Industrial Crops and Products 44 (2013) 139–144

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Industrial Crops and Products

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Green synthesis of biolubricant base stock from canola oil

Chandu S. Madankar a,b , Ajay K. Dalai a , S.N. Naik b,∗
a
Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, Saskatoon, SK S7N 5A9, Canada
b
Centre for Rural Development and Technology, Indian Institute of Technology, Hauz Khas, New Delhi 110016, India

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

Article history: A green process for the preparation of biolubricant base stock from canola oil was developed. Three
Received 10 July 2012 branched chain products were synthesized from commercially available canola oil. This process involves
Received in revised form 6 November 2012 two steps, first, the preparation of epoxidized canola oil by using amberlite IR 120 catalyst followed by ring
Accepted 7 November 2012
opening reaction with different alcohols such as n-butanol, amyl alcohol, and 2-ethylhexanol catalyzed
with Amberlyst-15 (dry). These products were confirmed by using FTIR, 1 H and 13 C NMR. The prepared
Keywords:
oleo chemical derivatives show improved low temperature properties determined by measuring pour
Canola oil
point and cloud point. These derivatives were used as additives in low lubricating diesel fuel and the
Biolubricants
Epoxidation
lubricating properties were studied by using HFRR wear scar. These derivatives have good anti-wear and
Lubricity friction reducing properties at relatively low concentrations. Thermal stability of these derivatives was
Ring opening reaction studied by using TGA. The material with higher chain alcohol had shown more lubricity and good thermal
stability. The finding of this study shows that derivatives of epoxy canola oil can be used as a starting
material for the lubricant formulations.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction air, which are potential threat to ecosystem (Nagendramma and

Kaul, 2012). The increased awareness about environment is driving
Renewable raw materials are playing important role in devel- force to develop new techniques and ecofriendly products. Today,
oping environmentally sustainable products. The consumption of the biggest challenge is the development of universal biodegrad-
oils and fats from vegetable and animal origin is increasing, as the able base stock that could replace mineral oil and synthetic
trend is moving towards more eco friendly products. It offers a products. From the better performance point of view these should
large number of possibilities for applications which can be rarely be friendly to the environment and be eventually biodegradable
met by petro chemical resources (Biermann et al., 2000). Lubricants (Woods, 1997). Synthetic oils include others polyalphaolefins,
based on mineral and synthetic oil are widely used in industry, synthetic esters and polyalkylene glycols. Polyalphaolefins are
it consists predominantly of hydrocarbons but also contain some petrochemical derived synthetic oils that mostly resemble mineral
sulphur and nitrogen compounds with traces of a number of met- oils. Synthetic esters form a large group of products, which can
als. Due to their inherent toxicity and non-biodegradable nature be either from petrochemical or oleochemical origin (Lathi and
petrochemical based lubricants poses a constant threat to ecology Mattiasson, 2007). The wide interest in ecofriendly product from
and vast ground water reserves (Adhvaryu et al., 2005). In recent vegetable oils with high content of oleic acid, are considered to be
years, pollution and environmental health aspects have become potential substitutes to conventional mineral oil-based products
increasingly important as public issues. In the area of lubrication, (Randles and Wright, 1992). Vegetable oils are having advantages
the concern is to focus on the issues related to large proportion of good lubricity, biodegradable nature, non toxic, low volatility
of lubricants lost in environment as, 50–60% of the synthetic and high viscosity index over mineral oil, other than its poor oxida-
lubricants are directly comes in to the contact with soil, water and tive, thermal stability and poor cold flow properties (Battersby
et al., 1992; Becker and Knorr, 1996). Attempts have been made to
improve the stability of vegetable oils via transesterification, selec-
tive hydrogenation and epoxidation (Adhvaryu et al., 2005). The
Abbreviations: ECO, epoxidized canola oil; H2 O2 , hydrogen peroxide; BCO, ring synthesis of esters of trimethylolpropane (TMP) with C5–C18 acids,
opening of ECO with n butanol; ACO, ring opening of ECO with amyl alcohol; EHCO, were studied by Akermana et al. (2011) with the aim to provide
ring opening of ECO with 2-ethylhexanol; HFRR, High Frequency Reciprocating Rig; a clean and effective process to produce biolubricants suited for
LLDF, low lubricating diesel fuel; CoF, coefficient of friction.
∗ Corresponding author. Tel.: +91 11 26591162; fax: +91 11 26591121. low temperature applications. The conversion of unsaturation in
E-mail addresses: sn [email protected], [email protected], vegetable oil C C bonds to oxirane ring via epoxidation were stud-
[email protected] (S.N. Naik). ied by Goud et al. (2007). Epoxides have a rich variety of chemical

