EP2181181A1 - Compositions d'huile de lubrification - Google Patents

Compositions d'huile de lubrification

Info

Publication number
EP2181181A1
EP2181181A1 EP08828627A EP08828627A EP2181181A1 EP 2181181 A1 EP2181181 A1 EP 2181181A1 EP 08828627 A EP08828627 A EP 08828627A EP 08828627 A EP08828627 A EP 08828627A EP 2181181 A1 EP2181181 A1 EP 2181181A1
Authority
EP
European Patent Office
Prior art keywords
lubrication oil
oil composition
ether glycol
acid ester
base fluid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08828627A
Other languages
German (de)
English (en)
Inventor
Hari Babu Sunkara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP2181181A1 publication Critical patent/EP2181181A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/402—Castor oils
    • 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
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two 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
    • 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
    • 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
    • C10N2030/02—Pour-point; 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
    • 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

Definitions

  • compositions comprising (i) an acid ester (monoester and/or diester) of polytrimethylene ether glycol; and (ii) a vegetable oil lubricant.
  • the invention also relates to the use of such compositions as lubrication oils.
  • PO3G esters Certain mono- and diesters of polytrimethylene ether glycol (“PO3G esters”) have properties that make them useful in a variety of fields, including as lubricants, as disclosed in commonly owned U.S. Application Serial No. 11/593,954, filed November 7, 2006, entitled “POLYTRIMETHYLENE ETHER GLYCOL ESTERS”.
  • the present invention is directed to specific lubricant compositions based on combinations of such PO3G esters with vegetable oil lubricants.
  • the present invention relates to the use of mixtures of one or more PO3G esters and one or more vegetable oil-based lubricants, optionally along with one or more polytrimethylene ether glycols ("PO3Gs") and one or more additives, as a lubrication oils.
  • the present invention thus provides a lubrication oil composition comprising a base fluid stock comprising: (i) a PO3G ester fluid (an ester of a polytrimethylene ether glycol that is a fluid at ambient temperature); and (ii) a vegetable oil- based lubricant.
  • a PO3G ester fluid an ester of a polytrimethylene ether glycol that is a fluid at ambient temperature
  • a vegetable oil- based lubricant When the PO3G ester (and PO3G when utilized) is based on biologically produced 1 ,3-propanediol, lubricant compositions with a very high renewable content can be provided.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • the base fluid stock for use in the lubrication oil compositions of the present invention comprises a PO3G ester that is a fluid at ambient temperature (25°C), in combination with a vegetable oil-based lubricant.
  • the base fluid stock may also comprise PO3G that is preferably fluid at ambient temperature (25°C), and/or other synthetic fluid co-lubricants.
  • Vegetable oil-based lubricants suitable for use in the present invention are generally derived from plants and are generally composed of triglycerides. Normally, these are liquid at room temperature. Although many different parts of plants may yield oil, in actual practice oil is generally extracted primarily from the seeds of oilseed plants. These oils include both edible and inedible oils, and include, for example, high oleic sunflower oil, rapeseed oil, soybean oil, castor oil and the like, as well as modified oils such as disclosed in US6583302 (fatty acid esters) and I. Malchev, "Plant-Oil- Based Lubricants” (available from the Department of Plant Agriculture, Ontario Agriculture College, University of Guelph, 50 Stone Road W., Guelph, Ontario, Canada N1 G 2W1 ).
  • Synthetic fluid co-lubricants include lubricating oils such as hydrocarbon oils such as polybutylenes, polypropylenes, pro- pylene-isobutylene copolymers; polyoxyalkylene glycol polymers (other than PO3G) and their derivatives such as ethylene oxide and propylene oxide copolymers; and esters of dicarboxylic acids with a variety of alcohols such as dibutyl adipate, di(2- ethylhexyl) sebacate , di-hexyl fumarate, dioctyl sebacate, diisoctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, and the 2-ethylhexyl diester of linoleic acid dimer.
  • lubricating oils such as hydrocarbon oils such as polybutylenes, polypropylenes, pro- pylene-isobut
  • the base stock comprises a predominant amount PO3G ester (or mixture with PO3G) (greater than 50 wt% based on the weight of the base stock).
  • the base stock can comprise the PO3G ester (or mixture) in an amount of about 66 wt% or greater, or about 75 wt% or greater, or about 90 wt% or greater, or about 95 wt% or greater, based on the total weight of the base fluid stock.
  • the base stock comprises a predominant amount of the vegetable oil-based lubricant (greater than 50 wt% based on the weight of the base stock).
  • the base stock can comprise the vegetable oil-based lubricant in an amount of about 66 wt% or greater, or about 75 wt% or greater, or about 90 wt% or greater, or about 95 wt% or greater, based on the total weight of the base fluid stock.
