EP3483233A1 - Compositions d'huile de base lubrifiante d'esters d'acide dibasique mono-insaturé comprenant des alcools ramifiés - Google Patents

Compositions d'huile de base lubrifiante d'esters d'acide dibasique mono-insaturé comprenant des alcools ramifiés Download PDF

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Publication number
EP3483233A1
EP3483233A1 EP17200996.1A EP17200996A EP3483233A1 EP 3483233 A1 EP3483233 A1 EP 3483233A1 EP 17200996 A EP17200996 A EP 17200996A EP 3483233 A1 EP3483233 A1 EP 3483233A1
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EP
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Prior art keywords
formula
lubricant
composition
use according
dibasic
Prior art date
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EP17200996.1A
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German (de)
English (en)
Inventor
Jean-Luc Dubois
Jean-Luc Couturier
Svajus Asadauskas
Linas LABANAUSKAS
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Arkema France SA
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Arkema France SA
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Priority to EP17200996.1A priority Critical patent/EP3483233A1/fr
Priority to PCT/EP2018/079169 priority patent/WO2019091786A1/fr
Publication of EP3483233A1 publication Critical patent/EP3483233A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids 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
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/288—Partial esters containing free carboxyl groups
    • 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
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/067—Unsaturated Compounds
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • 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
    • C10N2030/74—Noack Volatility
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • the present invention relates to the use of a dibasic ester composition comprising specific monounsaturated ⁇ - ⁇ dibasic ester compounds, as a main component in a lubricant ("basestock”) or an additive in lubricant compositions, the lubricant composition resulting from such a use, its related uses. More particularly, said composition is used in lubricant basestocks which are issued from renewable resources and which are degradable in the environment ("biodegradable” may be used in the present invention with same meaning).
  • biodegradable may be used in the present invention with same meaning.
  • the said dibasic ester compositions and compounds are issued from linear monounsaturated ⁇ - ⁇ dicarboxylic acids ("fatty diacids") and do not contain either branched isomers or estolide compounds derived from fatty diacids.
  • fatty diacids linear monounsaturated ⁇ - ⁇ dicarboxylic acids
  • estolide compounds derived from fatty diacids.
  • detrimental are estolides, representing products of addition of the carboxy group of one fatty diacid on the unsaturation of anotherfatty diacid with a resulting middle-chain esterfunction.
  • estolide compounds if present in the linear monounsaturated fatty diacids used for preparing the dibasic ester compositions of the present invention are in a content of less than 1% w/w more preferably of less than 0.1% or less than 0.05% and even more preferably, the content is 0% of estolides with respect to the weight of said dibasic ester composition.
  • the absence of estolide in the case of the present invention is verified by 13 C NMR by the absence of a characteristic peak at 71 ppm corresponding to estolides.
  • the disclosed products are compositions of various C 22 -dimer esters, containing dibasic esters from mostly branched monounsaturated ⁇ - ⁇ diacids (over 50%), only with some linear monounsaturated ⁇ - ⁇ homologues as well as branched estolide compounds and other pyrolysis / esterification products of 10-undecenoic acid.
  • Abundance of branched isomers in reported C 22 -dimer esters is admitted by authors in this reference and it is also obvious to a person skilled-in-art from low solidification temperatures and Viscosity Index values that branched structures are involved.
  • Significant presence of C 22 estolides in addition to identified ⁇ - ⁇ diacids is evident from much lower acidity than expected theoretically.
  • estolide compounds For a formulated mixture exposed to metal surfaces and to degradation products, a significant estolide fraction will tend to be present in a separate phase from that of linear C 22 -dimer esters, which fact is harmful for the lubricant, because the functional additives do migrate to the different phases and consequently do perform inefficiently or negatively. This causes wear, corrosion, foaming, haziness and other problems, which jeopardize lubricant performance.
  • the abundance of branched C 22 -dimer esters also has some negative implications, particularly due to faster viscosity reduction with heating, as expressed by Viscosity Index (VI).
  • Vegetable oils, fatty derivatives and synthetic esters of petrochemical origin, such as adipate esters or esters of polyhydric alcohols are used as biodegradable basestocks in lubricant formulation for transport, agriculture and industrial applications.
  • the basestock usually comprises around 80-100% w/w of lubricant with remaining 0-20% taken up by additives to impart necessary rheology, low friction, anti-wear properties, low temperature fluidity, corrosion resistance, elastomer compatibility, oxidative stability, water rejection, foam inhibition, air release, microbial resistance, odor, color and many other characteristics.
