Industrial Crops and Products 35 (2012) 237–240

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Industrial Crops and Products

journal homepage: www.elsevier.com/locate/indcrop

10-Undecenoic acid-based polyol esters as potential lubricant base stocks

Korlipara V. Padmaja a , Bhamidipati V.S.K. Rao a , Rondla K. Reddy a , Potula S. Bhaskar a ,
Arun K. Singh b , Rachapudi B.N. Prasad a,∗
a
Centre for Lipid Research, Indian Institute of Chemical Technology, Hyderabad 500 007, India
b
Indian Institute of Petroleum, Dehradun 248 005, India

a r t i c l e i n f o a b s t r a c t

Article history: A new class of polyol esters were prepared by esterification of 10-undecenoic acid (UDA) with three
Received 15 February 2011 polyols namely trimethylolpropane (TMP), neopentyl glycol (NPG) and pentaerythritol (PE) in 92–96%
Received in revised form 2 July 2011 yields. The esters were characterized by IR, 1 H NMR, HPLC and mass spectral studies. Polyol esters were
Accepted 5 July 2011
evaluated for basic lubrication properties and found to be: viscosity at 40 ◦ C, 11.2–36.1 cSt; at 100 ◦ C,
Available online 29 July 2011
3.2–7.3 cSt; viscosity index (VI), 162–172; pour point +3 to −36 ◦ C; flash point, 254–296 ◦ C. All the three
polyol esters synthesized exhibited good thermal stability with TGA onset temperatures above 260 ◦ C.
Keywords:
The lubricating properties of the products compared well with polyol esters based on oleic acid.
Biolubricant
Polyol esters © 2011 Elsevier B.V. All rights reserved.
Neopentylglycol
Trimethylolpropane
Pentaerythritol
Undecenoic acid

1. Introduction
In recent years, natural triglycerides are getting increased atten-
tion as they are generally environment friendly and their lubricity
(antiwear, antifriction and load carrying capacity) characteristics
are vastly superior to those of mineral oil based lubricants (Arnsek
and Vizintin, 2000). However, glycerol, a component of the triglyc-
eride molecule is readily destructible at high temperatures. This
disadvantageous property stems from the presence of hydrogen
atoms in ␤ position in the glycerol molecule (Bünemann et al.,
2000). This structural feature is conducive to the partial fragmenta-
tion of the molecule and the formation of unsaturated compounds.
The compounds formed undergo polymerization, increasing the
liquid’s viscosity and resulting in the formation of precipitate parti-
cles. This problem can be solved by replacing glycerol with another
polyhydric alcohol which does not contain ␤-hydrogen atoms, like
NPG, TMP or PE. Although such alcohols also decompose at high
temperatures, their thermal decomposition has a radical charac-
ter and proceeds slowly (Wilson, 1998). Polyol esters are produced
by the reaction of polyols such as PE, NPG, and TMP with various
fatty acids. The fatty acids are generally obtained by the saponi-
fication of animal oils such as beef tallow, lard, mutton tallow or
from vegetable oils like sunflower oil, rapeseed oil, castor oil, olive
∗ Corresponding author. Tel.: +91 040 27193179; fax: +91 040 27193370.
E-mail address: rbnprasad@iict.res.in (R.B.N. Prasad).
oil, palm kernel oil, and coconut oil. The fatty acids derived from
these oils and fats are saturated acids like lauric, myristic, palmitic,
stearic, behenic acids or olefinic fatty acids such as oleic, linolenic
or ricinoleic acids.
Biodegradable polyol esters derived from transesterifica-
tion/esterification of plant oils and branched neopolyols such as
TMP and PE were developed for various applications (Bongardt
et al., 1996; Gryglewicz et al., 2003; Lawate and Lal, 1998;
Uosukainen et al., 1998; Yunus et al., 2003a,b, 2004). The properties
of the esters depend on the structure of the constituent fatty acids
i.e. on the length of the aliphatic chain and the number and relative
position of unsaturated bonds. Saturated acids are highly resistant
to oxidation at high temperature, but their pour point is high due
to the linear structure of the acids. Polyunsaturated fatty acids are
the most susceptible to oxidation and thermal degradation, even
though their esters exhibit lower pour points. To make polyol esters
based on vegetable and animal fats like rapeseed oil, olive oil and
lard fatty acid methyl esters were transesterified with NPG and
TMP using calcium methoxide as catalyst (Gryglewicz et al., 2003).
