, beef tallow-ethylenediamine, hydrogenated tallow-ethylenediamine and soybean- Ethylenediamine such as ethylenediamine; laurylpropylenediamine, coconut propylenediamine n-tridecyl propylene diamine, myristyl propylene diamine, n-pentadecyl propylene diamine, palmityl propylene diamine, n-heptadecyl propylene diamine, stearyl propylene diamine, n-nonadecyl propylene diamine, n-eicosyl propylene diamine, n- Henecosylpropylenediamine, n-docosylpropylenediamine, n-tricosylpropylenediamine, n-pentacosylpropylenediamine, diethylenetriamine (DETA) or triethylenetetramine (TETA), oleylpropylenediamine, beef tallow-propylenediamine, hydrogen Propylene diamine such as beef tallow-propylene diamine and soybean-propylene diamine; lauryl butylene diamine, coconut butylene diamine , N-tridecyl butylene diamine, myristyl butylene diamine, n-pentadecyl butylene diamine, stearyl butylene diamine, n-eicosyl butylene diamine, n-heneicosyl butylene diamine, n-docosyl butylene diamine, n-tricosyl Butylene diamines such as butylene diamine, n-pentacosyl butylene diamine, oleyl butylene diamine, beef tallow butylene diamine, hydrogenated beef tallow butylene diamine and soybean butylene diamine; and lauryl pentylene diamine, coconut pentylene diamine, myristyl pentylene diamine , Palmityl pentylene diamine, stearyl pentylene diamine, oleyl pentylene diamine, beef tallow-pentylene diamine, hydrogenated beef tallow-pentylene diamine and soy bean And pentylenediamine such as nthylenediamine.

  Demulsifiers include synthetic alkyl aryl sulfonates such as alkoxylated phenols and phenol-formaldehyde resins and metal dinonyl naphthalene sulfonates. The demulsifier is a major amount of water-soluble polyoxyalkylene glycol having a preselected molecular weight of any value in the range of about 450 to 5000 or more. A particularly preferred series of water-soluble polyoxyalkylene glycols useful in the compositions of the present invention are also those produced from alkoxylation of n-butanol with a mixture of alkylene oxides to form a random alkoxylation product. May be.

  The functional fluid according to the present invention has a pour point of less than about −20 ° C. and is compatible with a wide range of antiwear and extreme pressure additives. Formulations according to the present invention also do not have the fatigue failure normally expected by those skilled in the art when processed with a polar lubricant base stock.

  The polyoxyalkylene glycol useful in the present invention is an addition polymerization of alcohol or glycol ether and one or more alkylene oxide polymers such as ethylene oxide, butylene oxide, or propylene oxide using a strong base such as potassium hydroxide as a catalyst. The polyalkylene oxide having hydroxyl end groups may be produced by a well-known method for producing a block copolymer. In such a process, the polymerization is generally carried out under a catalyst concentration of 0.3 to 1.0 mol% potassium hydroxide relative to the monomer and at an elevated temperature such as 100 ° C to 160 ° C. It is a well-known fact that the catalyst potassium hydroxide is mostly bonded to the chain end of the resulting polyalkylene oxide in the form of alkoxide in the polymer solution thus obtained.

  A particularly preferred family of soluble polyoxyalkylene glycols useful in the compositions of the present invention are also those prepared from alkoxylation of n-butanol with a mixture of alkylene oxides to form a random alkoxylation product. Also good.

  Antifoaming agents include polymers of alkyl methacrylates that are generally understood to be alkyl methyl, ethyl, propyl, isopropyl, butyl, or isobutyl, particularly useful polyalkyl acrylate polymers, and dimethyl having a viscosity range of 100 cSt to 100,000 cSt. Included are polymers of dimethyl silicone that form a material called a siloxane polymer. Other additives are antifoaming agents, such as silicone polymers, the most widely used antifoaming agents post-reacted with various carbon-containing moieties. Organic polymers are sometimes used as antifoam agents, although much higher concentrations are required.

  Metal deactivating compounds / corrosion inhibitors include alkyltriazoles and benzotriazoles. Examples of dibasic acids useful as corrosion inhibitors other than sebacic acid that may be used in the present invention are adipic acid, azelaic acid, dodecanedioic acid, 3-methyladipic acid, 3-nitrophthalic acid, 1, 10-decanedicarboxylic acid and fumaric acid. The corrosion inhibiting combination is a linear or branched saturated or unsaturated monocarboxylic acid or ester thereof. Preferably, the acid is a substituted C4 to substituted C22 linear unsaturated monocarboxylic acid. The preferred concentration of this additive is 0.001% to 0.35% by weight of the total lubricating oil composition. However, other suitable substances are oleic acid itself; valeric acid and erucic acid. The component of the corrosion protection combination is a triazole as defined above. Triazole should be used at a concentration of 0.005% to 0.25% by weight of the total composition. Preferred triazoles are tolyltriazoles that may be included in the compositions of the present invention and include triazoles, thiazoles and certain diamine compounds that are useful as metal deactivators or metal passivators. Examples include substituted benzotriazoles such as triazole, benzotriazole and alkyl substituted derivatives. Alkyl substituents generally contain no more than 15 carbon atoms, preferably no more than 8 carbon atoms. Triazoles may contain other substituents such as halogen, nitro, amino, mercapto on the aromatic ring. Examples of suitable compounds are benzotriazole and tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole and nitrobenzotriazole. Benzotriazole and tolyltriazole are particularly preferred. A linear or branched saturated or unsaturated monocarboxylic acid optionally sulfurized in an amount that may be up to 35% by weight; or an ester of such an acid; and triazole or an alkyl derivative thereof, or no more than 5 Short chain alkyl of carbon atoms; n is zero or an integer from 1 to 3 including both ends; and hydrogen, morpholino, alkyl, amide, amino, hydroxy or alkyl or aryl substituted derivatives thereof; or 1, 2, 4-triazole, 1,2,3-triazole, 5-anilo-1,2,3,4-thiatriazole, 3-amino-1,2,4-triazole, 1-H-benzotriazol-1-yl- A triazole selected from methisocyanide, methylene-bis-benzotriazole and naphthotriazole.

