CN107849476A - Purposes of the polyglycerol ester as the friction modifier in lubricant formulation agent - Google Patents
Purposes of the polyglycerol ester as the friction modifier in lubricant formulation agent Download PDFInfo
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- CN107849476A CN107849476A CN201680043395.0A CN201680043395A CN107849476A CN 107849476 A CN107849476 A CN 107849476A CN 201680043395 A CN201680043395 A CN 201680043395A CN 107849476 A CN107849476 A CN 107849476A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/78—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids, hydroxy carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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Abstract
The present invention relates to the lubricant oil composite comprising polyglycerol partial ester and its for lubricating engine and reducing the purposes of friction, the polyglycerol partial ester is polyfunctional carboxylic acids and saturation or the polyglycerol partial ester of undersaturated, straight or branched aliphatic acid and/or poly- (hydroxy stearic acid).
Description
Technical field
The present invention relates to the lubricant oil composite comprising polyglycerol partial ester and its for lubricating engine and reducing friction
Purposes, the polyglycerol partial ester are polyfunctional carboxylic acids and saturation or undersaturated, straight or branched aliphatic acid and/or poly- (hydroxyl
Base stearic acid) polyglycerol partial ester.
Background technology
It can be reduced due to rubbing in the contact point lubricated by the way that friction modifier is added in lubricant formulation agent
Energy loss caused by wiping.Especially friction modifier is used and applies the tooth compared with low viscosity preparaton wherein in order to save energy
In wheel and engine oil formulations.While energy loss in a fluid is reduced, the lubricant with low viscosity is protected as possible
Hold slidingsurface it is completely separate from each other and need friction modifier by lubricant film keep on said surface.
Friction modifier is played a role by forming adsorption layer on the metal surface.They when the slidingsurface not
It is high-importance under the conditions of mixed lubrication when always being separated by the lubricant film of adequate thickness.Such condition is available can
Tug (MTM) simulation of coefficient of friction is measured under a broad range of conditions.
The antifriction additive for having been used to improve fuel economy is fallen into three main chemically defined classifications, they
It is organic, metal is organic and oil is insoluble.Organic antifriction additive is fallen into four primary categories in itself, they
(i) carboxylic acid or their derivative, it includes partial ester, (ii) nitrogen-containing compound, such as acid amides, acid imide, amine and they
Derivative, (iii) Phosphoric acid or phosphonic acid derivative and (iv) organic polymer.
In current business practice, the example of antifriction additive is glycerin mono-fatty acid ester and oleamide, both of which
It is derived from unrighted acid, or molybdenum dialkyldithiocarbamacompositions.Use in addition with polyethylene glycol block
Copolymer (WO 2011/107739 and WO 2015/065801) or other alkoxide compound polymer (WO 2014/
139935).It is further known can will be by via ether functional group (US 7,803,745) or ester functional group (WO 2015/
044639) polyglycereol of the long alkyl chain solubilising of connection is used as friction modifier.
The content of the invention
It has now surprisingly been found that polyfunctional carboxylic acids and saturation or insatiable hunger, straight or branched aliphatic acid and/or poly-
The polyglycerol partial ester of (hydroxy stearic acid) shows the superior function as the friction modifier for lubricant." superior ", which refers to, to rub
Wipe the largely reduction of coefficient and/or due to more effective antifriction function caused by relatively low handling rate (treat rate)
And/or the preferable combination of oil compatibility and antifriction performance.
In the first embodiment, the present invention relates to lubricant oil composite, it includes lubricating base oil and polyglycerol partial ester,
It is characterized in that the polyglycerol partial ester can be obtained by polyglycereol mixture with the esterification of following material：
(i) polyfunctional carboxylic acids, and
(ii) saturation or undersaturated, straight or branched aliphatic acid, and/or
(ii) poly- (hydroxy stearic acid).
Polyglycerol ester is found especially mainly containing the non-pole of API IIs, III and/or IV groups as lubricating base oil
Played a role in property preparaton.
American Petroleum Institute (API) (API) defines five groups of lubricant bases (API publications 1509) at present.I, II and III
Group is mineral oil, the saturate and the amount of sulphur and classified by their viscosity index (VI) that they are contained by them.Following table explanation
These API classification of I, II and III groups.
| Group | Saturate | Sulfur content | Viscosity index (VI) (VI) |
| I | <90% | >0.03% | 80-120 |
| II | At least 90% | Not more than 0.03% | 80-120 |
| III | At least 90% | Not more than 0.03% | At least 120 |
Group I base-material is the mineral oil of solvent refining, and they are to prepare generally the least expensive base-material, and account for base-material at present
The major part of sale.They provide satisfied oxidation stability, volatility, cryogenic property and hauling ability, and with for adding
Add the extraordinary dissolving power of agent and pollutant.