0926-6690/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
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140 C.S. Madankar et al. / Industrial Crops and Products 44 (2013) 139–144

reactivity, which leads to a wide spectrum of commercial uses for resin, ionic form H+), butanol, amyl alcohol, and 2-ethyl hexanol
these products and it received special attention because of the wide were purchased from Sigma and used without further purification.
range of feasible reactions that can be carried out under moderate Amberlite IR-120H ion exchange resin (Rohm & Haas Co., Philadel-
reaction conditions due to the high reactivity of the oxirane ring. phia, PA, USA) was used for the study.
For instance, the epoxide can react with different nucleophiles
to produce mono-alcohols, diols, alkoxyalcohols, hydroxyesters, 2.2. Analytical methods
N-hydroxyalkylamides, mercaptoalcohols, aminoalcohols, hydrox-
ynitriles (Padwa and Murphree, 2006; Lathi and Mattiasson, 2007). The oxirane oxygen content of each sample was determined
Fatty epoxides can be used directly as plasticizers to improve flexi- using the direct method with hydrobromic acid solution in acetic
bility, elasticity and toughness for the stability of polymer towards acid, and the iodine value was determined using Wijs solution.
heat and UV radiation. Because of the high reactivity of the oxirane Fourier transform infrared (FTIR) spectroscopy experiments were
ring, epoxides act as raw materials for products such as alcohols, performed on canola oil and ECO using a PerkinElmer (Wellesley,
glycols, alkanolamines and carbonyl olefinic compound polymers MA, USA) Spectrum GX instrument equipped with DTGS detector
(Mungroo et al., 2011). Epoxidized vegetable oil can be used as high and a KBr beam splitter. The spectra for each analysis were aver-
temperature lubricants and its ring opening product can be used aged over 64 scans with a nominal 4 cm−1 resolution. 1 H NMR
as low temperature lubricants (Hang and Yang, 1999). Epoxide and 13 C NMR spectra were recorded using a Bruker (Ettlingen,
with higher Oxirane value and lower iodine value is considered to Germany) AMX-500 FT spectrometer. 1 H NMR and 13 C NMR spec-
be of higher quality. Due to the importance of epoxides in polymer tra were recorded using a Bruker (Ettlingen, Germany) AMX-500
and lubricant industry, the industrial scale research of different FT spectrometer. The pour point is measured as per the ASTM D-97
vegetable oils was carried out, most importantly soyabean oil, using K46100 Cloud Point & Pour Point Apparatus. Viscosity of the
which is having as annual production of 200,000 tonnes worldwide samples was measured at 40 ◦ C using a Brookfield model RVTDCP,
(Klaas and Warwel, 1999; Goud et al., 2007). cone and plate viscometer (Brookfield Engineering Laboratories,
Canola is a major crop in Canada and produces Stoughton, MA). The viscometer was calibrated by Cannon certified
about 9.1 million tonnes of the rapeseed variant in 2006 viscosity standard. The weight loss of the sample with respect to
(http://www.canolacouncil.org). Saskatchewan province produces temperature was measured using a PerkinElmer thermo gravimet-
38% of the total canola oil production in western Canada (Kulkarni ric differential thermal analyzer (TG/DTA) under a flow of argon
et al., 2006). Canola oil contains about 60% of oleic acid which is (flow rate of 40 ml/min) at a constant heating rate of 10 ◦ C/min.
advantageous for epoxidation reaction and it is a promising source Lubricity determinations were made at 60 ◦ C (controlled to less
of biolubricant feed stock for chemical industry. The epoxidation than ±1 ◦ C), according to ASTM D 6079 using a PCS Instruments
can be carried out by following methods (1) The epoxidation using (London, UK) High Frequency Reciprocating Rig (HFRR) lubricity