  • the weight ratio of PO3G/PO3G ester in the base fluid stock is greater than 1 :1 (the PO3G being the predominant component), or about 1.5:1 or greater, or about 2:1 or greater, or about 5:1 or greater, or about 20:1 or greater. Also, the weight ratio is preferably about 25:1 or less, or about 20:1 or less, or about 10:1 or less.
  • the weight ratio of PO3G ester/PO3G in the base fluid stock is greater than 1 :1 (the PO3G ester being the predominant component), or about 1.5:1 or greater, or about 2:1 or greater, or about 5:1 or greater, or about 20:1 or greater. Also, the weight ratio is preferably about 25:1 or less, or about 20:1 or less, or about 10:1 or less.
  • the weight ratio of PO3G/PO3G ester in the base fluid stock is about 1 :1 (approximately equivalent weight amounts of the two compo- nents).
  • the lubrication oil composition preferably comprises the base oil stock in an amount of about 50 wt% or greater, based on the total weight of the lubrication oil composition.
  • the lubrication oil can comprise the base stock in an amount of about 75 wt% or greater, or about 90 wt% or greater, or about 95 wt% or greater, based on the total weight of the lubrication oil composition.
  • the P03G esters comprise one or more compounds of the formula (I):
  • R 2 is H or R 3 CO
  • each of R 1 and R 3 is individually a substituted or unsubstituted aromatic, saturated aliphatic, unsaturated aliphatic or cyclo- aliphatic organic group, containing 4 to 40 carbon atoms, preferably at least 6 carbon atoms, more preferably at least 8 carbon atoms.
  • each of Ri and R 3 has 20 carbon atoms or fewer, and in some embodiments 10 carbon atoms or fewer. In some preferred embodiments, each of Ri and R 3 has 8 carbon atoms.
  • PO3G esters are preferably prepared by polycondensation of hydroxyl groups- containing monomers (monomers containing 2 or more hydroxyl groups) predominantly comprising 1 ,3-propanediol to form a PO3G (as disclosed in further detail below), followed by esterification with a monocarboxylic acid (or equivalent), as disclosed in U.S. Application Serial No. 11/593,954, filed November 7, 2006, entitled "POLYTRIMETHYLENE ETHER GLYCOL ESTERS”.
  • the PO3G ester thus prepared is a composition preferably comprising from about 50 to 100 wt%, more preferably from about 75 to 100 wt%, diester and from 0 to about 50 wt%, more preferably from 0 to about 25 wt%, monoester, based on the total weight of the esters.
  • the mono- and diesters are esters of 2-ethylhexanoic acid.
  • the PO3G used for preparing the ester need not be the same as the PO3G co- component of the base fluid stock.
  • PO3G for the purposes of the present invention is an oligomeric or polymeric ether glycol in which at least 50% of the repeating units are trimethylene ether units. More preferably from about 75% to 100%, still more preferably from about 90% to 100%, and even more preferably from about 99% to 100%, of the repeating units are trimethylene ether units.
  • PO3G is preferably prepared by polycondensation of monomers comprising 1 ,3-propanediol, preferably in the presence of an acid catalyst, thus resulting in polymers or copolymers containing -(CH 2 CH 2 CH 2 O)- linkage (e.g, trimethylene ether repeating units). As indicated above, at least 50% of the repeating units are trimethylene ether units.
  • the resulting product preferably contains less than about 20 ppm, more preferably less than about 10 ppm, of sulfur.
  • trimethylene ether glycol encompasses PO3G made from essentially pure 1 ,3-propanediol, as well as those oligomers and polymers (including those described below) containing up to about 50% by weight of comonomers.
  • the 1 ,3-propanediol employed for preparing the PO3G may be obtained by any of the various well known chemical routes or by biochemical transformation routes. Preferred routes are described in, for example, US5015789, US5276201 , US5284979, US5334778, US5364984, US5364987, US5633362, US5686276, US5821092, US5962745, US6140543, US6232511 , US6235948, US6277289, US6297408, US6331264, US6342646, US7038092, US708431 1 , US7098368, US7009082 and US20050069997A1.
  • the 1 ,3-propanediol is obtained biochemically from a renewable source ("biologically-derived" 1 ,3-propanediol).
  • a particularly preferred source of 1 ,3-propanediol is via a fermentation process using a renewable biological source.
  • a renewable biological source biochemical routes to 1 ,3-propanediol (PDO) have been de- scribed that utilize feedstocks produced from biological and renewable resources such as corn feed stock.
  • PDO biochemical routes to 1 ,3-propanediol
  • bacterial strains able to convert glycerol into 1 ,3- propanediol are found in the species Klebsiella, Citrobacter, Clostridium, and Lactobacillus. The technique is disclosed in several publications, including US5633362, US5686276 and US5821092.
  • US5821092 discloses, inter alia, a process for the bio- logical production of 1 ,3-propanediol from glycerol using recombinant organisms.
  • the process incorporates E. coli bacteria, transformed with a heterologous pdu diol dehydratase gene, having specificity for 1 ,2-propanediol.
