CN108026464A - For reducing the side chain diester of engine fuel consumption - Google Patents

Abstract

The present invention relates to the fuel consumption that engine is reduced using the lubricant compositions comprising specific diester and additive.

Description

For reducing the side chain diester of engine fuel consumption

Technical field

This application involves side chain diester compound, it can be used for reduction engine, the fuel of particularly automobile engine to disappear Consumption, and improve the cleannes of engine, particularly automobile engine.

Background technology

Lubricant is widely used in the friction reduced between moving component surface, wears so as to reduce and prevents from damaging the table Face and component.Lubricant is mainly made of basestocks and one or more lubricant additives.Basestocks can be opposite high score The hydrocarbon of son amount.In the application of a large amount of pressure is applied to moving component, the lubricating composition being only made of hydrocarbon base material tends to Fail and component is damaged.Lubricant manufacturer is constantly needed to improve its formula, is wanted with the higher solved to fuel economy Ask, while balance the needs for improving Engine Cleanliness Level or reducing discharge.These requirements force manufacturer to solve its preparation ability And/or find the new basestocks that satisfiability can require.

In order to manufacture the lubricants such as machine oil, transmission fluid, gear oil, industrial lubricant, Metalworking fluid, it is necessary to always Since the oil or suitable polymerization petrochemical fluids of the lubricating oil grade of oil plant.A small amount of addition is mixed in the basestocks Agent chemicals is to improve material character and performance, such as strengthens lubricity, suppresses the abrasion and corrosion of metal, and slow down fluid Heated and oxidation infringement.Therefore, suitable various additives can be added with conventional effective dose, such as oxidation and corrosion inhibitor, Dispersant, high pressure additive, defoamer, matal deactivator and share other additives in lubricant formulations.Know for a long time Road, synthetic ester both may be used as basestocks, the additive being also used as in lubricant.With relatively inexpensive but poor Environmental Safety ore deposit Thing oil phase ratio, in the case where desired viscosity/temperatures meet strict demand, synthetic ester is mainly used as base oil.Environment connects The problem of being become more and more important by degree and biological degradability etc. is to need to expect behind based on mineral oil substitute in lubrication applications Driving factors.

The content of the invention

The present invention provides the compound comprising at least one lower formula (I) and the lubricant group of at least one lubricant additive Application of the compound in engine, the preferably fuel consumption of automobile engine is reduced, the lubricant additive are selected from by following The list of material composition：Detergent additives, antiwear additive, friction modifier additive, EP agent, antioxidant Additive, dispersant, pour point depressant additive, defoamer, thickener, viscosity index improver and its two or more mixing Thing,

Wherein:

N is less than 1.1,

R1 represents straight or branched, saturation or undersaturated C3-C20,

R ' represents straight or branched, saturation or undersaturated C2-C16,

R represents straight or branched, saturation or undersaturated C1-C20.

According to an embodiment, in the formula (I)：

N is 1；

The total amount of carbon atom is more than 15 and less than 40.

According to an embodiment, in the formula (I),

R1 represents straight or branched, saturation or undersaturated C5-C15 alkyl；

R ' represents straight or branched, saturation or undersaturated C3-C8 alkyl；

R represents straight or branched, saturation or undersaturated C1-C15 alkyl.

According to an embodiment, in the formula (I),

R1 represents the straight chain C 5-C12 alkyl of the straight chain C 5-C15 alkyl, more preferably saturation of saturation；

R ' represents the straight chain C 5-C8 alkyl of the straight chain C 3-C8 alkyl, more preferably saturation of saturation；

R represents the straight or branched C5-C10 alkyl of the straight or branched C5-C15 alkyl, more preferably saturation of saturation.

According to an embodiment, in the formula (I),

R1 represents the straight chain C 5-C8 alkyl of the straight chain C 5-C10 alkyl, more preferably saturation of saturation；

R ' represents the straight chain C 5-C8 alkyl of saturation；

R represents the straight chain C 5-C10 alkyl of saturation, straight or branched C5-C10 alkyl, preferably saturation.

According to an embodiment, formula (I) compound is formula (Ia) compound,

According to an embodiment, in the formula (I)：

R1 represents the straight chain C 8-C12 alkyl of the straight or branched C5-C15 alkyl, more preferably saturation of saturation；

R ' represents the straight chain C 5-C8 alkyl of saturation；

R represents the side chain C5-C10 alkyl of saturation, straight or branched C5-C10 alkyl, preferably saturation.

According to an embodiment, formula (I) compound is formula (Ib) compound

According to an embodiment, the gross weight based on lubricant compositions, the lubricant compositions include 0.1 weight Measure % to 50 weight %, formula (I) compound of preferably 1 weight % to 50 weight %, more preferably 5 weight % to 30 weight %.

According to an embodiment, the lubricant compositions are also comprising at least one lubricant base oil.

According to an embodiment, the lubricant base oil is Group III lubricant base oil.

According to an embodiment, the gross weight based on lubricant compositions, the lubricant compositions include 50 weights Measure % to 99 weight %, the lubricant base oil of preferably 50 weight % to 80 weight %.

According to an embodiment, the additive is at least one viscosity index improver, preferably at least a kind of polymerization Property viscosity index improver, is more preferably selected from：

Polyacrylate and polymethacrylates,

Olefin homo or copolymer, optimal ethylene/propylene,

Styrol copolymer, the preferably copolymer with isoprene or diene such as butadiene, hydrogenate or do not hydrogenate, isoamyl two Alkene polymer, preferably free radical hydrogenated polyisoprene,

Polystyrene is esterified, is preferably esterified poly- (styrene-maleic anhydride copolymer),

Mixture more than above two.

According to an embodiment, the present invention is further used for improving engine, particularly automobile engine, more preferably vapour The cleannes of at least one piston of car engine.

Embodiment

Method this application involves the composition of diester compound and for synthesis of diester compound, the diester compound Basestocks as lubricant application, or assigned clearly for finished lubricant composition or for fuel economy and to engine The basestocks blend component of the application-specific of cleanliness.Pass through diester definite based on micro- coking test (MCT), of the invention also table Reveal improved detergency.

Fuel economy is with different driving cycles, particularly NEDC (new European Driving Cycle New European Driving Cycle) gain measure, and with the trihydroxymethylpropanyl ester of the ester as known offer fuel economy (Nycobase 7300 (NB7300)) compares (see, for example, Dodos, G.S. etc., Renewable fuels and lubricants from Lunaria annual.Ind.Crops Prod.(2015),http://dx.doi.org/ 10.1016/j.indcrop.2015.05.046And DOI:10.1080/10402004.2015.1025934).

Cleannes are weighed with the grading of piston performance (piston merit), especially with respect to known in cleannes Effective PAO is weighed.