Esters of lard fatty acids showed higher pour points because of their
high saturated acid content. Vegetable oils with high oleic content
are considered to be potential candidates as substitutes for con-
ventional mineral oil-based lubricating oils and synthetic esters
(Asadauskas et al., 1996; Randles and Wright, 1992). Lower prices
of non-edible natural oils and fats make biodegradable lubricants
much more competitive in the market (Petran et al., 2008). Polyol
esters reported in the literature are mostly based on normal fatty

0926-6690/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.indcrop.2011.07.005
238 K.V. Padmaja et al. / Industrial Crops and Products 35 (2012) 237–240
acids present in the common edible vegetable oils and animal fats
or short chain fatty acids like C5 and C7. Little attention was given
for the preparation of non-edible oil-based polyol esters contain-
ing any unusual fatty acids. Hence, the present study is aimed at
employing 10-undecenoic acid, which is a commercially available
derivative of castor oil for the synthesis of polyol esters using NPG
(dihydric), TMP (trihydric) and PE (tetrahydric) and to assess the
potential of the synthesized esters as basestocks for biodegradable
lubricants.
2. Materials and methods
2.1. Materials
10-Undecenoic acid was purchased from Jayant Oil Mills
Ltd. (Mumbai, India), NPG, TMP and PE were procured from
Sigma–Aldrich (St. Louis, USA). Basic alumina and stannous chloride
were purchased from Sd Fine Chem Ltd. (Mumbai, India). Hex-
ane and ethyl acetate were purchased from Industrial Solvents
and Chemicals Pvt. Ltd. (Mumbai, India). All the chemicals were of
reagent grade and were used directly without further purification.
2.2. Analysis
1H
NMR spectra were obtained using a Bruker AR X 400 Spec-
trometer (400, 200 MHz). IR spectra were recorded on a Perkin
Elmer (Model: Spectrum BX; Connecticut, USA) FT-IR spectrometer
neat as thin film. Mass spectra were recorded on a VG Auto Spec-
M (Manchester, UK) and data is given in mass units (m/z). HPLC
analysis was performed on an Agilant 1200 series system equipped
with an evaporative light scattering detector (Alltech ELSD 2000,
Deerfield, IL, USA). C-18 Reverse phase column (250 mm × 4.5 mm,
5.0 ␮ particle size) was used for the analysis of the polyol esters
using solvent system acetonitrile–DCM (60:40) at a flow rate of
1 ml min−1 ; 30 min. Colour was measured using Lovibond PFX 995
Tintometer and density by Anton Paar DMA 4500M density meter.
The hydroxyl value was determined by AOCS Official Method Cd
13-60 and acid value by Cd 3d-63.
2.3. Viscosity
Viscosity measurements were made at 40 and 100 ◦ C using
Cannon Fenske viscometer tubes in a Cannon Constant Tem-
perature Viscosity Bath (Cannon Instrument Co., State College,
PA). Viscosity and the viscosity index were calculated using
ASTM methods D445 and D2270, respectively. All viscosity mea-
surements were made in triplicate, and the average value was
reported.
2.4. Pour point
Pour points were determined by ASTM method D97 with an
accuracy of ±3 ◦ C using Automatic Pour Point Tester manufactured
by Dott. Gianni Scavini & Co., Italy. All the runs were carried out in
duplicate. Sample temperature was measured in 3 ◦ C increments at
the top of the sample until it stopped pouring.
2.5. Flash point
Flash point of the products was determined using Koehler Inc.
apparatus as per ASTM D 93 method. The lowest temperature at
which application of the test flame causes the vapour above the sur-
face of the liquid to ignite is taken as the flash point of the product
at ambient barometric pressure.