  Alkyl is linear or branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl.

  Alkenyl is straight-chain or branched, for example 2-propenyl, 2-butenyl, 2-methyl-2-propenyl, 2-pentenyl, 2,4-hexadienyl, 10-decenyl or 2-eicosenyl. Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, adamantyl or cyclododecyl. Aralkyl is, for example, benzyl, 2-phenylethyl, benzhydryl or naphthylmethyl.

  Aryl is for example phenyl or naphthyl. The heterocyclic group is, for example, a morpholine, pyrrolidine, piperidine or perhydroazepine ring. Alkylene moieties include, for example, methylene, ethylene, 1: 2- or 1: 3-propylene, 1: 4-butylene, 1: 6-hexylene, 1: 8-octylene, 1: 10-decylene and 1: 12-dodecylene. Is included.

  Arylene moieties include, for example, phenylene and naphthylene. 1- (or 4)-(dimethylaminomethyl) triazole, 1- (or 4)-(diethylaminomethyl) triazole, 1- (or 4)-(di-isopropylaminomethyl) triazole, 1- (or 4)- (Di-n-butylaminomethyl) triazole, 1- (or 4)-(di-n-hexylaminomethyl) triazole, 1- (or 4)-(di-isooctylaminomethyl) triazole, 1- (or 4)-(di- (2-ethylhexyl) aminomethyl) triazole, 1- (or 4)-(di-n-decylaminomethyl) triazole, 1- (or 4)-(di-n-dodecylaminomethyl) Triazole, 1- (or 4)-(di-n-octadecylaminomethyl) triazole, 1- (or 4)-(di-n-ray) Silaminomethyl) triazole, 1- (or 4)-[di- (2′-propenyl) aminomethyl] triazole, 1- (or 4)-[di- (2′-butenyl) aminomethyl] triazole, 1- (Or 4)-[di- (2′-eicosenyl) aminomethyl] triazole, 1- (or 4)-(di-cyclohexylaminomethyl) triazole, 1- (or 4)-(di-benzylaminomethyl) triazole 1- (or 4)-(di-phenylaminomethyl) triazole, 1- (or 4)-(4′-morpholinomethyl) triazole, 1- (or 4)-(1′-pyrrolidinomethyl) triazole, 1- (or 4)-(1′-piperidinomethyl) triazole, 1- (or 4)-(1′-perhydroazepinomethyl) tri Sol, 1- (or 4)-[(2 ′, 2 ″ -dihydroxyethyl) aminomethyl] triazole, 1- (or 4)-(dibutoxypropyl-aminomethyl) triazole, 1- (or 4)-( Dibutylthiopropyl-aminomethyl) triazole, 1- (or 4)-(di-butylaminopropyl-aminomethyl) triazole, 1- (or -4)-(1-methanomine))-N, N-bis (2-ethylhexyl) -methylbenzotriazole, N, N-bis- (1- or 4-triazolylmethyl) laurylamine, N, N-bis- (1- or 4-triazolylmethyl) oleylamine, N , N-bis- (1- or 4-triazolylmethyl) ethanolamine and N, N, N ′, N′-tetra (1- Or 4-triazolylmethyl) ethylenediamine.

  Metal deactivators that can be used in the lubricating oil composition of the present invention include benzotriazole and 4-alkylbenzotriazoles such as 4-methylbenzotriazole and 4-ethylbenzotriazole; 5-methylbenzotriazole, 5 5-alkylbenzotriazoles such as ethylbenzotriazole; 1-alkylbenzotriazoles such as 1-dioctylaminomethyl-2,3-benzotriazole; 1-alkyltoltriazoles such as 1-dioctylaminomethyl-2,3- Benzotriazole derivatives such as toltriazole; benzimidazole and benzimidazole derivatives or concentrates and / or mixtures thereof.

  Antiwear / extreme pressure additive / friction reducing agents: aryl phosphates and phosphites, and metal or ashless carbamates. The phosphate ester or salt may be a monohydrocarbyl, dihydrocarbyl or trihydrocarbyl phosphate in which each hydrocarbyl group is saturated. In one embodiment, each hydrocarbyl group independently contains from about 8 to about 30, or from about 12 to about 28, or from about 14 to about 24, or from about 14 to about 18 carbon atoms. contains. In one embodiment, the hydrocarbyl group is an alkyl group. Examples of hydrocarbyl groups include tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl groups and mixtures thereof.

  A phosphate ester or salt is a phosphate ester made by reacting one or more phosphoric acids or anhydrides with a saturated alcohol. Phosphoric acid or acid anhydride is generally an inorganic phosphorus reagent, such as phosphorus pentoxide, phosphorus trioxide, phosphorus tetroxide, phosphorous acid, phosphoric acid, phosphorus halides, lower phosphorus esters, or phosphorus sulfides including phosphorus pentasulfide. is there. Lower phosphate esters generally contain from 1 to about 7 carbon atoms in each ester group. Alcohols are used to make phosphate esters or salts. Examples of commercially available alcohols and alcohol mixtures include Alfol 1218 (a mixture of synthetic primary linear alcohols containing 12-18 carbon atoms); Alfol 20 + alcohol (GLC (Gas-Liquid Chromatography). And a mixture of C18-C28 primary alcohols with C20 alcohols as measured by chromatography); and Alfol 22+ alcohols (C18-C28 primary alcohols containing mainly C22 alcohols). Alfol alcohol is available from the Continental Oil Company. Another example of a commercially available alcohol mixture is Adol 60 (about 75 wt% linear C22 primary alcohol, about 15% C20 primary alcohol and about 8% C18 and C24 alcohol). is there. Adol alcohol is marketed by Ashland Chemical.