The diester of embodiment may be constructed lubricating base feed composition or for finished lubricants group according to the present invention Basestocks blend components in compound, or they can be mixed with further to finished lubricants with one or more additives Optimization, or for specifically applying.The suitable application that can be used includes but not limited to (Two-way Cycle) engine oil, especially It is automobile engine.As understood by those skilled in the art, diester according to the present embodiment can also have alternative Chemical use and application.The content of the diester of embodiment of the present invention can be easily found out.In some respects, finished lubricants Composition can include about 1 weight % to the diester of about 25 weight %, the lubricating base oil of about 50 weight % to about 99 weight % and The additive of about 1 weight % to about 25 weight %, particularly additive bag.

The suitable non-limiting examples of additive can include detergent, antiwear agents, antioxidant, metal passivation Agent, extreme pressure (EP) additive, dispersant, viscosity modifier (viscosity modifiers), pour point depressant, anticorrosive, Coefficient of friction modifiers, colouring agent, defoamer and demulsifier etc..

The present invention diester preferably with viscosity modifier combination.Viscosity improver is well known in the art, and its Description is found in Chemistry and Technology of Lubricants-Editors:Mortier,Roy M.,Fox, Malcolm F., Orszulik, Stefan, Ed 2010, is incorporated into herein by quoting.

Viscosity improver is typically：

- polyacrylate and polymethacrylates, commonly referred to as PMA；

- olefin homo or copolymer, commonly referred to as optimal ethylene/propylene, OCP (olefin copolymer)

- styrol copolymer, the preferably copolymer with isoprene or diene such as butadiene, hydrogenate or do not hydrogenate, such as HSD (hydrogenated styrene diene), isoprene copolymer, such as SIP (styrene isoprene polymer), preferably free radical hydrogen Change polyisoprene (HRI),

-ester polystyrene, is preferably esterified poly- (styrene-maleic anhydride copolymer), is known as SPE (styrenated polyesters),

Mixture more than-above two, particularly PMA/OCP.

The amount of viscosity improver can change, and the gross weight based on lubricant compositions, be usually 0.01 weight % To 15 weight %, preferably 1 weight % to 10 weight %.

Suitable base oil can be any conventional use of lubricating oil, such as mineral oil, artificial oil or mineral oil and conjunction Into the blend of oil, or be natural oil and natural oil derivatives in some cases, it is all individually or its combination.For The mineral lubricating oil basestocks for preparing lubricant compositions can be from paraffin, cycloalkane and crude oil derived any of mixed base The basestocks of regular refiner.Lubricating base oil can include the polyolefin-based of polyalphaolefin (PAO) and poly-internal-olefins (PIO) type Plinth material.The oil of lubricant viscosity from coal or shale is also useful.

The example of artificial oil includes hydrocarbon ils, such as polymerization and mutual polyolefin (such as polybutene, polypropylene, propylene isobutene Copolymer)；Poly- (1- hexenes), poly- (1- octenes), poly- (1- decene) and its mixture；Alkylbenzene is (for example, detergent alkylate, ten Tetraalkyl benzene, dinonyl benzene, two-(2- ethylhexyls)-benzene)；Polyphenyl (such as biphenyl, terphenyl, alkylated polyphenyls)；Alkylation Diphenyl ether and alkylated diphenyl sulfides and its derivative, analog and homologue.

Alkylene oxide polymer and interpretation and its terminal hydroxyl by be esterified and etherification modified derivative form can be with The another kind of known synthetic lubricant fluid used.These can enumerate what is prepared by the polymerization of ethylene oxide or propylene oxide Oil, these polyoxyalkylene polymers alkyl and aryl ether (such as number-average molecular weight be 1000 methyl-polyisopropylene glycol ethers, Molecular weight is the diphenyl ether of the polyethylene glycol of 500-1000, and molecular weight is the polypropylene glycol Anaesthetie Ether of 1000-1500) or its Single-and polycarboxylate, such as acetic acid esters, the C of mixing_3-8Fatty acid ester, the C of tetraethylene glycol₁₃Oxygen-containing acid diesters, or PAG, such as PO/BO, as disclosed in WO201270007 and WO2013164457.

The another kind of suitable synthetic lubricant fluid that can be used includes dicarboxylic acids (such as phthalic acid, butanedioic acid, alkyl Butanedioic acid, alkenyl succinic, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimer, third Diacid, alkyl malonic acid and alkenyl malonic acids) with various alcohol (for example, butanol, hexanol, dodecanol, 2-Ethylhexyl Alcohol, second Glycol, diethylene glycol monoether and propane diols) ester.The instantiation of these esters includes dibutyl adipate, decanedioic acid two-(2- Ethylhexyl) ester, the just own ester of fumaric acid two, di-n-octyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, adjacent benzene two Formic acid dioctyl ester, didecyl phthalate, decanedioic acid two (eicosyl) ester, the 2- ethylhexyl diester of linoleic acid dimer The complex ester to be formed is reacted with by 1 mole of decanedioic acid and 2 moles of tetraethylene glycols and 2 moles of 2 ethyl hexanoic acids.As artificial oil Ester further include by C₅To C₁₂The polyalcohols such as monocarboxylic acid and neopentyl glycol, trimethylolpropane and pentaerythrite, or it is all The ester as prepared by the polyol ethers such as dipentaerythritol and tripentaerythritol.

Poly- alkyl-, poly- aryl-, poly-alkoxyl-or poly- aryloxy group-silicone oil and silicate oil etc. is based on silicon Oil includes another kind of useful syntholube, such as tetraethyl orthosilicate, silicic acid tetra-isopropyl, silicic acid four-(2- ethylhexyls) Ester, silicic acid four-(4- methylhexyls) ester, silicic acid four-(to tert-butyl-phenyl) ester, hexyl-(4- methyl -2- amoxys) two silica Alkane, poly- (methyl) siloxanes and poly- (aminomethyl phenyl) siloxanes.Other synthetic lubricant fluids include phosphorous sour liquid ester (such as The diethylester of tricresyl phosphate, trioctyl phosphate and decane phosphonic acids) and polymerism tetrahydrofuran.

The oil that is unpurified, refined and re-refining of type disclosed above, either natural or synthesis (and Mixture more than any two in these) it can be used as lubricating base oil in lubricant compositions.Unrefined oil is Without the oil that processing is further purified and is directly obtained from natural or synthetic source.For example, the page directly obtained from retorting operation Shale oil, the oil oil directly obtained from primary distillation or directly obtains from esterification technique and does not use after further treatment Ester oil can be unrefined oil.Refined oil is similar to unrefined oil, and difference is that they are dynamic in one or more purifying Further handled in work to improve one or more properties.Many such purification techniques are known to the skilled in the art, example As solvent extraction, second distillation, acid or alkali carries take, filter, be percolated, rerefined oils pass through with having made in service for obtaining The similar technique of refined oil obtains.Such rerefined oils are also referred to as reclaimed oil or reprocessed oils, and typically also through It is intended to remove useless additive and in addition the technology of oil decomposition product is handled.

The oil of lubricant viscosity can also be determined according to the regulation in American Petroleum Institute (API) (API) base oil interchangeability guide Justice.Five base oil groups are as shown in the table.I, II and III groups are mineral oil basestocks.In some embodiments, lubrication is viscous The oil of degree is I, II, III, IV or V group oil or its mixture.