Group II base-material is the mineral oil of most of hydrogenated processing, their the commonly provided improvement compared with Group I base-material
Volatility and oxidation stability.
Group III base-material is the mineral oil through strict hydrotreating, or they can be prepared via wax or paraffin isomerizationization.
They are known to have than I and the more preferable oxidation stability of II group base-materials and volatility, but the business with limited range can obtain
Obtain viscosity.
Group IV base-material and the difference of I, II and III groups are that they are the synthesis bases for including such as polyalphaolefin (PAO)
Material.PAO has good oxidation stability, volatility and low pour point.Shortcoming includes polar additive (such as wear-resistant addition
Agent) moderate solubility.
II, II and IV groups oil with they to oxidation and the outstanding stability of high temperature but it is known, but they are only provided
For the limited solubility of polar additive (such as friction modifier).For this reason, according to the lubricating oil group of the present invention
Compound contains the ester base oil according to API Group V for being up to 10% as solubilizer.
Group V base-material is the whole base-materials not being included in other groups.Example include alkylnaphthalene, Alkylaromatics,
Vegetable oil, ester (including polyol ester, diester and monoesters), makrolon, silicone oil and PAG.
Can be in the preparation with and without other eater base stocks according to the friction modifier performance of the polyglycerol partial ester of the present invention
Realized in agent.
In a preferred embodiment, it is characterised by that they are included according to the lubricant oil composite of the present invention to be based on
The gross weight meter of the lubricant oil composite：
(a) 90-100 weight % non-polar oil, it is selected from API IIs, III and IV groups and/or their mixture；With
(b) the polarity ester oil of the Group V of the 0-10% definition according to American Petroleum Institute (API) (API).
The polyglycerol partial ester of poly- (hydroxy stearic acid) and polyfunctional carboxylic acids is known as in cosmetics or pharmaceutical formulation
W/O emulsifying agents and as auxiliary agent (B1 of EP 1 500 427 and the EP for being dispersed in inorganic micro- pigment in oil dispersion
1 683 781 B1)。
For the optimum performance as friction modifier, parameter surface-active or polarity and oil-soluble must be balanced and adjust
The whole polarity for arriving the respective oil mixture as base-material.Polarity and the balance of nonpolar moiety in the polymer is by calculating
HLB value describes.This can be completed by the polyglycereol and selection carboxylic acid and polycarboxylic acid for selecting to be characterized by certain degree of polymerization.It is polycarboxylic
The molecular weight (being measured by SEC) measured for obtained component especially has main influence.The ratio of acid and alcohol functional group is weight
Want, because which determining esterification degree and therefore determining the amount of unreacted OH functional groups (by the OH values by titration determination
Description).Free acid functional group is undesirable and should be maintained under minimum level (by being retouched by the acid number of titration determination
State).
Relative to the superior function of other friction modifiers be attributed to polyglycerol moiety it is highly polar, due to part ester
Free OH functional groups caused by change and the material that multiple interaction sites are provided between the surface and the antifriction component
Polymer property.The polymer property of the friction modifier is even more important for the dissolubility of the component, because
Very the structure division of polarity must keep dissolving in the molecule.
These polyfunctional carboxylic acids and saturation or undersaturated, straight or branched aliphatic acid and/or poly- (hydroxy stearic acid)
Polyglycerol partial ester can pass through polyglycereol mixture and obtained with the esterification of following material：With 8 to 22 carbon atoms, preferably 12 to
The saturation of 18 carbon atoms or undersaturated, straight or branched aliphatic acid, and there are 4 to 54 carbon atoms, preferably 6 to 36
Carbon atom, even more preferably more preferably 6 to 18 carbon atoms and 6 to 12 carbon atoms and average functionality be 2 to 4, preferably 2 to
3 and more preferably 2 to 2.5 polyfunctional carboxylic acids, the esterification degree of the polyglycereol mixture is between the 30 of OH groups and 75%.
Following formula can be used to determine for the average functionality of the mixture of polyfunctional carboxylic acids：
Wherein
xi=single polyfunctional carboxylic acids i mass fraction [%]
Ni=single polyfunctional carboxylic acids i degree of functionality
The saturated fat acid constituents of specially suitable straight or branched is selected from octanoic acid, capric acid, laurate, tridecanoic acid, meat
Myristic acid, palmitic acid, pearly-lustre resin acid, stearic acid, isostearic acid, arachidic acid, behenic acids and their mixture.Suitable saturation
Aliphatic acid also has 12- hydroxy stearic acids.Naturally occurring mixture is, for example, coconut fatty acid, and it contains laurate as main
Composition and the also C14 containing saturation to C18 aliphatic acid and may a small amount of saturation C8 to C18 aliphatic acid and unsaturated fat
Acid, and tallow acid, it is substantially palmitic acid and stearic mixture.