  • the transformed E. coli is grown in the presence of glycerol as a carbon source and 1 ,3-propanediol is isolated from the growth media. Since both bacteria and yeasts can convert glucose (e.g., corn sugar) or other carbohydrates to glycerol, the processes disclosed in these publications provide a rapid, inexpensive and environmentally responsible source of 1 ,3-propanediol monomer.
  • the biologically-derived 1 ,3-propanediol such as produced by the processes described and referenced above, contains carbon from the atmospheric carbon dioxide incorporated by plants, which compose the feedstock for the production of the 1 ,3- propanediol.
  • the biologically-derived 1 ,3-propanediol preferred for use in the context of the present invention contains only renewable carbon, and not fossil fuel-based or petroleum-based carbon.
  • compositions of the present invention can be characterized as more natural and having less environmental impact than similar compositions comprising petroleum based glycols.
  • the biologically-derived 1 ,3-propanediol, PO3G and PO3G esters may be distinguished from similar compounds produced from a petrochemical source or from fossil fuel carbon by dual carbon-isotopic finger printing. This method usefully distin- guishes chemically-identical materials, and apportions carbon in the copolymer by source (and possibly year) of growth of the biospheric (plant) component.
  • the isotopes, 14 C and 13 C bring complementary information to this problem.
  • the radiocarbon dating isotope ( 14 C) with its nuclear half life of 5730 years, clearly allows one to apportion specimen carbon between fossil (“dead”) and biospheric ("alive”) feedstocks (Cur- rie, L.
  • 14 C has acquired a second, geo- chemical time characteristic. Its concentration in atmospheric CO 2 , and hence in the living biosphere, approximately doubled at the peak of nuclear testing, in the mid- 1960s.
  • f M is defined by National Institute of Standards and Technology (NIST) Standard Reference Materials (SRMs) 4990B and 4990C, known as oxalic acids standards HOxI and HOxII, respectively.
  • SRMs Standard Reference Materials
  • the fundamental definition relates to 0.95 times the 14 C/ 12 C isotope ratio HOxI (referenced to AD 1950). This is roughly equivalent to decay-corrected pre-lndustrial Revolution wood.
  • f M 1.1.
  • the stable carbon isotope ratio ( 13 C/ 12 C) provides a complementary route to source discrimination and apportionment.
  • the 13 C/ 12 C ratio in a given biosourced material is a consequence of the 13 C/ 12 C ratio in atmospheric carbon dioxide at the time the carbon dioxide is fixed and also reflects the precise metabolic pathway. Regional variations also occur. Petroleum, C 3 plants (the broadleaf), C 4 plants (the grasses), and marine carbonates all show significant differences in 13 C/ 12 C and the corresponding ⁇ 13 C values. Furthermore, lipid matter of C 3 and C 4 plants analyze differently than materials derived from the carbohydrate components of the same plants as a consequence of the metabolic pathway.
  • 13 C shows large variations due to isotopic fractionation effects, the most significant of which for the instant invention is the photosynthetic mechanism.
  • the major cause of differences in the carbon isotope ratio in plants is closely associated with differences in the pathway of photosynthetic carbon metabolism in the plants, particularly the reaction occurring during the primary carboxylation, i.e., the initial fixation of atmospheric CO 2 .
  • Two large classes of vegetation are those that incorporate the "C 3 " (or Calvin-Benson) pho- tosynthetic cycle and those that incorporate the "C 4 " (or Hatch-Slack) photosynthetic cycle.
  • C 3 plants, such as hardwoods and conifers, are dominant in the temperate climate zones.
  • the primary CO 2 fixation or carboxylation reaction involves the enzyme ribulose-1 ,5-diphosphate carboxylase and the first stable product is a 3-carbon compound.
  • C 4 plants include such plants as tropical grasses, corn and sugar cane.
  • an additional carboxylation reaction involving another enzyme, phosphenol-pyruvate carboxylase is the primary carboxylation reaction.
  • the first stable carbon compound is a 4-carbon acid, which is subsequently decarboxylated. The CO 2 thus released is refixed by the C 3 cycle.
  • Biologically-derived 1 ,3-propanediol, and compositions comprising biologically- derived 1 ,3-propanediol may be completely distinguished from their petro- chemical derived counterparts on the basis of 14 C (f M ) and dual carbon-isotopic fingerprinting, indicating new compositions of matter.
  • the ability to distinguish these products is beneficial in tracking these materials in commerce. For example, products comprising both "new” and “old” carbon isotope profiles may be distinguished from products made only of "old” materials.
  • the instant materials may be followed in commerce on the basis of their unique profile and for the purposes of defining competition, for determining shelf life, and especially for assessing environmental impact.
  • the 1 ,3-propanediol used as the reactant or as a component of the reactant will have a purity of greater than about 99%, and more preferably greater than about 99.9%, by weight as determined by gas chromatographic analysis.