In one aspect, diester is prepared by the double acting approach of transesterification and saturated fatty acid addition.In other aspects, two Ester is prepared by three action pathway of transesterification, formic acid addition and saturated fatty acid addition.

Transesterification is well known to those skilled in the art and can be described by formulas below：RCOOR^a+R^bOH →RCOOR^b+R^aOH.Reactant ester typically (fat) acid alkyl ester, including the C derived from natural oil₁-C₂₀(fat) dialkylaminobenzoic acid Ester.In some embodiments, C₁-C₂₀(fat) acid alkyl ester can be unsaturated alkyl ester, such as unrighted acid first Base ester.In further embodiment, such ester can include 9-DAME (9- decylenic acids methyl ester), 9-UDAME (9- 11 Carbon enoic acid methyl ester) and/or 9-DDAME (9- dodecenoic acids methyl ester).Transesterification reaction is big at about 60 DEG C -80 DEG C and about 1 Carried out under air pressure.

Such fatty acid alkyl esters can be produced conveniently by certainly-double decomposition of natural oil and/or intersection-double decomposition.It is multiple Decomposition is a kind of catalytic reaction, it is related to formation and cutting by carbon-to-carbon double bond, in the chemical combination containing one or more double bonds Alkylidene unit is exchanged between thing (i.e. olefinic compounds).Intersection-double decomposition can as etc. schematically show shown in Formulas I：

(I)

R^a- CH=CH-R^c+R^a- CH=CH-R^d+R^b- CH=CH-R^c+R^b- CH=CH-R^d

+R^a- CH=CH-R^a+R^b- CH=CH-R^b+R^c- CH=CH-R^c+R^d- CH=CH-R^d

Wherein R^a、R^b、R^cAnd R^dIt is organic group.

It can be schematically shown from-double decomposition as shown in formulas below II：

(II)

Wherein R^aAnd R^bIt is organic group.

Specifically, natural oil from-double decomposition or natural oil and alkene intersects-double decomposition.Suitable alkene is tool There are one or more carbon-to-carbon double bonds and with the internal olefin or alpha-olefin of about 2 to about 30 carbon atoms.The mixed of alkene can be used Compound.Alkene can be monounsaturated C₂-C₁₆Alpha-olefin, such as monounsaturated C₂-C₁₀Alpha-olefin.Alkene can also include C₄-C₉Internal olefin.Therefore, the alkene properly used includes such as ethene, propylene, 1- butylene, cis and trans -2- butylene, 1- penta Alkene, dissident's alkene, 1- hexenes, 3- hexenes, 1- heptene, 1- octenes, 1- nonenes and 1- decene etc., and their mixture, and Include alpha-olefin, such as ethene, propylene, 1- butylene, 1- hexenes and 1- octenes etc. in some instances.In WO 2008/048522 In disclose the non-limiting examples of the method that fatty acid alkyl esters are manufactured by double decomposition, its content is incorporated to this by quoting Text.Specifically, the embodiment 8 and 9 of WO 2008/048522 can be used for production 9- decenoates and 9- dodecenoic acid first Ester.Suitable method is also appeared in U.S. Patent Application Publication No. 2011/0113679, is incorporated to by quoting to be instructed Herein.

Metathesis catalyst in this reaction can include any catalyst or catalyst system of catalysed metathesis reaction. Any of metathesis catalyst can be used alone or be used with one or more other catalyst combinations.Some subdivisions It can be heterogeneous or homogeneous catalyst to solve catalyst.Nonrestrictive exemplary metathesis catalyst and process conditions are described in The 18-47 pages of PCT/US2008/009635, is incorporated into by quoting.Shown many metathesis catalysts by Materia, Inc. (Pasadena, CA) are manufactured.

Intersection-double decomposition by natural oil and alkene is reacted in the presence of homogeneous or heterogeneous metathesis catalyst come Complete.When natural oil is from-double decomposition, alkene is omitted, but identical catalyst type can be used.Suitable homogeneous subdivision Solve the halide or oxo halide (such as WOCl of catalyst including transition metal₄Or WCl₆) and alkylation co-catalyst (such as Me₄Sn combination).Homogeneous catalyst can include alkylidene (or the carbon clearly limited of transition metal, particularly Ru, Mo or W Alkene) complex compound.These include the first generation and second generation Grubbs catalyst and Grubbs-Hoveyda catalyst etc..It is suitable sub- Alkyl catalyst can have with lower structure：

M[X¹X²L¹L²(L³)_n]=C_m=C (Rⁱ)Rⁱⁱ

Wherein M is the 8th group 4 transition metal, L¹、L²And L³It is neutral electron donor ligand, n is 0 (so that L³It can not deposit ) or 1, m be 0,1 or 2, X¹And X²It is anion ligand, and RⁱAnd RⁱⁱIndependently selected from H, alkyl, the alkyl being substituted, containing miscellaneous The alkyl of atom, be substituted contain heteroatomic alkyl and functional group.X¹、X²、L¹、L²、L³、RⁱAnd RⁱⁱIn any two more than can To form cyclic group, and any one in these groups can be connected to support.

First-generation Grubbs catalyst falls into the category, wherein m=n=0, and such as U.S. Patent Application Publication Described in No.2010/0145086 (" ' 086 disclosure "), to n, X¹、X²、L¹、L²、L³、RⁱAnd RⁱⁱEspecially selected, by helping Draw the teaching for being incorporated to and being related to all metathesis catalysts.

Second generation Grubbs catalyst can also have an above-mentioned formula, but L¹It is carbene ligands, wherein carbene carbon side joint N, O, S or P atoms, such as two N atoms.Carbene ligands can be a part for cyclic group.Suitable second generation Grubbs is urged The example of agent is also appeared in ' 086 disclosure.

In another kind of suitable alkylidene catalyst, L¹It is the strong coordination in the first generation and second generation Grubbs catalyst Neutral electron donor, and L²And L³It is the weak coordinating neutral e donor ligands of optionally substituted heterocyclic group form.Therefore, L²And L³It is pyridine, pyrimidine, pyrroles, quinoline or thiophene etc..

In the suitable alkylidene catalyst of another class, bidentate ligand or tridentate ligand, example are formed using a pair of of substituent Such as diphosphine, two alkoxide or alkyldiketonate/salt.Grubbs-Hoveyda catalyst is wherein L²And R²Such catalysis of connection The subgroup of agent.Neutral oxygen or nitrogen can be coordinated with metal, at the same can also be bonded to relative to carbene carbon for α-, β-or γ- Carbon on to provide bidentate ligand.The example of suitable Grubbs-Hoveyda catalyst is also appeared in ' 086 disclosure.

