CN101784645A - Lubricating oil composition - Google Patents

Abstract

The present invention relates to lubricating oil composition, described lubricating oil composition comprises (i) base fluids raw material, described base fluids raw material comprises (a) PO3G fluid (being the fluidic polytrimethylene ether glycol at ambient temperature) and (b) PO3G ester fluid (being fluidic polytrimethylene ether glycol ester at ambient temperature) and (ii) one or more fuel 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 60/957,716 jointly with its name of submitting to simultaneously is called " LUBRICATION OILCOMPOSITIONS "; And hold U.S. Provisional Application sequence number 60/957722 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 (i) polytrimethylene ether glycol and the (ii) acid esters of polytrimethylene ether glycol (monoesters and/or diester).

Background technology

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 and polytrimethylene ether glycol (PO3G) combination.

Summary of the invention

In one embodiment, the present invention relates to use the mixture of one or more PO3G and one or more PO3G esters and one or more additives to be used as lubricating oil.Therefore, the invention provides lubricating oil composition, described lubricating oil composition comprises (i) base fluids raw material (basefluid stock), described base fluids raw material comprises (a) PO3G fluid (at ambient temperature for fluidic polytrimethylene ether glycol) and (b) mixture and (ii) one or more lubricating oil additives of PO3G ester fluid (being fluidic polytrimethylene ether glycol ester at ambient temperature).

When PO3G and PO3G ester for make based on biology 1, during ammediol, can provide 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 comprise its end points, and all integers and the mark that are positioned at this scope, unless point out separately.When scope 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.

The base fluids raw material

As indicated above, the base fluids raw material packet that is used for lubricating oil composition of the present invention is contained under the envrionment temperature (25 ℃) mixture for fluidic PO3G and PO3G ester.Described base fluids raw 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-BasedLubricants " (comes from Department of Plant Agriculture, OntarioAgriculture College, University of Guelph, 50 Stone Road W., Guelph, Ontario, Canada N1G 2W1) in disclosed those.

Synthetic fluid lubricant (being different from PO3G and PO3G ester) altogether comprises lubricating oil such as hydrocarbon ils, as polybutene, polypropylene, propylene-isobutylene copolymers; Poly suboxygen alkyl diol polymer (being different from PO3G) and their derivative are such as the multipolymer of oxyethane and propylene oxide; And the ester of dicarboxylic acid and multiple alcohol, such as two (2-ethylhexyls) of Polycizer W 260, sebacic acid two (2-ethylhexyl), fumaric acid dihexyl, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, DOP dioctyl phthalate, didecyl phthalate and linoleic acid dimer.

Preferably, described basic material comprises the PO3G/PO3G ester mixture that accounts for most of amount (by described basic material weight greater than 50 weight %).In some embodiments, described basic material can comprise by described base fluids raw 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/PO3G ester mixture.In some preferred embodiments, described base fluids raw material only comprises (or only comprising substantially) PO3G/PO3G ester mixture.

In one embodiment, in the base fluids raw material weight ratio of PO3G/PO3G ester greater than 1: 1 (PO3G is a main ingredient), or about 1.5: 1 or bigger, or about 2: 1 or bigger, or about 5: 1 or bigger, or about 20: 1 or bigger.And described weight ratio is preferably about 25: 1 or lower, or about 20: 1 or lower, or about 10: 1 or lower.

In another embodiment, in the base fluids raw material weight ratio of PO3G ester/PO3G greater than 1: 1 (the PO3G ester is a main ingredient), or about 1.5: 1 or bigger, or about 2: 1 or bigger, or about 5: 1 or bigger, or about 20: 1 or bigger.And described weight ratio is preferably about 25: 1 or lower, or about 20: 1 or lower, or about 10: 1 or lower.

In another embodiment, the weight ratio of PO3G/PO3G ester is about 1: 1 (waiting two kinds of components of weight amount approximately) in the base fluids raw material

Described lubricating oil composition preferably comprises by described lubricating oil composition gross weight counts about 50 weight % or more substantial feed of base oil.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 material.

