CN109072120A - Lubricant compositions based on polyalkylene glycol - Google Patents

Lubricant compositions based on polyalkylene glycol Download PDF

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Publication number
CN109072120A
CN109072120A CN201780017740.8A CN201780017740A CN109072120A CN 109072120 A CN109072120 A CN 109072120A CN 201780017740 A CN201780017740 A CN 201780017740A CN 109072120 A CN109072120 A CN 109072120A
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indicates
alkyl group
group
formula
branch
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劳拉·布鲁坦
尼古拉斯·奥布雷赫特
纳贾特·凯利吉-叙德迈尔
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TotalEnergies Marketing Services SA
Dow Global Technologies LLC
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Total Marketing Services SA
Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
    • C10M2209/1065—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • C10M2209/1075—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106 used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
    • C10M2209/1085—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines

Abstract

This application involves a kind of lubricant compositions, it includes :-it is selected from the oil of polyalkylene glycol (PAG)；With-selected from formula (I) compound antiwear additive

Description

Lubricant compositions based on polyalkylene glycol
This application involves the fields of lubricating composition, in particular for vehicle engine, especially motorized traffic work Has the field of the lubricating composition of engine.Particularly, especially motor-driven this application involves for lubricating vehicle engine The lubricating composition based on poly- alkylation glycol (PAG or polyalkylene glycol) of the vehicles.
The energy efficiency of motor car engine and reduced fuel consumption more and more attention has been paid to.It is known that motor-driven Engine lubricant used in the vehicles plays a significant role in this regard.
In order to prepare economical fuel lubricant or saving of fuel agent (economizers), it is known that using being used Lubricating substance (lubricating base) viscosity.It is also known that viscosity index (VI) (VI) is improved using polymer, or It uses friction regulator (friction modifier) (MF).However, the polymer for improving viscosity index (VI), which has to reduce, wherein to be made The shortcomings that with the Engine Cleanliness Level of their lubricating composition.However, current engine, which has, to be caused significantly to deposit now The high thermal stress of elephant.With the component near combustion chamber and therefore deposit is that the chemistry of lubricant in most hot component turns Change related.
Fuel economy lubricating composition based on PAG is described in document WO 2013/164449, wherein group Closing object also has the good property for engine.
However, the use of these PAG there may come a time when that the abrasion for the mechanical part for leading to engine increases, and therefore reduce The service life of the engine.
Thus it is of interest that lubricating composition is provided, in particular for the lubricating combination of automotive engine Object, to overcome all or part of disadvantage of the prior art.
It is an object of the present invention to provide the lubricating compositions based on PAG, especially start for automotive The lubricating composition based on PAG of machine, the composition provide improved wear-resistant property.
It is a further object to provide the lubricating compositions based on PAG, especially send out for automotive The lubricating composition based on PAG of motivation, the composition provide improved wear-resistant property and satisfactory fuel economy Both matter.
It is a further object to provide the lubricating compositions based on PAG, in particular for automotive hair The PAG lubricating composition of motivation, the composition provide improved wear-resistant property and do not reduce Engine Cleanliness Level.
It is a further object to provide the lubricating compositions based on PAG, in particular for automotive hair The PAG lubricating composition of motivation, the composition provide improved wear-resistant property and satisfactory fuel economy property, simultaneously Do not reduce Engine Cleanliness Level.
It is a further object to provide the lubricating compositions based on PAG, especially send out for automotive The lubricating composition based on PAG of motivation, the composition provide improved wear-resistant property and are easy to prepare.
In order to realize above object and overcome the shortcomings that mentioning in the prior art, the invention proposes lubricating combinations Object, the composition include:
It is selected from the oil of poly- alkyl diol (PAG or polyalkylene glycol), and
The antiwear additive of compound selected from formula (I)
Wherein can be identical or different R1 and R2 independently indicates comprising the carbon atom from 2 to 7, preferably from 3 The secondary alkyl group of a straight chain to 6 carbon atoms or the secondary alkyl group of branch.
In the context of the present invention, term is " secondary comprising the secondary alkyl of the straight chain of carbon atom from 2 to 7 or branch Alkyl " is understood to imply the alkyl that the O for being selected to be attached to it forms secondary alcohol.
Particularly advantageously, lubricating composition of the invention is to be used for engine, the preferably vehicles, more preferably motor-driven The lubricating composition of the vehicles.