The several diagrams for the suitable catalyst that can be used are merely provided with lower structure：

Include some rheniums and molybdenum compound suitable for the heterogeneous catalysis of certainly-double decomposition or intersection-metathesis reaction, such as Such as J.C.Mol existsGreen Chem.4Described in the 11-12 pages of (2002) 5.Instantiation is included by alkylation co-catalysis The Re on aluminium oxide that agent (such as tetraalkyl tin-lead, germanium or silicon compound) promotes₂O₇Catalyst system.It is other including by four MoCl on the silica of tin alkyl activation₃Or MoCl₅。

For the other example from-double decomposition or the suitable catalyst of intersection-double decomposition, referring to U.S. Patent No. 4,545, No. 941, instructed and citation therein is incorporated herein by quoting.Referring further toJ.Org.Chem.46(1981) 1821；J.Catal.30(1973)118；Appl.Catal.70(1991)295；Organometallics,13(1994)635；Olefin Metathesis and Metathesis Polymerization by Ivin and Mol(1997),andChem.&Eng.News 80(51), Dec.23,2002, p.29, it also discloses that useful metathesis catalyst.Appropriate catalytic The illustrative example of agent includes ruthenium and osmium carbene catalysts, as U.S. Patent No. 5,312,940,5,342,909,5,710,298, 5,728,785、5,728,917、5,750,815、5,831,108、5,922,863、6,306,988、6,414,097、6,696, 597th, 6,794,534,7,102,047, No. 7,378,528 and U.S. Patent Application Publication No. 2009/0264672A1 and PCT/ Whole these, are incorporated herein by the catalyst disclosed in the 18-47 pages of US2008/009635 by quoting.Can be favourable Many metathesis catalysts that ground is used for metathesis reaction are manufactured and sold by by Materia, Inc. (Pasadena, Calif.).

Raw material is suitable as with the natural oil by certainly-double decomposition or with olefin cross-double decomposition generation fatty acid alkyl esters It is well-known.Suitable natural oil include vegetable oil, algal oil, animal tallow, tall oil, these oily derivatives and its Combination.Therefore, suitable natural oil is included for example：It is soya-bean oil, palm oil, rapeseed oil, coconut oil, palm-kernel oil, sunflower oil, red Caul-fat, sesame oil, corn oil, olive oil, peanut oil, cottonseed oil, canola oil (canola oil), castor oil, linseed oil, paulownia Oil, jatropha oil, mustard oil, field pennycress oily (pennycress oil), camellia oil, coriander oil, apricot kernel oil, wheat-germ oil, Animal oil, tallow, lard, poultry fat and fish oil etc..Soya-bean oil, palm oil, rapeseed oil and its mixture are the unrestricted of natural oil Property example.

Fatty acid alkyl esters including unsaturated fat acid alkyl ester are under the conditions of well known by persons skilled in the art Carry out transesterification.Such alcohol can represent by R-OH, and wherein R is required ester group, such as short hydrocarbon, such as C₁-C₂₀Hydrocarbon, such as C₃-C₁₅Hydrocarbon.Such hydrocarbon can include alkyl, aryl, alkenyl, alkynyl, they can be straight or branched.In some embodiment party In formula, alcohol can include methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, amylalcohol, isoamyl Base, hexanol, cyclohexanol, enanthol, 2-Ethylhexyl Alcohol, octanol, decyl alcohol, tip-nip, dodecanol, eicosanol.

Suitable catalyst for transesterification reaction includes the non-volatile esterification catalyst of any acidity, lewis acid, Blang Si Taide acid, organic acid, substantially nonvolatile inorganic acid and its partial ester (partial ester) and heteropoly acid.It is especially suitable Esterification catalyst include alkyl sulfonic acid, aryl sulfonic acid or alkarylsulphonic acid, such as methanesulfonic acid, naphthalene sulfonic acids, p-methyl benzenesulfonic acid and Dodecyl benzene sulfonic acid.Suitable acid can also include aluminium chloride, boron trifluoride, dichloroacetic acid, hydrochloric acid, acid iodide, phosphoric acid, nitre Acid, acetic acid, stannic chloride, titanium tetraisopropylate, dibutyltin oxide and trichloroacetic acid.The dosage of these catalyst can be natural oil About 0.1 weight % of raw material to 5 weight %.

In some embodiments, the second effect is that the aliphatic acid carried out in the double bond of unsaturated fat acid alkyl ester adds Into.In another embodiment, the 3rd effect is the aliphatic acid addition carried out in the double bond of unsaturated fat acid alkyl ester.Fat Fat acid is saturated fatty acid, and can be straight or branched acid, and is linear saturated fatty acids in some instances.Saturation Some non-limiting examples of aliphatic acid include propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, hendecanoic acid, Dodecylic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, Heptadecanoic acide, octadecanoid acid, nonadecylic acid, 20 Alkanoic acid, heneicosanoic acid, behenic acid, tricosanic acid, lignoceric acid, hyenic acid, hexacosoic acid, 27 Alkanoic acid (heptacosylic), carboceric acid (carboceric), octocosoic acid, montanic acid, melissic acid, 30 Two alkanoic acids, psyllic acid, gheddic acid, pentatriacontane acid.

The reaction of saturated fatty acid and unsaturated fat acid alkyl ester is by strong acid catalyst.Strong acid can be lewis acid, cloth Lanace platform moral acid or solid acid catalyst.Such sour example includes transition metal fluoroform sulphonate and lanthanide series fluoroform Sulfonate, hydrochloric acid, nitric acid, perchloric acid, tetrafluoro boric acid or trifluoromethanesulfonic acid.Acid can include alkyl sulfonic acid, aryl sulfonic acid or alkane Aryl sulfonic acid, such as methanesulfonic acid, naphthalene sulfonic acids, trifluoromethanesulfonic acid, p-methyl benzenesulfonic acid and dodecyl benzene sulfonic acid.Solid acid catalyst It can include cation exchange resin, such as15、35、120、 Monosphere M-31、Monosphere DR-2030 and acid and acid active mesoporous material are glued with natural Soil, such as kaolin, bentonite, Attagel (attapulgites), montmorillonite and zeolite.The dosage of these catalyst can be About 0.1 weight % of natural oil raw material to 5 weight %.

The reaction of saturated fatty acid and unsaturated fat acid alkyl ester produces diester product and its isomer mixture.Below Display uses a non-limiting reaction schemes of the 9-DAME as the above-mentioned synthesis of unsaturated alkyl ester progress：

In above reaction scheme, R and R1 can be the one or more in following group：C₁-C₂₀Alkyl, such as C₃- C₂₀Alkyl, it can be straight or branched, saturation or undersaturated.Other non-limiting diester will below in an example Show.

In some embodiments, the three action pathway systems that diester passes through transesterification, formic acid addition and saturated fatty acid addition It is standby.