Suitable unsaturated fat acid constituents is single ethylenic unsaturated acid, such as gaidic acid, octadecenoic acid, such as
Oleic acid (cis -9- octadecenoic acids) or elaidic acid (eladidic acid) (elaidic acid), eicosenoic acid
And docosenoic acid, such as erucic acid (cis-13-docosenoic acid) or the brassidic acid (dodecylenes of anti-form-1 3- bis-
Acid), polyunsaturated fatty acid, such as octadecadienoic acid and octatecatrienoic acid, such as linoleic acid plus linolenic acid, castor oil acid
With their mixture.
Liquid fatty acid containing 18 to 22 carbon atoms, i.e. oleic acid, castor oil acid, erucic acid and isostearic acid, it is special
Suitably.Due to branched, freezing point is less than 35 DEG C.Fatty acid mixt can also be used, it can also contain waxy component, example
Such as hydrogenated castor oleic acid.
Poly- (hydroxy stearic acid) being used in conjunction with according to the present invention is, for example, that (preferably 12- hydroxyls are hard by hydroxy stearic acid
Resin acid) polycondensation prepare, the hydroxy stearic acid is to pass through known formula by castor oil acid or technical grade Castor Oil Fatty Acid
Method hardening obtains.The average degree of polymerization that they have is 1 to 10 unit, preferably 2 to 8 units and particularly 2 to 5 lists
Member.
The polyfunctional carboxylic acids can be dicarboxylic acids, tricarboxylic acids or polycarboxylic acid.The polyfunctional carboxylic acids can be unsubstituted
Or optionally substituted by one, two or three oh group, preferably substituted by an oh group.
Aliphatic dicarboxylic acid for the esterification should have the chain length of 3 to 18 carbon atoms.They can be straight chain or
Side chain, such as malonic acid, butanedioic acid, fumaric acid, maleic acid, dimethylated pentanedioic acid, adipic acid, trimethyladipic acid, nonyl two
Acid, decanedioic acid, dodecanedioic acid, hexadecandioic acid (hexadecane diacid) (hecadecanedioic), octadecane diacid and their acid anhydrides.
Dicarboxylic acids used can also be dimer (fatty acid) yl.As it is known, these are acyclic and ring-type dicarboxylic acids
Mixture, it is obtained by the catalytic dimerization reaction of the unrighted acid with 12 to 22 carbon atoms.
Preparation and use and their physics and chemical property for dimer acids, with reference to publication " The Dimer
Acids:The chemical and physical properties, reactions and applications " (dimers
Acid：Physical and chemical performance, reaction and application), editor E.C.Leonard；Humko Sheffield Chemical,1975,
Memphis,Tenn。
The dicarboxylic acids can also contain trifunctional and polyfunctional carboxylic acids in lesser degree.The degree of functionality of the mixture is not
Average 2 to 2.5 moles value should be exceeded.
In addition, as polyfunctional carboxylic acids, phthalic acid, trimellitic acid and pyromellitic acid can be used.
Included wrapping glycerinated polyglycereol according to the term " polyglycereol " of the present invention.Therefore, for the meter of quantity, quality etc.
Calculate, it is necessary to consider the content of the glycerine.Term " glycerin oligomer " or " one or more polyglycereol " include it is linear and
The structure of ring-type.
Suitable polyglycereol particularly has>2, preferably 3 to 6 average condensation degree those.It is sweet that these are that technical grade gathers
Oil mixture, it is for example to be obtained by the base catalyzed condensation of glycerine at elevated temperatures, and if it is desired to can be passed through
The way of distillation is obtained with the fraction for wishing condensation degree from it.In addition suitably by other methods, such as from epichlorohydrin or contracting
The polyglycereol that water glycerine obtains.Business polyglycereol can obtain from such as Solvay, Spiga Nord, Daicel or Lonza company.
In the polyglycerol partial ester according to the present invention, the 30 to 75% of the polyglycereol, preferably 50 to 65% hydroxyl
Group is esterified.Their initially use aliphatic acid are esterified to 25 to 60%, preferably 35 to 50% esterification degree, and in second step
In, be esterified to using dicarboxylic acids 30 to 75%, preferably 50 to 65% overall esterification degree.In order to obtain favourable product, pass through
Hydrophilic and lipophilic molecule ratio is suitably selected, 3 to 7 HLB value will be targeted by.
