CN101842469A - Lubrication oil compositions - Google Patents

Lubrication oil compositions Download PDF

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Publication number
CN101842469A
CN101842469A CN200880103881A CN200880103881A CN101842469A CN 101842469 A CN101842469 A CN 101842469A CN 200880103881 A CN200880103881 A CN 200880103881A CN 200880103881 A CN200880103881 A CN 200880103881A CN 101842469 A CN101842469 A CN 101842469A
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China
Prior art keywords
lubricating oil
oil composition
acid
weight
acid esters
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CN200880103881A
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Chinese (zh)
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H·B·森卡拉
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EIDP Inc
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EI Du Pont de Nemours and Co
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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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/64—Environmental friendly compositions

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

Abstract

This invention relates to lubrication oil compositions comprising (i) a base fluid stock comprising an acid ester of a polytrimethylene ether glycol that is a fluid at ambient temperature, and (ii) one or more lube oil additives.

Description

Lubricating oil composition
The cross reference of related application
What the name that present patent application relates on November 7th, 2006 to be submitted to was called " POLYTRIMETHYLENEETHER GLYCOL ESTERS " holds U.S. Patent Application Serial Number 11/593,954 jointly; Hold U.S. Provisional Application sequence number 60/957,728 jointly with its name of submitting to simultaneously is called " LUBRICATION OIL COMPOSITIONS "; Hold U.S. Provisional Application sequence number 60/957,725 jointly with its name of submitting to simultaneously is called " LUBRICATION OILCOMPOSITIONS "; And hold U.S. Provisional Application sequence number 60/957,722 jointly with name that it is submitted to simultaneously is called " LUBRICATION OIL COMPOSITIONS ".
Invention field
The present invention relates to composition and this based composition purposes as lubricating oil, described composition comprises some acid esters (monoesters and/or diester) of (i) polytrimethylene ether glycol and (ii) some additive.
Background of invention
Some monoesters of polytrimethylene ether glycol and diester (" PO3G ester ") have makes them can be used for the performance in a plurality of fields, comprise as lubricant, as the name of submitting on November 7th, 2006 be called " POLYTRIMETHYLENE ETHER GLYCOL ESTERS " to hold U.S. Patent Application Serial Number 11/593,954 jointly disclosed.
The present invention relates to particular lubricants composition based on this type of PO3G ester.
Summary of the invention
In one embodiment, the present invention relates to one or more PO3G esters and one or more additives purposes as lubricating oil.Therefore, the invention provides a kind of lubricating oil composition, described composition comprises (i) and comprises the basic fluid material of PO3G ester fluidic (being the acid esters of fluidic polytrimethylene ether glycol at ambient temperature); (ii) one or more lubricating oil additives.
When the PO3G ester for based on biology make 1, during ammediol, it can provide the lubricant compositions with high renewable content.
DESCRIPTION OF THE PREFERRED
Employed all scientific and technical terminologies of this paper have the implication identical with the implication of those skilled in the art's common sense, unless otherwise defined.As conflict, be as the criterion with this specification sheets and included definition thereof.
Trade mark represents with upper case, unless otherwise indicated.
Unless point out separately, all per-cents, umber, ratio etc. are all by weight.
When quantity, concentration or other numerical value or parameter provide with scope, preferable range or a series of preferred upper limit numerical value and preferred lower limit numerical value, it should be understood that open particularly any a pair of all scopes that constitute by any range limit or preferred value and any scope lower limit or preferred value, and no matter whether described scope is by open individually.Allly provide a certain numerical range part in this article, this scope all is intended to all integers and the mark that comprise its end points and be positioned at this scope, unless point out separately.When the range of definition, be not intended to scope of the present invention is defined in cited concrete numerical value.
When term " about " was used for the end points of description value or scope, disclosure should be understood to include concrete value or related end points.
As used herein, term " comprises ", " comprising ", " containing ", " having ", " containing " or its any other modification are intended to comprise comprising of nonexcludability.For example, comprise that technology, method, goods or the equipment of key element tabulation needn't only limit to those key elements, but can comprise clearly do not list or this technology, method, goods or equipment institute other key elements of inherent.In addition, unless opposite offering some clarification on arranged, " or " be meant inclusive " or ", rather than refer to exclusiveness " or ".For example, below all satisfy condition A or B:A of any situation be that real (or existence) and B are false (or non-existent), A is that false (or non-existent) and B are real (or existence), and A and B are real (or existence).
" one " or " a kind of " are used to describe key element of the present invention or component.This only is for convenience and provides general sense of the present invention.This description should be understood to include one or at least one, and this odd number also comprises plural number, anticipates unless clearly refer to him in addition.
The material of this paper, method and embodiment only are illustrative, are not to be intended to limit, unless specifically indicate.Although also can be used for practice of the present invention or test with methods described herein and materials similar or the method that is equal to and material, this paper has described suitable method and material.
Basic fluid material
As indicated above, the basic fluid material that is used for lubricating oil composition of the present invention is included in and is fluidic PO3G ester under the envrionment temperature (25 ℃).Described basic fluid material also can comprise other natural and/or common lubricants of synthetic fluid.
The natural fluid altogether example of lubricant comprises lubricant based on vegetables oil, and it is generally derived from plant, and generally is made up of triglyceride level.These at room temperature are generally liquid.Though many different pieces of plant can produce oil, however in actually operating, general main from the seed of oil seed plant extract oil.These seeds comprise edible oil and edible oil not, and comprise for example high oleic sunflower oil, rapeseed oil, soybean oil, Viscotrol C or the like, and modified oil such as US6583302 (fatty acid ester) and I.Malchev " Plant-Oil-Based Lubricants " (comes from Department of Plant Agriculture, Ontario Agriculture College, University of Guelph, 50 Stone Road W., Guelph, Ontario, CanadaN1G 2W1) in disclosed those.
Synthetic fluid lubricant (being different from the PO3G ester) altogether comprises lubricating oil such as hydrocarbon ils, as polybutene, polypropylene, propylene-isobutylene copolymers; Polyoxyalkylene glycol polymkeric substance and their derivative, as the multipolymer of oxyethane and propylene oxide, and PO3G self; The ester of dicarboxylic acid and multiple alcohol is such as (2-ethylhexyl) diester of Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, fumaric acid dihexyl, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate (DOP), didecyl phthalate and linoleic acid dimer.
Preferably, described basic raw material comprises the PO3G ester that accounts for most of amount (by described basic raw material weight greater than 50 weight %).In some embodiments, described basic raw material can comprise by described basic fluid material gross weight counts about 66 weight % or bigger, or about 75 weight % or bigger, or about 90 weight % or bigger, or about 95 weight % or more substantial PO3G ester.In other embodiments, described basic fluid material only comprises (or only comprising basically) PO3G ester.