Transesterification condition is similar with those described above.Second effect is the first carried out in the double bond of unsaturated fat acid alkyl ester Sour addition.Its reactivity is about the 10 of its higher carbon number analog to formic acid being unique in that in straight-chain monobasic carboxylic acid's classification Times.Specifically, the pKa value of formic acid is 3.75, and the pKa value of acetic acid and propionic acid is 4.75 and 4.87.The opposite peracid of formic acid The meaning of property is in formic acid, addition need not add strong acid catalyst in unsaturated fat acid alkyl ester.The province of strong acid catalyst Product quality can be slightly caused to improve and produce specific structure isomer products.The use of formic acid has the advantages that other, such as exists When free hydroxyl group material is target compound, the preparation of methanoyl base ester is favourable.For example, preparing the feelings of acetic acid addition product Under condition, the saponification of acetoxyl group ester can produce the acetic acid salt waste of stoichiometry.On the contrary, the saponification of methanoyl base ester will produce water Property alkalescence formates.

Non-limiting examples using 9- decenoates as unsaturated fat acid alkyl ester, add formic acid, obtain first Acyloxy derivative (9-OCHO-DAME).Then generation 9- hydroxydecanoic acid methyl esters are hydrolyzed in the derivative.The technique it is anti- Answer scheme as follows：

Then the hydroxyl saturated fatty acid of 9- hydroxydecanoic acid methyl esters and esterification catalyst are esterified.Saturated fatty acid Some non-limiting examples include propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, hendecanoic acid, dodecane Acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, Heptadecanoic acide, octadecanoid acid, nonadecylic acid, arachic acid, two Hendecanoic acid, behenic acid, tricosanic acid, lignoceric acid, hyenic acid, hexacosoic acid, carboceric acid, two Heptadecanoic acide, octocosoic acid, montanic acid, melissic acid, lacceroic acid, psyllic acid, gheddic acid, 30 Five alkanoic acids.Transesterification catalyst can be acid non-volatile catalyst, lewis acid, Bronsted acid, organic acid, substantially Nonvolatile inorganic acid and its partial ester and heteropoly acid.Specially suitable esterification catalyst includes alkyl sulfonic acid, aryl sulfonic acid or alkane Aryl sulfonic acid, such as methanesulfonic acid, naphthalene sulfonic acids, p-methyl benzenesulfonic acid and dodecyl benzene sulfonic acid.Suitable acid can also include chlorination Aluminium, boron trifluoride, dichloroacetic acid, hydrochloric acid, acid iodide, phosphoric acid, nitric acid, acetic acid, stannic chloride, titanium tetraisopropylate, dibutyltin oxide And trichloroacetic acid.

Another non-limiting reaction scheme shown below using 9-DAME as the above-mentioned synthesis of unsaturated alkyl ester：

In above reaction scheme, R and R1 can be the one or more in following group：C₁-C₂₀Alkyl, such as C₃- C₂₀Alkyl, it can be straight or branched, saturation or undersaturated.

Other non-limiting examples of synthesized diester can include with lower structure：

Mark represents the origin of each component.Breviary term can be used for describing these compositions.For above diester, composition can With labeled as C12/9-DA-2EH, to quote C12 aliphatic acid, 9-DAME and 2-Ethylhexyl Alcohol.

Other non-limiting diester will be shown in the examples below, can include its isomers, including cis and trans Isomers.

Embodiment

Acid number：Acid number is measuring for total acid present in oil.Acid number can be by known to persons of ordinary skill in the art Any suitable titration method determines.For example, acid number can be by neutralizing the amount of the KOH needed for given oil samples come really It is fixed, and therefore can be shown with mg KOH/g oil meters.

NOACK volatility (TGA) is that the evaporation loss of lubricating base oil is measured in a period of time.The value of report passes through ASTM method ASTM D6375-09 are measured.

Pour point is measured by ASTM method D97-96a.Viscosity/kinematic viscosity is measured by ASTM method D445-97.It is viscous Degree/kinematic viscosity is measured by ASTM method D445-97.Viscosity index (VI) (is criticized for 1998 again by ASTM method D2270-93 It is accurate) measurement.

The transesterification program of the 9-DAME of the various unsaturated alkyl esters of the preparation of diester raw material-be used to prepare

Three neck round bottom installs Dean-Stark traps under condenser.Reaction vessel loads the required of 1.0 molar equivalents Unrighted acid methyl ester (FAME, such as 9- decenoates, 9- dodecenoic acids methyl esters), 1.2 molar equivalents it is required Alcohol (such as 2-Ethylhexyl Alcohol, 1- octanols, isobutanol) and 10 weight % octanols.The mixture is with 0.025 molar equivalent to first Benzene sulfonic acid processing, and temperature is risen to 130 DEG C.In order to help to remove methanol, headroom is continuously purged with nitrogen, and react Every 30 minutes of the temperature of mixture increases by 5 DEG C, has been consumed until GC-FID shows all FAME (for example,≤4 when small when reacting Between).Catalyst is quenched with the KOH aqueous solutions (0.1N concentration) of equivalent.Then mixture is separated, and organic phase is used Water washing three times (20g water/100g reaction mixtures), uses MgSO₄It is dry, and filter.Beta-unsaturated esters pass through distillation purifying, separation Yield can be the 75% to 90% of theoretical yield afterwards.

Diester preparation procedure

In double neck RBF equipped with heating mantle and stirring rod, the unsaturated alkyl ester of 1.0mol equivalents and 1.25mol are worked as The saturated fatty acid and 5.0wt% trifluoromethanesulfonic acids of amount merge.Reagent is stirred at 60 DEG C 18 it is small when, it is desirable to reaction is not present Water, particularly on the humidity big date (ester hydrolysis can cause many accessory substances).The 5M of trifluoromethanesulfonic acid equimolar equivalent KOH aqueous solutions are quenched and (if using 7mmol TfOH for example, reacting, are quenched with the aqueous solution of 7mmol KOH).Washed Three times, as far as possible without using any brine.The pH for being greater than about 6.5 is provided (as it may occur that dividing using pH bars before distillation Solution).Distillation occurs<(head temperature may by 2Torr>230 DEG C, tank temperature>245℃).The alkaline oxygen dry to sinter funnel addition Change aluminium plug (aluminium oxide 0.5 " -1 "), and filtered with very weak vacuum (about 650Torr).If acid number is greater than about 0.5mg KOH/g, then repeat to filter beyond the Great Wall in identical aluminium oxide.Before aluminium oxide is handled, carried out with the hexane solution of 5%EtOAc Stir to discharge the residual diester of appearance.Then this part can be merged with complete evaporation with Bulk Product (bulk product). If necessary to relatively low acid number, then it is probably useful product is entered in hexane before by alumina filter.Except alkalescence Outside aluminium oxide, there are many products for being commonly used in reducing acid number by filtering, such as a kind of magnesium silicates of Florisil-. Yield can be 35% to 45% after separation.

