CN104471042A - Lubricating composition - Google Patents

Lubricating composition Download PDF

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Publication number
CN104471042A
CN104471042A CN201380032409.5A CN201380032409A CN104471042A CN 104471042 A CN104471042 A CN 104471042A CN 201380032409 A CN201380032409 A CN 201380032409A CN 104471042 A CN104471042 A CN 104471042A
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China
Prior art keywords
lubricating composition
repeating unit
carbon atom
comb shaped
shaped polymer
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CN201380032409.5A
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Chinese (zh)
Inventor
M·J·维拉斯
R·T·迪克森
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of CN104471042A publication Critical patent/CN104471042A/en
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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
    • C10M169/047—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution 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
    • 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
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/08—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing non-conjugated dienes
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products 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
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • 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
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C10M2209/062—Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
    • 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
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • 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
    • C10N2020/011—Cloud point
    • 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
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2020/071—Branched chain compounds
    • 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
    • C10N2030/02—Pour-point; 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/68—Shear stability
    • 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
    • C10N2030/74—Noack Volatility
    • 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

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

Abstract

A lubricating composition for use in the crankcase of an engine comprising a base oil and one or more additives, wherein the base oil comprises a Fischer-Tropsch derived base oil and wherein the lubricating composition comprises one or more comb polymers. The lubricating composition of the present invention has been found to improve sustained fuel economy properties whilst obtaining improved piston cleanliness properties and improved dispersancy properties.

Description

Lubricating composition
Technical field
The present invention relates to lubricating composition, this lubricating composition comprises base oil and one or more additives, is used in particular in base chamber.Especially, the present invention relates to for the lubricating composition comprising base oil and one or more additives in base chamber, for providing dispersiveness and the piston cleanliness of continuous fuel economy and the improvement improved in diesel motor.
Background technology
Government regulations and the market requirement continue to emphasize the protection to fossil oil in transport industry.Exist the increase demand of the more effective vehicles of fuel to meet CO 2emission reduction targets.Therefore, in automotive field, any incremental improvements of fuel economy (FE) has great importance.Lubricant can play a significant role in the fuel consumption reducing the vehicles, and there is the lasting demand to the fuel economy performance improving in oil engine the lubricant compositions contained, particularly long-term or continuous fuel economic performance.
Carry out multiple trial to improve the fuel economy performance of lubricating engine oil.US2010/0190671 relates to use comb shaped polymer to reduce fuel consumption.Especially, comb shaped polymer disclosed in it comprises at least one repeating unit obtained from the polyolefin-based macromonomer of at least one in main chain, with at least one repeating unit obtained from least one low molecular weight monomers, described at least one low molecular weight monomers is selected from: the styrene monomer with 8-17 carbon atom, there is in alcohol radical (methyl) alkyl acrylate of 1-10 carbon atom, there is in acyl group the vinyl ester of 1-11 carbon atom, there is in alcohol radical the vinyl ether of 1-10 carbon atom, there is in alcohol radical fumaric acid (two) alkyl ester of 1-10 carbon atom, there is in alcohol radical toxilic acid (two) alkyl ester and their mixture of 1-10 carbon atom, wherein mole degree of branching is 0.1-10mol% and comprises at least one repeating unit obtained from the polyolefin-based macromonomer of at least one of altogether at least 80 % by weight and at least one repeating unit obtained from least one low molecular weight monomers based on the total weight comb shaped polymer of comb shaped polymer repeating unit.But, openly do not use this comb shaped polymer for providing the long-term of improvement or continuous fuel economy in US2010/0190671.
Also need the lubricating composition be provided in base chamber, wherein said composition provides the dispersiveness of improvement and piston cleanliness benefit and long-term or continuous fuel economic benefits.
Summary of the invention
According to the present invention, provide a kind of for the lubricating composition in base chamber, it comprises base oil and one or more additives, and wherein base oil comprises fischer-tropsch source base oil and wherein said lubricating composition comprises one or more comb shaped polymers.Except the long-term or continuous fuel economy improved, lubricating composition of the present invention provides the dispersiveness of improvement and the piston cleanliness of improvement.
According to another aspect of the present invention, provide the purposes of lubricating composition described herein in base chamber, for improvement of the economic character of continuous fuel, obtain the piston cleanliness character of improvement simultaneously.
According to another aspect of the present invention, provide the purposes of lubricating composition in base chamber, for improvement of the economic character of continuous fuel, obtain the dispersed character of improvement simultaneously.
Embodiment
As used herein, term " continuous fuel economy " refers to the good fuel economy of whole oil draining period.The lubricant showing continuous fuel economy, as when initial, has comparable good fuel economic performance in the whole oil draining period.
Although do not wish to be limited by theory, think that the viscosity that the cigarette ash dispersiveness of the improvement that lubricating composition of the present invention shows causes lubricating oil composition lower in the oil draining period increases, and therefore improve the economic character of continuous fuel.
There is not special restriction (condition is that base oil comprises at least fischer-tropsch source base oil) about the base oil used in lubricating composition of the present invention, and multiple conventional mineral oil, synthetic oil and natural origin ester such as vegetables oil can be used expediently.
Except the base oil of fischer-tropsch source, the base oil used in the present invention can comprise the mixture of one or more mineral oil and/or one or more synthetic oils expediently; Therefore, according to the present invention, term " base oil " can refer to the mixture containing being greater than a kind of base oil (comprising at least one fischer-tropsch source base oil).Mineral lubricating oils after mineral oil comprises the solvent treatment of liquid petroleum and paraffinic hydrocarbons, naphthenic hydrocarbon or combination chain alkane/naphthene types or after acid treatment, it can be refined further by unifining process and/or dewaxing.