The monoesters of polytrimethylene ether glycol and diester

In some embodiments, described PO3G ester comprises the compound of one or more formulas (I):

Wherein Q represents the residue of capturing hydroxyl polytrimethylene ether glycol afterwards, R ₂Be H or R ₃CO, and R ₁And R ₃Respectively independently 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 ETHERGLYCOL ESTERS " 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 to 100 weight % for the gross weight by described ester, more preferably from about 75 to 100 weight % diester and 0 to about 50 weight %, more preferably 0 composition to about 25 weight % monoesters.Preferably, monoesters and diester are the ester of 2 ethyl hexanoic acid.

The PO3G that is used for preparing described ester need not PO3G with the base fluids raw material, and component is identical altogether.

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 for example is described 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, utilize biologically-derivedly 1, the PO3G of ammediol and ester thereof 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.van Leeuwen 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 organism of the invariable feasible work of C concentration ¹⁴C 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 ¹⁴The C 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 nearly 7 to 10 years prolongation " transformation period ".(the back understanding that a kind of transformation period can not literally look like; On the contrary, people must use detailed atmosphere nuclear input/decay function to follow the trail of in atmosphere and the biosphere ¹⁴The variation of C after the nuclear age begins.) back just a kind of biosphere 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 AD1950).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/ ¹²C and corresponding δ ¹³Demonstrate significant difference on the C 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.Food Chem., 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 ‰, be 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.Deviation thousand mark δ with PDB ₁₃C represents.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.

Preferably, determine that as reactant or as 1 of reactant composition, the purity of ammediol is by weight greater than about 99% as gas chromatographic analysis, 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 that has of composition ^*a ^*b ^*" b ^*" colour is less than about 0.15 (according to ASTMD6290), and in the absorption at 270nm place less than about 0.075; And/or

(3) peroxide compositions is less than 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 cyclohexane dimethanol and Isosorbide; And polyol, for example glycerine, TriMethylolPropane(TMP) and tetramethylolmethane.The preferred group of comonomer diol is selected from 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 or basically by have following formula (II) and (III) compound of structure form:

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 1000, and more preferably at least about 2000.Described Mn is preferably less than about 10000, is more preferably less than approximately 5000, and is more preferably less than about 3500.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.

Be used for PO3G of the present invention and preferably have, and be more preferably less than the value of color of about 50APHA and be preferably greater than the viscosity of PO3G ester viscosity less than about 100APHA.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 purposes of the present 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 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 reaction mixture about 0.01 to about 10 weight %, be preferably reaction mixture 0.1 to about 5 weight %, and more preferably from about 0.2 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.In order to obtain 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 ₃Independently of one another for containing replacement or unsubstituted aromatics, radical of saturated aliphatic, unsaturated aliphatic or the alicyclic organic group of 6 to 40 carbon atoms; The scope of m make Mn about 200 to about 10000 scope; And the content of formula (III) compound makes the content of allyl group end group (preferably all unsaturated ends or end group) in about scope of 0.003 to about 0.03meq/g.

Described PO3G ester preferably has the viscosity lower than PO3G viscosity.The preferred viscosities of 40 ℃ of following PO3G esters at about 20cS to about 150cS scope, and 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 material and one or more additives as described in the present invention, wherein use every kind of additive, to be used for improving basic 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 additive preferably can be miscible in PO3G and/or PO3G ester.

Described lubricating oil additive preferably comprises at least a ashless dispersant, metal detergent, viscosity modifier, anti-wear agent, antioxidant, friction modifier, pour point depressant, 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 depressant, 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 material any mode easily.Therefore, concentration level that can be required by every kind of component is dispersed or dissolved in the basic material, directly joins it in basic 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 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 prolong 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 counts about 0.1 to about 10 weight % by the gross weight of described lubricating oil composition, and preferred about 0.2 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 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 depressant 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 foam regulating effect can be provided by chemical compound lot, comprises polysiloxane type defoamer, for example silicone oil or polydimethylsiloxane.