  • additives usually comprises around 80-100% w/w of lubricant with remaining 0-20% taken up by additives to impart necessary rheology, low friction, anti-wear properties, low temperature fluidity, corrosion resistance, elastomer compatibility, oxidative stability, water rejection, foam inhibition, air release, microbial resistance, odor, color and many other characteristics.
  • esters so far have targeted the applications as plasticizers, where the issues of volatility, oxidative stability or viscosity are less problematic than in lubricants.
  • the global lubricant market comprises nearly 50-60 MMT (millions of metric tons), out of which nearly 40 MMT can be considered the global volume of basestocks for engine oils and hydraulic fluids.
  • these basestocks are produced from mineral oils, with synthetic and biobased basestocks comprising less than 10%.
  • Synthetic hydraulic fluids usually fall into ISO VG 46 viscosity grade and to a lesser extent into ISO VG 32. Their kinematic viscosities at 40°C must fall into the intervals of 42-50 mm 2 /s and 28.8-35.2 mm 2 /s respectively.
  • Most engine oils belong to SAE 30 specifications, such as SAE 5W-30 or SAE 10W-30.
  • Viscosities at 100°C must fall into the interval of 9.3 - 12.5 mm 2 /s with good low temperature fluidity at -35°C and -30°C respectively.
  • SAE 40 and SAE 20 are also quite widespread (viscosities at 100°C within 12.5 - 16.3 mm 2 /s and 5.6 - 9.3 mm 2 /s respectively).
  • engine oils 3 MMT or so are made from non-mineral basestocks, the majority of which belongs to poly alpha-olefins (poly ⁇ -olefins), produced petrochemically from ethylene (C 2 H 4 ).
  • the basestocks from vegetable or animal sources comprise about 1 MMT globally. However, their proportion can increase at the expense of poly ⁇ -olefins, if manufacture costs and technical properties become favorable.
  • Viscosity Index is another important parameter. It defines how fast viscosity of a lubricant goes down viscosity with increasing temperature [ASTM D2270 "Standard Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 °C and 100 °C"]. High VI is usually very desirable for engine oils, hydraulic fluids and other lubricants, since their films are more effective in protecting moving surfaces from wear when heated.
  • Performance of lubricants at high temperatures is also dictated by their volatility, because with sizeable losses of any lubricant component the properties of the residual liquid change significantly. This is especially evident in mineral basestocks, which contain significant portion of lower mol. wt. fractions. Volatility losses are less appreciable in synthetic basestocks, constituting a significant performance benefit.
  • lubricant basestocks must retain their fluidity at low temperatures in order to assure reliable performance in winter or cold conditions.
  • Final lubricant formulations are tested using several protocols for low temperature fluidity, such as extended storage, cold cranking and similar. Pour point is considered as a very important parameter for describing the low temperature properties of the basestock.
  • Typical lubricant additives such as Anti-Wear (AW) agent, antioxidant, corrosion inhibitor, friction modifier, alkalinity carrier, water demulsifier, dispersant, detergent, elastomer conditioner, dye, copper passivator, pour point depressant, tackifier, thickener, viscosity index improver, surfactant, defoamer or similar could dissolve in basestocks.
  • Affinity of esters towards above additives is usually better than that of hydrocarbons.
  • the first subject-matter of the present invention relates to the use of a composition of specific dibasic esters of monounsaturated linear ⁇ , ⁇ - diacids as a lubricant basestock or constituent.
  • a second subject-matter relates to a lubricant composition issued from the said use.
  • a third subject-matter relates to the use of said lubricant composition for engine oils and hydraulic fluids in transport, agriculture, food and industrial applications.
  • the total number of carbon atoms in the diester compound according to formula (I) as defined above can vary from 34 to 42 and preferably from 38 to 42 carbon atoms.
  • Predominant component as b1) means in the present case to represent more than 60% of the mixture b1) + b2) and preferably at least 70% and more preferably at least 80% of the mixture b1) + b2).
  • the said branch of said branched alcohols is in C 2 to C 6 or in C 1 in case of a multiple branches meaning at least 2 branches present.
  • the presence of a C 1 branch is preferred when at least another additional branch in C 1 or in C 2 to C 6 is present, with a total number of branches (multiple number) of at least 2 branches with at least one in C 1 and another one in C 2 to C 6 or at least two in C 1 or more particularly at least 3 branches with at least one in C 1 and two others in C 2 to C 6 or at least 2 in C 1 and one in C 2 to C 6 or at least 3 in C 1 .