  • Particularly preferred are the purified 1 ,3-propanediols as disclosed in US7038092, US7098368, US7084311 and US20050069997A1 , as well as PO3G made therefrom as disclosed in US20050020805A1.
  • the purified 1 ,3-propanediol preferably has the following characteristics:
  • a concentration of total organic impurities (organic compounds other than 1 ,3-propanediol) of less than about 400 ppm, more preferably less than about 300 ppm, and still more preferably less than about 150 ppm, as measured by gas chromatography.
  • the starting material for making PO3G will depend on the desired PO3G, availability of starting materials, catalysts, equipment, etc., and comprises "1 ,3-propanediol reactant.”
  • 1 ,3-propanediol reactant is meant 1 ,3-propanediol, and oligomers and prepolymers of 1 ,3-propanediol preferably having a degree of polymerization of 2 to 9, and mixtures thereof. In some instances, it may be desirable to use up to 10% or more of low molecular weight oligomers where they are available.
  • the starting material comprises 1 ,3-propanediol and the dimer and trimer thereof.
  • a particularly preferred starting material is comprised of about 90% by weight or more 1 ,3- propanediol, and more preferably 99% by weight or more 1 ,3-propanediol, based on the weight of the 1 ,3-propanediol reactant.
  • PO3G can be made via a number of processes known in the art, such as disclosed in US6977291 and US6720459. The preferred processes are as set forth in US7074969, US7157607, US7161045 and US7164046.
  • PO3G may contain lesser amounts of other polyalkylene ether repeating units in addition to the trimethylene ether units.
  • the monomers for use in preparing polytrimethylene ether glycol can, therefore, contain up to 50% by weight (preferably about 20 wt% or less, more preferably about 10 wt% or less, and still more preferably about 2 wt% or less), of comonomer polyols in addition to the 1 ,3-propanediol reactant.
  • Comonomer polyols that are suitable for use in the process include aliphatic diols, for example, ethylene glycol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10-decanediol, 1 ,12-dodecanediol, 3,3,4,4,5,5-hexafluro-1 ,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1 ,6-hexanediol, and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluoro-1 ,12-dodecanediol; cycloaliphatic diols, for example, 1 ,4-cyclohexanediol, 1
  • a preferred group of comonomer diols is selected from the group consisting of ethylene glycol, 2-methyl-1 ,3-propanediol, 2,2-dimethyl-1 ,3-propanediol, 2,2-diethyl-1 ,3- propanediol, 2-ethyl-2-(hydroxymethyl)-1 ,3-propanediol, C 6 - Ci 0 diols (such as 1 ,6-hexanediol, 1 ,8-octanediol and 1 ,10-decanediol) and isosorbide, and mixtures thereof.
  • a particularly preferred diol other than 1 ,3-propanediol is ethylene glycol, and C 6 - Cio diols can be particularly useful as well.
  • poly(trimethylene-ethylene ether) glycol such as described in US20040030095A1.
  • Preferred poly(trimethylene-ethylene ether) glycols are prepared by acid catalyzed polycondensation of from 50 to about 99 mole% (preferably from about 60 to about 98 mole%, and more preferably from about 70 to about 98 mole%) 1 ,3-propanediol and up to 50 to about 1 mole% (preferably from about 40 to about 2 mole%, and more preferably from about 30 to about 2 mole%) ethylene glycol.
  • the PO3G after purification has essentially no acid catalyst end groups, but may contain very low levels of unsaturated end groups, predominately allyl end groups, in the range of from about 0.003 to about 0.03 meq/g.
  • Such a PO3G can be considered to comprise (consist essentially of) the compounds having the following formulae (II) and
  • m is in a range such that the Mn (number average molecular weight) is within the range of from about 200 to about 10000, with compounds of formula (III) being present in an amount such that the allyl end groups (preferably all unsaturation ends or end groups) are present in the range of from about 0.003 to about 0.03 meq/g.
  • the preferred PO3G for use in the invention has an Mn (number average molecular weight) of at least about 250, more preferably at least about 500, and still more preferably at least about 1000.
  • the Mn is preferably less than about 10000, more preferably less than about 5000, and still more preferably less than about 2500.
  • Blends of PO3Gs can also be used.
  • the PO3G can comprise a blend of a higher and a lower molecular weight PO3G, preferably wherein the higher molecular weight PO3G has a number average molecular weight of from about 1000 to about 5000, and the lower molecular weight PO3G has a number average molecular weight of from about 200 to about 950.
  • the Mn of the blended PO3G will preferably still be in the ranges mentioned above.
  • PO3G preferred for use herein is typically polydisperse having a polydispersity (i.e. Mw/Mn) of preferably from about 1.0 to about 2.2, more preferably from about 1.2 to about 2.2, and still more preferably from about 1.5 to about 2.1.
  • the polydispersity can be adjusted by using blends of PO3G.
  • PO3G for use in the present invention preferably has a color value of less than about 100 APHA, and more preferably less than about 50 APHA, and a viscosity which is preferably greater than the viscosity of the PO3G ester.
