CN106414686A

CN106414686A - Lubricating composition

Info

Publication number: CN106414686A
Application number: CN201580029625.3A
Authority: CN
Inventors: M·C·索斯比; 高宏; 陈成; C·A·钦; B·L·帕普克
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2014-06-19
Filing date: 2015-06-17
Publication date: 2017-02-15
Also published as: US20170275555A1; JP2017518426A; RU2692794C2; EP3158034A1; RU2017101549A; RU2017101549A3; WO2015193395A1

Abstract

A lubricating composition for use in the crankcase of an engine comprising (i) a base oil; (ii) one or more organo-molybdenum compounds at a level sufficient to provide from 100 to 1000 ppmw of molybdenum; and (iii) from 0.2 wt% to 5.0 wt%, by weight of the lubricating composition, of one or more organic polymeric friction reducing additives, wherein the one or more organic polymeric friction reducing additives has a molecular weight ranging from 1000 to 30000 Daltons and is the reaction product of: a) a hydrophobic polymeric sub unit which comprises a hydrophobic polymer selected from polyolefins, polyacrylics and polystyrenyls; b) a hydrophilic polymeric sub unit which comprises a hydrophilic polymer selected from polyethers, polyesters, polyamides; c) optionally at least one backbone moiety capable of linking together polymeric sub units; and d) optionally a chain terminating group. The lubricating composition provides improvements in terms of reduced friction and wear, in addition to improved fuel economy performance.

Description

Lubricating composition

The present invention relates to lubricant oil composite, particularly it is suitable for lubricating internal combustion engines and it has friction and wear and lowers The lubricant oil composite of the fuel economy of the improvement of aspect and improvement.

Automotive regulatory for discharge and fuel efficiency aspect regulation increasingly severeer so that manufacturers of engines and profit Lubrication prescription makers-up persistently needs to provide the effective scheme improving fuel economy.

To optimize lubricant by using high-performance base raw material and new additive is a kind of to choose for increasing The flexible scheme of war.

Antifriction additive (it is also referred to as friction modifiers) is the lubricant composition of important reduction fuel consumption, and multiple Such additive is known in the art.

Friction modifiers can be compatibly divided into two classes that is to say, that (having containing the friction modifiers of metal and no ash Machine) friction modifiers.

Organic molybdenum is modifying agent containing metal friction wherein most commonly.Typical organic molybdenum includes two sulfur For carbamic acid molybdenum (MoDTC), molybdenum dithiophosphate (MoDTP), molybdenum amine, molybdenum alcoholates and molybdenum alcohol-aminate.WO-A-98/ 26030th, WO-A-99/31113, WO-A-99/47629 and WO-A-99/66013 describe for three in lubricant oil composite Core molybdenum compound.

However, it is desirable to the trend of low ash lubricant oil composite has promoted people to be increasingly using Ashless friction change Property agent come to realize low friction and improve fuel economy.

Ester, the fat of fatty acid and polyhydric alcohol has been generally included in no ash (organic) friction modifiers using in the past Sour amide, the amine from fatty acid and organic disulfide are for carbamate or phosphordithiic acid ester compounds.

But, the strategy of the antifriction of current fuel economy oil aspect is insufficient for original equipment manufacturer (Original Equipment Manufacturers, OEM) fuel economy objectives gradually stepping up that set.Although exist simply using no Ash friction modifiers go to reach the improved challenge of friction of similar level, but molybdenum friction modifiers are generally in borderline region It is better than Ashless friction modifying agent in (boundary regime).

Although organic molybdenum can be used for providing high-caliber friction to improve, these compounds there is also known limit System.For example, the friction modifiers based on molybdenum can negatively affect sealing and TEOST cleanliness testing.

Use relatively low water in view of the fuel economy demands to electromotor being gradually increased it is still desirable to improve further The flat antifriction of the internal combustion engine of the friction modifiers based on molybdenum and fuel economy.

WO2011/107739 discloses the automobile engine oil comprising basic material and organic polymer antifriction additive And/or fuel.

Present inventors have surprisingly discovered that, comprise organic molybdenum and the group of organic polymer antifriction additive The lubricant oil composite closing has improved friction and wear to be reduced and improved fuel economy, simultaneously need to fall is low-level Organic molybdenum.

Content of the invention

Therefore, the invention provides for the lubricating composition in the crankcase of electromotor, it comprises (i) base oil； (ii) one or more organic molybdenum, its level be enough to provide the molybdenum of 100-1000ppmw；(iii) with lubricating composition Weight meter, one or more organic polymer antifriction additive of 0.2 weight % to 5 weight %, wherein said a kind of or many Kind of organic polymer antifriction additive have 1000-30000 dalton molecular weight and be following components product：

A) hydrophobic polymer subunit, it comprises selected from polyolefin, polyacrylic and polystyrene type (polystyrenyls) hydrophobic polymer.

B) hydrophilic polymer subunit, its comprise selected from polyethers, polyester, polyamide hydrophilic polymer；

C) optionally, at least one skeleton part that polymeric subunits can be linked together；With

D) optionally, chain termination group.

Brief description

Fig. 1 shows for the compositionss shown in table 2, and the friction coefficient measurement value in border and Mixed Zone is with speed The figure of degree change.