According to the present invention, the PAG of lubricating composition according to the present invention can be block polymer or atactic polymer.
PAG according to the present invention includes alkyl group, and the length of hydrocarbon chain can change.According to the present invention, the length of hydrocarbon chain Degree is defined by carbon atom number purpose average value.
Preferably, the PAG of composition according to the present invention is the block polymer of formula (II) or the atactic polymerization of formula (II) Object
Wherein:
The C of-R3 expression straight chain1-C30The C of alkyl group or branch1-C30Alkyl group, the preferably C of straight chain4-C12- The C of alkyl group or branch4-C12Alkyl group；
- n indicates range from 2 to 60, preferably from 5 to 30 or from 7 to 15 number；
Identical or different R4 and R5 independently indicates hydrogen atom or C1-C2Alkyl group.
For PAG according to the present invention, n can indicate range from 2 to 60, preferably range from 5 to 30 or from 7 to 15 Number.
The C of straight chain is indicated for preferred PAG according to the present invention, R34-C12The C of alkyl group or branch4-C12Alkane Base group, R4 and R5 is different and independently indicates the C of hydrogen atom or straight chain1-C2Alkyl group, and n indicate range from 7 to 15 number.
It is further preferred that the PAG of composition according to the present invention be formula (IIA) block polymer or formula (IIA) it is random Polymer
Wherein:
The C of-R3 expression straight chain1-C30The C of alkyl group or branch1-C30Alkyl group, the preferably C of straight chain4-C12- The C of alkyl group or branch4-C12Alkyl group；
- m indicates range from 2 to 60, preferably from 5 to 30 or from 7 to 15 number；
- R6 and R7 indicates hydrogen atom；Or R6 indicates hydrogen atom and R7 indicates methyl group；Or R6 indicates methyl group simultaneously And R7 indicates hydrogen atom；Or R6 and R7 indicates methyl group；Or R6 indicates ethyl group and R7 indicates hydrogen atom；Or R6 is indicated Hydrogen atom and R7 expression ethyl group.
For PAG according to the present invention, m can indicate range from 2 to 60, preferably range from 5 to 30 or from 7 to 15 Number.
The C of straight chain is indicated for preferred PAG according to the present invention, R34-C12The C of alkyl group or branch4-C12Alkane Base group, R6 and R7 is different and independently indicates hydrogen atom, methyl group or ethyl group, and m indicates range from 7 to 15 Number.
It is further preferred that the PAG of composition according to the present invention be formula (IIB) block polymer or formula (IIB) it is random Polymer
Wherein:
The C of-R3 expression straight chain1-C30The C of alkyl group or branch1-C30Alkyl group, the preferably C of straight chain4-C12- The C of alkyl group or branch4-C12Alkyl group, the more preferably C of straight chain8-C12The C of alkyl group or branch8-C12Alkyl Group；
- p and q independently indicates range from 1 to 30, preferably from 2 to 15 or from 2 to 8 number；
- R8 and R9 indicates hydrogen atom；Or R8 indicates hydrogen atom and R9 indicates methyl group；Or R8 indicates methyl group simultaneously And R9 indicates hydrogen atom；Or R8 and R9 indicates methyl group；Or R8 indicates ethyl group and R9 indicates hydrogen atom；Or R8 is indicated Hydrogen atom and R9 expression ethyl group；
- R10 and R11 indicates hydrogen atom；Or R10 indicates hydrogen atom and R11 indicates methyl group；Or R10 indicates methyl Group and R11 expression hydrogen atom；Or R10 and R11 indicates methyl group；Or R10 indicates ethyl group and R11 indicates that hydrogen is former Son；Or R10 indicates hydrogen atom and R11 indicates ethyl group.
For PAG according to the present invention, p and q can independently indicate range from 1 to 30, preferably from 2 to 15 or from 2 To 8 number.
As special PAG according to the present invention, it can be mentioned that:
Wherein R8, R9, R10 and R11 indicate the PAG of hydrogen atom；Or
Wherein R8 and R10 indicates hydrogen atom and R9 and R11 indicates the PAG of methyl group；Or
Wherein R8 and R10 indicates hydrogen atom and R9 and R11 indicates the PAG of ethyl group；Or
Wherein R8 and R10 indicates hydrogen atom, and R9 indicates methyl group and R11 indicates the PAG of ethyl group；Or
Wherein R8 and R10 indicates hydrogen atom, and R9 indicates ethyl group and R11 indicates the PAG of methyl group；Or
Wherein R8, R9 and R11 indicate hydrogen atom and R10 indicates the PAG of methyl group；Or
Wherein R8, R10 and R11 indicate hydrogen atom and R9 indicates the PAG of methyl group.