  Various mixtures of monohydric fatty alcohols derived from natural triglycerides ranging in chain length from C8 to C18 are available from Procter & Gamble Company. These mixtures contain varying amounts of fatty alcohols containing 12, 14, 16, or 18 carbon atoms. For example, CO-1214 is a fatty alcohol mixture containing 0.5% C10 alcohol, 66.0% C12 alcohol, 26.0% C14 alcohol and 6.5% C16 alcohol.

  Another group of commercially available mixtures includes Shell Chemical Co. The “Neodol” product available from is included. For example, Neodol 23 is a mixture of C12 and C13 alcohols; Neodol 25 is a mixture of C12-C15 alcohols; Neodol 45 is a mixture of C14-C15 linear alcohols. The phosphate contains from about 14 to about 18 carbon atoms in each hydrocarbyl group. The hydrocarbyl group of the phosphate is generally derived from a mixture of fatty alcohols having from about 14 to about 18 carbon atoms. Hydrocarbyl phosphate may also be derived from fatty vicinal diols. Fat vicinal diols include those available from Ashland Oil under the generic names Adol 114 and Adol 158. The former is derived from the C11-C14 linear alpha olefin fraction and the latter is derived from the C15-C18 fraction.

  Phosphate salts may be prepared by reacting an acidic phosphate ester with an amine compound or metal base to form an amine or metal salt. The amine may be a monoamine or a polyamine. Useful amines include those amines disclosed in US Pat.

  Monoamines generally contain hydrocarbyl groups containing 1 to about 30, or 1 to about 12, or 1 to about 6 carbon atoms. Examples of primary monoamines useful in the present invention include methylamine, ethylamine, propylamine, butylamine, cyclopentylamine, cyclohexylamine, octylamine, dodecylamine, allylamine, cocoamine, stearylamine, and laurylamine. Examples of secondary monoamines include dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclopentylamine, dicyclohexylamine, methylbutylamine, ethylhexylamine and the like.

  Amines are fatty (substituted C8-30) amines including n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, oleylamine and the like. Useful fatty amines also include Armen C, Armen O, Armen OL, Armeen T, Armeen HT, Armeen S, and Armeen SD, which are related to fatty groups, such as the letter name coco, oleyl, beef tallow, or stearyl groups. , Commercially available fatty amines such as “Armeen” amine (a product available from Akzo Chemicals (Chicago, Ill.)).

  Other useful amines include the formula R ″ (OR ′) xNH 2, wherein R ′ is a divalent alkylene group having from about 2 to about 6 carbon atoms; x is from 1 to about 150; Or a number from about 1 to about 5, or 1; R ″ is a hydrocarbyl group of from about 5 to about 150 carbon atoms). Examples of ether amines are available under the name SURFAM® amine produced and marketed by the Mars Chemical Company (Atlanta, Ga). Preferred ether amines are exemplified by those identified as SURFAM P14B (decyloxypropylamine), SURFAM P16A (linear C16), SURFAM P17B (tridecyloxypropylamine). The SURFAMS carbon chain lengths described above, as used herein below (ie, C14, etc.) are approximate and include oxygen ether linkages.

  The amine is a tertiary aliphatic primary amine. Generally, aliphatic groups, preferably alkyl groups, contain from about 4 to about 30, or from about 6 to about 24, or from about 8 to about 22 carbon atoms. Typically, the tertiary alkyl primary amine is a monoamine, the alkyl group is a hydrocarbyl group containing from 1 to about 27 carbon atoms, and R6 is a hydrocarbyl group containing from 1 to about 12 carbon atoms. It is. Such amines include tertiary butylamine, tertiary hexylamine, 1-methyl-1-amino-cyclohexane, tertiary octylamine, tertiary decylamine, tertiary dodecylamine, tertiary tetradecylamine, tertiary hexadecylamine, tertiary Illustrated with trioctadecylamine, tertiary tetracosanylamine, and tertiary octacosanylamine. Mixtures of tertiary aliphatic amines may also be used in the manufacture of phosphate salts. “Primene 81R”, a mixture of C11-C14 tertiary alkyl primary amines and “Primene JMT”, a similar mixture of C18-C22 tertiary alkyl primary amines (both available from Rohm and Haas Company Exemplify amine mixtures of this type. Tertiary aliphatic primary amines and methods for their preparation are known to those skilled in the art. Tertiary aliphatic primary amines useful for the purposes of the present invention and methods for their preparation are described in US patents. The amine is a heterocyclic polyamine. Heterocyclic polyamines include aziridine, azetidine, azolidine, tetra- and dihydropyridine, pyrrole, indole, piperidine, imidazole, di- and tetra-hydroimidazole, piperazine, isoindole, purine, morpholine, thiomorpholine, N-aminoalkylmorpholine , N-aminoalkylthiomorpholine, N-aminoalkyl-piperazine, N, N'-diaminoalkylpiperazine, azepine, azocine, azonin, azecine and the respective tetra-, di- and perhydro derivatives thereof, and their heterocyclic amines A mixture of two or more of the following. Preferred heterocyclic amines are saturated 5- and 6-membered heterocyclic amines containing only one nitrogen, oxygen and / or sulfur in the heterocycle, especially piperidine, piperazine, thiomorpholine, morpholine, pyrrolidine and the like. Piperidine, aminoalkyl substituted piperidine, piperazine, aminoalkyl substituted piperazine, morpholine, aminoalkyl substituted morpholine, pyrrolidine, and aminoalkyl substituted pyrrolidine are particularly preferred. Usually, the aminoalkyl substituent is substituted on the nitrogen atom that forms part of the heterocycle. Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine, and N, N'-diaminoethylpiperazine. Hydroxy heterocyclic polyamines are also useful. Examples include N- (2-hydroxyethyl) cyclohexylamine, 3-hydroxycyclopentylamine, parahydroxyaniline, N-hydroxyethylpiperazine and the like.

