EP1051465B1 - Verwendung biologisch abbaubarer olsäure-estolid-ester als basisöl und schmieröl - Google Patents

Verwendung biologisch abbaubarer olsäure-estolid-ester als basisöl und schmieröl Download PDF

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Publication number
EP1051465B1
EP1051465B1 EP98958608A EP98958608A EP1051465B1 EP 1051465 B1 EP1051465 B1 EP 1051465B1 EP 98958608 A EP98958608 A EP 98958608A EP 98958608 A EP98958608 A EP 98958608A EP 1051465 B1 EP1051465 B1 EP 1051465B1
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Prior art keywords
estolide
estolide compound
oleic
formula
lubricants
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Expired - Lifetime
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EP98958608A
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English (en)
French (fr)
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EP1051465A4 (de
EP1051465A1 (de
Inventor
Terry A. Isbell
Thomas P. Abbott
Svajus Asadauskas
Joseph E. Lohr, Jr.
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Lambent Technologies Inc
US Department of Agriculture USDA
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Lambent Technologies Inc
US Department of Agriculture USDA
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Priority claimed from US09/191,907 external-priority patent/US6018063A/en
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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
    • 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
    • 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/04—Fatty oil fractions
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • This invention relates to esters of oleic acid estolides and their use as biodegradable base stocks and lubricants.
  • Synthetic esters such as polyol esters and adipates, low viscosity poly alpha olefins (PAO), such as PAO 2, vegetable oils, especially Canola oil and oleates are used industrially as biodegradable basestocks to formulate lubricants.
  • Lubricants usually contain 80-100% wt. basestock and 0-20% wt. additives to tailor their viscometric properties, low temperature behavior, oxidative stability, corrosion protection, demulsibility and water rejection, friction coefficients, lubricities, wear protection, air release, color and other properties. Biodegradability cannot be improved by using additives.
  • estolides are a unique oligomeric fatty acid that contains secondary ester linkages on the alkyl backbone of the molecule.
  • US-A-4 867 965 describes a diester derived from a fatty acid such as oleic acid.
  • the diester in US-A-2 652 411 describes a compound based on an ester backbone of 18 C atoms in which a C atom close to the middle of the chain is substituted with an ester group.
  • Estolides have typically been synthesized by the homopolymerization of castor oil fatty acids [Modak et al., JAOCS 42 :428 (1965); Neissner et al., Fette Seifen Anstrichm 82 :183 (1980)] or 12-hydroxystearic acid [Raynor et al., J. Chromatogr . 505 :179 (1990); Delafield et al., J. Bacteriol. 90 :1455 (1965) under thermal or acid catalyzed conditions.
  • Yamaguchi et al. [Japanese Patent 213,387, (1990)] recently described a process for enzymatic production of estolides from hydroxy fatty acids (particularly ricinoleic acid) present in castor oil using lipase.
  • Estolides derived from these sources are composed of esters at the 12 carbon of the fatty acids and have a residual hydroxyl group on the estolide backbone.
  • the level of unsaturation in the produced estolides is not significantly lower than that in raw materials, i.e., hydroxy fatty acids.
  • estolide compounds derived from oleic acids and characterized by superior properties for use as lubricant base stocks. These estolides may also be used as lubricants without the need for fortifying additives normally required to improve the lubricating properties of base stocks.
  • polyestolides is used herein to refer to the acid form of compounds having the structure of Formula I, wherein n is greater than 1.
  • ester estolide ester
  • estolides are esters resulting from secondary ester linkages between fatty acid chains, and every effort will be made herein to distinguish the actual estolide from the ester thereof.
  • the oleic acid estolides for use in making the esters of this invention can be recovered by any conventional procedure. Typically, the preponderance of low boiling monomer fraction (unsaturated fatty acids and saturated fatty acids) and also dimer acids that may form are removed. In a preferred embodiment, reaction conditions will be selected such that no, or substantially no, dimer acids are produced in the course of reaction, with only estolides being formed and the residue fraction comprising substantially pure estolides.
  • the oleic estolides are esterified by normal procedures, such as acid-catalyzed reduction with an appropriate alcohol.
  • R 1 and R 2 are not both hydrogen, and more preferably, neither R 1 nor R 2 is hydrogen. That is, it is preferred that the reactant alcohol be branched.
  • the oleic estolide esters are selected from the group of isopropyl ester, 2-ethylhexyl ester and isostearyl ester.
  • the average value of n in Formula I is greater than 1.0.
  • esters which are characterized by: a viscosity at 40° C of at least 20 cSt and preferably at least about 32 cSt; a viscosity at 100° C of at least 5 cSt and preferably at least about 8 cSt; a viscosity index of at least 150; a pour point of less than -21° C and preferably at least -30° C; a volatility of less than 10% at 175° C; an insignificant ( ⁇ 10%) oxypolymerization in 30 min at 150° C in the micro oxidation test [Cvitkovic et al., ASLE Trans .
