&

Europäisches Patentamt
(19) European Patent Office

Office européen des brevets (11) EP 1 051 465 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C10M 105/34 (2006.01) C10M 107/30 (2006.01)
23.08.2006 Bulletin 2006/34 C07C 69/66 (2006.01) C08G 63/08 (2006.01)
C10M 101/04 (2006.01) C10N 60/00 (2006.01)
(21) Application number: 98958608.6
(86) International application number:
(22) Date of filing: 16.11.1998 PCT/US1998/024469

(87) International publication number:

WO 1999/025794 (27.05.1999 Gazette 1999/21)

(54) BIODEGRADABLE OLEIC ESTOLIDE ESTER BASE STOCKS AND LUBRICANTS

VERWENDUNG BIOLOGISCH ABBAUBARER OLSÄURE-ESTOLID-ESTER ALS BASISÖL UND
SCHMIERÖL
UTILISATION D’ESTERS D’ESTOLIDES DERIVES D’ACIDES OLEIQUES COMME HUILES DE
BASE ET LUBRIFIANTS

(84) Designated Contracting States: • ABBOTT, Thomas, P.

AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU Peoria, IL 61614 (US)
MC NL PT SE • ASADAUSKAS, Svajus
Peoria, IL 61614 (US)
(30) Priority: 14.11.1997 US 65726 P • LOHR, Joseph, E., Jr.
13.11.1998 US 191907 Hoffman Estates, IL 60195 (US)

(43) Date of publication of application: (74) Representative: Bohmann, Armin K.

15.11.2000 Bulletin 2000/46 Bohmann & Loosen,
Anwaltssozietät,
(73) Proprietors: Sonnenstrasse 8
• The United States of America, represented by The 80331 München (DE)
Secretary of Agriculture
Washington, DC 20250-0302 (US) (56) References cited:
• Lambent Technologies, Inc. US-A- 2 049 072 US-A- 2 652 411
Norcross, GA 30093-2966 (US) US-A- 4 428 850 US-A- 4 431 673
US-A- 4 567 037 US-A- 4 639 369
(72) Inventors: US-A- 4 806 572 US-A- 4 867 965
• ISBELL, Terry, A. US-A- 5 518 728
Elmwood, IL 61529 (US)
EP 1 051 465 B1

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 1 051 465 B1

Description

Background of the Invention

5 Field of the Invention

[0001] This invention relates to esters of oleic acid estolides and their use as biodegradable base stocks and lubricants.

Description of the Prior Art

10
[0002] 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,
15 lubricities, wear protection, air release, color and other properties. Biodegradability cannot be improved by using additives.
[0003] In the recent prior art, a fair amount of attention has been given to estolides as having potential for base stocks
and lubricants. An estolide is a unique oligomeric fatty acid that contains secondary ester linkages on the alkyl backbone
of the molecule.
[0004] US-A-4 867 965 describes a diester derived from a fatty acid such as oleic acid. The diester in US-A-2 652
20 411 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.
[0005] 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.
25 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.
[0006] 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. In addition, the level of unsaturation in the produced estolides (ex-
pressed through e.g. iodine value) is not significantly lower than that in raw materials, i.e., hydroxy fatty acids.
30 [0007] Erhan et al. [JAOCS, 70:461 (1993)], reported the production of estolides from unsaturated fatty acids using
a high temperature and pressure condensation over clay catalysts. Conversion of the fatty acid double bond into an
ester functionality is a strikingly different method than the hydroxy esterification process.

Summary of the Invention

35
[0008] We have now discovered a family of novel 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.
[0009] The estolide esters of this invention are generally characterized by Formula (I):
40

45

50

55

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 EP 1 051 465 B1

10

15

20
wherein x and y are each equal to 1 or greater than 1;
wherein x+y=10;
wherein n is 1, or greater than 1;
wherein R is CHR1R2;
25 wherein R1 and R2 are independently selected from hydrogen and C1 to C36 hydrocarbon which may be saturated or
unsaturated, branched or straight chain, and substituted or unsubstituted;
wherein R3 is a residual fragment of oleic, stearic or other fatty acid chain; and
wherein the predominant species of secondary ester linkage is at the 9 or 10 position; that is, wherein x=5 or 6 and y=5
or 4, respectively.
30 [0010] In accordance with this discovery, it is an object of this invention to provide novel estolide compounds having
utility as lubricant base stocks and also as lubricants without the necessity for inclusion of conventional additives.
[0011] It is a further object of this invention to provide a family of estolides which are biodegradable and which have
superior oxidative stability, low temperature and viscometric properties.
[0012] Other objects and advantages of this invention will become readily apparent from the ensuing description.
35
Detailed Description