Described lubricating oil composition preferably comprises by described lubricating oil composition gross weight counts about 50 weight % or more substantial basic oily raw material.In a plurality of embodiments, described lubricating oil can comprise by described lubricating oil composition gross weight counts about 75 weight % or bigger, or about 90 weight % or bigger, or about 95 weight % or more substantial basic raw material.
The monoesters of polytrimethylene ether glycol and diester
In some embodiments, described PO3G ester comprises the compound of one or more formulas (I):
Figure GPA00001032573400041
Wherein the residue of hydroxyl polytrimethylene ether glycol afterwards, R are seized in the Q representative 2Be H or R 3CO, and R 1And R 3Independently of one another for comprising 4 to 40 carbon atoms, preferably at least 6 carbon atoms, the more preferably replacement of at least 8 carbon atoms or unsubstituted aromatics, radical of saturated aliphatic, unsaturated aliphatic or alicyclic organic group.In some embodiments, R 1And R 3Respectively have 20 carbon atoms or still less, and have 10 carbon atoms or still less in some embodiments.In some preferred embodiments, R 1And R 3Respectively have 8 carbon atoms.
The U.S. Patent Application Serial Number 11/593 that is called " POLYTRIMETHYLENE ETHER GLYCOLESTERS " as the name of submitting on November 7th, 2006,954 is disclosed, preferably by mainly comprising 1, the polycondensation of the hydroxyl monomer of ammediol (monomer that comprises 2 or more a plurality of hydroxyls) generates PO3G (as disclosed in hereinafter being described in further detail), uses monocarboxylic acid (or equivalent) to carry out esterification then and prepares the PO3G ester.
The PO3G ester that makes thus preferably comprises about 50 weight % to 100 weight % for the gross weight by described ester, and more preferably from about 75 weight % to 100 weight % diester and 0 weight % are to about 50 weight %, and more preferably 0 weight % is to the composition of about 25 weight % monoesters.Preferably, monoesters and diester are the ester of 2 ethyl hexanoic acid.
Polytrimethylene ether glycol (PO3G)
For purposes of the present invention, PO3G is oligomeric or polymeric ether glycol, and wherein at least 50% repeating unit is the propylidene ether unit.More preferably about 75% to 100%, also more preferably from about 90% to 100%, even more preferably from about 99% to 100% repeating unit is the propylidene ether unit.
Preferably by comprising 1, the monomer polycondensation of ammediol makes PO3G, and described reaction is preferably carried out in the presence of acid catalyst, thereby obtains to contain-(CH 2CH 2CH 2O)-connect the polymkeric substance or the multipolymer of base (for example propylidene ether repeating unit).As indicated above, at least 50% repeating unit is the propylidene ether unit.
When using acid catalyst (such as sulfuric acid) based on sulphur when preparing PO3G, products therefrom preferably comprises less than about 20ppm, is more preferably less than the sulphur of about 10ppm.
Except the propylidene ether unit, can there be other unit of less amount, as other polyalkylene ether repeating units.In the context of the disclosure content, term " polytrimethylene ether glycol " has been contained by pure 1 basically, and ammediol and those comprise the PO3G that the oligopolymer of about 50 weight % comonomers at most and polymkeric substance (comprise following described those) make.
Be used to prepare 1 of PO3G, ammediol can obtain by any approach in various known chemistry routes or the biochemical conversion approach.Preferred approach is described in, for example, among US5015789, US5276201, US5284979, US5334778, US5364984, US5364987, US5633362, US5686276, US5821092, US5962745, US6140543, US6232511, US6235948, US6277289, US6297408, US6331264, US6342646, US7038092, US7084311, US7098368, US7009082 and the US20050069997A1.
Preferably, 1, ammediol is obtained by renewable source (" biologically-derived " 1, ammediol) in biochemical mode.
Especially preferred 1, the ammediol source obtains via the fermentation process that uses the recyclable organism source.As the illustrative example of the starting raw material that derives from renewable source, described obtaining 1, the biochemical route of ammediol (PDO), the raw material that described approach utilization is made by biological renewable resources such as maize raw material.For example, can be 1 with transformation of glycerol, the bacterial isolates of ammediol is present in bacterial classification klebsiella, citric acid bacterium, clostridium and the lactobacillus.Described technology is disclosed in some announcements, comprises US5633362, US5686276 and US5821092.US5821092 discloses the biological preparation 1 of a kind of use recombinant organisms cause glycerine, the method for ammediol especially.This method has been introduced and has been used 1, the intestinal bacteria of the allos pdu dioldehydrase gene transformation that the 2-propylene glycol is special.The intestinal bacteria that transformed grow in the presence of glycerine, and glycerine is as carbon source, and separate 1 from growth medium, ammediol.Because bacterium and yeast can both be converted into glycerine with glucose (as primverose) or other carbohydrate, be disclosed in therefore that these methods in announcing provide fast, cheapness and environmental protection 1, ammediol monomer source.
Biologically-derived 1, ammediol, for example the method preparation by mentioned above and reference is the sort of, comprises the carbon from atmospheric carbon dioxide that is absorbed by plant, and this plant has constituted preparation 1, the raw material of ammediol.Like this, be preferred for the biologically-derived 1 of the context of the invention, ammediol only contains reproducible carbon, and does not contain fossil fuel or petroleum-based carbon.Therefore, based on utilizing of this biologically-derived 1, the PO3G of ammediol and ester are less to the influence of environment, this be because composition used 1, ammediol does not have the depletion fossil oil, and after the degraded carbon is discharged and get back in the atmosphere to be utilized once more by plant.Therefore, the feature of composition of the present invention is more natural, and compares with the analogous composition that comprises the petroleum base glycol, and is littler to the influence of environment.