The base oil being suitable for lubricating oil composition of the present invention is: I-III class mineral base oil (preferred III class), the poly-alhpa olefin of IV class (PAO), II-III class fischer-tropsch source base oil (preferred III class), V class ester group oil, and their mixture.
" I class ", " II class ", " III class " and " IV class " and " V class " base oil refer to the lubricant base of definition of to classify according to American Petroleum Institute (API) (API) I, II, III, IV and V in the present invention.This API is sorted in API publication the 1509,15th edition, annex E, defines in 2002 4 months.
Fischer-tropsch source base oil is as known in the art.Term " fischer-tropsch source " refers to that base oil is or originates from the synthetic product of fischer-tropsch process.Fischer-tropsch source base oil is also referred to as GTL (Synthetic Oil Production from Natural Gas) base oil.The suitable Fisher-Tropsch derived base oil that can be easily used as base oil in lubricating oil composition of the present invention is those such as disclosed in Publication about Document: EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO00/14187, WO 00/14183, WO 00/14179, WO 00/08115, WO 99/41332, EP 1 029 029, WO 01/18156 and WO 01/57166.
Usually, the aromatic content (compatibly being measured by ASTM D 4629) of fischer-tropsch source base oil will be usually less than 1wt.%, preferably lower than 0.5wt.% with more preferably less than 0.1wt.%.Compatibly, total paraffinicity of base oil is at least 80wt.%, preferably at least 85, more preferably at least 90, again more preferably at least 95 and most preferably at least 99wt.%.It compatibly has the saturates content (being measured by IP-368) being greater than 98wt.%.The saturates content of preferred base oil is greater than 99wt.%, more preferably greater than 99.5wt.%.It also preferred maximum normal paraffin content be 0.5wt.%.Base oil also preferred naphthenic compound content is that 0-is less than 20wt.%, more preferably 0.5-10wt.%.
Usually, fischer-tropsch source base oil or the kinematic viscosity of base oil blend at 100 DEG C (being measured by ASTM D 7042) are 1-30mm 2/ s (cSt), preferred 1-25mm 2/ s (cSt), and more preferably 2mm 2/ s-12mm 2/ s.Preferably, the fischer-tropsch source kinematic viscosity of base oil at 100 DEG C (being measured by ASTM D 7042) is at least 2.5mm 2/ s, more preferably at least 3.0mm 2/ s.In one embodiment of the invention, the fischer-tropsch source kinematic viscosity of base oil at 100 DEG C is 5.0mm at the most 2/ s, preferably 4.5mm at the most 2/ s, more preferably 4.2mm at the most 2/ s (such as " GTL4 ").In another embodiment of the invention, the fischer-tropsch source kinematic viscosity of base oil at 100 DEG C is 8.5mm at the most 2/ s, preferably 8mm at the most 2/ s (such as " GTL 8 ").
In addition, the fischer-tropsch source kinematic viscosity of base oil usually at 40 DEG C (being measured by ASTM D7042) is 10-100mm 2/ s (cSt), preferred 15-50mm 2/ s.
In addition, fischer-tropsch originates the preferred pour point of base oil (measuring according to ASTM D 5950) lower than-30 DEG C, more preferably less than-40 DEG C, with most preferably lower than-45 DEG C.
Fischer-tropsch source base oil flash (being measured by ASTM D92) is preferably greater than 120 DEG C, is more preferably even greater than 140 DEG C.
Fischer-tropsch source base oil preferred viscosities index (according to ASTM D 2270) is 100-200.Preferably, the viscosity index of fischer-tropsch source base oil is at least 125, preferably 130.Also preferred viscosities index is lower than 180, preferably lower than 150.
When fischer-tropsch source base oil comprises the blend of two or more fischer-tropschs source base oil, above-mentioned value is applied to the blend of two or more fischer-tropschs source base oil.
Lubricating oil composition preferably comprises the fischer-tropsch source base oil of 80wt% or more.
Synthetic oil comprises: hydrocarbon ils, and such as olefin oligomer (comprises polyalphaolefin base oil; PAO), diester, polyol ester, polyalkylene glycol (PAG), alkylnaphthalene and the wax isomerized products (isomerate) after dewaxing.The synthesis alkyl oil that Shell Group sells with trade(brand)name " Shell XHVI " (trade mark) can use easily.
Poly-alhpa olefin base oil (PAO) and their preparation are well known in the art.In lubricating composition of the present invention, operable preferred poly-alhpa olefin base oil can be derived from straight chain C 2-C 32, preferred C 6-C 16, alhpa olefin.The particularly preferably raw material of described poly-alhpa olefin is 1-octene, 1-decene, 1-laurylene and 1-tetradecylene.
Consider the high preparation cost of PAO, strongly preferably use fischer-tropsch source base oil relative to PAO base oil.Therefore, preferably, base oil contains and is greater than 50wt.%, is preferably greater than 60wt.%, more preferably greater than 70wt.%, even more preferably greater than 80wt.%.Most preferably be greater than 90wt.% fischer-tropsch source base oil.In particularly preferred embodiments, be not more than 5wt.%, the base oil being preferably not more than 2wt.% is not fischer-tropsch source base oil.Even more preferably the base oil of 100wt% is based on one or more fischer-tropschs source base oil.
The preferred 60-99wt.% of base oil total amount mixed in lubricating composition of the present invention, more preferably 65-90wt.% and most preferably 70-85wt.%, relative to lubricating composition gross weight.
Usually, base oil (or base oil blend) kinematic viscosity at 100 DEG C (according to ASTM D445) used according to the invention is higher than 2.5cSt with lower than 5.6cSt.According to a preferred embodiment of the invention, the kinematic viscosity of base oil at 100 DEG C (according to ASTM D445) is 3.5-4.5cSt.When base oil contains the blend of two or more base oils, the kinematic viscosity of preferred blends at 100 DEG C is 3.5-4.5cSt.