  • a preferred viscosity is about 10OcS or greater at 40 0 C.
  • the esterification of the PO3G is carried out by reaction with an acid and/or equivalent, preferably a monocarboxylic acid and/or equivalent.
  • monocarboxylic acid equivalent compounds that perform substantially like monocarboxylic acids in reaction with polymeric glycols and diols, as would be generally recognized by a person of ordinary skill in the relevant art.
  • Mono- carboxylic acid equivalents for the purpose of the present invention include, for example, esters of monocarboxylic acids, and ester-forming derivatives such as acid halides (e.g., acid chlorides) and anhydrides.
  • a monocarboxylic acid having the formula R-COOH, wherein R is a substituted or unsubstituted aromatic, aliphatic or cycloaliphatic organic moiety containing from 6 to 40 carbon atoms.
  • the monocarboxylic acid (or equivalent) can be aromatic, aliphatic or cycloaliphatic.
  • aromatic monocarboxylic acids are monocarboxylic acids in which a carboxyl group is attached to a carbon atom in a benzene ring system such as those mentioned below.
  • Aliphatic monocarboxylic acids are monocarboxylic acids in which a carboxyl group is attached to a fully saturated carbon atom or to a carbon atom which is part of an olefinic double bond. If the carbon atom is in a ring, the equivalent is "cycloaliphatic.”
  • the monocarboxylic acid (or equivalent) can contain any substituent groups or combinations thereof (such as functional groups like amide, amine, carbonyl, halide, hydroxyl, etc.), so long as the substituent groups do not interfere with the esterification reaction or adversely affect the properties of the resulting ester product.
  • substituent groups or combinations thereof such as functional groups like amide, amine, carbonyl, halide, hydroxyl, etc.
  • the monocarboxylic acids and equivalents can be from any source, but preferably are derived from natural sources or are bio-derived.
  • acids and their derivatives are specifically preferred: lauric, myris- tic, palmitic, stearic, arachidic, benzoic, caprylic, erucic, palmitoleic, pentadecanoic, heptadecanoic, nonadecanoic, linoleic, arachidonic, oleic, valeric, caproic, capric and 2-ethylhexanoic acids, and mixtures thereof.
  • Particularly preferred acids or derivatives thereof are 2-ethylhexanoic acid, benzoic acid, stearic acid, lauric acid and oleic acid.
  • the PO3G can be contacted, preferably in the presence of an inert gas, with the monocarboxylic acid(s) at temperatures ranging from about 100 0 C to about 275°C, preferably from about 125°C to about 250 0 C.
  • the process can be carried out at atmospheric pressure or under vacuum. During the contacting water is formed is formed and can be removed in the inert gas stream or under vacuum to drive the reaction to completion.
  • an esterfication catalyst is generally used, preferably a mineral acid catalyst.
  • mineral acid catalysts include but are not restricted to sulfuric acid, hydrochloric acid, phosphoric acid, hydriodic acid, and heterogeneous catalysts such as zeolites, heteropolyacid, amber- lyst, and ion exchange resin.
  • Preferred esterification acid catalysts are selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric acid and hydroiodic acid.
  • a particularly preferred mineral acid catalyst is sulfuric acid.
  • the amount of catalyst used can be from about 0.01 wt% to about 10 wt% of the reaction mixture, preferably from 0.1 wt% to about 5 wt%, and more preferably from about 0.2 wt% to about 2 wt%, of the reaction mixture.
  • Any ratio of carboxylic acid, or derivatives thereof, to glycol hydroxyl groups can be used.
  • the preferred ratio of acid to hydroxyl groups is from about 3:1 to about 1 :2, where the ratio can be adjusted to shift the ratio of monoester to diester in the product.
  • a 0.5:1 ratio or less of acid to hydroxyl is used.
  • a preferred method for esterification comprises polycondensing 1 ,3-propanediol reactant to polytrimethylene ether glycol using a mineral acid catalyst, then adding carboxylic acid and carrying out the esterification without isolating and purifying the PO3G.
  • the etherification or polycondensation of 1 ,3-propanediol reactant to form polytrimethylene ether glycol is carried out using an acid catalyst as disclosed in US6977291 and US6720459.
  • the etherification reaction may also be carried out using a polycondensation catalyst that contains both an acid and a base as described in JP2004-182974A.
  • the polycondensation or etherification reaction is continued until desired molecular weight is reached, and then the calculated amount of monocarboxylic acid is added to the reaction mixture. The reaction is continued while the water byproduct is removed. At this stage both esterification and etherification re- actions occur simultaneously.
  • the acid catalyst used for polycondensation of diol is also used for esterification. If necessary additional esterification catalyst can be added at the esterification stage.
  • the viscosity (molecular weight) of the resulting product is controlled by the point at which the carboxylic acid is added.
  • the esterification reaction can be carried out on purified PO3G by addition of an esterification catalyst and carboxylic acid followed by heating and removal of water.