per carboxylic acid which is a well known industrial method, (2) tester. The test ball was visually inspected for wear and the dimen-
with organic and inorganic peroxides, (3) with halohydrin for sions of an observed wear scar (␮m) on the ball were averaged. All
epoxidation of olefins having electron deficient double bonds, wear scar data (Fig. 6) are the averages of two replicates.
which, however, is environmentally unfriendly. (4) The epoxida-
tion with molecular oxygen which is environmentally safe and 2.3. Experimental set-up
clean (Mungroo et al., 2011). Chemical modification of the fatty
chains of the vegetable oil has been shown to affect its lubricating 2.3.1. Epoxidation of canola oil
properties as well as its physical properties, such as pour point Epoxidation reaction was carried out in a three-necked round-
and cloud point (Erhan et al., 2003). The coefficient of friction bottom flask (250 ml capacity), equipped with a magnetic stirrer
of epoxidized soybean oil in hexadecane and poly alpha olefin and placed in a water bath, with temperature controlled to within
significantly reduced and its oxidative stability is also improved ±1 ◦ C of the desired temperatures. The central neck of the flask
compared to their olefinic counterparts (Kurth et al., 2007; Sharma was connected to a reflux condenser, and a thermometer was
et al., 2008). It was reported that the epoxidized vegetable oil introduced through one of the side necks in order to record the
can be used in metal working fluid and as lubricating additives temperature of the reaction mixture.
(Watanabe et al., 1988; Vlcek and Petrovic, 2006). The epoxidation method reported by Goud et al. (2007) was
In the present work the epoxidation of canola oil was carried used. A calculated amount of canola oil (90.4 g) was placed in
out using per carboxylic acid generated in situ and using Amber- the flask, the necessary amount of acetic acid (carboxylic acid
lite IR-120H ion exchange resin as a catalyst. The ring opening of to ethylenic unsaturation molar ratio, 0.5:1) and 22% of catalyst
the epoxidized canola oil was further carried out by using differ- Amberlite IR-120H (based on wt% of canola oil) were added, and
ent alcohols butanol, amyl alcohol, 2-ethyl hexanol with catalyst the mixture was continuously stirred for 30 min at 65 ◦ C. Then, 68 g
Amberlyst 15 (dry). In study we have reported the viscosity, ther- of 30% aqueous hydrogen peroxide (1.5 moles of hydrogen perox-
mal stability, cold flow properties, and tribological behaviour of ide per mole of ethylenic unsaturation) was added dropwise to
these compounds. the reaction mixture at such a rate that the hydrogen peroxide
addition was completed within 30 min. After the complete addi-
tion of hydrogen peroxide, the reaction was continued for 7 h with
2. Materials and methods rapid stirring. The reaction product was filtered and extracted with
diethyl ether in a separating funnel, followed by cold and slightly
2.1. Materials hot water successively to remove free acid, and then analyzed for
oxirane content 5.6%, iodine value 7.5 g I2 /100 g of oil and glycol
Canola oil was supplied by Loblaws Inc. (Montreal, Canada). In content of 0.08 mol/100 g of oil.
addition sources of other chemicals are as follows: glacial acetic
acid (100%) from EMD Chemicals Inc. (Darmstadt, Germany), GR 2.3.2. Ring opening reaction
grade hydrogen peroxide (30 wt%) from EMD Chemicals Inc., Iodine The experimental set-up consisted 100 ml three-necked round-
monochloride and Wijs’ solution were provided by VWR (San bottom flask with the assembly as described above. In a typical
Diego, CA, USA). 33% HBr in acetic acid was obtained from EMD reaction, the epoxidized canola oil (ECO) taken from the above
Chemicals Inc. Amberlyst 15 (Dry) (% water content-1.5 m3 /m3 of experiment (20 g, 0.1 mol of epoxy group), 2% of (w/w of ECO)
 C.S. Madankar et al. / Industrial Crops and Products 44 (2013) 139–144 141