  • Said branched alcohols R'1OH and R'2OH may be primary or secondary alcohols and preferably primary alcohols.
  • the chain length (in carbon atoms) of these branched alcohols does not include the number of carbon atoms of the branches.
  • the chain length is in C 6 , with one branch in C 2 in position 2 of the hexyl main chain (longer linear chain).
  • branched alcohol R'1OH and R'2OH a branch or the branch in position 2 (with respect to the -OH functionality), said branch being in C 2 to C 6 and possibly in C 1 under the provision that there are at least 2 branches, at least one being in C 1 , preferably at least 3 branches with at least one in C 1 .
  • the number of carbon atoms of R1 or R2 is from 5 to 26 (C 5 to C 26 ) and more preferably from 5 to 22 (C 5 to C 22 ).
  • x + y in formula (I) ranges from 10 to 16.
  • x is from 6 to 9.
  • the ethylenic unsaturation is preferably located in position from 7 to 10.
  • R1 or R2 are residues of branched alcohols selected from the group consisting of : 2-ethylhexyl, 2-butyl octyl, 2-propyl heptyl, phytyl (3,7,11,15-tetramethyl-2-hexadecenyl), 1-methyl heptyl (from 2-octanol), 3,5,5-trimethyl hexyl (isononyl) residue of terpenic alcohols, residue of farnesol, including their partially hydrogenated homologues, isocetyl, isostearyl, isooctyl (2,4,4-trimethylpentyl), cyclohexyl, abietyl and of their mixtures, preferably at least one of : 2-butyl octyl, 2-propyl heptyl, phytyl (3,7,11,15-tetramethyl-2-hexadecenyl), 3,5,5-tri
  • dibasic ester is the 2-ethylhexyl diester of 9-octadecenedioic diacid, having the ethylenic unsaturation in position 9 with 2-ethyl hexanol as branched alcohol.
  • the double bond (ethylenic unsaturation) can be cis or trans or a mixture of both.
  • the proportion may be about 75% mol/mol trans and 25% cis but predominant or near 100% cis is more preferred over trans since the cold flow properties are better.
  • the proportion of cis is at least of 15% mol.mol, preferably of at least 20%.
  • the at least one monounsaturated ⁇ - ⁇ dibasic ester compound of Formula (I) of said dibasic ester composition can be a blend of at least two different compounds of Formula (I).
  • the said at least two different compounds of Formula (I) may be different in :
  • R1 and R2 are different and are residues of a blend of different branched alcohols.
  • Said dibasic ester of Formula (II) can be issued by the esterification of the corresponding diacid.
  • Said diacid can be obtained either by a metathesis route from the corresponding fatty monoacid or obtained by the hydrolysis of a mixture of other diesters of said diacid or by the fermentation route of a fatty monoacid.
  • the dibasic esters can be formed starting from monounsaturated fatty diacids which comprise either 18 carbon atoms by molecule 9-octadecenedioic or 22 carbon atoms by molecule 11-docosenedioic.
  • monounsaturated fatty diacids which comprise either 18 carbon atoms by molecule 9-octadecenedioic or 22 carbon atoms by molecule 11-docosenedioic.
  • the preparation of such fatty diacids is disclosed in Ngo, H.L. et al. in "Metathesis of Unsaturated Fatty Acids: Synthesis of Long Chain Unsaturated- ⁇ , ⁇ - Dicarboxylic Acids", published in JAOCS J. of Am. Org. Chem. Soc. 2006, 83 (7), 629-634 .
  • the dibasic esters used within the framework of the invention can be either symmetrical, with the alcohol used for esterification being the same one for the two carboxy acid functions or asymmetrical with two different alcohols.
  • Transesterification of light alcohol esters (such as methyl and/or ethyl esters) of said fatty diacids with heavier alcohols as defined according to the present invention can be used for the preparation of the specific dibasic esters used in the present invention. More particularly, the said fatty diacid can be issued from a self-metathesis reaction of a fatty monounsaturated monoacid or said dibasic ester of Formula (II) is issued from a self-metathesis of a fatty monounsaturated monoacid ester. Diacid can also be obtained from fermentation of monounsaturated fatty acid (especially for the C 18 ).
  • the dibasic ester can be formed by self-metathesis reaction from unsaturated monoesters, such a reaction can be either the main reaction or a side reaction during a cross-metathesis reaction.
  • the fatty diacid can also be produced by fermentation of the corresponding fatty mono acid.
