Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Lubricant compounds containing complex esters
Field of the invention
The invention is in the field of lubricants. It relates
to lubricant compositions comprising complex esters of
elevated viscosity, and to the use of these lubricant
compositions as, for example, transmission oil,
industrial oil or motor oil.
State of the art
The commercially available lubricant compositions or
else lubricants are produced from a multitude of
different natural or synthetic components. To improve
the required properties, according to the field of use,
additions and/or further additives are added. The base
oils often consist of mineral oils, highly refined
mineral oils, alkylated mineral oils, poly-a-olefins
(PAOs), polyalkylene glycols, phosphate esters,
silicone oils, diesters and esters of polyhydric
alcohols. Especially mineral oils of the Solvent
Neutral class and mineral oils of the XHVI, VHVI, group
II and group III classes are used.
The different lubricants, such as motor oil, turbine
oil, hydraulic fluid, transmission oil, compressor oil
and the like, must satisfy extremely high criteria such
as high viscosity index, good lubricant performance,
high oxidation sensitivity, good thermal stability or
comparable properties.
High-performance lubricant oil formulations which are
used as transmission, industrial or motor oils are
especially oils with a high performance profile with
regard to shear stability, low-temperature viscosity,
long life, evaporation loss, fuel efficiency, seal
compatibility and wear protection. Such oils are
currently being formulated preferentially with PAO
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(especially PAO 6) or group II or Group III mineral
oils as carrier fluids, and with specific polymers
(polyisobutylenes = PIBs, olefin copolymers = ethylene/
propylene copolymers = OCPs, polyalkyl methacrylates =
PMAs) as thickeners or viscosity index improvers in
addition to the customary additive components. Together
with PAOs, low-viscosity esters, for example DIDA
(diisodecyl adipate), DITA (diisotridecyl adipate) or
TMTC (trimethylolpropane caprylate), are typically also
being used especially as solubilizers for polar
additive types and for optimizing seal compatibilities.
Disadvantages in the case of use of the PAOs or of the
polymers are generally the high costs and the low shear
stability, and also the low-temperature viscosity of
the lubricants in the case of use of polymers.
Ester-based lubricant oils are known per se and have
already been used for some time (see Ullmanns
Encyklopadie der technischen Chemie, 3rd Edition,
volume 15, 1964, p. 285-294). Common esters are
reaction products of dicarboxylic acids with alcohols,
for example 2-ethylhexanol, or reaction products of
polyols, for example trimethylolpropane, and fatty
acids, for example oleic acid or a mixture of n-
octanoic acid and n-decanoic acid. When, for example,
dicarboxylic acids are used as well as monocarboxylic
acids and polyols in the ester preparation, the
dicarboxylic acid has crosslinking action, which leads
to an increase in molecular weights of the ester and
ultimately to higher viscosities and improved
thickening actions in lubricant formulations. Such
esters are typically referred to as complex esters.
Low-temperature viscosities of the formulations
produced with esters and hence improved handling at low
temperatures have been described especially for esters
with branched alkyl chains.
The industrial requirements on lubricant oils are
reflected in the common specifications according to
classes, for example multiregion oils which satisfy
.
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viscosity classes SAE 75-W90 for transmision oils, or
O-W20 or O-W30 for motor oils, can be used virtually in
all seasons.
There is still a particular demand for additions of
polymeric or oligomeric nature which, used as
additives, contribute to the satisfaction of
requirements for very shear-stable lubricant
compositions which can be used within wide ranges.
These additives should additionally at least not worsen
the viscosity index. Some viscosity index improvers are
known which, however, do not exhibit good shear
stability, as shown, for example, in US 4,156,673. EP
488432 (=US5070131) discloses polymers with good shear
stability, which are prepared from poly(polyalkenyl)
couplings.
DE 3544061 (=US4822508) describes high-shear stability
transmision oils which comprise viscosity index-
improving additives based on esters of acrylic acid
and/or methacrylic acid.
US 5,451,630 describes olefin copolymers (OCPs) which
have good shear stability. It is additionally stated
that the good shear stability decreases with the size
of the molecule and hence with an elevated viscosity.