Usually, lubricating composition of the present invention should but be not limited at SAE J300 viscosity grade 0W-20, utilize in 0W-30,0W-40,5W-20,5W-30 and 5W-40, because the grade of these to be targets be fuel economies.Along with new SAE J300 viscosity grade is announced, have the viscosity lower than current 0W-20, the present invention also can be highly suitable for these new viscosity lower grades.Be appreciated that the present invention also can utilize higher viscosity grade to use.
The preferred Noack volatility of lubricating composition of the present invention (according to ASTM D 5800) is lower than 15wt.%.Usually, the Noack volatility (according to ASTM D 5800) of composition is 1-15wt.%, preferably lower than 14.6wt.% with more preferably less than 14.0wt.%.
Lubricating composition of the present invention comprises one or more comb shaped polymers, and preferred solid polymer content is 0.1wt%-10wt%, more preferably 0.25wt%-7wt%, and even more preferably 0.5wt%-4wt%, based on the weight of total lubricating composition.
The comb shaped polymer preferably used herein comprises at least one repeating unit obtained from the polyolefin-based macromonomer of at least one and at least one repeating unit obtained from least one low molecular weight monomers in main chain, described at least one low molecular weight monomers is selected from: the styrene monomer with 8-17 carbon atom, there is in alcohol radical (methyl) alkyl acrylate of 1-10 carbon atom, there is in acyl group the vinyl ester of 1-11 carbon atom, there is in alcohol radical the vinyl ether of 1-10 carbon atom, there is in alcohol radical fumaric acid (fumurate) (two) alkyl ester of 1-10 carbon atom, there is in alcohol radical toxilic acid (two) alkyl ester and their mixture of 1-10 carbon atom, wherein mole degree of branching is 0.1-10mol%, with the gross weight based on comb shaped polymer repeating unit, (or on the other hand based on the gross weight of comb shaped polymer), comb shaped polymer comprises at least one repeating unit obtained from the polyolefin-based macromonomer of at least one of altogether at least 80 % by weight and at least one repeating unit obtained from least one low molecular weight monomers.
Preferably, comb shaped polymer used herein has the repeating unit being derived from polyolefin-based macromonomer of 8%-30 % by weight, and mole degree of branching of comb shaped polymer is 0.3%-1.1%.
Term used herein " comb shaped polymer " refers to that the side chain relatively grown is bonded to main polymer chain (usually also referred to as skeleton).The comb shaped polymer used in the present invention has at least one repeating unit being derived from polyolefin-based macromonomer.Accurate ratio is clearly by a mole degree of branching.Term used herein " main chain " must not represent that the chain length of main chain is greater than the chain length of side chain.On the contrary, this term relates to the composition of this chain.Although side chain has very a high proportion of olefinic repeating unit, be particularly derived from alkene or diolefine (such as ethene, propylene, n-butylene, iso-butylene, divinyl, isoprene) unit, main chain comprise relative vast scale at the unsaturated polar monomer of above-detailed.
Term " repeating unit " is well known by persons skilled in the art.Comb shaped polymer of the present invention can be obtained by the method relating to the radical polymerization of macromonomer and low molecular weight monomers, and wherein double bond is launched to form covalent linkage.Therefore, repeating unit comes from the monomer of use.But comb shaped polymer can by polymkeric substance analogue (analagous) reaction and graft copolymerization preparation.In this case, the repeating unit be converted of main chain calculates as the repeating unit being derived from polyolefin-based macromonomer.When same situation is applied to and prepares comb shaped polymer by graft polymerization.
The further details of the preparation method of comb shaped polymer used herein can find in US2010/0190671 and US2008/0194443 (it is incorporated to herein by reference).
The comb shaped polymer used in the present invention comprises the repeating unit being derived from polyolefin-based macromonomer.These repeating units comprise and are derived from polyolefinic at least one group.The polyolefinic example be applicable to comprises: C 2-C 10alkene, such as ethene, propylene, n-butylene, iso-butylene, norbornylene, and/or C 4-C 10diolefine, such as divinyl, isoprene, norbornadiene, and analogue.
The repeating unit being derived from polyolefin-based macromonomer preferably comprises the group being derived from alkene and/or diolefine of at least 70 % by weight and more preferably at least 80 % by weight and most preferably at least 90 % by weight, based on the weight of repeating unit being derived from polyolefin-based macromonomer.
Polyolefine group also can exist with hydrogenated form.Except being derived from the group of alkene and/or diolefine, the repeating unit being derived from polyolefin-based macromonomer can also comprise other group.These comprise the copolymerisable monomer of small proportion, comprise especially: (methyl) alkyl acrylate, styrene monomer, fumarate, maleic acid ester, vinyl ester and/or vinyl ether.These ratios based on the group of copolymerisable monomer preferably at the most 30 % by weight, more preferably at the most 15 % by weight, based on the weight of repeating unit being derived from polyolefin-based macromonomer.The repeating unit being derived from polyolefin-based macromonomer can comprise starting group and/or stop group, and it is related to functionalized or is caused by the preparation of the repeating unit being derived from polyolefin-based macromonomer.These starting group and/or the ratio preferably at the most 30 % by weight stopping group, more preferably at the most 15 % by weight, based on the weight of repeating unit being derived from polyolefin-based macromonomer.
Be derived from the preferred 500-50000g/mol of number-average molecular weight of the repeating unit of polyolefin-based macromonomer, more preferably 700-10000g/mol, even more preferably 1500-4900g/mol and most preferably 2000-3000g/mol.