The HLB value is that the molecule is measuring for hydrophilic or lipophilic degree, and it is by calculating the molecule not
With region value determine.For the purposes of the present invention, the HLB value of the polyglycerol partial ester is calculated as follows：
HLB=(mp/ (mp+ma)) × 20,
Wherein mp is the quality of polyglycereol, and ma be used in the synthesis of polyglycerol ester include mono-, di- and polycarboxylic acid
And the quality of the mixture of carboxylic acids of poly-hydroxy fatty acid.For example, 100g polyglycereol and 90g monocarboxylic acids and the ester of 10g dicarboxylic acids
Change will cause the HLB to be (100g/ (90g+10g+100g)) × 20=10, its independently of the polyglycereol the degree of polymerization and use
The type of carboxylic acid.
For the present invention, it is necessary that the polyglycerol backbone of the polyglycerol partial ester includes 2 to 8, preferably 2.5 to 6, especially
It is preferred that 3 to 4.5 average degree of polymerization.Determine the proper method bag of the oligomer distribution of the polyglycereol in given polyglycerol partial ester
Ester hydrolysis or the alcoholysis partially are included, gained polyglycereol is separated with the carboxylic acid compound formed, and pass through gas after derivatization
Analysis of hplc.
It can be prepared in a way known by following process according to the polyglycerol partial ester of the present invention：Heating response component
Obtained reaction water is removed with by distilling.The reaction can be accelerated by means of following material：Acidic catalyst, such as sulphur
Acid, phosphoric acid or phosphorous acid, or base catalyst, such as alkali metal or alkaline earth oxide or hydroxide, alcoholates or salt,
Or lewis acid, such as pink salt.However, addition catalyst is not indispensable.The polyglycerol partial ester is preferably in two-step method
Middle preparation, the two-step method are equally implemented in a way known.In the first step, using mono-functional fatty acid or described
Some in aliphatic acid are esterified the polyglycereol.After the largely or entirely aliphatic acid is reacted, addition is described more
Functional carboxylic acid and the continuation esterification.Can be for example via the reaction water of removal, by measuring acid number or passing through infrared spectrum
Monitor the process of the reaction.Generally,<20, preferably<10 acid number in final product is preferable.Have<5 acid number
Product be particularly preferred.The acid number is measured according to DIN EN ISO 2114.
The polyglycerol partial ester claimed determined via SEC relative to polymethyl methacrylate (PMMA) reference material
Weight average molecular weight MwIn the range of 2,000 to 15,000g/mol, preferably in the range of 4,000 to 10,000g/mol, wherein
Polydispersity index is 1.5 to 5, preferably 2 to 4.
According to the OH values of the polyglycerol partial ester of the present invention 50 to 180mg KOH/g, preferably 80 to 170mg KOH/g scopes
It is interior and most preferably in the range of 110 to 150mg KOH/g.The OH values are measured according to the 240-2 of DIN 53.
For engine oil, presence of the organic polymer antifriction additive in automobile engine oil be horizontal be based on
0.2 to 5 weight % of the gross weight meter of the lubricant oil composite, preferably 0.3 to 3 weight % and even more preferably 0.5 to 2 weight
Measure %.
Therefore, a preferred embodiment of the invention is related to a kind of lubricant oil composite, and it is included：
(a) 0.2 to 5 weight % of the gross weight meter based on the lubricant oil composite, preferably 0.3 to 3 weight %, even
More preferably 0.5 to 2 weight % polyglycerol partial ester,
(b) 85 to 99.8 weight % of the gross weight meter based on the lubricant oil composite, preferably 87 to 99.7 weight %,
Even more preferably 88 to 99.5 weight % nonpolar base-material, it is selected from API IIs, III and IV groups and/or their mixing
Thing, and
(c) 0 to 10 weight % of the gross weight meter based on the lubricant oil composite according to American Petroleum Institute (API) (API)
Definition Group V polarity ester oil.
In a preferred embodiment, (a), (b) and (c) amounts to 100 weight %.
In addition to the polyglycerol partial ester according to the present invention, the lubricant oil composite that is described in detail herein can also include it is a kind of or
A variety of other additives.These additives include viscosity index (VI) (VI) modifier, pour-point depressant and scattered agent inhibitor
(DI) additive, its be selected from dispersant, detergent, defoamer, corrosion inhibitor, antioxidant, wear-resistant and EP agent and
Other friction modifier.
E.g. poly- (methyl) acrylate polymers of suitable viscosity index improver, ethylene-propylene copolymer,
Styrene-isoprene copolymer, the styrene-isoprene copolymer of hydrogenation, polyisobutene and dispersant type viscosity index
Modifier.
E.g. poly- (methyl) acrylate polymers of suitable pour-point depressant.