Fig. 2 shows for the compositionss shown in table 4, and the friction coefficient measurement value in border and Mixed Zone is with speed The figure of degree change.

Specific embodiment

One required component of lubricating composition of the present invention is one or more organic molybdenum, and its level be enough to provide The molybdenum of 100-1000ppmw, preferably its level be enough to provide the molybdenum of 100-300ppmw.

Organic molybdenum for this paper is preferably chosen from molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), molybdenum amine, molybdenum alcoholates, molybdenum alcohol-aminate (molybdenum alcohol-amide) and its mixture.Preferably Organic molybdenum for this paper is molybdenum dithiocarbamate (MoDTC).In a preferred embodiment of this paper, Organic molybdenum comprises three core molybdenums (referred herein as " molybdenum trimer " (moly trimer)).

Another required component of the lubricating composition of the present invention is one or more organic polymer antifriction additive, its Described in one or more organic polymer antifriction additive there is the molecular weight of 1000-30000 dalton and be following components Product：

A) hydrophobic polymer subunit, it comprises the hydrophobic polymeric selected from polyolefin, polyacrylic and polystyrene type Thing；

D) optionally, chain termination group.

Hydrophobic polymer subunit preferably comprises hydrophobic polymer, and it is polyolefin or polyalphaolefin, more preferably polyene Hydrocarbon.

Polyolefin is preferably derived from having monoolefine such as ethylene, propylene, butylene and the isobutene., more of 2-6 carbon atom The polymer of preferred isobutene., described polymer comprises 15-500, the chain of preferred 50-200 carbon atom.

Hydrophilic polymer subunit comprises the hydrophilic polymer selected from polyethers, polyamide or polyester.The example of polyester includes Polyethylene terephthalate, polylactic acid and polycaprolactone.The example of polyethers includes polyglycereol and poly alkylene glycol.One In individual particularly preferred embodiment, hydrophilic polymer subunit includes such hydrophilic polymer, and it is water soluble alkylen The polymer of glycol.Preferably hydrophilic polymer subunit includes the hydrophilic polymer that it is Polyethylene Glycol (PEG), preferably PEG has the molecular weight of 300-5000 dalton, more preferably 400-1000 dalton, especially 400-800 dalton.Or, can Using poly- (ethylene glycol and 1,2-propylene glycol) of mixing or poly- (ethylene glycol-butanediol) of mixing, as long as they reach desired water solublity Standard.Exemplary hydrophilic polymer subunit for the present invention includes PEG 400, PEG 600 and PEG 1000.

Other suitable hydrophilic polymer subunits may include such hydrophilic polymer, and it is polyethers and derived from glycol With the polyamide of diamidogen, it comprises acidic-group such as hydroxy-acid group, sulfonyl group (such as sulfonated styrene base), amine groups (such as tetren (TEPA) or polyethylene imine (PEI)) or hydroxyl (such as glycosyl list-or co-polymer).

Hydrophilic polymer subunit can be linear or branch.

During the course of the reaction, some are hydrophobic and hydrophilic polymer subunit can be connected together to form block copolymer list Unit.One or both of hydrophobic and hydrophilic polymer subunit can comprise to allow them to the functional group being connected with other subunits. For example, hydrophobic polymer subunit can be derivatized so that it is by anti-with unsaturated dibasic acid or anhydride (such as maleic anhydride) Answer and there is binary acid/anhydride group.Binary acid/anhydride can be by (for example poly- with hydroxy-end capped hydrophilic polymer subunit Aklylene glycol) it is esterified and react.In further example, hydrophobic polymer subunit can be by (for example crossing benzene with peracid Formic acid or peracetic acid) epoxidation reaction and be derivatized.Epoxide can then hydrophilic polymeric with hydroxyl and/or acid blocked Thing subunit reacts.In further example, the hydrophilic polymer subunit with hydroxyl can be by using unsaturated monocarboxylic Such as vinyl acids, especially acrylic or methacrylic acid are esterified and are derivatized.The hydrophilic polymer of this derivatization Subunit can and then be reacted by radical copolymerization with polyolefin hydrophobic polymer subunit.

Particularly preferred hydrophobic polymer subunit includes polyisobutylene polymer, and it is already subjected to maleation (maleinisation) be 300-5000 dalton to form molecular weight, preferred 500-1500 dalton, especially 800-1200 road Polyisobutylene succinic anhydride (PIBSA) in the range of that.Polyisobutylene succinic anhydride is by having end unsaturated group The commercially available compound of poly- (isobutene .) additive reaction preparation and maleic anhydride between.