The fusing point being derived from the repeating unit of polyolefin-based macromonomer is preferably less than or equal to-10 DEG C, is more preferably less than or equals-20 DEG C, be even more preferably less than or equal-40 DEG C, passing through dsc measurement.Most preferably, DSC fusing point cannot be measured for the repeating unit being derived from polyolefin-based macromonomer.
Except being derived from the repeating unit of polyolefin-based macromonomer, the comb shaped polymer used in the present invention comprises the repeating unit being derived from low molecular weight monomers, described low molecular weight monomers is selected from: the styrene monomer with 8-17 carbon atom, there is in alcohol radical (methyl) alkyl acrylate of 1-10 carbon atom, there is in acyl group the vinyl ester of 1-11 carbon atom, there is in alcohol radical the vinyl ether of 1-10 carbon atom, there is in alcohol radical fumaric acid two (alkyl) ester of 1-10 carbon atom, there is in alcohol radical toxilic acid (two) alkyl ester of 1-10 carbon atom, with the mixture of these monomers.
The molecular weight of lower molecular weight repeating unit or low molecular weight monomers preferably 400g/mol at the most, more preferably 200g/mol and most preferably 150g/mol at the most at the most.
The example with the styrene monomer of 8-17 carbon atom is: vinylbenzene, there is in side chain the substituted phenylethylene of alkyl substituent, such as, Alpha-Methyl-vinylbenzene and α-ethyl-styrene, ring has the substituted phenylethylene of alkyl substituent, such as Vinyl toluene p-vinyl toluene, halogenated styrenes, such as monochlorostyrene, dichlorostyrene, phenylstilbene bromide, and tetrabromo-benzene ethene.
Term " (methyl) acrylate " comprises acrylate and methacrylic ester, and also comprises the mixture of acrylate and methacrylic ester.(methyl) alkyl acrylate in alcohol radical with 1-10 carbon atom comprises: (methyl) acrylate being derived from saturated alcohol, such as (methyl) methyl acrylate, (methyl) ethyl propenoate, the n-propyl ester of (methyl) vinylformic acid, (methyl) isopropyl acrylate, (methyl) n-butylacrylate, (methyl) vinylformic acid uncle-butyl ester, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) vinylformic acid 2-ethyl-own ester, (methyl) heptylacrylate, (methyl) vinylformic acid 2-tert-butyl heptyl ester, (methyl) Octyl acrylate, (methyl) vinylformic acid 3-sec.-propyl heptyl ester, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, be derived from (methyl) acrylate of unsaturated alcohol, such as (methyl) vinylformic acid 2-propynyl ester, (methyl) allyl acrylate, (methyl) vinyl acrylate, (methyl) vinylformic acid grease, (methyl) acrylate base ester, such as (methyl) vinylformic acid ring pentyl ester, and (methyl) vinylformic acid 3-vinyl cyclohexyl ester.
Preferably (methyl) alkyl acrylate comprises 1-8 at alcohol radical, more preferably 1-4 carbon atom.Alcohol radical herein can be straight or branched.
The example in acyl group with the vinyl ester of 1-11 carbon atom comprises: vinyl formate, vinyl-acetic ester, propionate, vinyl butyrate.Preferred vinyl ester comprises 2-9 at acyl group, more preferably 2-5 carbon atom.Acyl group can be straight or branched.
The example in alcohol radical with the vinyl ether of 1-10 carbon atom comprises: vinyl methyl ether, EVE, vinyl propyl ether, vinyl butyl ether.Preferred vinyl ether comprises 1-8 at alcohol radical, more preferably 1-4 carbon atom.Alcohol radical can be straight or branched.
The mixture of term used herein " (two) ester " refers to use (particularly fumaric acid and/or toxilic acid) monoesters, diester and ester.Fumaric acid (two) alkyl ester in alcohol radical with 1-10 carbon atom comprises: monomethyl fumarate, dimethyl fumarate, monomethyl ester, DEF, fumaric acid Methylethyl, monobutyl fumarate, dibutyl fumarate, fumaric acid diamyl ester and fumaric acid dihexyl.Preferred fumaric acid (two) alkyl ester comprises 1-8 in alcohol radical, more preferably 1-4 carbon atom.Alcohol radical can be straight or branched.
Toxilic acid two (alkyl) ester in alcohol radical with 1-10 carbon atom comprises: monomethyl maleate, dimethyl maleate, ethyl maleate, ethyl maleate, methyl ethyl maleate, butyl maleate, dibutyl maleinate.Preferred toxilic acid (two) alkyl ester comprises 1-8 in alcohol radical, more preferably 1-4 carbon atom.Alcohol radical herein can be straight or branched.
Except the repeating unit of above-detailed, comb shaped polymer used herein can comprise the other repeating unit being derived from other comonomer, their ratio is at the most 20 % by weight, preferably at the most 10 % by weight and more preferably at the most 5 % by weight, and based on the weight of repeating unit.
These also comprise (methyl) alkyl acrylate (particularly (methyl) vinylformic acid undecane ester being derived from alcohol radical and having 11-30 carbon atom, (methyl) vinylformic acid 5-methylundecane ester, (methyl) lauryl ester, (methyl) vinylformic acid 2-methyl dodecane ester, (methyl) vinylformic acid tridecane ester, (methyl) vinylformic acid 5-methyltridec ester, (methyl) vinylformic acid tetradecane ester, (methyl) vinylformic acid pentadecane ester, (methyl) vinylformic acid n-Hexadecane ester, (methyl) vinylformic acid 2-methyl n-Hexadecane ester, (methyl) vinylformic acid heptadecane ester, (methyl) vinylformic acid 5-sec.-propyl heptadecane ester, (methyl) vinylformic acid 4-tert-butyl octadecane ester, (methyl) vinylformic acid 5-ethyl octadecane ester, (methyl) vinylformic acid 3-sec.-propyl octadecane ester, (methyl) octadecyl ester, (methyl) vinylformic acid nonadecane ester, (methyl) vinylformic acid eicosane ester, (methyl) vinylformic acid hexadecyl eicosane ester, (methyl) octadecyl base eicosane ester, (methyl) behenyl ester and/or (methyl) vinylformic acid eicosyl tetratriacontane ester) repeating unit.