Biologically-derived 1, ammediol, PO3G and PO3G ester can come distinguish mutually with the prepared analogue compounds of the carbon of originating by the petrochemical industry source or by fossil oil by two carbon isotope fingerprintings.This method can be used for distinguishing chemically identical materials, and distributes the carbon in the multipolymer by the growth source (may be year) of biosphere (plant) component.Isotropic substance 14C and 13C provides side information for this problem.Its nuclear transformation period be 5730 the radiocarbon dating isotropic substance ( 14C) can between fossil (" dead ") and biosphere (" living ") raw material, distribute sample carbon (Currie clearly, L.A. " Source Apportionment of Atmospheric Particles ", Characterization of Environmental Particles, J.Buffle and H.P.vanLeeuwen edit, in IUPAC Environmental Analytical Chemistry Series (Lewis Publishers, Inc) (1992) 3-74) the I volume 1.The basic assumption of radioactive carbon dating is in the atmosphere 14In the invariable organism that causes living of C concentration 14C's is invariable.When handling isolating sample, the age of sample can be derived like close by following:
t＝(-5730/0.693)ln(A/A 0)
Wherein the t=age, 5730 is the transformation period of radiocarbon C14, and A and A 0Be respectively the concrete of sample and contemporary standard product 14C activity (Hsieh, Y., Soil Sci.Soc.Am J., 56,460, (1992)).Yet, because since the atmosphere nuclear test of nineteen fifty and the combustion of fossil fuel of beginning in 1850, 14C has obtained second geochemistry temporal characteristics.In middle 1960s, in Atmospheric CO 2In, and therefore in the biosphere of living, its concentration is near the twice of nuclear test peak value.Since then it the cosmogenesis that little by little returns to stable state (atmosphere) baseline isotropic substance ratio ( 14C/ 12C), this ratio is about 1.2 * 10 -12, have the prolongation " transformation period " of nearly 7-10.(this a kind of transformation period of back necessarily can not be understood according to letter; On the contrary, must adopt full and accurate atmosphere nuclear input/decay function to follow the trail of from examining atmosphere and the biosphere that the age begins 14C changes). 14The temporal characteristics of C allow people seen to modern age biosphere carbon carry out the hope of dating. 14C can measure by accelerator mass spectrometry (AMS), and the result is with " umber of contemporary carbon " (f M) provide for unit.f MBy standard reference material (SRM) 4990B of USA National Institute of Standard and Technology (NIST) and 4990C (being called oxalic acid standard HOxI and HOxII) definition.Basic definition relates to 0.95 and multiply by 14C/ 12C isotope ratio HOxI (with reference to AD 1950).This roughly is equivalent to the preceding timber of the Industrial Revolution that decay correction is crossed.For current living organism circle (vegetable material), f M≈ 1.1.
Stable carbon isotope ratio ( 13C/ 12C) the additional approach that provides the source to distinguish and distribute.In given biogenetic derivation material, 13C/ 12The C ratio is when carbon dioxide fixation in the atmospheric carbon dioxide 13C/ 12The ratio of C, and reflected accurate pathways metabolism.Regional change has also taken place.Oil, C 3Plant (broad-leaved), C 4Plant (draft) and marine carbonate all exist 13C/ 12Demonstrate significant difference on C and the corresponding δ 13C value.In addition, since pathways metabolism, C 3And C 4The decomposition of the lipid material of plant is with different derived from the material of identical plant carbohydrates component.In the precision of measuring, because the isotope fractionation effect 13C demonstrates very big variation, and the most significant for the present invention is photosynthesis mechanism.In the plant in the major cause of carbon isotope rate variance and the plant difference of photosynthesis carbon pathways metabolism closely related, the especially reaction that during elementary carboxylation reaction, is taken place, i.e. Atmospheric CO 2Initial fixation.Plant is divided into two big class, i.e. those employings " C 3" plant and those employings " C of photosynthetic cycle (be also referred to as Calvin-Benson circulation) 4" plant of photosynthetic cycle (be also referred to as Hatch-Slack circulation).C as hardwood and needle 3The type plant is mainly in the tierra templada.At C 3In the type plant, elementary CO 2Fixing or carboxylation reaction relates to the enzyme ribulose-1,5-bisphosphate, 5-bisphosphate carboxylase, and first stable product is the 3-carbon compound.On the other hand, C 4The type plant comprises the plant as tropical pasture, corn and sugarcane and so on.At C 4In the type plant, relate to another kind of enzyme, the extra carboxylation reaction of phosphoric acid enol pyruvic acid carboxylase is elementary carboxylation reaction.First stable carbon compound is a 4-carbonic acid, and it is subsequently by decarboxylation.The CO of Shi Fanging thus 2By C 3Circulation is fixing once more.
C 4And C 3Plant all shows type 13C/ 12C isotope ratio scope, but typical value is about-10 to-14 per thousand (C 4) and-21 to-26 per thousand (C 3) (people such as Weber, J.Agric.FoodChem., 45,2942 (1997)).Coal and oil generally drop in the back scope. 13C measurement degree be at first with intend the belemnite fossil (pee dee belemnite, PDB) limestone is zero to define, wherein numerical value provides with thousand marks of the deviation of material therewith." δ 13C " value is thousand marks (some thousandths of), is abbreviated as %, is calculated as follows:
Because PDB reference material (RM) exhausts gradually, the international isotopic laboratory of IAEA, USGS, NIST and other selections has developed a series of alternative RM cooperatively.Represent with δ 13C with deviation thousand marks of PDB.Be on 44,45 and 46 the molion to CO by high-precision stable ratio mass spectrum (IRMS) in quality 2Measure.
Therefore, biologically-derived 1, ammediol and comprise biologically-derivedly 1, the composition of ammediol can basis 14C (f M) and show two carbon isotope fingerprintings that novel substance is formed and differentiate fully with petrochemical industry deutero-similar substance.The ability of distinguishing these products helps following the tracks of these materials in the commercial applications.For example, the product that comprises " newly " and " old " two kinds of Carbon Isotope Characteristics figure can be differentiated with the product of only being made by " old " material.Therefore, can follow the tracks of present material according to its unique characteristic pattern, and be used for limiting competition, determining storage time, in particular for the influence of assessment to environment commercial.
Determine that as gas chromatographic analysis preferably, as reactant or as 1 of reactant composition, the purity of ammediol is by weight greater than about 99%, and more preferably greater than about 99.9%.Especially 1 of preferred purifying, ammediol, as disclosed among US7038092, US7098368, US7084311 and the US20050069997A1, and by its PO3G that makes, as disclosed among the US20050020805A1.
1 of purifying, ammediol preferably have following properties:
(1) ultraviolet radiation absorption at 220nm place is less than about 0.200, and the 250nm place is less than about 0.075, and at the 275nm place less than about 0.075; And/or
(2) L*a*b* " b* " colour that has of composition is less than about 0.15 (according to ASTMD6290), and in the absorption at 270nm place less than about 0.075; And/or
(3) less than the peroxide compositions of about 10ppm; And/or
(4) adopt gas chromatographic measurement, the concentration of total organic impurity (removing 1, the organic compound outside the ammediol) is more preferably less than about 300ppm less than about 400ppm, also is more preferably less than about 150ppm.
The starting raw material that is used to prepare PO3G will depend on the availability of required PO3G, starting raw material, catalyzer, equipment etc., and comprise " 1, the ammediol reactant "." 1, the ammediol reactant " is meant 1, ammediol, 1, ammediol oligopolymer and prepolymer (preferably the polymerization degree is 2 to 9) and their mixture.In some cases, but may be desirably in the low-molecular-weight oligomer time spent and use as many as 10% or more low-molecular-weight oligomer.Therefore, starting raw material preferably includes 1, ammediol and its dimer and tripolymer.Especially preferred starting raw material is by by 1, the about 90 weight % of the weight meter of ammediol reactant or more 1, and ammediol, and more preferably 99 weight % or more 1, ammediol constitutes.