  • the said composition is a mixture as defined above according to option b). More particularly, said mixture as defined above according to option b) comprises up to 99.9% w/w with respect to said mixture of b1) selected from at least one dibasic ester compound as defined above according to Formula (I) and at least 0.1% w/w of b2) at least one dibasic ester compound as defined according to Formula (II).
  • the second subject of the invention relates to a lubricant composition which results from the use as a lubricant constituent (or additive having same meaning) of at least one dibasic ester composition as defined above according to the present invention. More particularly, the weight ratio of b1)/b2) can vary from 0.85/0.15 to 0.99/0.01.
  • a second subject of the invention relates to a lubricant composition which results from the use as a lubricant constituent, of at least one dibasic ester composition as defined above according to the present invention.
  • Said lubricant composition in addition to said dibasic ester composition at a content of at least 80% w/w, preferably from 90 to 99.7% with respect to the total weight of said lubricant composition, can further comprise up to 20%, preferably from 0.3 to 10% w/w of other additives selected from the group consisting of another lubricant additive, antiwear agent, antioxidant, corrosion inhibitor, friction modifier, alkalinity carrier, biocide, buffering agent, chelating additive, coupler, water demulsifier, dispersant, detergent, elastomer conditioner, dye, mist suppressant, odorant, copper passivator, pour point depressant, tackifier, thickener, viscosity index improver, surfactant or defoamer.
  • additives selected from the group consisting of another lubricant additive, antiwear agent, antioxidant, corrosion inhibitor, friction modifier, alkalinity carrier, biocide, buffering agent, chelating additive, coupler, water demulsifier, dispersant,
  • Said lubricant composition is preferably a lubricant basestock composition. More particularly, said lubricant basestock composition is issued from renewable resources and it is biodegradable. More particularly, said lubricant composition is a lubricant basestock composition. Said lubricant basestock composition is particularly issued from renewable resources and it is a biodegradable lubricant basestock.
  • the present invention also covers the use of the said lubricant composition as engine oils or as hydraulic fluids in transport, agriculture, food and industrial applications.
  • Colloquial lipid terminology i.e. lipid number
  • Table 1 The list of moiety denominations, compound codes and IUPAC names is provided in Table 1. Table 1.
  • the codes of dibasic esters are assigned mostly based on the segment lengths of the alcohol and diacid moieties in the compound molecule.
  • the branches of the alcohol moiety are encoded based on the number of C atoms in the IUPAC name of the alcohol.
  • 2-ethyl hexanol contains two branches of C 2 and C 6 , hence a prefix "26" is assigned.
  • isoalkyl, oleyl and mixed esters do not follow this rule strictly.
  • a suffix letter is inserted to indicate, whether the fatty diacid moiety is fully saturated ("S") or unsaturated ("U").
  • the rest of the code denotes the chain length of the fatty diacid moiety.
  • azelaic acid ⁇ , ⁇ C9:0
  • ⁇ - ⁇ C18:1 fatty diacid is denoted "18”.
  • Most of the latter esters were synthesized in-house by Arkema or CPST by transesterifying 1U18, which was produced in-house by metathesis. However, it must be pointed out that other production pathways for 1U18 are also possible (see Fig. 1 with a scheme of production of 1U18 by self-metathesis).
  • Poly ⁇ -olefin (code "PAO8") was received from Ineos Oligomers as Durasyn 168 with reported density of 0.832 g/mL at 15°C, average molecular weight (avg mol Wt) of 629 g/mol, viscosities of 47 mm 2 /s (cSt) and 0.00078 cm 2 /s 7.8 mm 2 /s (cSt) at 40°C and 100°C respectively, pour point below -50°C, flash point above 245°C, bromine number below 4 mg Br/g and water contents below 25 ppm.
  • PEO8 Poly ⁇ -olefin
  • Cloud points were determined during the same run by visual inspection of the sample appearance at low temperature. The samples were removed from the freezer every 3°C for visual inspection and, if cloudy, meniscus movement with inversion. The pour point resembled the last measurement, at which the meniscus boundary was still moving within 5 seconds of horizontal inversion. All samples were tested in duplicate. If the recorded values did not match at 3°C replicates, more measurements were carried out until a statistically reliable result was obtained.
  • the mixture was evacuated with mild heating to remove excess alcohol and resultant methanol.
  • other types of branched alcohols were also utilized for synthesis, such as isononyl or isoamyl.