These also comprise the repeating unit of the monomer being derived from dispersion oxygen-and nitrogen-functionalized, such as, listed by [0036]-[0059] section being incorporated to US2010/0190671 herein by reference those.
Comb shaped polymer used herein preferred mole of degree of branching is 0.1-10mol%, more preferably 0.3-6mol%, even more preferably 0.3-1.1mol%, particularly 0.4-1.0mol% and most preferably 0.4-0.6mol%.
Mole degree of branching f of comb shaped polymer branchcalculated by following formula:
f branch = Σ a = 1 A n a Σ a = 1 A n a + Σ b = 1 B n b
Wherein:
A is the number of the type of the repeating unit being derived from polyolefin-based macromonomer,
B is the number of the type of the repeating unit being derived from low molecular weight monomers; described low molecular weight monomers is selected from: the styrene monomer with 8-17 carbon atom; there is in alcohol radical (methyl) alkyl acrylate of 1-10 carbon atom; there is in acyl group the vinyl ester of 1-11 carbon atom; there is in alcohol radical the vinyl ether of 1-10 carbon atom; there is in alcohol radical fumaric acid (two) alkyl ester of 1-10 carbon atom; there is in alcohol radical toxilic acid (two) alkyl ester of 1-10 carbon atom; with the mixture of these monomers
N athe number of the repeating unit of the polyolefin-based macromonomer being derived from type a in comb shaped polymer molecule,
N bit is the number of the repeating unit of the low molecular weight monomers being derived from type b in comb shaped polymer molecule; described low molecular weight monomers is selected from: the styrene monomer with 8-17 carbon atom; there is in alcohol radical (methyl) alkyl acrylate of 1-10 carbon atom; there is in acyl group the vinyl ester of 1-11 carbon atom; there is in alcohol radical the vinyl ether of 1-10 carbon atom; there is in alcohol radical fumaric acid (two) alkyl ester of 1-10 carbon atom; there is in alcohol radical toxilic acid (two) alkyl ester of 1-10 carbon atom, and the mixture of these monomers.
If comb shaped polymer is prepared by the copolymerization of lower molecular weight and macromonomer, then mole degree of branching comes from the ratio of the monomer of use usually.In order to calculate, the number-average molecular weight of macromonomer may be used herein.
If comb shaped polymer is reacted by polymkeric substance analogue or obtained by graft copolymerization, then by determining that the currently known methods of transformation efficiency finds mole degree of branching.
Be derived from and be selected from following monomer and (there is the styrene monomer of 8-17 carbon atom, there is in alcohol radical (methyl) alkyl acrylate of 1-10 carbon atom, there is in acyl group the vinyl ester of 1-11 carbon atom, there is in alcohol radical the vinyl ether of 1-10 carbon atom, there is in alcohol radical fumaric acid (two) alkyl ester of 1-10 carbon atom, there is in alcohol radical toxilic acid (two) alkyl ester of 1-10 carbon atom, with the mixture of these monomers) lower molecular weight repeating unit and be derived from polyolefin-based macromonomer repeating unit at least 80 % by weight, preferably the ratio of at least 90 % by weight is the weight based on repeating unit.Except repeating unit, polymkeric substance also comprises the starting group and termination group that can be formed by initial reaction and termination reaction usually.In one aspect of the invention, think to be derived from and be selected from following monomer and (there is the styrene monomer of 8-17 carbon atom, there is in alcohol radical (methyl) alkyl acrylate of 1-10 carbon atom, there is in acyl group the vinyl ester of 1-11 carbon atom, there is in alcohol radical the vinyl ether of 1-10 carbon atom, there is in alcohol radical fumaric acid (two) alkyl ester of 1-10 carbon atom, there is in alcohol radical toxilic acid (two) alkyl ester of 1-10 carbon atom, with the mixture of these monomers) lower molecular weight repeating unit and be derived from polyolefin-based macromonomer repeating unit at least 80 % by weight, preferably at least 90 % by weight is the weight based on comb shaped polymer.
Comb shaped polymer used herein preferably has 8-30 % by weight, more preferably the repeating unit being derived from polyolefin-based macromonomer of 10-26 % by weight, based on the gross weight of repeating unit.
It is 500,000-1,000,000g/mol that preferred comb shaped polymer used herein comprises weight-average molecular weight Mw, more preferably 100,000-500,000g/mol and most preferably 150,000-450,000g/mol those.
Number-average molecular weight Mn can preferably 20,000-800,000g/mol, and more preferably 40,000-200,000g/mol and most preferably 50,000-150,000g/mol.
The polydispersity index Mw/Mn of preferred comb shaped polymer used herein is 1-5, more preferably 2.5-4.5.Number-average molecular weight and weight-average molecular weight can be determined by known method such as gas-permeable chromatography (GPC).
In particular aspects of the present invention, comb shaped polymer has the olefinic double bond of low ratio.Iodine number is preferably less than or equal to 0.2g/g comb shaped polymer, is more preferably less than or equals 0.1g/g comb shaped polymer.This ratio can at 180 DEG C, under a reduced pressure, extraction year oil and lower molecular weight residual monomer be determined after 24 hours according to DIN 53241.
In preferred embodiment herein, comb shaped polymer has the repeating unit being derived from the n-butyl ester of methacrylic acid and/or n-butylacrylate.Preferably, the ratio being derived from the repeating unit of the n-butyl ester of methacrylic acid and/or n-butylacrylate is at least 50 % by weight, more preferably at least 60 % by weight, and based on the gross weight of repeating unit.