This decomposition of the polymers as a result of
elevated shear forces leads to a reduction in the
viscosity in the lubricant.
An optimal viscosity index improver exhibits a minor
contribution to the viscosity of the lubricant at low
temperatures, and a major contribution at operating
temperatures. Moreover, a high stability should also be
present under elevated shear forces.
It was thus an object of the invention to increase the
shear stability of the lubricant composition and to
achieve a good low-temperature viscosity. Both are
generally worsened by polymeric or oligmeric additions,
for example thickeners, viscosity index improvers or
polymeric dispersants.
EP 1281701 discloses synthetic lubricants prepared from
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polyneopentylpolyol and a mixture of linear and
branched acids, wherein the ester has a viscosity of
from 68 to 400 mm2/s at 40 C. These have been developed
for use in cooling compressor fluids.
EP 938536 discloses lubricants which comprise synthetic
esters which are obtained by reacting polyols with
mixtures of monocarboxylic acids and optionally
polybasic acids, and which have an elevated thermal and
oxidative stability. The viscosity of the esters at
100 C is not more than approx. 80 mm2/s. No statements
regarding the shear stability were made.
It was firstly an object of the invention to provide
high-shear stability lubricant compositions comprising
novel thickener systems, which at least do not worsen
the viscosity index and are usable within wide ranges.
Low-temperature viscosities and/or shear stabilities
should be improved in comparison to customary
thickeners or VI improvers corresponding to the state
of the art, and the compatibility of the thickener
system with the remaining components of the lubricant
formulations, especially at relatively low
temperatures, should remain guaranteed. It was a
further object of the invention either to reduce or to
eliminate the content of common polymeric and/or
oligomeric thickeners or VI improvers (e.g. OCPs, PIBs,
polyalkyl methacrylates) in the lubricant compositions,
and to replace expensive carrier components such as
PAOs with group II or III oils. For lubricant oils
which are already formulated with group II or group III
oils, in contrast, a replacement of these group II and
III oils with cheaper group I oils was desirable. In
industry, the reduction or elimination of customary
polymers should give rise to advantages with regard to
shear stability and low-temperature viscosity.
There is a particular problem when the lubricants, as
well as elevated oxidation stability and low-
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temperature viscosity, must have improved compatibility
with respect to seal materials. The known lubricants
based on linear esters with good oxidation stability
are saturated in nature, but lead to the softening of
the customary seal materials. Conversely, unsaturated
ester types which originate, for example, from oleic
acid have better behavior toward seal materials but
have significantly reduced oxidation stabilities.
Particular problems occur with respect to seal
materials such as NBR (nitrile butyl rubber) and
hydrogenated variants thereof (HNBR).
There is still a need for improved lubricants with high
biodegradability. A further object of the present
invention consisted in providing lubricants which, as
well as the properties mentioned, have a good
compatibility with respect to seal materials.
At the same time, the other properties, especially the
lubricity and rheological properties of the lubricant,
must not be adversely affected.
It has been found that particular high-viscosity esters
solve the problems outlined above in an outstanding
manner.
Description of the invention
The invention provides a lubricant composition having a
good shear stability determined by the loss of
kinematic viscosity at 100 C, comprising base oil and a
synthetic complex ester, said complex ester having a
kinematic viscosity at 40 C of greater than 400 and up
to 50 000 mmz/s and being obtained by reaction of:
a) polyols and monocarboxylic acids and
dicarboxylic acids or of
b) polyols and monoalcohols and dicarboxylic acids
or of
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c) polyols and monoalcohols and monocarboxylic
acids and dicarboxylic acids.
For the complex esters mentioned, it has been found
that the shear stability of the lubricant composition
comprising these esters achieves very good results and
decreases the viscosity only slightly. Furthermore, it
has been possible to reduce the content of polymers.