The C of straight chain is indicated for preferred PAG according to the present invention, R34-C12The C of alkyl group or branch4-C12Alkane Base group, R8, R10 and R11 indicate hydrogen atom and R9 indicates that methyl group, p indicate range from 3 to 5, such as 4.5 number, And q indicates range from 1 to 3, such as 2 number.
The C of straight chain is indicated for preferred PAG according to the present invention, R38-C12The C of alkyl group or branch8-C12- Alkyl group, R8 indicates hydrogen atom and R9 indicates methyl group, and R10 indicates hydrogen atom and R11 indicates ethyl group.P table From 3 to 8, such as 5 number is enclosed in demonstration, and q indicates range from 3 to 8, such as 4 number.
It is highly preferred that the PAG of composition according to the present invention be formula (III) block polymer or formula (III) it is random Polymer
Wherein:
The C of-R3 expression straight chain4-C12The C of alkyl group or branch4-C12Alkyl group, the preferably C of straight chain4Alkyl The C of group or branch4Alkyl group；
- p indicates range from 1 to 30, preferably from 2 to 15 or from 2 to 8 number；
- q indicates range from 1 to 30, preferably from 1 to 10 number.
The example of PAG as formula (III), it can be mentioned that by the commercially available Synalox of Dow ChemicalSeries (rang) product.
Most particularly preferably, the PAG of composition according to the present invention is the block polymer of formula (IV) or the nothing of formula (IV) Advise polymer
Wherein:
The C of-R3 expression straight chain8-C12The C of alkyl group or branch8-C12Alkyl group；
The number of-p expression range from 2 to 6；
The number of-q expression range from 2 to 5；
PAG for composition according to the present invention can be prepared by following: be made at least one comprising from 1 to 30 Then the alcohol type initiator of a carbon atom reacts and with the epoxy bond of one or more of alkylene oxides (alkylene oxide) Reaction carries out (propagation) to obtain these polymer.Preferred alkylene oxide is ethylene oxide, propylene oxide and epoxy Butane.The method of the PAG of formula (IV) is used to prepare in international patent application WO-2012/070007 or in international patent application It is described in WO-2013/164449.
Most particularly preferably, the PAG of composition according to the present invention be formula (V) block polymer or formula (V) it is random Polymer
Wherein:
The C of-R3 expression straight chain4-C12The C of alkyl group or branch4-C12Alkyl group, the preferably C of straight chain4Alkyl The C of group or branch4Alkyl group；
- r indicates range from 2 to 60, preferably from 5 to 30 or from 7 to 15 number.
The example of PAG as formula (III), it can be mentioned that by the commercially available Synalox of Dow ChemicalSeries Product.
It is highly preferred that PAG is the block polymer of formula (VI) or the atactic polymer of formula (VI)
Wherein:
The C of-R12 expression straight chain1-C30The C of alkyl group or branch1-C30Alkyl group, the preferably C of straight chain8-C15- The C of alkyl group or branch8-C15Alkyl group；
- s and t independently indicates the average of range from 1 to 5.
For preferred PAG according to the present invention, R12 indicates group selected from the following: the C of straight chain8Alkyl group；Branch The C of chain8Alkyl group；The C of straight chain9Alkyl group；The C of branch9Alkyl group；The C of straight chain10Alkyl group；Branch C10Alkyl；The C of straight chain11Alkyl group；The C of branch11Alkyl group；The C of straight chain12Alkyl group；The C of branch12Alkyl Group；The C of straight chain13Alkyl group；The C of branch13Alkyl group；The C of straight chain14Alkyl group；The C of branch14Alkyl base Group；The C of straight chain15Alkyl group；The C of branch15Alkyl group.
For preferred PAG according to the present invention:
- s is greater than or equal to t；Or
The average of-s expression range from 2 to 4.5；Or
The average of-t expression range from 1.5 to 4.
For preferred PAG according to the present invention:
The average of-s expression range from 2.5 to 3.5；Or
The average of-t expression range from 2 to 3.
For preferred PAG according to the present invention:
- s indicates the average equal to 2.5 and t indicates to be equal to 2 average；Or
- s indicates the average equal to 3.5 and t indicates to be equal to 2.8 average.