  • viscosity of the resulting product is predominantly a function of the molecular weight of the PO3G utilized.
  • esterification step any by products are removed, and then the catalyst residues remaining from polycondensation and/or esterification are removed in order to obtain an ester product that is stable, particularly at high temperatures.
  • This may be accomplished by hydrolysis of the crude ester product by treatment with water at about 80 0 C to about 100 0 C for a time sufficient to hydrolyze any residual acid esters derived from the catalyst without impacting significantly the carboxylic acid esters.
  • the time required can vary from about 1 to about 8 hours. If the hydrolysis is carried out under pressure, higher temperatures and correspondingly shorter times are possible.
  • the product may contain diesters, monoesters, or a combination of diesters and monoesters, and small amounts of acid catalyst, unreacted carboxylic acid and diol depending on the reaction conditions.
  • the hydrolyzed polymer is further purified to remove water, acid catalyst and unreacted carboxylic acid by the known conventional techniques such as water washings, base neutralization, filtration and/or distillation.
  • Unreacted diol and acid catalyst can, for example, be removed by washing with deionized water.
  • Unreacted carboxylic acid also can be removed, for example, by washing with deionized water or aqueous base solutions, or by vacuum stripping.
  • Hydrolysis is generally followed by one or more water washing steps to remove acid catalyst, and drying, preferably under vacuum, to obtain the ester product.
  • the water washing also serves to remove unreacted diol. Any unreacted monocarboxylic acid present may also be removed in the water washing, but may also be removed by washing with aqueous base or by vacuum stripping.
  • the product can be fractionated further to isolate low molecular weight esters by a fractional distillation under reduced pressure.
  • Proton NMR and wavelength X-ray fluorescence spectroscopic methods can be used to identify and quantify any residual catalyst (such as sulfur) present in the polymer.
  • the proton NMR can, for example, identify the sulfate ester groups present in the polymer chain, and wavelength x-ray fluorescence method can determine the total sulfur (inorganic and organic sulfur) present in the polymer.
  • the esters made from the process described above are substantially sulfur free and thus useful for high temperature applications.
  • the PO3G esters after purification have essentially no acid catalyst end groups, but may contain very low levels of unsaturated end groups, predominately allyl end groups, in the range of from about 0.003 to about 0.03 meq/g.
  • Such PO3G ester can be considered to comprise or consist essentially of the compounds having the following formulae (IV) and (V):
  • R 2 is H or R 3 C(O); each of Ri and R 3 is individually a substituted or unsubsti- tuted aromatic, saturated aliphatic, unsaturated aliphatic, or cycloaliphatic organic group containing from 6 to 40 carbon atoms; m is in a range such that the Mn is within the range of from about 200 to about 3000; and with compounds of formula (III) being present in an amount such that the allyl end groups (preferably all unsaturation ends or end groups) are present in the range of from about 0.003 to about 0.03 meq/g.
  • the PO3G ester has a viscosity which is less than the viscosity of PO3G (when utilized).
  • Preferred viscosities of PO3G esters range from about 2OcS to about 150 cS at 40 0 C, and more preferably are about 10OcS or less.
  • PO3G esters can be determined based upon the preferences stated above for PO3G in and of itself. For example, preferred molecular weights and polydispersities are based on the preferred molecular weights and polydispersities of the PO3G component of the ester.
  • Synthetic lube oil compositions in accordance with the present invention comprise a mixture of the base stock and one or more additives, where each additive is employed for the purpose of improving the performance and properties of the base stock in its intended application, e.g., as a hydraulic fluid, a gear oil, a brake fluid, a compressor lubricant, a textile and calender lubricant, a metalworking fluid, a refrigeration lubricant, a two-cycle engine lubricant and/or crankcase lubricant.
  • each additive is employed for the purpose of improving the performance and properties of the base stock in its intended application, e.g., as a hydraulic fluid, a gear oil, a brake fluid, a compressor lubricant, a textile and calender lubricant, a metalworking fluid, a refrigeration lubricant, a two-cycle engine lubricant and/or crankcase lubricant.
  • the additives can generally be added in amounts based on the type of additive and desired level of additive effect, which can generally be determined by those skilled in the relevant art.
  • the additives are miscible in either or both of the PO3G and PO3G esters.
  • the additives used will be water miscible at least to some extent when miscible in the glycols, and will be oil miscible at least to some extent when miscible in the esters.
  • the lube oil additive(s) comprise at least one of ashless dispersant, metal detergent, viscosity modifier, anti-wear agent, antioxidant, friction modifier, pour point depressant, anti-foaming agent, corrosion inhibitor, demulsifier, rust inhibitor and mixtures thereof.
  • the lube oil additive(s) preferably comprise at least one of extreme pressure and antiwear additive, oxidation and thermal stability improver, corrosion inhibitor, viscosity index improver, pour point depressant, floe point depressant, detergent, anti-foaming agent, viscosity adjuster and mixtures thereof.