The loss of kinematic viscosity was determined at 1000C
i) for transmission oils, axle oils and clutch oils
for automatic and manual transmission to CEC L-45-
T-93 (20 hours) and is less than 8%, preferably
less than 5o and especially preferably less than
4%;
ii) for hydraulic fluids, for industrial transmission
oils with stationary uses, for oils for
lubricating wind turbines, for gas turbine oils,
for compressor oils and shock absorber fluids,
determined to CEC L-45-T-93 (20 hours), and is
less than 15%, and preferably less than 8%;
iii) for two-stroke and four-stroke engine oils and for
diesel and gasoline motor oils, determined after
shear to ASTM D 3945 (30 cycles), and is less than
15%, preferably less than 10o and especially
preferably less than 7%.
In the context of the invention, shear is considered to
be permanent shear. Since the viscosity of the base oil
decreases as a result of shear only to a very
insignificantly minor degree, if at all, the
determination of the loss of viscosity after shear is
meaningful as a parameter for the complex esters.
Moreover, it has surprisingly been found that oil
temperatures in transmission or axle applications are
lower when lubricants are formulated with the high-
viscosity complex esters. This has been found by means
of the industry standard ARKL test (VW PV 1454).
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In addition, it has been found that the further
utilization of low concentrations of a polar polymer,
for example of an alkyl fumarate-a-olefin, of a
polyalkyl methacrylate or of an alkyl methacrylate-a-
olefin system, in a lubricant composition comprising
the relatively high-viscosity ester in many cases acts
as a solubilizer for the ester, and can lower low-
temperature viscosities of the lubricant composition in
a synergistic manner.
It has additionally been found that expensive, high-
viscosity PAO types, for example PAO 60 or PAO 100, or
customary thickeners such as OCP or PIB, which have
been added to the lubricants as thickeners, can
alternatively be formulated with the complex esters to
be present in accordance with the invention and lead to
comparably good or improved properties. Preference is
given to the simultaneous addition of polar polymers as
a further component, for example those mentioned above.
The kinematic viscosity of the complex ester for use is
preferably from 800 to 25 000 mm2/s, especially from
1200 to 10 000 mm2/s, more preferably from 1300 to
5000 mm2/s and most preferably from 1500 to 3000 mmz/s.
It has been found that, surprisingly, the use of these
esters leads to very low losses in the kinematic
viscosity of the lubricant composition after permanent
shear. This property makes possible use in lubricants
which are exposed to high shear stress.
Preference is given in accordance with the invention to
lubricant compositions comprising the complex ester in
a concentration of from 3 to 90% by weight based on the
total amount of lubricant composition. Especially
preferred is a concentration of 7-50% by weight and
more preferably of 10-34 s by weight.
In a further preferred embodiment, the lubricant
compositions are characterized in that the
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monocarboxylic acids used in the reaction according to
a) are branched monocarboxylic acids or mixtures of
linear and branched monocarboxylic acids, each of which
has a carbon number of from 5 to 40 carbon atoms, where
the content of branched monoacid is preferably greater
than 90 mol% based on the total content of the acid
mixture. The monocarboxylic acids preferably have from
8 to 30 carbon atoms and especially from 10 to 18
carbon atoms. In particular, the monocarboxylic acids
are selected from the group formed by the following
branched acids: 2,2-dimethylpropanoic acid,
neoheptanoic acid, neooctanoic acid, neononanoic acid,
isohexanoic acid, neodecanoic acid, 2-ethylhexanoic
acid, 3-propylhexanoic acid, 3,5,5-trimethylhexanoic
acid, isoheptanoic acid, isooctanoic acid, isononanoic
acid, isostearic acid, isopalmitic acid, Guerbet acid
C32, Guerbet acid C34 or Guerbet acid C36, and
isodecanoic acid. The linear acids are preferably
selected from the group formed by valeric acid, caproic
acid, heptanoic acid, caprylic acid, pelargonic acid,
capric acid, undecanoic acid, lauric acid, tridecanoic
acid, tetradecanoic acid, pentadecanoic acid, palmitic
acid, margaric acid, stearic acid, nonadecanoic acid,
arachic acid, behenic acid, lignoceric acid, myristic
acid, cerotic acid, mellissic acid, tricosanoic acid
and pentacosanoic acid, 2-ethylhexanoic acid,
isotridecanoic acid, myristic acid, palmitoleic acid,
oleic acid, elaidic acid, petroselic acid, linoleic
acid, linolenic acid, elaeostearic acid, gadoleic acid
and erucic acid, and the technical-grade mixtures
thereof. Preferred branched monocarboxylic acids are
isononanoic acid, isostearic acid and 2-ethylhexanoic
acid.