Such block copolymer unit (if present) can be connected directly to one another and/or they can pass through at least one bone Frame part links together.Preferably, they are linked together by least one skeleton part described.Can be by block copolymerization The selection of the skeleton part that thing unit links together depend on the connection of unit whether two hydrophobic polymer subunits it Between, between two hydrophilic polymer subunits or between hydrophobic polymer subunit and hydrophilic polymer subunit.Generally, many First alcohol and polycarboxylic acid form suitable skeleton part.Polyhydric alcohol can be the two of dihydroxylic alcohols, trihydroxylic alcohol, tetrahydroxylic alcohol and/or correlation The chain-extension polymerization thing of polymers or trimer or these compounds.The example of suitable polyhydric alcohol includes glycerol, neopentyl glycol, three hydroxyls Methyl ethane, trimethylolpropane, tri hydroxy methyl butane, tetramethylolmethane, dipentaerythritol, tripentaerythritol and Sorbitol.? One preferred embodiment in, polyhydric alcohol is glycerol.Suitably, described at least one skeleton part is derived from polycarboxylic acid, example As two-or tricarboxylic acids.Dicarboxylic acids are preferred polycarboxylic acids, but side chain dicarboxylic acids are also likely to be suitable.It is particularly suitable to There is the unbranched dicarboxylic acid of the chain length of 2-10 carbon atom, such as oxalic acid, maleic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, heptan two Acid, suberic acid, Azelaic Acid and decanedioic acid.Unsaturated dicarboxylic such as maleic acid is also likely to be suitable.Connect described unit Particularly preferred polycarboxylic acid skeleton part is adipic acid.Alternative connecting framework part is the alkenyl succinic anhydride of low-molecular-weight (ASA) such as C₁₈ASA.

In any organic polymer antifriction additive, can be using similar and different skeleton part by such block Copolymer unit links together.When it is present, the quantity of the block copolymer unit in organic polymer antifriction additive is led to It is often 1-20 unit, preferred 1-15, more preferably 1-10 and especially 1-7 unit.

When product end has reactive group (for example, as the OH in PEG), in some cases, will The end that chain termination group introduces product is probably desired or useful.For example, carboxylic acid is connected to PEG by ester bond On the hydroxyl of exposure be particularly simple.In this respect, any aliphatic carboxylic acid will be suitable.Suitable fatty acid includes C₁₂-C₂₂Straight chain saturation, chain is saturated, straight chain be unsaturated and side chain unsaturated acids, including but not limited to lauric acid, sinapic acid, different Stearic acid, Palmic acid, Oleic acid and linoleic acid, preferably Palmic acid, Oleic acid and linoleic acid.Particularly preferred and surfactant package Fatty acid be ready denier oil acid (TOFA) (a kind of derivant of tall oil), it is mainly Oleic acid.

The organic polymer antifriction additive using in the present invention has 1000-30000 dalton, preferred 1500- The molecular weight of 25000 dalton, more preferably 2000-20000 dalton.Generally, comprise the group of organic polymer antifriction additive Compound is by the polymer chain comprising a series of different chain length so that there will be a series of molecule matter in particular composition Amount.In such circumstances it is desirable to the substantial portion of organic polymer antifriction additive molecule is in above-mentioned magnitude range.

The organic polymer antifriction additive of this paper has the desired acid number less than 20, preferably smaller than 15.

In an embodiment of the invention, organic polymer antifriction additive is the product of following components：

B) hydrophilic polymer subunit, its comprise selected from polyethers, polyester, polyamide hydrophilic polymer；With

D) chain termination group.

For such embodiment, preferred molecular weight ranges are 1000-3000 dalton and desired acid number is less than 15.

In a single embodiment of the present invention, organic polymer antifriction additive is that the reaction of following components is produced Thing：

C) at least one skeleton part that polymeric subunits can be linked together.

For such embodiment, preferred molecular weight ranges are 3000-25000 dalton, more preferably 5000- 20000 dalton.Desired acid number is preferably smaller than 10, more preferably less than 7.

In another embodiment, organic polymer antifriction additive is the product of following components：

C) at least one skeleton part that polymeric subunits can be linked together；With

D) chain termination group.

For such embodiment, preferred molecular weight ranges are 2000-10000, more preferably 2000-5000 dongle ?.Desired acid number is preferably smaller than 15, more preferably less than 10.

The composition of reaction a), b) and c) (when it is present) and d) (when it is present) can mix in single-step process, or They can mix in multistage method.

The organic polymer antifriction additive describing above herein be commercial can be from Croda with trade name Perfad 3050 and Perfad 3006 obtain.

The presence level of organic polymer antifriction additive is 0.2wt%-5.0wt%, preferred levels are 0.3wt%- 3.0wt%, more preferably 0.2wt%-1.5wt%, it is in terms of the weight of lubricating composition.

Be introduced into the total amount of the base oil in the lubricant oil composite of the present invention, preferably with the amount in the range of 60-92wt.%, Exist more preferably with the amount in the range of 75-90wt.% and most preferably with the amount in the range of 75-88wt.%, it is with respect to lubricating oil The gross weight of compositionss.

It is not particularly limited with regard to base oil used in the present invention, and can be compatibly using various conventionally known mineral Oil and artificial oil.

One or more mineral oil and/or one or more artificial oil can compatibly be included for the base oil in the present invention Mixture.

Mineral oil includes alkane that saxol and solvent are processed or acid treatment, cycloalkanes or mixing alkane/naphthenic The mineral lubricating oil of type, it can be processed by hydrofinishing and/or dewax and refine further.

Cycloalkanes base oil has low-viscosity index (VI) (usual 40-80) and low pour point.This base oil is from rich in cycloalkanes The raw material of hydrocarbon and low wax content produces, and to be mainly used in wherein color and colour stability be important and VI and oxidation-stabilized Property is in secondary lubricant.

Alkane base oil has higher VI (generally>95) and high pour point.Described base oil is from the raw material rich in alkane Produce, and be in important lubricant for wherein VI and oxidation stability.