  • any one or more of the specified additives alone or in combination with one or more of the remain- ing specified additives. It is also within the scope of the present invention to use more than one of any specified additive, e.g., one or more friction modifiers, either alone or in combination of one or more of the other specified additives, e.g., in combination with one or more corrosion inhibitors.
  • each of the components may be added directly to the base stock by dispersing or dissolving it in the base stock at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
  • all or some of the additives can be blended into a concentrate or additive package that is subsequently blended into base stock to make finished lubri- cant.
  • the concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the formulation when the concentrate is combined with a predetermined amount of base lubricant.
  • the ashless dispersant comprises polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
  • the dispersants comprise amine, alcohol, amide and/or ester polar moieties attached to the polymer backbone often via a bridging group.
  • the ashless dispersant may be, for example, selected from salts, esters, amino-esters, amides, imides and oxazolines of long chain hydrocarbon substituted mono- and dicarboxylic acids and/or their anhydrides, thiocarboxylate derivatives of long chain hydrocarbons, long chain aliphatic hydrocarbons having a polyamine attached directly thereto, and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
  • the viscosity modifier functions to impart high and low temperature oper- ability to a lubricating oil.
  • the VM used may have that sole function, or may be multi- functional.
  • Multifunctional viscosity modifiers that also function as dispersants are also known.
  • Illustrative viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylat.es, meth- acrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl com- pound, inter polymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and iso- prene/divinylbenzene.
  • Metal-containing or ash-forming detergents function both as detergents to re- prise or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
  • Detergents generally comprise a polar head with long hydrophobic tail, with the polar head comprising a metal salt of an acid organic compound.
  • the salts may contain a substantially stoichiometric amount of the metal in which they are usually described as normal or neutral salts, and would typi- cally have a total base number (TBN), as may be measured by ASTM D-2896 of from 0 to about 80. It is possible to include large amounts of a metal base by reacting an excess of a metal compound such as an oxide or hydroxide with an acid gas such as carbon dioxide.
  • the resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g., carbonate) micelle.
  • Such overbased detergents may have a TBN of about 150 or greater, and typically from about 250 to about
  • Illustrative detergents include neutral and overbased sulfonates, phenates, sul- furized phenates, thiophosphonates, salicylates, and naphthenates and other oil- soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., so- dium, potassium, lithium, calcium, and magnesium.
  • a metal particularly the alkali or alkaline earth metals, e.g., so- dium, potassium, lithium, calcium, and magnesium.
  • the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
  • Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from about 20 to about 450, and neutral and overbased calcium phenates and sulfurized phenates having TBN of from about 50 to about 450.
  • Dihydrocarbyl dithiophosphate metal salts are frequently used as anti-wear and antioxidant agents.
  • the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper.
  • the zinc salts are most commonly used in lubricating oil in amounts of from about 0.1 to about 10 wt%, preferably from about 0.2 to about 2 wt%, based upon the total weight of the lubricating oil composition. They may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alco- hoi or a phenol with P 2 Ss and then neutralizing the formed DDPA with a zinc compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
  • any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed.
  • Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralization reaction.
  • the lube oil compositions are preferably substan- tially zinc free.
  • Oxidation inhibitors or antioxidants reduce the tendency of base stocks to deteriorate in service which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth.
  • oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to Ci 2 alkyl side chains, calcium nonyl- phenol sulfide, ashless oil soluble phenates and sulfurized phenates, phosphosul- furized or sulfurized hydrocarbons, phosphorous esters, metal thiocarbamates, oil- soluble copper compounds as described in US4867890, and molybdenum containing compounds.
  • Friction modifiers may be included to improve fuel economy.
  • Oil-soluble alkoxy- lated mono- and di-amines are well known to improve boundary layer lubrication.
  • the amines may be used as such or in the form of an adduct or reaction product with a bo- ron compound such as boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.
  • Illustrative rust inhibitors are selected from the group of nonionic polyoxyal- kylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids.
  • Copper and lead bearing corrosion inhibitors may also be used.
  • such compounds are the thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof.
  • Other additives are the thio- and polythio- sulfena- mides of thiadiazoles such as those described in UK1560830. Benzotriazole derivatives also fall within this class of additives.
  • demulsifying component is described in EP-A-0330522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol.
  • Pour point depressants otherwise known as lube oil improvers, lower the minimum temperature at which the fluid will flow or can be poured.
  • Such additives are well known. Typical of those additives which improve the low temperature fluidity of the fluid are C 8 and Ci 8 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylat.es and the like.
  • C 8 and Ci 8 dialkyl fumarate/vinyl acetate copolymers polyalkylmethacrylat.es and the like.
  • Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • an antifoamant of the polysiloxane type for example, silicone oil or polydimethyl siloxane.
  • Some of the above-mentioned additives can provide a multiplicity of effects; thus, for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and does not require further elaboration.