  The lubricating composition may also include a reaction product of a fatty imidazoline or fatty carboxylic acid and at least one polyamine. Fatty imidazolines have fatty substituents containing from 8 to about 30, or from about 12 to about 24 carbon atoms. Substituents may be saturated or unsaturated, heptadecenyl-derived oleyl groups, preferably saturated. In one aspect, the fatty imidazoline may be made by reacting a fatty carboxylic acid with a polyalkylene polyamine, such as those discussed above. The fatty carboxylic acid is generally a mixture of straight and branched chain fatty carboxylic acids containing about 8 to about 30, or about 12 to about 24, or about 16 to about 18 carbon atoms. Carboxylic acids include polycarboxylic acids or carboxylic acids or acid anhydrides having 2 to about 4, preferably 2 carbonyl groups. Polycarboxylic acids include succinic acid and acid anhydrides as well as Diels-Alder (such as acrylic, methacrylic, maleic, fumaric, crotonic and itaconic acids) with unsaturated monocarboxylic acids and unsaturated carboxylic acids. Diels-Alder) reaction products are included. Preferably, the fatty carboxylic acid has about 8 to about 30, preferably about 12 to about 24 carbon atoms, such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid, tall oil acid, etc. A fatty monocarboxylic acid, preferably stearic acid. The fatty carboxylic acid is reacted with at least one polyamine. The polyamine may be aliphatic, alicyclic, heterocyclic or aromatic. Examples of polyamines include alkylene polyamines and heterocyclic polyamines.

  A hydroxyalkyl group is to be understood as meaning, for example, monoethanolamine, diethanolamine or triethanolamine, and the term amine also includes diamines. The amine used for neutralization depends on the phosphate ester used. The EP additive according to the invention has the following advantages: it has a very high effectiveness when used at low concentrations, it does not contain chlorine. For neutralization of the phosphate ester, the latter is taken and the corresponding amine is added slowly with stirring. The resulting heat of neutralization is removed by cooling. The EP additive according to the invention can be incorporated into the respective base liquid using fatty substances (eg tall oil fatty acids, oleic acid, etc.) as solubilizers. Base liquids used are naphthenic or paraffinic base oils, synthetic oils (eg polyglycols, mixed polyglycols), polyolefins, carboxylic acid esters and the like.

  The composition includes at least one phosphorus-containing extreme pressure additive. An example of such an additive is an amine phosphate extreme pressure additive such as those known under the trade name IRGALUBE 349. Such amine phosphate is suitably present in an amount of 0.01 to 2%, preferably 0.2 to 0.6% by weight of the lubricating oil composition.

  At least one linear and / or branched saturated or unsaturated monocarboxylic acid optionally sulfurized in an amount which may be up to 35% by weight; and / or esters of such acids. At least one triazole or an alkyl derivative thereof, or a short-chain alkyl and hydrogen, morpholino, alkyl, amide, amino, hydroxy or alkyl or aryl substituted derivatives thereof of up to 5 carbon atoms; or 1,2,4-triazole, Triazoles selected from 1,2,3-triazole, 3-amino-1,2,4-triazole, 1-H-benzotriazol-1-yl-methyl isocyanide, methylenebis-benzotriazole and naphthotriazole; and formulations The neutral organic phosphate that forms the component may be present in an amount of 0.01 to 4%, preferably 1.5 to 2.5% by weight of the composition. Any of the amine phosphates described above and the aforementioned benzo- or tolyltriazoles can be mixed together to form a single component that can provide antiwear performance. Neutral organic phosphates are also a common component of lubricating compositions, and any such neutral organic phosphates that fall within the formula range as defined above may be used.

  Phosphate for use in the present invention includes phosphates, acid phosphates, phosphites and acid phosphites. Phosphate includes triaryl phosphates, trialkyl phosphates, trialkylaryl phosphates, triarylalkyl phosphates and trialkenyl phosphates. Specific examples of these include triphenyl phosphate, tricresyl phosphate, benzyl diphenyl phosphate, ethyl diphenyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethyl phenyl diphenyl phosphate, diethyl phenyl phenyl Phosphate, propylphenyldiphenyl phosphate, dipropylphenylphenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyl diphenyl phosphate, dibutylphenylphenyl phosphate, tributylphenyl phosphate, trihexyl phosphate, tri (2-ethylhexyl) phosphate, tridecyl phosphate Eto, trilauryl phosphate, trimyristyl phosphate, tri palmityl phosphate, tristearyl phosphate, and trioleyl phosphate are mentioned. Acid phosphates include, for example, 2-ethylhexyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, and Isostearyl acid phosphate is included.

  Examples of phosphites include triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tri (nonylphenyl) phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl. Phosphites, triisooctyl phosphites, diphenylisodecyl phosphites, tristearyl phosphites, and trioleyl phosphites are included.

  Acid phosphites include, for example, dibutyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, distearyl hydrogen phosphite, and diphenyl hydrogen phosphite. The amines that form amine salts with such phosphates include, for example, mono-substituted amines, di-substituted amines, and tri-substituted amines. Examples of monosubstituted amines include butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine and benzylamine; those of disubstituted amine include dibutylamine, dipentylamine, Dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearylmonoethanolamine, decylmonoethanolamine, hexylmonopropanolamine, benzylmonoethanolamine, phenylmonoethanolamine, and An example is tolyl monopropanolamine. Examples of tri-substituted amines include tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, dioleyl monoethanolamine, dilauryl mono Propanolamine, dioctylmonoethanolamine, dihexylmonopropanolamine, dibutylmonopropanolamine, oleyldiethanolamine, stearyldipropanolamine, lauryldiethanolamine, octyldipropanolamine, butyldiethanolamine, benzyldiethanolamine, phenyldiethanolamine, tolyldipropanolamine, xylyl Diethanolamine, triethanolamine, and tripro Noruamin and the like.