  • the esters were synthesized directly from a free ⁇ - ⁇ C18:1 dibasic acid by esterifying it with a respective alcohol in the presence of dimethyl aminopyridine (DMAP). Details of both syntheses are described below. Further details for the synthesis can be found in Hojabri, L. et al. in "Fatty acid-derived diisocyanate and biobased polyurethane produced from vegetable oil: synthesis, polymerization, and characterization” published in Biomacromolecules, 2009, 10 (4), 884-891, American Chemical Society Edition .
  • reaction mixture was cooled to r.t (room temperature) and dissolved in toluene (300 ml). The solution was washed with 10% w/w Na 2 CO 3 aqueous solution (200 ml) and with water (200 ml). After desiccation with Na 2 SO 4 , a solution was eluted (toluene 2 L) through a pad of silica gel (5 cm height). Solvent was evaporated on rotary evaporator and residual volatiles were removed under reduced pressure (0-1 mmHg).
  • Viscosity is the most important property of nearly any lubricant basestock. Viscosities for hydraulic fluids and engine oils are regulated by several specifications, see Table 2. Table 2. The most widespread viscosity specifications for hydraulic fluids (VG - Viscosity Grade) and engine oils (SAE - Soc.
  • the most appealing viscosities belong to the dibasic esters, whose molecular weight falls into the interval from 500 to 700 g/mol, such as 2-propylheptyl ester of ⁇ - ⁇ C18:1 fatty diacid (code 37U18) of 593 g/mol recording 28.7 mm 2 /s at 40°C. It can be expected that 2-ethyl hexyl ester of ⁇ - ⁇ C24:1 fatty diacid would demonstrate the viscosity of ISO VG 32 or SAE 0W-20 specification, due to mol. wt. of 621 g/mol.
  • Viscosity can be increased by adding polymers and this is often utilized in lubricant formulations.
  • polymers are degraded by mechanical shear, which brings down the viscosity.
  • it is better to use the basestock whose volatility is lower, i.e. flash points are higher.
  • Lower viscosity of basestock usually means more problematic flash points, while polymer additives do not affect volatility significantly.
  • Table 3 Viscosities of saturated and mono-unsaturated ⁇ - ⁇ dibasic esters.
  • Viscosities in Table 3 show that many dibasic esters of ⁇ - ⁇ C18:1 fatty diacid have VI of approximately 200. Such value is considered very beneficial for lubricants.
  • Polymer additives so called VI Improvers, are often used in final lubricant formulations to increase VI. Consequently, esters of ⁇ - ⁇ dibasic acids might need lower proportions of VI Improvers additives. Even more importantly, VI improvers tend to degrade in hydraulic pumps due to mechanical shear, which leads to increased temperature of the hydraulic system. Consequently, more rapid wear and higher energy losses are observed. Therefore, basestocks with inherently high VI, such as dibasic esters of linear monounsaturated fatty diacids, will command a distinct advantage in hydraulic fluid formulations.
  • low temperature fluidity is primarily determined by pour points [ASTM D97]. Generally, pour points below -30°C are considered sufficient. Some polymer additives, e.g. "Pour Point Depressants” (PPD), are able to improve low temperature fluidity. It must be noted that esters without PPD additives, which demonstrate pour points below -30°C, usually meet the requirements of cold storage, pumpability and cold cranking tests. Therefore, initially pour points and cloud points [ASTM D2500 "Standard Test Method for Cloud Point of Petroleum Products and Liquid Fuels"] of ⁇ - ⁇ dibasic esters were evaluated and shown in Table 4.
  • Isononyl dibasic ester 9U18 which contains 3 methyl branches on each alcohol moiety, shows an acceptable pour point of -33°C. Even better pour point of -66°C is demonstrated by the mixed dibasic ester 2026U18, whose monounsaturated phytyl moiety contains 4 methyl branches.
  • Hydrogenated dibasic esters 17S18 and 26S18 showed very problematic low temperature fluidity. Since the moieties trans-double bonds might often engage into the same molecular packing structures as saturated moieties, it is important that monounsaturated dibasic esters contain some cis-isomers, preferably in excess of 15% mol/mol.
  • the above method accounts for longer term decomposition reactions due to exposure to metal surfaces and oxidation, which is prevalent in hydraulic applications. Therefore, using the thin-film method short-term vapor losses were measured after 16 hrs and decomposition trends were compared after 36 hrs of testing. Heating temperature of 120°C was selected to compare thin films of ⁇ , ⁇ dibasic esters with commercial basestocks. Table 5.