Fig. 1. Comparison of the infrared spectra of the epoxidized canola oil (ECO), product of ring-opening reaction of ECO with n-butanol (BCO), amyl alcohol (ACO), and 2-ethyl
hexanol (EHCO).

catalyst Amberlyst 15 (Dry), and an alcohol was agitated at speed of present at 5.2–5.4 ppm. These have been disappeared in epoxi-
1000 rpm and 100 ◦ C. Clear samples were withdrawn periodically dised canola oil suggests that the C C is converted to epoxide.
and titrated to measure the concentration of epoxide. The reaction Epoxidised canola oil indicates that the epoxy group is present in
was carried out for 15 h and a ring opening product of ECO using the 2.98–3.1 ppm region. The peaks at 2.98–3.1 ppm region repre-
n-butanol, amyl alcohol, and 2-ethylhexanol (BCO, ACO, EHCO) sent the CH-proton attached to the oxygen atom of both epoxy
were further analyzed by FTIR and NMR. groups. The chemical shift of the epoxy group was observed at
2.98–3.1 ppm in epoxidised canola oil. The methine proton of CH2 -
3. Results and discussion CH-CH2 appears at 5–5.2 ppm, CH2 proton adjacent to two epoxy
group at 2.8–3.0 ppm, CH proton of epoxy group at 3.1–3.2 ppm,
3.1. Characterization of product ␣-CH2 to epoxy group at 1.7–1.9 ppm, ␤-CH2 to epoxy group at
1.4–1.6 ppm, terminal CH3 group at 0.8–1.0 ppm. The ring opening
3.1.1. FT-IR spectroscopy product BCO retain most of the characteristic peaks except peak of
Canola oil has the characteristic peak at 3007 cm−1 attributed hydrogen attached to the epoxy group at 2.8–3.2 ppm and methy-
to the C H stretching of the double C C H. The peak at 3007 cm−1 lene group adjacent to epoxy at 1.4–1.6 ppm (Fig. 2). The 13 C NMR
disappeared after the reaction and is indicating that almost all spectra of canola oil and epoxidised canola oil shown in Fig. 3 reveal
C C bonds had taken part in the epoxidation reaction (Fig. 1). the complete disappearance of the olefin carbon atom between 100
The new peaks appeared at 823 cm−1 , attributed to the epoxy and 150 ppm in final product, when compared with the starting of
group. The other new peak at the 3463 cm−1 was attributed to canola oil. Also, the ECO show signals between 53 and 60 ppm, in
the hydroxyl O H stretching, indicating that the epoxy group is addition to the glycerol carbon signal at 68 and 62 ppm for the beta
opened. The intensity of the 3463 cm−1 band indicated the extent and alpha atoms respectively. These additional peaks, which are
of hydroxyl group of epoxidized canola oil. Vlcek and Petrovic completely absent at the starting Canola Oil, are due to the epoxy or
(2006) reported the presence of epoxy groups at 822–833 cm−1 , glycol carbon of the ECO. Ring opening product BCO does not show
which agreed well with this spectrum, where the epoxy group was the above peaks due to the conversion of epoxy group to hydroxyl
detected at 823 cm−1 . The ring opening reactions with different group (Fig. 3).
alcohols were confirmed by FTIR spectra of the starting material
and product. Fig. 1 shows the loss of the epoxide bands from 827 3.1.3. Viscosity
to 840 cm−1 , and the corresponding increase in the ester carbonyl The physicochemical properties of the ECO, BCO, ACO, EHCO are
at 1740 cm−1 , confirming the ester structure of the product. Addi- listed in Table 1. The kinematic viscosity of the product was mea-
tionally, an increase in the hydroxyl group band at 3500 cm−1 was sured at 40 ◦ C using a Brookfield model RVTDCP, cone and plate
the confirmation of the product. viscometer. The viscosity is a paramount property of a lubricant.
In this case it follows the order BCO > ACO > ECO > EHCO (Table 1).
3.1.2. NMR spectroscopy The alcohols having less number of carbon atoms are having more
1 H NMR and 13 C NMR confirmed the formation of epoxide prod- viscosity. This may be due to more polar structure of BCO which
uct of canola oil. The olefinichydrogens (CH CH) of canola oil is results in stronger intermolecular bonds.
142 C.S. Madankar et al. / Industrial Crops and Products 44 (2013) 139–144