For preferred PAG according to the present invention:
According to ASTM D445 canonical measure in 100 DEG C its kinematic viscosity range from 2.5mm2.s-1To 4.5mm2.s-1；Or
Its viscosity index (VI) is greater than 160 or between 160 and 210；Or
Its pour point is lower than -40 DEG C；Or
Its dynamic viscosity (CCS) according to ASTM D5293 canonical measure at -35 DEG C is less than 1,200mPa.s.
The method for being used to prepare the PAG of formula (VI) is described in application WO-2016/016362.
Preferably, PAG according to the present invention includes at least one epoxybutane unit.
Preferably, lubricating composition according to the present invention includes by weight from 1% to 99.5% PAG.
Preferably, lubricating composition according to the present invention include by weight from 1% to 99.5%, preferably from 5% to 80%, such as from 5% to 70%, from 5% to 60%, from 5% to 50%, from 5% to 40%, preferably from 10% to 80%, Such as 10% to 70%, 10% to 60%, 10% to 50%, 10% to 40%, preferably 20% to 80%, for example, 20% to 70%, 20% to 60%, from 20% to 50%, from 20% to 40%, preferably from 30% to 80%, such as from 30% to 70%, from 30% to 60%, from 30% to 50%, from 30% to 40% PAG.
It is highly preferred that lubricating composition according to the present invention include by weight from 1% to 30%, preferably from 1% to 20%, more preferably from 1% to 15% PAG.
In another preferred mode, lubricating composition according to the present invention include by weight from 40% to 99.5%, preferably from 50% to 99.5%, more preferably from 60% to 99.5%, even more preferably from 70% to 99.5%, advantageously from 80% to 99.5% PAG.
Other than PAG, lubricant compositions according to the present invention also include the wear-resistant addition of the compound selected from formula (I) Agent
Wherein can be identical or different R1 and R2 independently indicates comprising the carbon atom from 2 to 7, preferably from 3 The secondary alkyl group of a straight chain to 6 carbon atoms or the secondary alkyl group of branch.
In a preferred manner, antiwear additive is selected from the compound of formula (I)
Wherein identical or different R1 and R2 indicates secondary C3Alkyl group or secondary C6Alkyl group.
It is highly preferred that identical or different group R1 and group R2 indicates dimethylbutyl group or isopropyl group.
Even further preferably, identical group R1 and group R2 indicates dimethylbutyl group or isopropyl group.
In another preferred mode, antiwear additive includes mixture below:
The compound of at least one formula (I), wherein R1 indicates secondary C3Alkyl group, and R2 indicates secondary C6Alkyl group,
The compound of at least one formula (I), wherein identical R1 and R2 indicates secondary C6Alkyl group.
In another preferred mode, antiwear additive includes mixture below:
The compound of at least one formula (I), wherein R1 indicates secondary C6Alkyl group, and R2 indicates secondary C3Alkyl group,
The compound of at least one formula (I), wherein identical R1 and R2 indicates secondary C6Alkyl group.
The example of compound as formula (I), it can be mentioned that by the commercially available Lubrizol of LubrizolProduct.
Preferably, lubricating composition according to the present invention include by weight from 0.1% to 3%, preferably from 0.1% to 2%, the compound of more preferably from 0.1% to 1% formula (I).
Other than PAG and the compound of formula (I), lubricating composition according to the present invention may include base oil.
In general, lubricating composition according to the present invention may include the synthesis suitable for its purposes or natural, animal or Any kind of lubricating base oil, the minerals of plant.
Therefore, defined in the base oil used in lubricating composition according to the present invention can be and be classified according to API Classification belong to I group to V group mineral oil or synthesis source oil (or according to ATIEL classification their equivalent) (Table A) or Their mixture.
Preferably, base oil is different from PAG.
Table A
The minerals base oil that can be used for lubricating composition according to the present invention includes any kind of base oil, described Any kind of base oil under the atmosphere of crude oil and vacuum by distilling, then by refining operation, for example (,) it is solvent extraction, de- Salt, with solvent dewaxing, hydrotreating, be hydrocracked, hydroisomerization and hydrofinishing obtain.Can also use synthetic oil and The mixture of mineral oil.
Lubricating composition according to the present invention is usually prepared to different lubricating substances is used, and there is no limitations, in addition to it Must have property, especially viscosity, viscosity index (VI), sulfur content and inoxidizability, be more particularly suitable for for engine or use In the property of vehicles speed changer.