  The phosphates or their amine salts are added to the base oil in an amount of 0.03 to 5% by weight, preferably 0.1 to 4% by weight, based on the total weight of the composition. Carboxylic acids to be reacted with amines include, for example, aliphatic carboxylic acids, dicarboxylic acids (dibasic acids), and aromatic carboxylic acids. Aliphatic carboxylic acids have 8 to 30 carbon atoms and may be saturated, unsaturated, linear or branched. Specific examples of aliphatic carboxylic acids include pelargonic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, eicosanoic acid, behenic acid, triacontanoic acid, caproleic acid, undecylenic acid, olein Examples include acids, linolenic acid, erucic acid, and linoleic acid. Specific examples of dicarboxylic acids include octadecyl succinic acid, octadecenyl succinic acid, adipic acid, azelaic acid, and sebacic acid. An example of an aromatic carboxylic acid is salicylic acid. Examples of amines to be reacted with carboxylic acids include, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, dipropylenetriamine, tetrapropylenepentamine, and hexabutylene. Polyalkylene-polyamines such as heptamine; and alkanolamines such as monoethanolamine and diethanolamine are included. Of these, a combination of isostearic acid and tetraethylenepentamine and a combination of oleic acid and diethanolamine are preferred. The reaction product of carboxylic acid and amine is added to the base oil in an amount of 0.01 to 5% by weight, preferably 0.03 to 3% by weight, based on the total weight of the composition.

  An important ingredient is phosphite. As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it means a group in which the carbon atom is directly bonded to the rest of the molecule and has predominantly hydrocarbon character. Examples of hydrocarbyl groups include: hydrocarbon substituents, ie aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and aliphatic A cyclic-substituted aromatic substituent, as well as a cyclic substituent in which the ring is completed by another part of the molecule (eg, two substituents together form an alicyclic radical); a substituted hydrocarbon substituent That is, in the context of the present invention, mainly non-hydrocarbon groups that do not alter the hydrocarbon substituent, substituents containing hydroxy, alkoxy, nitro; heteroatom-containing substituents, ie in the context of the present invention, Substituents that contain other hydrocarbons in the ring or chain consisting of carbon atoms while having predominantly hydrocarbon character. Heteroatoms include sulfur, oxygen, nitrogen and include substituents such as pyridyl, furyl, thienyl and imidazolyl. In general, no more than 2, preferably no more than 1 non-hydrocarbon substituent will be present for every 10 carbon atoms in the hydrocarbyl group; typically, the non-hydrocarbon substituent is not present in the hydrocarbyl group at all It will not exist.

  The term “hydrocarbyl group” in the context of the present invention is also intended to encompass cyclic hydrocarbyl or hydrocarbylene groups in which two or more of the alkyl groups in the above structure together form a cyclic structure. . The hydrocarbyl or hydrocarbylene groups of the present invention are generally alkyl or cycloalkyl groups containing at least 3 carbon atoms. Preferably or optimally containing sulfur, nitrogen or oxygen, they will contain 4 to 24, alternatively 5 to 18 carbon atoms. In another embodiment they contain about 6 or exactly 6 carbon atoms. The hydrocarbyl groups can be tertiary or preferably primary or secondary groups; in one embodiment, the component is a di (hydrocarbyl) hydrogen phosphite, each of the hydrocarbyl groups being a primary alkyl In another embodiment, the component is a di (hydrocarbyl) hydrogen phosphite and each of the hydrocarbyl groups is a secondary alkyl group. In yet another embodiment, the component is hydrocarbylene hydrogen phosphite.

  Examples of straight chain hydrocarbyl groups include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, stearyl, n-hexadecyl, n-octadecyl , Oleyl, and cetyl. Examples of branched chain hydrocarbon groups include isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, 2-ethylhexyl, and 2,6-dimethylheptyl. Examples of cyclic groups include cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, and cyclooctyl. A few examples of aromatic and mixed aromatic-aliphatic hydrocarbyl groups include phenyl, methylphenyl, tolyl, and naphthyl.

The R group can also include a mixture of hydrocarbyl groups derived from commercially available alcohols. Some examples of monohydric alcohols and alcohol mixtures include the commercially available “Alfol ^™ ” alcohol marketed by Continental Oil Corporation. Alfol ^™ 810 is a mixture containing, for example, an alcohol consisting essentially of a linear primary alcohol having 8 to 12 carbon atoms. Alfol ^™ 12 is a mixture of mainly C12 fatty alcohols; Alfol ^™ 22+ contains C18-28 primary alcohols with predominantly C22 alcohols, and so forth. Various mixtures of monohydric fatty alcohols derived from natural triglycerides in the C8-C18 chain length range are available from Procter & Gamble Company. “Neodol ^™ ” alcohol is available from Shell Chemical Co. Where, for example, Neodol ^™ 25 is a mixture of C12-C15 alcohols.

  Some specific examples of phosphites within the scope of the present invention include phosphorous acid, mono-, di-, or tri-propyl phosphite; mono-, di-, or tri-butyl phosphite, di- -Or tri-amyl phosphite; mono-, di- or tri-hexyl phosphite; mono-, di- or tri-phenyl phosphite; mono-, di- or tri-tolyl phosphite; mono- , Di- or tri-cresyl phosphite; dibutylphenyl phosphite or mono-, di- or tri-phosphite, amyl dicresyl phosphite.

