Industrial Crops & Products 107 (2017) 378385

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Industrial Crops & Products

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Camelina (Camelina Sativa) oil polyols as an alternative to Castor oil MARK

Tolibjon S. Omonov, Ereddad Kharraz, Jonathan M. Curtis
Lipid Chemistry Group (LCG), Department of Agricultural, Food and Nutritional Science (AFNS),University of Alberta, Edmonton, Alberta T6G 2P5 Canada

A R T I C L E I N F O A B S T R A C T

Keywords: Castor oil is a natural polyol and widely used in many applications. Although castor oil is a renewable biobased
Castor oil product, its production is geographically limited to tropical regions, resulting in uctuations in supply and price
Camelina oil stability. This work explores the possibility of the production of castor oil alternatives from camelina oil grown
Biobased polyol in temperate regions as an industrial crop and its subsequent use in polyurethane formulations. Castor oil re-
Castor oil replacement
placement polyols were produced from camelina oil via controlled epoxidation using in-situ generated performic
Plant oil polyol
acid and a subsequent hydroxylation via acid catalyzed epoxy ring opening with alcohol. The viscosity and
hydroxyl functionality of camelina oil polyol was targeted to match castor oil since these parameters dictate the
performance of these polyols as drop-in replacements. The reaction of camelina oil polyols and castor oil with
polymeric diphenylmethane diisocyanate to produce polyurethane was studied via their rheological behavior
during curing, which indicated their relative reactivities. In polyurethane applications, it was found that whilst
camelina oil polyols showed lower reactivity towards isocyanates, reactivity can be readily adjusted to match
castor oil by the addition of small amount of common catalysts. The thermo-mechanical properties of cured
polyurethanes from camelina oil polyols (expressed via glass transition temperature) were evaluated using
dierential scanning calorimetry and found to signicantly exceed those made using castor oil. Overall, this
study demonstrates that polyols from camelina oil can be produced with a range of viscosities and hydroxyl
functionalities and are suitable to replace castor oil in polyurethane applications. The ability to adjust these
parameters oers a signicant advantage over castor oil.

1. Introduction used as a feedstock in the production of specialty monomers for en-

Castor oil is an inedible industrial oil that is used in many com-
mercial applications (McKeon et al., 2016; Vignolo, 1992). It is ob-
tained by processing the seeds of the castor oil plant Ricinus communis.
A large proportion of castor oil is produced in the countries with nearly
tropical climates such India, China, and Brazil. Annual worldwide
production of the castor oil has reached its maximum of 705 Mt in
2015/2016 but was projected to decrease to 655 Mt in 2016/2017 due
to the production decit in India and Brazil. However, the annual
consumption of castor oil remains at at the levels of 690 Mt (Mielke,
2017).
Castor oil is a naturally occurring polyol that has typical tria-
cylglyceride structure but also with unique fatty acid prole. The ma-
jority of castor oil fatty acids are 18-carbon fatty acids and primarily
(90%) consist of ricinoleic acid ((R,Z)-12-hydroxyoctadec-9-enoic
acid), which is unsaturated -9 fatty acid with a secondary hydroxyl
functionality at carbon-12 position (Scheme 1).
Castor oil and its derivatives are widely used in many commercial
applications with or without modications. For example, castor oil is
gineering plastics and synthetic nylon bers; in polyurethane (PU)
foams and coatings; in the production of waxes, polishes, greases, lu-
bricants, surfactants, detergents, inks; in personal care products, cos-
metics and pharmaceuticals etc.
Due to the high concentration of ricinoleic acid in the oil, the che-
mical transformation of castor oil is usually focused on modications of
hydroxyl groups (Mubofu, 2016; Vignolo, 1992) via esterication re-
actions. The esterication of castor oil (Erciyes et al., 1991; Erdem-
Senatalar et al., 1994; Isbell and Cermak, 2002; Kulkarni and Sawant,
2003) or castor oil fatty acids by fatty acids of various chain-length
(Modak and Kane, 1965) to make estolides has been reported. The
hydroxyl groups of castor oil can also be acetylated (Grummitt and
Fleming, 1945) or alkoxylated (Zhang et al., 2015). The elimination of
castor oils hydroxyl groups by dehydration, resulting in double bond
formation, was described (Bhowmick and Sarma, 1977); this leads to
the formation of a conjugated oil that can be used to produce drying oils
(Grummitt, 1957). In addition, chemical alteration of the unsaturation
in castor oil via hydrogenation (Alwaseem et al., 2014; Patterson, 2009;
Sreenivasan et al., 1957), via epoxidation of castor oil (Borugadda and