Fischer-tropsch derived base oil can be suitably used as the base oil in lubricant oil composite of the present invention, such as EP-A- 776959、EP-A-668342、WO-A-97/21788、WO-00/15736、WO-00/14188、WO-00/14187、WO-00/ 14183rd, WO-00/14179, WO-00/08115, WO-99/41332, EP-1029029, WO-01/18156 and WO-01/57166 Disclosed in Fischer-Tropsch (Fischer-Tropsch) derive base oil.

Synthetic method enables molecule to set up from better simply material or make the structurally-modified required to give of them Precise nature.

Artificial oil includes hydrocarbon ils such as olefin oligomer (PAO), the waxy raffinate of dibasic acid ester, polyol ester and dewaxing Liquid.The synthesis hydrocarbon sold by Royal Dutch/Shell Group company can compatibly be used with title " XHVI " (trade name) Base oil.

Preferably, base oil comprises mineral oil and/or artificial oil, and it comprises more than 80 weight %, preferably greater than 90 weights The saturate of amount %, measures according to ASTM D2007.

It is further preferred that base oil comprises the sulfur less than 1.0 weight %, preferably smaller than 0.1 weight %, it is with elementary sulfur Calculate and measured according to ASTM D2622, ASTM D4294, ASTM D4927 or ASTM D3120.

Preferably, more than 80, more preferably above 120, it measures the viscosity index (VI) of base oil according to ASTM D2270.

Preferably, lubricant oil composite has at 100 DEG C is 2-80mm²/ s, more preferably 3-70mm²/ s, most preferably 4- 50mm²Kinematic viscosity in the range of/s.

The total amount of the phosphorus in the lubricant oil composite of the present invention preferably in the range of 0.04-0.12 weight %, more preferably In the range of 0.04-0.09 weight % and most preferably in the range of 0.045-0.08 weight %, it is based on lubricating oil composition The gross weight of thing.

The lubricant oil composite of the present invention preferably has no more than 2.0 weight %, more preferably no more than 1.0 weight % and It is preferably no greater than the sulfated ash content of 0.8 weight %, its gross weight based on lubricant oil composite.

The sulfur content that the lubricant oil composite of the present invention has is not more than 1.2 weight %, more preferably no more than 0.8 weight % And most preferably no greater than 0.2 weight %, its gross weight based on lubricant oil composite.

The lubricant oil composite of the present invention can further include other additive for example antioxidant, antiwear additive, Cleaning agent, dispersant, friction modifiers in addition, VI improver, pour point depressor, corrosion inhibitor, defoamer and Sealing is fixing or seals compatilizer.

It is used for special with what organic molybdenum and herein above described organic polymer antifriction additive combined herein Preferably other additive is hydroxy alkyl amine friction modifiers, the commercially available trade name Adeka FM926 of such as Adeka.When In the presence of, hydroxy alkyl amine friction modifiers with the level of 0.2wt%-3.0wt%, more preferably with 0.3wt%-1.0wt%'s Level exists, and it is in terms of the weight of lubricating composition.

The antioxidant that can compatibly use includes those selected from amine antioxidants and/or phenol antioxidant.

In a preferred embodiment, the amount of described antioxidant in the range of 0.1-5.0 weight %, more preferably In the range of 0.3-3.0 weight % and most preferably in the range of 0.5-1.5 weight %, total based on lubricant oil composite Weight.

The example of the amine antioxidants that can compatibly use include alkylated diphenylamine, phenyl-a-naphthylamine, phenyl-β- Naphthylamines and alkylation αnaphthylamine.

Preferably amine antioxidants includes dialkyl diphenylamine such as p, p'- dioctyl-diphenylamines, p, p'- bis--α-first Base benzyl-diphenylamines and N-p- butyl phenyl-N-p'- octyl group aniline, for example single-t- butyl diphenylamines of monoalkyl diphenylamines and List-octyl diphenylamine, double (dialkyl phenyl organic) amine such as two-(2,4- diethyl phenyl) amine and two (2- ethyl -4- nonyl benzenes Base) amine, alkyl phenyl-naphthalidine such as octyl phenyl-naphthalidine and n-t- dodecylphenyl-naphthalidine, naphthalidine, aryl Naphthylamines such as phenyl-1-naphthylamine, phenyl-2-naphthylamine, N- hexyl phenyl-2-naphthylamine and N- octyl phenyl -2- naphthylamines, phenylenediamine Such as N, N'- diisopropyl-p-PDA and N, N'- diphenyl-p-PDA, and phenothiazines such as phenothiazine and 3,7- bis- Octyl group phenothiazine.

Preferably amine antioxidants include following discuss face to face the name of an article obtainable those：" Sonoflex OD-3 " (comes from Seiko Kagaku Co.), " Irganox L-57 " (coming from Ciba Specialty Chemicals Co.) and phenothiazine (go out From Hodogaya Kagaku Co.).