The phosphorus compound of the present invention is produced by a known reaction. One route is by reaction of alcohol or phenol with phosphorus trichloride or transesterification. Alcohols and phenols can be reacted with phosphorus pentoxide to provide a mixture of alkyl or aryl phosphate and dialkyl or diaryl phosphate. Alkyl phosphates can also be prepared by oxidation of the corresponding phosphites. In any case, the reaction can be carried out with mild heating. In addition, various phosphorus esters can be produced by reactions using other phosphorus esters as starting materials. Thus, medium chain (C9-C22) phosphorus esters have been prepared by reaction of dimethyl phosphite with a mixture of medium chain alcohols using thermal transesterification or acid- or base-catalyzed transesterification; See Reference 6. Most such materials are also commercially available; for example, triphenyl phosphite from Albright and Wilson as Duraphos TPP ^™ ; di-n-butyl hydrogen phosphite from Albright and Wilson as Duraphos DBHP ^™ ; Phenyl thiophosphate is available from Ciba Specialty Chemicals as Irgalube TPPT ^™ .

  Another major component of the composition of the present invention is a hydrocarbon having ethylenic unsaturation. This is usually described as an olefin or diene, triene, polyene, etc., depending on the number of ethylenic unsaturations present. Preferably, the olefin is monounsaturated, i.e. contains only one ethylenic double bond per molecule. The olefin can be a cyclic or linear olefin. In the case of linear olefins, it is an internal olefin or an alpha-olefin. The olefin can also contain aromatic unsaturation, ie one or more aromatic rings, provided that it also contains ethylenic (non-aromatic) unsaturation.

  The olefin will usually contain from 6 to 30 carbon atoms. Olefins with significantly less than 6 carbon atoms tend to be volatile liquids or gases that are not normally suitable for formulation into compositions suitable as antiwear lubricants. Preferably the olefin will contain 6 to 18 or 6 to 12 carbon atoms, alternatively 6 to 8 carbon atoms.

  Among the preferred olefins, alkyl-substituted cyclopentene, hexene, cyclohexene, alkyl-substituted cyclohexene, heptene, cycloheptene, alkyl-substituted cycloheptene, diisobutylene-containing octene, cyclooctene, alkyl-substituted cyclooctene, nonene, decene, undecene, propylene tetramer Examples include dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, cyclooctadiene, norbornene, dicyclopentadiene, squalene, diphenylacetylene, and styrene. Highly preferred olefins are cyclohexene and 1-octene.

  The mixture of alcohols may be a mixture of different primary alcohols, a mixture of different secondary alcohols, or a mixture of primary and secondary alcohols. Examples of useful mixtures include n-butanol and n-octanol; n-pentanol and 2-ethyl-1-hexanol; isobutanol and n-hexanol; isobutanol and isoamyl alcohol; isopropanol and 2-methyl-4- Examples include pentanol; isopropanol and sec-butyl alcohol; isopropanol and isooctyl alcohol.

  Organic triesters of phosphoric acid are also used in lubricating oils. Typical esters include triaryl phosphates, trialkyl phosphates, neutral alkyl aryl phosphates, alkoxyalkyl phosphates, triaryl phosphites, trialkyl phosphites, neutral alkyl aryl phosphites, neutral phosphonate esters and neutral phosphines. Oxide esters are included. In one embodiment, long chain dialkylphosphonate esters are used. More preferentially, dimethyl-, diethyl-, and dipropyl-oleyl phosphonate can be used. The neutral acid of phosphoric acid is a triester or acid salt rather than an acid (HO-P).

  Any C4-C8 alkyl or higher phosphate ester may be used in the present invention. For example, tributyl phosphate (TBP) and triisooctyl phosphate (TOF) can be used. Specific triphosphate esters or ester combinations can be readily selected by those skilled in the art to adjust the density, viscosity, etc. of the formulation fluid. Mixed esters, such as dibutyl octyl phosphate, rather than a mixture of two or more trialkyl phosphates may be used.

  Although trialkyl phosphates are often useful for adjusting the specific gravity of the formulation, it is desirable that the specific trialkyl phosphate be liquid at low temperatures. Consequently, mixed esters containing at least one partially alkylated group with C3-C4 alkyl, such as 4-isopropylphenyl diphenyl phosphate or 3-butylphenyl diphenyl phosphate, are highly desirable. Even more desirable are triaryl phosphates prepared by partial alkylation of phenol with butylene or propylene as taught in US Pat. No. 6,037,049 to form mixed phenols which are then reacted with phosphorus oxychloride.

  Any mixed triaryl phosphate (TAP), such as lower alkylphenyl / phenyl phosphate, such as cresyl diphenyl phosphate, tricresyl phosphate, mixed xylyl cresyl phosphate, mixed isopropylphenyl / phenyl phosphate, t-butylphenylphenyl phosphate ) Esters may be used. These esters are widely used as plasticizers, functional fluids, gasoline additives, flame retardant additives and the like.

  Phosphate esters, thiophosphate esters, and amine salts thereof can be selected from known compounds that function to enhance lubricating performance and are commonly used as extreme pressure additives. Phosphoric esters having alkyl groups, alkenyl groups, alkylaryl groups, or aralkyl groups, each containing approximately 3 to 30 carbon atoms, or their amine salts are generally used.

  Examples of phosphate esters include aliphatic phosphate esters such as triisopropyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, trilauryl phosphate, tristearyl phosphate, and trioleyl phosphate; Benzyl phenyl phosphate, allyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, ethyl diphenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethyl phenyl diphenyl phosphate, diethyl phenyl phenyl phosphate, propyl phenyl diphenyl phosphate, dipropyl phenyl Phenyl phosphate, triethyl pheny Phosphate, tripropyl phenyl phosphate, butylphenyl diphenyl phosphate, dibutyl phenyl phosphate, and aromatic phosphoric acid esters such as tributyl phenyl phosphate and the like. Preferably, the phosphate ester is a trialkylphenyl phosphate.

  The amine salts of the above-mentioned phosphates can also be used. Amine salts of acidic alkyl or aryl esters of phosphoric acid and thiophosphoric acid can also be used. Preferably, the amine salt is an amine salt of a trialkylphenyl phosphate or an amine salt of an alkyl phosphate.