Suitable dispersant is, for example, alkenyl succinimide, alkenyl succinate acid esters, is modified with other organic compounds
Alkenyl succinimide, the modified alkenyl succinimide of post processing is carried out by using ethylene carbonate or boric acid, pentaerythrite,
Phenolate thing salicylate (phenatesalicylate) and their post-treated analog, alkali metal or mixed alkali metal,
Alkaline earth metal borate, the dispersion of Hydrated Alkali Metals Borates, the dispersion of alkaline earth metal borate, polyamide ashless dispersants
Agent and analog, or the mixture of these dispersants.
Suitable detergent is, for example, metal detergent, it include the neutral and overbasic sulfonate of the oil-soluble of metal,
Phenates, phenates, thio-phosphonates, salicylate and the naphthenate of vulcanization and other oil-soluble carboxylates, the metal are special
It is alkali metal or alkaline-earth metal, such as barium, sodium, potassium, lithium, calcium and magnesium.The most frequently used metal is calcium and magnesium, and both of which can
It is present in the detergent used in the lubricant, and the mixture of calcium and/or magnesium and sodium.Particularly convenient metal detergent is
Neutral and overbasic sulfoacid calcium with 20 to 450 TBN, with 50 to 450 TBN neutral and overbasic phenol calcium with
The phenol calcium of vulcanization, and neutral and overbasic magnesium salicylate or calcium with 20 to 450 TBN.The group of detergent can also be used
Close, it is either overbasic or neutral or the two.
Suitable defoamer is selected from (methyl) acrylate polymers, silicone oil and dimethyl polymerizable organosilicon
Thing.
Suitable corrosion inhibitor is divided into rust-inhibiting additive and matal deactivator/passivator in many cases.It is used
Rust-inhibiting additive can especially sulfonate (ester), such as petroleum sulfonate (ester) or (overbasic in many cases) synthesis
Alkylbenzenesulfonate (ester), such as dinonylnaphthalene sulfonic acid salt (ester)；Carboxylic acid derivates, such as lanolin (lanolin) (wool
Fat (wool fat)), oxidized paraffin wax, zinc naphthenate, alkylated succinic acid, 4- Nonylphenoxies-acetic acid, acid amides and acid imide
(N- acyl group methyl amimoacetic acids, imidazolidine derivatives)；The list and Acidic phosphates salt (ester) that amine neutralizes；Morpholine, dicyclohexylamine or two
Monoethanolamine.Matal deactivator/the passivator includes BTA, tolyl-triazole, tolytriazole (tolutriazole) (example
Such as887 or 887E), 2-mercaptobenzothiazole, dialkyl group -2,5- dimercapto -1,3,4- thiadiazoles；N, N '-two
Salicylidene ethylenediamine, N, N the salicylidene propane diamine of '-two；Zinc dialkyl dithiophosphate and dialkyldithiocarbamacompositions
Salt (ester).
Suitable antioxidant is, for example, phenolic (phenols) oxidation retarder, such as 4,4 '-methylene-bis- (2,6- bis-
Tert-butyl phenol), 4,4 '-bis(2,6-di-butyl phenol), 4,4 '-bis- (2- methyl-6-tert-butylphenols), 2,2 '-methylene
Base-bis- (4- methyl-6-terts butyl-phenol), 4,4 '-butane-bis- (3 methy 6 tert butyl phenol), 4,4 '-isopropylidene
Base-bis(2,6-di-butyl phenol), 2,2 '-methylene-bis- (4- methyl -6- nonyl phenols), 2,2 '-different butane-bis- (4,
6- xylenols), 2,2 '-methylene-bis- (4- methyl -6- cyclohexylphenols), 2,6 di tert butyl 4 methyl phenol, 2,
6- di-t-butyl -4- ethyl -phenols, 2,6 di t butyl phenol, 2,4- dimethyl -6- t-butyl-phenols, the tert- 1- bis- of 2,6- bis-
Methylamino-p-Cresol, the tert- 4- of 2,6- bis- (N, N '-dimethyl amino-methyl phenol), 4,4 '-thiobis (2- methyl -6-
Tert-butyl phenol), 2,2 '-thiobis (4- methyl-6-tert-butylphenols), double (3- methyl -4- hydroxyl -5- t-butylbenzyls) -
Thioether and pair (3,5- di-tert-butyl-4-hydroxyl benzyls).Other types of oxidation retarder includes the diphenylamine (example of alkylation
Such as derive from BASF lrganox L-57), metal dithiocarbamate (such as zinc dithiocarbamate) and methylene
Double (dibutyl dithiocaarbamate) esters.
Suitable antiwear additive is, for example, phosphate (salt), phosphite ester (salt), carbamate (salt), ester, sulfur-bearing
Compound and molybdenum match.
Suitable EP agent is, for example, zinc dialkyl dithiophosphate (one-level alkyl, secondary alkyl and aryl class
Type), sulfurized oil, diphenyl sulfide, trichlorine methyl stearate, chlorinated naphthalene, fluoroalkylpolysiloxane and lead naphthenate.