[0013] For purposes of this invention, the term " monoestolides" is used generically to refer to the acid form of com-
pounds having the structure of Formula I, wherein n=0. The term " polyestolides" is used herein to refer to the acid form
40 of compounds having the structure of Formula I, wherein n is greater than 1. The terms "ester", "estolide ester" and the
like are generally used herein to refer to products produced by esterifying the residual fatty acid (attachment of the R
group in Formula I) on the estolide or estolide mixtures as described below. Of course, 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.
45 [0014] The production of monoestolides and polyestolides by various routes is fully described in Isbell et al. (I) [JAOCS,
Vol. 71, No. 1, pp. 169-174 (February 1994)], Erhan et al. [JAOCS, Vol. 74, No. 3, pp. 249-254 (1997)], and Isbell et al.
(II) [JAOCS, Vol. 74, No. 4, pp. 473-476 (1997)], all of which are incorporated herein by reference. Though not required,
it is preferred for purposes of quality control that the starting material be as pure in oleic acid as practical. Isbell et al.
(III) [JAOCS, Vol. 71, No. 1, pp. 379-383 (April, 1994)], characterize the oleic estolides produced by acid catalysis as
50 being mixtures of monoestolides and polyestolide oligomers up to eight or more fatty acid molecules interesterified
through secondary ester linkages on the alkyl backbone. This publication also teaches that the positions of these sec-
ondary ester linkages were centered around the original C-9 double bond position, with linkages actually ranging from
positions C-5 to C-13 and most abundantly at the C-9 and C-10 positions in approximately equal amounts. Likewise,
the remaining unsaturation on the terminal fatty acid was distributed along the fatty acid backbone, presumably also
55 from C-5 to C-13.
[0015] The linkages of the estolides of this invention would have the same or approximately the same distribution of
linkages reported by Isbell et al. 1994. Therefore, it is to be understood that Formula I, supra, is a generalization of the
estolide backbone structure of the compounds contemplated herein, and that the formula is intended to encompass

3
 EP 1 051 465 B1

normal distributions of reaction products resulting from the various reaction procedures referenced above. Applicants
believe that the superior properties of the subject estolide esters are dictated not so much by positions of the linkage
and the site of unsaturation, but more by the combination of the degree of oligomerization, decrease in level of unsatu-
ration, the virtual absence of hydroxyl functionalities on the estolide backbone, and the nature of the specific ester moiety
5 (R). However, the process inherently introduces a distribution of secondary linkage positions in the estolide, which in
general, affects low temperature and viscometric behavior very favorably. Minor components other than oleic acid, such
as linoleic acid or stearic acid may lead to variations in the basic estolide structure shown in Formula I.
[0016] 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
10 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.
[0017] The oleic estolides are esterified by normal procedures, such as acid-catalyzed reduction with an appropriate
alcohol. In the preferred embodiment of the invention, R1 and R2 are not both hydrogen, and more preferably, neither
15 R1 nor R2 is hydrogen. That is, it is preferred that the reactant alcohol be branched. In the most preferred embodiment
of the invention, 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.
[0018] Particularly contemplated within the scope of the invention are those 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
20 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. 22:395 (1979); Asadauskas, PhD Thesis, Pennsylvania State Univ. p.88
(1997)]; and a biodegradability in the OECD Test greater than 70%. Determination of these properties by conventional
test procedures are routine. Therefore, identification of oleic estolide esters within the scope of Formula I would be fully
25 within the skill of the ordinary person in the art.
[0019] As previously indicated and as demonstrated in the Examples, below, 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.
30 [0020] 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.
[0021] In the preparation of lubricants, any of a variety of conventional lubricant additives may optionally be incorporated
into the base stock in an effective amount. Illustrative of these additives are detergents, antiwear agents, antioxidants,
35 viscosity index improvers, pour point depressants, corrosion protectors, friction coefficient modifiers, colorants, antifoam
agents, demulsifiers and the like.
[0022] The expression " effective amount" as used herein is defined to mean any amount that produces a measurable
effect for the intended purpose. For example, 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
40 does not include the agent.