Corresponding author at: 360D South Academic Building (SAB), University of Alberta Edmonton, Alberta, Canada.
E-mail address: jcurtis1@ualberta.ca (J.M. Curtis).

http://dx.doi.org/10.1016/j.indcrop.2017.05.041
Received 31 March 2017; Received in revised form 8 May 2017; Accepted 21 May 2017
Available online 15 June 2017
0926-6690/ 2017 Elsevier B.V. All rights reserved.
T.S. Omonov et al. Industrial Crops & Products 107 (2017) 378385

Scheme 1. Conceptual structure of castor oil.

Goud, 2015; Jankovic et al., 2014; Sinadinovic-Fiser et al., 2012) and

castor FAMEs (Borugadda and Goud, 2014) or via vulcanization of
castor oil (Zhao et al., 2016) were also reported. Although castor oil is a
renewable biobased product, its production is geographically limited in
tropical regions, resulting in large uctuations in supply and price.
Furthermore, since castor beans also contain ricin, which is highly toxic
to humans and animals, there are considerable regulations restricting
the expansion of its production.
The main aim of this work is to produce polyols from camelina oil,
which could serve as an alternative to castor oil in certain applications.
Camelina sativa is grown as non-food grade crop in some parts of the
Europe and North America, although the use of cold-pressed camelina
oil as a food ingredient is also allowed, for example in Canada (Health
Canada, 2017). Camelina oil contains a high percentage of unsaturates
(see Table 1) with an iodine value (IV) of about 151 mg I2/g oil. For- Scheme 2. The strategy used to produce the castor oil replacement polyol from vegetable
tuitously, the levels of unsaturates found in camelina oil are such that oil having oleic, linoleic and linolenic acids. (A)-conceptual structure of the oil, (B)-
following hydroxylation they can produce polyols with hydroxyl partially epoxidized oil and (C)-castor oil replacement polyol (COROL).
numbers and physical properties that approximately match those of
castor oil (Curtis et al., 2015b). In this research, the controlled epox- functionality, were targeted to match those of castor oil. These para-
idation of the camelina oil followed by epoxy ring opening of epoxides meters determine the suitability of COROL as versatile alternative to
with alcohols were used to produce castor oil replacement polyols, re- castor oil in polyurethane applications.
ferred to as COROL. Scheme 2 represents the overall concept of the
COROL synthesis process from vegetable oil.
It is evident from Scheme 2 that COROL polyol does not have a 2. Experimental
structure that is identical to triricinolein, so cannot be used as a starting
material for some castor oil derivatives, such as 12-hydroxystearic acid 2.1. Materials
(12-HSA) used in the production of Nylon. However, there are many
applications for which the physical properties and reactivity of COROL Camelina oil (rened, bleached and deodorized) was provided by
are a suitable alternative to castor oil. Linnaeus Plant Sciences (Vancouver, BC, Canada) and was used as
Thus, this work explores the possibility of the production of castor supplied. Castor oil was acquired from Columbus Vegetable Oils (Des
oil alternatives from camelina oil, and its subsequent use in poly- Plaines, IL, USA). Formic acid (85%) and aqueous H2O2 (35%) were
urethane formulations. Two main parameters, viscosity and hydroxyl purchased from Univar Inc. (Downers Grove, IL, USA) and are used in
the epoxidation of camelina oil. Anhydrous methanol was purchased
Table 1
from Sigma-Aldrich Canada Co. (Oakville, ON, Canada) and used in the
Fatty acid composition (%) and physical properties of castor oil and camelina oil. epoxy ring opening reaction of epoxidized camelina oil (ECamO).
Sodium chloride (NaCl) of food grade and anhydrous sodium sulfate
Fatty acids Abbreviation Castor oila Camelina oil (Na2SO4) of technical grade were purchased from Univar Inc. ACS
Palmitic C16:0 0.7 7.2
grade (99.5%) ethyl acetate and hydrogen bromide (HBr), 33 wt%
Stearic C18:0 0.9 3.1 solution in glacial acetic acid, were purchased from the Fisher Scientic
Arachidic C20:0 0.3 1.9 Company (Ottawa, ON, Canada). Glacial acetic acid (99.7%) was ob-
Behenic C22:0 0.4 tained from Caledon Laboratories Ltd. (Georgetown, ON, Canada) and
Palmitoleic C16:19 0.1
used to prepare a 0.1N HBr solution for the oxirane oxygen content
Oleic C18:19 2.8 19.6
Linoleic C18:29,12 4.4 23.4 (OOC) titration of epoxides. Amberlyst 15 Dry, a strongly acidic,
Linolenic C18:39,12,15 0.2 27.5 macroreticular polymeric ion exchange resin, was purchased from Dow
Ricinoleic 12-OH-18:19 90.2 Water & Process Solutions and used as a catalyst in the hydroxylation
Dihydroxystearic 9,10-OH-18:0 0.5 process. Medium functionality polymeric diphenylmethane diisocya-
Eicosenoic acid C20:19 12.3
Eicosadienoic C20:2 11,14 1.3
nate (p-MDI, Mondur MRS) with an isocyanate content of 31.1 wt% was
Eicosatrienoic C20:3 11,14,17 0.7 received from Bayer Corp. (Pittsburgh, PA, USA) and used in prepara-
Erucic C22:113 2.5 tion of polyurethanes. A Dabco 33-LV catalyst (33 wt% solution of
OHV [mg KOH/g] 176.9 0.2 triethylenediamine in dipropylene glycol) was purchased from Air
Viscosity @25 C [Pa.s] 0.70 0.01 0.06 0.01
Products and Chemicals, Inc. (Allentown, PA, USA) and used as a cat-
Iodine Value [g I2/100 g] 85.5 1.0 150.9 1.0
Average MW [g/mol] 928b 893 alyst in polyurethane preparation.

