CN110168065A

CN110168065A - Low-viscosity lubricating oil composition for turbomachinery

Info

Publication number: CN110168065A
Application number: CN201780081833.7A
Authority: CN
Inventors: 梅雷迪思·R·吉卜森; 安格拉·S·加利亚诺-罗思; 杰西卡·L·普林斯; 安德烈亚·B·沃德洛
Original assignee: ExxonMobil Research and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 2016-12-30
Filing date: 2017-12-28
Publication date: 2019-08-23
Also published as: WO2018125956A1; JP2020503412A; EP3562924B1; EP3562924A1; EP3562924B8

Abstract

This disclosure relates to which a kind of low viscosity turbine lube oil, has the composition comprising lube oil base stocks as main component and one or more lube oil additives as accessory constituent.The turbine lube oil has at 40 DEG C that about 16cSt is to the kinematic viscosity of about 22cSt, the density of about 0.8g/ml to about 0.9g/ml, and absolute evaporation loss at 150 DEG C less than about 4%.Present disclosure also relates to a kind of to improve the method for energy efficiency in the turbomachinery lubricated with low viscosity turbine lube oil.Present disclosure also relates to a kind of to improve energy efficiency maintenance simultaneously in the turbomachinery lubricated with low viscosity turbine lube oil or improve sediment monitoring and the solvent method of lube oil additive.Present disclosure also relates to dissolubility, the method for compatibility and dispersibility of a kind of improvement polar additive in low viscosity turbine lube oil.

Description

Low-viscosity lubricating oil composition for turbomachinery

Technical field

This disclosure relates to low viscosity turbine lube oil.Present disclosure also relates to one kind to moisten with low viscosity turbine lube oil Improve the method for energy efficiency in sliding turbomachinery.It is being lubricated present disclosure also relates to a kind of with low viscosity turbine lube oil Improve energy efficiency in turbomachinery and maintains or improve sediment monitoring and the solvent method of lube oil additive simultaneously.This public affairs It opens and is further directed to a kind of dissolubility, compatibility and dispersibility for improving polar additive in low viscosity turbine lube oil Method.

Background technique

Turbine oil for power generation applications plays an important role in turbine bearing(s) except heat and in cooling down.Turbine bearing(s) The reduction of temperature is converted into the increased energy efficiency and additional power generation of turbine.The reduction of turbine bearing(s) temperature can be with System amount of cooling water needed for reducing, to provide additional energy conservation.

In power generation applications, generating the energy efficiency that more electric power (KW) export for equal fuel input, there is need It asks.In the power plant of annual operation 8000 hours, the turbine bearing(s) improved efficiency based at least 10% brings about 0.1% Overall system efficiency benefit can realize the additional output of 164kW under similar burn rate.The improvement of 0.05%/kW can 66,000 dollars of annual value of production can be provided for each turbine can electric power for sale.

It, can be by being changed to realize these energy compared with the turbine lube oil of low viscosity in one kind possible solution Efficiency gain.Currently, equipment manufacture quotient (EB) and original equipment manufacturer (OEM) require minimum turbine lube oil viscosity for 32cSt at 40 DEG C.However, compared with low viscosity turbine lube oil the problem of be that they do not meet and be acceptable for turbine and answer Physical property constraint.

Although turbine lube oil technology makes progress, the turbine bearing(s) for being effectively improved turbine energy efficiency is used Lubricating oil, there are still demands.In addition, for being effectively improved energy efficiency while maintaining or improving sediment monitoring and lubricating oil The solvent turbine lube oil of additive, there is also demands.

Summary of the invention

Disclosure part is related to a kind of lubricating oil, have comprising lube oil base stocks as main component and one kind or Composition of the various kinds of lubricating oil additive as accessory constituent.It is about 16cSt at 40 DEG C that the lubricating oil, which has according to ASTM D445, It is density of the about 0.8g/ml to about 0.9g/ml according to ASTM D1298 to the kinematic viscosity of about 22cSt, and according to ASTM D972 is absolute evaporation loss at 150 DEG C less than about 4%.The lubricating oil is preferably turbine lube oil.

The disclosure also relate in part to it is a kind of by using formulated oil as lubricating oil in the turbine with the oil lubrication Improve the method for energy efficiency in machinery.The formulated oil have comprising lube oil base stocks as main component and one kind or Composition of the various kinds of lubricating oil additive as accessory constituent.It is about 16cSt at 40 DEG C that the formulated oil, which has according to ASTM D445, It is density of the about 0.8g/ml to about 0.9g/ml according to ASTM D1298 to the kinematic viscosity of about 22cSt, and according to ASTM D972 is absolute evaporation loss at 150 DEG C less than about 4%.

In one embodiment, for turbomachinery, with use have according to ASTM D445 be 40 DEG C at about The kinematic viscosity of 16cSt to about 22cSt but do not have according to ASTM D1298 be about 0.8g/ml to the density of about 0.9g/ml or It is compared according to the energy efficiency that ASTM D972 is realized for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4%, energy Amount efficiency is improved.

In one embodiment, for turbomachinery, with use have according to ASTM D445 be 40 DEG C at about The kinematic viscosity of 16cSt to about 22cSt but do not have according to ASTM D1298 be about 0.8g/ml to the density of about 0.9g/ml or It is compared according to the bearing temperature that ASTM D972 is realized for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4%, axis Hold temperature reduction.

In one embodiment, for turbomachinery, with use have according to ASTM D445 be 40 DEG C at about The kinematic viscosity of 16cSt to about 22cSt but do not have according to ASTM D1298 be about 0.8g/ml to the density of about 0.9g/ml or The energy efficiency realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4%, deposit Control is compared with lube oil additive dissolving power, and energy efficiency is improved and sediment monitoring and lube oil additive dissolve Power is maintained or is improved.

It is molten in non-polar lubricant oil base oil material that the disclosure also relates in part to a kind of improvement polar emollient oil additive The method of Xie Xing, compatibility and/or dispersibility.The described method includes: providing comprising non-polar lubricant oil base oil material as master Want the lubricating oil of component and one or more polar emollient oil additives as accessory constituent；And it is blended in the lubricating oil At least one auxiliary oil base stock (co-base stock).It is about 16cSt at 40 DEG C that the lubricating oil, which has according to ASTM D445, It is density of the about 0.8g/ml to about 0.9g/ml according to ASTM D1298 to the kinematic viscosity of about 22cSt, and according to ASTM D972 is absolute evaporation loss at 150 DEG C less than about 4%.

The disclosure also relates in part to a kind of method for realizing significant energy efficiency gains in turbomachinery.It is described Method includes selecting comprising non-polar lubricant oil base oil material as main component and one or more polar emollient oil additives Lubricating oil as accessory constituent.The lubricating oil has about 3.0J/g DEG C to about 3.3J/g DEG C of specific heat, according to ASTM D972 be at 150 DEG C less than about 4% absolutely evaporation loss and according to ASTM D445 be at 40 DEG C about 16cSt to about The kinematic viscosity of 22cSt.The method also includes selection non-polar lubricant oil base oil material or combinations thereof, so that energy-saving potential is most Bigization, so that according to the following formula, the lubricating oil has at least about 10, preferably at least about 12, more preferably at least about 14 lubrication effect The rate factor:

The lubricating efficiency factor=[19.200 (specific heat)]-[6.679 (evaporation loss)]-[1.028 (dynamics

Viscosity)] -12.178.

It was surprisingly found that low viscosity turbine lube oil can be prepared according to the disclosure, has and be acceptable for Physical property needed for purposes of turbine application.The turbine lube oil of the disclosure has the movement of about 16cSt to about 22cSt at 40 DEG C Viscosity.On the contrary, the MV minium viscosity of conventional turbine machine lubricating oil requirements is 32cSt at 40 DEG C.

Also, it has therefore been surprisingly found that viscous using the movement with about 16cSt to about 22cSt at 40 DEG C according to the disclosure The absolute lubricating oil of evaporation loss at degree, density of the about 0.8g/ml to about 0.9g/ml and 150 DEG C less than about 4%, can be with The improvement of energy efficiency is obtained in turbomachinery.

Further, it has therefore been surprisingly found that according to the disclosure, use the fortune with about 16cSt to about 22cSt at 40 DEG C The absolute lubricating oil of evaporation loss at the density of kinetic viscosity, about 0.8g/ml to about 0.9g/ml and 150 DEG C less than about 4%, Bearing temperature can be reduced in turbomachinery.

Further, it has therefore been surprisingly found that according to the disclosure, using there is at 40 DEG C about 16cSt to about 22cSt's The absolute lubrication of evaporation loss at the density of kinematic viscosity, about 0.8g/ml to about 0.9g/ml and 150 DEG C less than about 4% Oil can improve energy efficiency in turbomachinery and can maintain or improve sediment monitoring and lube oil additive dissolution Power.

Particularly, astonishing discovery, according to the disclosure, individual viscosity reduction is not enough to realize the significant of turbine oil Energy efficiency improves.Viscosity is with volatility and the balance of density requirements for realizing that improved energy efficiency results are important.

The other objects and advantages of the disclosure will become apparent from subsequent detailed description.

Detailed description of the invention

Fig. 1 be include base oil and additive system preparation table, and according to embodiment determine preparation property.

Fig. 2 is the table according to the detailed preparation including base oil and additive of embodiment preparation.

Fig. 3 is the lubricating efficiency factor for showing the preparation determined according to embodiment and the table of relevant nature.

Detailed description

All numerical value in the detailed description and claims of this paper are by indicated by "about" or "approximately" modification Value, and the variation that experimental error and those of ordinary skill in the art can expect is taken into account.

According to the disclosure, when being tested in the test of the efficiency of bearing platform as described in paragraph [00273] herein, with Conventional turbine machine oil is compared, and the cooling and energy efficiency benefit of raising are realized.The low viscosity turbine oil of the disclosure reduces Churning loss and other viscosity losses.The low-density turbine oil of the disclosure, which generates heat transfer, to be improved, and is caused relative to existing quotient Industry turbine oil, except heat improves and bearing temperature is lower under identical flow rate pump.The turbine oil of the disclosure overcomes pair The technological challenge that oil film, volatility and flash distillation problem are balanced.Using the turbine oil of the disclosure, hydrodynamic shaft is realized It holds lubrication and metal and a possibility that metal contacts is minimum.More smooth surface allow smaller axis to bearing of journals gap-more Thin oil.In addition, tin babbit metal bearing allows transient state boundary lubrication.

In one embodiment, the disclosure uses low viscosity/low-density hydrocarbon mixture, such as oil base stock and prothetic group Plinth oil plant except the typical turbomachine engine oil viscosity range of ISO VG 32,46 and 68 and is still answered being acceptable for turbine In physical property constraint, to provide unexpected energy efficiency benefit.

The turbine oil of the disclosure is except conventional turbine engine oil viscosity range, and it is important that being acceptable for whirlpool In the physical property constraint of turbine application.By reducing viscosity, this public affairs while maintaining the performance characteristic of conventional turbine machine oil It is opened in the risk that additional energy conservation is provided in power plant without damaging performance or increase mechanical breakdown.

The important performance standard of the turbine oil of the disclosure include for example show at least 10%, preferably at least 12%, more Preferably at least 14% energy efficiency improves, while meeting claimed below: flash-point is greater than 215 DEG C；Absolute maximum evaporation loss is small In 4%；The balance low viscosity candidate of low specific heat/low-density；And maintain all bearing protections and lubricant requirement.

Viscosity is reduced with volatility and the balance of density requirements for realizing that unexpected efficiencies are important.Tool Have and provides generally better energy efficiency gains compared with the disclosure turbine oil of low-density.This is considered as due to lubricant Density and its specific heat capacity and overall thermal control it is related.Furthermore, it is possible to add V class oil base stock to further increase these performances Attribute simultaneously provides additive dissolving power and sediment monitoring necessary to the reliability in purposes of turbine application.

As used herein, turbine or turbomachinery refer to the machinery for generating continuous power, wherein usually dress It is rotated with vaned wheel or rotor by the flowing of the water, steam, gas, air or other fluids that fast move. There is at least one to be known as the moving parts of rotor assembly for the turbine or turbomachinery, be attached with blade axis or Drum.Mobile fluid matasomatism is on blade, so that they move and assign rotating energy to rotor.Preferred turbomachinery is combustion gas Turbine, or the combined cycle including combustion gas turbine and steam turbine.

It has been found that in turbomachinery, and use that have according to ASTM D445 be about 16cSt to about 22cSt at 40 DEG C Kinematic viscosity but not have according to ASTM D1298 be about 0.8g/ml to the density of about 0.9g/ml or according to ASTM D972 The energy efficiency realized for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4% is compared, and improved energy can be obtained Amount efficiency.

In addition, it has been found that in turbomachinery, with use have according to ASTM D445 be at 40 DEG C about 16cSt to about The kinematic viscosity of 22cSt but not have according to ASTM D1298 be about 0.8g/ml to the density of about 0.9g/ml or according to ASTM D972 compares for the bearing temperature that the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4% is realized, can reduce bearing Temperature.

Furthermore, it has been found that in turbomachinery, with use have according to ASTM D445 be at 40 DEG C about 16cSt to about The kinematic viscosity of 22cSt but not have according to ASTM D1298 be about 0.8g/ml to the density of about 0.9g/ml or according to ASTM Energy efficiency, sediment monitoring and the lubrication that D972 is realized for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4% Oil additive dissolving power is compared, and can be improved energy efficiency and can be maintained or improve sediment monitoring and lube oil additive Dissolving power.

As described herein, the low viscosity turbine lube oil of the disclosure has and is acceptable for needed for purposes of turbine application Physical property.Such physical property includes such as density, absolute evaporation loss, Noack volatility, flash-point and specific heat.

The turbine lube oil of the disclosure has viscous according to the movement that ASTM D445 is about 16cSt to about 22cSt at 40 DEG C Degree.On the contrary, the MV minium viscosity of conventional turbine machine lubricating oil requirements is 32cSt at 40 DEG C.Preferably, the turbine lubrication of the disclosure Oil has the kinematic viscosity of about 17cSt to about 21cSt at 40 DEG C, and the movement of about 18cSt to about 20cSt is glued at more preferable 40 DEG C Degree.

According to the disclosure, the turbine lube oil of the disclosure, which has, is acceptable for density needed for purposes of turbine application. It is density of the about 0.8g/ml to about 0.9g/ml that the turbine lube oil of the disclosure, which has according to ASTM D1298,.Preferably, originally Disclosed turbine lube oil has the density of about 0.81g/ml to about 0.89g/ml, and more preferably from about 0.82g/ml is to about The density of 0.88g/ml.

In addition, the turbine lube oil of the disclosure, which has, to be acceptable for needed for purposes of turbine application according to the disclosure Absolute evaporation loss.It is absolutely to steam at 150 DEG C less than about 4% that the turbine lube oil of the disclosure, which has according to ASTM D972, Hair loss.Preferably, the turbine lube oil of the disclosure has absolute evaporation loss at 150 DEG C less than about 3%, and more preferably Absolute evaporation loss at 150 DEG C less than about 2%.

Further, according to the disclosure, the turbine lube oil of the disclosure, which has, is acceptable for institute in purposes of turbine application The Noack volatility needed.The turbine lube oil of the disclosure, which has, to volatilize according to ASTM D5800 for the Noack less than about 15% Degree.Preferably, the turbine lube oil of the disclosure has the Noack volatility less than about 12%, and more preferably less than about 10% Noack volatility.

Further, according to the disclosure, the turbine lube oil of the disclosure, which has, to be acceptable in purposes of turbine application Required flash-point.The flash-point that it is greater than about 215 DEG C according to ASTM D92 that the turbine lube oil of the disclosure, which has,.Preferably, originally Disclosed turbine lube oil has greater than about 220 DEG C of flash-point, and more preferably greater than about 225 DEG C of flash-point.

Still further, the turbine lube oil of the disclosure, which has, to be acceptable in purposes of turbine application according to the disclosure Required specific heat.The turbine lube oil of the disclosure has about 3.0J/g DEG C to about 3.3J/g DEG C of specific heat.Preferably, originally Disclosed turbine lube oil has about 3.05J/g DEG C to about 3.25J/g DEG C of specific heat, and more preferably from about 3.1J/g DEG C To about 3.2J/g DEG C of specific heat.

Other than desired energy efficiency, sediment monitoring and lube oil additive dissolving power, the disclosure is additionally provided Turbine lubricants composition with desired wear-resistant property.Antiwear additive is usually to reduce two in turbine operation equipment A surface of solids is in contact required for the abrasion of place.In the case where no wear-resistant chemical substance, the surface can be with It rubs together, causes the material loss on one or two surface, equipment malfunction and failure may finally be caused.Antiwear additive It can produce protectiveness superficial layer, reduce abrasion and material loss.Most commonly, interested material is metal, for example, steel and Other iron containing alloys.However, other materials such as ceramics, polymer coating, diamond-like carbon, corresponding composite material etc. can also For manufacturing the durable surface in modern wind turbine equipment.The turbine lubricants composition of the disclosure can be to such surface Wear-resistant property is provided.

Lube oil base stocks and auxiliary oil base stock

Various lubrication base oil plants are as known in the art.The lubrication base oil plant that can be used in the disclosure is Natural oil, mineral oil and synthetic oil, and can be used it is unpurified, purification or re-refine (the latter also referred to as regenerate or Reprocessed oils) it is unconventional oil (or mixtures thereof).Unrefined oil is to directly obtain and be not subject to from natural or synthetic source Purifying those of just uses oil.The stone that they include the shale oil directly obtained from retorting operation, are directly obtained from primary distillation Oil and the ester oil directly obtained from esterification process.Refined oil is similar to oil discussed in unrefined oil, and difference is refined oil One or more purification steps be experienced to improve at least one lubricating oil property.Many purifying works familiar to those skilled in the art Skill.These techniques include solvent extraction, secondary distillation, acid extracts, alkali carries take, filter and are percolated.Rerefined oils are by similar It had been obtained in the past as the oil that raw material uses in the technique but use of refined oil.

I, II, III, IV and V class are by American Petroleum Institute (API) (American Petroleum Institute) (API Publication 1509；www.API.org) exploitation and definition oil base stock major class, to create the finger of lubricant base oil South.I class oil base stock has the viscosity index (VI) between about 80 to 120 and containing greater than about 0.03% sulphur and/or less than about 90% Saturated hydrocarbons.II class oil base stock has the viscosity index (VI) between about 80 to 120 and containing less than or equal to about 0.03% sulphur and greatly In or equal to about 90% saturated hydrocarbons.Group III oil plant has greater than about 120 viscosity index (VI) and containing less than or equal to about 0.03% Sulphur and greater than about 90% saturated hydrocarbons.IV class includes polyalphaolefin (PAO).V class oil base stock includes the base being not included in I-IV class Plinth oil plant.The following table 1 summarizes these five types of respective properties.

Table 1

The property of basic oils

Natural oil includes animal oil, vegetable oil (such as castor oil and lard) and mineral oil.It can be used with advantageous The animal and plant oil of thermo oxidative stability.In natural oil, mineral oil is preferred.Mineral oil is by their crude oil origin Variation is extensive, such as by them is alkane, cycloalkane or mixing paraffinic-naphthenic.From coal or shale Oil is also useful.Natural oil is also pressed for their production and the method for purifying and different, for example, they boiling range and they be It is straight run or cracking, hydrofinishing or solvent extraction.

II class and/or Group III hydrotreating or the oil base stock being hydrocracked are also well known oil base stock.

Synthetic oil includes hydrocarbon ils.Hydrocarbon ils include such as olefin polymerization and mutual polyolefin oil (for example, polybutene, polypropylene, Propylene isobutylene copolymers, ethylene-olefin copolymer and ethylene-alpha-olefin copolymer).Polyalphaolefin (PAO) oil base oil material is Common synthetic hydrocarbon oil.For example, can use from C₈、C₁₀、C₁₂、C₁₄The PAO of or mixtures thereof alkene.It is special referring to the U.S. Sharp No.4,956,122；4,827,064；With 4,827,073.

As known material and usually can be big commercial size from supplier such as ExxonMobil Chemical The number-average molecular weight for the PAO that Company, Chevron Phillips Chemical Company, BP and other suppliers obtain Usually from about 250 to about 3,000 etc., but PAO can be made into being up to about the viscosity of 150cSt (100 DEG C).PAO is usually wrapped The hydropolymer or oligomer of relatively low molecular weight containing alhpa olefin, the alhpa olefin include but is not limited to C₂To about C₃₂Alhpa olefin, And C₈To about C₁₆Alhpa olefin such as 1- octene, 1- decene, 1- laurylene etc. is preferred.Preferred polyalphaolefin is that poly- 1- is pungent Alkene, poly- 1- decene and poly- 1- laurylene and its mixture and the polyolefin from mixed olefins.However, in C₁₂To C₁₈ The dimer of higher olefins in range may be used to provide the low viscosity oil base stock with acceptable low volatility.It takes Certainly in viscosity grade and starting oligomer, the PAO mainly can be the dimer of the starting olefin, trimer and four gathers Object, with a small amount of even lower level and/or higher oligomer, with 1.5 to 12cSt range of viscosities.The PAO of special-purpose flows Body may include 3cSt, 3.4cSt and/or 3.6cSt and combinations thereof.If desired, it is 1.5 to about that range of viscosities, which can be used, The mixture of 150cSt or higher PAO fluid.Unless otherwise stated, all viscosity cited herein are at 100 DEG C Lower measurement.

The PAO fluid can by the presence of polymerization catalyst such as Friedel-Crafts catalyst to alhpa olefin It is polymerize and is easily manufactured, the Friedel-Crafts catalyst includes such as alchlor, boron trifluoride, Huo Zhesan The compound of boron fluoride and water, alcohol such as ethyl alcohol, propyl alcohol or butanol, carboxylic acid or ester such as ethyl acetate or ethyl propionate.Herein In can be convenient use such as method as disclosed in United States Patent (USP) No.4,149,178 or 3,382,291.PAO synthesis other Description sees following United States Patent (USP) No.3,742,082；3,769,363；3,876,720；4,239,930；4,367,352；4, 413,156；4,434,408；4,910,355；4,956,122；With 5,068,487.It is described in United States Patent (USP) No.4,218,330 C₁₄To C₁₈The dimer of alkene.

Other useful lube oil base stocks include wax isomerization object oil base stock and base oil, including hydroisomerization Content of wax oil plant (for example, content of wax oil plant of gas oil, slack wax, fuels hydrocracker oil foot etc.), hydroisomerization Fischer-Tropsch (Fischer-Tropsch) wax, natural gas liquefaction (GTL) oil base stock and base oil and other wax isomerization objects Or mixtures thereof the oil base stock and base oil of hydroisomerization,.Fischer-tropsch wax, the higher boiling residual oil of Fiscber-Tropscb synthesis are that sulphur contains Measure low-down higher alkane hydrocarbon.Hydrotreating for producing such oil base stock can be used unbodied plus hydrogen and split Change/hydroisomerisation catalysts, such as special lube are hydrocracked one of (LHDC) catalyst, or crystallization plus hydrogen Cracking/hydroisomerisation catalysts, preferred zeolite catalyst.For example, a kind of useful catalyst be such as United States Patent (USP) No.5, ZSM-48 described in 075,269, the disclosure of which are incorporated herein by reference in their entirety.In such as United States Patent (USP) No.2,817, 693；4,975,177；4,921,594 and 4,897,178 and British patent No.1,429,494；1,350,257；1,440, Manufacture is described in 230 and 1,390,359 is hydrocracked/hydro-isomerised fraction oil and is hydrocracked/hydroisomerized wax Technique.Each of aforementioned patent is integrally incorporated herein.It is described in European patent application No.464546 and 464547 especially Advantageous technique, the patent application is also by being incorporated herein by reference.It is retouched in United States Patent (USP) No.4,594,172 and 4,943,672 The technique using fischer-tropsch wax charging is stated, the disclosure of which is incorporated herein by reference in their entirety.