Example 1

Preparation of 2-Ethylhexyl Oleic Estolide (Laboratory).

45
[0023] To 1000 ml of commercial grade oleic acid (70% oleic) in a 3000 ml 3-neck flask evacuated to 27 in (686mm)
of Hg is added 50 ml sulfuric acid over the course of 4 min. The temperature was maintained at 55° C for 24 hr and a
stirring rate of 300 rpm. After breaking the vacuum with nitrogen, 373 ml (2.39 moles, 1.1 mole equivalents) of 2-ethylhexyl
alcohol was added to the flask over 5 min and then the vacuum was restored. After mixing for 2 hrs. at 55° C, 190 g of
50 Na2HPO4 in 2 L of water was added with vigorous stirring. The mixture was allowed to stand overnight and the water
layer was removed. Product was recovered by removing the alcohol utilizing vacuum distillation at 13.3 to 66.7 Pa
(0.1-0.5) torr at 100° C.
[0024] Over the course of three runs, the overall yield of product ranged from 82-84%, and the average value of n in
Formula I was 1.2.
55

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 EP 1 051 465 B1

Example 2 (Comparative)

Preparation of 2-Ethylhexyl Oleic Estolide (Pilot).

5 [0025] A pilot scale production of 2-ethylhexyl oleic estolide was conducted as follows:
[0026] Two hundred fifty pounds (113 kg) of oleic acid (commercial grade) was added to a plastic-lined drum and
degassed with a nitrogen sparge for 15 minutes. Twenty-three pounds (10 kg) of concentrated sulfuric acid was added
slowly with stirring, maintaining the temperature below 55° C by the rate of addition.The drum temperature was maintained
after the sulfuric acid was all added by storing in a heated room at 55° C. After 24 hours, one forty-pound (18 kg) sample
10 was removed and the acid value and iodine value were checked. Sixty-eight pounds (31 kg) of 2-ethylhexanol were then
added, and after 2 hours the hydroxyl value was confirmed as being less than 10.0, signaling completion of the reaction.
The reaction mixture was washed by mixing with a 10% solution of potassium hydrogen phosphate [50 lbs (23 kg)
K2HPO4 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
15 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.

Example 3

20 Characterization of Physical Properties of 2-Ethylhexyl Oleic Estolide from Example 2.

[0027] 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
25 than the nonesterified estolides.
[0028] 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 biode-
30 gradable lubricants are compared to 2-ethylhexyl (2EH) ester of oleic estolide in Table II.
[0029] Advantage of the 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.
35 [0030] 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
40 polyol esters of higher viscosities.
[0031] 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.
45 [0032] 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.
[0033] Oxidative stability of estolide is comparable to that of fully saturated materials such as PAOs, polyol esters and
50 adipates. Vegetable oils and most of fluids derived from them are clearly inferior to the estolides.
[0034] In general, 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 biode-
gradability.

55 Example 4

[0035] 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

5
 EP 1 051 465 B1

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.

Example 5
5
[0036] The pour points of 12-hydroxy stearic (Guerbet) acid esters and 2-ethylhexyl ester of ricinoleic estolide and
oleic estolide were compared (Table VII).