In preferred embodiment herein, comb shaped polymer has and is derived from cinnamic repeating unit.The ratio being derived from cinnamic repeating unit is preferably 0.1-30 % by weight, more preferably 5-25 % by weight.
In preferred embodiment herein, comb shaped polymer has the repeating unit being derived from alkyl (methyl) alkyl acrylate with 11-30 carbon atom, and preferred content is 0.1%-15 % by weight, more preferably 1-10 % by weight.
In preferred embodiment herein, comb shaped polymer has the repeating unit being derived from cinnamic repeating unit He being derived from the n-butyl ester of methacrylic acid.The preferred 1:1-1:9 of weight ratio of repeating styrene units and methacrylic acid n-butyl ester repeating unit, more preferably 1:2-1:8.
In a further preferred embodiment, comb shaped polymer has the repeating unit being derived from methyl methacrylate and the repeating unit being derived from the n-butyl ester of methacrylic acid, and preferred weight ratio is 1:1-0:100, more preferably 3:7-0:100.
Be suitable for commercially available comb shaped polymer used herein to obtain from Evonik with trade(brand)name Viscoplex 3-201.
Lubricating composition of the present invention also comprises one or more additives, such as: antioxidant, and wear preventive additive, dispersion agent, purification agent, high alkaline detergent, extreme-pressure additive, friction modifier, viscosity index improver, pour point depressant, metal passivator, inhibiter, emulsion splitter, defoamer, sealing compatilizer and additive dilution base oil, etc.
Because those skilled in the art are familiar with above-mentioned and other additive, these additives do not discuss in detail herein further.The specific examples of this additive is described in such as Kirk-OthmerEncyclopedia of Chemical Technology, the 3rd edition, the 14th volume, 477-526 page.
The antioxidant that can use expediently comprises phenyl-naphthylamines (" the IRGANOX L-06 " that such as can obtain from Ciba Specialty Chemicals) and pentanoic (" the IRGANOX L-57 " that such as can obtain from Ciba Specialty Chemicals) disclosed in such as WO 2007/045629 and EP 1,058 720 B1, phenol antioxidant, etc.The instruction of WO 2007/045629 and EP 1 058 720 B1 is incorporated to herein by reference.
The wear preventive additive that can use expediently comprises zinc compound, such as be selected from dialkyl group-, the phosphorodithioic acid zn cpds of diaryl-and/or alkylaryl-zinc dithiophosphate, molybdate compound, boron-containing compound and ashless wear preventive additive such as replace or do not replace thiophosphoric acid, and their salt.
The example of this molybdate compound can comprise expediently: molybdenum dithiocarbamate, three core molybdenum compounds (such as described in WO 98/26030), the sulfide of molybdenum and molybdenum dithiophosphate.
The boron-containing compound that can use expediently comprises: boric acid ester, borated fatty amine, boration epoxide, basic metal (or mixed alkali metal or alkaline-earth metal) borate and boration high alkalinity metal salt.
The preferred ashless dispersant of dispersion agent used.The example of the ashless dispersant be applicable to is polybutylene succinimide polyamine and Mannich bases dispersion agent.
The purification agent used is preferably high alkaline detergent or the purification agent mixture containing such as salicylate (alkali), sulfonate (alkali) and/or phenates-type purification agent.
The example of the viscosity index improver that can use expediently in lubricating composition of the present invention comprises: styrene butadiene radial copolymer, styrene-isoprene radial copolymer and polymethacrylate copolymer and ethylene-propylene copolymer (also referred to as olefin copolymer), crystallization and non-crystalline type.Dispersant viscosity index improving agent may be used in lubricating composition of the present invention.But preferably composition according to the present invention contains and is less than 1.0wt.%, is preferably less than the viscosity index improver enriched material (namely VI improving agent adds " carrying oily " or " thinner ") of 0.5wt.%, based on the gross weight of composition.Most preferably, composition is not containing viscosity index improver enriched material.Term " viscosity modifier " implication used as hereafter (such as in table 2) is the same with term mentioned above " viscosity index improver enriched material ".
Preferably, composition contains the pour point depressant of at least 0.1wt.%.As an example, alkylated naphthalene and phenol polymer, polymethacrylate, maleic acid ester/fumarate copolymer ester can be used as effective pour point depressant expediently.Preferred use is not more than the pour point depressant of 0.3wt.%.
In addition, compound such as alkenyl succinic acid or its ester moiety, benzotriazole based compound and thiodiazole-based compounds can be used as inhibiter expediently in lubricating composition of the present invention.
Compound is polysiloxane such as, and dimethyl polycyclohexane and polyacrylic ester can be used as defoamer expediently in lubricating composition of the present invention.
The compound that can be used as sealing fixing agent or sealing compatilizer in lubricating composition of the present invention expediently comprises such as commercially available aromatic ester.
Lubricating composition of the present invention can by preparing comb shaped polymer and base oil and one or more additive fusion expediently.
The usual amount of above-mentioned additive is 0.01-35.0wt.%, and based on the gross weight of lubricating composition, preferred amount is 0.05-25.0wt.%, more preferably 1.0-20.0wt.%, based on the gross weight of lubricating composition.
Preferably, composition contains at least 9.0wt.%, preferably at least 10.0wt.%, more preferably at least 11.0wt% comprise wear preventive additive, metal detergent, the additive-package of ashless dispersant and antioxidant.
Lubricating composition of the present invention can be so-called " low SAPS " (SAPS=sulfate ash, p and s), " medium SAPS " or " conventional SAPS " preparaton.