Fig. 2. Comparison of the 1 H NMR spectra of the epoxidized canola oil ECO (a), product of ring-opening reaction of ECO with n-butanol BCO (b), amyl alcohol ACO (c), and
2-ethyl hexanol EHCO (d).

Table 1 3.1.4. Low temperature properties

Viscosity and low temperature properties of hydroxy ester products.
The pour point and cloud point are important parameters of the
Product Kinematic viscosity Pour point (◦ C) Cloud point (◦ C) lubricants. The cold flow properties of the vegetable oils are poor
40 ◦ C (mm2 s−1 ) and thus limits their use in subzero temperature. The cold flow
ECO 151 10 14 properties can be improved by adding chain lengths or by branch-
BCO 251.7 −5 −2 ing of the fatty acid chain. Also improvement in low temperature
ACO 190.5 −8 −3 flow behaviour of fatty acid esters can be achieved by attaching
EHCO 85.5 −15 −11
ester branching at the double bond sites on the fatty acid chains.

Fig. 3. Comparison of the 13 C NMR spectra of the epoxidized canola oil ECO (a), product of ring-opening reaction of ECO with n-butanol BCO (b), amyl alcohol ACO (c), and
2-ethyl hexanol EHCO (d).
 C.S. Madankar et al. / Industrial Crops and Products 44 (2013) 139–144 143

Fig. 4. Coefficient of friction (CoF) data on 5 wt% concentrations of hydroxy ester Fig. 5. Wear scar diameter (wsd) of 5 wt% concentrations of hydroxy ester products
products in low lubricity diesel fuel (LLDF) obtained using High Frequency Recipro- in low lubricity diesel fuel (LLDF) obtained using High Frequency Reciprocating Rig
cating Rig (HFRR) configuration: load 200 g, 50 Hz, temperature 60 ◦ C, 75 min. (HFRR) configuration: load 200 g, 50 Hz, temperature 60 ◦ C, 75 min.