Natural gas liquefaction (GTL) base oil, the base oil from fischer-tropsch wax and the hydroisomerizing from other waxes Change (wax isomerization object) base oil to be advantageously used in the disclosure, and can have about 2cSt to about 50cSt, preferably from about Useful kinematic viscosity at 2cSt to about 30cSt, more preferably from about 3cSt to 100 DEG C of about 25cSt is with kinematic viscosity at 100 DEG C For the GTL4 that about 4.0cSt and viscosity index (VI) are about 141.These natural gas liquefaction (GTL) base oils, from fischer-tropsch wax Base oil and hydroisomerizing base oil from other waxes can have about -20 DEG C or lower useful pour point, and It can have about -25 DEG C or lower advantageous pour point under the conditions of some, and about -30 DEG C to about -40 DEG C or lower useful incline Point.Such as United States Patent (USP) No.6,080,301；Natural gas liquefaction (GTL) basis is elaborated in 6,090,989 and 6,165,949 The useful composition of oil, the base oil from fischer-tropsch wax and the hydroisomerizing base oil from wax, the patent pass through Reference is integrally incorporated herein.

Alkyl aromatic hydrocarbons may be used as base oil or base oil component and can be at least about 5% being originated from containing its weight In aromatic fractions such as benzene-type part or cycloalkanes type part or any hydrocarbyl molecular of their derivative.These alkyl aromatic hydrocarbons packets Include alkylbenzene, alkylnaphthalene, alkyl biphenyl, alkyl diphenyl ether, alkyl naphthol, alkyl diphenyl thioether, alkylated bisphenols A, alkylation Thiodiphenol etc..The aromatic hydrocarbons can be monoalkylation, dialkylation, it is polyalkylated, etc..The aromatic hydrocarbons can be with It is single or multiple functionalized.The hydrocarbyl group also may include alkyl group, alkenyl group, alkynyl, group of naphthene base, cyclenes The mixture of base group hydrocarbyl group related to other.The hydrocarbyl group can be in about C₆Until about C₆₀In the range of, wherein About C₈To about C₂₀Range it is often preferred.The mixture of hydrocarbyl group is often preferred, and there may be most about Three such substituent groups.The hydrocarbyl group can substituent group optionally containing sulfur-bearing, oxygen and/or nitrogen.The aromatic group Natural (petroleum) source can be derived from, condition be at least about the 5% of the molecule to be made of the aromatic fractions of the above-mentioned type.It is right For the alkyl aromatic component, the viscosity at preferably 100 DEG C is about 2cSt to about 50cSt, and often more preferably viscosity is About 3cSt to about 20cSt.It in one embodiment, mainly include the alkylnaphthalene of 1- hexadecylene using wherein alkyl group. Other alkylates of aromatic hydrocarbons can also be advantageously used.For example, naphthalene or methyl naphthalene can be by alkene such as octene, decene, ten Diene, tetradecene or more advanced alkene, the mixture of similar alkene etc. are alkylated.Alkylated naphthalene and analog can also reside in ring knot The composition that isomery on α the and β carbon potential of structure with alkylation group is distributed.The distribution of group can be on the position α and β of naphthalene nucleus In the range of 100:1 to 1:100, more often 50:1 to 1:50.Depending on application, alkyl aromatic hydrocarbons has in lubricant oil composite It can be about 2% to about 25%, preferably from about 4% to about 20%, and more preferably from about 4% to about 15% with concentration.

The alkyl aromatic hydrocarbons of the alkylated aromatic hydrocarbons such as disclosure can pass through the well known Friedel- of aromatic compounds Crafts is alkylated to generate.Referring to " Friedel-Crafts and correlated response " (Friedel-Crafts and Related Reactions), Olah, G.A. (write), Inter-science Publishers, New York, and 1963.For example, aromatics Object such as benzene or naphthalene is closed to be alkylated by alkene, alkyl halide or alcohol in the presence of friedel-crafts catalysts.Referring to " Friedel-Crafts and correlated response ", volume 2, part 1, the chapter of the 14th, 17 and 18, referring to Olah, G.A. (is write), Inter-science Publishers, New York, 1964.Many homogeneous or out-phase solid catalysts are art technologies Known to personnel.The selection of catalyst depends on the reactivity and product quality requirement of starting material.It is, for example, possible to use strong acid Such as AlCl₃、BF₃Or HF.In some cases, relatively mild catalyst such as FeCl₃Or SnCl₄It is preferred.Newest alkane Base technology uses zeolite or solid super-strong acid.

Ester constitutes useful oil base stock.By using ester, for example, binary acid and single alkanol ester and monocarboxylic acid it is polynary Alcohol ester, it can be ensured that additive dissolving power and seal compatibility characteristic.The ester of previous seed type includes that such as dicarboxylic acids is for example adjacent Phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, oneself two Acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic etc. and various alcohol such as butanol, hexanol, lauryl alcohol, 2- The ester of ethyl hexanol etc..The specific example of the ester of these types include dibutyl adipate, decanedioic acid two (2- ethylhexyl) ester, The just own ester of fumaric acid two, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate, neighbour Double eicosane base esters of phthalic acid didecyl, decanedioic acid etc..

Particularly useful synthetic ester is by one or more polyalcohols, preferably (such as neopentyl is polynary for hindered polyhydric alcohols Alcohol for example neopentyl glycol, trimethylolethane, 2- methyl-2-propyl -1,3- propylene glycol, trimethylolpropane, pentaerythrite and Dipentaerythritol) with the alkanoic acid containing at least about 4 carbon atoms ester those of is reacted and obtains, it is described to contain at least about 4 The alkanoic acid of carbon atom is preferably C₅To C₃₀Acid, such as saturated straight chain fatty acid, including octanoic acid, capric acid, lauric acid, nutmeg Acid, palmitinic acid, stearic acid, arachidic acid and behenic acid, or corresponding branched chain fatty acid or unsaturated fatty acid such as oleic acid, or appoint What a mixture of these materials.

Suitable synthetic ester component includes trimethylolpropane, tri hydroxy methyl butane, trimethylolethane, pentaerythrite And/or the ester of dipentaerythritol and one or more monocarboxylic acids containing about 5 to about 10 carbon atoms.These esters are can extensive quotient Purchase, such as Mobil P-41 and the P-51 ester of ExxonMobil Chemical Company.

Ester from recyclable materials such as coconut, palm, rapeseed, soybean, sunflower etc. is also useful.These Ester can be monoesters, diester, polyol ester, complex ester, or mixtures thereof.These esters are widely commercially available, such as The Mobil P-51 ester of ExxonMobil Chemical Company.

Turbine oil preparation containing renewable ester is included in the present disclosure.For such preparation, the ester can Regeneration content is generally greater than about 70 weight %, preferably greater than about 80 weight % and most preferably greater than about 90 weight %.

Other useful fluids with lubricant viscosity are including being processed, preferred catalytic is processed or synthesize to provide high-performance The non-conventional base oil material of lubrication property.

Non-conventional base oil material/base oil includes one or more of: being derived from one or more natural gas liquefactions (GTL) mixture of the oil base stock of material, and the isomerate from native paraffin or wax feed/isomerization dewaxing compound Oil base stock, mineral and/or non-mineral oil waxy feeds such as slack wax, native paraffin and content of wax oil plant such as gas oil, the content of wax Fuels hydrocracker oil foot, waxy residue liquid, hydrocrackates, hot tearing carburetion or other mineral, mineral oil are even originated from In the mixing of waxy material and such oil base stock that nonoil waxy material is for example obtained from coal liquefaction or shale oil Object.

GTL material is to contain via one or more synthesis, combination, conversion, rearrangement and/or degradation/deconstruction from gaseous state Carbon compound, hydrogen-containing compound and/or element as raw material for example hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, Material derived from ethylene, acetylene, propane, propylene, propine, butane, butylene and butine.GTL oil base stock and/or base oil are logical It often originates from the GTL material with lubricant viscosity of hydrocarbon, such as content of wax synthesis hydrocarbon, described hydrocarbon itself is derived from simpler gaseous state Carbon compound, hydrogen-containing compound and/or the element as raw material.GTL oil base stock and/or base oil include that boiling point is lubricating Oil in oily boiling range, the oil are (1) from the GTL material of synthesis for example by distilling and being then subjected to final wax procedure of processing And separation/fractionation, the wax procedure of processing include one or both of catalytic dewaxing process or solvent dewaxing process, to generate tool There is reduction/low pour point lubricating oil；(2) the wax isomerization object synthesized, it includes such as Hydrodewaxings or hydroisomerization catalytic The synthetic wax or waxy hydrocarbon of agent and/or solvent dewaxing；(3) Hydrodewaxing or hydroisomerisation catalysts and/or solvent dewaxing Fischer-Tropsch (Fischer-Tropsch, F-T) material (that is, hydrocarbon, waxy hydrocarbon, wax with possible similar oxygenate)；Preferably plus hydrogen Dewaxing or hydroisomerization/be followed by catalyst and/or solvent dewaxing and the F-T waxy hydrocarbon or Hydrodewaxing that dewax add hydrogen Isomerization/be followed by catalyst (or solvent) dewaxing and dewax F-T wax, or mixtures thereof.

From GTL material, especially Hydrodewaxing or hydroisomerization/it is followed by catalyst and/or solvent dewaxing The GTL oil base stock and/or base oil of wax or wax feed preferably originate from oil base stock and/or base oil in F-T material, Usually to have about 2mm²/ s to about 50mm²Kinematic viscosity (ASTM D445) is characterized at 100 DEG C of/s.They are also usually with tool There are -5 DEG C to about -40 DEG C or lower pour point (ASTM D97) is characterized.They are also usually to have about 80 to about 140 or bigger Viscosity index (VI) (ASTM D2270) be characterized.

In addition, the GTL oil base stock and/or base oil are usually higher alkane hydrocarbon (> 90% saturated hydrocarbons), and can be with The mixture being combined containing monocycle alkane and polycyclic alkane and non-cyclic isoparaffins.Cycloalkane in such combination The ratio of (i.e. loop chain alkane) content changes with used catalyst and temperature.In addition, GTL oil base stock and/or basis Oil usually has low-down sulphur and nitrogen content, typically contain less than about 10ppm and more typically less than about 5ppm each this A little elements.The sulphur and nitrogen content of the GTL oil base stock and/or base oil that obtain from F-T material, especially F-T wax are substantially zeroed. In addition, there is no phosphorus and aromatic hydrocarbons, and this material to be made to be particularly suitable for preparing low SAP product.

Term GTL oil base stock and/or base oil and/or wax isomerization object oil base stock and/or base oil are interpreted as Each fraction including these materials with wide range of viscosities recycled in process of production evaporates as two or more Point mixture and one or two or more low viscosity fraction and one, two, or more viscosity higher fraction Mixture is to generate admixture, wherein the admixture shows target kinematic viscosity.

The GTL material in the GTL oil base stock and/or base oil institute source is preferably F-T material (that is, hydrocarbon, the content of wax Hydrocarbon, wax).

Base oil used in the formulated oil that can be used in the disclosure corresponds to API I class, II class, Group III, IV Any and its mixture of all kinds of oil of class and V class oil, preferably API II class, Group III, IV class and V class oil and its mixture, More preferable Group III is to V class base oil, this is because their excellent volatility, stability, viscosimetric analysis and spatter property feature. A small amount of I class oil plant, such as the amount for diluting the additive being admixed in formulated lubricant products, can tolerate, but It should be maintained at bottom line, i.e. it is related to be only used as the diluent/carrier oil of the additive used by " sample " to them for the amount.I.e. Make for II class oil plant, it is also preferred that the II class oil plant is within the scope of better quality relevant to the oil plant, i.e., viscosity index (VI) is 100 II class oil plant in the range of < VI < 120.

The base oil constitutes the main component of the turbine lube oil composition of the disclosure, and is based on the composition Total weight, usually with about 80 to about 99.8 weight %, preferably from about 90 to about 99.5 weight % and more preferably from about 95 to about 99 weights The amount measured within the scope of % exists.The base oil can selected from be typically used as industry oil and turbomachinery lubricating oil synthesis or Any one of natural oil.The base oil easily have according to ASTM standard be 40 DEG C at about 7cSt to about 46cSt (or mm²/ s) and preferably 40 DEG C at about 10cSt to about 32cSt (or mm²/ s), often the movement of more preferably from about 15cSt to about 22cSt is viscous Degree.If desired, the mixture of synthesis and natural foundation oil can be used.If desired, I, II can be used, III, IV and/ Or the bimodal of the mixture of V class oil base stock, three peaks and other combinations.

Prothetic group plinth stock components are to be enough to provide dissolubility of the polar additive in lubricating oil, compatibility and dispersibility Amount exists.Prothetic group plinth stock components are with about 1 to about 99 weight %, preferably from about 5 to about 95 weight %, more preferably from about 10 to about 90 weights The amount of amount % is present in the lubricating oil of the disclosure.

The following table 2 summarizes the available quantity and preferred amounts of the illustrative lubricating base oil according to the disclosure.

Table 2

The available quantity and preferred amounts of illustrative lubricating base oil

Lube oil additive

The formulated oil that can be used in the disclosure can be in addition containing one or more common lubricants performance additions Agent, including but not limited to antiwear additive, dispersing agent, detergent, viscosity modifier, corrosion inhibitor, antirust agent, metal deactivating Agent, EP agent prevent seizing dose (anti-seizure agent), wax modifiers, viscosity modifier, fluid loss addition Agent, sealing compatilizer, lubricity agent (lubricity agent), anti-dye agent, colour former, defoaming agent, demulsifier, thickener, Wetting agent, gelling agent, adhesive, colorant and other.For the summary of many commonly-used additive, referring to Klamann, lubrication Agent and Related product (Lubricants and Related Products), Verlag Chemie, Deerfield Beach, FL；ISBN 0-89573-177-0.Referring also to " lubricant additive (the Lubricant Additives) " of M.W.Ranney, (1973) are published by Noyes Data Corporation of Parkridge, NJ；United States Patent (USP) No.7,704 is seen also, 930, the disclosure of which is integrally incorporated herein.These additives usually with can be the 5 weight % to 50 weight % in the range of Different amounts of flux oil is delivered together.

Workable additive need not be dissolved in lubricating oil in the disclosure.Insoluble additives in oil can be dispersed in this In disclosed lubricating oil.

The type of performance additive and amount for combining the disclosure to use in lubricant oil composite be not by herein as saying The bright and limitation of example that shows.

Antiwear additive

Alkyl dithiophosphoric acid (ester/salt), aryl phosphoric acids (ester/salt) and phosphorous acid (ester/salt) can be used for the disclosure Illustrative antiwear additive in lubricating oil.The illustrative antiwear additive can substantially free of metal or they can To contain metal salt.

Phosphate or salt can be single alkyl, dialkyl or trialkyl phosphoric acid (ester/salt), wherein each hydrocarbyl group is full Sum.In one embodiment, each hydrocarbyl group independently contains about 8 to about 30 or about 12 until about 28 or about 14 is straight To about 24 or about 14 until about 18 carbon atoms.In one embodiment, the hydrocarbyl group is alkyl group.Alkyl base The example of group includes tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl and its mixture.

Phosphate or salt are by reacting one or more phosphoric acids (phosphorus acid) or acid anhydrides with saturated alcohols And the phosphate ester-containing prepared.The phosphoric acid or acid anhydrides are usually inorganic phosphorus reagent, for example, phosphorus pentoxide, diphosphorus trioxide, Phosphorus tetroxide, phosphorous acid (phosphorous acid), phosphoric acid, phosphorus Halides, rudimentary phosphide or phosphoric sulfide, including five vulcanizations Two phosphorus, etc..Rudimentary phosphate ester-containing contains 1 to about 7 carbon atom usually in each ester group.Alcohol is used to prepare phosphate ester-containing Or salt.The example of commercially available pure and mild alcohol mixture includes Alfol 1218 (synthesis containing 12-18 carbon atom, primary, straight chain The mixture of alcohol)；Alfol 20+ alcohol (determines the C18-C28 primary alconol mainly with C20 alcohol by GLC (gas-liquid chromatography) Mixture)；With Alfol 22+ alcohol (the C18-C28 primary alconol for mainly containing C22 alcohol).Alfol alcohol is available from Continental Oil Company.Another example of commercially available alcohol mixture is (22 primary alconol of straight chain C of about 75 weight %, about of Adol 60 15% C20 primary alconol and about 8% C18 and C24 alcohol).The Adol alcohol is sold by Ashland Chemical.

From naturally occurring triglycerides and the various mixing of unitary fatty alcohol of the chain length within the scope of C8 to C18 Object is available from Procter&Gamble Company.These mixtures contain various amounts containing 12,14,16 or 18 carbon atoms Fatty alcohol.For example, CO-1214 is the C16 of the C10 alcohol, 66.0% C12 alcohol, 26.0% C14 pure and mild 6.5% containing 0.5% The fatty alcohol mixture of alcohol.

Another kind of commercially available alcohol mixture includes " Neodol " product for being available from Shell Chemical Co.For example, Neodol 23 is the mixture of C12 and C13 alcohol；Neodol 25 is mixture of the C12 to C15 alcohol；Neodol 45 be C14 extremely The mixture of C15 straight chain alcohol.The phosphoric acid (ester/salt) contains about 14 to about 18 carbon atoms in each hydrocarbyl group.It is described The hydrocarbyl group of phosphoric acid (ester/salt) is typically originated from about 14 until the mixture of the fatty alcohol of about 18 carbon atoms.It is described Hydrocarbyl phosphate (ester/salt) may originate from fatty vicinal diols.Fatty vicinal diols include with general commodity name Adol 114 Those of Ashland Oil is available from Adol 158.The former is derived from the straightαolefin fraction of C11-C14, and the latter is derived from C15-C18 fraction.

The phosphate can by make acid phosphoric acid ester react with amine compounds or metal base to be formed amine or metal salt come Preparation.The amine can be monoamine or polyamines.Useful amine includes those amine disclosed in United States Patent (USP) No.4,234,435.

Illustrative monoamine is usually contained containing 1 to about 30 carbon atom or 1 to about 12 or 1 to about 6 carbon atom Hydrocarbyl group.The example that can be used for the primary monoamines of the disclosure includes methylamine, ethamine, propylamine, butylamine, cyclopentamine, cyclohexylamine, pungent Amine, dodecyl amine, allylamine, coco amine, stearylamine and lauryl amine.The example of secondary monoamine includes dimethylamine, diethylamine, dipropyl Amine, dibutyl amine, two cyclopentamines, dicyclohexyl amine, methylbutylamine, ethylhexylamine etc..

Amine is fatty (C8-C30) amine comprising n-octyl amine, n-Decylamine, n-dodecane amine, n-tetradecane amine, hexadecane Amine, n-octadecane amine, oleyl amine etc..Useful fatty amine further includes commercially available fatty amine, such as " Armeen " amine (is available from The product of Akzo Chemicals, Chicago, Ill.), as Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein letter names and fat group for example cocoyl, oil base, tallow or Stearyl groups are related.

Other useful amine include primary ether amine, such as those represented by the following formula

R"(OR')x NH2

Wherein R' is the divalent alkylene groups with about 2 to about 6 carbon atoms；X is 1 to about 150 or about 1 to about 5, Or 1 number；And R " is the hydrocarbyl group of about 5 to about 150 carbon atoms.The example of ether amines can be with trade name Amine obtains, which is produced and sold by Mars Chemical Company, Atlanta, Ga.Preferred ether amines are to be accredited as Those of SURFAM P14B (decyloxy propylamine), SURFAM P16A (linear C16), SURFAM P17B (three decyloxy propylamine) For.Carbon chain lengths (i.e. C14 etc.) described above with the SURFAMS used below are approximate and including oxygen-ether linkage.

Illustrative amine is tertiary aliphatic primary amine.In general, aliphatic group, preferably alkyl, containing about 4 to about 30 or about 6 to About 24 or about 8 to about 22 carbon atoms.In general, the primary t-alkyl-amine is monoamine, the alkyl group is containing 1 to about 27 The hydrocarbyl group of a carbon atom.Such amine is with tert-butylamine, tertiary hexylamine, 1- methyl-1-amino-cyclohexanecarboxylic, t-octanylamine, the tertiary last of the ten Heavenly stems Amine, tertiary dodecyl amine, tertiary tetradecylamine, tertiary cetylamine, tertiary octadecylamine, tertiary lignocerane amine and tertiary octacosane amine come Explanation.The mixture of tert-aliphatic amine can also be used for preparing phosphate.Illustrative this kind of amine blends are as the tertiary alkane of C11-C14 " the Primene 81R " of the mixture of base primary amine, the and " Primene of the similar mixtures as C18-C22 primary t-alkyl-amine JMT " (the two is available from Rohm and Haas Company).Tertiary aliphatic primary amine and preparation method thereof is the common skill in this field Known to art personnel.

Another illustrative amine is heterocyclic polyamines.The heterocyclic polyamines includes aziridine, azetidine, azo alkane (azolidines), tetrahydro and dihydropyridine, pyrroles, indoles, piperidines, imidazoles, dihydro and imidazolidine, piperazine, iso-indoles, fast Purine, morpholine, thiomorpholine, N- aminoalkylmorpholines, N- aminoalkyl thiomorpholine, N- aminoalkyl-piperazine, N, N'- diamino Yl-alkyl piperazines, azatropylidene, azocine, azonine, azecines and above-mentioned respective tetrahydro, dihydro and perhydro derivative with And the mixture of two or more in these heterocyclic amines.Preferred heterocyclic amine is in heterocycle only containing nitrogen, oxygen and/or sulphur It is saturated 5- and 6- circle heterocyclic ring amine, described heterocycle especially piperidines, piperazine, thiomorpholine, morpholine, pyrrolidines etc..Piperidines, amino alkane Morpholine, pyrrolidines and the aminoalkyl that piperazine, morpholine, the aminoalkyl that piperidines, piperazine, the aminoalkyl of base substitution replace replace Substituted pyrrolidines is particularly preferred.In general, the aminoalkyl substituent group is on the nitrogen-atoms of a part for forming heterocycle It is substituted.The specific example of such heterocyclic amine includes n-aminopropyl morpholine, N- aminoethylpiperazine and N, N'- diamino second Base piperazine.Hydroxyl heterocyclic polyamines is also useful.Example includes N- (2- ethoxy) cyclohexylamine, 3- hydroxycyclopent amine, to hydroxyl Aniline, N- hydroxyethyl piperazine etc..