Table I
10
Property, units (test method) Estolide TMP trioleate Canola oil PAO 2 polyol ester tridecyl adipate
Modified Sturm test, % in 28 >80% 70% >85% >70% <40% <30%
days (OECD 301 B)

15

Table II
Property, units (test Estolide 2EH TMP trioleate Canola oil PAO 2 polyol esters tridecyl adipate
method)
20 Viscosity at 40°C (ASTM 53.6 49 38.5 5.55 78.3 27
D 445)
Viscosity at 100°C 9.42 9.9 8.5 1.8 11.9 5.35
(ASTM D 445)
25 VI (ASTM D 2270) 161 190 207 - 147 135

Table III
30 Property, units (test Estolide 2EH TMP trioleate Canola oil PAO 2 polyol ester tridecyl adipate
method)
Pour Point, °C (ASTM D -27 -24 -18 -72 -21 -54
97)

35 Cold storage at -25°C, 7+ <1 <1 7+ <1 7+

days

Table IV
40
Property, units (test Estolide 2EH TMP trioleate Canola oil PAO 2 polyol ester tridecyl adipate
method)
Flash Point, °C (ASTM D) 250 315 162 160 n.a. 221

45
Evaporation, 30 min at 3 1 1 98 n.a. 10
150°C, %wt. (micro
oxidation)

50 Table V
Property, units (test Estolide 2EH TMP trioleate Canola oil PAO 2 polyol ester tridecyl adipate
method)
High MW products, 30 min 7 30 35 - <4 <4
55 at 150°C, %wt. (micro
oxidation)

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 EP 1 051 465 B1

(continued)
Property, units (test Estolide 2EH TMP trioleate Canola oil PAO 2 polyol ester tridecyl adipate
method)
5 Solid deposits, 30 min at 0 3 5 - 0 0
150°C, %wt. (micro
oxidation)

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Table VII
Pour Points (°C)

5 Guerbet ester 2-EH ester

ricinoleic estolide -12 not available
oleic estolide -43 -27 to -35

10
Claims

1. An estolide compound of the formula:

15

20

25

wherein x and y are each equal to 1 or greater than 1;

30 wherein x+y=10;
wherein n is 1, or greater than 1 ;
wherein R is CHR1R2;
wherein R1 and R2 are independently selected from hydrogen and C1 to C36 hydrocarbon which may be saturated
or unsaturated, branched or straight chain, and substituted or unsubstituted;
35 wherein R3 is a residual fragment of oleic, stearic or other fatty acid chain; and
wherein the predominant species of secondary ester linkage is at the 9 or 10 position; that is,
wherein x=5 or 6 and y=5 or 4, respectively.

2. The estolide compound of claim 1, wherein at least one of R1 and R2 is a C1 to C36 hydrocarbon.
40
3. The estolide compound of claim 1, wherein both R1 and R2 are C1 to C36 hydrocarbons.

4. The estolide compound of claim 1, wherein R is methyl.

45 5. The estolide compound of claim 1, wherein R is butyl.

6. The estolide compound of claim 1, wherein R is isopropyl.

7. The estolide compound of claim 1, wherein R is 2-ethylhexyl.

50
8. The estolide compound of claim 1, wherein R is isostearyl.

9. A lubricant composition comprising (1):

55 an estolide compound of the formula:

10
 EP 1 051 465 B1

10

wherein x and y are each equal to 1 or greater than 1;

wherein x+y=10;
wherein n is 1, or greater than 1 ;
15 wherein R is CHR1R2;
wherein R1 and R2 are independently selected from hydrogen and C1 to C36 hydrocarbons which may be saturated
or unsaturated, branched or straight chain, and substituted or unsubstituted;
wherein R3 is a residual fragment of oleic, stearic or other fatty acid chain; and
wherein the predominant species of secondary ester linkage is at the 9 or 10 position; that is,
20 wherein x=5 or 6 and y=5 or 4, respectively;
and (2), an effective amount of lubricating agent.

10. The lubricant composition of claim 9, wherein said lubricating agent is selected from the group consisting of mineral
oil, vegetable oil, estolide other than that defined by formula I, poly alpha olefin, polyol ester, oleate, and diester.
25
11. The lubricant composition of claim 9 and further comprising an effective amount of a lubricant additive selected from
the group consisting of detergent, antiwear agent, antioxidant, viscosity index improver, pour point depressant,
corrosion protector, friction coefficient modifier, colorants, antifoam agents and demulsifiers.

30
Patentansprüche

1. Estolidverbindung mit der Formel:

35

40

45
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;
50 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.
55
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.

11
 EP 1 051 465 B1

4. Estolidverbindung nach Anspruch 1, wobei R Methyl ist.

5. Estolidverbindung nach Anspruch 1, wobei R Butyl ist.

5 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.