2.6. Oxidation stability by Rotating Bomb Oxidation Test (RBOT)
Rotating Bomb Oxidation Tests (RBOTs) of the products are car-
ried out in presence of copper catalyst at 150 ◦ C in dry conditions
as per ASTM Test Method D-2272. In the RBOT, the vessel is sealed,
charged with 90 psi pressure with oxygen, and rotated axially in
a constant temperature oil bath set at 150 ◦ C. The pressure in the
bomb is continuously recorded. The RBOT time is the time at which
the pressure of the bomb has dropped by 25 psi.
2.7. Thermogravimetric Analysis (TGA)
TGA studies were carried out in non-isothermal mode in a Met-
tler Toledo TGA instrument to get the decomposition pattern of
the polyol esters. About 3.0 mg of the sample was taken in an
aluminium crucible and was heated in air at the heating rate of
10 ◦ C min−1 up to 600 ◦ C. The starting temperature and comple-
tion of the decomposition of polyols were obtained from TGA
curve.
2.8. Copper strip corrosion test
Determination of corrosiveness of the products was done using
Koehler Inc. apparatus as per ASTM D 130 method. A polished Cu
strip was immersed in 30 ml of the sample being tested at 100 ◦ C
for 3 h. After 3 h, the Cu strip was removed, washed and the colour
and tarnish level were assessed against the ASTM Copper Strip Cor-
rosion Standard.
2.9. Synthetic methods
2.9.1. Preparation of neopentylglycol diesters of 10-undecenoic
acid (NPG-di-undecenoate)
Neopentylglycol (52 g, 0.5 mol), 10-undecenoic acid (368 g,
2.0 mol) and xylene (500 ml) were stirred at 145–150 ◦ C under
nitrogen atmosphere in presence of stannous chloride (0.42 g) for
6 h. The course of the reaction was monitored by TLC and after
completion of the reaction, the yielded crude product was dis-
tilled at 140–145 ◦ C and 2–3 mmHg to remove xylene and excess
10-undecenoic acid. The product was passed over basic alumina to
remove the residual undecenoic acid to obtain the product in 95.5%
yield. The structure of the title product was established by 1 H NMR
and IR and mass studies.
1 H NMR (CDCl , ı ppm): 0.87 [s, 6H, (–CH ) ], 1.2–1.4 [m,
3 3 2
20H, 2 × (–CH2 )5 ], 1.6 [m, 4H, 2 × (–CO–CH2 –CH2 )], 2.0 [q, 4H,
2 × (–CH2 –CH CH2 )], 2.3 [t, 4H, 2 × (–CO–CH2 –)], 3.8 [s, 4H,
2 × (–O–CH2 –)2 ], 4.9–5.0 [m, 4H, 2 × (–CH CH2 )], 5.6–5.8 [m,
2H,2 × (–CH CH2 )]; IR (neat, cm−1 ): 2927 (C–H), 1741 (C O), 1161
(C–C( O)–O); ESI MS: m/z 454 [M+NH4 ]+ .
2.9.2. Preparation of trimethylolpropane triesters of
10-undecenoic acid (TMP-tri-undecenoate)
Trimethylolpropane (67 g, 0.5 mol), 10-undecenoic acid (552 g,
3.0 mol) and xylene (500 ml) were stirred at 145–150 ◦ C under
nitrogen atmosphere in presence of stannous chloride (0.62 g) and
carried out the reaction as described in Section 2.9.1 to obtain the
product in 96.2% yield. The structure of the title product was estab-
lished by 1 H NMR, IR and mass studies.
1 H NMR(CDCl , ı ppm): 0.9 [t, 3H, –CH ], 1.2–1.5 [m, 32H,
3 3
CH3 –CH2 –, 3 × (–CH2 –)5 ], 1.5–1.7 [m, 6H, 3 × (–CO–CH2 –CH2 )], 2.0
[q, 6H, 3 × (–CH2 –CH CH2 )], 2.3 [t, 6H, 3 × (–CO–CH2 –)], 4.0 [s, 6H,
3 × (–O–CH2 –)], 4.9–5.0 [m, 6H, 3 × (–CH CH2 )], 5.7–5.8 [m, 3H,
3 × (–CH CH2 )]; IR (neat, cm−1 ): 2927 (C–H), 1741 (C O), 1164
(C–C( O)–O); ESI MS: m/z 650 [M+NH4 ]+ .