The base oil of lubricating composition according to the present invention is also selected from synthetic oil, such as certain carboxylates and alcohol, with And poly alpha olefin.Poly alpha olefin as base oil is for example obtained by the monomer comprising the carbon atom from 4 to 32, such as by pungent Alkene or decene obtain, and according to ASTM D445, in 100 DEG C its viscosity in 1.5mm2.s-1And 15mm2.s-1Between.According to ASTM D5296, average molecular weight is usually between 250 and 3000.
Advantageously, according to the present invention, base oil can be selected from III group oil, IV group oil and V group oil.
Advantageously, lubricating composition according to the present invention may include the gross mass relative to composition by weight extremely Few 50% base oil.More advantageously, lubricating composition according to the present invention may include the total weight relative to composition By weight at least 60%, or even by weight at least 70% base oil.Particularly advantageously, lubrication according to the present invention Composition may include the total weight relative to composition by weight from 50%, 60% or 70% to 99.9%, or by weight One or more of base oils of the meter from 50%, 60% or 70% to 90%.
Lubricating composition according to the present invention can also include at least one other additive.Many other additives It can be used for lubricating composition according to the present invention.It is preferred for the other additive choosing of lubricating composition according to the present invention From detergent additives, the different antiwear additives for the compound for coming from formula (I), friction adjustment agent addition agent, extreme pressure addition Agent, dispersing agent, pour point improver, defoaming agent, thickener and its mixture.
Preferably, lubricating composition according to the present invention includes at least one organic friction regulator, organic friction Regulator is selected from ester, is preferably chosen from the monoesters of polyalcohol, is more preferably selected from monoglyceride.It is highly preferred that organic friction tune The whole dose of monoglyceride obtained selected from the esterification passed through between glycerol and the carboxylic acid or unsaturated carboxylic acid of saturation, it is described full The carboxylic acid of sum or unsaturated carboxylic acid include at least ten carbon atom, preferably 10 to 20 carbon atoms, more preferably 15 To 20 carbon atoms, advantageously 15 to 18 carbon atoms.
As the example of organic friction regulator according to the present invention, it can be mentioned that Monoolein.
Preferably, lubricating composition according to the present invention includes by weight from 0.1% to 2%, preferably by weight From 0.1% to 1.5%, more preferably by weight from 0.5% to 1.5% organic friction regulator.
In the presence of the various other different antiwear additives of the compound from formula (I).
Amine phosphate (amine phosphate) is also can be wear-resistant used in the lubricating composition according to the present invention Additive.However, the phosphorus provided by these additives can serve as the poisonous substance of the catalysis system of automobile, because these additives are Ash content propellant (ash generator).These influences can be by with non-phosphorus additive such as polysulfide, especially Sulfur-bearing hydrocarbon fraction amine phosphate is substituted to minimize.
Advantageously, lubricating composition according to the present invention may include relative to lubricating composition and other wear-resistant addition By weight from the 0.01% to 6% of the total weight of agent, preferably by weight from 0.05% to 4%, more preferably by weight Meter from 0.1% to 2%.
Lubricating composition according to the present invention may include at least one inorganic friction adjustment agent addition agent.Inorganic friction is adjusted Whole agent addition agent can be selected from the compound and ashless point of compound of offer metallic element.The compound of metallic element is being provided In, it can be mentioned that transition metal complex, such as Mo, Sb, Sn, Fe, Cu and Zn, ligand can be comprising oxygen, nitrogen, sulphur or phosphorus Hydrocarbon compound.
Advantageously, lubricating composition according to the present invention may include at least one anti-oxidant additives.Antioxidant Additive is commonly used to delay the degradation using middle lubricating composition.This, which degrades, can particularly lead to formation, the dirt of deposit The increase of the viscosity of the presence or lubricating composition of mud.
Antioxidant serves in particular as the disrupting agent of free radical inhibitors or hydroperoxides.Common anti-oxidant In agent addition agent, it can be mentioned that phenol antioxidant additive, amine antioxidants additive, antioxidant phosphorus sulfur additives. It is some in these anti-oxidant additives, such as phosphorus sulphur anti-oxidant additives, it can be ash content propellant.Phenols is anti-oxidant Agent addition agent can be ash free or can be in neutrality or the form of alkaline metal salt.Anti-oxidant additives can be particularly Selected from sterically hindered phenol, steric hindrance phenolic ester and sterically hindered phenol comprising thioether bridge, diphenylamines, by least one C1-C12Alkane The diphenylamines and N that base group replaces, N'- dialkyl group-aryl diamine and its mixture.