a
Fatty acid prole of the castor oil is taken from (Conceio et al., 2007).
b
An average MW of castor oil is taken from (Da Silva et al., 2011).

379
T.S. Omonov et al.
2.2. Procedures
2.2.1. Epoxidation of camelina oil
The epoxidation process was carried out using a 22 L glass reactor
(Chemglass Life Sciences, Vineland, NJ, USA) equipped with a bottom
drain, a water jacket and attached to a recirculating liquid cooler/
heater (Julabo F25, Julabo USA, Inc. Allentown, PA, USA). The desired
amount of oil (2000 g) was added at a temperature of 25 C. Then,
the required amounts of aqueous H2O2 solution (35%, 1632 g) were
loaded into the vessel and the mixture was stirred vigorously
(350 10 rpm) with an overhead mechanical stirrer (RZR 2021,
Heidolph North America, Elk Grove Village, IL, USA) before pro-
ceeding. Then, formic acid (85% aqueous solution, 152 g) was added
dropwise through the addition funnel into the reactor at a rate of
10 g/min. After the complete addition of formic acid to the mixture,
the temperature of the reaction was increased at the rate of 5 C every
10 min up to the epoxidation temperature of 60 C, while carefully
monitoring the reaction temperature for any uncontrolled rise due to
the exothermicity of the reaction. The time (between 2.5-6.0 h) used for
the epoxidation of camelina oil was adjusted in order to meet the
planned epoxide oxirane content.
2.2.2. Hydroxylation of epoxidized camelina oil
Polyols were produced by hydroxylation of the partially epoxidized
camelina oil (p-ECamO) through epoxy ring opening reactions with an
alcohol in the presence of an acidic catalyst. The required amount of p-
ECamO (1000 g) with selected OOC was loaded into a 22 L jacketed
glass reactor equipped with a bottom drain, while mixing at
350 10 rpm. After the temperature of the p-ECamO was equilibrated
to 60 C, methanol was added into the reactor, to give a ratio of me-
thanol to p-ECamO of about 1.0: 1.0 (w/w). The p-ECamO and me-
thanol mixture was agitated until the temperature reached 60 C, then
the heterogeneous solid catalyst (Amberlyst 15, dry) was added at an
amount equal to 10% of the weight of p-ECamO. The epoxy ring
opening process was continued for about 6 h. After completion, (or
OOC < 0.02%) the solid catalyst was removed by ltration and the
product (polyol) was concentrated from methanol by vacuum eva-
poration. The recovered methanol (84w%) could be reused in further
reactions.
2.2.3. Polyurethane (PU) preparation
A variety of polyurethanes from COROL polyols and castor oil were
produced using p-MDI). The ratio of the hydroxyl functionality of polyol
to the isocyanate functionality of p-MDI was 1.0: 1.2. The diagram in
Fig. 1 demonstrates the PU sample preparation protocol for rheological
Fig. 1. Polyurethane sample preparation protocol to carry out the real-time curing ex-
periments in rheometer.
380
Industrial Crops & Products 107 (2017) 378385
experiments. This protocol includes: 1 min of mixing of the polyol (ei-
ther castor oil or replacement polyols) with p-MDI at room temperature;
1 min degassing of mixture in vacuum oven (20 mbar) at a tem-
perature of 70 C; transferring desired amount of mixture into the
rheometer (1.5 min) and preconditioning of the sample in rheometer
(1.5 min); and nally the equilibration of the sample temperature at
70 C (2 min) prior to measuring real-time viscoelastic properties of the
polyurethane.
Note that during the sample transfer the temperature of prepolymer