The example of the phenol antioxidant that can compatibly use includes double (1,1- the dimethyl-ethyI) -4- hydroxyl-benzene of 3,5- The C of propanoic acid₇-C₉Branched alkyl ester, 2-t- butylphenol, 2-t- butyl -4- sylvan, 2-t- butyl -5- sylvan, 2,4- bis--t- Butylphenol, 2,4- dimethyl -6-t- butylphenol, 2-t- butyl -4- methoxyl group phenol, 3-t- butyl -4- methoxyl group phenol, 2,5- bis- - T- butylhydroquinone, 2,6- bis--t- butyl -4- alkyl phenol such as 2,6- bis--t- butylphenol, 2,6- bis--t- butyl -4- sylvan and 2,6- bis--t- butyl -4- ethyl phenol, 2,6- bis--t- butyl -4- alkoxyl phenols such as 2,6- bis--t- butyl -4- methoxyl group phenol With 2,6- bis--t- butyl -4- ethyoxyl phenol, 3,5- bis--t- butyl -4- hydroxybenzyl sulfydryl octyl group acetass, alkyl -3- (3, 5- bis--t- butyl -4- hydroxy phenyl) propionic ester such as n- octadecyl -3- (3,5- bis--t- butyl -4- hydroxy phenyl) propanoic acid Ester, n- butyl -3- (3,5- bis--t- butyl -4- hydroxy phenyl) propionic ester and 2'- ethylhexyl -3- (3,5- bis--t- butyl -4- Hydroxy phenyl) propionic ester, 2,6-d-t- butyl-alpha-alpha-dimethyl amino-p- cresol, 2,2' methylene bis (4- alkyl -6-t- fourth Base phenol) such as 2,2' methylene bis are (4- methyl -6-t- butylphenol and 2,2- di-2-ethylhexylphosphine oxide (4- ethyl -6-t- butylphenol), double (3- methyl -6-t- butylphenol, 4,4' methylene bis (2,6- bis--t- butylphenol), 4,4'- are double for phenol such as 4,4' butylidene biss (2,6- bis--t- butylphenol), 2,2- (two-p- hydroxy phenyls) propane, double (the 3,5- bis--t- butyl -4- hydroxy phenyl) third of 2,2- Double (2,6-t- butylphenol), the six ethylidene glycols-bis- [3- (3,5- bis--t- butyl -4- hydroxy phenyl) of alkane, 4,4'- cyclohexylene Propionic ester], tri ethylene glycol double [3- (3-t- butyl -4- hydroxy-5-methyl base phenyl) propionic ester], 2,2'- sulfydryl-[diethyl Base -3- (3,5- bis--t- butyl -4- hydroxy phenyl) propionic ester], the double { 1,1- dimethyl -2- [3- (3-t- butyl -4- hydroxyl of 3,9- Base -5- aminomethyl phenyl) propiono epoxide] ethyl 2,4,8,10- tetra- oxaspiro [5,5] hendecane, double (the 3- first of 4,4'- sulfydryl Base -6-t- butylphenol) and 2,2'- sulfydryl double (4,6- bis--t- butyl resorcinol), polyphenol such as four [methylene -3- (3,5- Two-t- butyl -4- hydroxy phenyls) propionic ester] methane, 1,1,3- tri- (2- methyl -4- hydroxyl -5-t- butyl phenyl) butane, 1, 3,5- trimethyl -2,4,6- three (3,5- bis--t- butyl -4- hydroxybenzyl) benzene, double-[double (4'- hydroxyl -3'-t- butyl of 3,3'- Phenyl) butanoic acid] diol ester, 2- (3', 5'- bis--t- butyl -4- hydroxy phenyl) methyl -4- (2 ", 4 "-two-t- butyl -3 "-hydroxyl Base phenyl) double (2'- hydroxyl -3'-t- butyl -5'- the methyl-benzyl) -4- sylvan of methyl -6-t- butylphenol and 2,6- and p-t- Butylphenol-formaldehyde condensation products and p-t- butylphenol-acetaldehyde condensation thing.

Preferably phenol antioxidant include following face trade name obtainable those:" Irganox L-135 " (comes from Ciba Specialty Chemicals Co.), " Yoshinox SS " (comes from Yoshitomi Seiyaku Co.), " Antage W-400 " (comes from Kawaguchi Kagaku Co.), and " Antage W-500 " (comes from Kawaguchi Kagaku ), Co. " Antage W-300 " (coming from Kawaguchi Kagaku Co.), " Irganox L109 " (comes from Ciba Speciality Chemicals Co.), " Tominox 917 " (comes from Yoshitomi Seiyaku Co.), " Irganox L115 " (comes from Ciba Speciality Chemicals Co.), and " Sumilizer GA80 " (comes from Sumitomo ), Kagaku " Antage RC " (coming from Kawaguchi Kagaku Co.), " Irganox L101 " (comes from Ciba Speciality Chemicals Co.), " Yoshinox 930 " (comes from Yoshitomi Seiyaku Co.).

The lubricant oil composite of the present invention may include one or more phenol antioxidant and one or more amine antioxygen The mixture of agent.

In a preferred embodiment, lubricant oil composite may include single zinc dithiophosphate or two or more The combination of kind of zinc dithiophosphate as antiwear additive, described or every kind of zinc dithiophosphate be selected from dialkyl group-, two virtues Base-or alkylaryl zinc dithiophosphate.

Zinc dithiophosphate is additive well known in the art and can compatibly be represented by formula II：

Wherein R²-R⁵Can identical or different and individually comprise the primary alkane of 1-20 carbon atom, preferred 3-12 carbon atom Base, comprises the aryl that 3-20 carbon atom, the secondary alkyl of preferred 3-12 carbon atom, aryl or alkyl replace, described alkyl Substituent group includes 1-20 carbon atom, preferred 3-18 carbon atom.