Preferably, according to the present invention, sterically hindered phenol is selected from the compound comprising phenolic groups, wherein having alcohol functional group Carbon at least one adjacent carbon (vicinal carbon) by least one C1-C10Alkyl group, preferably C1-C6Alkyl base Group, preferably C4Alkyl group replaces, and is preferably replaced by tertiary butyl groups.
Amine compounds are the another kind of antioxidant additions that can be optionally applied in combination with phenol antioxidant additive Agent.The example of amine compounds is aromatic amine, such as formula NRaRbRcAromatic amine, wherein RaIndicate the rouge being optionally substituted Fat race group or aromatic group, RbIndicate the aromatic group being optionally substituted, RcIndicate hydrogen atom, alkyl group, aryl Group or formula RdS(O)zReGroup, wherein RdIndicate alkylidene group or alkenylene group, ReIndicate alkyl group, alkenyl base Group or aryl group, and z indicates 0,1 or 2.
The alkyl phenol of vulcanization or its alkali metal salt and alkali salt are also used as anti-oxidant additives.
Another kind of anti-oxidant additives are copper compound, such as copper thiophosphate or dithiophosphates, copper and carboxylic Hydrochlorate, dithiocar-bamate, sulfonate, phenates, cupric acetylacetonate.Mantoquita I and II, succinic acid or acid can also be used Acid anhydride salt.
Lubricating composition according to the present invention may include all types of antioxidants well known by persons skilled in the art Additive.
Additionally advantageously, lubricating composition according to the present invention include relative to composition total weight by weight from 0.5% to 2% at least one anti-oxidant additives.
Lubricating composition according to the present invention can also include at least one detergent additives.Detergent additives are usual Allow to the formation of the deposit on the surface by dissolution secondary oxidation and combustion product to reduce metal parts.
Can the detergent additives used in lubricating composition according to the present invention can be comprising long lipophilicity hydrocarbon The anionic compound of chain and hydrophilic head.Relevant cation can be the metal cation of alkali or alkaline earth metal. Detergent additives are preferably chosen from the alkali metal salt or alkaline-earth metal of carboxylic acid, sulfonate, salicylate, naphthenate and phenates Salt.Alkali and alkaline earth metal ions are preferably calcium, magnesium, sodium or barium.These metal salts are generally comprised with the gold of the amount of stoichiometry The metal of category or amount excessive therefore with the amount greater than stoichiometry.Then these are overbased detergent additives；Wherein Bring the excessive metal of high alkalinity characteristic then usual in the form of insoluble in oily metal salt for detergent additives, such as carbon Hydrochlorate, hydroxide, oxalates, acetate, glutamate, preferably carbonate.
Advantageously, lubricating composition according to the present invention may include relative to lubricating composition total weight by weight The detergent additives of meter from 2% to 4%.
Additionally advantageously, lubricating composition according to the present invention can also include at least one pour point improver additive.
By slowing down the formation of paraffin crystal, pour point improver additive generally improves lubricating composition according to the present invention Cold behavior.
As the example of pour point improver additive, it can be mentioned that polyalkyl methacrylate, polyacrylate, poly- virtue Amide, poly- alkyl phenol, poly- alkylnaphthalene and alkylated polystyrene.
Advantageously, lubricating composition according to the present invention can also include at least one dispersing agent.Dispersing agent can be selected from Mannich base, succinimide and its derivative.
Additionally advantageously, lubricating composition according to the present invention may include the total weight relative to lubricating composition by weight The dispersing agent of meter from 0.2% to 10%.
Advantageously, lubricating composition can also include at least one polymer for improving viscosity index (VI).Improve viscosity index (VI) Polymer example include styrene, butadiene and isoprene, polymethacrylates (PMA) hydrogenation or it is non-hydrogenated Polymer esters, homopolymer or copolymer.
Additionally advantageously, lubricating composition according to the present invention may include the total weight relative to lubricating composition by weight The polymer of the improvement viscosity index (VI) of meter from 1% to 15%.
Preferably, lubricating composition according to the present invention is used for engine, the preferably vehicles, more preferably motor-driven friendship The lubrication of logical tool.
Therefore, the invention further relates to lubricating compositions according to the present invention for lubricating engine, the preferably vehicles, The more preferably purposes of automotive.