decreases to a certain degree and equilibrates again at 70 C during
preconditioning in rheometer. After taking the desired amount of the
prepolymer the remaining product is transferred back to the oven with
preheated temperature of 70 C for overnight curing. These PU samples
were used for dierential scanning calorimetry (DSC) analysis to de-
termine the glass transition temperatures.
2.3. Methods
2.3.1. Oxirane oxygen content (OOC)
Epoxidation of camelina oil was carried out using in-situ generated
performic acid from formic acid and hydrogen peroxide. The extent of
epoxide formation was followed by measuring OOC (expressed as grams
of oxirane oxygen per 100 g of epoxidized product) of the epoxidized
products according to the ASTM standard titrimetric method (ASTM-
D1652-11E1, 2011). For these purposes the aliquots (15 mL) of
epoxidized products were taken periodically every 30 min without in-
terrupting the epoxidation process. These samples were diluted with an
equal amount of ethyl acetate and washed with an equal amount of
saturated NaCl solution at least three times (or until pH 6) to remove
the formic acid and unreacted H2O2. Then, the epoxide solution in ethyl
acetate was dried with anhydrous Na2SO4, and nally concentrated
from ethyl acetate using rotary evaporator at low atmospheric pressure
(@60 C, 20 mbar). The epoxidation process was stopped when the
targeted OOC has been achieved, as explained in Section 3.1 below.
2.3.2. Iodine value (IV)
The iodine value of the partially epoxidized products, and as well as
polyols were measured according to ASTM standards (ASTM-D5554-15,
2015).
2.3.3. Transmission fourier transform infrared spectroscopy (FTIR)
The hydroxyl values (OHV) of the COROL polyols and castor oil
were measured using in-house developed FTIR method with ABB-
Bomems WorkIR (ABB-Bomem, QC, Canada) FTIR spectrometer con-
trolled by Windows-based Universal Method Platform for Infrared
Evaluation (UMPIRE) software (Thermal-Lube, QC, Canada). IR
spectra (4000400 cm1, 16 scans, 4 cm1 resolution) of the products
were collected using CaF2 transmission cell. This method is based on
the measurement of desired amount of p-toluenesulfonyl isocyanate (p-
TSI) peak in the toluene solution, as described elsewhere (Tavassoli-
Kafrani et al., 2015). The dierence of the peak area corresponding to p-
TSI solution (control) and after the reaction with hydroxyl group of the
sample (if any) is proportional to the OHV value of the product. To
minimize moisture vapor variation, the spectrometer was purged with
dry air using a Balston Dryer (Balston, Lexington, MA).
2.3.4. Gel permeation chromatography (GPC)
A 1200 series high performance liquid chromatograph (HPLC) from
Agilent Technologies (Agilent Technologies Inc, Santa Clara, CA, USA)
equipped with an Agilent 1200 evaporating light scattering detector
(ELSD) was used for all GPC experiments to measure MW distributions
of the epoxidation products. A Styragel HR 4E THF column (with the
size of 4.6 300 mm) from Waters Corporation, (Milford, MA, USA)
was used along with tetrahydrofuran (THF) as mobile phase and at a
ow rate 0.5 mL/min. For every run, the eluent was the same as the
sample buer. The random run-to-run dierence in retention times for
T.S. Omonov et al.
our system was < 0.1%. All data were processed using the Agilents
ChemStation for LC 3D Systems (Rev. B.03.01). The SEC calibration
curve for the column was carried out using the lipid and polystyrene
standards.