The metal salt of phosphate ester-containing is prepared by reacting for metal base and acid phosphorus ester.The metal base can be energy Enough form any metallic compound of metal salt.The example of metal base includes metal oxide, hydroxide, carbonate, sulfuric acid Salt, borate etc..The metal of metal base includes IA, IIA, IB to VIIB and group VIII metal (the CAS editions periodic table of elements).These Metal includes alkali metal, alkaline-earth metal and transition metal.In one embodiment, the metal is Group IIA metal such as calcium Or magnesium, Group IIB metal such as zinc or VIIB race metal such as manganese.Preferably, the metal is magnesium, calcium, manganese or zinc.Can with contain The example of the metallic compound of phosphatase reaction includes zinc hydroxide, zinc oxide, Kocide SD, copper oxide etc..

The lubricating oil of the disclosure may also comprise the reaction product of fatty imidazolines or aliphatic carboxylic acid and at least one polyamines. Fatty imidazolines have the fatty substituents containing 8 to about 30 or about 12 to about 24 carbon atoms.The substituent group can be saturation Or unsaturated, such as oil base derived from 17 alkenyls (olyel) group, be preferably saturated.In one aspect, fatty miaow Oxazoline can be prepared by reacting aliphatic carboxylic acid with polyalkylenepolyamines.Aliphatic carboxylic acid is usually containing about 8 to about 30 Carbon atom or about 12 to about 24 or about 16 to about 18 straight chains of carbon atom and the mixture of Branched fatty carboxylic acid.Carboxylic acid includes Polycarboxylic acid or carboxylic acid or acid anhydrides with 2 to about 4, preferably 2 carbonyl groups.Polycarboxylic acid includes succinic acid and acid anhydrides and not It is saturated monocarboxylic acid and unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid) Diels-Alder reaction product.Preferably, aliphatic carboxylic acid is the rouge with about 8 to about 30, preferably from about 12 to about 24 carbon atoms Fat monocarboxylic acid, such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid and tall oil acid, preferably stearic acid.Aliphatic carboxylic acid with At least one polyamines reaction.The polyamines can be aliphatic, alicyclic, heterocycle or aromatics.The example of the polyamines includes Asia Alkyl polyamine and heterocyclic polyamines.

The antiwear additive of the disclosure has the following advantages that.When being used with low concentration it have very high validity and Without chlorine.For neutralising phosphoric acid ester, takes the latter and be slowly added corresponding amine under stiring.In caused by cooling remove And heat.The antiwear additive of the disclosure can be by means of the fatty material (such as ready denier oil acid, oleic acid etc.) as solubilizer And it is incorporated into corresponding basal liquid.Basal liquid used is cycloalkane or alkane base oil, synthetic oil (such as poly- second Glycol, mixing polyethylene glycol), polyolefin, carboxylate etc..

In one embodiment, the lubricating oil of the disclosure can contain at least one phosphorous antiwear additive.It is such to add The example for adding agent is amine phosphate antiwear additive, such as with those of known to trade name IRGALUBE 349 and/or triphenyl Thiophosphate antiwear additive, such as those of known to trade name IRGALUBE TPPT.Such amine phosphate can be with The amount of 0.01-2 weight %, the preferably 0.2-1.5 weight % of lubricant compositions exists, and such thiophosphate be suitble to The amount of 0.01-3 weight %, the preferably 0.5-1.5 weight % of lubricant compositions exists.Amine phosphate and thio phosphorus can be used The mixture of acid esters.

Neutral organophosphorus acid (ester/salt) can exist with the 0-4 weight % of composition, the amount of preferably 0.1-2.5 weight %. Above-mentioned amine phosphoric acid (ester/salt) may be mixed together to form the one-component for being capable of providing abrasion resistance.Neutral organophosphorus acid (ester/salt) is also the conventional ingredient of lubricating oil.

Phosphoric acid (ester/salt) for the disclosure includes phosphoric acid (ester/salt), acid phosphate (ester/salt), phosphorous acid (ester/salt) With acid phosphite (ester/salt).The phosphoric acid (ester/salt) includes triaryl phosphate, trialkylphosphate, trialkylphosphate virtue Base ester, tricresyl phosphate alkyl aryl and tricresyl phosphate alkenyl esters.As their specific example, triphenyl phosphate, phosphorus should be mentioned that Sour front three phenolic ester, phosphoric acid benzyl diphenyl ester, ethyl diphenyl ester, tributyl phosphate, ethyl dibutyl ester, phosphoric acid cresyl Diphenyl ester, di(2-ethylhexyl)phosphate cresyl phenyl ester, ethyl phenyl diphenyl ester, di(2-ethylhexyl)phosphate ethylphenyl phenyl ester, phosphoric acid propyl phenyl two Phenyl ester, di(2-ethylhexyl)phosphate propyl phenyl phenyl ester, phosphoric acid triethylbenzene ester, tricresyl phosphate propyl phenyl ester, phosphoric acid butyl phenyl diphenyl ester, phosphoric acid Dibutylphenyl phenyl ester, tricresyl phosphate butyl phenyl ester, tri hexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, phosphoric acid Three Lauryl Esters, tricresyl phosphate nutmeg base ester, tricresyl phosphate palm base ester, tricresyl phosphate stearyl and trioleyl phosphate.

The acid phosphate (ester/salt) includes such as acid phosphate 2- ethylhexyl, acid phosphate ester, acid phosphate fourth Ester, acid phosphate oil base ester, acid phosphate lignocerane base ester, acid phosphate isodecyl ester, acid phosphate Lauryl Ester, acid phosphorus Sour tridecane base ester, acid phosphate stearyl and acid phosphate iso stearyl ester.

Phosphorous acid (ester/salt) includes such as triethyl phosphite, tributyl phosphite, triphenyl phosphite, phosphorous acid three Cresols ester, phosphorous acid three (nonyl phenyl) ester, phosphorous acid three (2- ethylhexyl) ester, tridecyl phosphite, three laurel of phosphorous acid Ester, the different monooctyl ester of phosphorous acid three, three oil base ester of diphenylisodecyl ester, three stearyl of phosphorous acid and phosphorous acid.

Acid phosphite (ester/salt) includes such as hydrogen phosphite dibutyl ester, hydrogen phosphite dilauryl ester, hydrogen phosphite two Oil base ester, hydrogen phosphite distearyl base ester and hydrogen phosphite diphenyl ester.

The amine for forming amine salt with such phosphoric acid (ester/salt) includes for example monosubstituted amine, two substitution amine and three substitution amine.It is single The example for replacing amine includes butylamine, amylamine, hexylamine, cyclohexylamine, octylame, lauryl amine, stearylamine, oleyl amine and benzylamine；Two replace amine Example include dibutyl amine, diamylamine, dihexylamine, dicyclohexyl amine, dioctylamine, dilaurylamine (DLA), distearyl amine, two oleyl amines, dibenzyl Amine, stearyl monoethanolamine, decyl monoethanolamine, hexyl list Propanolamine, benzyl monoethanolamine, phenyl monoethanolamine and tolyl Single Propanolamine.The example of three substitution amine includes tri-n-butylamine, triamylamine, trihexylamine, tricyclohexyltin amine, trioctylamine, Alamine 304, three hard Rouge amine, three oleyl amines, tribenzylamine, two oil base monoethanolamine, dilauryl list Propanolamine, dioctyl monoethanolamine, dihexyl list third Hydramine, dibutyl list Propanolamine, oil base diethanol amine, stearyl dipropanolamine, Lauryl Diethanolamine, octyl dipropanolamine, Butyl diethanolamine, benzyl diethanol amine, phenyldiethanol-amine, tolyl dipropanolamine, xylyl diethanol amine, three ethyl alcohol Amine and tripropanol amine.Relative to the total weight of composition, phosphoric acid (ester/salt) or its amine salt are with 0 to 5 weight %, and preferably 0.1 to 2 The amount of weight % is added in the base oil.

The illustrative carboxylic acid reacted with amine includes such as aliphatic carboxylic acid, dicarboxylic acids (binary acid) and aromatic carboxylic acid.The rouge Race's carboxylic acid has 8 to 30 carbon atoms, and can be saturated or unsaturated and linear chain or branched chain.The aliphatic series The specific example of carboxylic acid includes n-nonanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitinic acid, stearic acid, isostearic acid, eicosane Acid, behenic acid, melissic acid, decylenic acid, undecenoic acid, oleic acid, linolenic acid, erucic acid and linoleic acid.The tool of the dicarboxylic acids Body example includes octadecylsuccinic acid, octadecenyl succinic acid, adipic acid, azelaic acid and decanedioic acid.One of aromatic carboxylic acid Example is salicylic acid.Illustrative amines with carboxylic acid reaction include such as polyalkylenepolyamines, such as diethylenetriamines, Sanya second Urotropine, tetren, penten, six ethylidene, seven amine, seven ethylidene, eight amine, dipropylenetriamine, four Asias Seven amine of five amine of propyl and six butylidenes；And alkanolamine, such as monoethanolamine and diethanol amine.These, it is preferred to different hard The combination of resin acid and tetren and the combination of oleic acid and diethanol amine.Relative to the total weight of composition, carboxylic acid and The reaction product of amine can be added in the base oil with 0 to 5 weight %, the amount of preferably 0.03 to 3 weight %.

Other illustrative antiwear additives include phosphorous acid (ester/salt), thiophosphorous acid (ester/salt), phosphoric acid (ester/salt) With thiophosphoric acid (ester/salt) comprising have such as one or two sulphur atom, i.e. single thio or two thio-compounds mixing Material.As used herein, term " hydrocarbyl substituent " or " hydrocarbyl group " are used with its usual meaning, this is meant that this Well known to the technical staff of field.Specifically, it refers to the carbon atom being connected directly with molecule rest part and mainly has The group of hydrocarbon characteristic.

The specific example of some phosphorous acid (ester/salt) and thiophosphorous acid (ester/salt) within the scope of the disclosure includes: phosphorous Acid, mono-, di- or three thiophosphorous acids, phosphorous acid mono-, di- or three propyl ester or mono-, di- or three thiophosphorous acid mono-, di-s or 3 third Ester；Phosphorous acid mono-, di- or tributyl or mono-, di- or three thiophosphorous acid mono-, di-s or tributyl；Phosphorous acid mono-, di- or 3 penta Ester or mono-, di- or three thiophosphorous acid mono-, di-s or triamyl；Phosphorous acid mono-, di- or three own esters or mono-, di- or three thio phosphorous Sour mono-, di- or three own esters；Phosphorous acid mono-, di- or triphenylmethyl methacrylate or mono-, di- or three thiophosphorous acid mono-, di-s or triphenylmethyl methacrylate；Phosphorous acid Mono-, di- or front three phenyl ester or mono-, di- or three thiophosphorous acid mono-, di-s or front three phenyl ester；Phosphorous acid mono-, di- or front three phenolic ester, or Mono-, di- or three thiophosphorous acid mono-, di-s or front three phenolic ester；Phosphorous acid dibutyl phenyl ester or mono-, di- or three thiophosphorous acids, two fourth Base phenyl ester；Phosphorous acid amyl diformazan phenolic ester or mono-, di- or three thiophosphorous acid amyl diformazan phenolic esters；And there is substituent group Such as any of above substance of chlorphenyl or chlorobutyl.

The specific example of some phosphoric acid (ester/salt) and thiophosphoric acid (ester/salt) within the scope of the disclosure includes: phosphoric acid, single, Two or three thiophosphoric acids, phosphoric acid mono-, di- or three propyl ester or mono-, di- or the propyl ester of three thio mono phosphoric acid esters, two or three；Phosphoric acid mono-, di- or Tributyl or mono-, di- or three thio mono phosphoric acid esters, two or tributyl；Phosphoric acid mono-, di- or triamyl or mono-, di- or three thiophosphoric acids Mono-, di- or triamyl；Phosphoric acid mono-, di- or three own esters or mono-, di- or the own ester of three thio mono phosphoric acid esters, two or three；Phosphoric acid mono-, di- or Triphenylmethyl methacrylate or mono-, di- or three thio mono phosphoric acid esters, two or triphenylmethyl methacrylate；Phosphoric acid mono-, di- or front three phenyl ester or mono-, di- or three thio phosphorus Sour mono-, di- or front three phenyl ester；Phosphoric acid mono-, di- or front three phenolic ester or mono-, di- or three thio mono phosphoric acid esters, two or front three phenolic ester；Phosphoric acid Dibutyl phenyl ester or mono-, di- or three thio di(2-ethylhexyl)phosphate butyl phenyl esters；Phosphoric acid amyl diformazan phenolic ester or mono-, di- or three thiophosphoric acids Amyl diformazan phenolic ester；And any of above substance with substituent group such as chlorphenyl or chlorobutyl.

These phosphorus compounds can be prepared by well known reaction.A kind of approach be alcohol or phenol with phosphorus trichloride react or it is logical Cross ester exchange reaction.Pure and mild phenol can be reacted with phosphorus pentoxide, to provide alkyl or aryl phosphoric acid and dialkyl group or diaryl phosphorus The mixture of acid.Alkyl phosphate can also be prepared by aoxidizing corresponding phosphite ester.Thiophosphate can pass through Asia Phosphate and elementary sulfur react to prepare.Under any circumstance, the reaction can carry out under appropriate heating.In addition, can To prepare various phosphorus esters as the reaction of starting material by using other phosphides.Therefore, middle chain (C9-C22) phosphorus ester Be by dimethyl phosphite and the mixture of middle chain alcohol by the transesterification of hot transesterification or acid or base catalysis react come Preparation.See, for example, United States Patent (USP) No.4,652,416.Most of such materials are also commercially available；For example, phosphorous acid Triphenylmethyl methacrylate can be used as Duraphos TPP^TMDerived from Albright and Wilson；Hydrogen phosphite di-n-butyl can be used as Duraphos DBHP^TMDerived from Albright and Wilson；And triphenylphosphorothionate can be used as Irgalube TPPT^TMDerived from Ciba Specialty Chemicals.

The example of the ester of dialkyl dithiophosphoric acid includes by dialkyl dithiophosphoric acid and α, beta-unsaturated carboxylic acid (example Such as methyl acrylate) and optional alkylene oxide for example propylene oxide reaction obtain ester.

Weight based on total composition, one or more above-mentioned metal dithionites can be used about 0 to about for phosphoric acid (ester/salt) 2 weight %, more typically from about 0.1 to about 1 weight %.

Alkyl in the phosphordithiic acid (ester/salt) can be alkyl, naphthenic base, aralkyl or alkylaryl group, or The hydrocarbyl group of substantially similar structure.Illustrative alkyl group includes isopropyl, isobutyl group, normal-butyl, sec-butyl, various penta Base group, n-hexyl, methyl-isobutyl, heptyl, 2- ethylhexyl, diisobutyl, iso-octyl, nonyl, behenyl base, decyl, ten Dialkyl group, tridecyl etc..Illustrative lower alkyl phenyl group includes butyl phenyl, amyl phenyl, heptyl phenyl etc..Ring Alkyl group be equally it is useful, they mainly include cyclohexyl and lower alkyl-cyclohexyl group.Also many can be used to take The hydrocarbyl group in generation, such as chlorine amyl, dichlorophenyl and dichloro decyl.

It is well known for preparing the phosphordithiic acid for the metal salt that can be used in the disclosure.Dihydrocarbyl dithiophosphate phosphoric acid and metal The example of salt, and the technique of the such acid of preparation and salt are found in such as United States Patent (USP) No.4, and 263,150；4,289,635； 4,308,154；With 4,417,990.These patents are incorporated herein by reference.

Phosphordithiic acid is prepared by reacting for phosphorus sulfide and alcohol or phenol or alcohol mixture.Typical reaction is related to 4 Mole alcohol or phenol and 1 mole of phosphorus pentasulfide, and can be carried out within the temperature range of about 50 DEG C to about 200 DEG C.Cause This, O, it is anti-at about 100 DEG C that the preparation of O- di-n-hexyl phosphordithiic acid is related to 1 mole of phosphorus pentasulfide and 4 moles of n-hexyl alcohols It should be about 2 hours.Hydrogen sulfide is released, residue is required acid.These acid metal salt preparation can by with this field Well known metallic compound reaction is to realize.

The metal salt that can be used for the dihydrocarbyl dithiophosphate phosphoric acid (ester/salt) of the disclosure includes containing I race metal, II race gold Those of category, aluminium, lead, tin, molybdenum, manganese, cobalt and nickel salt.II race metal, aluminium, tin, iron, cobalt, lead, molybdenum, manganese, nickel and copper belong to preferably Metal.Zinc and copper are particularly useful metals.The example for the metallic compound that can be reacted with the acid includes lithia, hydrogen-oxygen Change lithium, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, silver oxide, magnesia, magnesium hydroxide, calcium oxide, zinc hydroxide, Strontium hydroxide, cadmium oxide, cadmium hydroxide, barium monoxide, aluminium oxide, ferric carbonate, Kocide SD, lead hydroxide, butyric acid tin, hydroxide Cobalt, nickel hydroxide, nickelous carbonate etc..

In some cases, for example a small amount of metal acetate of certain ingredients or acetic acid and the metal reactant are mixed Promotion is reacted and generates improved product.For example, the combination using most about 5% zinc acetate and the desired amount of zinc oxide has Help to form the zinc dithiophosphate with potential improved performance characteristics.

Particularly useful metal thiophosphate can be prepared by phosphordithiic acid, and phosphordithiic acid is further through five vulcanizations two Phosphorus and alcohol mixture react to prepare.In addition, making it possible to utilize relatively inexpensive alcohol, these alcohol lists using such mixture Oil-soluble phosphordithiic acid may not be able to solely be generated.Therefore, the mixture of isopropanol and hexanol can be used for producing very effective Oil soluble metal dithiophosphates.For the same reason, the mixture of phosphordithiic acid can be with the metallic compound Reaction is to form relatively inexpensive oil-soluble salt.

The alcohol mixture can be the mixture, the different mixtures of secondary alcohol or the mixing of primary and secondary alcohol of different primary alconols Object.The example of useful mixture includes: n-butanol and n-octyl alcohol；N-amyl alcohol and 2- ethyl -1- hexanol；Isobutanol and just oneself Alcohol；Isobutanol and isoamyl alcohol；Isopropanol and 2- methyl -4- amylalcohol；Isopropanol and sec-butyl alcohol；Isopropanol and isooctanol；Etc..

Organic three ester of phosphoric acid is also used in lubricant.Typical ester include triaryl phosphate, trialkyl phosphates, Neutral alkyl aryl phosphate ester, alkoxyalkyl phosphate, triarylphosphite, trialkyl phosphite, neutral alkyl virtue Base phosphite ester, neutral phosphonate ester and neutral alumina phosphine ester.In one embodiment, using long-chain dialkyl phosphonate.More Preferably, dimethyl-, diethyl-and dipropyl-oleyl phosphonic ester can be used.The quinaldine acid of phosphoric acid be three esters rather than The salt of sour (HO-P) or acid.

Any C4 can be used for the disclosure to C8 alkyl or more advanced phosphate.It is, for example, possible to use tributyl phosphates (TBP) and triisooctyl phosphate (TOF).Those skilled in the art can be readily selected the combination of specific triguaiacyl phosphate or ester To adjust the density of prepared fluid, viscosity etc..It can be used mixed ester, such as phosphoric acid dibutyl monooctyl ester etc., rather than two The mixture of kind or more trialkylphosphate.

Trialkylphosphate usually can be used for adjusting the specific gravity of the preparation, it may be desirable to the specific trialkylphosphate It is liquid at low temperature.It therefore, is ideal, example by C3 to the alkylated mixed ester of C4 moieties containing at least one Such as phosphatase 24-isopropyl phenyl diphenyl or phosphoric acid 3- butyl phenyl diphenyl.Even more preferably such as United States Patent (USP) 3, As taught in 576,923, mixed phenol is formed by being alkylated phenol moieties with butylene or propylene and then makes itself and phosphorus Acyl chloride reaction and the triaryl phosphate generated.

Any mixed triaryl phosphate (TAP) can be used as phosphoric acid cresols diphenyl, tricresyl phosphate, mixing Phosphoric acid xylyl cresols ester, phosphoric acid low alkyl group phenyl ester/phenyl phosphate, such as mixed p isopropylbenzoic acid base phenyl ester/phosphoric acid benzene Ester, phosphoric acid tert-butyl phenyl phenyl ester.These esters are widely used as plasticizer, functional fluid, gasoline additive, flame-retardant additive etc..

Metal alkylthiophosphates and more particularly wherein the metal component be zinc the thio phosphorus of metal dialkyl two Hydrochlorate or zinc dialkyl dithiophosphate (ZDDP) can be the useful constituent of the lubricating oil of the disclosure.ZDDP can be derived from Or mixtures thereof primary alconol, secondary alcohol.ZDDP compound usually has following formula

Zn[SP(S)(OR¹)(OR²)]₂

Wherein R¹And R²It is C1-C18 alkyl group, preferably C2-C12 alkyl group.These alkyl groups can be straight chain or Branch.Alcohol for ZDDP can be propyl alcohol, 2- propyl alcohol, butanol, sec-butyl alcohol, amylalcohol, hexanol such as 4- methyl -2- amylalcohol, N-hexyl alcohol, n-octyl alcohol, 2-Ethylhexyl Alcohol, alkylating phenol etc..It can the preferred mixture of secondary alcohol or the mixture of primary and secondary alcohol. Also kiki fang alkyl group can be used.

Preferred commercially available zinc dithiophosphate includes secondary zinc dithiophosphate, for example, with trade name " LZ 677A ", " LZ 1095 " and " LZ 1371 " derives from such as Lubrizol Corporation, is derived from for example with trade name " OLOA 262 " Chevron Oronite, and such as those of Afton Chemical is derived from trade name " HITEC 7169 ".

Although not needing their presence to obtain the benefit of the disclosure, the total weight based on lubricating oil, ZDDP is usual With about 0 to about 3 weight %, preferably from about 0.05 weight % to about 2 weight %, more preferably from about 0.1 weight % to about 1.5 weight %, And the amount of more preferably about 0.1 weight % to about 1 weight % uses, but more or fewer amounts can often be advantageously used. Secondary (secondary) ZDDP can be preferably, and with the presence of the amount of 0 to 1 weight % of lubricating oil total weight.

Extreme pressure, wear-resistant and seizureproof agent

Can be used extreme pressure agent and the extreme pressure agent based on sulphur, for example, sulfide, sulfoxide, sulfone, thiophosphinic acid (ester/salt), Thiocarbonic acid (ester/salt), sulfurized fatty and oil, olefine sulfide etc.；Extreme pressure agent based on phosphorus, such as phosphate (such as tricresyl phosphate Cresols ester) (TCP) etc.), phosphite ester, phosphate amine salt, phosphite ester amine salt etc.；Extreme pressure agent based on halogen, such as chloro Hydrocarbon etc.；Organic metal extreme pressure agent, such as thiophosphate (for example, zinc dithiophosphate (ZnDTP) etc.) and thiocarbamic acid Salt etc..