It is highly preferred that being used to lubricate vehicle engine the invention further relates to lubricating composition according to the present invention, more The preferably purposes of automotive.
The invention further relates to lubrication automotive, the preferably method of automotive, this method includes at least One makes motor vehicle and the step of lubricating composition according to the present invention contacts.
The invention further relates to the wear-resistant properties that the nitrogen compound of formula (I) improves the lubricating composition comprising the oil selected from PAG Purposes.
All characteristics related with the compound of above-described formula (I) and PAG and preference are suitable for this purposes.
It will illustrate the present invention using non-limiting embodiment now.
Embodiment 1: lubricating composition according to the present invention
Prepare lubricating composition according to the present invention according to the following table 1 (composition (g) meter by weight provides).
In composition below:
- PAG 1: the PAG comprising propylene oxide and epoxybutane unit and the end OH (termination) (corresponds to formula (IV), wherein p ≈ 2.8 and q ≈ 2.2)
- PAG 2: include propylene oxide and epoxybutane unit and-OCH3The PAG of end (corresponds to formula (VI), wherein s ≈ 3.5 and t ≈ 2.8)
Antiwear additive (Anti-wear) 1 is (by the commercially available Lubrizol of LUBRIZOL): wherein R1 and R2 indicates two The compound of the formula (I) of methyl butyl group and wherein R1 and R2 indicate the mixture of the compound of the formula (I) of isopropyl group
Antiwear additive 2 is (commercially available by RheinChemie): wherein R1 and R2 indicates the formula (I) of pentyl group Compound and wherein R1 and R2 indicate the mixture of the compound of the formula (I) of butyl group
Antiwear additive 3 is (commercially available by Kangtai Lubricant Additives): wherein R1 and R2 is indicated The compound of the formula (I) of primary C-8 alkyl group
Friction regulator 1: Monoolein
Friction regulator 2 is (by the Sakuralube of Adeka companies market): molybdenum dithiocarbamate
Table 1
Embodiment 2: the assessment of wear-resistant property
This assessment is according to the program based on ASTM D2670 standard, it is desirable that uses FALEX friction gauge, and its test-strips Part is described as follows.
Testing piece: FALEX steel
Merge (break-in) time: 300s
Test time: 180min
Adjustment load: 445N
Test load: 1335N
Speed: 290rpm
Environment temperature
As a result it is presented in table 2, and μm to indicate；The value of acquisition is lower, and the wear-resistant property of evaluated composition is got over It is good.
Table 2
The results show that lubricating composition (comparative composition 1 and comparative composition 2) is compared compared with, it is according to the present invention Lubricating composition (composition 1, composition 2, composition 3 and composition 4) has improved wear-resistant property.

Claims (14)

1. composition, comprising by weight 1% to 99.5% oil selected from poly- alkyl diol (PAG or polyalkylene glycol) and The antiwear additive of compound selected from formula (I)
Wherein can be identical or different R1 and R2 independently indicates comprising the carbon atom from 2 to 7, preferably from 3 to 6 The secondary alkyl group of the straight chain of a carbon atom or the secondary alkyl group of branch.
2. composition according to claim 1, wherein the PAG be formula (II) block polymer or formula (II) it is random Polymer
Wherein:
The C of-R3 expression straight chain1-C30The C of alkyl group or branch1-C30Alkyl group, the preferably C of straight chain4-C12Alkyl base The C of group or branch4-C12Alkyl group；
- n indicates range from 2 to 60, preferably from 5 to 30 or from 7 to 15 number；
Identical or different R4 and R5 independently indicates hydrogen atom or C1-C2Alkyl group.