10
9. Schmiermittelzusammensetzung umfassend (1):

eine Estolidverbindung der Formel:

15

20

25
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;
30 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.
35
10. Schmiermittelzusammensetzung nach Anspruch 9, wobei das Schmiermittel ausgewählt ist aus der Gruppe beste-
hend aus Mineralöl, Pflanzenöl, Estolid, das verschieden ist von dem durch Formel I definierten, Poly-alpha-olefin,
Polyolester, Oleat und Diester.

40 11. Schmiermittelzusammensetzung nach Anspruch 9, und weiter umfassend eine wirksame Menge eines Schmier-
mittelzusatzes, der ausgewählt ist aus der Gruppe bestehend aus Reinigungsmittel, Verschleißschutzstoff, Antioxi-
dationsmittel, Viskositätsindexverbesserer, Fließpunkterniedriger, Korrosionsschutzmittel, Reibungskoeffizienten-
modifikationsmittel, Färbemittel, Antischaummittel und Demulgatoren.

45
Revendications

1. Composé étholide de formule :

50

55

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10

où x et y sont chacun égaux à 1 ou supérieurs à 1 ;

où x + y = 10 ;
15 où n vaut 1, ou est supérieur à 1 ;
où R est CHR1R2 ;
où R1 et R2 sont indépendamment choisis parmi un atome d’hydrogène et un hydrocarbure en C1 à C36 qui peut
être saturé ou insaturé, ramifié ou à chaîne linéaire, et substitué ou non substitué ;
où R3 est un fragment résiduel d’une chaîne d’acide oléique, stéarique ou autre acide gras ; et
20 où l’espèce prédominante de l’enchaînement ester secondaire est en position 9 ou 10 ; à savoir, où x = 5 ou 6 et y
= 5 ou 4, respectivement.

2. Composé étholide selon la revendication 1, dans lequel au moins l’un de R1 et R2 est un hydrocarbure en C1 à C36.

25 3. Composé étholide selon la revendication 1, dans lequel tant R1 que R2 sont des hydrocarbures en C1 à C36.

4. Composé étholide selon la revendication 1, dans lequel R est un groupe méthyle.

5. Composé étholide selon la revendication 1, dans lequel R est un groupe butyle.

30
6. Composé étholide selon la revendication 1, dans lequel R est un groupe isopropryle.

7. Composé étholide selon la revendication 1, dans lequel R est un groupe 2-éthylhexyle.

35 8. Composé étholide selon la revendication 1, dans lequel R est un groupe isostéaryle.

9. Composition lubrifiante comprenant (1) :

un composé étholide de formule :

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où x et y sont chacun égaux à 1 ou supérieurs à 1 ;

où x + y = 10 ;
55 où n vaut 1, ou est supérieur à 1 ;
où R est CHR1R2 ;
où R1 et R2 sont indépendamment choisis parmi un atome d’hydrogène et des hydrocarbures en C1 à C36 qui
peuvent être saturés ou insaturés, ramifiés ou à chaîne linéaire, et substitués ou non substitués ;

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 EP 1 051 465 B1

où R3 est un fragment résiduel de chaîne d’acide oléique, stéarique ou autre acide gras ; et
où l’espèce prédominante de l’enchaînement ester secondaire est en position 9 ou 10 ; à savoir, où x = 5 ou 6
et y = 5 ou 4, respectivement ; et (2), une quantité efficace d’agent lubrifiant.
10. Composition lubrifiante selon la revendication 9, dans laquelle ledit agent lubrifiant est choisi dans le groupe
5 constitué par l’huile minérale, l’huile végétale, un étholide autre que celui-ci défini par la formule I, une poly
(alpha-oléfine), un polyol ester, un oléate et un diester.
11. Composition lubrifiante selon la revendication 9, et comprenant en outre une quantité efficace d’un additif
lubrifiant choisi dans le groupe constitué par un détergent, un agent antiusure, un antioxydant, un améliorateur
d’indice de viscosité, un abaisse-point d’écoulement, un protecteur contre la corrosion, un modificateur de
10 coefficient de frottement, des colorants, des agents antimousses et des agents désémulsionnants.

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