Embodiment 1-octanoic acid (caprylic acid, octanoic acid)

C8:0/2-EH-9-DA

2- ethylhexyl -9- decylenic acids are handled with trifluoromethanesulfonic acid (Sigma Aldrich, 98%, 10g, 0.067mol) The mixture of ester (>=98%, 200g, 0.708mol) and octanoic acid (Sigma Aldrich, >=98%, 306g, 2.12mol).Will Mixture stirred at 60 DEG C 18 it is small when.Mixture is cooled to 25 DEG C, and with 3x 100mL saturated sodium bicarbonate aqueous solutions and 100ml salt water washings.Organic phase is dried over magnesium sulfate and filters.Product under 210 DEG C -220 DEG C, 2Torr by being evaporated in vacuo Recycling；Discard light fraction and bottoms (bottoms).Sediment is removed by sinter funnel vacuum filter, so as to obtain 103g Colorless oil.Physical property record is as follows：Kinematic viscosity (KV) at 100 DEG C is 3.24cSt, and the KV at 40 DEG C is 12.02cSt, viscosity index (VI) (VI) 143, pour point<- 45 DEG C, NOACK volatility 15wt%.

In a particular aspects, diester is by following representation

9- (octanoyloxy) capric acid 2- ethylhexyls can also be referred to as herein.

C8:0/ octyl group -9-DA

With trifluoromethanesulfonic acid (Sigma Aldrich 98%, 10g, 0.067mol) processing octyl group -9- decenoates (> 98%, 200g, 0.708mol) and it is sad (Aldrich, >=98%, 306g, 2.12mol).Mixture is stirred 20 at 60 DEG C Hour.At room temperature, saturation NaHCO3 solution (250mL) is added in reaction vessel and stirred 30 minutes.Mixture is turned Move on in separatory funnel and be separated.Organic phase is washed with brine (200mL x 3), is dried with MgSO4, and at 234 DEG C, Distilled under 2torr.Distillate is washed with water again and is dried by rotary evaporation, produces the colorless oil of 77g clarifications.Thing Rationality matter record is as follows：KV at 100 DEG C is 3.16cSt, and the KV at 40 DEG C is 11.3cSt, VI 151, NOACK volatility 10wt%.The diester is referred to as 9- (octanoyloxy) octyl herein.This is the ester of Formulas I (a).

2-capric acid of embodiment (capric acid, decanoic acid)

C10:0/2-EH-9-DA

With trifluoromethanesulfonic acid (20g, 0.133mol) processing 2- ethylhexyl -9- decenoates (>=98%, 400g, 1.42mol) and capric acid (Aldrich, >=98%, 489g, 2.83mol) mixture.It is small that mixture is stirred at 60 DEG C to 20 When.The mixture is cooled to 25 DEG C, is quenched with 150ml 1M KOH, this results in precipitation.Water is added into mixture simultaneously It is vigorously stirred.Gained lotion is transferred in separation vessel and is separated.Mixture is continuously washed with 5x 150mL H2O. Product is recycled by being evaporated in vacuo under 225 DEG C, 2Torr；Discard light fraction and bottoms.Distillation obtains 223.1g as isomery The product of body mixture, is 99% by GC-FID purity.Physical property record is as follows：KV at 100 DEG C is 3.6cSt, 40 DEG C Under KV be 14.1cSt, VI 145, pour point<- 45 DEG C, NOACK volatility 10wt%.

C10:0/2-EH-9-DA

With trifluoromethanesulfonic acid (Aldrich, >=98%, 40g) processing 2- ethylhexyl -9- decenoates (>=98%, 800g, 2.83mol) and capric acid (Aldrich, >=98%, 490.2g, 2.84mol) mixture.Mixture is stirred at 60 DEG C Mix 20 it is small when.Then reaction mixture is cooled to room temperature, and adds 67g NaHCO₃.Continuously stir suspension>24 it is small when, directly PH >=6 (neutralize also by bleach dark-coloured reaction mixture to yellow show) are shown to pH bars.By mixture gravity filtration, 224 DEG C, by the way that recovery product is evaporated in vacuo under 2Torr；Raw material is recycled as lightweight fraction, discards bottoms.Main lease making weight The product (397g, 0.87mol) as colorless oil is obtained by filtration in power.Merge the light fraction during distilling to provide containing 2- The 512g of ethylhexyl -9- decenoates (69 weight %, pass through GC-FID) and capric acid (26 weight %, pass through GC-FID) is mixed Thing.When full dose is handled with trifluoromethanesulfonic acid (Aldrich, >=98%, 10g) and stirring 18 is small at 60 DEG C.At room temperature, will be mixed Compound and NaHCO₃(17g, 0.2mol) is stirred until pH >=6 together.It is pure by the way that progress is evaporated in vacuo under 2Torr at 224 DEG C Change, obtain the product (170g, 0.37mol) as colorless oil.The product fraction that two reactions are obtained merges, and passes through GC-FID verifies purity.Physical property record is as follows：KV at 100 DEG C is 3.6cSt, and the KV at 40 DEG C is 14.0cSt, VI 146, pour point<- 45 DEG C, NOACK volatility 10wt%.

3-laurate of embodiment

C12:0/2- ethylhexyl -9- decenoates

By 2- ethylhexyl -9- decenoates (>=98%, 200g, 0.708mol) and dodecylic acid (Sigma Aldrich, >=98%, 425g, 2.12mol) mixture be heated to 60 DEG C, then with trifluoromethanesulfonic acid (Sigma Aldrich, >=98%, 10g, 0.067mol) processing.When by reaction, stirring 22 is small at 60 DEG C.Then it is reaction mixture is cold But to 45 DEG C, and 100mL hexanes are added.The content of reaction vessel is transferred in dropping funel, by should at -20 DEG C Mixture is added drop-wise in isopropanol and dodecylic acid is recrystallized from solution.Gained suspension is true by 6 filter paper of Whatman Sky filtering.Filter vacuum is concentrated, grease 0.1M K₂CO₃Aqueous solution washing is 7 up to pH, is then washed with water.It is organic Mutually use Na₂SO₄It is dry, then at 218 DEG C, purified under 0.1Torr by being evaporated in vacuo, obtain 69g grease.Lead to distillate Cross Al₂O₃Bed, the colorless oil clarified.KV at 100 DEG C is 3.97cSt, and the KV at 40 DEG C is 15.62cSt, VI 160.6, -40 DEG C of pour point, NOACK volatility 5.5wt%.The diester of synthesis be properly termed as 10- [(2- ethylhexyls) epoxide]- 10- oxa- dodecane -2- base dodecylates.This is the ester of Formulas I (b).

C12:0/iBu-9- decenoates

Merge isobutyl group -9- decenoates (>=98%, 399.2g) and dodecylic acid (Sigma Aldrich, >=98%, 1056g,5.3mol).Heat the mixture to 60 DEG C, then with trifluoromethanesulfonic acid (Sigma Aldrich, >=98%, 20g, 0.13mol) handle.When by reaction, stirring 22 is small at 60 DEG C.By the way that reaction mixture is added drop-wise in the dry ice bath of isopropanol, And separate out laurate.By the cold filtering of suspension.Filter vacuum is concentrated, is then transferred into separatory funnel and with water (150mL X 7) washing.Organic phase Na₂SO₄It is dry, and purified by distillation.Main point conduct under 215 DEG C, 0.1Torr 292 grams of grease obtain.Distillate is filtered by alkali alumina.KV at 100 DEG C is 3.35cSt, and the KV at 40 DEG C is 12.24cSt, VI 154, pour point<- 18 DEG C, NOACK volatility 12wt%.