  • Table 5 shows that despite lower viscosity, monounsaturated ⁇ - ⁇ dibasic esters have similar volatility to that of conventional synthetic basestock PAO8. It must be noted that all monounsaturated ⁇ - ⁇ dibasic esters were prepared in the laboratory, which made it difficult to avoid contaminants and byproducts of volatile nature. Their absence was one reason, why commercially produced ⁇ - ⁇ dibasic ester 26S12 showed much lower volatility. Reaction on the double bond site is another reason of decomposition processes in monounsaturated ⁇ - ⁇ dibasic esters, which increases the rates of long-term vaporization. Volatility of LEAR appears similar to 48U18 initially, but later its film solidifies and the volatile emissions cannot be reliably measured.
  • Lubricants often degrade during field use because of oxidation and exposure to high temperatures. Although oxidative degradation can be controlled to some extent by using free radical scavengers, peroxide decomposers, metal passivators and other types of antioxidants, lubricant basestock plays a key role on the oxidation rate. The presence of double bonds accelerates oxidation significantly. Consequently, monounsaturated ⁇ , ⁇ dibasic esters might oxidize faster than poly ⁇ -olefin (“PAO8”) or other commercial basestocks.
  • PAO8 poly ⁇ -olefin
  • Oxidation can be monitored by using a number of techniques, which usually address degradation reactions, primarily viscosity increase due to oxidative polymerization. Formation of oxypolymers might not only increase the viscosity, but may also result in formation of insoluble residues or even solidification of the whole lubricant.
  • the thin-film method determines how resistant oil is against formation of insoluble residues during oxidation. Degradation durations until initial formation of solid residues and complete solidification directly relate to oxidative stability. Test results are listed in Table 6. Table 6. Durations until initial formation of insoluble residues were observed in 500 ⁇ m thick films of ⁇ - ⁇ dibasic esters at 120°C Vapor losses at test duration when full film solidification was observed are also listed Code Alcohol moiety Remainder Initial residues observed Full solidification observed Vapor loss at solidification hrs hrs % w/w Dibasic esters as Exhibits 26U18 2-ethylhexyl ⁇ , ⁇ C18:1 248 320 57% 37U18 2-propylheptyl ⁇ , ⁇ C18:1 248 324 54% 48U18 2-butyloctyl ⁇ , ⁇ C18:1 248 320 47% 4826U18 2-butyloctyl: 2-ethylhexyl ⁇ , ⁇ C18:1 248
  • rapeseed oil produces insolubles in just 26 hrs, which is much faster than any other sample.
  • LEAR rapeseed oil
  • oxidative stability of monounsaturated ⁇ - ⁇ dibasic esters is more similar to that of PAO8 than to LEAR.
  • the intermediate character of resistance to oxidation is fully sufficient for monounsaturated ⁇ - ⁇ dibasic esters to function as hydraulic fluids.
  • the additives were selected to represent different chemical categories: soaps, heterocycles, phosphorous derivatives, polymers, etc. Most of these additives are designed to be dissolved in paraffinic mineral oils and synthetic lubricants with some heating. It is often thought that esters are better solvents than mineral oils or synthetic hydrocarbons like poly ⁇ -olefins. Therefore, the tested concentrations were much higher than additive proportions for hydraulic fluids, as recommended by the additive manufacturers.
  • Additives did not show any problems when blending in with ⁇ - ⁇ dibasic esters 26U18 and 26S12. Initial solution appearance was bright and clear. The appearance of stored solutions after 1 week at room temperature remained unchanged. Presence of monounsaturation did not affect additive solubility negatively. Since tested concentrations were so much higher than recommended additive proportions, additive solubility does not present any problem. All tested additives stayed dissolved in mineral oil 350N as well, except tolyl triazole, which is widely used in hydraulic fluids as corrosion inhibitor. Initially, it fully dissolved at 1% w/w concentration in 350N with heating. However, after some storage at room temperature significant portion precipitated out and made the formulation cloudy, see Fig. 7 . This demonstrates that solubilizing power of dibasic esters is better compared to mineral oils and paraffinic hydrocarbons.

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WO2014106724A1 (fr) 2013-01-07 2014-07-10 Arkema France Procédé de métathèse croisée
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WO2016083746A1 (fr) 2014-11-27 2016-06-02 Arkema France Compositions elastomeres contenant au moins un plastifiant forme par un ester de diacide gras insature, de preference mono-insature

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WO2012106238A2 (fr) * 2011-01-31 2012-08-09 Rhodia Operations Fluides hydrauliques contenant des esters dibasiques et leurs procédés d'utilisation
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