3. composition according to claim 1 or 2, wherein the PAG is selected from
The block polymer of zero formula (IIA) or the atactic polymer of formula (IIA)
Wherein:
The C of-R3 expression straight chain1-C30The C of alkyl group or branch1-C30Alkyl group, the preferably C of straight chain4-C12Alkyl base The C of group or branch4-C12Alkyl group；
- m indicates range from 2 to 60, preferably from 5 to 30 or from 7 to 15 number；
- R6 and R7 indicates hydrogen atom；Or R6 indicates hydrogen atom and R7 indicates methyl group；Or R6 indicates methyl group and R7 Indicate hydrogen atom；Or R6 and R7 indicates methyl group；Or R6 indicates ethyl group and R7 indicates hydrogen atom；Or R6 indicates that hydrogen is former Son and R7 expression ethyl group；
The block polymer of zero formula (IIB) or the atactic polymer of formula (IIB)
Wherein:
The C of-R3 expression straight chain1-C30The C of alkyl group or branch1-C30Alkyl group, the preferably C of straight chain4-C12Alkyl base The C of group or branch4-C12Alkyl group, the more preferably C of straight chain8-C12The C of alkyl group or branch8-C12Alkyl group；
- p and q independently indicates range from 1 to 30, preferably from 2 to 15 or from 2 to 8 number；
- R8 and R9 indicates hydrogen atom；Or R8 indicates hydrogen atom and R9 indicates methyl group；Or R8 indicates methyl group and R9 Indicate hydrogen atom；Or R8 and R9 indicates methyl group；Or R8 indicates ethyl group and R9 indicates hydrogen atom；Or R8 indicates that hydrogen is former Son and R9 expression ethyl group；
- R10 and R11 indicates hydrogen atom；Or R10 indicates hydrogen atom and R11 indicates methyl group；Or R10 indicates methyl group And R11 indicates hydrogen atom；Or R10 and R11 indicates methyl group；Or R10 indicates ethyl group and R11 indicates hydrogen atom； Or R10 indicates hydrogen atom and R11 indicates ethyl group.
4. according to claim 1 to composition described in one in 3, wherein the PAG is selected from
The block polymer of formula (III) or the atactic polymer of formula (III)
Wherein:
The C of-R3 expression straight chain4-C12The C of alkyl group or branch4-C12Alkyl group, the preferably C of straight chain4Alkyl group Or the C of branch4Alkyl group；
- p indicates range from 1 to 30, preferably from 2 to 15 or from 2 to 8 number；
- q expression range from 1 to 30, preferably from 1 to 10 number, or
The block polymer of formula (IV) or the atactic polymer of formula (IV)
Wherein:
The C of-R3 expression straight chain8-C12The C of alkyl group or branch8-C12Alkyl group；
The number of-p expression range from 2 to 6；
The number of-q expression range from 2 to 5；
The block polymer of formula (V) or the atactic polymer of formula (V)
Wherein:
The C of-R3 expression straight chain4-C12The C of alkyl group or branch4-C12Alkyl group, the preferably C of straight chain4Alkyl group Or the C of branch4Alkyl group；
- r indicates range from 2 to 60, preferably from 5 to 30 or from 7 to 15 number.
5. composition according to claim 1, wherein the PAG be formula (VI) block polymer or formula (VI) it is random Polymer
Wherein:
The C of-R12 expression straight chain1-C30The C of alkyl group or branch1-C30Alkyl group, the preferably C of straight chain8-C15Alkyl The C of group or branch8-C15Alkyl group；
- s and t independently indicates the average of range from 1 to 5.
6. including by weight 1% to 99.5% PAG to composition described in one in 5 according to claim 1.
Include by weight from 1% to 30% 7. composition according to any one of claim 1 to 6, preferably from 1% to 20%, more preferably from 1% to 15% PAG.
8. composition according to any one of claim 1 to 6 includes by weight from 40% to 99.5%, preferably From 50% to 99.5%, more preferably from 70% to 99.5% PAG.
9. composition according to any one of claim 1 to 6, include by weight from 5% to 80%, preferably from 10% to 80%, such as from 10% to 70%, such as from 20% to 60%, preferably from 30% to 50% PAG.
10. according to claim 1 to composition described in one in 9, wherein the antiwear additive is selected from the chemical combination of formula (I) Object
Wherein identical or different R1 and R2 indicates secondary C3Alkyl group or secondary C6Alkyl group.
11. including by weight from 0.1% to 3%, preferably according to claim 1 to composition described in one in 10 From 0.1% to 2%, the compound of more preferably from 0.1% to 1% formula (I).
12. including lubricating base oil according to claim 1 to composition described in one in 11.
It is described organic to rub 13. also include organic friction regulator according to claim 1 to composition described in one in 12 It wipes regulator and is selected from ester, be preferably chosen from the monoesters of polyalcohol, be more preferably selected from the monoesters of glycerol.
14. according to claim 1 to lubricating composition described in one in 13 for lubricating vehicle engine, preferably The purposes of automotive.
CN201780017740.8A 2016-03-15 2017-03-14 Lubricant compositions based on polyalkylene glycol Pending CN109072120A (en)

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