PO3G can prepare via several different methods known in the art, as disclosed method among US6977291 and the US6720459.Described in preferable methods such as US7074969, US7157607, US7161045 and the US7164046.
As mentioned above, except the propylidene ether unit, PO3G also can comprise a spot of other polyalkylene ether repeating units.Therefore, the monomer that is used to prepare polytrimethylene ether glycol is except 1, outside the ammediol reactant, can also comprise as many as 50 weight % (preferred about 20 weight % or still less, 10 weight % or still less more preferably from about, and 2 weight % or still less more preferably from about) the comonomer polyvalent alcohol.The comonomer polyvalent alcohol that is applicable to present method comprises aliphatic diol, ethylene glycol, 1 for example, 6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,12-dodecanediol, 3,3,4,4,5,5-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene glycol and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-ten hexafluoros-1,12-dodecanediol; Alicyclic diol, for example 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and Isosorbide; And polyol, for example glycerine, TriMethylolPropane(TMP) and tetramethylolmethane.The preferred group of comonomer diol is selected from the group of being made up of following: ethylene glycol, 2-methyl isophthalic acid, ammediol, 2,2,2-diethyl-1, ammediol, 2-ethyl-2-(methylol)-1, ammediol, C 6-C 10Glycol (as 1,6-hexylene glycol, 1,8-ethohexadiol and decamethylene-glycol) and Isosorbide and their mixture.Non-1, the especially preferred glycol of ammediol is an ethylene glycol, and C 6-C 10Glycol also is particularly useful.
A kind of preferred PO3G that comprises comonomer is poly-(propylidene-ethyleneether) glycol described in US20040030095A1.Preferred poly-(propylidene-ethyleneether) glycol is by (preferred about 60 to about 98 moles of % from 50 to about 99 moles of % under the acid catalysis, and more preferably from about 70 to about 98 moles of %) 1, ammediol and as many as 50 to the ethylene glycol of about 1 mole of % (preferred about 40 to about 2 moles of %, and more preferably from about 30 to about 2 moles of %) carries out polycondensation and prepares.
PO3G behind the purifying preferably is substantially free of the acid catalyst end group, but can comprise the unsaturated end group of utmost point low levels, mainly is the allyl group end group, and its scope is about 0.003 to about 0.03meq/g.Can think that this type of PO3G comprises that (being made up of it basically) have the following formula (II) and (III) compound of structure:
HO-((CH 2) 3O) m-H????????????(II)
HO-((CH 2) 3-O) mCH 2CH＝CH 2???(III)
Wherein m within the specific limits, make Mn (number-average molecular weight) about 200 to about 10000 scopes, the content of same up-to-date style (III) compound make the content of allyl group end group (preferably all unsaturated ends or end group) about 0.003 to about 0.03meq/g scope.
The Mn (number-average molecular weight) that is used for preferred PO3G of the present invention is at least about 250, more preferably at least about 500, and more preferably at least about 1000.Described Mn is preferably less than about 10000, is more preferably less than approximately 5000, and is more preferably less than about 2500.Also can use the blend of PO3G.For example, PO3G can comprise the blend of the PO3G of the PO3G of higher molecular weight and lower molecular weight, and preferably wherein the number-average molecular weight of the PO3G of higher molecular weight is about 1000 to about 5000, and the number-average molecular weight of the PO3G of lower molecular weight is about 200 to about 950.The Mn of the PO3G of blend is preferably still in above-mentioned scope.
The PO3G that is preferred for this paper is generally the polydispersion body, and described polydispersion body has preferred about 1.0 to about 2.2, and more preferably from about 1.2 to about 2.2, and 1.5 to about 2.1 polymolecularity (being Mw/Mn) more preferably from about.Polymolecularity can be regulated by using the PO3G blend.
The colour that is used for PO3G of the present invention is preferably less than about 100APHA, and is more preferably less than about 50APHA.The viscosity of PO3G is preferably greater than the viscosity of PO3G ester.Preferred viscosities under 40 ℃ is about 100cS or bigger.
Acid and equivalent
By with acid and/or equivalent, the esterification of PO3G is implemented in preferred monocarboxylic acid and/or equivalent reaction.
So-called " monocarboxylic acid equivalent " is meant at the basic compound the same with monocarboxylic acid of performance aspect polymeric ethylene glycol and glycol reaction, as those of ordinary skill in the related art will recognize usually.For the object of the invention, the monocarboxylic acid equivalent comprises for example monocarboxylic ester, forms the derivative of ester, as carboxylic acid halides (as acyl chlorides) and acid anhydrides.
Preferably, use the monocarboxylic acid with formula R-COOH, wherein R is replacement or unsubstituted aromatics, aliphatic series or the alicyclic organic moiety that contains 6 to 40 carbon atoms.
The different monocarboxylic acids and/or the mixture of equivalent also are fit to.
As indicated above, monocarboxylic acid (or equivalent) can be aromatics, aliphatic series or alicyclic.In this regard, the monocarboxylic acid of " aromatics " is that wherein carboxyl is connected to monocarboxylic acid on the carbon atom in the phenyl ring system, for example hereinafter mentioned those.The monocarboxylic acid of " aliphatic series " is that wherein carboxyl is connected to complete saturated carbon atom or forms monocarboxylic acid on the carbon atom of olefinic double bond.If carbon atom is on ring, then equivalent is " alicyclic ".
Monocarboxylic acid (or equivalent) can comprise any substituting group or their combination (for example functional groups such as acid amides, amine, carbonyl, halogenide, hydroxyl), needs only the character that substituting group does not disturb esterification or influences the gained ester products unfriendly.
Monocarboxylic acid and equivalent can be from any sources, but preferably derived by natural origin or biologically-derived.
The derivative of following acid and they is particularly preferred: lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, phenylformic acid, sad, erucic acid, Zoomeric acid, pentadecylic acid, margaric acid, nondecylic acid, linolic acid, arachidonic acid, oleic acid, valeric acid, caproic acid, capric acid and 2 ethyl hexanoic acid and their mixture.Especially preferred sour or derivatives thereof is 2 ethyl hexanoic acid, phenylformic acid, stearic acid, lauric acid and oleic acid.
Esterification process
In order to prepare ester, preferably exist rare gas element in the presence of, make PO3G and monocarboxylic acid (one or more) at about 100 ℃ to about 275 ℃, contact under preferred about 125 ℃ of temperature to about 250 ℃ of scopes.This method can be implemented under normal atmosphere or vacuum.At period of contact, formed water and its and can in inert gas flow or under the vacuum, be removed to order about reaction and finish.