Preference is given to lubricant compositions which
comprise complex esters which are obtained by reacting
polyols with dicarboxylic acids and branched
monocarboxylic acids. These preferred esters formed
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from polyols, dicarboxylic acids and branched
monocarboxylic acids preferably have a viscosity from
1300 to 5000 mm2/s and most preferably from 1500 to
3000 mm2/s .
In the context of the invention, the base oil present
in the lubricant composition is understood to mean an
oil which is selected from the group formed by mineral
oils, highly refined mineral oils, alkylated mineral
oils, poly-a-olefins, polyalkylene glycols, phosphate
esters, silicone oils, diesters and esters of
polyhydric alcohols, and also mineral oils of the
Solvent Neutral class and mineral oils of the XHVI,
VHVI, group II and group III and GTL basestock (gas-to-
liquid base oil) classes. The poly-a-olefins may
preferably be formed from C6 to C18-a-olefins and
mixtures thereof. Especially preferred are poly-a-
decenes.
According to the invention, the polyols are branched or
linear alcohols of the general formula (I) R1(OH)n in
which R' is an aliphatic or cycloaliphatic group having
from 2 to 20 carbon atoms and n is at least 2. The
polyols are preferably selected from the group formed
by neopentyl glycol, 2,2-dimethylolbutane,
trimethylolethane, trimethylolpropane, trimethylol-
butane, monopentaerythitol, dipentaerythritol,
tripentaerythritol, ethylene glycol, propylene glycol,
polyalkylene glycol, 1,4-butanediol, 1,3-propanediol
and glycerol. Especially preferred are
trimethylolpropane, monopentaerythritol and
dipentaerythritol.
In further preferred embodiments, the lubricant
compositions are characterized in that, in the reaction
according to b), the monoalcohols used are branched or
linear alcohols of the general formula (II)(R2OH) in
which R2 is an aliphatic or cycloaliphatic group having
from 2 to 24 carbon atoms and bears 0 and/or 1, 2 or 3
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double bonds. The monoalcohols are preferably selected
from the group formed by caproic alcohol, capryl
alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl
alcohol, isotridecyl alcohol, myristyl alcohol, cetyl
alcohol, palmitoleyl alcohol, stearyl alcohol,
isostearyl alcohol, oleyl alcohol, elaidyl alcohol,
petroselinyl alcohol, linolyl alcohol, linolenyl
alcohol, elaeostearyl alcohol, arachyl alcohol,
gadoleyl alcohol, behenyl alcohol, erucyl alcohol and
brassidyl alcohol, and technical-grade mixtures
thereof.
The dicarboxylic acids used in accordance with the
invention to prepare the complex esters are preferably
oxalic acid, malonic acid, succinic acid, glutaric
acid, adipic acid, pimelic acid, suberic acid, azelaic
acid, sebacic acid, brassylic acid, thapsic acid and
phellogenic acid. The anhydrides of the dicarboxylic
acids are also suitable in accordance with the
invention for the reaction. Especially preferred are
azelaic acid or sebacic acid, and anhydrides thereof.
The conversion to the reaction products of the complex
esters proceeds in syntheses known per se for preparing
esters. The preparation of the esters can also be
carried out in accordance with the invention by known
processes such that free carboxyl groups and/or free
hydroxyl groups are present in a controlled manner, and
these products with free carboxyl and/or free hydroxyl
groups are used in the lubricant composition. According
to the invention, the free carboxyl groups present may
be reacted further with amines to give amides, and the
resulting compounds may be present in the lubricant
composition as complex esters in the context of the
invention.
In further preferred embodiments, the inventive
lubricant compositions comprise, as a further
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component, a polar polymer in a concentration of from
0.5 to 30% by weight based on the total amount of
lubricant composition. Preference is given to a
concentration of from 1 to 18% by weight and more
preferably from 2 to 12% by weight.