  • the oleic estolide esters of this invention have superior properties which render them useful as base stocks for biodegradable lubricant applications, such as crankcase oils, hydraulic fluids, drilling fluids, two-cycle engine oils and the like. Certain of these esters meet or exceed many, if not all, specifications for some lubricant end-use applications without the inclusion of conventional additives.
  • the subject esters When used as a base stock, the subject esters can be admixed with an effective amount of other lubricating agents such as mineral or vegetable oils, other estolides, poly alpha olefins, polyol esters, oleates, diesters, and other natural or synthetic fluids.
  • other lubricating agents such as mineral or vegetable oils, other estolides, poly alpha olefins, polyol esters, oleates, diesters, and other natural or synthetic fluids.
  • any of a variety of conventional lubricant additives may optionally be incorporated into the base stock in an effective amount.
  • these additives are detergents, antiwear agents, antioxidants, viscosity index improvers, pour point depressants, corrosion protectors, friction coefficient modifiers, colorants, antifoam agents, demulsifiers and the like.
  • an effective amount of an antiwear agent used in a lubricant composition is an amount that reduces wear in a machine by a measurable amount as compared with a control composition that does not include the agent.
  • the reaction mixture was washed by mixing with a 10% solution of potassium hydrogen phosphate [50 lbs (23 kg) K 2 HPO 4 in 500 lbs (227 kg) city water]. After separation for 1 hour by settling, the pH was checked in both layers to be 5-6 and the water layer was decanted. After separation, the estolide ester was transferred to a kettle and vacuum dried to 105° C and 29 in of Hg to remove excess water and 2-ethylhexanol. The vacuum drying was followed by pressure filtration using 0.5% filter aid. The value of n in Formula I was 0.5.
  • Biodegradation is usually tested using the Modified Sturm test, measuring the percent degradation in 28 days (OECD 301 B). Biodegradabilities of the major basestocks are compared to that of nonesterified oleic estolide in Table I. It is expected that the 2-ethylhexyl ester of the oleic estolides would not have substantially different biodegradability than the nonesterified estolides.
  • Viscometric properties determine the flow characteristics of the lubricants, their film thickness, and their ability to maintain a lubricating film under varying temperatures. In the lubricant industry these properties are determined by measuring kinematic viscosities using Cannon-Fenske viscometers and then assigned to viscosity grades. ISO 32 and ISO 46 grades are the most popular. Key viscometric properties of major basestocks used industrially to make biodegradable lubricants are compared to 2-ethylhexyl (2EH) ester of oleic estolide in Table II.
  • 2EH 2-ethylhexyl
  • estolide is its high viscosity index (VI) and viscosity grade of ISO 46. This compares to viscometric properties of oleates and vegetable oils. This estolide would not need thickeners which are necessary for tridecyl adipate or PAO 2. Presence of polymer based thickeners or viscosity modifiers may cause shear stability problems in formulated lubricants.
  • Low temperature properties are important for lubricant pumpability, filterability, fluidity as well as cold cranking and startup.
  • Pour point is the most common indicator of the low temperature behavior.
  • Basestocks derived from vegetable oils usually cannot remain liquid in the cold storage test for more than 1 day, therefore, in addition to the pour point, the cold storage test is being developed by ASTM D02 to assess lubricants suitability.
  • Key low temperature properties are compared in Table III.
  • the estolide has significantly better low temperature properties than trioleates, vegetable oils or polyol esters of higher viscosities.
  • Volatility is very important for lubricant vapor pressure, flammability, volatile burnoff and emissions. Volatility relates to the flash point, which is measured using Cleveland Open Cup test method. Micro oxidation data allows to quantify the volatility at particular temperatures, in this case 150°C (same range as hydraulic system or engine crankcase). Key volatility properties are compared in Table IV. The estolides are much less volatile than low viscosity PAOs or adipates.
  • Oxidative stability defines durability of lubricant and its ability to maintain functional properties during its use. Vegetable oil and oleate based lubricants usually suffer from poor oxidative stability. Micro oxidation is recognized in the lubricant industry as a technique to rank oxidative stabilities by quantifying oxypolymerization tendencies. Micro oxidation data are compared in Table V.
  • Oxidative stability of estolide is comparable to that of fully saturated materials such as PAOs, polyol esters and adipates. Vegetable oils and most of fluids derived from them are clearly inferior to the estolides.
  • the 2-ethylexyl estolide ester has advantages over vegetable oils and oleates in its oxidative stability and low temperature properties, over low viscosity PAOs and adipates, in volatility, viscometric properties and biodegradability.
  • the methyl, butyl, decyl, oleyl, isopropyl, isostearyl and branched C24 esters of oleic estolide were prepared substantially as described in Example 1 for the 2-ethylhexyl ester. These esters were evaluated for melting point, viscosity index, and viscosity at each of 100° F (38°C), 40° C and 100° C in comparison with known vegetable oils, fatty acids and other estolides and vegetable oil derivatives. The results are given in Table VI.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (11)