For car motor oil (PCMO) engine oil, above-mentioned scope refers to:
-sulfated ash content (according to ASTM D 874) is respectively 0.5wt.% at the most, 0.8wt.% and at the most 1.5wt.% at the most;
-phosphorus content (according to ASTM D 5185) is respectively 0.05wt.% at the most, at the most 0.08wt.% and usual 0.1wt.% at the most; With
-sulphur content (according to ASTM D 5185) is respectively 0.2wt.% at the most, at the most 0.3wt.% and usual 0.5wt.% at the most.
For heavy duty diesel engine oil, above-mentioned scope refers to:
-sulfated ash content (according to ASTM D 874) is respectively 1wt.% at the most, 1wt.% and at the most 2wt.% at the most;
-phosphorus content (according to ASTM D 5185) is respectively 0.08wt.% (low SAPS) and at the most 0.12wt.% (medium SAPS) at the most; With
-sulphur content (according to ASTM D 5185) is respectively 0.3wt.% (low SAPS) and at the most 0.4wt.% (medium SAPS) at the most.
In yet another aspect, the invention provides the purposes of lubricating composition of the present invention as the engine oil in base chamber, for improvement of the economic character of continuous fuel, also improve dispersed and piston cleanliness character simultaneously.Engine oil can comprise heavy duty diesel engine oil, car motor oil, and the engine oil of other types.
Hereafter describe the present invention about following examples, following examples are not intended for use to limit scope of the present invention by any way.
Embodiment
Lubricating oil composition
Prepare the various engines oil used in crankcase engine.
Table 1 indicates the base oil properties of use.Table 2 indicates composition and the character of the tested engine oil formulations prepared completely; The content of component provides with wt.%, based on the gross weight of the preparaton prepared completely.
" base oil 1 " is commercially available III class base oil, and the kinematic viscosity (ASTM D445) at 100 DEG C is 4.2cSt (mean value).Base oil 1 is commercially available from such as SK Energy (Ulsan, South Korea) (with name of concluding the business " Yubase 4 ").
" base oil 2 " is commercially available III class base oil, and the kinematic viscosity (ASTM D445) at 100 DEG C is 6.5cSt (mean value).Base oil 2 is commercially available from such as SK Energy (Ulsan, South Korea) (with name of concluding the business " Yubase 6 ").
" base oil 3 " is fischer-tropsch source base oil (" GTL 4 "), and the kinematic viscosity (ASTM D445) at 100 DEG C is about 4cSt (mm 2s -1).This GTL 4 base oil can conveniently by the method preparation described in such as WO 02/070631 (its instruction is incorporated herein by this reference).
" base oil 4 " is fischer-tropsch source base oil (" GTL 8 "), and the kinematic viscosity (ASTM D445) at 100 DEG C is about 8cSt (mm 2s -1).This GTL 8 base oil can conveniently by the method preparation described in such as WO 02/070631 (its instruction is incorporated herein by this reference).
All engine oil formulations carrying out testing comprise base oil, comb shaped polymer (or in the case of comparative example 1 other viscosity modifier), additive-package, optional pour point depressant, with the combination of optional friction modifier, described additive-package is identical all carrying out in the composition tested.
Additive-package is so-called " medium SAPS " (medium sulfate ash, p and s) preparaton.
Additive-package comprises and comprises antioxidant, zinc-base wear preventive additive, ashless dispersant, the additive combination of high alkaline detergent mixture and about 10ppm defoamer.
Comb shaped polymer is with trade(brand)name " Viscoplex 3-201 " obtainable commercially available comb shaped polymer from Evonik.
Pour point depressant in comparative example 1 is Viscoplex 6-054, and it is by the commercially available dispersion agent PMA of Evonik.
Viscosity modifier in comparative example 1 is common styrene-hydrogenation isoprene copolymer viscosity modifier enriched material, commercially available with name of concluding the business " SV 201 " by Infineum.
Friction modifier is conventional friction modifying agent, commercially available with trade(brand)name LZ8621 by Lubrizol.
The composition of embodiment and comparative example obtains by utilizing traditional lubrication agent blended program to be mixed with other component by base oil.
In order to prove the fuel economy character of the present composition, in embodiment and comparative example, carry out fuel economy measurement according to industrial standards M111 fuel economy testing method (according to CEC-L-054-96).The result display of these tests in table 2.
In order to prove the piston cleanliness character of the present composition, in embodiment and comparative example, carry out piston cleanliness measurement according to industrial standards VW TDI testing scheme (according to CEC-L-078-99).The method " passes through " value thinking to be more than or equal to reference oil (being 65 value (merit) in this case).The result display of these tests in table 2.
In order to prove the dispersed character of the diesel soot of the present composition, testing (according to CEC-L-093-04) according to industrial standards DV4 and measuring in embodiment and comparative example.The result display of these tests in table 2.
In order to prove that when subjected to elevated temperatures (thermostability) lubricating composition of the present invention forms sedimental tendency, embodiment and comparative example is made to stand micro-coking test (MCT) method.In MCT method, by 0.6cm 3lubricating composition is placed in heating one end (focus) and regulates at the other end in the groove of aluminium-alloy sheets of (cold spot).Temperature survey between these 2 allows to set up thermal gradient between the two ends of groove, and supposition is linear.The standard duration of test is 90 minutes.At the end of test, determine and assess the initial temperature that settling is formed according to CEC M-02-A-78 code of practice.The result display of these tests in table 2.
Table 1
1according to ASTM D 445.Quote mean values
2according to ASTM D 2270.Quote minimum value.
3according to ASTM D 5950.Quote maximum value.
4according to CEC L-40-A-93/ASTM D 5800.Quote maximum value.