The polar polymers for use in accordance with the
invention are preferably selected from the group formed
by alkyl fumarate-a-olefin copolymer, alkyl maleate-a-
olefin copolymer, polyalkyl methacrylate, propylene
oxide polymer, ethylene oxide-propylene oxide copolymer
and alkyl methacrylate-a-olefin copolymer.
In addition to good shear stability, the complex esters
for use in accordance with the invention exhibit a high
compatibility toward seal materials which typically
find use. The test for compatibility toward seal
materials can be carried out, for example, according to
the standard test ASTM D 471, for example over 168 h at
100 C. According to this test, the complex esters for
use in accordance with the invention exhibit, for the
seal materials, a volume increase of not more than 20%,
preferably not more than 10%, a hardness loss of less
than 15%, preferably less than 100, and a decrease in
the elongation at break of less than 50%, preferably
less than 30%.
Stability problems of seal materials with respect to
lubricant compositions based on esters occur
particularly in the case of use of nitrile rubber or
acrylonitrile-butadiene rubber or hydrogenated variants
thereof. Typically, these seal materials are softened
by esters as lubricants, which is manifested by an
increase in volume. This softening leads to reduced
hardness and reduced breaking strength or elongation at
break.
In a preferred embodiment of the invention, the complex
esters for use are compatible toward seal materials
which are selected from the group formed by NR (natural
rubber), NBR (nitrile-butadiene rubber), HNBR
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(hydrogenated nitrile butyl rubber), FPM (fluorine
rubber), ACM (acrylate rubber), PTFE (Teflon), PU
(polyurethane), silicone, polyacrylate and neoprene,
more preferably toward NBR, HNBR and ACM.
In a preferred embodiment of the inventive use, the
stability of the seal materials toward esters with
branched alkyl groups is determined by the ASTM D 471
test mentioned, and the criteria specified are met.
The complex esters for use in accordance with the
invention exhibit, in addition to the properties
already mentioned, also good oxidation stability and
thermal stability. This has been determined to DIN EN
ISO 4263-3.
In the context of the invention, the terms "lubricant
composition", "lubricant", "lubricant oil" and
"formulation" are used synonymously.
In addition to the further components mentioned, the
inventive lubricant composition may comprise further
additives which are selected from the group formed by
polymer thickeners, viscosity index improvers,
antioxidants, corrosion inhibitors, detergents,
dispersants, demulsifiers, defoamers, dyes, wear
protection additives, EP (extreme pressure) and AW
(antiwear) additives and friction modifiers.
The invention further provides for the use of the
inventive lubricant composition, especially in the
preferred embodiments, as a vehicle transmission oil,
axle oil, industrial transmission oil, compressor oil,
turbine oil or motor oil. Particular preference is
given to use as a vehicle transmission oil, axle oil,
clutch oil or industrial transmission oil.
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Examples
Examples 1-10 (El-E10):
Comparison of different lubricant compositions
Table 1 shows a compilation of example and comparative
example formulations.
It is found clearly that, based on the high-viscosity
esters HVE I or HVE II, transmission oils of SAE class
75W-90 were formulable with good low-temperature
properties (low dynamic viscosities, all
<300,000 mPa.s; measured at -400C). What is noticeable
is the improved shear stability of the example
formulations (apart from E5 and E6, which are aimed
exclusively at one inventive effect of improving low-
temperature properties and the possibility of utilizing
group III mineral oils instead of PAO 6) as compared
with the comparative example (CE1) . The effect is all
the clearer when it is considered that- CE1 has been
formulated with PIB and OCP systems which are
classified as particularly shear-stable. It is
noticeable that the utilization of high-viscosity
esters makes available formulations with good low-
temperature viscosities likewise by means of PAO 8 or a
group III mineral oil instead of by means of PAO 6 (see
E4, E5, E6). It is found that the utilization of
particular polymers in relatively low concentrations
has synergistic effects on an improvement of low-
temperature viscosities (see E2 in comparison with E3,
E2 in comparison with E7, E2 in comparison with El0 and
E5 in comparison with E6) . This was shown by means of
alkyl methacrylate polymers (see E5 and E6), alkyl
methacrylate-a-olefin copolymers (see E3), alkyl
maleate-a-olefin copolymers (see E7) and by means of
alkyl fumarate-a-olefin copolymers (see E10). In the
case of utilization of alkyl methacrylate polymers, the
shear stability of the formulations was found to be
worse (see E5 and E6), which was attributable to the
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shear of the alkyl methacrylate polymer. It is likewise
apparent that formulations based on HVE II bring
advantages in the mean end of test temperature in the
ARKL test (VW PV 1454) (see CE1 in comparison to E8 and
E9) . This test reflects operating oil temperatures in
transmission and axle applications and is all the more
positive the lower the temperatures observed are. It
was likewise apparent that friction values had
decreased, as had wear as a result of utilization of
the inventive oils. This was shown by means of the
industry standard SRV test (see CE1 in comparison to
E2).