  One or any combination of compounds selected from the group consisting of phosphate esters and their amine salts may be used. The phosphate ester and / or its amine salt can be selected from known compounds that function to enhance lubricating performance and are commonly used as extreme pressure additives. Phosphoric esters or amine salts thereof having an alkyl group, alkenyl group, alkylaryl group, or aralkyl group, each containing approximately 3 to 30 carbon atoms, are generally used.

  Examples of phosphites include triisopropyl phosphite, tributyl phosphite, ethyl dibutyl phosphite, trihexyl phosphite, tri-2-ethylhexyl phosphite, trilauryl phosphite, tristearyl phosphite, and trioleyl phosphite. Aliphatic phosphites such as phites; and benzylphenyl phosphite, allyl diphenyl phosphite, triphenyl phosphite, tricresyl phosphite, ethyl diphenyl phosphite, tributyl phosphite, ethyl dibutyl phosphite, cresyl diphenyl phosphite Phyto, dicresyl phenyl phosphite, ethyl phenyl diphenyl phosphite, diethyl phenyl phenyl phosphite, propyl phenyl diphenyl phosphite, Propylphenyl phenyl phosphite, triethyl phenyl phosphite, tripropyl phenyl phosphite, butylphenyl diphenyl phosphite, dibutyl phenyl phenyl phosphite, and aromatic phosphite such as tri-butylphenyl phosphite and the like. Dilauryl phosphite, dioleyl phosphite, dialkyl phosphite, and diphenyl phosphite are also advantageously used. Preferably, the phosphite is a dialkyl phosphite or a trialkyl phosphite.

  The phosphate salt may be derived from a polyamine. Polyamines include alkoxylated diamines, fatty polyamine diamines, alkylene polyamines, hydroxy-containing polyamines, condensed polyamine aryl polyamines, and heterocyclic polyamines. Commercially available examples of alkoxylated diamines include those amines where y is 1 in the above formula. Examples of these amines include Ethodomeen T / 13 and T / 20, which are ethylene oxide condensation products of N-tallow trimethylenediamine containing 3 to 10 moles of ethylene oxide per mole of diamine, respectively.

  In another embodiment, the polyamine is a fatty diamine. Fatty diamines include mono- or dialkyl, symmetric or asymmetric ethylene diamine, propane diamine (1, 2, or 1, 3), and the polyamine analogs described above. Suitable commercially available fatty polyamines are Duomeen C (N-coco-1,3-diaminopropane), Duomeen S (N-soybean-1,3-diaminopropane), Duomeen T (N-tallow-1,3-diamino). Propane), and Duomeen O (N-oleyl-1,3-diaminopropane). “Duomen” is a product of Armak Chemical Co. (Chicago, Ill.) Commercially available.

  Such alkylene polyamines include methylene polyamine, ethylene polyamine, butylene polyamine, propylene polyamine, pentylene polyamine, and the like. Also included are higher homologs and related heterocyclic amines such as piperazine and N-aminoalkyl substituted piperazines. Specific examples of such polyamines include ethylenediamine, triethylenetetramine, tris (2-aminoethyl) amine, propylenediamine, trimethylenediamine, tripropylenetetramine, tetraethylenepentamine, hexaethyleneheptamine, pentaethylenehexamine and the like. is there. Higher homologues obtained by condensing two or more of the above alkylene amines are as useful as are mixtures of two or more of the above polyamines.

  In one embodiment, the polyamine is an ethylene polyamine. Such polyamines are found in Non-Patent Document 2 and are described in detail under ethyleneamine. Ethylene polyamines are often complex mixtures of polyalkylene polyamines containing cyclic condensation products.

  Another useful class of polyamine mixtures results from stripping the above polyamine mixtures leaving behind what is often referred to as "polyamine bottoms". In general, the alkylene polyamine bottoms can be characterized as having a material boiling below about 200 ° C. of less than 2% by weight, usually less than 1% by weight. A typical sample of such ethylene polyamine bottoms obtained from Dow Chemical Company (Freeport, Tex.) Is referred to as “E-100”. These alkylene polyamine tower bottom liquids include piperazine and cyclic condensation products such as higher analogs such as diethylenetriamine and triethylenetetramine. These alkylene polyamine bottoms can be reacted exclusively with acylating agents, or they can be used with other amines, polyamines, or mixtures thereof. Another useful polyamine is a condensation reaction of at least one hydroxy compound with at least one polyamine reactant containing at least one primary or secondary amino group. The hydroxy compounds are preferably polyhydric alcohols and amines. Polyhydric alcohols are described below. (See carboxylic ester dispersants.) In one embodiment, the hydroxy compound is a polyvalent amine. Multivalent amines include any of the above monoamines reacted with alkylene oxides having 2 to about 20 or 2 to about 4 carbon atoms (eg, ethylene oxide, propylene oxide, butylene oxide, etc.). . Examples of polyvalent amines include tri- (hydroxypropyl) amine, tris (hydroxymethyl) aminomethane, 2-amino-2-methyl-1,3-propanediol, N, N, N ′, N′-tetrakis. (2-hydroxypropyl) ethylenediamine and N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine, preferably tris (hydroxymethyl) aminomethane (THAM).

  Polyamines that react with polyhydric alcohols or amines to form condensation products or condensed amines are described above. Preferred polyamines include triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and mixtures of polyamines such as the “amine tower bottom” described above.

  These extreme pressure additives can be used individually or in the form of a mixture, conveniently in an amount in the range of 0.1 to 2 parts by weight per 100 parts by weight of the base oil. All of the above are various co-base stocks, AN, AB, ADPO, ADPS, ADPM, and / or in combination with low sulfur, low aromatic, low iodine number, low bromine number, high analine point isoparaffins Various monobasic, dibasic and tribasic esters can be used to enhance performance.