In order to help the reaction of PO3G and carboxylic acid, generally use esterifying catalyst, be preferably inorganic acid catalyst.The example of inorganic acid catalyst includes but not limited to sulfuric acid, hydrochloric acid, phosphoric acid, hydroiodic acid HI and heterogeneous catalyst, as zeolite, heteropolyacid, macroporous resin (amberlyst) and ion exchange resin.Preferred esterified acid catalyst is selected from the group of being made up of following: sulfuric acid, phosphoric acid, hydrochloric acid and hydroiodic acid HI.Especially preferred inorganic acid catalyst is a sulfuric acid.
The amount of used catalyzer can for about 0.01 weight % of reaction mixture to about 10 weight %, the 0.1 weight % that is preferably reaction mixture is to about 5 weight %, and more preferably from about 0.2 weight % to about 2 weight %.
Can use any ratio of carboxylic acid or its derivative and glycol hydroxyl.Acid is about 3: 1 to about 1: 2 with the preferred ratio of hydroxyl, wherein can regulate the ratio of this ratio with monoesters and diester in the change product.In general, for obtaining more diester product, use the ratio that was a bit larger tham 1: 1.For obtaining more monoesters products, used 0.5: 1 or the lower acid and the ratio of hydroxyl.
The preferred method that is used for esterification comprises: use inorganic acid catalyst with 1, the polycondensation of ammediol reactant becomes polytrimethylene ether glycol, adds carboxylic acid and carries out esterification under the situation of not separating with purifying PO3G then.In the method, use and implement 1 as disclosed acid catalyst among US6977291 and the US6720459, the etherificate of ammediol reactant or polycondensation are to form polytrimethylene ether glycol.Etherification reaction also can use and comprise the two polycondensation catalyst of bronsted lowry acids and bases bronsted lowry and implement, as described in the JP2004-182974A.Continue polycondensation or etherification reaction up to reaching required molecular weight, the monocarboxylic acid with calculated amount joins in the reaction mixture then.Continue reaction, remove water byproduct simultaneously.In this stage, esterification and etherification reaction take place simultaneously.Therefore, in this preferred esterification process, the acid catalyst that is used for the glycol polycondensation also is used for esterification.If desired, can add extra esterifying catalyst in Esterification Stage.
In the method, the time point that is added by carboxylic acid is controlled the viscosity (molecular weight) of products therefrom.
In an alternative method, the PO3G that can adopt following method that purifying is crossed carries out esterification: add esterifying catalyst and carboxylic acid, heat then and remove water.In the method, the viscosity of products therefrom is mainly the function of used PO3G molecular weight.
No matter adopt which kind of esterification process, all will remove all by products after the esterif iotacation step, remove the catalyst residues that polycondensation and/or esterification stay then, so that obtain stable, stable ester products especially at high temperature.This can finish by following hydrolysis reaction: about 80 ℃ to about 100 ℃ down with water treatment ester crude products, the enough hydrolysis of the time of processing are from any remaining acid esters of catalyzer, and can the remarkably influenced carboxylicesters.The required time can change in about 1 to about 8 hours.If hydrolysis is carried out, then may use higher temperature and corresponding short time under pressure.At this moment, according to reaction conditions, product can comprise combination and a spot of acid catalyst, unreacted carboxylic acid and the glycol of diester, monoesters or diester and monoesters.By being further purified hydrating polymer to remove water, acid catalyst and unreacted carboxylic acid such as washing, alkali neutralization, filtration and/or distillatory known conventional technology.Unreacted two pure and mild acid catalysts can remove by for example deionized water wash.Unreacted carboxylic acid also can wash or remove by coupling vacuum stripping by for example deionized water or alkali aqueous solution.
Normally one or more water-washing steps are to remove acid catalyst after the hydrolysis, and drying is preferably dry under vacuum then, to obtain ester products.Washing also is used for removing unreacted glycol.Existing any unreacted monocarboxylic acid also used water flush away removes, yet also can remove by soda lye wash or coupling vacuum stripping.
If desired, can come further with the ester of product fractionation by fractionation under reduced pressure with the separate low molecular amount.
Can use proton magnetic resonance (PMR) and wavelength x ray fluorescence spectrometry to differentiate and any remainder catalyst (as sulphur) that quantitatively is present in the polymkeric substance.Proton magnetic resonance (PMR) can be differentiated the thioester group that for example is present in the polymer chain, and the wavelength x-ray fluorescence method can be measured the total sulfur (inorganic and organosulfur) that is present in the polymkeric substance.The ester of the present invention that is made by aforesaid method is sulfur-bearing not basically, therefore can be used for high temperature and uses.
Preferably, the PO3G ester behind the purifying is substantially free of the acid catalyst end group, but can contain the unsaturated end group of utmost point low levels, mainly is the allyl group end group, and scope is about 0.003 to about 0.03meq/g.Can think that this type of PO3G ester comprises that (being made up of it basically) have following formula (IV) and a compound (V):
R 1-C(O)-O-((CH 2) 3O) m-R 2????????????(IV)
R 1-C(O)-O-((CH 2) 3-O) mCH 2CH＝CH 2????(V)
R wherein 2Be H or R 3C (O); R 1And R 3Respectively independently for comprising replacement or unsubstituted aromatics, radical of saturated aliphatic, unsaturated aliphatic or the alicyclic organic group of 6 to 40 carbon atoms; M within the specific limits, make Mn about 200 to about 3000 scopes; And the content of formula (III) compound make the content of allyl group end group (preferably all unsaturated ends or end group) about 0.003 to about 0.03meq/g scope.
Described PO3G ester preferably has the viscosity lower than PO3G viscosity (when using).The preferred viscosities of 40 ℃ of following PO3G esters at about 20cS to about 150cS scope, and at 40 ℃ of more preferably about 100cS or lower.
According to the above-mentioned preferred requirement of PO3G self, can determine other preferred characteristics of PO3G ester.For example, preferred molecular weight and polymolecularity are based on the preferred molecular weight of the PO3G component of described ester and polymolecularity.
Additive
The ucon oil composition comprises the mixture of basic raw material and one or more additives as described in the present invention, wherein use every kind of additive, to be used for improving basic raw material, for example as fluid pressure type fluid, gear oil, braking fluid, compressor lubricant, textile manufacturing machine and lubricating rollers agent, metal working fluid, refrigeration lubricant, two-cycle engine lubricants and/or crankcase lubricant in the performance of its expection application and the purpose of characteristic.
General according to the type of additive and required additive efficacy levels, add certain quantity of additive, described amount generally can be determined by those skilled in the relevant art.
Described lubricating oil additive preferably comprises at least a ashless dispersant, metal detergent, viscosity modifier, anti-wear agent, antioxidant, friction modifier, pour point reducer, defoamer, corrosion inhibitor, emulsion splitter, rust-preventive agent and their mixture.