Some provided multi-efficiencies in the above-mentioned additive.Therefore, for example, a kind of 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.

Illustrative pour point depression and/or fall the friedel-crafts condensation product that flocculation agent comprises polymethacrylate, vinyl-vinyl acetate copolymer, succinamic acid-olefin copolymer, ethene-alpha-olefin copolymer and wax and naphthalene or phenol.

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 additive should can be miscible in basic material to small part (greater than about 50 weight %).In general, this means additive therefor at least to a certain extent, and preferably be oil-soluble to a great extent.

Therefore, the described lubricating oil composition component mixture that should be uniform substantially 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.

Embodiment

All umbers, percentage ratio etc. all by weight, except as otherwise noted.

By adopting NMR analysis of spectral method end group or, can determining the number-average molecular weight (Mn) of polyether glycol and polyether glycol ester by the hydroxyl titration.

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

Preparation-the PO3G1 of PO3G homopolymer

In the 22L 4 neck round-bottomed flasks that are equipped with nitrogen inlet and still head, add 1 of 11877g, ammediol.With 10L/ minute speed with nitrogen with the liquid bubbling, and about 15 minutes of mechanical stirring (using the stirring magneton that drives by flask below magnetic stirring apparatus).After 15 minutes, by separating funnel by in eck during at least 5 minutes in slow dropping 108g sulfuric acid.When finishing, with 1 of 15g, ammediol (PDO) joins in the separating funnel, and whirlpool is to remove any residual sulfuric acid.It is joined in the flask.Mixture stirred and bubbling as mentioned above, and be heated to 160 ℃.Remove water in the reaction by distillation, and during polyreaction, collect continuously.Reaction continues 25 hours, makes its cooling (keeping simultaneously stirring and bubbling) to 45 ℃ afterwards.

Following with the coarse fodder hydrolysis.Rough polymkeric substance is joined in the 5 neck round-bottomed flasks (being equipped with condenser and mechanical stirrer) of 22L with isopyknic distilled water.With this mixture mechanical stirring, and with about 150mL/ minute speed nitrogen bubble, and be heated to 100 ℃.It was refluxed 4 hours, stop heating then, and make mixture be cooled to 45 ℃.Interrupt stirring, and bubbling is reduced to minimum degree.During cooling be separated.Shift out and discard and contain water.The distilled water that volume is equaled initial amount joins in the wet polymer that remaines in the flask.With stirring, bubbling be heated to 100 ℃ and carried out 1 hour, stop heating thereafter, and make described material cooling as in the previous once more.Shift out and discard and contain water.

Determine residual sulfuric acid by titration, and neutralize with the excessive hydrogen calcium oxide.Polymkeric substance 90 ℃ of following drying under reduced pressure 3 hours, is filtered the Whatman filter paper by precoating CELPURE C-65 flocculating aids then.Gained PO3G has 940 number-average molecular weight.

Poly-(propylidene-ethyleneether) diol copolymer-PO3G2 of preparation

Repeat aforesaid method, different is, 1, and the amount of ammediol (8811.2g), 1 (3080.8g) and sulfuric acid (108g) changes, and what obtain to have 890 number-average molecular weights (Mn) gathers (propylidene-ethyleneether) diol copolymer.

Preparation 2 ethyl hexanoic acid PO3G ester

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, be heated to 170 ℃ on one side Yi Bian stir with 120rpm then.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, continue to stir one side with 180rpm on one side then and make temperature of reaction rise to 160 ℃, and under this temperature, kept 6 hours.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 polytrimethylene ether glycol esters product 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 1

The PO3G1 (by the weight 25 weight % of described base fluids raw material) and the PO3G ester (by the weight 75 weight % of described base fluids raw material) that as above make are mixed, and the following lubricating oil composition (weight percent is pressed general composition weight meter) that makes:

Base fluids blend 97.3%

IRGALUBE

TPPT?????????????????0.40％

VANLUBE

7723?????????????????0.30％

VANLUBE

887E?????????????????0.20％

PANA??????????????????????0.40％

VANLUBE RD???????????????????0.80％

IRGALUBE

349??????????????????0.40％

CUVAN

826??????????????????0.10％

Table 2 has been listed blend fluidic lubricating property.