The phosphate, thiophosphate and its amine salt play the role of improving greasy property, and can be selected from conventional use Make the known compound of extreme pressure agent.Usually used is with alkyl group, alkenyl group, alkylaryl group or aromatic alkyl group Phosphate, thiophosphate or its amine salt, any one of described group contain about 3 to 30 carbon atoms.

The example of the phosphate includes aliphatic phosphate, such as tricresyl phosphate isopropyl ester, tributyl phosphate, ethyl two Butyl ester, tri hexyl phosphate, tricresyl phosphate -2- ethylhexyl, tricresyl phosphate lauryl, tricresyl phosphate stearyl ester and tricresyl phosphate grease；And virtue Race's phosphate, such as phosphoric acid benzyl phenyl ester, phosphoric acid allyl diphenyl ester, triphenyl phosphate, tricresyl phosphate, ethyl two Phenyl ester, phosphoric acid cresyl diphenyl ester, di(2-ethylhexyl)phosphate cresyl phenyl ester, ethyl phenyl diphenyl ester, di(2-ethylhexyl)phosphate ethylphenyl phenyl ester, Phosphoric acid propyl phenyl diphenyl ester, di(2-ethylhexyl)phosphate propyl phenyl phenyl ester, phosphoric acid triethylbenzene ester, tricresyl phosphate propyl phenyl ester, phosphoric acid butyl Phenyl diphenyl ester, phosphoric acid dibutylphenyl phenyl ester and tricresyl phosphate butyl phenyl ester.Preferably, the phosphate is trialkylphosphate Phenyl ester.

The example of the thiophosphate includes aliphatic phosphorothioate esters, such as tri o cresyl thiophosphate isopropyl ester, thiophosphoric acid Tributyl, thiophosphoric acid ethyl dibutyl ester, the own ester of tri o cresyl thiophosphate, tri o cresyl thiophosphate -2- ethylhexyl, tri o cresyl thiophosphate laurel Ester, tri o cresyl thiophosphate stearyl ester and tri o cresyl thiophosphate grease；With aromatics thiophosphate, such as thiophosphoric acid benzyl phenyl ester, sulphur For phosphoric acid allyl diphenyl ester, trithiophenyl phosphate, tri o cresyl thiophosphate cresols ester, thiophosphoric acid ethyl diphenyl ester, thio phosphorus Sour cresyl diphenyl ester, thiophosphoric acid diformazan phenolic group phenyl ester, thiophosphoric acid ethylphenyl diphenyl ester, thiophosphoric acid diethyl phenyl Phenyl ester, thiophosphoric acid propyl phenyl diphenyl ester, thiophosphoric acid dipropyl phenyl phenyl ester, thiophosphoric acid triethylbenzene ester, thio phosphorus Sour tripropyl phenyl ester, thiophosphoric acid butyl phenyl diphenyl ester, thiophosphoric acid dibutylphenyl phenyl ester and tri o cresyl thiophosphate butyl benzene Ester.Preferably, the thiophosphate is tri o cresyl thiophosphate alkyl phenyl ester.

The amine salt of above-mentioned phosphate and thiophosphate can also be used.The acidic alkyl of phosphoric acid and thiophosphoric acid can also be used Or the amine salt of aryl ester.Preferably, the amine salt is the amine salt of trialkylphosphate phenyl ester or the amine salt of alkylphosphonate.

One of compound selected from phosphate, thiophosphate and its amine salt or any combination can be used.

The phosphate ester-containing and/or its amine salt play the role of improving greasy property, and can be selected from being conventionally used as extreme pressure The known compound of agent.Usually used is have alkyl group, alkenyl group, alkylaryl group or aromatic alkyl group phosphorous Acid esters or its amine salt, any one of described group contain about 3 to 30 carbon atoms.

The example of the phosphate ester-containing includes aliphatic phosphate ester-containing, such as triisopropyl phosphite, tributyl phosphite, Asia Ethyl dibutyl ester, the own ester of phosphorous acid three, three -2- ethylhexyl of phosphorous acid, trilauryl phosphite, three stearyl ester of phosphorous acid And trioleyl phosphite；With aromatics phosphate ester-containing, such as phosphorous acid benzyl phenyl ester, phosphorous acid allyl diphenyl ester, phosphorous acid three Phenyl ester, phosphorous acid front three phenolic ester, phosphorous acid ethyl diphenyl ester, tributyl phosphite, phosphorous acid ethyl dibutyl ester, phosphorous acid cresols Base diphenyl ester, phosphorous acid diformazan phenolic group phenyl ester, phosphorous acid ethylphenyl diphenyl ester, phosphorous acid diethyl phenyl phenyl ester, phosphorous acid Propyl phenyl diphenyl ester, phosphorous acid dipropyl phenyl phenyl ester, phosphorous acid triethyl group phenyl ester, phosphorous acid tripropyl phenyl ester, phosphorous acid Butyl phenyl diphenyl ester, phosphorous acid dibutylphenyl phenyl ester and phosphorous acid tributyl phenyl ester.Also phosphorous acid two is advantageously used Lauryl Ester, two oil base ester of phosphorous acid, dialkyl phosphite and diphenyl phosphite.Preferably, the phosphate ester-containing is sub- Phosphate dialkyl ester or trialkyl phosphite.

The phosphate can be derived from polyamines.The polyamines includes alkoxylated diamine, fat polyamine diamines, alkylidene Polyamines, hydroxyl polyamines, condensation polyamines aryl polyamines and heterocyclic polyamines.The example of these amine include Ethoduomeen T/13 and T/20, they are the epoxy second for the N- tallow trimethylene diamine that every mole of diamines contains 3 and 10 moles of ethylene oxide respectively Alkane condensation product.

In another embodiment, the polyamines is aliphatic diamine.The aliphatic diamine includes list or dialkyl group, symmetrical Or asymmetric ethylenediamine, propane diamine (1,2 or 1,3) and above-mentioned polyamine analogs.Suitable commercial fatty polyamines is Duomeen C (N- cocoyl -1,3- diaminopropanes), Duomeen S (N- soybean-based -1,3- diaminopropanes), Duomeen T (N- tallow -1,3- diaminopropanes) and Duomeen O (N- oil base -1,3- diaminopropanes)." Duomeens " can be from Commercially available from Armak Chemical Co., Chicago, Ill.

This alkylene polyamine includes methylene polyamines, ethylene, butylidene polyamines, propylidene polyamines, pentylidene Polyamines etc..It further include higher homologue and relevant heterocyclic amine, such as the piperazine that piperazine and N- aminoalkyl replace.It is such more The specific example of amine is ethylenediamine, trien, three-(2- aminoethyl) amine, propane diamine, trimethylene diamine, Sanya third Urotropine, tetren, six ethylidene, seven amine, penten etc..By being condensed two or more above-mentioned alkylenes The higher homologue that base amine obtains is same as the mixture of two or more aforementioned polyamines useful.

In one embodiment, the polyamines is ethylene.In " the chemical technology pandect of Kirk Othmer (Encyclopedia of Chemical Technology) ", second edition, volume 7,22-37 pages of (Interscience Publishers, New York (1965)) in ethylene amines (Ethylene Amines) title under be described in detail it is such Polyamines.Ethylene is often the complex mixture of polyalkylenepolyamines, includes cyclic condensation product.

The polyamine mixture of other useful types is that " polyamines is commonly referred to as left by above-mentioned polyamine mixture as stripping The residue of footing (polyamine bottoms) " it is generated those.In general, alkylene polyamine footing can be by table Sign is material less than about 2% of the boiling point below about 200 DEG C, is typically less than 1% (weight).The allusion quotation of such ethylene footing Pattern product derive from Dow Chemical Company of Freeport, Tex, entitled " E-100 ".These alkylene polyamine footing Including cyclic condensation product, such as piperazine and diethylenetriamines, the advanced analog of trien etc..These alkylenes Quito amine footing can only with acylation reaction or they can be used together with or mixtures thereof other amine, polyamines.It is another The useful polyamines of kind is that at least one hydroxy compounds and at least one polyamines containing at least one primary or secondary amino group are anti- Answer the condensation reaction between object.The hydroxy compounds is preferably polynary alkohol and amine.The polyalcohol is described below.At one In embodiment, the hydroxy compounds is polyamine.Polyamine includes and has 2 to about 20 carbon atoms or 2 to about 4 Any of above monoamine of alkylene oxide (such as ethylene oxide, the propylene oxide, epoxy butane etc.) reaction of carbon atom.The reality of polyamine Example includes three-(hydroxypropyl) amine, three-(methylol) aminomethanes, 2-Amino-2-methyl-1,3-propanediol, N, N, N', N'- tetra- (2- hydroxypropyl) ethylenediamine and N, N, N', N'- tetra- (2- ethoxy) ethylenediamine, preferably three (methylol) aminomethanes (THAM)。

Described above is the polyamines to form condensation product or amine condensation is reacted with polyalcohol or amine.Preferred polyamines includes three Ethylene tetra (TETA), tetren (TEPA), penten (PEHA) and polyamine mixture are for example above-mentioned " amine footing ".

The example of EP agent includes the EP agent based on sulphur, such as dialkyl sulfide, dibenzyl sulfide, dioxane Quito thioether, benzyldithio toluene, alkyl hydrosulfide, dibenzothiophenes and bis- thiobis of 2,2'- (benzothiazole)；Pole based on phosphorus Press additive, such as trialkylphosphate, triaryl phosphate, phosphonic acids trialkyl ester, trialkyl phosphite, three virtue of phosphorous acid Base ester and dialkyl group hydrazine phosphite ester, and the EP agent based on p and s, such as zinc dialkyl dithiophosphate, dioxane Base thiophosphoric acid, trialkyl thiophosphate, acid thiophosphate and three thio trialkylphosphates.EP agent can be with It is used alone or uses as a mixture, easily used with the amount within the scope of 0 to 2 weight % of lubricant oil composite.

Dispersing agent

During machine operation, the insoluble oxidized byproduct of oil is generated.Dispersing agent helps to maintain these by-products molten In liquid, to reduce their depositions on the metal surface.The dispersing agent used in lubricant formulations substantially can be nothing It is ash content or that ash content is formed.It is preferred that the dispersing agent is ash free.So-called ashless dispersant is after combustion substantially The organic material of ash content is not formed.For example, being considered ash free without metal or the dispersing agent without boration metal.Phase Instead, discussed above to form ash content after combustion containing metal brightener.

Suitable dispersing agent usually contains the polar group connecting with the higher hydrocarbon chain of molecular weight.The polar group is usual Contain at least one nitrogen, oxygen or P elements.Typical hydrocarbon chain contains 50 to 400 carbon atoms.

Particularly useful dispersing agent classification is (more) alkenylsuccinic derivatives, the amber usually replaced by long chain hydrocarbon groups Amber acid compound is usually that succinic anhydride and polyhydroxy that alkyl replaces or multiamino compound react to generate.It constitutes and assigns The long chain hydrocarbon groups for giving the lipophilic fraction of the deliquescent molecule of oil are usually polyisobutylene group.Such point Many examples of powder are well known in commercial and document.The exemplary U patent for describing such dispersing agent is that the U.S. is special Sharp No.3,172,892；3,2145,707；3,219,666；3,316,177；3,341,542；3,444,170；3,454,607； 3,541,012；3,630,904；3,632,511；3,787,374 and 4,234,435.United States Patent (USP) Nos.3,036,003；3, 200,107；3,254,025；3,275,554；3,438,757；3,454,555；3,565,804；3,413,347；3,697, 574；3,725,277；3,725,480；3,726,882；4,454,059；3,329,658；3,449,250；3,519,565；3, 666,730；3,687,849；3,702,300；4,100,082；Other kinds of dispersing agent is described in 5,705,458.Dispersion Further describing for agent can see such as European patent application No.471071, refer to for this purpose to it.

The succinic anhydride derivative that the succinic acid and alkyl that alkyl replaces replace is useful dispersing agent.In particular, passing through The succinic acid chemical combination that the succinic acid compound that hydrocarbon replaces, the hydrocarbon at least 50 carbon atoms in the preferably described hydrocarbon substituent replace Succinimide, succinate or the succinate ester amides that object is prepared with the reacting for alkylene amines of at least monovalent are special Useful.

Succinimide is that the condensation reaction between the succinic anhydride and amine replaced by alkyl is formed.Molar ratio can Changed with depending on polyamines.For example, the molar ratio of succinic anhydride and TEPA that alkyl replaces can become from about 1:1 to about 5:1 Change.Representative example is shown in United States Patent (USP) No.3,087,936；3,172,892；3,219,666；3,272,746；3, 322,670；With 3,652,616,3,948,800；And in Canadian Patent No.1,094,044.

Succinate is that the condensation reaction between the succinic anhydride and alcohol or polyalcohol replaced by alkyl is formed.It rubs You change than that can depend on used alcohol or polyalcohol.For example, the contracting of succinic anhydride and pentaerythrite that alkyl replaces Closing product is useful dispersing agent.

Succinate ester amides are that the condensation reaction between the succinic anhydride and alkanolamine replaced by alkyl is formed.Example Such as, suitable alkanolamine includes that the more alkyl polyamines of ethoxylation, the more alkyl polyamines of propoxylation and polyalkylenepolyamines are for example more Ethylene.One example is propoxylation hexamethylene diamine.Representative example is in United States Patent (USP) No.4,426,305 Middle display.

The molecular weight for the succinic anhydride that the alkyl replaces used in earlier paragraphs is usually in 800 and 2,500 dalton Or it is higher between.Above-mentioned product is anti-after can carrying out with various reagents such as sulphur, oxygen, formaldehyde, carboxylic acid such as oleic acid It answers.Above-mentioned product reacts after can also carrying out with the boron compound such as dispersing agent of boric acid, borate or high boration, to be formed Every mole of dispersant reaction product generally has the borated dispersants of about 0.1 to about 5 mole of boron.

Mannich base (Mannich base) dispersing agent is made of the reaction of alkyl phenol, formaldehyde and amine.Referring to United States Patent (USP) No.4,767,551, it is incorporated herein by reference.Processing aid and catalyst, such as oleic acid and sulfonic acid are also possible to described The part of reaction mixture.The molecular weight of the alkyl phenol is in the range of 800 to 2,500.Representative example is in United States Patent (USP) No.3,697,574；3,703,536；3,704,308；3,751,365；3,756,953；3,798,165；In 3,803,039 Display.

The Mannich condensation product that the typical high molecular weight aliphatic acid that can be used in the disclosure is modified can be by macromolecule Measure alkyl-substituted hydroxy arene or containing HNR₂It is prepared by the reactant of group.

Alkyl replaces amine ashless dispersants agent addition agent to be well known to those skilled in the art；See, for example, United States Patent (USP) No.3,275,554；3,438,757；3,565,804；3,755,433,3,822,209 and 5,084,197.

Preferred dispersing agent includes the succinimide of boration and non-boration, including from single succinimide, double Those of the mixture of succinimide and/or single and double succinimide derivative, wherein the hydrocarbyl succinimide source From in alkylene (hydrocarbylene) group, such as M_nIt is about 500 to about 5000 dalton or about 1000 to about 3000 Er Dun or about 1000 is to the polyisobutene of about 2000 dalton or the mixture of such alkylen group, the alkylene base Group often has advanced terminal ethylene group.Other preferred dispersing agents include succinic acid -ester and amide, alkyl phenol-polyamines-idol The Mannich adduct of connection, their capped derivatives and other related components.

Polymethacrylates or polyacrylate derivatives are another kind of dispersing agents.These dispersing agents, which usually pass through, to be made to contain Nitrogen monomer in ester group containing 5-25 carbon atom methacrylate or acrylate reactions prepare.It is representative Example is shown in United States Patent (USP) No.2,100,993 and 6,323,164.Polymethacrylates and polyacrylate dispersant Just it is being commonly used for multi-functional viscosity modifier.The form of lower molecular weight can be used as lubricant dispersing agent or fuel oil detergent.

The illustrative preferred dispersants that can be used for the disclosure include the list or dicarboxylic acids, acid anhydrides replaced from polyene-based Or those of ester, the dispersing agent with number-average molecular weight be at least 900 polyene-based part and each polyene-based part have it is big In 1.3 to 1.7, preferably greater than 1.3 to 1.6, most preferably greater than 1.3 to 1.5 functional group (part for generating list or dicarboxylic acids) (medium degree of functionality dispersing agent).Degree of functionality (F) can determine according to the following formula:

F=(SAP x M_n)/((112,200x A.I.)-(SAP x 98))

Wherein SAP is saponification number (that is, being measured according to ASTM D94, the complete neutralization in 1 gram of reaction product containing succinic acid The milligram number of KOH consumed by acid groups)；Mn is the number-average molecular weight of starting olefin polymer；And A.I. is containing succinic acid Reaction product Percent Active Ingredient (remaining is unreacted olefin polymer, succinic anhydride and diluent).

The number-average molecular weight of the polyalkenyl part of dispersing agent can be at least 900, suitably at least 1500, preferably 1800 To between 3000, such as between 2000 to 2800, more preferably from about 2100 to 2500, most preferably from about 2200 to about 2400.Dispersing agent Molecular weight usually indicated with the molecular weight of polyalkenyl part.This is because the accurate molecular weight range of dispersing agent depends on many Parameter, the quantity of type, functional group including the polymer for obtaining the dispersing agent and the type of nucleophilic group used.

Polymer molecular weight, especially Mn can be determined by various known technologies.A kind of convenient method is gel infiltration Chromatography (GPC), also offer molecular weight distribution information is (referring to W.W.Yau, J.J.Kirkland and D.D.Bly, " modern ruler Very little exclusion liquid chromatography (Modern Size Exclusion Liquid Chromatography) ", John Wiley and Sons, New York, 1979).Another kind determines the process useful of molecular weight, is especially used for the polymer of lower molecular weight, It is vapor-pressure osmometry (for example, ASTM D3592).

Polyalkenyl part in dispersing agent preferably has narrow molecular weight distribution (MWD), also referred to as polydispersity, You Chongjun Molecular weight (M_w) and number-average molecular weight (M_n) ratio determine.M_w/M_nPolymer less than 2.2, preferably smaller than 2.0 is most ideal 's.The polydispersity of suitable polymer is about 1.5 to 2.1, preferably from about 1.6 to about 1.8.

The suitable polyolefin for being used to form dispersing agent includes homopolymer, interpretation or lower molecular weight hydrocarbon.It is such poly- One family of conjunction object includes the polymer of the C3-C26 alpha-olefin of ethylene and/or at least one following formula

H₂C=CHR¹

Wherein R¹It is the linear or branched alkyl group comprising 1 to 26 carbon atom, and wherein the polymer contains carbon-to-carbon The terminal vinylidene degree of unsaturation of degree of unsaturation and height.Preferably, such polymer includes on ethylene and at least one The interpretation of the alpha-olefin of formula, wherein R¹It is the alkyl of 1 to 18 carbon atom, the alkyl of more preferably 1 to 8 carbon atom, more The alkyl of preferably 1 to 2 carbon atom.

Another kind of useful polymer is the polymerization prepared by the cationic polymerization of monomer such as isobutene and styrene Object.Common polymer in this kind of includes by polymerization of butadiene content be 35 to 75wt% and isobutene content be 30 to The polyisobutene that the C4 oil plant stream of 60wt% obtains.Preferred monomers source for manufacturing poly-n-butene is petroleum feeding Stream, such as raffinate II (Raffinate II).These raw materials are disclosed in this field, such as in United States Patent (USP) No.4, In 952,739.Preferred embodiment is utilized is gathered by prepared by pure isobutene stream or raffinate I (Raffinate I) stream Isobutene is to prepare the reactive isobutene polymer with terminal vinylidene alkene.The polyisobutylene polymer that can be used It is typically based on 1500 to 3000 polymer chain.

The dispersing agent is preferably non-polymeric (such as single or double succinimide).Such dispersing agent can pass through routine The preparation of technique disclosed in technique such as U.S. Patent Application Publication No.2008/0020950, the public affairs of the U.S. Patent application Content is opened to be incorporated herein by reference.

The dispersing agent can pass through conventional means, such as United States Patent (USP) No.3,087,936,3,254,025 and 5,430,105 In generally disclose as carry out boration.

Dispersing agent can be with 0 to the 10 weight weight % of % or 0.01 to 8, preferably from about 0.1 to 5 weight % or more preferable 0.5 Amount to 3 weight % uses.Or such dispersing agent can be or more excellent with 0 to 8 weight %, preferably from about 0.01 to 5 weight % The amount of 0.1 to 3 weight % is selected to use.On the basis of active constituent, such additive can be with 0 to 10 weight %, preferably from about The amount of 0.3 to 3 weight % uses.It the hydrocarbon part of the dispersing agent atom can be in C60 to C1000 or C70 to C300 or C70 To C200.These dispersing agents can the mixture containing both neutral and basic nitrogens and the two.Dispersing agent can be with It is blocked by borate and/or cyclic carbonate.Nitrogen content in product oil can be about 0 to about 2000ppm to differ by weight, It is preferred that about 100ppm to about 1200ppm by weight by weight.Basic nitrogen can be for by weight about 0 to about 1000ppm not Deng preferably by weight about 100ppm to about 600ppm by weight.

Dispersing agent as described herein can advantageously serve to the composition of the disclosure.In addition, in one embodiment, making Composition with the one or more dispersing agents preparation disclosure be by by the ingredient of the disclosure plus optional oil base stock and Lubricant additive be higher than such ingredient fusing point, particularly one or more M- carboxylates (M=H, metal, two kinds or More kinds of metals, its mixture) fusing point at a temperature of merge in the mixture and realize.

As used herein, dispersant concentration is based on " sending state " and provides.In general, active dispersing agents and processing oil It is delivered together." sending state " dispersing agent contains about 20 weight % extremely usually in " sending state " the dispersing agent product The active dispersing agents of about 80 weight % or about 40 weight % to about 60 weight %.

Detergent

Can be used for illustrative detergent in the disclosure include such as alkali metal detergent, alkaline-earth metal detergent or The mixture of one or more alkali metal detergents and one or more alkaline-earth metal detergents.Typical detergent is anion Material, the lesser anion or oleophobic hydrophilic segment of chain hydrophobic part and molecule containing molecule.The detergent Anion part typically originates from organic acid, for example, sulfur acid, carboxylic acid (such as salicylic acid), phosphoric acid, phenol, or mixtures thereof. Counter ion counterionsl gegenions are usually alkaline-earth metal or alkali metal.As described herein, the detergent can be overbasic.

The detergent be preferably the metal salt of organic or inorganic acid, phenol metal salt, or mixtures thereof.The metal is excellent Choosing is selected from alkali metal, alkaline-earth metal and its mixture.The organic acid or inorganic acid are selected from aliphatic organic or inorganic acid, alicyclic Organic or inorganic acid, aromatics organic or inorganic acid and its mixture.

The metal is preferably selected from alkali metal, alkaline-earth metal and its mixture.It is highly preferred that the metal is selected from calcium (Ca), magnesium (Mg) and its mixture.

The organic acid or inorganic acid are preferably selected from sulfur acid, carboxylic acid, phosphoric acid and its mixture.

Preferably, the metal salt of organic or inorganic acid or the metal salt of phenol include phenol calcium, sulfoacid calcium, calcium salicylate, phenol magnesium, Sulfonic acid magnesium, magnesium salicylate, high alkalinity detergent and its mixture.