 K.V. Padmaja et al. / Industrial Crops and Products 35 (2012) 237–240
Table 1
Physico-chemical properties of 10-undecenoic acid based polyol esters.
Property NPG-di-undecenoate
TAN (mg KOH/g) 0.05
Hydroxyl Value (mg KOH/g) 0.3
Colour ASTM D-1500 1.0
Density @ 150 ◦ C ASTM D-4052 0.9231
Viscosity at 40 ◦ C, cSt 11.2
Viscosity at 100◦ C, cSt 3.2
Viscosity index 162
Pour point (◦ C) −33
Flash point (◦ C) 254
Copper strip corrosion 1a
TGA onset temperature (◦ C) 264
2.9.3. Preparation of pentaerythritol tetra esters of
10-undecenoic acid (PE-tetra-undecenoate)
Pentaerythritol (68 g, 0.5 mol), 10-undecenoic acid (736 g,
4 mol) and xylene (800 ml) were stirred at 145–150 ◦ C under nitro-
gen atmosphere in presence of stannous chloride (0.8 g) and carried
out the reaction as described in Section 2.9.1 to obtain the product
in 91.6% yield. The structure of the title product was established by
1 H NMR, IR and mass studies.
1 H NMR (CDCl , ı ppm): 1.1–1.4 [m, 40H, 4 × (–CH ) ], 1.5–1.6
3 2 5
[m, 8H, 4 × (–CO–CH2 –CH2 )], 2.0 [q, 8H, 4 × (–CH2 –CH CH2 )], 2.3 [t,
8H, 4 × (–CO–CH2 –)], 4.0 [s, 8H, 4 × (–O–(CH2 –)], 4.8–4.95 [m, 8H,
4 × (–CH CH2 )], 5.6–5.8 [m, 4H, 4 × (–CH CH2 )]; IR (neat, cm−1 ):
2928 (C–H), 1739 (C O), 1162 (C–C( O)–O); ESI MS: m/z 818
[M+NH4 ]+ .
3. Results and discussion
Polyol esters derived from plant oils and branched neopoly-
ols have been used as lubricants and they are expanding their
applications because of their superior properties and performance
relative to mineral oils. Most of the vegetable oil-based polyol
esters reported in the literature so far are mainly based on high
oleic oils such as sunflower, canola and soybean oils. These high
monounsaturated oils are optimal performance raw materials to
generate environment friendly higher performance lubricants. At
the same time, these oils are edible and their use for the develop-
ment of lubricants indirectly burden the food sector. I0-Undecenoic
acid which is a derivative of castor oil is also a monounsat-
urated fatty acid like oleic acid and commercially available in
bulk. Hence, the polyol esters developed based on undecenoic
acid are expected to have similar lubricant properties compared
to oleic polyol esters. Keeping this in view, we have developed
UDA-based polyol esters with dihydric, trihydric and tetrahydric
alcohols namely, NPG, TMP and PE in presence of stannous chloride
(0.1% based on reactants) under nitrogen atmosphere. Comple-
tion of the esterification reaction was monitored by collecting
the generated water using Dean Stark apparatus and by check-
ing disappearance of the hydroxy group at 3450–3480 cm−1 in the
infrared spectrum and also by TLC. After completion of reaction,
excess 10-undecenoic acid was distilled out under reduced pres-
sure. The yield of polyol esters was found to be in the range of
91.6–96.2%. The synthesized compounds were characterized using
IR, NMR and mass spectral data. The molecular ions 454 [M+NH4 ]+ ,
650 [M+NH4 ]+ and 818 [M+NH4 ]+ correspond to compounds NPG-
di-undecenoate, TMP-tri-undecenoate and PE-tetra-undecenoate
respectively. Purity of the polyol esters was determined by HPLC
analysis and found to be more than 98% pure. Hydroxy values
(<1.0 mg KOH/g) of polyol esters confirmed almost complete ester-
ification of hydroxy moiety of polyols with UDA. All the polyol
esters were characterized for their physico-chemical properties like
239
TMP-tri-undecenoate PE-tetra-undecenoate
0.05 0.1
0.3 0.7
1.0 1.0
0.9313 0.9480
23.8 36.1
5.3 7.3
165 172
−36 +3
286 296
1a 1a
336 390
total acid number, hydroxy value, density and colour and evalu-
ated for lubricant properties namely, viscosity, viscosity index (VI),
pour point, flash point, copper corrosion value and thermal stability
(Table 1).