Table 2

Characteristic	The ASTM method	Embodiment 2
			Viscosity under 40 ℃, cSt	??D445	??38.5
Viscosity index		??182
			Pour point, ℃	??D97	??0
Flash-point, ℃	??D-92	??240
			Evaporation	??D-972	??0.42％
Foaming sequence 1,2,3	??D-892	Do not have
			Copper corrosion	??D-130	??1B
Four ball wear diameters, mm	??D-4172	??0.69
			Load wear index	??D-2783	??24.5
(scar, mm) kilocalorie is stung load (scar, mm) fusion load, kg to last non seizure load	??D-2783	??40kg(.31)??160kg(2.59)??200
			Falex Pin ﹠ V block ultimate load, lb	??D3233	??3400

Embodiment 2

The PO3G1 (by the weight 75 weight % of described base fluids raw material) and the PO3G ester (by the weight 25 weight % of described base fluids raw material) that as above make are mixed, and make lubricating oil composition (weight percent is hereinafter pressed general composition weight meter) by adding following additive:

Base fluids blend 97.6%

TPPT??????????????????????0.50％

PANA??????????????????????0.50％

VANLUBE

RD????????????????????1.00％

IRGALUBE

349???????????????????0.30％

CUVAN

826???????????????????0.10％

Embodiment 3

The PO3G2 (by the weight 75 weight % of described base fluids raw material) and the PO3G ester (by the weight 25 weight % of described base fluids raw material) that as above make are mixed, and make lubricating oil composition (weight percent is pressed general composition weight meter) by adding following additive:

Base fluids blend 97.60%

IRGALUBE

TPPT??????????????????0.50％

PANA??????????????????????0.50％

VANLUBE

RD????????????????????1.00％

IRGALUBE

349???????????????????0.30％

CUVAN

826???????????????????0.10％

Table 3 has been listed blend fluidic lubricating property.

Embodiment 4

The PO3G2 (by the weight 25 weight % of described base fluids raw material) and the PO3G ester (by the weight 75 weight % of described base fluids raw material) that as above make are mixed, and make lubricating oil composition (weight percent is pressed general composition weight meter) by adding following additive:

Base fluids blend 97.60%

IRGALUBE

TPPT??????????????????0.50％

PANA??????????????????????0.50％

VANLUBE

RD????????????????????1.00％

IRGALUBE

349???????????????????0.30％

CUVAN 826???????????????????0.10％

Table 3 has been listed blend fluidic lubricating property.

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

Embodiment 5

By following additive-package is joined poly-(propylidene-ethyleneether) glycol (Mn=1100, PO3G3) in to form initial composition, make lubricating oil composition.

PO3G3????????????????????????97.85％

Defoamer DC 200cSt 0.0025%

VANLUBE 7723????????????????????????0.3％

VANLUBE

887E????????????????????????0.4％

IRGANOX

1135????????????????????????0.2％

IRGALUBE

TPPT????????????????????????0.5％

IRGALUBE 349?????????????????????????0.4％

VANLUBE

RD??????????????????????????0.25％

CUVAN

826?????????????????????????0.1％

Make this lubricating oil composition (by gross weight 90 weight %) and 2 ethyl hexanoic acid PO3G ester (by the gross weight 10 weight %) blend that makes as mentioned above.

Table 4 has been listed for example lubricating property of the finished product of rotating machinery lubricant (gear, bearing) and hydraulic fluid of suitable work.