Second embodiment of the invention is related to the engine oil for including lubricant oil composite as previously described.
The method that third embodiment of the invention is directed to use with lubricant oil composite lubrication engine as previously described.
Fourth embodiment of the invention is related to be reduced by application/by adding lubricant oil composite as previously described
The method to be rubbed in engine.
Embodiment
The present invention is illustrated by following non-limiting example.
Experimental section
Embodiment 1：By polyglycereol, isostearic acid, decanedioic acid and gathered according to the B1 of EP 1 500 427 synthetic example 2
Polycarboxylate prepared by (hydroxy stearic acid)
At 240 DEG C, by isostearic acid (91.1g, 0.320mol) and poly- (hydroxy stearic acid) while nitrogen flows through
(61.9g, 0.121mol, hydroxyl value are the mixture polyglycereol of (141.7g, 0.120mol, acid number are 47mg KOH/g)
950mg KOH/g) esterification.At such a temperature after 2 hours, the acid number of the reactant mixture<10.Then, by the mixture
130 DEG C are cooled to, the mixture is simultaneously again heated to 240 DEG C by addition decanedioic acid (20.2g, 0.100mol).At such a temperature 3
After hour, had<The sticky product of 5 acid number.
Comparative example 1：The polycarboxylate prepared by ethoxylation soya-bean oil, oleic acid and dimer acids
By with oxirane-[O] content be 6.3% epoxidized soybean oil (300g, 0.302mol), oleic acid (331g,
1.18mol) and dimer acids (57.5g；0.101mol, include about 2% monoacid, about 96% dimer acids and about 2%
Tripolymer acid and higher level polyacid) mixture be heated to 240 DEG C until acid number<10mg KOH/g.
The structure of this polymer is different from the polyglycerol partial ester according to the present invention, and therefore the present invention does not include this gather
Compound.
Comparative example 2：The polycarboxylate prepared by polyglycereol, isostearic acid and decanedioic acid
At 240 DEG C, by the mixture of 72g isostearic acids and 11g decanedioic acid 17g polyglycereol while nitrogen flows through
(average degree of polymerization=3) are esterified.When reaching 12 acid number, reaction is cooled down.
The OH values of this polymer are far below the favourable scope according to the present invention.
Comparative example 3：
Can be by the polymer-type friction modifier Perfad commercially available from Croda Inc.TM3006 (for structure referring to US
2013/0079536th, the A1 of WO 2011/107739, and for physical property referring to Lube Magazine, the 120th phase, 2014
April, page 27).
The structure of this polymer is different from the polyglycerol partial ester according to the present invention, and therefore the present invention does not include this gather
Compound.
Comparative example 4：
Can be by the polymer-type friction modifier Perfad commercially available from Croda Sucursal ColombiaTM3057,
PerfadTM3050 dilute form is (for structure referring to the A1 of US2013/0079536, WO 2011/107739, and for physics
Performance is referring to Lube Magazine, the 120th phase, in April, 2014, page 27).
The structure of this polymer is different from the polyglycerol partial ester according to the present invention, and therefore the present invention does not include this gather
Compound.
Table 1：The physical data of embodiment and comparative example
PMMA (polymethyl methacrylate) is used as reference material measurement M via GPCnAnd Mw
*)For PerfadTM3050 values provided；PerfadTM3057 be PerfadTM3050 dilute form
By all polymer dilutions in Nexbase 3043, Nexbase 3043 is according to American Petroleum Institute (API)
(API) Group III oil.Final blend has the about 4.45cSt similar kinematic viscosity (KV at 100 DEG C100)。
For comparative example 3 and 4,0.5% handling rate is recommended by manufacturer.
Table 1：The viscosity number of the blend of test
(KV100=the kinematic viscosity at 100 DEG C)
The measure of antifriction function：
The measurement of coefficient of friction is carried out in the small-sized drawing machine (MTM) derived from PCS Instruments at 100 DEG C
's.The test is made up of following process：Evaluation rubs present in the contact point lubricated formed by steel ball and steel disk
It is horizontal.The speed of the ball and the disk is independently driven.By the ball load and in the case where rolling sliding condition against institute
Steel disk friction is stated, the contact point is completely submerged in oil.
For each sample, the test is carried out in two steps：
1) lead-in stage (Run In phase)
For the stage, the condition described in table 2 below is applied, SRR refers to slide-roll ratio.The parameter is small at described 2
When test during keep constant, and be defined as follows：
Wherein " U balls-USB flash disk " represents gliding cable structure and " U " representative by " U=(U balls+USB flash disk)/2 " entraining velocity provided
Table 2：Test parameter for lead-in stage
2) Stribeck curve evaluations
Then Stribeck is obtained by measuring coefficient of friction under conditions of being shown in Table 3.