C10:0/2- ethylhexyl -9- dodecylene acid esters

2- ethylhexyl -9- dodecylenes are handled with trifluoromethanesulfonic acid (Sigma Aldrich, 98%, 20g, 0.13mol) Acid esters (>=98%, 416g, 1.47mol) and dodecylic acid (Sigma Aldrich, >=98%, 357g, 2.07mol) and 60 When stirring 18 is small at DEG C.Under agitation the reaction is cooled to 25 DEG C, while by the way that KOH solution is added dropwise (in 75mL H2O 7.5g KOH) catalyst is quenched in reaction vessel.Mixture is transferred in separatory funnel and is separated.Organic phase is used Deionized water (200mL x 2) is washed, and uses MgSO₄Dry and filter.Product 224 DEG C,<By distillation purifying under 1Torr, and Pass through Al in sinter funnel under 650Torr₂O₃Vacuum filter is carried out, obtains the faint yellow oil of 230g clarifications.At 100 DEG C KV is 3.9cSt, and the KV at 40 DEG C is 15.7cSt, VI 149, pour point<- 45 DEG C, NOACK volatility 6.0wt%.

C12:0/2- ethylhexyl -9- decenoates

Add 9-OH-2- ethylhexyl decylates into 500mL three neck round bottom at 23 DEG C under the atmosphere of air (50g, 0.17mol), dodecylic acid (40g), methanesulfonic acid (0.8g) and toluene.Then on flask installation with heating mantle, Dean-Stark distills the electric thermo-couple temperature adjuster of trap and water condenser.Nitrogen pin entrance is provided with the top of condenser Rubber stopper.N is passed through by the headroom of the device₂(flow velocity=2.5 cubic feet/hour) 10 minutes, then, temperature liter Height is to 125 DEG C.About 8 it is small when after, about 3mL water will be collected in trap, and with still head and receive flask and replace Dean- Stark traps, and toluene is removed by distillation.Vacuum (2Torr), temperature are increased to 150 DEG C to remove excessive dodecylic acid.1 After hour, more distillates are not observed, crude product is filtered by alkali alumina.Product is separated into lurid oily Thing, 45g (55%).KV at 100 DEG C is 3.9cSt, and the KV at 40 DEG C is 15.78cSt, VI 157, pour point<-45℃.

Each imparting final structure in three kinds of components (methyl ester, alcohol and saturated fatty acid) of diester compositions can be pre- The performance quality of survey.Therefore, the property of diester can be adjusted to adapt to specific performance by carefully selecting the combination of raw material Specification.

4-formic acid of embodiment

Methyl -9- decenoates/formic acid

Methyl -9- decenoates (50g, 0.27mol) and formic acid (100mL) are added under 23 DEG C and air atmosphere In 2 neck round-bottom flasks of 250mL.Then electric thermo-couple temperature adjuster of the installation with heating mantle and water condenser on flask.It is cold The rubber stopper of nitrogen pin entrance is provided with the top of condenser.N is passed through by the headroom of the device₂(flow velocity=2.5 cube Foot/hour) 10 minutes, then, temperature is increased to 105 DEG C.About 15 it is small when after, remove heating source, reaction is cooled to ring Border temperature.Aliquot is taken to be used for GCMS (method GCMS1) to assess conversion.Reaction mixture is transferred to single neck round-bottom flask In, excessive formic acid is removed by rotary evaporator (50Torr, 35 DEG C).Obtain the 9- as light yellow/brown oil OCHO-DAMe, 60.15g (97%), can be used without being further purified.

9- decylenic acids 2- ethylhexyls/formic acid

9- decylenic acid 2- ethylhexyls (282g, 1mol) and formic acid (460g) are added to 2L under 23 DEG C and air atmosphere 3 neck round-bottom flasks in.Then electric thermo-couple temperature adjuster of the installation with heating mantle and water condenser on flask.Condenser Top be provided with the rubber stopper of nitrogen pin entrance.N is passed through by the headroom of the device₂(the cubic feet per of flow velocity=2.5 Ruler/hour) 10 minutes, then, temperature is increased to 105 DEG C.About 15 it is small when after, add other formic acid (200g) and continue anti- Should.It is other 24 it is small when after, remove heating source, reaction is cooled to environment temperature.Aliquot is taken to be used for GCMS (method GCMS1) To assess conversion.Reaction mixture is transferred in single neck round-bottom flask, was removed by rotary evaporator (50Torr, 35 DEG C) The formic acid of amount, is then evaporated in vacuo (2Torr, 125 DEG C).Obtain the 9-OCHO-2- ethyl hexyls as light yellow/brown oil Base decenoate, 320g (97%).9-OCHO-DAEH and 6M potassium hydroxide aqueous solutions are added in 1 liter of round-bottomed flask of single neck. Reaction flask reflux condenser is installed and be heated to reflux 24 it is small when.Reaction is cooled down, separates each layer, organic product passes through vacuum When stripping (5Torr, 100 DEG C) dry 1 is small, so as to obtain the required 9- hydroxyls -2- ethylhexyl last of the ten Heavenly stems as light brown oily substance Acid esters, 275g (91%).

The physicochemical characteristics of the ester of following table display type I (a) and I (b).By these esters compared with various base oils. Thus by these esters compared with Group III base oil (YUBASE4), and with the known trihydroxy methyl with superperformance Propane ester (NYCOBASE 7300 or NB7300) is compared.

Table 1：The physicochemical characteristics of the ester of Formulas I (a) and I (b) compared with other base oils

VI：Viscosity index (VI)

KV：Kinematic viscosity

Both esters 0W-20 engines formula in known additive bag, i.e. Pack Infineum P6660 together Assessment.SV261 is the VI modifiers of known Infineum, it is the polyisobutene styrene (PISH) of hydrogenation.Infineum V385 is known pour point depressant.

The formula of preparation is 0W-20 formulas.They are carried out under iso-HTHS (2.6mPa.s).HTHS is cut in high temperature height The value cut.The composition and characteristic for the formula tested are given in the table below.

Composition (ester I (a) and ester I (b)) according to the present invention has improved " cold " behavior.

Detergent

Micro- coking test (MCT) is carried out to assess the detergency of ester of the present invention.The standard of application is GFC-Lu-027-T- 07。

As a result in the following table.

Engine Block Test

Engine Cleanliness Level

Prepare following composition.