The salt of metal containing substantially stoichiometric amount is referred to as neutral salt and (TBN is pressed with 0 to 80 total base number ASTM D2896 measurement).Many compositions be it is overbasic, containing largely by excessive metallic compound (for example, metallic hydrogen Oxide or oxide) reacted with sour gas (such as carbon dioxide) and the metal base that obtains.Useful detergent can be Neutral, slight high alkalinity or height are overbasic.These detergents can be with neutrality, high alkalinity, the overbasic calcium bigcatkin willow of height Hydrochlorate, sulfonate, phenates and/or magnesium salicylate, sulfonate, phenates mixture carry out using.TBN range can from it is low, In arrive high TBN product variations, including down to 0 up to 600.Preferably, the TBN delivered by the detergent is between 1 and 20. More preferably between 1 and 12.The mixture of basic, normal, high TBN can be together with the mixture of the detergent based on calcium and magnesium metal It uses, and includes sulfonate, phenates, salicylate and carboxylate.Metal can be with metal ratio than the stain release mix for 1 2 detergent and metal is used in combination than being up to 5 detergent.Also the detergent of boration can be used.

Alkaline earth phenates are another kind of useful detergents.These detergents can be by making alkaline earth metal hydroxide or oxygen Compound (such as CaO, Ca (OH)₂、BaO、Ba(OH)₂、MgO、Mg(OH)₂) react and be made with alkyl phenol or sulfenyl phenolate.Have Alkyl group includes linear chain or branched chain C1-C30 alkyl group, it is preferable that or mixtures thereof C4-C20.The reality of suitable phenol Example includes isobutyl group phenol, 2- ethylhexyl phenol, nonyl phenol, dodecylphenol etc..It should be noted that starting alkyl phenol can contain It is more than one to be the alkyl substituent of linear chain or branched chain each independently and be used with 0.5 to 6 weight %.When using non- When sulfenyl phenolate, the sulfur product can be obtained by method as known in the art.These methods include by alkyl phenol It is heated with the mixture of vulcanizing agent (including elementary sulfur, halogenation sulphur such as sulfur dichloride etc.), then makes the phenol red and alkali The reaction of earth metal alkali.

According to the disclosure, the metal salt of carboxylic acid is preferred detergent.These carboxylic acid detergents can be by making alkaline gold Belong to compound and removes free water at least one carboxylic acid reaction and from reaction product to prepare.These compounds can be high-alkali Property, it is horizontal to generate desired TBN.The detergent prepared from salicylic acid is a kind of detergent class for being preferably derived from carboxylic acid Not.Useful salicylate includes long chain alkyl salicylates.A kind of useful constituent family is following formula

Wherein R is the alkyl group with 1 to about 30 carbon atom, and n is 1 to 4 integer, and M is alkaline-earth metal.It is excellent The R group of choosing is at least C11, preferably C13 or bigger alkyl chain.R can not interfered taking for the detergent function optionally Replace for base.M is preferably or mixtures thereof calcium, magnesium, barium.More preferable M is calcium.

The salicylic acid that alkyl replaces can be reacted by Kolbe to be prepared (referring to United States Patent (USP) No.3,595,791) from phenol. The salicylic metal salt that the alkyl replaces can be made by double decomposition of the metal salt in polar solvent such as water or alcohol It is standby.

Alkali earth metal phosphate also serves as detergent and is as known in the art.

Detergent can be simple detergent or so-called mix or complicated detergent.The detergent of the latter can provide two The property of kind detergent, without blending separated material.Referring to United States Patent (USP) No.6,034,039.

Preferred detergent includes calcium sulfonate, magnesium sulfonate, calcium salicylate, magnesium salicylate, calcium phenates, magnesium phenol Salt and other related components (including boration detergent) and its mixture.Preferred stain release mix include sulfonic acid magnesium and Calcium salicylate, sulfonic acid magnesium and sulfoacid calcium, sulfonic acid magnesium and phenol calcium, phenol calcium and calcium salicylate, phenol calcium and sulfoacid calcium, phenol calcium and salicylic acid Magnesium, phenol calcium and phenol magnesium.High alkalinity detergent is also preferred.

Although not needing their presence to obtain the benefit of the disclosure, the total weight based on lubricating oil, the disclosure Detergent concentration in lubricating oil can be in 0 to about 6.0 weight %, preferably 0 to about 5.0 weight %, more preferably from about 0.01 weight In the range of amount % to about 3.0 weight %.

As used herein, the detergent concentration is provided based on " sending state ".In general, the active detergents with Processing oil is delivered together." sending state " detergent contains about 20 weights usually in " sending state " the detergent product Measure the active detergents of % to about 100 weight % or about 40 weight % to about 60 weight %.

Viscosity modifier

May include viscosity modifier in the lubricant oil composite of the disclosure, (also referred to as making viscosity index improver, (VI changes Into agent) and viscosity improver).

Viscosity modifier provides high and low temperature operability to lubricant.These additives assign cutting at elevated temperatures Cut stability and acceptable viscosity at low temperature.

Suitable viscosity modifier includes high-molecular-weight hydrocarbons, polyester and the viscosity for having both viscosity modifier and dispersing agent function Regulator dispersing agent.The typical molecular weight of these polymer is between about 10,000 to 1,500,000, more typically from about 20,000 to 1,200,000, and more usually between about 50,000 and 1,000,000.

The example of suitable viscosity modifier is the linear of methacrylate, butadiene, alkene or alkylated styrenes Or star polymer and copolymer.Polyisobutene is common viscosity modifier.Another suitable viscosity modifier is poly- first Base acrylate (for example, copolymer of the alkyl methacrylate of various chain lengths), its some preparations act also as pour point drop Low dose.Other suitable viscosity modifiers include that the hydrogenated diblock of the copolymer of ethylene and propylene, styrene and isoprene is total Polymers and polyacrylate (for example, copolymer of the acrylate of various chain lengths).Specific example includes 50,000 to 200, Styrene-based-isoprene of 000 molecular weight or the polymer of styrene-butadiene.

Olefin copolymer can be from Chevron Oronite Company LLC with trade name(example As "8921 " and "8941 ") commercially available；From Afton Chemical Corporation is with trade name(such as "5850B ") it is commercially available；And from Lubrizol Corporation with trade name "7067C " is commercially available.Hydrogenated polyisoprene star polymer can be from Infineum International Limited is for example commercially available with trade name " SV200 " and " SV600 ".Hydrogenated diene-styrene Object from Infineum International Limited for example with trade name " SV 50 " commercially available from.

Polymethacrylates or polyacrylate polymers can be linear polymer, can be from Evnoik Industries is with trade name(such as Viscoplex 6-954) is obtained；Or star polymer, it can be from Lubrizol Corporation is with trade name Asteric^TM(such as Lubrizol 87708 and Lubrizol 87725) is obtained.

The illustrative polymer containing vinyl-arene that can be used for the disclosure can be derived mainly from vinyl aromatic monomer. The illustrative copolymer containing vinyl-arene that can be used for the disclosure can be expressed by the following formula:

A-B

Wherein A is the polymeric blocks being derived mainly from vinyl aromatic monomer, and B is derived mainly from conjugate diene monomer Polymeric blocks.

Although not needing their presence to obtain the benefit of the disclosure, the total weight based on lubricant oil composite is glued Spending regulator can be to be less than about 10 weight %, and the amount of preferably less than about 7 weight %, more preferably less than about 4 weight % use, and It and in some cases, can be less than 2 weight %, preferably less than about 1 weight %, the more preferably less than about amount of 0.5 weight % It uses.Viscosity modifier adds in Macrodilution oil usually as concentrate.

As used herein, viscosity modifier concentration is provided based on " sending state ".In general, the living polymer with Flux oil is delivered together.In the polymer concentrates of " sending state ", the viscosity modifier of " sending state " is for poly- methyl The living polymer of 20 weight % to 75 weight % is usually contained for acrylate or polyacrylate polymers, or for alkene 8 weights are usually contained for hydrocarbon copolymer, hydrogenated polyisoprene star polymer or hydrogenated diene-styrene block copolymer Measure the living polymer of % to 20 weight %.

Antioxidant

Antioxidant hinders base oil in the oxidative degradation of viability.Such degradation may cause on metal surface The viscosity of deposit, the presence of greasy filth or lubricant increases.Those skilled in the art will know that varied can be used for lubricating oil group Close the oxidation retarder in object.See, e.g. previously cited Klamann, lubricant and Related product (Lubricants and Related Products) and United States Patent (USP) No.4,798,684 and 5,084,197.

The oxidation retarder of two kinds of general types is to react with initiator, peroxy radical and hydroperoxides to form nothing Those of reactive compound, and these materials are decomposed to form those of lower compound of activity.Example is the (alkyl that is obstructed Change) phenol, such as (the tert-butyl) -4- of 6- bis- sylvan [2,6- bis- (tert-butyl)-paracresol, DBPC] and aromatic amine, such as N- benzene Base-alpha-naphthylamine.They are for planning in long-term running turbine oil, circulation machine oil and hydraulic oil.

Useful antioxidant includes hindered phenol.These phenolic antioxidants can be the phenols chemical combination of no ash content (no metal) The neutrality or alkaline metal salt of object or certain phenolic compounds.Typical phenolic antioxidant compound is hindered phenol, is The phenol of hydroxyl group containing steric hindrance, and they include wherein hydroxyl group each other in adjacent or contraposition dihydroxy aryl The derivative of compound.Typical phenol antioxidant includes the hindered phenol and these hindered phenols replaced by C6+ alkyl group The derivative of alkylidene coupling.The example 2- tert-butyl -4- heptyl phenol of such phenolic material；2- tert-butyl -4- octyl Phenol；2- tert-butyl -4- dodecylphenol；2,6- di-t-butyl -4- heptyl phenol；2,6- di-t-butyl -4- dodecylphenol；2- first Base -6- tert-butyl -4- heptyl phenol；With 2- methyl-6-tert butyl -4- dodecylphenol.Other useful single phenol class antioxygens that are obstructed Agent may include the 2,6- dialkyl group phenols propanoate ester derivatives being for example obstructed.Bis-phenol kind antioxidant can also be advantageously combined this It is open to use.The example of the phenol of ortho position coupling includes: 2,2 '-bis- (4- heptyl -6- tert-butyl phenols)；2,2 '-bis- (4- octyl -6- Tert-butyl phenol)；With 2,2 '-bis- (4- dodecyl -6- tert-butyl phenols).The bis-phenol of contraposition coupling includes such as 4,4 '-bis- (2,6- Di-tert-butylphenol) and 4,4 '-methylene-it is bis- (2,6- di-tert-butylphenol).

Other examples of antioxidant based on phenol include: 2- tert-butyl phenol, 2- tert-butyl -4- sylvan, 2- tert-butyl - 5- sylvan, 2,4- di-tert-butylphenols, 2,4- dimethyl -6- tert-butyl phenols, 2- tert-butyl -4- methoxyl group phenol, 3- tert-butyl -4- Methoxyl group phenol, 2,5- di-tert-butyl hydroquinones (Kawaguchi Kagaku Co. manufacture, trade name " Antage DBH "), 2,6- Di-tert-butylphenol and 2,6- di-t-butyl -4- alkyl phenol such as 2,6- di-t-butyl -4- sylvan and 2,6- di-t-butyl -4- second Base phenol；2,6- di-t-butyl -4- alkoxy phenol such as 2,6- di-t-butyl -4- methoxyl group phenol and 2,6- di-t-butyl -4- ethoxy Base phenol, 3,5- di-tert-butyl-4-hydroxyl benzyl sulfydryl octyl acetic acid esters, alkyl -3- (3,5- di-tert-butyl-hydroxy phenyl) third Acid esters such as n-octyl -3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester (Yoshitomi Seiyaku Co. manufacture, quotient The name of an article is " Yonox SS "), dodecyl -3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester and 2'- ethylhexyl - 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester；2,6- di-t-butyls-alpha-alpha-dimethyl amino paracresol, 2,2'- methylene Bis- (4- alkyl -6- tert-butyl phenol) compound such as 2,2' methylene bis (4- methyl-6-tert butyl phenol) (Kawaguchi Kagaku Co. manufacture, trade name " Antage W-400 ") and 2,2'- di-2-ethylhexylphosphine oxide (4- ethyl -6- tert-butyl phenol) (Kawaguchi Kagaku Co. manufacture, trade name " Antage W-500 ")；Bis-phenol such as 4,4' butylidene biss (3- first Base -6- tert-butyl phenol) (Kawaguchi Kagaku Co. manufacture, trade name " Antage W-300 ") and 4,4'- methylene Bis- (2,6- di-tert-butylphenols) (Laporte Performance Chemicals manufacture, trade name " Ionox 220AH ").

Other examples of antioxidant based on phenol include: 4,4'- bis- (2,6- di-tert-butylphenols), 2,2- (two pairs of hydroxyls Phenyl) propane (bisphenol-A), 2,2- bis- (3,5- di-tert-butyl-hydroxy phenyl) propane, bis- (2,6- bis- uncles of 4,4'- cyclohexylenes Butylphenol), bis- [3, (3,5- di-tert-butyl-hydroxy phenyl) propionic ester] (the Ciba Speciality Chemicals of hexylene glycol Co. manufacture, trade name " Irganox L109 "), bis- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic acid of triethylene glycol Ester] (Yoshitomi Seiyaku Co. manufacture, trade name " Tominox 917 "), 2,2'- thio [diethyl -3- (3,5- Di-tert-butyl-hydroxy phenyl) propionic ester] (Ciba Speciality Chemicals Co. manufacture, trade name " Irganox L115 "), 3,9- bis- { 1,1- dimethyl -2- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionyloxy] Ethyl } 2,4,8,10- tetra- oxaspiro [5,5] hendecanes (Sumitomo Kagaku Co. manufacture, trade name " Sumilizer GA80 ") and 4,4'- thiobis (3- methyl-6-tert butyl phenol) (Kawaguchi Kagaku Co. manufacture, trade name " Antage RC "), 2,2'- thiobis (4,6- di-tert-butyl resorcin)；[methylene -3- (bis- uncle of 3,5- of polyphenol such as four Butyl -4- hydroxy phenyl) propionate conjunction] methane (Ciba Speciality Chemicals Co. manufacture, trade name " Irganox L101 "), 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane (Yoshitomi Seiyaku Co. manufacture, trade name " Yoshinox 930 "), 1,3,5- trimethyl -2,4, (3, the 5- di-t-butyl -4- hydroxyl benzyls of 6- tri- Base) benzene (Ciba Speciality Chemicals manufacture, trade name " Irganox 330 "), bis- [3,3'- bis- (4'- hydroxyls Base -3'- tert-butyl-phenyl) butyric acid] diol ester, 2- (3', 5'- di-tert-butyl-hydroxy phenyl)-methyl -4- (2 ", 4 "-two uncles Butyl -3 "-hydroxy phenyl) methyl-6-tert butyl phenol and bis- (2'- hydroxyl -3'- tert-butyl -5'- the methylbenzyl) -4- first of 2,6- Base phenol；With phenol/aldehyde condensate, such as p-tert-butylphenol and formaldehyde condensation product and p-tert-butylphenol and acetaldehyde condensation product.

The phenol antioxidant includes the phenol antioxidant of vulcanization and unvulcanised.Terms used herein " phenolic " or " phenol antioxidant " includes the compound with one or more than one hydroxyl group in conjunction with aromatic ring, itself can be with It is monokaryon, such as benzyl or multicore, such as naphthalene and spiral shell aromatic compounds.Therefore, " phenolic " includes phenol itself, youngster Tea phenol, resorcinol, quinhydrones, naphthols etc. and its alkyl or alkenyl and alkyl monosulfide or alkenyl derivative and bisphenol type Object is closed, including this bisphenol compound connected by alkylidene bridge sulphur bridge or oxygen bridge.Alkyl phenol includes single and more alkyl or alkene Base phenol, the alkyl or alkenyl group contain 3-100 carbon, preferably 4 to 50 carbon and its sulphurated derivatives, exist in aromatic ring The quantity of alkyl or alkenyl group be 1 remaining to the aromatic ring after the hydroxyl value at most in calculating in conjunction with aromatic ring Unsaturated valence can be used.

Therefore, in general, phenol antioxidant can be indicated by following general formula:

(R)_x—Ar—(OH)_y

Wherein Ar is selected from:

Wherein R is C3-C100 alkyl or alkenyl group, the alkyl or alkenyl group that sulphur replaces, preferably C4-C50 alkyl or The alkyl group that the alkyl or alkenyl group that alkenyl group or sulphur replace, more preferable C3-C100 alkyl or sulphur replace, most preferably C4-C50 alkyl group, R^GIt is the alkylidene group that C1-C100 alkylidene or sulphur replace, preferably C2-C50 alkylidene or sulphur replaces Alkylidene group, the alkylidene group that more preferable C2-C20 alkylidene or sulphur replace, Y is at least 1 to most Ar available valence, Available valence of the range of x from 0 to most Ar-y, the range from 1 to 10 of Z, the range from 0 to 20 of n, m be 0 to 4 and p be 0 or 1, the preferably range from 1 to 3 of y, the range from 0 to 3 of x, the range from 1 to 4 of z, the range from 0 to 5 of n and p is 0.

Preferred phenolic antioxidant compound is hindered phenol and phenolic ester, the hydroxyl group containing steric hindrance, and They include wherein hydroxyl group each other in the derivative of adjacent or contraposition dihydroxy aryl compound.Typical phenolic antioxidant The derivative that alkylidene including the hindered phenol and these hindered phenols that are replaced by C1+ alkyl group is coupled.Such phenols The example of material includes 2- tert-butyl -4- heptyl phenol；2- tert-butyl -4- octyl phenol；2- tert-butyl -4- dodecylphenol；2,6- Di-t-butyl -4- heptyl phenol；2,6- di-t-butyl -4- dodecylphenol；2- methyl-6-tert butyl -4- heptyl phenol；2- methyl- 6- tert-butyl -4- dodecylphenol；2,6- di-t-butyl -4- sylvan；2,6- di-t-butyl -4- ethyl phenol；With bis- uncle of 2,6- Butyl -4- alkoxy phenol；With

Phenolic antioxidant lubrication industry in be it is well known, commercial embodiments are for example4710、 1076、L 1035、1010、L109、L118、L135 Etc. be known to those skilled in the art.It only provides in an illustrative manner above, rather than limitation can be used Phenol antioxidant type.

Also a effective amount of one or more catalytic antioxidants can be used.The catalytic antioxidants include a effective amount of A) the more metallo-organic compounds of one or more oil-solubles；And a effective amount of b) one or more substituted N, N'- diaryl Phenylenediamine compound or c) one or more hindered phenol compounds；Or b) and c) combination.United States Patent (USP) No.8,048, Catalytic antioxidants are more fully described in 833, the patent passes through reference herein and is integrally incorporated.

The non-phenol type oxidation inhibitors that can be used include aromatic amine antioxidant, and they can itself using or with Phenols is applied in combination.The representative instance of non-phenol antioxidant includes: alkylation and non-alkylating aromatic amine, such as the virtue of following formula Race's monoamine:

R⁸R⁹R¹⁰N

Wherein R⁸It is aliphatic series, aromatics or substitution aromatic group, R⁹It is aromatics or replaces aromatic group, and R¹⁰It is H, alkane Base, aryl or R¹¹S(O)_XR¹², wherein R¹¹It is alkylidene, alkenylene or sub- aromatic alkyl group, R¹²Be compared with higher alkyl group, Or alkenyl, aryl or alkylaryl group, and x is 0,1 or 2.Aliphatic group R⁸1 to about 20 carbon atom can be contained, and Preferably comprise from about 6 to 12 carbon atoms.The aliphatic group is radical of saturated aliphatic group.Preferably, R⁸And R⁹The two be all aromatics or Replace aromatic group, and the aromatic group can be fused ring aromatic group, such as naphthalene.Aromatic group R⁸And R⁹It can be with Other groups such as S connects together.

Aromatic amine antioxidant includes phenyl-α-naphthylamine, is described by following molecular structure:

Wherein R^zIt is hydrogen or C1-C14 straight chain or C3-C14 branched alkyl group, preferably C1-C10 straight chain or C3-C10 branch Alkyl group, more preferable linear chain or branched chain C6-C8 and n are the integers in 1 to 5 range, preferably 1.Specifically example is Irganox L06。

Typical aromatic amine antioxidant has the alkyl substituents groups of at least about 6 carbon atoms.The reality of aliphatic group Example includes hexyl, heptyl, octyl, nonyl and decyl.In general, the aliphatic group will be free from more than 14 carbon atoms.It can use The general type of amine antioxidant in the present composition include diphenylamines, nonox, phenthazine, imide dibenzyl and Diphenyl-phenylene-diamine.The mixture of two or more aromatic amines is also useful.Also Polymeric amine antioxidants can be used.It can Specific example for the aromatic amine antioxidant in the disclosure includes: p, p'- dioctyl diphenylamine；T-octyl phenyl-α naphthalene Amine；Phenyl-alpha-naphthylamine；With to octyl phenyl-αnaphthylamine.

Other examples of antioxidant amine-based include dialkyl diphenylamine, such as p, p'- dioctyl diphenylamine (Seiko Kagaku Co. manufacture, trade name " Nonflex OD-3 "), p, bis--α-methylbenzyl of p'--diphenylamines and N-p- Butyl phenyl-N-p'- octyl aniline；For example single tert-butyl diphenylamine of monoalkyl diphenylamines and single octyl diphenylamine；Bis- (dioxanes Base phenyl) (2,4- diethyl phenyl) amine of amine such as two and two (2- ethyl -4- nonyl phenyl) amine；Alkyl phenyl-naphthalidine example Such as octyl phenyl-naphthalidine and the tertiary dodecylphenyl-naphthalidine of N-；Aryl naphthylamines such as naphthalidine, phenyl-1-naphthylamine, benzene Base -2- naphthylamines, N- hexyl phenyl-2-naphthylamine and N- octyl phenyl -2- naphthylamines, phenylenediamine such as N, N'- diisopropyl-is to benzene two Amine and N, N'- diphenyl-p-phenylenediamine and phenothiazines such as phenthazine (Hodogaya Kagaku company manufacture: phenthazine) With 3,7- dioctyl phenthazine.

Sulphur-containing antioxidant can be the antioxidant of any and all sulfur-bearings, for example including dialkyl thiodipropionate As thiodipropionate dilauryl and thio-2 acid distearyl base ester, dialkyldithiocarbamacompositions derivative (do not wrap Include metal salt), the reaction of bis- (3,5- di-tert-butyl-4-hydroxyl benzyl) thioethers, mercaptobenzothiazoler, phosphorus pentoxide and alkene Product and double hexadecyl thioether.These, it is preferred to dialkyl thiodipropionate, such as thiodipropionic acid dilauryl osmanthus Base ester and thio-2 acid distearyl base ester.