Table 3：Condition for Stribeck curve evaluations
Stribeck curves are depicted in Fig. 1.Curve NB3043-Ref refers to containing 100% referred to as Nexbase's 3043
The preparaton of Group III oil.
Brief description of the drawings
Fig. 1：Stribeck curved measurements after the lead-in stage of 2 hours
In order to which the friction for representing to be obtained by working Examples 1 with % is reduced, can quantitative result be expressed as obtaining
Number：
Using trapezoidal rule, the friction valve curve is integrated in the range of-the 2.5m/s of sliding speed 0.005.
" the total friction " that the area corresponds in the whole velocity interval of inspection.The area is smaller, the polymer checked
Antifriction function is bigger.
It is compiled in by the percentage friction reduction on the reference oil of its calculating in table 4 below.
Table 4：The reduced quantitative assessment of friction
Data in table 4 and Fig. 1 clearly show that polymer of the invention has from using different chemical prior arts
Corresponding comparative polymer compare effect much better in terms of the reduction that rubs.As disclosed in table 5 below, the institute in low speed scheme
It is even more notable to state effect.
Due to the application for the lubricant compositions according to the present invention, low speed is that especially have economic interests, therefore table 5
Show the integration data of the friction valve curve in the range of 0.005 to 0.090m/s sliding speed.
The area of measure and the percentage friction on reference oil calculated by it are reduced to be collected with the similar mode of table 4
In table 5.
Table 5：The reduced quantitative assessment (0.005 to 0.090m/s) that rubs at low frequencies
Data in table 5 clearly show that polymer of the invention has contrast corresponding to prior art polymerization again
Thing compares effect much better in terms of the reduction that rubs.
Compared with the result as shown in table 4, the friction increasing for lubricant compositions used according to the invention is found
It is most clearly significant to add effect, especially in the range of low sliding speed.
Claims (14)
1. lubricant oil composite, it is included：
(a) 0.2 to 5 weight % of the gross weight meter based on lubricant oil composite polyglycerol partial ester, it is characterised in that institute
Polyglycerol partial ester is stated to be obtained with the esterification of following material by polyglycereol mixture：
(i) polyfunctional carboxylic acids, and
(ii) saturation or undersaturated, straight or branched aliphatic acid, and/or
(ii) poly- (hydroxy stearic acid),
The esterification degree of wherein described polyglycereol mixture is the 30-75% of OH groups；
(b) 85 to 99.8 weight % of the gross weight meter based on the lubricant oil composite nonpolar base-material, the nonpolar base
Material is selected from API IIs, III and IV groups and/or their mixture；With
(c) 0 to 10 weight %'s of the gross weight meter based on the lubricant oil composite determines according to American Petroleum Institute (API) (API)
The polarity ester oil of the Group V of justice.
2. lubricant oil composite according to claim 1, it is characterised in that the polyglycereol has 3 to 6 average condensation degree.
3. according to the lubricant oil composite of claim 1 or 2, it is characterised in that the aliphatic acid is saturation or undersaturated, straight
The aliphatic acid of chain or side chain, it has 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
4. according to the lubricant oil composite of claim 1,2 or 3, it is characterised in that the saturated fatty acid be selected from octanoic acid, capric acid,
Laurate, tridecanoic acid, myristic acid, palmitic acid, pearly-lustre resin acid, stearic acid, isostearic acid, arachidic acid, behenic acids, 12- hydroxyls
Base stearic acid and their mixture.
5. according to the lubricant oil composite of claim 1,2,3 or 4, it is characterised in that the unrighted acid is selected from 16 carbon
Olefin(e) acid, octadecenoic acid, eicosenoic acid, docosenoic acid, octadecadienoic acid, octatecatrienoic acid, castor oil acid and
Their mixture.
6. according to the lubricant oil composite of claim 1,2,3,4 or 5, it is characterised in that the polyfunctional carboxylic acids have 4 to 54
Individual carbon atom, preferably 6 to 12 carbon atoms, and 2 to 2.5 average functionality.
7. according to the lubricant oil composite of claim 1,2,3,4,5 or 6, it is characterised in that the polyfunctional carboxylic acids are aliphatic series two
Carboxylic acid, it is selected from malonic acid, butanedioic acid, fumaric acid, maleic acid, dimethylated pentanedioic acid, adipic acid, trimethyladipic acid, nonyl two
Acid, decanedioic acid, dodecanedioic acid and their acid anhydrides.
8. according to the lubricant oil composite of claim 1,2,3,4,5,6 or 7, it is characterised in that the polyglycerol partial ester has 3
To 7 HLB value.