When described lubricating oil composition was used as refrigeration lubricant, described lubricating oil additive preferably comprised depressant prescription, washing composition, defoamer, viscosity modifier and their mixture under at least a extreme-pressure anti-friction additive, oxidation and thermostability improving agent, corrosion inhibitor, viscosity index improver, pour point reducer, the flock point.
Use separately any or multiple specified additive or remaining specifies additive combination to use all will to fall within the scope of the present invention with one or more.Use to surpass a kind of any appointment additive also in category of the present invention, for example one or more friction modifiers can be specified the additive combination use separately or with one or more other, for example are used in combination with one or more corrosion inhibitors.
Can independent additive be incorporated in the basic raw material any mode easily.Therefore, concentration level that can be required by every kind of component is dispersed or dissolved in the basic raw material, directly joins it in basic raw material.This blend can take place under envrionment temperature or high temperature.
Alternatively, all or part additive can be blended in enriched material or the additive-package, subsequently described enriched material or additive-package be blended in the basic raw material, to make finished lubricants.When with the lubricant base stock blend of enriched material and predetermined amount, preparation comprises the described enriched material of appropriate amount additive usually, so that required concentration to be provided in described preparation.
Be the non-limiting illustrative example of various additives below.
Ashless dispersant comprises the polymeric hydrocarbon main chain, described main chain have can with treat the associating functional group of discrete particles.Described dispersion agent comprises amine, alcohol, acid amides and/or the ester polarity part that generally is connected with main polymer chain via bridging group usually.Described ashless dispersant can be selected from, for example, the monocarboxylic acid that long chain hydrocarbon replaces and salt, ester, amino ester, acid amides, imide He the oxazoline of dicarboxylic acid and/or their acid anhydrides, the thio carboxy acid ester derivative of long chain hydrocarbon, long chain aliphatic hydrocarbon with polyamines direct-connected, and the phenol that replaces by long-chain and formaldehyde and polyalkylene polyamine condensation and the Mannich condensation product that forms with it.
Viscosity modifier (VM) is used for giving high temperature and cold operation to lubricating oil.Used VM can have this simple function, perhaps can be multi-functional.
The multi-functional viscosity modifier that also can be used as dispersion agent also is known.Illustrative viscosity modifier is a polyisobutene, the multipolymer of ethene and propylene and high alpha-olefin, polymethacrylate, polyalkyl methacrylate, alkylmethacrylate polymer, the multipolymer of unsaturated dicarboxylic acid and vinyl compound, the interpolymer of vinylbenzene and acrylate, with the partial hydrogenation multipolymer of styrene/isoprene, phenylethylene/butadiene and isoprene/butadiene, and the partial hydrogenation homopolymer of divinyl and isoprene and isoprene/Vinylstyrene.
Containing metal or become grey washing composition both to can be used as washing composition to reduce or to remove settling also can be used as acid neutralizing agent or rust-preventive agent, thereby reduces wearing and tearing and corrosion, and prolongs service life of a machine.Washing composition generally comprises polar head and long hydrophobicity afterbody, and described polar head comprises the metal-salt of acidic organic compound.Described salt can comprise the metal that is essentially stoichiometry, and wherein they generally are described to normal salt or neutral salt, and will have total basicnumber (TBN) usually, and described total basicnumber can be measured as 0 to about 80 by ASTM D-2896.By making excessive metallic compound such as oxide compound or oxyhydroxide and sour gas, can comprise a large amount of metal base such as carbon dioxide reaction.Gained high alkalinity washing composition comprises the washing composition that is neutralized, as metal base (for example carbonate) micellar skin.This type of high alkalinity washing composition can have about 150 or bigger, and is generally about 250 to about 450 or bigger TBN.
Illustrative washing composition comprises neutrality and overbased sulfonate, phenates, sulfuration phenates, thio-phosphonates, salicylate and naphthenate and other oil soluble carboxylate salts of metal, especially basic metal or alkaline-earth metal (for example sodium, potassium, lithium, calcium and magnesium).The most frequently used metal is calcium and magnesium (it all can be present in the washing composition that is used for lubricant), and the mixture of calcium and/or magnesium and sodium.Especially easily metal detergent is that TBN is about 20 to about 450 neutrality and high alkaline calcium sulfonate, and TBN is about 50 to about 450 neutrality and high alkalinity phenol calcium and sulfurized calcium phenate.
Dialkyl phosphorodithioic acid metal-salt is commonly used for anti-wear agent and antioxidant.Described metal can be basic metal or alkaline-earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel or copper.Zinc salt is most commonly used in the lubricating oil, and its amount is counted about 0.1 weight % to about 10 weight % by the gross weight of described lubricating oil composition, and preferred about 0.2 weight % is to about 2 weight %.They can make according to known technology, at first usually via one or more alcohol or phenol and P 2S 5Reaction generate dialkyl phosphorodithioic acid (DDPA), then with in the zn cpds with the DDPA that is generated.For example, by with the mixture reaction of primary alconol and secondary alcohol, can make phosphorodithioic acid.Alternatively, can make multiple phosphorodithioic acid, be sechy-drocarbyl all on the alkyl feature on wherein a kind of phosphorodithioic acid, and all be uncle's alkyl on the alkyl feature on other phosphorodithioic acid.For making zinc salt, can use any alkalescence or neutral zn cpds, still the most frequently used is oxide compound, oxyhydroxide and carbonate.Commercial additive generally comprises excessive zinc, and this is excessive basic zinc compound in the neutralization reaction due to.
Yet in one embodiment, described lubricating oil composition preferably is substantially free of zinc.
Oxidation retarder or antioxidant have reduced the in use rotten trend of basic raw material, this rotten can the confirmation by oxidation products (such as sludge on the metallic surface and varnish shape throw out) and viscosity increase.This type of oxidation retarder comprises hindered phenol, preferably has a C 5-C 12The alkaline earth salt of the alkylphenol thioesters of alkyl group side chain, nonylphenol sulfurated lime, ashless oil soluble phenates and sulfuration phenates, sulphur phosphatization or sulfuration hydrocarbon, phosphorous acid ester, thiocarbamate metal-salt, the oil-soluble copper compounds described in US4867890 and molybdate compound.
Can comprise friction modifier to improve fuel combustion efficiency.Oil soluble alkoxylate monoamine and the diamines known can improve the frictional belt oilness.Can use described amine itself, or use and the adducts of boron compound (such as boron oxide, halogenation boron, metaborate, boric acid or boric acid one alkyl ester, boric acid dialkyl or trialkyl borate) or the amine of reaction product form.
Other friction modifiers are known.Wherein these are carboxylic acid and acid anhydrides and alkanol reaction and the ester that forms.Other conventional friction modifiers are generally by forming with the terminal polar group (for example carboxyl or hydroxyl) of lipophilicity hydrocarbon chain covalent bonding.The ester of carboxylic acid and acid anhydrides and alkanol is described among the US4702850.The example of another kind of conventional friction modifier is the organo-metallic molybdenum.