Wherein R²-R⁵Phosphordithiic acid zinc compounds all different each other can be used alone or with wherein R²-R⁵All same Phosphordithiic acid zinc compound is used in mixed way.

Preferably, for described in the present invention or every kind of zinc dithiophosphate is zinc dialkyl dithiophosphate.

The example of suitably commercially available zinc dithiophosphate include coming from Lubrizol Corporation with Trade name " Lz 1097 " and " Lz 1395 " obtain those, come from Chevron Oronite with trade name " OLOA 267 " and " OLOA 269R " obtain those and come from what Afton Chemical was obtained with trade name " HITEC 7197 "；Dithio Zinc phosphate class for example comes from Lubrizol Corporation can with trade name " Lz 677A ", " Lz 1095 " and " Lz 1371 " Those obtaining, come from that Chevron Oronite is obtained with trade name " OLOA 262 " and come from Afton Chemical Those being obtained with trade name " HITEC 7169 "；With zinc dithiophosphate class for example come from Lubrizol Corporation with Trade name " Lz 1370 " and " Lz1373 " obtain those and come from Chevron Oronite and obtained with trade name " OLOA 260 " ?.

Lubricant oil composite according to the present invention can generally comprise the zinc dithiophosphate in the range of 0.4-1.2 weight %, Its gross weight based on lubricant oil composite.

10008 additionally or alternatively, antiwear additive can be suitably employed in the compositionss of the present invention.

The typical cleaning agent that can be used in the lubricating oil of the present invention includes one or more salicylate and/or phenates And/or sulphonic acid ester cleaning agent.

But, due to the organic sulfate ash that can promote lubricant oil composite with inorganic alkaline salt as cleaning agent of metal Content, therefore in a preferred embodiment of the present invention, the amount of this additive is minimized.

In order to keep low levels, may be adapted to salicylate cleaning agent.

Therefore, in one embodiment, can to comprise one or more salicylate clear for the lubricant oil composite of the present invention Clean dose.

Level in order to keep total sulfated ash content of lubricant oil composite of the present invention is preferably no greater than 2.0 weights Amount %, more preferably level are not more than 1.0 weight % and most preferably level is not more than 0.8 weight % (based on lubricant oil composite Gross weight meter), described cleaning agent is preferably with 0.05-20.0 weight %, more preferably in the range of 1.0-10.0 weight % and most preferably Amount in the range of 2.0-5.0 weight % exists, its gross weight meter based on lubricant oil composite.

Furthermore it is preferred that TBN (total base number) value that described cleaning agent independently has, in 10-500mg.KOH/g, more preferably exists In the range of 30-350mg.KOH/g and most preferably in the range of 50-300mg.KOH/g, it measures according to ISO 3771.

The lubricant oil composite of the present invention can additionally comprise no ash dispersant, and it is preferably with 5-15 weight % scope Interior amount mixing, the gross weight meter based on lubricant oil composite.

The example of spendable no ash dispersant includes polyalkenyl butanimide and polyalkenyl succinate, its disclosure In Japan Patent No.1367796,1667140,1302811 and 1743435.Preferably dispersant includes boration succinyl Imines.

The example of the VI improver being suitably employed in the lubricant oil composite of the present invention includes styrene-fourth Diene copolymers, styrene-isoprene radial copolymer and polymethacrylate copolymer and ethylene-propylene copolymer. Such VI improver can compatibly be used with the amount of 1-20 weight % scope, its gross weight based on lubricant oil composite Gauge.

Polymethacrylates can be suitably employed in the lubricant oil composite of the present invention as effective pour point depressor.

Additionally, compound such as alkenyl succinic acid or its ester moiety, the compound based on benzotriazole and be based on thiadiazoles Compound compatibly can be used as corrosion inhibitor in the lubricant oil composite of the present invention.

Compound such as polysiloxanes, dimethyl polycyclohexane and polyacrylate can be compatibly in the lubricating oil of the present invention It is used as defoamer in compositionss.

Fixing or sealing compatilizer the compound of sealing compatibly can be used as in the lubricant oil composite of the present invention include, For example, commercially available aromatic ester.

The lubricating composition of the present invention can be compatibly using conventional formulation technologies, by by base oil and organic molybdenum It is mixed together at a temperature of 60 DEG C and to prepare with polymer antifriction additive and one or more other optional additives.

In yet another embodiment of the present invention, there is provided the method for lubricating internal combustion engines, it includes it being applied herein Foregoing lubricant oil composite.

Invention further provides lubricating composition as herein described is used for reducing the purposes of friction.

Invention further provides lubricating composition as herein described is used for reducing the purposes of abrasion.

Invention further provides lubricating composition as herein described is used for improving the purposes of fuel economy

To be described by referring to the following examples below the present invention, it is not intended to be limiting in any manner the present invention Scope.

Embodiment

Program is blended using conventional lubricantss and prepares the lubricating composition (" reference oil A ") with the composition shown in table 1 below.

The amount of component is given with weight % based on the gross weight of compositionss.