ECO is having a pour point of 10 ◦ C as it tends to crystallize at room starts functioning towards the metal to metal contact process and
temperature. The pour point of BCO, ACO, and EHCO are −5, −8, and molecules developed anti-frictional film thereby reducing friction
−15 ◦ C respectively. Attachment of an ester side chain, with opti- and wear.
mum length and medium branched chain alcohol (2-ethyl hexanol)
at the 9–10 position of the fatty acid chain improves the pour point 3.1.6. Thermogravimetric analysis
significantly. It is due to the presence of a large branching point on Thermal behaviour of the hydroxy ester products were studied
the fatty acid ester creates a steric barrier around the individual using a PerkinElmer thermo gravimetric differential thermal ana-
molecules and inhibits crystallization, resulting in lower pour and lyzer (TG/DTA) under a flow of argon (flow rate of 40 ml/min) at a
cloud point (Table 1). The introduction of butanol and amyl alcohol constant heating rate of 10 ◦ C/min. Fig. 6 shows the thermogram
did not lower the pour point significantly; this may be due to the of the epoxidized canola oil (ECO), and products of ring-opening
polar nature of the structure and higher viscosity. reaction with different alcohols. It is clear from the graph that
ECO is thermally stable below the temperature of 320 ◦ C. 95% of
3.1.5. Friction and wear properties weight loss was observed for the material ECO in the tempera-
The important property of lubricants is to maintain a stable ture range of 320–445 ◦ C. The corresponding ring opening products
lubricating film at the metal contact zone which can prevent the BCO, ACO, and EHCO are thermally stable below the temperature of
wear of metal surfaces. Vegetable oils and fatty acid esters are 355 ◦ C, 361 ◦ C and 405 ◦ C and about 94% of weight loss was observed
known to provide excellent lubricity due to their ester functional- for each material within the temperature range of 355–475 ◦ C,
ity. The lubricating properties of hydroxy ester derivatives of canola 361–510 ◦ C and 405–516 ◦ C respectively. It can be seen that the TGA
oil were studied using 60 ◦ C (controlled to less than ±1 ◦ C), accord- curves of all the samples have similar behaviour which is summa-
ing to ASTM D 6079 using a PCS Instruments (London, UK) High rized in Table 2.
Frequency Reciprocating Rig (HFRR) lubricity tester. The HFRR test
involves a steel ball and a static steel disk submerged in a tested 3.1.7. Reusability of catalyst
sample at a temperature of 60 ◦ C. The test ball oscillates against The catalyst Amberlite IR 120 and Amberlyst 15 (dry) was used
the disk with a constant frequency of 50 Hz for 75 min. The wear in epoxidation of canola oil and its ring opening reaction respec-
scar diameter left on the ball after performing the test is mea- tively. Both the catalyst was tested for reusability and stability.
sured by means of a microscope and is reported as the HFRR test After reaction the catalyst was filtered and washed with water and
result (Madankar et al., 2013). Samples BCO, ACO, EHCO were tested diethyl ether. The washed catalyst was refluxed with alcohol to
two times at 5.0% concentration in reference to low lubricity diesel
fuel (LLDF). The lubricating property of hydroxy ester products as
additives in low lubricating diesel fuel (LLDF) is demonstrated by
the coefficient of friction (CoF) obtained using the HFRR experi-
ment. The CoF values of BCO, ACO, and EHCO are 0.12, 0.1, and
0.08 respectively, a considerable improvement over the value of
0.4 observed for neat LLDF. The CoF values reported in Fig. 4 are
averages of two independent experiments. Initially the wear scar
diameter of LLDF was 651 ␮m, after addition of 5%, it improves
to 196 ␮m, 158 ␮m and 161 ␮m for BCO, ACO and EHCO respec-
tively (Fig. 5), thus the addition of small amount of hydroxyl ester
product improves the lubricity of diesel fuel significantly, and low-
ered the wear scar diameter by more than 400 ␮m in all cases. It
can be noticed that, as the branching chain length of the hydroxyl
derivative increases (EHCO), the ester become more effective, and it
shows improved tribological properties. The increased in lubricity
of the hydroxy ester product may be caused by the two extra polar
functional groups apart from the ester group of fatty acid ester.
Oxygen moieties, like the hydroxy and ester functionalities at 9, 10
Fig. 6. TGA thermogram of the epoxidized canola oil (ECO), product of ring-opening
positions on the fatty acid, help the compounds adhere to the metal reaction of ECO with n-butanol (BCO), amyl alcohol (ACO), and 2-ethyl hexanol
surface and reduce friction. The active group of the compounds (EHCO).
144 C.S. Madankar et al. / Industrial Crops and Products 44 (2013) 139–144

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ECO 320 330–365 375–445 biodegradability of oil products in the CEC L-33-T-82 and modified sturm tests.
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