Illustrative rust-preventive agent is selected from nonionic polyoxyalkylene polyol and ester, polyoxyalkylene phenol and negatively charged ion alkylsulphonic acid.
Also can use cupric and plumbous corrosion inhibitor.Usually this compounds is the thiadiazoles polysulfide that comprises 5 to 50 carbon atoms, their derivative and their polymkeric substance.Other additives are sulfo-and polythio sulfinyl amines of thiadiazoles, such as described in the UK1560830 those.Benzotriazole derivatives also belongs to examples of such additives.
The illustrative example of breakdown of emulsion component is described among the EP-A-0330522.It can obtain by the reaction of alkylene oxide and adducts, and described adducts can obtain by the reaction of di-epoxide and polyvalent alcohol.
Pour point reducer also is called as the lubricating oil improving agent, and it can reduce that fluid can flow or the minimum temperature can be toppled over the time.Examples of such additives is known.Improve in those additives of fluid low temperature flowable, be typically fumaric acid C 8And C 18Dialkyl/vinyl acetate copolymer, polyalkyl methacrylate or the like.The pour point of lubricating oil composition according to the present invention, the lubricating oil composition that preparation does not contain pour point reducer also is possible.Yet, exist some to use, wherein wish further to reduce very low pour point.
The foam regulating effect can be provided by chemical compound lot, comprises polysiloxane type defoamer, for example silicone oil or polydimethylsiloxane.
Some above-mentioned additive can provide multiple efficacies.Therefore, for example, single additive can be used as dispersion agent-oxidation retarder.This method is known, and does not need to be described in further detail.
Be to specify the illustrative limiting examples of additive that is used for compression refrigerating system below.
Illustrative extreme-pressure anti-friction additive comprises compound, the organic acid metal-salt of phosphorus compound that phosphoric acid salt, phosphoric acid ester (xylenylphosphate), phosphite, thiophosphate (two organic radical zinc dithiophosphates), chlorinated wax, sulfurized fatty and alkene, organo-lead compound, lipid acid, molybdenum complex, halogen substituted organosilicon compound, borate, organic ester, halogen replace, sulfuration Di Ersi-Alder adducts, organic sulfide, chloride and sulphur.
Illustrative oxidation and thermostability improving agent comprise the metal-salt of sterically hindered phenol (BHT), arylamine, dithiophosphates, phosphite, sulfide and dithio acid.
Illustrative corrosion inhibitor comprises organic acid, organic amine, organophosphate, organic alcohol, metal sulfonate and organic phosphite.
Viscosity index is measuring of viscosity with temperature variation, and the variation of high numeric representation viscosity with temperature is very little.The high viscosity index (HVI) of lubricating oil composition according to the present invention, the lubricating oil composition that preparation does not contain viscosity index improver also is possible.Yet, there are some application, wherein wish further to improve viscosity index.Illustrative viscosity index improver comprises polyisobutene, polymethacrylate and polyoxyethylene alkylphenyl ethene.
Depressant prescription comprises the friedel-crafts condensation product of polymethacrylate, vinyl-vinyl acetate copolymer, succinamic acid-olefin copolymer, ethene-alpha-olefin copolymer and wax and naphthalene or phenol under illustrative pour point and/or the flock point.
Illustrative washing composition comprises aromatic sulfonic acid that sulfonate, chain alkyl replaces, phosphonate, thio-phosphonates, phenates, alkylphenol metal-salt, alkyl sulfur compounds, alkylphenol-aldehyde condensation products, substituted salicylic acid metal-salt, by the reaction product of unsaturated acid anhydride and amine the N-oligopolymer or the polymkeric substance that replace and be mixed with polyester and be connected basic multipolymer such as vinyl-acetic ester-copolymer-maleic anhydride.
Illustrative defoamer is a siloxane polymer.
Illustrative viscosity modifier comprises polyisobutene, polymethacrylate, polyoxyethylene alkylphenyl ethene, naphthenic oil, alkylbenzene oil, paraffin oil, polyester, polyvinyl chloride and polyphosphate.
In the present invention, described lubricating oil additive should (greater than about 50 weight %) can be miscible in ester at least in part.In general, this means that additive therefor should be at least to a certain extent, and preferably be dissolvable in water in the ester to a great extent.
Therefore, described lubricating oil composition should be substantially the mixture of component uniformly, essentially no sedimentation or be separated.
Described lubricating oil composition preferably comprises by the additive of described lubricating oil composition gross weight content less than 50 weight %.In each embodiment, it is about 25 weight % or lower that described lubricating oil can comprise by described lubricating oil composition gross weight content, or about 10 weight % or lower, or about 5 weight % or lower additive.
The viscosity of 40 ℃ of following lubricating oil compositions preferably at about 20cS to about 150cS scope, and under 40 ℃ more preferably about 100cS or lower.
Embodiment
All umbers, percentage ratio etc. all by weight, except as otherwise noted.
Number-average molecular weight (Mn) can be by adopting nuclear magnetic resonance spectrometry analysis end group or determining by the titration hydroxyl.
ASTM method D445-83 and ASTM method D792-91 are respectively applied for kinematic viscosity and the density of determining polymkeric substance.
Other ASTM methods of the listed use of according to the form below.
Under the situation that contains and do not contain the lubricating oil additive bag, measure material of the present invention.The used bag of test period comprises component listed in the table 1.
Table 1
Figure GPA00001032573400191
Embodiment 1: the preparation that does not add the PO3G ester (basic raw material) of additive
This embodiment has described 2-ethylhexanoate synthetic of polytrimethylene ether glycol.
With 1, ammediol (2.4kg, 31.5 moles) joins in the 5L flask that is equipped with agitator, condenser and nitrogen inlet.At room temperature use the liquid 30 minutes in the drying nitrogen purge flask, stir with the speed of 120rpm on one side then, Yi Bian be heated to 170 ℃.When temperature reaches 170 ℃, add 12.6g (the 0.5 weight %) vitriol oil.Make to be reflected at and carried out under 170 ℃ 3 hours, make temperature rise to 180 ℃ and kept 135 minutes down then at 180 ℃.Collect the 435mL distillate altogether.Reaction mixture adds 2.24kg (14.6 moles) 2 ethyl hexanoic acids (99%) then.Under nitrogen gas stream,, make temperature of reaction rise to 160 ℃ on one side, and under this temperature, kept 6 hours then on one side with the lasting stirring of 180rpm speed.Collect 305mL distilled water again in this stage.Stop heating and stir the standing and reacting mixture.Product is decanted, thereby be separated with about 5g lower floor immiscible by product.The nuclear magnetic resonance spectroscopy of by product phase confirms not exist carboxylicesters.