All methods used and the exact names of the feedstocks
used are explained in table 1.
CA 02655040 2008-12-11
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WO 2007/144079 PCT/EP2007/004908
- 17 - PAO 4: Nexbase 2004 from Neste Oil Corp.
PAO 6: Nexbase 2006 from Neste Oil Corp.
PAO 8: Nexbase 2008 from Neste Oil Corp.
HVE I: commercially available high-viscosity ester
with a kinematic viscosity measured at 40 C of
445 mmz/s (e.g. Synative ES 3237 from Cognis)
HVE II: high-viscosity ester with a kinematic viscosity
measured at 40 C of 2000 mm2/s; determined by
known methods by reacting pentaerythritol,
isostearic acid and sebacic acid
DIDA: diisodecyl adipate, e.g. Synative ES DIDA from
Cognis Deutschland Gmbh & Co. KG
Group III mineral oil: Nexbase 3043 from Neste Oil
Corp.
Alkyl methacrylate-a-olefin copolymer I: Viscobase 11-
574 from RohMax
Alkyl methacrylate I: Viscoplex 0-101 from RohMax
Alkyl maleate-a-olefin copolymer I: Gear-Lube 7930
Alkyl fumarate-a-olefin copolymer I: Gear-Lube 7960
Additive package I: Anglamol 6004 J from Lubrizol
PIB I: Lubrizol 8406 from Lubrizol
OCP I: Lubrizol 8407 from Lubrizol
*SRV test conditions:
- SRV1 instrument from Optimol Instruments
Pruftechnik GmbH
- Load increased to 200 N within 22 minutes, 300
N for a further 5 minutes, 600 N for the
remaining 43 minutes; test time: 70 minutes
- Temperature: 100 C
- Sliding path of the sphere: 1.00 mm
- Frequency: 50 Hz
- Material pair: 10 mm diameter sphere on
cylinder with lapped surface
Several motor oils were produced with esters according
to the present invention (E13 - E15) and their
properties were tested. For comparison, the test
results for comparable prior art motor oils (Ell and
CA 02655040 2008-12-11
WO 2007/144079 PCT/EP2007/004908
- 18 -
E12) are listed as well. The results can be found in
table 2 below:
Composition E11 E12 E13 E14 E15
PAO 4 20 47 20 41.5 47
PAO 6 44.2 11.1 44.5 9.8 26
HVE II 3.5 19 15
Group III mineral 20 20 20 17.7
oil
Alkyl 3.5 9.9
methacrylate-a-
olefin copolymer
I
Alkyl 0.3
methacrylate I
Additive package 12 12 12 12 12
I
Results
kinem. visc. 10.77/ 10.59/
100 C (DIN 51562) 7.18 10.61 6.93 10.48 9.50
kinem. visc. 40 C
(DIN 51562) 38.82 61.79 38.71 62.40 59.40
dyn.visc. -35 C 5800 26100 8500
(DIN 51398)
Viscosity index 150 166 140 160 142
Shear stability:
loss of kinemat. 36.81 3.0%
visc. at 100 C
(DIN 51562; CEC
L-45-T-93)