9. according to the lubricant oil composite of claim 1,2,3,4,5,6,7 or 8, it is characterised in that the polyglycerol partial ester has
OH values in the range of 50 to 180mg KOH/g.
10. according to the lubricant oil composite of claim 1,2,3,4,5,6,7,8 or 9, it is characterised in that it additionally comprises one kind
Or a variety of other additives.
11. lubricant oil composite according to claim 10, it is characterised in that the other additive of the one or more is selected from
Viscosity index (VI) (VI) modifier, pour-point depressant, dispersant, detergent, defoamer, corrosion inhibitor, antioxidant, it is wear-resistant and
EP agent and friction modifier.
12. according to the lubricant oil composite of claim 1,2,3,4,5,6,7,8,9,10 or 11, it is characterised in that described poly- sweet
Oily partial ester have 2,000 to 15,000g/mol, preferably 4,000 to 10,000g/mol weight average molecular weight.
13. lubricate the method for engine using the lubricant oil composite of any one according to claim 1 to 12.
14. the side of the friction in engine is reduced according to the lubricant oil composite of any one of claim 1 to 12 by application
Method.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15178187 | 2015-07-24 | ||
| EP15178187.9 | 2015-07-24 | ||
| PCT/EP2016/065904 WO2017016825A1 (en) | 2015-07-24 | 2016-07-06 | Use of polyclycerin esters as friction modifiers in lubricant formulations |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107849476A true CN107849476A (en) | 2018-03-27 |
Family
ID=53761989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680043395.0A Pending CN107849476A (en) | 2015-07-24 | 2016-07-06 | Purposes of the polyglycerol ester as the friction modifier in lubricant formulation agent |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20180216023A1 (en) |
| EP (1) | EP3325582A1 (en) |
| JP (1) | JP6761851B2 (en) |
| KR (1) | KR20180032622A (en) |
| CN (1) | CN107849476A (en) |
| BR (1) | BR112018001430A2 (en) |
| CA (1) | CA2993333A1 (en) |
| MX (1) | MX2018000786A (en) |
| RU (1) | RU2726194C2 (en) |
| WO (1) | WO2017016825A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210418A (en) * | 2019-07-10 | 2021-01-12 | 百达精密化学股份有限公司 | Liquid organic wear improvers |
| CN114106627A (en) * | 2021-12-14 | 2022-03-01 | 广州市印道理印刷有限公司 | Environment-friendly water-based ink and preparation method and application thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2019000424A (en) | 2016-07-19 | 2019-03-28 | Evonik Degussa Gmbh | Use of polyolesters for producing porous plastic coatings. |
| CN109563021B (en) | 2016-08-18 | 2021-11-26 | 赢创运营有限公司 | Cross-linked polyglycerol esters |
| DE102017009541A1 (en) | 2017-10-13 | 2019-04-18 | Daimler Ag | Valve drive for an internal combustion engine of a motor vehicle |
| KR20210119400A (en) * | 2019-01-23 | 2021-10-05 | 피터 그레벤 게엠베하 운트 코. 카게 | Estolide esters and their use as base oils in lubricants |
| JP2022158116A (en) * | 2021-04-01 | 2022-10-17 | Ｅｎｅｏｓ株式会社 | Lubricant composition |
| CN113512460B (en) * | 2021-08-13 | 2022-10-21 | 福建科恩优路润滑油有限公司 | Anti-wear clean type vehicle lubricating oil and preparation process thereof |
| CN113801310B (en) * | 2021-09-24 | 2023-03-21 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | Three-component catalytic initiation system catalyst and application thereof |
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| CN112210418A (en) * | 2019-07-10 | 2021-01-12 | 百达精密化学股份有限公司 | Liquid organic wear improvers |
| CN114106627A (en) * | 2021-12-14 | 2022-03-01 | 广州市印道理印刷有限公司 | Environment-friendly water-based ink and preparation method and application thereof |
| CN114106627B (en) * | 2021-12-14 | 2022-05-17 | 广州市印道理印刷有限公司 | Environment-friendly water-based ink and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3325582A1 (en) | 2018-05-30 |
| RU2726194C2 (en) | 2020-07-09 |
| WO2017016825A1 (en) | 2017-02-02 |
| JP6761851B2 (en) | 2020-09-30 |
| MX2018000786A (en) | 2018-08-29 |
| CA2993333A1 (en) | 2017-02-02 |
| JP2018525480A (en) | 2018-09-06 |
| US20180216023A1 (en) | 2018-08-02 |
| BR112018001430A2 (en) | 2018-09-11 |
| RU2018106697A (en) | 2019-08-26 |
| RU2018106697A3 (en) | 2019-12-09 |
| KR20180032622A (en) | 2018-03-30 |
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