2.0kg PO3G ester products is mixed with 0.5kg water, then the gained mixture was heated 6 hours down at 95 ℃.Water is separated with polymer phase, use twice of 2.0kg water washing polymer phase then.With the product of gained under 120 ℃, 200 millitorrs heating to remove volatile matter (255g).Gained PO3G ester products has following properties:
Number-average molecular weight (Mn)=500
Viscosity difference=24 and 5.5cSt under 40 ℃ and 100 ℃
Viscosity index (VI)=180
Use proton nuclear magnetic resonance analysis gained PO3G ester.The discovery peak relevant with unreacted 2 ethyl hexanoic acid not with sulfuric ester.Do not detect sulphur when using WDXRF analysis of spectral method polymkeric substance.
Embodiment 2: contain the preparation of this fluid material of PO3G ester group of additive
Make lubricating oil composition (weight percent is based on composition total weight) by PO3G ester among the embodiment 1 and following additive:
PO3G ester 97.60%
TPPT???????????0.50％
PANA???????????0.50％
VANLUBE
Figure GPA00001032573400201
RD?????1.00％
IRGALUBE
Figure GPA00001032573400202
349???0.30％
CUVAN 826??????0.10％
Table 2 has been listed the characteristic of base oil and lubricating oil composition.
Table 2
Characteristic Testing method Embodiment 1 (comparing embodiment) Embodiment 2
Pour point, ℃ ??ASTM?D-97 ??-60 ??-63
Flash-point, ℃ ??ASTM?D-92 ??238 ??242
Four ball wear diameters, mm ??ASTM?D-4172 ??0.67 ??0.45
Load wear index last non seizure load (scar) fusion load ??ASTM?D-2783 ??21.5??50kg(0.36mm)??126kg ??23??40kg(0.32mm)??200kg
Falex Pin ﹠ V block tests ultimate load, lb ??ASTM?D-3233 ??1000 ??3000
Embodiment 3
With number-average molecular weight (Mn) is that poly-(propylidene-ethyleneether) glycol (75 weight %) of 890 mixes with the PO3G ester (25 weight %) of embodiment 1 and makes lubricating oil composition (weight percent is based on total composition weight) by adding following additive.Table 3 has been listed blend fluidic lubricating property.
Basic fluid material blend 97.60%
TPPT??????????????????0.50％
PANA??????????????????0.50％
VANLUBE
Figure GPA00001032573400211
RD????????????1.00％
IRGALUBE
Figure GPA00001032573400212
349??????????0.30％
CUVAN
Figure GPA00001032573400213
826?????????????0.10％
Embodiment 4
With number-average molecular weight (Mn) is that poly-(propylidene-ethyleneether) glycol (25 weight %) of 890 mixes with the PO3G ester (75 weight %) of embodiment 1 and makes lubricating oil composition (weight percent is based on total composition weight) by adding following additive.Table 3 has been listed blend fluidic lubricating property.
Basic fluidic blend 97.60%
TPPT????????????????0.50％
PANA????????????????0.50％
VANLUBE
Figure GPA00001032573400214
RD??????????1.00％
IRGALUBE
Figure GPA00001032573400215
349????????0.30％
CUVAN
Figure GPA00001032573400216
826???????????0.10％
Table 3
Characteristic Testing method Embodiment 3 Embodiment 4
Four ball wear diameters, mm ??ASTM?D-4172 ??0.40 ??0.63
The kilocalorie of load wear index last non seizure load (scar) is stung load (scar) fusion load ??ASTM?D-2783 ??33.6??63kg(0.36mm)??160kg(2.69mm)??200kg ??27.2??50kg(0.33mm)??160kg(2.68mm)??200kg
Falex Pin ﹠ V block tests ultimate load, lb ??ASTM?D-3233 ??4500 ??4500

Claims (16)

1. lubricating oil composition, described lubricating oil composition comprises: (i) comprise the basic fluid material of the acid esters of polytrimethylene ether glycol, it is fluid at ambient temperature; (ii) one or more lubricating oil additives.
2. the lubricating oil composition of claim 1, wherein said basic fluid material is counted about 50 weight % or bigger by the gross weight of described lubricating oil composition.
3. the lubricating oil composition of claim 1, wherein said basic fluid material is counted about 75 weight % or bigger by the gross weight of described lubricating oil composition.
4. the lubricating oil composition of claim 1, wherein said basic fluid material is counted about 95 weight % or bigger by the gross weight of described lubricating oil composition.
5. the lubricating oil composition of claim 1, wherein said basic fluid material is made of the acid esters of described polytrimethylene ether glycol basically.
6. the lubricating oil composition of claim 1, the acid esters of wherein said polytrimethylene ether glycol comprises by the diester of about 50 to the 100 weight % of the weight of described acid esters and 0 monoesters to about 50 weight %.
7. the lubricating oil composition of claim 1, wherein said lubricating oil additive comprise at least a in following: ashless dispersant, metal detergent, viscosity modifier, anti-wear agent, antioxidant, friction modifier, pour point reducer, defoamer, corrosion inhibitor, emulsion splitter or rust-preventive agent.
8. the lubricating oil composition of claim 1, wherein said lubricating oil additive at least 50% can be miscible in described basic fluid.
9. the lubricating oil composition of claim 1, wherein said lubricating oil composition are the mixture of uniform described component substantially, do not have sedimentation substantially or are separated.
10. the lubricating oil composition of claim 1, the acid esters of wherein said polytrimethylene ether glycol is the acid esters of monocarboxylic acid and/or equivalent.
11. the lubricating oil composition of claim 10, wherein said monocarboxylic acid has formula R-COOH, and wherein R is replacement or unsubstituted aromatics, aliphatic series or the alicyclic organic moiety that comprises 6 to 40 carbon atoms.
12. the lubricating oil composition of claim 1, the acid esters of wherein said polytrimethylene glycol are the compounds of one or more formulas (I):
Figure FPA00001032573300021
Wherein the residue of hydroxyl polytrimethylene ether glycol is afterwards seized in the Q representative; R 2Be H or R 3CO, and R 1And R 3Independently of one another for to contain the replacement of 6 to 40 carbon atoms or not replace aromatics, radical of saturated aliphatic, unsaturated aliphatic or alicyclic organic group.
13. the lubricating oil composition of claim 1, wherein said acid esters has the number-average molecular weight based on polytrimethylene ether glycol, and described polytrimethylene ether glycol has at least about 250 to less than about 3000 number-average molecular weight.
14. the lubricating oil composition of claim 1, wherein said acid esters by biology make 1, ammediol preparation.
15. the lubricating oil composition of claim 1, wherein said acid esters have the viscosity of about 20cS to about 150cS under 40 ℃.
16. the lubricating oil composition of claim 15, wherein said acid esters have about 100cS or lower viscosity under 40 ℃.
CN200880103881A 2007-08-24 2008-08-21 Lubrication oil compositions Pending CN101842469A (en)

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