The example of antioxidant based on sulphur includes dialkyl sulfide, such as double dodecyl thioethers and double octadecyl sulphur Ether；Thiodipropionate, such as the double dodecyl esters of thio-2 acid, thio-2 acid double stearyls, thio-2 acid Myristyl ester and thio-2 acid dodecyl stearyl and 2-mercaptobenzimidazole.Sulfenyl phenolate and its Alkali or alkaline earth metal salt is also useful antioxidant.

The other oxidation retarder for being proved to can be used for lubricant oil composite are chlorinated aliphatic hydrocarbons, such as chlorinated wax；It is organic Sulfide and polysulfide, for example, benzyl disulfide, bis- (chlorobenzyl) disulfides, four thioether of dibutyl, oleic acid methyl ester, Sulfenyl phenolate, sulfurized dipentene and vulcanization terpenes；Phosphosulfurized hydrocarbon, such as phosphoric sulfide and turpentine oil or methyl oleate react Product, phosphorus ester mainly include two hydrocarbon and three hydrocarbon phosphite esters such as dibutyl phosphite, two heptyl ester of phosphorous acid, phosphorous acid two Cyclohexyl, phosphorous acid amyl phenyl ester, phosphorous acid diamyl phenyl ester, tridecyl phosphite, phosphorous acid distearyl base ester, phosphorous acid two Methyl naphthalene ester, phosphorous acid oil base 4- amyl phenyl ester, the phenyl-phosphite of polypropylene (molecular weight 500) substitution, diisobutyl replace Phenyl-phosphite；Metal thiocarbamates, such as dioctyl zinc dithiocarbamate and the thio ammonia of heptyl phenyl two Base barium formate；II race metal dithiophosphates, such as dicyclohexyl zinc dithiophosphate, dioctyl zinc dithiophosphate, two (heptyl phenyl) phosphordithiic acid barium, dinonyl phosphordithiic acid cadmium and phosphorus pentasulfide and isopropanol, 4- methyl -2- penta The reaction product of the equimolar mixture of pure and mild n-hexyl alcohol.

The another kind of antioxidant that can be used in lubricant oil composite disclosed herein is oil-soluble copper compounds.It can incite somebody to action Any oil-soluble suitable copper compound is admixed in the lubricating oil.The example of suitable copper antioxidant includes dialkyl The mantoquita (natural or synthetic) of thio or phosphordithiic acid copper and carboxylic acid.Other suitable mantoquitas include the two of copper Thiocarbamate, sulfonate, phenates and acetylacetonate.Alkalinity, neutrality from alkenyl succinic acid or acid anhydrides or Acid copper Cu (I) and/or Cu (II) salt are particularly useful.

Preferred antioxidant includes hindered phenol, arylamine.These antioxidants can be used alone or each other by type It is applied in combination.Although not needing their presence to obtain the benefit of the disclosure, anti-oxidant additives can be with about 0.01 To 5 weight %, the amount of preferably from about 0.1 to 3 weight %, more preferable 0.1 to 2 weight %, more preferable 0.1 to 1.5 weight % is used.

Pour point depressant (PPD)

If desired, can add conventional pour point depressant to the composition of the disclosure, (also referred to as lubricating oil flow changes Into agent).These pour point depressants can be added in the lubricating composition of the disclosure to reduce the fluid and can flow or can incline Minimum temperature.The example of suitable pour point depressant include polymethacrylates, polyacrylate, polyarylamide, Halogenated alkane chloroflo and the condensation product of aromatic compounds, carboxylic acid vinyl ester polymer and dialkyl fumarate, fatty acid Vinyl esters and allyl vinyl ether terpolymer.United States Patent (USP) No.1,815,022；2,015,748；2,191, 498；2,387,501；2,655,479；2,666,746；2,721,877；2,721,878；It is described with 3,250,715 useful Pour point depressant and/or its preparation.Although not needing their presence to obtain the benefit of the disclosure, PPD additive can be with With 0 to 5 weight %, the amount of preferably from about 0.01 to 1.5 weight % is used.

Seal compatilizer

Sealing compatilizer passes through the chemical reaction or physical change for causing fluid in the elastomer, helps to be swollen elastomer Sealing element.The appropriate seal compatilizer of lubricating oil includes organophosphorus ester, aromatic ester, aromatic hydrocarbon, ester (for example, phthalic acid Butyl benzyl ester), polybutenyl succinic anhydride and sulfolane type sealing sweller for example Lubrizol 730- type sealing swelling addition Agent.Although not needing their presence to obtain the benefit of the disclosure, seal compatibility additive can with 0 to 3 weight %, The amount of preferably from about 0.01 to 2 weight % uses.

Defoaming agent

Defoaming agent can be advantageously added in lubricant compositions.These reagents prevent to form stable foam.Bubble Foam inhibitor includes the polymer of alkyl methacrylate, is especially useful that polyalkyl acrylate polymer, wherein alkane Base be generally understood as be methyl, ethyl, propyl, isopropyl, butyl or isobutyl group and dimethyl silscone polymer, The material for being referred to as dimethylsiloxane polymer being formed in the range of viscosities of 100cSt to 100,000cSt.Other additions Agent is defoaming agent, for example, with it is various carried out containing carbon part after the silicone polymer that reacts, be most widely used defoaming agent.It is organic Polymer is sometimes used as defoaming agent, but needs much higher concentration.

Defoaming agent is commercially available, and can be together with other additives such as demulsifier with conventional a small amount of use.Though Their presence is not needed so to obtain the benefit of the disclosure, but the merging amount of usually these additives less than 1 weight % and passes through Often less than 0.1 weight %.

Demulsifier

Demulsifier can be advantageously added in lubricant compositions.Demulsifier is for separating lotion (such as Water-In-Oil Lotion).Illustrative demulsification component is described in EP-A-330,522.It is by making alkylene oxide and passing through di-epoxide It is reacted and is obtained with the adduct that polyol reaction obtains.Demulsifier is commercially available, and can be with other additions Agent such as defoaming agent is together with conventional a small amount of use.Although not needing their presence to obtain the benefit of the disclosure, usually The merging amount of these additives is less than 1 weight % and frequently less than 0.1 weight %.

Demulsifier includes alkarylsulphonic acid (ester or salt) of alkoxylate phenol and phenolic resin and synthesis, such as metal dinonyl Naphthalene sulfonate.The primary amount of demulsifier is water-soluble polyether polyols, and preselected molecule amount is between about 450-5000 Any value or higher in range.It can be used for the particularly preferred water-soluble polyether polyols family of disclosure composition It can be and generated by n-butanol by the mixture alkoxylate of alkylene oxide with forming random alkoxylated polymerization product.

The polyether polyols that can be used for the disclosure can be by being used to prepare the public affairs of the polyalkylene oxide with hydroxyl end groups Perception method generates, the method includes while use highly basic such as potassium hydroxide as catalyst, make alcohol or glycol ethers with One or more alkylene oxide monomers such as ethylene oxide, epoxy butane or propylene oxide form block copolymerization in addition polymerization Object.In such method, polymerization usually under 0.3-1.0 moles of catalytic level of the % potassium hydroxide than monomer and high temperature such as It is carried out at 100 DEG C to 160 DEG C.Well known fact is that the potassium hydroxide as catalyst is most of in resulting polymer It is bonded in the form of alkoxide with the chain end of generated polyalkylene oxide in solution.

The particularly preferred soluble polyether polyols family that can be used for disclosure composition is also possible to by positive fourth Alcohol is formed random alkoxylated polymerization product by the mixture alkoxylate of alkylene oxide and generates.

Inhibitor and rust-inhibiting additive

Rust-inhibiting additive (or corrosion inhibitor) is that the metal surface lubricated is protected to resist water, air or other pollutants Chemical erosion additive.These diversified additives are commercially available.

A type of rust-inhibiting additive is preferential wetting metal surface to protect its polar compound with oil film.It is another The rust-inhibiting additive of seed type absorbs water by the way that water to be incorporated into water-in-oil emulsion, so that only oil contact metal surface. The rust-inhibiting additive chemical adhesion of another seed type is in metal, to generate non-reacted surface.The example packet of suitable additive Include zinc dithiophosphate, metal phenates, basic metal sulfonates, fatty acid and amine.Although not needing their presence to obtain The benefit of the disclosure, but inhibitor and rust-inhibiting additive can be with 0 to about 5 weight %, the amounts of preferably 0.01 to about 1.5 weight % It uses.

Rust-inhibiting additive includes (short chain) alkenyl succinic acid, its partial ester and its nitrogen containing derivative；And the alkaryl of synthesis Sulfonate, such as metal dinonylnaphthalene sulfonic acid salt.Antirust agent include monocarboxylic acid for example with 8 to 30 carbon atoms, alkyl or Alkenyl succinate acid ester or its partial ester, the hydroxy fatty acid with 12 to 30 carbon atoms and its derivative have 8 to 24 carbon originals Sarcosine and its derivative, amino acid and its derivative, aphthenic acids and its derivative, lanolin fatty acid, the sulfydryl fat of son Acid and alkane hydrocarbon oxide.

The example of monocarboxylic acid (C8-C30) include for example octanoic acid, n-nonanoic acid, capric acid, hendecanoic acid, lauric acid, myristic acid, Palmitinic acid, stearic acid, arachidic acid, behenic acid, cerinic acid, montanic acid, melissic acid, oleic acid, behenic acid, erucic acid, eicosylene Acid, tallow acid, soya bean fatty acid, coco-nut oil fatty acid, linoleic acid (linolic acid), linolenic acid (linoleic Acid), ready denier oil acid, 12- hydroxy stearic acid, Hamposyl L, myristoyl-N-methylaminoacetic acid, palmitoyl sarcosine, hard Acyl sarcosine, oleoyl sarcosine, alkylation (C8-C20) phenoxyacetic acid, lanolin fatty acid and C8-C24 sulfydryl fat Acid.

The example of polybasic carboxylic acid include alkenyl (C10-C100) succinic acid pointed out in such as CAS No.27859-58-1 and Its ester derivant, dimeric dibasic acid, N- acyl group-N- alkoxyalkyl aspartate (United States Patent (USP) No.5,275,749).

As rust-inhibiting additive or as the reaction product with above-mentioned carboxylate to generate the alkylamine that amide etc. works Example indicated by such as following primary amine: lauryl amine, coconut amine, n-tridecane amine, nutmeg amine, n-pentadecane amine, palm Amine, n-heptadecane amine, stearylamine, NSC 77136 amine, n-eicosane amine, Heneicosane amine, n-docosane amine, positive 23 Alkanamine, pentacosane amine, oleyl amine, beef tallow amine, hydrogenated butter amine and soybean amine.The example of secondary amine includes: dilaurylamine (DLA), two coconut palms Sub- amine, two n-tridecane amine, two nutmeg amine, two n-pentadecane amine, two palmitamides, two n-pentadecane amine, distearyl amine, two just Nonadecane amine, two n-eicosane amine, two Heneicosane amine, two n-docosane amine, two n-tricosane amine, two positive 25 Alkanamine, two oleyl amines, two beef tallow amines, dihydrogenated tallow amine and two soybean amine.

The example of N- alkyl polyalkylene diamines above-mentioned includes: ethylenediamine, such as lauryl ethylenediamine, coconut second two Amine, n-tridecane base ethylenediamine, myristyl ethylenediamine, n-pentadecane base ethylenediamine, palmityl ethylenediamine, n-heptadecane base second Diamines, stearyl ethylenediamine, NSC 77136 base ethylenediamine, n-eicosane base ethylenediamine, Heneicosane base ethylenediamine, positive 20 Dialkylaminoethylamine, n-tricosane base ethylenediamine, pentacosane base ethylenediamine, oil base ethylenediamine, butter ethylenediamine, hydrogenation Butter ethylenediamine and soybean ethylenediamine；Propane diamine such as lauryl propane diamine, coconut propane diamine, n-tridecane base propane diamine, meat Myristyl propane diamine, n-pentadecane base propane diamine, palmityl propane diamine, n-heptadecane base propane diamine, stearyl propylene diamine, positive ten Nine alkyl propane diamine, n-eicosane base propane diamine, Heneicosane base propane diamine, n-docosane base propane diamine, positive 23 Alkyl propane diamine, pentacosane base propane diamine, diethylenetriamines (DETA) or trien (TETA), oil base the third two Amine, butter propane diamine, h-tallow propane diamine and soybean propane diamine；Butanediamine, for example, lauryl butanediamine, coconut butanediamine, N-tridecane base butanediamine, myristyl butanediamine, n-pentadecane base butanediamine, stearyl butanediamine, n-eicosane base fourth two Amine, Heneicosane base butanediamine, n-docosane base butanediamine, n-tricosane base butanediamine, pentacosane base fourth two Amine, oil base butanediamine, butter butanediamine, h-tallow butanediamine and soybean butanediamine；And pentanediamine, such as lauryl penta 2 Amine, coconut pentanediamine, myristyl pentanediamine, palmityl pentanediamine, stearyl pentanediamine, oil base pentanediamine, butter pentanediamine, H-tallow pentanediamine and soybean pentanediamine.

Matal deactivator, passivator and corrosion inhibitor

This kind of component include 2,5- dimercapto -1,3,4- thiadiazoles and its derivative, mercaptobenzothiazoler, alkyl triazole and Benzotriazole.The example for the binary acid in addition to decanedioic acid that can be used as corrosion inhibitor that can be used in the disclosure be adipic acid, Azelaic acid, dodecanedioic acid, 3- methyl adipic acid, 3- nitrophthalic acid, 1,10- last of the ten Heavenly stems dicarboxylic acids and fumaric acid.It is anticorrosive Combination is linear chain or branched chain, saturated or unsaturated monocarboxylic acid or its ester, can optionally be vulcanized with the amount of at most 35 weight %.It is excellent Selection of land, the acid are C4 to C22 straight chain unsaturated monocarboxylic.The monocarboxylic acid can be vulcanization oleic acid.However, other are suitable Material is oleic acid itself；Valeric acid and erucic acid.Anticorrosive combined component is triazole as previously defined.Preferred triazole is to can wrap The azimido-toluene being contained in disclosure composition, comprising triazole, thiazole and it is certain can be used as metal deactivator or metal passivation The diamine compound of agent.Example includes triazole, benzotriazole and substituted benzotriazole, such as alkyl-substituted derivative.Institute It states alkyl substituent and usually contains at most 1.5 carbon atoms, preferably up to 8 carbon atoms.The triazole can be on aromatic ring Contain other substituent groups, such as halogen, nitro, amino, sulfydryl etc..The example of suitable compound is benzotriazole and tolyl Triazole, ethyl benzotriazole, hexyl benzotriazole, octyl benzotriazole, chlorobenzotriazole and nitrobenzene and triazolam.Benzotriazole It is particularly preferred with tolyl-triazole.

Illustrative substituent group includes the alkyl of such as linear chain or branched chain, such as methyl, ethyl, n-propyl, isopropyl, just Butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2- ethylhexyl, n-nonyl, positive decyl, dodecyl, N-tetradecane base, n-hexadecyl, n-octadecane base or n-eicosane base；The alkenyl of linear chain or branched chain, such as propyl- 2- alkenyl, But-2-ene base, 2- methyl -propyl- 2- alkenyl, amyl- 2- alkenyl, hex- 2,4- dialkylene, decyl- 10- alkenyl or 20 carbon -2- alkenyls； Naphthenic base is such as cyclopenta, cyclohexyl, cyclooctyl, cyclodecyl, adamantyl or cyclo-dodecyl；Aralkyl is example Such as benzyl, 2- phenylethyl, benzhydryl or naphthyl methyl；Aryl is such as phenyl or naphthyl；Heterocyclic group is example Such as morpholine, pyrrolidines, piperidines or perhydroazepine ring；Alkylene moiety comprising such as methylene, ethylidene, 1:2- or 1: 3- propylidene, 1:4- butylidene, 1:6- hexylidene, 1:8- octamethylene, 1:10- decylene and 1:12- sub-dodecyl.

Illustrative arylene portion include such as phenylene and naphthylene, 1- (or 4)-(dimethylaminomethyl) triazole, 1- (or 4)-(diethylaminomethyl) triazole, 1- (or 4)-(two-isopropyl aminomethyls) triazole, 1- (or 4)-(di-n-butyl ammonia Methyl) triazole, 1- (or 4)-(two-n-hexyl aminomethyls) triazole, 1- (or 4)-(two-isooctylaminomethyls) triazole, 1- (or 4)-(two (2- ethylhexyl) aminomethyls) triazole, 1- (or 4)-(two-positive decyl aminomethyls) triazole, 1- (or 4)-(two-positive ten Dialkyl amino methyl) triazole, 1- (or 4)-(two-n-octadecane base aminomethyls) triazole, 1- (or 4)-(two-n-eicosane base ammonia Methyl) triazole, 1- (or 4)-[two (propyl- 2'- alkenyl) aminomethyls] triazole, 1- (or 4)-[two (butyl- 2'- alkenyl) aminomethyls] three Azoles, 1- (or 4)-[two (20-2'- alkenyl) aminomethyls] triazole, 1- (or 4)-(two-cyclohexyl aminomethyls) triazole, 1- (or 4)-(two-benzyl aminomethyls) triazole, 1- (or 4)-(two-phenyl aminomethyls) triazole, 1- (or 4)-(4'- morpholinyl methyl) three Azoles, 1- (or 4)-(1'- pyrrolidinylmethyl) triazole, 1- (or 4)-(1'- piperidino methyl) triazole, 1- (or 4)-(1'- perhydro Azepines ylmethyl) triazole, 1- (or 4)-(2', 2 "-dihydroxy ethyl) aminomethyl] triazole, 1- (or 4)-(dibutoxy propyl- Aminomethyl) triazole, 1- (or 4)-(dibutyl sulfopropyl-aminomethyl) triazole, 1- (or 4)-(dibutylamine propyl-aminomethyl) Triazole, 1- (or -4)-(1- methylamine)-N, N- bis- (2- ethylhexyl)-methylbenzotrazoles, N, N- is bis--(1- or 4- triazolyl first Base) lauryl amine, N, N- is bis--(1- or 4- triazolyl methyl) oleyl amine, N, and N- is bis--(1- or 4- triazolyl methyl) ethanol amine and second N, N, N', N'- tetra- (1- or 4- triazolyl methyl) ethylenediamine.

The metal deactivator that can be used in lubricating oil includes such as benzotriazole and 4- alkyl benzotriazole, such as 4- methyl Benzotriazole and 4- ethyl benzotriazole；5- alkyl benzotriazole, such as 5- methylbenzotrazole, 5- ethyl benzotriazole；1- Alkyl benzotriazole, such as 1- dioctyl auaino methyl -2,3- benzotriazole；Benzotriazole derivatives, such as 1- alkyl first Benzotriazole, such as 1- dioctyl aminomethyl -2,3- tolytriazole；Benzimidazole and benzimidizole derivatives, such as 2- (alkyl two It is thio)-benzimidazole, such as 2- (octyl two is thio)-benzimidazole, 2- (decyl two is thio) benzimidazole and 2- (dodecane Base two is thio)-benzimidazole；2- (alkyl two is thio)-mebendazole, such as 2- (octyl two is thio)-mebendazole, the 2- (last of the ten Heavenly stems Base two is thio)-mebendazole and 2- (molybdenum didodecyl dithiophosphate)-mebendazole；Mebendazole class indazole and indazole derivative, example Such as 4- alkylindazole, 5- alkylindazole；Benzothiazole, 2-mercaptobenzothiazole derivative (Chiyoda Kagaku Co. manufacture, Trade name " Thiolite B-3100 ") and 2- (alkyl two is thio) benzothiazole, such as 2- (hexyl two is thio) benzothiazole With 2- (octyl two is thio) benzothiazole；2- (alkyl two is thio) toluene thiazole, for example, 2- (benzyl two is thio) toluene thiazole and 2- (octyl two is thio) toluene thiazole, 2- (N, N- dialkyldithiocarbamoyl) benzothiazole such as 2- (N, N- diethyl Base Dithiocarbamyl) benzothiazole, 2- (N, N- dibutyl dithio carbamoyl) benzothiazole and 2-N, N- bis- Hexyl Dithiocarbamyl) benzothiazole；2- (N, N- dialkyldithiocarbamoyl) toluene thiazoles benzo thiophene Zole derivatives such as 2- (N, N- diethyl-dithio carbamoyl) toluene thiazole, 2- (N, N- dibutyl dithio amino first Acyl group) toluene thiazole, 2- (N, N- dihexyl-Dithiocarbamyl) toluene thiazole；2- (alkyl two is thio) benzothiazole, example Such as 2- (octyl two is thio) benzothiazole, 2- (decyl two is thio)-benzothiazole and 2- (molybdenum didodecyl dithiophosphate) benzothiazole；2- (alkane Base two is thio) toluene azole benzoxazole derivative, such as 2- (octyl two is thio) toluene azoles, 2- (decyl two is thio) toluene azoles, 2- (molybdenum didodecyl dithiophosphate) toluene azoles；Bis- bis- (two sulphur of heptyl of (alkyl two is thio) -1,3,4- thiadiazoles such as 2,5- of 2,5- Generation) -1,3,4- thiadiazoles, 2,5- bis--(nonyl two is thio) -1, -3,4- thiadiazoles, 2,5- bis- (molybdenum didodecyl dithiophosphate) -1, 3,4- thiadiazoles and 2,5- it is bis--(octadecyl two is thio) -1,3,4- thiadiazoles；Bis- (N, the N- dialkyl group-dithiocarbamates of 2,5- Formoxyl) bis- (N, N- the diethyl-dithio carbamoyls) -1,3 of -1,3,4- thiadiazoles such as 2,5-, -4- thiadiazoles, 2,5- Bis- (N, N- dibutyl dithio carbamoyl) -1,3,4- thiadiazoles and bis- (N, N- the dioctyl dithiocarbamates formyls of 2,5- Base) 1,3,4- thiadiazoles；2-N, N- dialkyl group-Dithiocarbamyl -5- sulfydryl -1,3,4- thiadiazole thiadiazole derivs Object such as 2-N, N- dibutyl dithio carbamoyl -5- sulfydryl -1,3,4- thiadiazoles and the thio ammonia of 2-N, N- dioctyl-two Base formoxyl -5- sulfydryl -1,3,4- thiadiazoles, 1- alkyl -2,4- triazole type triazole derivative, such as 1- dioctyl aminomethyl - 2,4- triazoles or its concentrate and/or mixture.

Although not needing their presence to obtain the benefit of the disclosure, metal deactivator and corrosion inhibitor additive Can exist with the 0 of total lubricant oil composite to about 1 weight %, preferably 0.01% to about 0.5%.

Friction improver

Friction improver is the friction system that can change the surface of the fluid lubrication by any lubricant or containing this kind of material Several any materials.If necessary, the also referred to as friction improver of anti-friction agent or lubricity agent or oiliness improver, and change As other of the ability of the coefficient of friction on the surface that base oil, allotment lubricant compositions or functional fluid improvement are lubricated Reagent, the base oil or lubricant compositions that can be effectively combined the disclosure use.Reduce the friction improver of coefficient of friction It combines and is particularly advantageous with the base oil of the disclosure and lubricant oil composite.