Test for determining cleannes is based on piston performance.Each lubricant compositions (10kg) are in the cleaning for automobile Assessed in the test of degree diesel common rail (common rail).Engine is 4 Cylinder engines of 1.4L.Its power is 80kW.Test follows When the ring time is 96 small, alternately dally and 4000rpm schemes.The temperature of lubricating composition is 145 DEG C, the temperature of cooling water system For 100 DEG C.Any lubricating composition is not discharged or added during test.Use fuel EN590.Test carries out in two stages Amount to 106 it is small when, in first rinsing step grind (lapping) 10 it is small when, then in the second step with to be evaluated group Compound (4kg) carry out, finally with composition to be evaluated according to durability step continue 96 it is small when (4kg).During test, assessment The physical-chemical parameters of lubricant.Then the lubricant consumption during grinding and during test is assessed.

As a result summarize in the following table.

Embodiment	Help base-material	Piston
			Comparative example	PAO	65.75
Ester I (a)	Ester I (a)	70.76
			Ester I (b)	Ester I (b)	72.27

The selection of object of reference (PAO) is correct, its fraction is 65, this is expected higher for PAO.Therefore, go out In cleannes viewpoint by the ester of the present invention with good formula compared with, and can be seen that ester I (a) and I (b) comment this 5 points and 7 points have been respectively increased in score value.

Fuel economy

Prepare following composition.OLOA 249SX are the overbased sulfonates detergent from Oronite.

The test uses 2.0L displacement engines, and maximum power 180kW, is driven by dynamotor.By various lubricants Composition is compared with reference to lubricating composition (SAE 0W-30).Each rub measurement carry out about 12 it is small when, and can be detailed Carefully map the friction torque as caused by each lubricant compositions.Test carries out in the following order：

- by the use of having flushing oil flushing engine of the detergent as additive, then with lubricator rinsed with reference to composition,

- friction for measuring moment of torsion at four temperature with reference to composition is used,

- by the use of having flushing oil flushing engine of the detergent as additive, then rushed with lubricating composition to be evaluated Wash,

- friction of moment of torsion is measured at four temperature with lubricating composition to be evaluated,

- by the use of having flushing oil flushing engine of the detergent as additive, then rinsed with reference to composition,

- friction of moment of torsion is with lubricator measured at four temperature with reference to composition,

The excursion of the program and temperature levels are chosen to cover most representational operation in NEDC authentication periods Point.4 selected temperature levels are consistent with the cycle considered.

Implementing explanation is：

The water temperature of-engine output：40℃/60℃/90℃/110℃±2℃,

- oil temperature the gradient (oil temperature ramp)：40℃/60℃/90℃/110℃±2℃,

The air themperature of-inlet：21℃±2℃

Back pressure during-exhaust：40mbar under 4000rpm

Assess the friction gain of each lubricant compositions according to the temperature of measurement and engine speed, and with lubricant reference The friction of composition is compared.

After these friction gains understand and are handled by transmission function, have estimated due to the use of lubricating composition and Caused friction gain and the loss in NEDC standardization examination ＆ approval cycles.

Embodiment	Gain/loss
		Ester I (a)	- 0.03%
Ester I (b)	- 0.05%

Selection is the fact that known NB7300 provides elevated fuel economy with reference to the motivation of (NB7300).As a result table Bright, from the perspective of fuel economy, even if not being more preferable, these three formulas are also at least equivalent, gain 0.05% With 0.03%.

Claims (14)

1. the lubricant compositions of compound and at least one lubricant additive comprising at least one lower formula (I) are reducing hair Application in the fuel consumption of motivation, preferably automobile engine, the lubricant additive are selected from the row being made of following substances Table：It is detergent additives, antiwear additive, friction modifier additive, EP agent, anti-oxidant additives, scattered Agent, pour point depressant additive, defoamer, thickener, viscosity index improver and wherein two or more mixtures,

Wherein:

N is less than 1.1,

R1 represents straight or branched, saturation or undersaturated C3-C20,

R ' represents straight or branched, saturation or undersaturated C2-C16,

R represents straight or branched, saturation or undersaturated C1-C20.

2. application as claimed in claim 1, wherein, in the formula (I)：

N is 1；

The total amount of carbon atom is more than 15 and less than 40.

3. application as claimed in claim 1 or 2, wherein, in the formula (I),

R1 represents straight or branched, saturation or undersaturated C5-C15 alkyl；

R ' represents straight or branched, saturation or undersaturated C3-C8 alkyl；

R represents straight or branched, saturation or undersaturated C1-C15 alkyl.

4. the application as described in claim 1 or 3, wherein, in the formula (I),

R1 represents the straight chain C 5-C12 alkyl of the straight chain C 5-C15 alkyl, more preferably saturation of saturation；

R ' represents the straight chain C 5-C8 alkyl of the straight chain C 3-C8 alkyl, more preferably saturation of saturation；

R represents the straight or branched C5-C10 alkyl of the straight or branched C5-C15 alkyl, more preferably saturation of saturation.

5. apply according to any one of claims 1 to 4, wherein, in the formula (I),

R1 represents the straight chain C 5-C8 alkyl of the straight chain C 5-C10 alkyl, more preferably saturation of saturation；

R ' represents the straight chain C 5-C8 alkyl of saturation；

R represents the straight chain C 5-C10 alkyl of saturation, straight or branched C5-C10 alkyl, preferably saturation.

6. application as claimed in claim 5, wherein, formula (I) compound is formula (Ia) compound

7. apply according to any one of claims 1 to 4, wherein, in the formula (I)：

R1 represents the straight chain C 8-C12 alkyl of the straight or branched C5-C15 alkyl, more preferably saturation of saturation；

R ' represents the straight chain C 5-C8 alkyl of saturation；

R represents the side chain C5-C10 alkyl of saturation, straight or branched C5-C10 alkyl, preferably saturation.

8. application as claimed in claim 7, wherein, formula (I) compound is formula (Ib) compound

9. the application as any one of preceding claims, wherein, the gross weight based on lubricant compositions, the lubrication Agent composition includes 0.1 weight % to 50 weight %, preferably 1 weight % to 50 weight %, more preferably 5 weight % to 30 weight % Formula (I) compound.

10. the application as any one of preceding claims, wherein, the lubricant compositions are also comprising at least one profit Lubricant base oil.

11. the application as any one of preceding claims, wherein, the lubricant base oil is Group III lubricant Base oil.

12. the application as any one of preceding claims, wherein, the gross weight based on lubricant compositions, the profit Lubricant composition includes 50 weight % to 99 weight %, the lubricant base oil of preferably 50 weight % to 80 weight %.

13. the application as any one of preceding claims, wherein, the additive is that at least one viscosity index (VI) is improved Agent, preferably at least a kind of polymerism viscosity index improver, is more preferably selected from：

Polyacrylate and polymethacrylates,

Olefin homo or copolymer, optimal ethylene/propylene,

Styrol copolymer, the preferably copolymer with isoprene or diene such as butadiene, hydrogenate or do not hydrogenate, isoprene gathers Compound, preferably free radical hydrogenated polyisoprene,

Polystyrene is esterified, is preferably esterified poly- (styrene-maleic anhydride copolymer),

Mixture more than above two.

14. the application as any one of preceding claims, it is further used for improving engine, particularly car engine The cleannes of at least one piston of machine, more preferably automobile engine.