Table 1 (composition of reference oil A)

Component	Wt%
		GTL 4¹	79.50
Additive bag²	13.30
		Viscoplex 3-201³	6.90
PPD⁴	0.30

1. there is the Fischer-tropsch derived base oil of the kinematic viscosity (ASTM D445) of about 4cSt at 100 DEG C, it can be suitable for Ground is by the method preparation described in WO 02/070631.

2. full SAPS additive bag, it comprises polyisobutenyl succinimide dispersant, alkyl zinc dithiophosphate, high-alkali Property alkyl sodium salicylate cleaning agent, borated dispersants and Diphenylamine Antioxidant.

3. the commercial viscosity modifier that can obtain from Evonik.

4. poly- alkylmethacrylate pour point depressor.

Reference oil A has 8.02mm²The kV100 (being measured according to ASTM D445) of/s, 35.18mm²/ s kV40 (according to ASTM D445 measure), at -35 DEG C 4330mPa.s CCS (according to ASTM D5293 measure) and 2.74mPa.s HTHS (being measured according to ASTM D4741).

Amount shown in various friction modifiers table 2 below adds in reference oil A to produce many test oil.Add benchmark Friction modifiers in oily A are that (molybdenum dithiocarbamate (MoDTC) comprising three core molybdenums, in table 2 and figure for organic molybdenum It is referred to as molybdenum trimer "), polymer antifriction additive (from the commercially available Perfad of Croda 3006) and glyceryl monooleate in 1, one Friction modifiers known to kind and being usually used.

Rub measurement is based on the composition shown in table 2 using the tug (MTM) being manufactured by PCS Instruments Carry out.

MTM tests by R.I.Taylor, and E.Nagatomi, N.R.Horswill, D.M.James are described in " A Screener test for the fuel economy potential of engine lubricants " (the 13rd with regard to Put on display in the international symposium of tribology, in January, 2002) in.

Coefficient of friction tug uses the measurement of " ball on disk " construction.

Ball sample is the steel ball bearing of polishing, diameter 19.05mm.Disk sample is concentrically solid on engine driving bar Fixed.Disk sample is concentrically fixed on another engine driving bar.Ball loads against disk, with produce with minimum rotation and The point contact area of tilt component.On the contact point, the superficial velocity by adjusting ball and disk keeps 100% sliding rolling ratio.

Test 1.25GPa pressure (71N load) at a temperature of 115 DEG C as shown in Fig. 1 and Fig. 2 from 2600mm/s is carried out down under the various speed of 5mm/s.

Every kind of oil reaches 20 test scanning altogether using new ball and new looping test, and friction results obtain from last three scannings ?.

Measure the coefficient of friction of correlative measurement formation testing (listing as in table 2) and result is described in detail in table 2 below.In table 2, border Coefficient of friction is the meansigma methodss under the low speed of 0.05m/s to 0.05m/s, and mixed film friction coefficient is in 1.0m/s to 2.6m/s Fair speed under meansigma methodss.

Table 2- result

Program is blended using conventional lubricantss and prepares another the lubricating composition (" benchmark with the composition listed in table 3 below Oily B ").

Table 3 (composition of reference oil B)

Composition:	Wt%
		GTL4¹	80.70
SV277²	7.20
		Additive bag³	12.1

2. hydrogenated styrene-diene copolymer.

3. additive bag, it comprises polyisobutenyl succinimide dispersant, alkyl zinc dithiophosphate, high alkalinity alkyl Calcium carbolate and sulphonic acid ester cleaning agent and phenol antioxidant.

Reference oil B has 8.93mm²The kV100 (being measured according to ASTM D445) of/s, 45.20mm²/ s kV40 (according to ASTM D445 measures), 183 VI, at 150 DEG C 2.52cPs HTHS (being measured according to ASTM D4741) and at 100 DEG C The HTHS (being measured according to ASTM D4741) of 5.55cPs.

Amount shown in various friction modifiers table 4 below adds in reference oil B to produce some test oil.Add benchmark Friction modifiers in oily B are that (molybdenum dithiocarbamate (is referred to as " molybdenum trimerization in table 4 and Fig. 2 to organic molybdenum Body ")), polymer antifriction additive (from the commercially available Perfad of Croda 3050) and Adeka FM926 (commercially available hydroxy alkyl Amine friction modifiers).

Measure the coefficient of friction of correlative measurement formation testing (listing as in table 4) using above-mentioned MTM method and result is described in detail in table 4 below In.In table 4, boundary friction coefficient is the meansigma methodss under the low speed of 0.05m/s to 0.05m/s, and mixed film friction coefficient is Meansigma methodss under the fair speed of 1.0m/s to 2.6m/s.

Table 4 result

Fig. 2 shows for the composition shown in table 4, and the friction coefficient measurement value in border and Mixed Zone is with speed The figure of change.

Discuss

Regions of lubrication is divided into four kinds of main classifications：(1) hydrodynamic force type, wherein surface are completely separated by fluid film, (2) bullet Property hydrodynamic force type, wherein surface is separated by very thin fluid film, and (3) mixed type, wherein surface are by some Rough Contact parts Ground separates and (4) Boundary-Type, and wherein surface major part is contact, even if there is fluid film.Mix and borderline region relies on In chemical antiwear additive and/or friction modifiers etc., to reduce abrasion and to rub.