  Several tests were conducted to show the benefits of the inventive formulation. As shown in Table 3, seven examples are performed, labeled Examples A, B, C, D, E, F, and G.

  Blends C, D, and E are formulations that represent various inventive embodiments. Blends A, B, F, and G are typical commercial gas turbine engine oils for comparison. As can be seen in Table 3, Inventive Examples C, D, and E have superior properties in the 504 hour 120 ° C. Dry TOST sludge test compared to Comparative Examples A, B, and F. Comparative Example A has neither a polyol ester demulsifier nor a Mannich base dispersant. Comparative Example B has a polyol ester demulsifier but no Mannich base dispersant. Comparative Example F has a Mannich base dispersant but no polyol ester. Comparative Example G is a typical Group I commercial gas turbine oil that has the disadvantages of a Group I basestock that provides sufficient sticking control but has insufficient emulsion properties.

  Table 4 shows the benefits of adding a small amount of Pluronic L 121 to the formulations of the present invention. Example I shows an unexpected improvement in the sludge test compared to Example H, which is identical except for Pluronic L 121.

  Examples C, D, and E all have advantageous sticking control and emulsion properties. This is the importance in this embodiment of having either a Group II or Group III base stock or a combination thereof and having both a Mannich base dispersant, a polyol ester and a polyalkylene demulsifier. To demonstrate.

  While the examples are mostly for gas turbine engine oil formulations, those skilled in the art will recognize the applicability to all situations where good sticking control and emulsion properties are desired. Other suitable uses include, but are not limited to, compressor oil and hydraulic oil. Applicants intend to capture all situations where the claimed lubricant is beneficial.

Claims (20)

A lubricating oil having advantageous fixing varnish properties,
a) a large amount of base stock selected from the group consisting of Group II, Group III, GTL and any combination thereof;
b) a Mannich base dispersant comprising at least 0.1 weight percent and less than 2.0 weight percent of the lubricating oil; and c) a demulsifier comprising a polyol ester and a polyoxyalkylene alcohol, comprising at least 0 of the lubricating oil. A demulsifier comprising 0.002 weight percent to less than 2.0 weight percent,
d) Lubricating oil having a sticking control value of less than 60 using the 504 hour 120 ° C. Dry TOST sludge test.   It further comprises at least one additive selected from the group consisting of antiwear additives, metal passivators, demulsifiers, pour point depressants, rust inhibitors, defoamers and any combination thereof. The lubricating oil according to claim 1.   The lubricating oil according to claim 1, wherein the lubricating oil is a gas turbine oil. The polyol ester in the demulsifier accounts for less than 25% by weight of the demulsifier and has a molecular weight of less than 5000;
The lubricating oil of claim 1, wherein the lubricating oil has an ASTM D-1401 emulsion characteristic of less than 60 at 54 ° C.   The lubricating oil of claim 1 having an ASTM D-4308 conductivity value greater than 50.   The lubricating oil of claim 1 having less than 5 PPM calcium and less than 5 PPM zinc.   7. Lubricating oil according to claim 6, having a phosphorus of less than 50 PPM. A method for improving sticking control,
a) obtaining a lubricant with advantageous fixing varnish properties comprising:
The lubricating oil is
A large amount of base stock selected from the group consisting of Group II, Group III, GTL and any combination thereof;
A Mannich base dispersant comprising at least 0.1 and less than 2.0 weight percent of the lubricating oil, and a demulsifier comprising a polyol ester and a polyoxyalkylene comprising at least 0.002 weight percent to 2.0 weight percent of the lubricating oil. Including a demulsifier comprising less than a weight percent,
The lubricating oil includes a step of having a sticking control value of less than 60 using a 504 hour 120 ° C. Dry TOST sludge test; and b) lubricating with the lubricating oil.   It further comprises at least one additive selected from the group consisting of antiwear additives, metal passivators, demulsifiers, pour point depressants, rust inhibitors, defoamers and any combination thereof. The lubricating oil according to claim 8.   The lubricating oil according to claim 8, which is a gas turbine oil. The polyol ester in the demulsifier accounts for less than 25% by weight of the demulsifier and has a molecular weight of less than 5000;
The lubricating oil according to claim 8, wherein the lubricating oil has an ASTM D-1401 emulsion characteristic of less than 60 at 54C.   The lubricating oil of claim 8, having an ASTM D-4308 conductivity value greater than 50.   9. Lubricating oil according to claim 8, comprising less than 5 PPM calcium and less than 5 PPM zinc.   14. Lubricating oil according to claim 13, comprising less than 50 PPM phosphorus. A method of blending oils to provide improved sticking control and advantageous emulsion properties comprising:
a) a large amount of base stock selected from the group consisting of Group II, Group III, GTL and any combination thereof;
A Mannich base dispersant comprising at least 0.1 weight percent and less than 2.0 weight percent of the lubricating oil, and a demulsifier comprising a polyol ester and a polyoxyalkylene, comprising at least 0.002 weight percent to 2. Obtaining a demulsifier occupying less than 0 weight percent; and b) formulating the base stock, demulsifier and dispersant to achieve a sticking control value of less than 60 using the 120 ° C. Dry TOST sludge test for 504 hours A method comprising the steps of:   It further comprises at least one additive selected from the group consisting of antiwear additives, metal passivators, demulsifiers, pour point depressants, rust inhibitors, defoamers and any combination thereof. The lubricating oil according to claim 15. The polyol ester in the demulsifier accounts for less than 25% by weight of the demulsifier and has a molecular weight of less than 5000;
The method of claim 15, wherein the lubricating oil has an ASTM D-1401 emulsion property of less than 60 at 54 ° C.   The lubricating oil of claim 1 further comprising a propylene oxide block copolymer.   The lubricating oil according to claim 8, further comprising a propylene oxide block copolymer.   The lubricating oil of claim 15 further comprising a propylene oxide block copolymer.