  • Illustrative extreme pressure and antiwear additives include phosphates, phosphate esters (bicresyl phosphate), phosphites, thiophosphates (zinc diorganodithio- phosphates) chlorinated waxes, sulfurized fats and olefins, organic lead compounds, fatty acids, molybdenum complexes, halogen substituted organosilicon compounds, borates, organic esters, halogen substituted phosphorous compounds, sulfurized Diels Alder adducts, organic sulfides, compounds containing chlorine and sulfur, metal salts of organic acids.
  • phosphates phosphate esters (bicresyl phosphate), phosphites, thiophosphates (zinc diorganodithio- phosphates) chlorinated waxes, sulfurized fats and olefins, organic lead compounds, fatty acids, molybdenum complexes, halogen substituted organosilicon compounds
  • Illustrative oxidation and thermal stability improvers include sterically hindered phenols (BHT), aromatic amines, dithiophosphates, phosphites, sulfides and metal salts of dithio acids.
  • BHT sterically hindered phenols
  • aromatic amines aromatic amines
  • dithiophosphates dithiophosphates
  • phosphites phosphites
  • sulfides sulfides and metal salts of dithio acids.
  • Illustrative corrosion inhibitors include organic acids, organic amines, organic phosphates, organic alcohols, metal sulfonates and organic phosphites.
  • Viscosity index is the measure of the change in viscosity with temperature, and a high number suggests that the change in viscosity with temperature is minimal.
  • Illustrative viscosity index improvers include polyisobutylene, polymethacrylate and polyalkylstyrenes.
  • Illustrative pour point and or floe point depressants include polymethacrylate ethylene - vinyl acetate copolymers, succinamic acid - olefin copolymers, ethylene - alpha olefin copolymers and Friedel-Crafts condensation products of wax with naptha- lene or phenols.
  • Illustrative detergents include sulfonates, long-chain alkyl substituted aromatic sulfonic acids, phosphonates, thiophosphonates, phenolates, metal salts of alkyl phenols, alkyl sulfides, alkylphenol - aldehyde condensation products, metal salts of sub- stituted salicylates, N-substituted oligomers or polymers from the reaction products of unsaturated anhydrides and amines and co-polymers which incorporate polyester linkages such as vinyl acetate-maleic anhydride co-polymers.
  • Illustrative anti-foaming agents are silicone polymers.
  • Illustrative viscosity adjusters include polyisobutylene, polymethacrylates, polyalkylstyrenes, naphthenic oils, alkylbenzene oils, paraffinic oils, polyesters, polyvi- nylchloride and polyphosphates.
  • the lube oil additive(s) should be at least partially (greater than about 50% by weight) miscible in the base stock. Generally, this means that the additives used will be soluble in esters and vegetable oils at least to some extent, and preferably to a substantial extent.
  • the lube oil composition should thus preferably be a substantially uniform mixture, with substantially no settling or phase separation of components.
  • the lubrication oil composition preferably comprises the additives in an amount of less than 50 wt%, based on the total weight of the lubrication oil composition.
  • the lubrication oil can comprise the additives in an amount of about 25 wt% or less, or about 10 wt% or less, or about 5 wt% or less, based on the total weight of the lubrication oil composition.
  • the number-average molecular weights (Mn) of polyether glycol and polyether glycol ester were determined either by analyzing end-groups using NMR spectroscopic methods or by titration of hydroxyl groups.
  • ASTM method D445-83 and ASTM method D792-91 were used to determine the kinematic viscosity and density of the polymer, respectively.
  • the properties of various base stock fluids used to blend are shown in the following table.
  • the viscosity indices of polytrimethylene glycol polymers are significantly higher than the Vegetable oil base stock.
  • a lubrication composition was prepared by adding the following additives to the blend composition of Example 4.

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Abstract

Cette invention porte sur des compositions d'huile de lubrification comprenant (i) un ester d'acide (monoester et/ou diester) de polytriméthylène éther glycol ; et (ii) un lubrifiant d'huile végétale.
EP08828627A 2007-08-24 2008-08-21 Compositions d'huile de lubrification Withdrawn EP2181181A1 (fr)

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US95772207P 2007-08-24 2007-08-24
PCT/US2008/073853 WO2009029482A1 (fr) 2007-08-24 2008-08-21 Compositions d'huile de lubrification

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JP (1) JP2010537004A (fr)
KR (1) KR20100043109A (fr)
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AU (1) AU2008293758A1 (fr)
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BRPI0815243A2 (pt) 2019-09-24
WO2009029482A1 (fr) 2009-03-05
KR20100043109A (ko) 2010-04-27
MX2010002153A (es) 2010-03-18
CA2696371A1 (fr) 2009-03-05
JP2010537004A (ja) 2010-12-02
TW200914604A (en) 2009-04-01
US20090054284A1 (en) 2009-02-26
AU2008293758A1 (en) 2009-03-05
CN101784643A (zh) 2010-07-21

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