  1. Estolidverbindung mit der Formel:
    Figure imgb0006
     wobei x und y jeweils 1 oder größer als 1 sind;
    wobei x + y = 10;
    wobei n 1 oder größer als 1 ist ;
    wobei R CHR1R2 ist;
    wobei R1 und R2 unabhängig ausgewählt sind aus Wasserstoff und C1- bis C36-Kohlenwasserstoff, der gesättigt oder ungesättigt, verzweigt oder geradkettig, und substituiert oder unsubstituiert sein kann;
    wobei R3 ein Restfragment einer Ölsäure-, Stearinsäure- oder anderen Fettsäurekette ist; und
    wobei sich die vorherrschende Sekundäresterverbindungsspezies an der Position 9 oder 10 befindet; d. h., wobei x = 5 oder 6 bzw. y = 5 oder 4 ist.
  2. Estolidverbindung nach Anspruch 1, wobei wenigstens entweder R1 oder R2 ein C1-bis C36-Kohlenwasserstoff ist.
  3. Estolidverbindung nach Anspruch 1, wobei sowohl R1 als auch R2 C1- bis C36-Kohlenwasserstoffe sind.
  4. Estolidverbindung nach Anspruch 1, wobei R Methyl ist.
  5. Estolidverbindung nach Anspruch 1, wobei R Butyl ist.
  6. Estolidverbindung nach Anspruch 1, wobei R Isopropyl ist.
  7. Estolidverbindung nach Anspruch 1, wobei R 2-Ethylhexyl ist.
  8. Estolidverbindung nach Anspruch 1, wobei R Isostearyl ist.
  9. Schmiermittelzusammensetzung umfassend (1):
    eine Estolidverbindung der Formel:
    Figure imgb0007
    wobei x und y jeweils 1 oder größer als 1 sind;
    wobei x + y = 10 ist;
    wobei n 1 oder größer als 1 ist;
    wobei R CHR1R2 ist;
    wobei R1 und R2 unabhängig ausgewählt sind aus Wasserstoff und C1- bis C36-Kohlenwasserstoffen, die gesättigt oder ungesättigt, verzweigt- oder geradkettig, und substituiert oder unsubstituiert sein können;
    wobei R3 ein Restfragment einer Ölsäure-, Stearinsäure- oder anderen Fettsäurekette ist; und
    wobei sich die vorherrschende Sekundäresterverbindungsspezies an der Position 9 oder 10 befindet; d. h. wobei x = 5 oder 6 bzw. y = 5 oder 4 ist; und (2) eine wirksame Menge eines Schmiermittels.
  10. Schmiermittelzusammensetzung nach Anspruch 9, wobei das Schmiermittel ausgewählt ist aus der Gruppe bestehend aus Mineralöl, Pflanzenöl, Estolid, das verschieden ist von dem durch Formel I definierten, Poly-alpha-olefin, Polyolester, Oleat und Diester.
  11. Schmiermittelzusammensetzung nach Anspruch 9, und weiter umfassend eine wirksame Menge eines Schmiermittelzusatzes, der ausgewählt ist aus der Gruppe bestehend aus Reinigungsmittel, Verschleißschutzstoff, Antioxidationsmittel, Viskositätsindexverbesserer, Fließpunkterniedriger, Korrosionsschutzmittel, Reibungskoeffizientenmodifikationsmittel, Färbemittel, Antischaummittel und Demulgatoren.
EP98958608A 1997-11-14 1998-11-16 Verwendung biologisch abbaubarer olsäure-estolid-ester als basisöl und schmieröl Expired - Lifetime EP1051465B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US6572697P 1997-11-14 1997-11-14
US65726P 1997-11-14
US09/191,907 US6018063A (en) 1998-11-13 1998-11-13 Biodegradable oleic estolide ester base stocks and lubricants
US191907 1998-11-13
PCT/US1998/024469 WO1999025794A1 (en) 1997-11-14 1998-11-16 Biodegradable oleic estolide ester base stocks and lubricants