Table 2
1according to ASTM D 445
2according to ASTM D 4683
Discuss
Result in table 2 demonstrates: lubricating composition of the present invention against expectation shows the fuel economy of improvement, the piston cleanliness of improvement, and the cigarette ash that the high temperature deposition thing of reduction is formed and improves is dispersed.Only when there is the combination of GTL and comb shaped polymer simultaneously, can see that the high temperature deposition thing of fuel economy benefit and piston cleanliness and reduction is formed.

Claims (20)

1. the lubricating composition used in base chamber, it comprises base oil and one or more additives, and wherein base oil comprises fischer-tropsch source base oil, and wherein lubricating composition comprises one or more comb shaped polymers.
2. lubricating composition according to claim 1, wherein comb shaped polymer comprises at least one repeating unit obtained from the polyolefin-based macromonomer of at least one in main chain, with at least one repeating unit obtained from least one low molecular weight monomers, described at least one low molecular weight monomers is selected from: the styrene monomer with 8-17 carbon atom, there is in alcohol radical (methyl) alkyl acrylate of 1-10 carbon atom, there is in acyl group the vinyl ester of 1-11 carbon atom, there is in alcohol radical the vinyl ether of 1-10 carbon atom, there is in alcohol radical fumaric acid (two) alkyl ester of 1-10 carbon atom, there is in alcohol radical toxilic acid (two) alkyl ester and their mixture of 1-10 carbon atom, wherein mole degree of branching is 0.1-10mol%, with the gross weight based on comb shaped polymer repeating unit, comb shaped polymer comprises at least one repeating unit obtained from the polyolefin-based macromonomer of at least one of altogether at least 80 % by weight and at least one repeating unit obtained from least one low molecular weight monomers.
3. lubricating composition according to claim 2, wherein mole degree of branching of comb shaped polymer is 0.3-3.6mol%.
4., according to the lubricating composition of Claims 2 or 3, wherein comb shaped polymer has at least one repeating unit being derived from the polyolefin-based macromonomer of at least one of 8-30 % by weight, and mole degree of branching of comb shaped polymer is 0.3%-1.1%.
5., according to the lubricating composition of any one of claim 2-4, wherein comb shaped polymer has at least one repeating unit obtained from the polyolefin-based macromonomer of at least one of 11-26 % by weight.
6., according to the lubricating composition of any one of claim 2-5, at least one repeating unit wherein obtained from the polyolefin-based macromonomer of at least one has the number-average molecular weight of 700-10000g/mol.
7. according to the lubricating composition of any one of claim 2-6, wherein comb shaped polymer comprise at least 90 % by weight from the polyolefin-based macromonomer of at least one and the repeating unit that obtains from least one low molecular weight monomers, described at least one low molecular weight monomers is selected from: the styrene monomer with 8-17 carbon atom, there is in alcohol radical (methyl) alkyl acrylate of 1-10 carbon atom, there is in acyl group the vinyl ester of 1-11 carbon atom, there is in alcohol radical the vinyl ether of 1-10 carbon atom, there is in alcohol radical fumaric acid (two) alkyl ester of 1-10 carbon atom, there is in alcohol radical toxilic acid (two) alkyl ester and their mixture of 1-10 carbon atom.
8., according to the lubricating composition of any one of claim 2-7, wherein polydispersity index Mw/Mn is 1-5.
9., according to the lubricating composition of any one of claim 2-8, wherein mole degree of branching of comb shaped polymer is 0.4%-1.0%, preferred 0.4%-0.6%.
10., according to the lubricating composition of any one of claim 2-9, at least one repeating unit wherein obtained from the polyolefin-based macromonomer of at least one comprises from being selected from C 2-C 10alkene and C 4-C 10the group of the monomer acquisition of diolefine.
11. according to the lubricating composition of any one of claim 2-10, and at least one repeating unit wherein obtained from the polyolefin-based macromonomer of at least one comprises at least 80 % by weight be derived from and be selected from C 2-C 10alkene and C 4-C 10the group of the monomer of diolefine, based on the weight of at least one repeating unit being derived from the polyolefin-based macromonomer of at least one.
12. according to the lubricating composition of any one of claim 2-11, and the fusing point of at least one repeating unit wherein obtained from the polyolefin-based macromonomer of at least one is less than or equal to 10 DEG C.
13. according to the lubricating composition of any one of claim 2-12, and at least one repeating unit wherein obtained from the polyolefin-based macromonomer of at least one does not have fusing point through measuring.
14. according to the lubricating composition of any one of claim 2-13, and wherein comb shaped polymer has the repeating unit obtained from least one the n-butyl ester of methacrylic acid and n-butylacrylate, and the ratio preferably had is at least 50 % by weight.
15. according to the lubricating composition of any one of claim 2-14, and wherein comb shaped polymer has the repeating unit obtained from vinylbenzene, and the ratio preferably had is 5-25 % by weight.
16. according to the lubricating composition of any one of claim 2-15, and the weight-average molecular weight that wherein comb shaped polymer has is 100,000-500,000g/mol.
17. according to the lubricating composition of any one of claim 2-16, and wherein comb shaped polymer has the repeating unit that (methyl) alkyl acrylate from alkyl with 11-30 carbon atom obtains, and the ratio preferably had is 1-10 % by weight.
18. according to the lubricating composition of any one of claim 1-17, and wherein the kinematic viscosity of fischer-tropsch source base oil at 100 DEG C is 2mm 2/ s-10mm 2/ s.
19., according to the purposes of lubricating composition in base chamber of any one of claim 1-18, for improvement of the economic character of continuous fuel, obtain the piston cleanliness character of improvement simultaneously.
20., according to the purposes of lubricating composition in base chamber of any one of claim 1-18, for improvement of the economic character of continuous fuel, obtain the dispersed character of improvement simultaneously.
CN201380032409.5A 2012-06-21 2013-06-18 Lubricating composition Pending CN104471042A (en)

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