Table 4:

Characteristic	The ASTM method
			Viscosity under 40 ℃, cSt		??236
Viscosity index		??206
			Pour point, ℃	??D97	??-45
Flash-point, ℃	??D-92	??288
			Four ball wear diameters, mm	??D-4172	??0.37
Frictional coefficient	??D-4172	??0.033
			Load wear index	??D-2783	??61.5
Last non seizure load (scar, mm) fusion load, kg	??D-2783	??160kg(.52)??200
			Falex Pin ﹠ V block ultimate load, lb	??D3233	??3000

Characteristic	The ASTM method
			Oxidation test data viscosity changes, and the % acid number changes (Mg/KOH/g) vaporization losses %, weight of precipitate, mg	D4636 24 hours, 190 ℃	???1.49??0.07??0.65??4.4
Copper corrosion	??D-4646	Tarnish-ib

Claims (21)

1. lubricating oil composition, described lubricating oil composition comprises: (i) base fluids raw material, described base fluids raw material comprises (a) and for the fluidic polytrimethylene ether glycol and (b) is the mixture of the acid esters of fluidic polytrimethylene ether glycol and (ii) one or more lubricating oil additives at ambient temperature at ambient temperature.

2. the lubricating oil composition of claim 1, wherein said base fluids raw material is counted about 50 weight % or bigger by the gross weight of described lubricating oil composition.

3. the lubricating oil composition of claim 2, wherein said base fluids raw material is counted about 75 weight % or bigger by the gross weight of described lubricating oil composition.

4. the lubricating oil composition of claim 3, wherein said base fluids raw 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 base fluids raw material are made up of the mixture of the acid esters of described polytrimethylene ether glycol and described polytrimethylene ether glycol basically.

6. the lubricating oil composition of claim 1, wherein in described base fluids raw material, the weight ratio of the acid esters of polytrimethylene ether glycol and polytrimethylene ether glycol is 1: 1 or bigger.

7. the lubricating oil composition of claim 1, wherein in described base fluids raw material, the acid esters of polytrimethylene ether glycol and the weight ratio of polytrimethylene ether glycol are 1: 1 or bigger.

8. 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 %.

9. the lubricating oil composition of claim 1, described composition also comprises lubricating oil additive, and described additive comprises at least a following additive that is selected from: ashless dispersant, metal detergent, viscosity modifier, anti-wear agent, antioxidant, friction modifier, pour point depressant, defoamer, corrosion inhibitor, emulsion splitter and rust-preventive agent.

10. the lubricating oil composition of claim 1, wherein said lubricating oil additive at least 50% can be miscible in described base fluids raw material.

11. the lubricating oil composition of claim 1, wherein said lubricating oil composition is the mixture of uniform essentially no sedimentation substantially or the described component that is separated.

12. the lubricating oil composition of claim 1, the acid esters of wherein said polytrimethylene ether glycol are the acid esters of monocarboxylic acid and/or equivalent.

13. the lubricating oil composition of claim 12, 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.

14. the lubricating oil composition of claim 1, the acid esters of wherein said polytrimethylene glycol are the compounds of one or more formulas (I):

Wherein Q represents the residue of capturing hydroxyl polytrimethylene ether glycol afterwards; 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.

15. 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 10000 number-average molecular weight.

16. the lubricating oil of claim 1, wherein said polytrimethylene ether glycol have at least about 250 to less than about 10000 number-average molecular weight.

17. the lubricating oil of claim 1, wherein 99% to 100% repeating unit is the trimethylene ether unit in described polytrimethylene ether glycol.

18. the lubricating oil of claim 1, wherein said polytrimethylene ether glycol comprise trimethylene ether unit and more a spot of other polyoxyalkylene ether repeating unit.

19. the lubricating oil composition of claim 1, wherein said acid esters by biology make 1, ammediol prepares.

20. the lubricating oil composition of claim 1, wherein said polytrimethylene ether glycol can be by 1 of biology generation, and ammediol prepares.

21. the lubricating oil composition of claim 1, the acid esters of wherein said polytrimethylene ether glycol have than the lower viscosity of described polytrimethylene ether glycol viscosity.