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EP1051465A1 EP1051465A1 (de) 2000-11-15
EP1051465A4 EP1051465A4 (de) 2002-06-05
EP1051465B1 true EP1051465B1 (de) 2006-08-23

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AT (1) ATE337390T1 (de)
AU (1) AU1461399A (de)
CA (1) CA2309914C (de)
DE (1) DE69835694T2 (de)
ES (1) ES2272013T3 (de)
WO (1) WO1999025794A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018002891A1 (de) 2017-04-13 2018-10-18 Klüber Lubrication München Se & Co. Kg Neue Esterverbindungen, Verfahren zu ihrer Herstellung sowie ihre Verwendung

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6541061B2 (en) * 2000-04-07 2003-04-01 Monsanto Technology Llc Low calorie fat compositions
CN102549128B (zh) * 2009-09-24 2014-03-05 陶氏环球技术有限责任公司 具有出色的低温性质的长链酯组合物
US8637689B2 (en) 2010-08-31 2014-01-28 Biosynthetic Technologies, Llc Catalytic processes for preparing estolide base oils
AU2012271126B2 (en) 2011-06-17 2016-10-13 Biosynthetic Technologies, Llc Estolide compositions exhibiting high oxidative stability
CA2839174A1 (en) 2011-06-17 2012-12-20 Lubrigreen Biosynthetics, Llc Grease compositions comprising estolide base oils
WO2012173671A1 (en) 2011-06-17 2012-12-20 Lubrigreen Biosynthetics, Llc Compositions comprising estolide compounds and methods of making and using the same
WO2013009471A1 (en) * 2011-07-08 2013-01-17 Lubrigreen Biosynthetics, Llc Compositions and products containing estolide compounds
US8586771B1 (en) 2012-06-18 2013-11-19 Biosynthetic Technologies, Llc Processes of preparing estolide compounds that include removing sulfonate residues
KR20160046660A (ko) * 2014-10-21 2016-04-29 에스케이이노베이션 주식회사 결합제를 이용한 에스톨라이드의 제조 방법

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2049072A (en) * 1933-08-29 1936-07-28 Standard Oil Dev Co Lubricants
US2652411A (en) * 1952-07-18 1953-09-15 Howard M Teeter Alkyl acyloxy stearates
US4431673A (en) * 1980-05-02 1984-02-14 Revlon, Inc. Cosmetic compositions
US4428850A (en) * 1982-01-28 1984-01-31 Texaco Inc. Low foaming railway diesel engine lubricating oil compositions
US4567037A (en) * 1984-11-20 1986-01-28 Revlon, Inc. Fatty acid diesters
US4639369A (en) * 1986-03-03 1987-01-27 Revlon, Inc. Higher acyl lower alkyl hydroxystearates useful in cosmetics
US4867965A (en) * 1986-10-02 1989-09-19 Revlon, Inc. Fatty acid diesters
US4806572A (en) * 1987-05-04 1989-02-21 Creative Products Resource Asociates, Ltd. Hydrophilic foam pad for makeup removal
US5518728A (en) * 1994-08-08 1996-05-21 L'oreal S.A. Cosmetic compositions for non-white pigmented skin

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018002891A1 (de) 2017-04-13 2018-10-18 Klüber Lubrication München Se & Co. Kg Neue Esterverbindungen, Verfahren zu ihrer Herstellung sowie ihre Verwendung
WO2018188803A1 (de) 2017-04-13 2018-10-18 Klüber Lubrication München Se & Co. Kg Neue esterverbindungen, verfahren zu ihrer herstellung sowie ihre verwendung
EP3913039A1 (de) 2017-04-13 2021-11-24 Klüber Lubrication München SE & Co. KG Esterverbindungen, verfahren zu ihrer herstellung sowie ihre verwendung
EP3913039B1 (de) * 2017-04-13 2024-01-31 Klüber Lubrication München SE & Co. KG Mischung aus esterverbindungen

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EP1051465A4 (de) 2002-06-05
CA2309914A1 (en) 1999-05-27
AU1461399A (en) 1999-06-07
ES2272013T3 (es) 2007-04-16
ATE337390T1 (de) 2006-09-15
CA2309914C (en) 2007-03-06
DE69835694D1 (de) 2006-10-05
WO1999025794A1 (en) 1999-05-27
EP1051465A1 (de) 2000-11-15
DE69835694T2 (de) 2007-08-23

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