Or mixtures thereof illustrative friction improver may include such as organo-metallic compound or material,.It can be used for Illustrative organic metal friction improver in the turbine lube oil preparation of the disclosure includes such as molybdenum amine, molybdenum diamines, has Machine tungstates, molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum amine complex, carboxylic acid molybdenum etc. and its mixture.Similar Compound based on tungsten may be preferred.

Other the illustrative friction improvers that can be used in the turbine lube oil preparation of the disclosure include such as alcoxyl Base aliphatic ester, alkanolamide, polyol fatty acid ester, boration fatty acid glyceride, fatty alcohol ether and its mixture.

Illustrative alkoxy fatty acid ester includes such as Myrj 45, fatty acid polyethylene glycol ester. They may include that polyoxypropylene stearate, polybutylene stearate, polyoxyethylene isostearate, polyoxypropylene are different hard Resin acid ester, polyoxyethylene palmitate etc..

Illustrative alkanolamide includes such as lauric acid diethyl alkanolamide, palmitinic acid diethyl alkanolamide. They may include oleic acid diethyl alkanolamide, stearic acid diethyl alkanolamide, oleic acid diethyl alkanolamide, poly- ethoxy Base hydrocarbyl amide, poly- propoxylation hydrocarbyl amide etc..

Illustrative polyol fatty acid ester includes such as Monoolein, saturation mono-, di- and glyceryl ester, glycerol list Stearate etc..They may include polyol ester, hydroxyl polyol ester etc..

Illustrative boration fatty acid glyceride includes that such as boration Monoolein, boration are saturated mono-, di- With glyceryl ester, boration glyceryl monostearate etc..In addition to glycerine polyol, they can also include trihydroxy methyl third Alkane, pentaerythrite, sorbitan etc..These esters can be polyalcohol monocarboxylate, polynary alcohol esters of dicarboxylic acids and polyalcohol sometimes Tricarboxylic ester.It can be with preferably glycerine monoleate, diolein, glycerol trioleate, glyceryl monostearate, glycerol two Stearate and glycerol tristearate and three palmitinic acid of corresponding glycerol monopalmitate, dipalmitin and glycerol Ester and respective isostearate, linoleate etc..It sometimes, can the preferred glyceride and containing any of these Mixture.It can be made with the ethoxylation of preferred polyol, propoxylation, butoxylated aliphatic ester especially with glycerol For basic polyalcohol.

Illustrative fatty alcohol ether includes such as stearyl ether, myristyl ether.Alcohol is C3 to C50's including carbon number Those alcohol can be ethoxylated, propoxylation or butoxylated to form corresponding fatty alkyl ether.The basis alcohol part It may be preferred that stearyl, myristyl, C11-C13 hydrocarbon, oil base, iso stearyl etc..

In addition to fatty phosphites and fatty imidazolines, these other friction improvers all will be optional.It is such The useful list of other friction improver additives is comprised in United States Patent (USP) No.4,792,410.United States Patent (USP) No.5, 110,488 disclose the metal salt that can be used as the fatty acid of friction improver, especially zinc salt.Fatty acid is also useful friction Modifier.Other friction improver lists for being suitable for the disclosure include: (i) fatty phosphonate ester；(ii) fatty acid amide； (iii) fat epoxide；(iv) borated fatty epoxides；(v) fatty amine；(vi) glyceride；(vii) boration glycerol Ester；(viii) alkoxylated fats amine；(ix) borated alkoxylated fatty amine；(x) metal salt of fatty acid；(xi) vulcanize alkene Hydrocarbon；(xii) condensation product of carboxylic acid or equivalent and polyalkylenepolyamines；(xiii) metal salt of alkyl salicylate；(xiv) The amine salt of alkyl phosphoric acid；(xv) fatty ester；(xvi) condensation product of carboxylic acid or equivalent and polyalcohol and its mixture.

The representative of each in the friction improver of these types is known and is commercially available.For example, (i) wrapping Include the component of substantially vertical type:

(RO)₂PHO,

(RO) (HO) PHO, and

P (OR) (OR) (OR),

Wherein, in these structures, term " R " typically refers to alkyl group but it is also possible to be hydrogen.It is of course possible to described Alkyl group is actually alkenyl, therefore the term as used herein " alkyl " and " alkylation " will include saturated alkyl in the component Alkyl group other than group.The component should have enough hydrocarbyl groups so that its substantially oleophylic.In some embodiment party In formula, the hydrocarbyl group is substantially non-branched.Many suitable such components are commercially available, and can be such as the U.S. It is synthesized described in patent No.4,752,416.In some embodiments, the component contains 8 to 24 in each R group Carbon atom.In other embodiments, the component can be in each fat group containing 12 to 22 carbon atoms or The fatty phosphites of 16-20 carbon atom.In one embodiment, the fatty phosphites can be by oil base group shape At, therefore there are 18 carbon atoms in each fat group.

(iv) borated fatty epoxides can be known from Canadian Patent No.1,188,704.These oil-soluble boracics Composition by make boric acid or diboron trioxide 80 DEG C to 250 DEG C at a temperature of at least one fatty epoxy with following formula Compound is reacted to prepare:

Wherein R^l、R²、R³And R⁴Each of be hydrogen or aliphatic group, or in which any two connect with them Epoxy group carbon atom be formed together cyclic group.The fat epoxide preferably comprises at least eight carbon atom.

The borated fatty epoxides can be characterized with their preparation method, and the method is related to two kinds of materials Reaction.Reagent A can be diboron trioxide or any various forms of boric acid, including metaboric acid (HBO₂), ortho-boric acid (H₃BO₃) With tetraboric acid (H₂B₄0₇).Boric acid, especially ortho-boric acid are preferred.Reagent B can be at least one fat with above formula Epoxides.In the formula, each R group is most frequently hydrogen or aliphatic group, and wherein at least one is former containing at least six carbon The alkyl or aliphatic group of son.Reagent A and the molar ratio of reagent B are usually 1:0.25 to 1:4.It is preferred that the ratio of 1:1 to 1:3, About 1:2 is particularly preferred ratio.Borated fatty epoxides can be by only blending both reagents and at 80 DEG C to 250 DEG C, they are heated one section at a temperature of preferably 100 DEG C to 200 DEG C and are enough the time to react and prepare.If desired, anti- Should can it is substantially inert, normally be liquid organic diluent in the presence of carry out.During reaction, water is released and can be with It is removed by distillation.

(iii) non-borated fatty epoxides corresponding to mentioned reagent B also are used as friction improver.

Boration amine can usually be known from United States Patent (USP) No.4,622,158.Boration amine friction improver (including (ix) borated alkoxylated fatty amine) it is easily prepared by boron compound as described above with the reaction of corresponding amine. The amine can be the tertiary amine of simple fatty amine or hydroxyl.The boration amine can be by reacting boron as described above Object is added in amine reactant and at 50 DEG C to 300 DEG C, adds at preferably 100 DEG C to 250 DEG C or 130 DEG C to 180 DEG C with stirring It is prepared by heat mixture generated.It is described reaction proceed to until by-product water stopping released from reaction mixture, show Reaction is completed.

The amine that can be used for preparing boration amine includes business alkoxylated fats amine, it is known that and trade mark is " ETHOMEEN ", and It is available from Akzo Nobel.These ETHOMEEN^TMThe representative example of material is ETHOMEEN^TMC/12 (bis- [2- hydroxyl second Base]-coco amine)；ETHOMEEN^TMC/20 (polyoxyethylene [10] coco amine)；ETHOMEEN^TM(bis- [2- hydroxyethyls] are big by S/12 Beans amine)；ETHOMEEN^TMT/12 (bis- [2- hydroxyethyl] beef tallow amines)；ETHOMEEN^TMT/15 (polyoxyethylene-[5] beef tallow amine)； ETHOMEEN^TMO/12 (bis- [2- hydroxyethyl] oil base amine)；ETHOMEEN^TM18/12 (bis- [2- ethoxy] octadecylamines)； And ETHOMEEN^TM18/25 (polyoxyethylene [15] octadecylamine).Fatty amine and ethoxylated fatty amine are also described in the U.S. In patent No.4,741,848.Dihydroxy ethyl beef tallow amine is (commercially as ENT-12^TMSell) it is included in the amine of these types In.

(viii) alkoxylated fats amine and (v) fatty amine itself (such as oleyl amine and dihydroxy ethyl beef tallow amine) are usually available Make the friction improver in the disclosure.Such amine is commercially available.

The boration of glycerol and non-borated fatty acid esters can be employed as friction improver.(vii) the boration rouge of glycerol Fat acid esters with boric acid by by the aliphatic ester boration of glycerol and being removed reaction water and being prepared.Preferably, there are enough boron, So that each boron will be reacted with 1.5 to 2.5 hydroxyl groups present in reaction mixture.The reaction being not present or There are the temperature under any suitable organic solvent such as methanol, benzene, dimethylbenzene, toluene or oil, within the scope of 60 DEG C to 135 DEG C Lower progress.

(vi) aliphatic ester of glycerol itself can be prepared by various methods well known in the art.Many in these esters, Such as Monoolein and glycerol butter acid esters, it is to be manufactured with commercial size.Useful ester is oil-soluble, and preferably by C8 that C8 for example has found in natural products to or mixtures thereof C22 fatty acid and as described in more detail below is to C22 rouge The preparation of or mixtures thereof fat acid.The fatty-acid monoester of glycerol is preferred, but the mixture of monoesters and diester can be used.Example Such as, mixture of the business Monoolein containing 45 to 55 weight % monoesters and 55% to 45% diester.

Fatty acid can be used for preparing above-mentioned glyceride；They can also be used for preparing their (x) metal salt, (ii) amide and (xii) imidazoline, any of which also are used as friction improver.Preferred fatty acid is containing 10 to 24 carbon originals The fatty acid of son or 12 to 18 carbon atoms.The acid can be branch or straight chain, saturated or unsaturated.In some embodiment party In formula, the acid is straight-chain acid.In other embodiments, the acid is branch.Suitable acid includes capric acid, oleic acid, hard Resin acid, isostearic acid, palmitinic acid, myristic acid, palmitoleic acid, linoleic acid, lauric acid and linolenic acid, and come from natural products Butter, palm oil, olive oil, peanut oil, corn oil, coconut oil and Neat neat's foot oil acid.Particularly preferred acid is oleic acid.It is excellent The metal salt of choosing includes zinc salt and calcium salt.Example is high alkaline calcium salt and alkaline oleic acid-zinc salt complex compound, such as zinc oleate, It can be by general formula Zn₄Oleic acid₆O₁It indicates.Preferred amide is by contracting with ammonia or with primary amine or secondary amine such as ethamine and diethanol amine Close the amide of preparation.Fatty imidazolines are the cyclic condensation products of acid with diamines or polyamines such as polyethylene polyamine.Imidazoline is logical Often by following representation:

Wherein R is alkyl and R ' is hydrogen or hydrocarbyl group or substituted hydrocarbyl group, including-(CH₂CH₂NH) n-base Group.In a preferred embodiment, friction improver is condensation product of the C10 to C24 fatty acid and polyalkylenepolyamines, especially It is the product of isostearic acid and tetren.

The condensation product (xiii) of carboxylic acid and polyalkyleneamines usually can be imidazoline or amide.They can be derived from Above-mentioned any carboxylic acid and any polyamines as described herein.

Olefine sulfide (xi) is the well known commercial materials as friction improver.Particularly preferred olefine sulfide is basis The detailed teachings preparation of United States Patent (USP) No.4,957,651 and 4,959,168.Which describe two or more be selected from Under reactant co-vulcanization mixture: (1) at least one polyol fatty acid ester, (2) at least one fatty acid, (3) at least A kind of alkene, (4) at least one monohydric alcohol fatty acid esters.Reactant (3) olefin component includes at least one alkene.The alkene is excellent Choosing is aliphatic olefin, usually contains 4-40 carbon atom, preferably 8-36 carbon atom.Terminal olefin or alpha-olefin are preferred , especially there is those of 12 to 20 carbon atoms.The mixture of these alkene is commercially available, and such mixture It is contemplated for the disclosure.The co-vulcanization mixture of two or more reactants is by making the mixed of reactant appropriate Object is closed to react with sulphur source and prepare.The reactant (1) or 0.1 to 15 of mixture to be vulcanized containing 10 to 90 parts by weight The reactant (2) of parts by weight；Or 10 to 90 parts by weight, frequent 15 to 60 parts by weight, the reactant of more frequent 25 to 35 parts by weight (3) or the reactant of 10 to 90 parts by weight (4).In the disclosure, the mixture includes reactant (3) and is accredited as anti- Answer other members of at least one of the reactant group of object (1), (2) and (4).Vulcanization reaction is usually adjoint at elevated temperatures It stirs and is optionally carried out in an inert atmosphere in the presence of atent solvent.The vulcanizing agent that can be used for disclosed method includes element Sulphur is preferably the mixture of hydrogen sulfide, halogenation sulphur and vulcanized sodium and hydrogen sulfide and sulphur or sulfur dioxide.In general, every mole 0.5 to 3 mole of sulphur is commonly used in ethylene linkage.Olefine sulfide may also comprise sulfurized oil, such as vegetable oil, lard, oleic acid and alkene Mixture.

The metal salt (xiii) of alkyl salicylate includes long-chain (such as the alkyl-substituted salicylic calcium of C12 to C16) Salt and other salt.

The amine salt (xiv) of alkyl phosphoric acid includes the oil base ester of phosphoric acid and the salt of other long-chain esters and amine as described below.? The useful amine of this respect is tertiary aliphatic primary amine, with trade name Primene^TMIt sells.

In some embodiments, the friction improver is fatty acid or fat oil, the metal salt of fatty acid, fatty acyl Amine, sulfide fat oil or fatty acid, alkylphosphonate, alkylphosphate amine salt；The condensation product of carboxylic acid and polyamines, boration rouge Fat epoxides, fatty imidazolines, or combinations thereof.

In other embodiments, the friction improver can be isostearic acid and the condensation of tetren produces The poly- tetradecyl oxirane of condensation product, boration, the zinc oleate, hydroxyl of object, isostearic acid and 1- [three (methylol)] methylamine 17 alkenyl imidazoline of ethyl -2-, two oil base ester of phosphoric acid hydrogen, phosphoric acid C14-C18 Arrcostab or its amine salt, vulcanized vegetable oil, sulphur Change lard, vulcanization oleic acid, olefine sulfide, oleamide, Monoolein, soybean oil, or mixtures thereof.

In other other embodiments, the friction improver can be Monoolein, oleamide, isostearic acid With the reaction product of 2- amino -2- methylol -1,3- propylene glycol, dehydrated sorbitol mono-fatty acid ester, 9- octadecenoic acid, different hard Acyl amine, the different stearyl ester of single oleic acid or combinations thereof.

Although not needing their presence to obtain the benefit of the disclosure, friction improver can be with lubricant oil composite 0 to 2wt%, preferably 0.01wt% to 1.5wt% use.These ranges are applicable to individually rub present in the composition The amount of modifier or the amount of total friction modifier component in the composition are wiped, the latter may include that two or more frictions change The mixture of property agent.

Many friction improvers tend to also play emulsifier.This often due to friction improver often have it is non- Polarity fat tail portion and polar head group.Emulsifiable property, it is undesirable knot in hydraulic fluid that exactly breaking, which reduces, Fruit, wherein it is desirable to such composition separates with any water holding that the fluid may contact and do not carry any water secretly.This Disclosed friction improver can be used for improving the abrasion resistance of hydraulic fluid, however in some embodiments, it has to be noted that it keeps away It is horizontal to exempt from the friction improver having a negative impact using meeting to the breaking of fluid.

Presence or absence of friction improver, the lubricating oil of the disclosure shows desired property, such as Wear control.

Although not needing their presence to obtain the benefit of the disclosure, useful friction improver concentration can be 0.01 weight % to 5 weight %, or about 0.1 weight % to about 2.5 weight %, or about 0.1 weight % to about 1.5 weight %, or In the range of about 0.1 weight % to about 1 weight %.Concentration containing molybdenum material is often described according to Mo metal concentration.Advantageous Mo Concentration can be in the range of 25ppm to 700ppm or more, and preferred scope is often 50-200ppm.It is all types of to rub Wiping modifier can be used alone or used with the mixture of the material with the disclosure.Often, two or more frictions improve The mixture or friction modifiers of agent and the mixture of optional surface active material and desirable.

Molybdate compound (anti-friction agent)

The illustrative anti-friction agent containing molybdenum that can be used for the disclosure includes the decomposable organic molybdenum of such as oil-soluble, such as Molyvan^TM855, it is defined as the secondary diaryl amine of oil-soluble substantially free of active phosphorus and active sulfur. Molyvan^TM855 in Vanderbilt material data and security table (Vanderbilt's Material Data and Safety Sheet it is described as a kind of organic molybdenum in), density is that the viscosity at 1.04 and 100 DEG C is 47.12cSt.Generally For, organic molybdenum is preferred because of their excellent dissolubilities and validity.

Another illustrative molybdate compound is Molyvan^TML is United States Patent (USP) No.5, described in 055,174 Sulfonation dialkyl dithiophosphoric acid oxygen molybdenum, the United States Patent (USP) are incorporated herein by reference.

By R.T.Vanderbilt Company, Inc., the Molyvan of New York, N.Y., USA manufacture^TMA is also The molybdate compound of bright property, contains about 28.8wt%Mo, 31.6wt%C, 5.4wt%H and 25.9wt%S. Molyvan^TM855、Molyvan^TM822、Molyvan^TM856 and Molyvan^TM807 be also useful.

Sakura Lube^TM500 be also useful, is a kind of more readily soluble lubricant containing molybdenum dithiocarbamate Additive, derived from Asahi Denki Corporation and include about 20.2wt%Mo, 43.8wt%C, 7.4wt%H and 22.4wt%S.Sakura Lube^TM300 be the ratio of molybdenum and sulphur be the low-sulfur molybdenum dithiophosphate of 1:1.07, is that can be used for this Disclosed preferred molybdate compound.

Molyvan^TM807 be also useful, is about 50wt% double tridecyl dithiocarbonic acids molybdenum and about 50wt% ratio Weight is the mixture of about 38.4SUS and the aromatic oil containing about 4.6wt% molybdenum, also by R.T.Vanderbilt manufacture and as anti- Oxidant and antiwear additive sale.

Other sources are molybdenum Mo (Co)₆And molybdenum caprylate, by Aldrich Chemical Company, Milwaukee, Wis. MoO (the C containing about 8wt-%Mo sold₇H₁₅CO₂)₂With by Shephard Chemical Company, The thiocycloalkyl molybdenum caprylate of Cincinnati, Ohio sale.

Inorganic molybdenum compounds such as molybdenum sulfide and molybdenum oxide are obviously not so good as with Molyvan^TM855、Molyvan^TM822、 Molyvan^TM856 and Molyvan^TMThe organic compound of 807 descriptions is preferred.

Such as it is disclosed in U.S. Patent Application Publication No.2003/0119682 and can be used for the illustrative containing molybdenum of the disclosure Object is closed, is incorporated herein by reference.

Organic-molybdenum-nitrogen complex compound is also likely to be beneficial in these formulations.Term " organic-molybdenum nitrogen complex compound " includes beauty Organic-molybdenum nitrogen complex compound described in state patent No.4,889,647.The complex compound is fat oil, diethanol amine and molybdenum source Reaction product.The specified chemical structure of the complex compound is not specified.United States Patent (USP) No.4,889,647 reports the disclosure The infrared spectroscopy of typical reaction product；The amidocarbonylation at ester carbonyl group band and 1620cm 1 at Spectral Identification 1740cm 1 Band.The fat oil is containing at least 12 carbon atoms until the glyceride of the higher fatty acids of 22 carbon atoms or more.Institute Stating molybdenum source is oxygenatedchemicals, such as ammonium molybdate, molybdenum oxide and mixture.

Other organic molybdenum complex compounds that can be used for the disclosure are three cores described in EP 1 040 115 and WO 99/31113 Molybdenum sulfur compound and United States Patent (USP) No.4, molybdenum complex described in 978,464.

Although not needing their presence to obtain the benefit of the disclosure, containing molybdenum additives can be with 0 to 5.0 matter % is measured to use.Preferred dosage is at most 3,000ppm, more preferably in mass about 100ppm to about 2 in mass, 500ppm, more preferably in mass about 300 to about 2,000ppm, more preferable 300 to about 1,500ppm molybdenum in mass.

Boration ester compounds

Can be used for the disclosure illustrative boron-containing compound include such as borate, boric acid, other boron compounds for example Boron oxide.The boron compound is hydrolysis-stable and sends out for improving wear resistence, and as copper bearing and other metals Motivation component get rusty and corrosion inhibitor.The boration ester compounds serve as the inhibitor of metal erosion to prevent iron eka-gold Belong to or the corrosion of non-ferrous metal (such as copper, bronze, brass, titanium, aluminium etc.) or both, is deposited with effective concentration for inhibiting corrosion ?.

The patent for describing the technology of the basic salt for manufacturing sulfonic acid, carboxylic acid and its mixture includes United States Patent (USP) No.5,354,485；2,501,731；2,616,911；2,777,874；3,384,585；3,320,162；3,488,284；With 3, 629,109.Disclosures of these patents are incorporated herein by reference.The method for preparing boration overbased compositions sees beauty State patent No.4,744,920；4,792,410；With PCT Publication WO 88/03144.The disclosure of these references are herein It is incorporated by reference into.The oil-soluble of alkali metal salt or alkali salt is neutral or basic salt can also be reacted with boron compound.

The illustrative borate used in the disclosure by Exxon-Mobil USA with name of product (" MCP 1286 ") and MOBIL ADC700 manufacture.Test data shows that using viscosity of the D-445 method at 100 DEG C be 2.9cSt；Use the side D-445 Viscosity of the method at 40 DEG C is 11.9；Flash-point using D-93 method is 146；Pour point using D-97 method is -69；And it is logical Crossing the boron percentage that ICP method determines is 5.3%., the boration ester sold as wear-resistant/antiwear additive and anti-friction agent (Vanlube^TMIt 289) is the preferred boric acid ester that can be used in the disclosure.

The illustrative borate that can be used for the disclosure is by making about 1 mole of fat oil, about 1.0 to 2.5 moles of diethanols The reaction product that amine is reacted, then obtained with boric acid subsequent reactions with obtaining about 0.1 to 3 quality % boron.Think the reaction Product may include one or both of following two main component, and when reaction is pushed to fully hydrated, what other were listed Component is possible component:

Wherein R₁=H or C_xH_y, wherein x=1 to 60, and y=3 to 121

Wherein Y indicates fat oil residue.Preferred fat oil is the sweet of the higher fatty acids containing at least 12 carbon atoms Grease and carbon atom containing 22 carbon atoms or more.Such ester is commonly referred to as vegetable oil and animal oil.Especially have Vegetable oil is derived from the oil of coconut, corn, cottonseed, linseed, peanut, soybean and sunflower seed.Similarly, can make With animal tallow oil such as butter.

The boron source be boric acid or provide boron and can be reacted with the intermediate reaction product of fat oil and diethanol amine with Form the material of borate composition.

Although above-mentioned organic boric acid ester composition has been specifically discussed above, it is understood that, other organic boric acid esters Composition should also play the function of similar effect, such as institute in U.S. Patent Application Publication No.2003/0119682 in the disclosure Those of illustrate, which is incorporated herein by reference.In addition, the dispersion of borate salts such as potassium borate It can be useful.