NPG, TMP and PE undecenoates exhibited their kinematic vis-
cosity at 40 ◦ C in the range of ISO VG10, 22 and 32, respectively.
At 100 ◦ C the viscosity varied from 3.2 to 7.3 cSt. Viscosity of the
polyol ester base fluids generally increases based on the number of
acyl functionalities present (Gryglewicz et al., 2003) and UDA based
esters prepared with NPG, TMP and PE exhibited similar trend. All
the three synthesized esters exhibited high viscosity index of more
than 160 which is a desirable property for a lubricant as a high
viscosity index means that there is little change over a wide tem-
perature range. Base oils based on natural fatty acids in general
are known for their high viscosity index and can be considered
multi-range oils.
Generally, pour point of polyol esters prepared with unsatu-
rated fatty acids are very low and a similar trend was observed
for the pour points of NPG di-undecenoate (−33 ◦ C) and TMP tri-
undecenoate (−36 ◦ C). However, the pour point of UDA esters of
pentaerythritol is high. This is suggesting that the molecular con-
figuration of NPG and TMP esters are more effective at disrupting
molecule packing compared to PE esters. The flashpoint of all the
UDA based polyol esters is above 250 ◦ C indicating a low tendency
to evaporation which fulfils one of the basic requirements of lubri-
cants. Corrosiveness of the products is found to be very good (1a)
for all the three polyol esters.
NPG-di-undecenoate and TMP-tri-undecenoate exhibited RBOT
time of 12 and 15 min respectively and these values are similar to
common vegetable oils like canola and high oleic or synthetic esters
like TMP trioleate (Mckeon et al., 2007). The TGA study was con-
ducted in a non-isothermal mode to assess the thermal stability
of the polyol undecenoates. The TGA degradation onset temper-
ature indicates the resistance of the oil to thermal degradation.
This was determined by extrapolating the horizontal base line and
intercept of this line with tangent to the downward portion of the
weight curve was taken as onset temperature. The higher the onset
temperature of decomposition of lube basestock, the higher is its
thermal stability. The pentaerythritol esters of UDA possess excel-
lent thermal stability with onset temperature at 390 ◦ C followed by
TMP esters at 336 ◦ C and NPG at 264 ◦ C. These esters followed the
trend of decreasing order of thermal stability with PE esters having
higher thermal stability followed by TMP and NPG esters (Brown
et al., 2009).
Among the three polyol esters of undecenoic acid, TMP esters
exhibited superior pour point and better oxidation stability which
is similar to that of TMP trioleate (Mckeon et al., 2007) With its high
viscosity index, high thermal stability and low pour point this UDA
triester can be a potential biodegradable lubricant basestock in ISO
VG 22 range for industrial fluids.
240 K.V. Padmaja et al. / Industrial Crops and Products 35 (2012) 237–240
4. Conclusions
A new class of unsaturated medium chain fatty acid polyol esters
were prepared by esterification of 10-undecenoic acid with three
different polyols in 92–96% yields with high purity (98%). Among
the three polyol esters, TMP esters of UDA exhibited superior lubri-
cant properties like low pour point, high flash point and better
oxidation stability. The TMP tri ester of UDA exhibited similar oxi-
dation stability compared to TMP trioleate. The undecenoic acid
based polyol esters are found suitable for high performance lubri-
cant base stocks.
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