The total expectation of friction modifiers containing molybdenum shows preferably in reducing boundary friction and organic friction modifiers are recognized It is to be more effective under mixing condition.

As can be seen from Table 2, the polymer organic friction modifiers individually adding 0.75% reduce mixing in reference oil A Friction in region, but show and increased boundary friction.

When the Mo (3 weight %MoDTC) by 170ppm adds base together with 0.75% conventional organic friction modifiers GMO When in quasi- oil A, it is observed that somewhat reducing of boundary friction and significantly reducing of mixed film friction.

When the Mo (0.25wt%MoDTC) by only 140ppm is added together with 0.75% polymer organic friction modifiers Fashionable, surprisingly it has been found that the reduction further drastically reducing with mixed film friction of boundary friction.This looks like very Positive cooperative effect, and can not be according to other prediction of result of table 2.

Polymer organic friction modifiers seem only to increase boundary friction, however with the energy of friction modifier combination containing molybdenum Enough reach low-down boundary friction, it is more much lower than the friction modifiers containing molybdenum combining with conventional organic friction modifiers GMO.

0.5% alternative polymer organic friction modifiers (Perfad 3050) are added in reference oil B and significantly drops Lower boundary and mixed film friction.

Seem that hydroxy alkyl amine friction modifiers (Adeka FM926) are more effective in Mixed Zone, but reducing side Somewhat less effective in boundary's friction.

When by 300ppm Mo (comprise 0.55 weight % of three core molybdenums molybdenum dithiocarbamate (in table 2 and table 4, In fig 1 and 2, it is defined as " molybdenum trimer ")) when adding in reference oil B, it is observed that on both border and mixed film friction In very big decline although mixed film friction seems more slightly greater than what organic friction modifiers were reached.

When the Mo (0.36wt% molybdenum trimer) by 200ppm with 1% Perfad 3050 and 0.1% hydroxy alkyl amine When being added in combination in reference oil B it is seen that both border and the Mixed Zone that (Adeka FM925) friction modifiers merge Low-down friction.Surprisingly, only using the Mo of 200ppm in this combination, when being surveyed with the Mo being used alone 300ppm When comparing of amount, boundary friction is lower.

Claims

1. it is used for the lubricating composition in the crankcase of electromotor, it comprises (i) base oil；(ii) one or more organic-molybdenum Compound, its level be enough to provide the molybdenum of 100-1000ppmw；(iii) in terms of the weight of described lubricating composition, 0.2 weight % To one or more organic polymer antifriction additive of 5.0 weight %, wherein said one or more organic polymer antifriction Additive have 1000-30000 dalton molecular weight and be following components product：

A) hydrophobic polymer subunit, it comprises the hydrophobic polymer selected from polyolefin, polyacrylic and polystyrene type；

D) optionally, chain termination group.

2. lubricating composition according to claim 1, wherein said one or more organic polymer antifriction additive be The product of following components：

D) chain termination group.

3. lubricating composition according to claim 1, wherein said one or more organic polymer antifriction additive be The product of following components：

C) at least one skeleton part that polymeric subunits can be linked together.

4. lubricating composition according to claim 1, wherein said one or more organic polymer antifriction additive be The product of following components：

D) chain termination group.

5. the lubricating composition according to any one of claim 1-4, wherein said hydrophobic polymer subunit includes polyene Hydrocarbon hydrophobic polymer.

6. the lubricating composition according to any one of claim 1-5, wherein said hydrophobic polymer subunit comprises poly- different Butene polymers, it has carried out maleation to form the polyisobutylene amber with the molecular weight in the range of 300-5000 dalton Amber anhydride.

7. the lubricating composition according to any one of claim 1-6, wherein said hydrophilic polymer subunit comprises poly- second Glycol hydrophilic polymer.

8. the lubricating composition according to any one of claim 1-7, wherein said skeleton part is selected from polyhydric alcohol, polycarboxylic acid And its mixture.

9. the lubricating composition according to any one of claim 1-8, wherein said chain termination group is any aliphatic carboxylic acid.

10. the lubricating composition according to any one of claim 1-9, wherein said product comprises some block copolymerizations Thing unit, it links together during some described hydrophobic reactions with hydrophilic polymer subunit and is formed.

11. lubricating compositions according to claim 10, the quantity of wherein said block copolymer unit is 1-20, preferably 1-15, more preferably 1-7 unit.

12. lubricating compositions according to any one of claim 1-11, wherein said one or more organic molybdenum Selected from molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), molybdenum amine, molybdenum alcoholates and molybdenum alcohol-aminate and Its mixture.

13. lubricating compositions according to claim 12, wherein said one or more organic molybdenum is dithio Carbamic acid molybdenum (MoDTC).

14. lubricating compositions according to any one of claim 1-13, it additionally comprises hydroxy alkyl amine.

15. lubricating compositions according to any one of claim 1-14, wherein said base oil is Fischer-tropsch derived base oil.

16. according to the lubricating composition of any one of claim 1-15 in the crankcase of electromotor in order to reduce the use of friction On the way.

17. according to the lubricating composition of any one of claim 1-15 in the crankcase of electromotor in order to reduce the use of abrasion On the way.

18. according to the lubricating composition of any one of claim 1-15 in the crankcase of electromotor in order to improve fuel economy Purposes.