Other the illustrative organic boric acid ester/salt composites that can be used for the disclosure are disclosed in such as U.S. Patent Application Publication In No.2008/0261838, which is incorporated herein by reference.

In addition, disclosing other the illustrative organic acid esters/salt composites that can be used for the disclosure, such as United States Patent (USP) No.4,478,732, United States Patent (USP) No.4,406,802, United States Patent (USP) No.4,568,472 boration mixing hydroxy ester, alcoxyl Base amide and amine；The boration hydroxyethyl imidazole quinoline of United States Patent (USP) No.4,298,486；United States Patent (USP) No.4,328,113's Borated alkyl amine and alkyl diamine；United States Patent (USP) No.4,370,248 boration hydroxyl ester, including GMO；United States Patent (USP) The boration hydroxyl alkyl oxazoline of No.4,374,032；The boration sorbitan of United States Patent (USP) No.4,376,712 Ester；The boration ethoxylated amine of United States Patent (USP) No.4,382,006；The amide ethoxylates of United States Patent (USP) No.4,389,322 And its borate；The alkyl vicinal diols and pure and mild ester admixture and its borate of United States Patent (USP) No.4,472,289；The U.S. The borate of the hydrolysis hydrocarbyl epoxides of patent No.4,522,734；The ether diamine boric acid of United States Patent (USP) No.4,537,692 Ester；The mixture for replacing ester and its borate containing vicinal diols and hydroxyl of United States Patent (USP) No.4,541,941；United States Patent (USP) The boration mixture of the borate of the various hydroxyls and/or nitrogen of No.4,594,171；And United States Patent (USP) No.4,692, 257 various boration alcohol/glycol, the United States Patent (USP) are incorporated herein by reference.

Although not needing their presence to obtain the benefit of the disclosure, boron-containing compound can with 0 to 10.0%, More preferably from about 0.01% to about 5%, and most preferably from about 0.1% to about 3.0% uses.Effective element boron range is most 1000ppm is lower than 1% element boron.Therefore, the preferred concentration of element boron is 100 to 1000ppm, more preferable 100 to 300ppm.

When lubricant oil composite contains one or more above-mentioned additives, the additive is to be enough to make it to execute its The amount of predetermined function is admixed in the composition.The such additive that can be used in the disclosure is shown in following table 3 Typical amount.

It should be noted that many additives are as dense containing one or more additives and a certain amount of base oil diluent Contracting object is shipped from additive manufacturer there.Therefore the weight metering in following table 3 and other amounts referred to herein, Refer to the amount of active constituent (that is, non-diluted dose of part of the ingredient).The weight percent (wt%) being indicated below is to be based on The total weight of lubricant oil composite.

Table 3

The typical amount of industrial lubrication oil ingredient

Aforementioned additive is entirely commercially available material.These additives can be added independently, but usually combination exists in advance It can be from the packaging that lube oil additive supplier obtains.Additive packing with various composition, ratio and characteristic is existing At, select packaging appropriate to consider the indispensable purposes of final composition.

Following non-limiting embodiment is provided to illustrate the disclosure.

Embodiment

Prepare the preparation containing ingredient described in Fig. 1 and 2.All the components used herein are all commercially available.

Base oil used in preparation is described in Fig. 1 and 2.Additive and addition used in preparation are described in Fig. 2 Agent system.

Base oil used in preparation covers a series of chemical types and API oil base stock classification.Base oil include by Fischer-Tropsch (GTL) technique those of is made, low viscosity polyalphaolefin (PAO), synthetic ester (phthalic acid ester and polyalcohol) and alkane Base naphthalene (AN).

Additive system used in preparation includes the conventional additives of convention amount.Conventional additives used in preparation are Antioxidant, dispersing agent, pour point depressant, detergent, corrosion inhibitor, metal deactivator, seal compatibility additive, defoaming Agent, inhibitor, rust-inhibiting additive, optional friction improver, optional antiwear additive and other optional lubricant properties One of additive is a variety of.

The turbine oil specification of known manufacturer is also described in order to compare, in Fig. 1, it is shown that narrow model needed for lubricant Enclose property: the minimum permission viscosity including 28.8cSt at 40 DEG C.

The property of preparation is determined according to the ASTM program identified in Fig. 1 and 3.The property of preparation is listed in Fig. 1 and 3.

In Fig. 1 and Fig. 3, is reduced using low-loss " bearing test-bed test " assessment bearing temperature, be converted into calculating Efficiency benefits.Bearing test-bed test tilts pad bearing using scaled standard 4, using flooded lubrication.Bearing housing is matched There is resistance temperature detector, to measure the introducing and discharge temperature of lubricant.Apply axle speed and bearing load with specific combination, It is consistent with the typical operation conditions of power generation turbine.Then the lubricant measured under specific speed and load is used to introduce and arrange Temperature calculates the power loss of test lubricant out.

Using three kinds of different commercial additive systems, performance characteristics, such as combustion gas are provided for different purposes of turbine application Turbine use and combined cycle steam and combustion gas turbine application.It is led it is well known that reducing lubricant viscosity and would generally reduce Gravitation and churning loss, this may be to determine that full film floods the most important factor of contact (such as in turbine bearing(s)).

In fact, the MV minium viscosity lubricant in this test is (real compared with the commercial product (comparative example 1) of typical viscosities Apply example 4) show slight efficiency benefits.However, the lubricant of the MV minium viscosity does not provide most significant energy conservation.Make us Surprisingly, as shown in Figure 1, the embodiment of the present invention 1-3 all shows the efficiency benefits much higher than embodiment 4.

The key performance criteria of candidate includes the improved efficiency that display is greater than 15% while meeting claimed below: being dodged Point is greater than 215 DEG C；Absolute maximum evaporation loss is less than 4%；Balance low viscosity candidate with low specific heat/low-density；And it ties up Hold all bearing protections and lubricant requirement.

With previous understanding on the contrary, these for turbine oil the results show that only reducing viscosity and being not enough to realize significantly Improved efficiency.Viscosity is with volatility and the balance of density requirements for realizing that unexpected efficiencies are important.Data Statistical analysis for establishing the relationship of the new parameter lubricating efficiency factor, it is following to determine:

The lubricating efficiency factor=[19.200 (specific heat)]-[6.679 (evaporation loss)]-[1.028 (dynamic viscosity)]- 12.178。

Candidate of the lubricating efficiency factor greater than 10 is shown totally more in Fig. 1 and bearing test result shown in Fig. 3 Good efficiency gain.Furthermore, it is possible to add V class oil base stock to further increase these attribute of performance, and turbine is provided and is answered Additive dissolving power and sediment monitoring necessary to middle reliability.

PCT and EP clause:

1. a kind of lubricating oil has and adds comprising lube oil base stocks as main component and one or more lubricating oil Add composition of the agent as accessory constituent, wherein the lubricating oil have according to ASTM D445 be 40 DEG C at 16cSt to 22cSt's Kinematic viscosity, the density for being 0.8g/ml to 0.9g/ml according to ASTM D1298, and according to ASTM D972 for less than 4% Absolute evaporation loss at 150 DEG C.

2. a kind of improve energy in the turbomachinery with the oil lubrication as lubricating oil by using formulated oil The method of efficiency, the formulated oil, which has, adds comprising lube oil base stocks as main component and one or more lubricating oil Composition of the agent as accessory constituent, wherein the fortune that it is 16cSt to 22cSt at 40 DEG C according to ASTM D445 that the formulated oil, which has, Kinetic viscosity, according to ASTM D1298 be 0.8g/ml to 0.9g/ml density, and according to ASTM D972 be less than 4% 150 Absolute evaporation loss at DEG C.

3. it is a kind of improve dissolubility of the polar emollient oil additive in non-polar lubricant oil base oil material, compatibility and/ Or the method for dispersibility, which comprises

It provides comprising non-polar lubricant oil base oil material as main component and one or more polar emollient oil additives As the lubricating oil of accessory constituent, wherein the fortune that it is 16cSt to 22cSt at 40 DEG C according to ASTM D445 that the lubricating oil, which has, Kinetic viscosity, according to ASTM D1298 be 0.8g/ml to 0.9g/ml density, and according to ASTM D972 be less than 4% 150 Absolute evaporation loss at DEG C；And

At least one auxiliary oil base stock is blended in the lubricating oil.

4. a kind of method for improving energy efficiency in turbomachinery, which comprises

It selects comprising non-polar lubricant oil base oil material as main component and one or more polar emollient oil additives As the lubricating oil of accessory constituent, wherein the lubricating oil has 3.0J/g DEG C to 3.3J/g DEG C of specific heat, according to ASTM D972 is absolutely evaporation loss and the fortune for being 16cSt to 22cSt at 40 DEG C according to ASTM D445 at 150 DEG C less than 4% Kinetic viscosity；And

The non-polar lubricant oil base oil material is wherein selected, so that according to the following formula, the lubricating oil has at least about 10 The lubricating efficiency factor:

5. the method for the lubricating oil and clause 2-4 of clause 1, wherein it is small that the lubricating oil, which also has according to ASTM D5800, It is flash-point greater than 215 DEG C and 3.0J/g DEG C to 3.3J/g DEG C according to ASTM D92 in 15% Noack volatility Specific heat.

6. the method for the lubricating oil and clause 2-4 of clause 1, wherein the lubricating oil is turbine lube oil.

7. the method for the lubricating oil and clause 2-4 of clause 1, wherein the lube oil base stocks include I class base oil, II Or mixtures thereof class base oil, Group III base oil, IV class base oil, V class base oil.

8. the method for the lubricating oil and clause 2-4 of clause 1, wherein the lubricating oil also includes at least one auxiliary base oil Material.

9. the method for the lubricating oil and clause 2-4 of clause 1, wherein one or more lube oil additives include defoaming Agent, demulsifier, antioxidant, antiwear additive or rust-inhibiting additive.

10. the method for the lubricating oil and clause 2-4 of clause 1, wherein one or more lube oil additives further include Viscosity modifier, detergent, dispersing agent, pour point depressant, corrosion inhibitor, metal deactivator or inhibitor.

11. the method for the lubricating oil and clause 2-4 of clause 1, wherein the lube oil base stocks are selected, so that when passing through When efficiency of bearing bench run is evaluated, compared with the identical lubricating oil for being formulated into ISO VG 32, the lubricating oil is shown At least 10% energy efficiency improves.

12. the method for the lubricating oil and clause 2-4 of clause 1, wherein the lube oil base stocks are selected, so that under Formula, the lubricating oil have at least 10 lubricating efficiency factor:

13. the method for the lubricating oil and clause 2-4 of clause 1, wherein in turbomachinery, have with using according to ASTM D445 is the kinematic viscosity of 16cSt to 22cSt but not have according to ASTM D1298 be 0.8g/ml to 0.9g/ml's at 40 DEG C Density or the energy efficiency phase realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than 4% Than energy efficiency is improved.

14. the method for the lubricating oil and clause 2-4 of clause 1, wherein in turbomachinery, have with using according to ASTM D445 is the kinematic viscosity of 16cSt to 22cSt but not have according to ASTM D1298 be 0.8g/ml to 0.9g/ml's at 40 DEG C Density or the bearing temperature phase realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than 4% Than bearing temperature reduces.

15. the method for the lubricating oil and clause 2-4 of clause 1, wherein in turbomachinery, have with using according to ASTM D445 is the kinematic viscosity of 16cSt to 22cSt but not have according to ASTM D1298 be 0.8g/ml to 0.9g/ml's at 40 DEG C Density or the energy efficiency realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than 4% are sunk Product object control is compared with lube oil additive dissolving power, and energy efficiency is improved and sediment monitoring and lube oil additive Dissolving power is maintained or is improved.

All patents and patent applications for quoting herein, test procedure (such as ASTM method, UL method etc.) and its He is sufficiently combined file by reference, and reaching such disclosure, inconsistent and such combination is all not with the disclosure The degree of judiciary's license.

When listing numerical lower limits and numerical upper limits herein, it is contemplated to from any lower limit to the range of any upper limit. Although the illustrated embodiment of the disclosure has had been described in detail, it should be appreciated that various other modifications will be art technology Personnel are without departing substantially under spirit and scope of the present disclosure obvious and can make easily.Therefore, be not intended to by The range of this attached claims is limited to the embodiment and description illustrated herein, but the claim should be interpreted that The feature for covering all patentable novelties being present in the disclosure, including will be by disclosure fields All features that technical staff treats as its equivalent features.

Numerous embodiments are had been made with reference to above and specific embodiment describes the disclosure.It is retouched in detail in view of above It states, has prompted many variations to those skilled in the art.All variations obvious in this way are in the complete of appended claims Within desired extent.

Claims

1. a kind of lubricating oil has comprising lube oil base stocks as main component and one or more lube oil additives As the composition of accessory constituent, wherein the lubricating oil have according to ASTM D445 be at 40 DEG C about 16cSt to about 22cSt's Kinematic viscosity is density of the about 0.8g/ml to about 0.9g/ml according to ASTM D1298, and according to ASTM D972 be less than about Absolute evaporation loss at 150 DEG C of 4%.

2. lubricating oil according to claim 1, also having according to ASTM D5800 is the Noack volatilization less than about 15% Degree, the flash-point for being greater than about 215 DEG C according to ASTM D92, and about 3.0J/g DEG C to about 3.3J/g DEG C of specific heat.

3. lubricating oil according to claim 1, wherein in turbomachinery, with use have according to ASTM D445 be 40 The kinematic viscosity of about 16cSt to about 22cSt but not have according to ASTM D1298 be about 0.8g/ml to about 0.9g/ml at DEG C Density or the energy efficiency phase realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4% Than energy efficiency is improved.

4. lubricating oil according to claim 1, wherein in turbomachinery, with use have according to ASTM D445 be 40 The kinematic viscosity of about 16cSt to about 22cSt but not have according to ASTM D1298 be about 0.8g/ml to about 0.9g/ml at DEG C Density or the bearing temperature phase realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4% Than bearing temperature reduces.

5. lubricating oil according to claim 1, wherein in turbomachinery, with use have according to ASTM D445 be 40 The kinematic viscosity of about 16cSt to about 22cSt but not have according to ASTM D1298 be about 0.8g/ml to about 0.9g/ml at DEG C Density or the energy efficiency realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4%, Sediment monitoring is compared with lube oil additive dissolving power, and energy efficiency is improved and sediment monitoring and lubricating oil add Agent dissolving power is maintained or is improved.

6. lubricating oil according to claim 1 is turbine lube oil.

7. lubricating oil according to claim 1, wherein the lube oil base stocks include I class base oil, II class basis Or mixtures thereof oil, Group III base oil, IV class base oil, V class base oil.

8. lubricating oil according to claim 1 also includes at least one auxiliary oil base stock.

9. lubricating oil according to claim 1, wherein one or more lube oil additives include defoaming agent, demulsification Agent, antioxidant, antiwear additive or rust-inhibiting additive.

10. lubricating oil according to claim 9, wherein one or more lube oil additives further include viscosity-adjusting agent Agent, detergent, dispersing agent, pour point depressant, corrosion inhibitor, metal deactivator or inhibitor.

11. lubricating oil according to claim 1, wherein the total weight based on lubricating oil, the lube oil base stocks with The amount of about 90 weight % to about 99 weight % exists.

12. lubricating oil according to claim 1, wherein the total weight based on lubricating oil, one or more lubricating oil Additive exists with the amount of about 0.1 weight % to about 10 weight %.

13. lubricating oil according to claim 1, wherein the lube oil base stocks are selected, so that imitating when by bearing When rate bench run is evaluated, compared with the identical lubricating oil for being formulated into ISO VG 32, the lubricating oil is shown at least 10% energy efficiency improves.

14. lubricating oil according to claim 1, wherein the lube oil base stocks are selected, so that according to the following formula, it is described Lubricating oil has at least 10 lubricating efficiency factor:

The lubricating efficiency factor=[19.200 (specific heat)]-[6.679 (evaporation loss)]-[1.028 (dynamic viscosity)] -12.178.

15. a kind of improve energy efficiency in the turbomachinery with the oil lubrication as lubricating oil by using formulated oil Method, the formulated oil have comprising lube oil base stocks as main component and one or more lube oil additives work For the composition of accessory constituent, wherein the fortune that it is about 16cSt to about 22cSt at 40 DEG C according to ASTM D445 that the formulated oil, which has, Kinetic viscosity is density of the about 0.8g/ml to about 0.9g/ml according to ASTM D1298, and according to ASTM D972 be less than about Absolute evaporation loss at 150 DEG C of 4%.

16. according to the method for claim 15, wherein the lubricating oil also have according to ASTM D5800 be less than about 15% Noack volatility is greater than about 215 DEG C of flash-point according to ASTM D92, and about 3.0J/g DEG C to about 3.3J/ G DEG C of specific heat.

17. according to the method for claim 15, wherein in turbomachinery, with use have according to ASTM D445 be 40 The kinematic viscosity of about 16cSt to about 22cSt but not have according to ASTM D1298 be about 0.8g/ml to about 0.9g/ml at DEG C Density or the energy efficiency phase realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4% Than energy efficiency is improved.

18. according to the method for claim 15, wherein in turbomachinery, with use have according to ASTM D445 be 40 The kinematic viscosity of about 16cSt to about 22cSt but not have according to ASTM D1298 be about 0.8g/ml to about 0.9g/ml at DEG C Density or the bearing temperature phase realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4% Than bearing temperature reduces.

19. according to the method for claim 15, wherein in turbomachinery, with use have according to ASTM D445 be 40 The kinematic viscosity of about 16cSt to about 22cSt but not have according to ASTM D1298 be about 0.8g/ml to about 0.9g/ml at DEG C Density or the energy efficiency realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4%, Sediment monitoring is compared with lube oil additive dissolving power, and energy efficiency is improved and sediment monitoring and lubricating oil add Agent dissolving power is maintained or is improved.

20. according to the method for claim 15, wherein the lubricating oil is turbine lube oil.

21. according to the method for claim 15, wherein the lube oil base stocks include I class base oil, II class basis Or mixtures thereof oil, Group III base oil, IV class base oil, V class base oil.

22. according to the method for claim 15, wherein the lubricating oil also includes at least one auxiliary oil base stock.

23. according to the method for claim 15, wherein one or more lube oil additives include defoaming agent, demulsification Agent, antioxidant, antiwear additive or rust-inhibiting additive.

24. according to the method for claim 23, wherein one or more lube oil additives further include viscosity-adjusting agent Agent, detergent, dispersing agent, pour point depressant, corrosion inhibitor, metal deactivator or inhibitor.

25. according to the method for claim 15, wherein the total weight based on lubricating oil, the lube oil base stocks are with about The amount of 90 weight % to about 99 weight % exists.

26. according to the method for claim 15, wherein the total weight based on lubricating oil, one or more lubricating oil add Agent is added to exist with the amount of about 0.1 weight % to about 10 weight %.

27. according to the method for claim 15, wherein the turbomachinery is combustion gas turbine or comprising combustion gas turbine With the combined cycle of steam turbine.

28. according to the method for claim 15, wherein selecting the lube oil base stocks, so that when passing through efficiency of bearing When bench run is evaluated, compared with the identical lubricating oil for being formulated into ISO VG 32, the lubricating oil shows at least 10% Energy efficiency improve.

29. according to the method for claim 15, wherein selecting the lube oil base stocks, so that according to the following formula, it is described Lubricating oil has at least 10 lubricating efficiency factor:

30. it is a kind of improve dissolubility of the polar emollient oil additive in non-polar lubricant oil base oil material, compatibility and/or point Dissipate the method for property, which comprises

It provides comprising non-polar lubricant oil base oil material as main component and one or more polar emollient oil additive conducts The lubricating oil of accessory constituent, wherein the fortune that it is about 16cSt to about 22cSt at 40 DEG C according to ASTM D445 that the lubricating oil, which has, Kinetic viscosity is density of the about 0.8g/ml to about 0.9g/ml according to ASTM D1298, and according to ASTM D972 be less than about Absolute evaporation loss at 150 DEG C of 4%；And

At least one auxiliary oil base stock is blended in the lubricating oil.

31. according to the method for claim 30, wherein the lubricating oil also have according to ASTM D5800 be less than about 15% Noack volatility is greater than about 215 DEG C of flash-point according to ASTM D92, and about 3.0J/g DEG C to about 3.3J/ G DEG C of specific heat.

32. according to the method for claim 30, wherein in turbomachinery, with use have according to ASTM D445 be 40 The kinematic viscosity of about 16cSt to about 22cSt but not have according to ASTM D1298 be about 0.8g/ml to about 0.9g/ml at DEG C Density or dissolubility, the phase realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4% Capacitive and/or dispersibility are compared, and dissolubility, compatibility and/or dispersibility are improved.

33. according to the method for claim 30, wherein in turbomachinery, with use have according to ASTM D445 be 40 The kinematic viscosity of about 16cSt to about 22cSt but not have according to ASTM D1298 be about 0.8g/ml to about 0.9g/ml at DEG C Density or dissolubility, the phase realized according to ASTM D972 for the lubricating oil of evaporation loss absolute at 150 DEG C less than about 4% Capacitive and/or dispersibility and sediment monitoring are compared, and dissolubility, compatibility and/or dispersibility are improved and deposit Control is maintained or is improved.

34. according to the method for claim 30, wherein the lubricating oil is turbine lube oil.

35. according to the method for claim 30, wherein the lube oil base stocks include I class base oil, II class basis Or mixtures thereof oil, Group III base oil, IV class base oil, V class base oil.

36. according to the method for claim 30, wherein the auxiliary oil base stock of at least one is the auxiliary oil base stock of polarity.

37. according to the method for claim 30, wherein one or more lube oil additives include defoaming agent, demulsification Agent, antioxidant, antiwear additive or rust-inhibiting additive.

38. according to the method for claim 30, wherein one or more lube oil additives further include viscosity-adjusting agent Agent, detergent, dispersing agent, pour point depressant, corrosion inhibitor, metal deactivator or inhibitor.

39. according to the method for claim 30, wherein the total weight based on lubricating oil, the lube oil base stocks are with about The amount of 80 weight % to about 99 weight % exists.

40. according to the method for claim 30, wherein the total weight based on lubricating oil, one or more lubricating oil add Agent is added to exist with the amount of about 0.1 weight % to about 10 weight %.

41. a kind of method for improving energy efficiency in turbomachinery, which comprises

It selects comprising non-polar lubricant oil base oil material as main component and one or more polar emollient oil additive conducts The lubricating oil of accessory constituent, wherein the lubricating oil has about 3.0J/g DEG C to about 3.3J/g DEG C of specific heat, according to ASTM D972 be at 150 DEG C less than about 4% absolutely evaporation loss and according to ASTM D445 be at 40 DEG C about 16cSt to about The kinematic viscosity of 22cSt；And

The non-polar lubricant oil base oil material is wherein selected, so that according to the following formula, the lubricating oil has at least 10 lubrication Efficiency factor:

42. according to the method for claim 41, wherein the turbomachinery is combustion gas turbine or comprising combustion gas turbine With the combined cycle of steam turbine.