2.3.5. Real-time rheological experiments
Real-time rheological experiments on polyurethanes upon curing
were performed with an AR2000 Advanced Rheometer (TA
Instruments, New Castle, DE, USA). Isothermal time sweep tests were
performed with 25-mm disposable parallel plates geometry under
controlled displacement at a frequency of 1 Hz and, at a constant
temperature of 70 C to follow the change of viscoelastic properties of
the materials upon curing. Rheology Advantage Data Analysis (version
5.7.0) software was used to analyze the experimental data. The gelation
times (tgel) of the PUs were determined from the viscoelastic properties
obtained from the real-time rheological experiments upon curing.
2.3.6. Dierential scanning calorimetry (DSC)
DSC measurements on PU samples were performed with a Q100
series DSC (TA Instruments, New Castle, DE, USA) in a temperature-
modulated mode with a modulation of 1 C every 60 s.
Approximately 6.08.0 mg ( 0.1 mg) of the sample was placed in an
aluminum pan, which was then hermetically sealed. An empty alu-
minum pan was used as a reference, and the experiments were per-
formed under a nitrogen ow of 50 mL/min. The sample was trans-
ferred to the DSC cell, where it was equilibrated at 100 C for 3 min and
then cooled to 50 C at a ramp of 10 C/min. The sample was held
isothermally at 50 C for 3 min and heated to 100 C at a constant rate
of 2 C/min with a modulation of 1 C every 60 s. The TA Universal
Analysis (version 4.7A) software was used to analyze the experimental
data.
2.3.7. Gas chromatography (GC)
A Perkin Elmer (Waltham, Massachusetts, USA) Clarus 500 Gas
Chromatograph equipped with a Flame Ionization Detector (GC-FID)
was used for chromatographic analysis of oil derivatives. A
100 m 0.25 mm SP-2560 Supelco capillary column with lm thick-
ness of 0.20 m was selected for the fatty acid analysis of camelina oil
FAME. The oven temperature was maintained at 45 C for 4 min, in-
creased to 175 C at a rate of 13 C/min, maintained at 175 C for
27 min then increased to 215 C at a rate of 4 C/min, and nally held at
215 C for 35 min. The injector and detector temperatures were 240 and
280 C, respectively. Hydrogen was used as carrier gas at a owrate of
1.3 mL/min. A 1.0 L injection of sample solution was used with the GC
injection port in split mode at split ratio of 20:1. The individual FAMES
were identied by their retention times using the reference standard
mixture GLC-463 from Nu-Chek Prep, Inc (Elysian, Minnesota, USA).
The fatty acid prole is given as the peak area percentage taken from
duplicate measurements.
3. Results and discussion
The use of biobased polyol as an alternative to castor oil in certain
industrial applications is based on the concept of partially mimicking
the unique triacylglyceride structure of castor oil (McKeon et al., 2016).
The dominant fatty acid content of castor oil is ricinoleic acid, which is
9 unsaturated fatty acid with a secondary hydroxyl functionality at the
carbon-12 position. The fatty acid prole and properties of castor and
camelina oils are compared in Table 1.
The high amount of naturally occurring hydroxyl functionality
(OHV = 177 mg KOH/g) along with the presence of unsaturates
(IV = 85 g I2/100 g) makes castor oil industrially attractive since it can
directly participate in many types of chemical reactions. In addition,
the presence of unsaturates in castor oil results in low viscosity which
benet its direct use as a natural polyol. Hydroxyl functionality and
viscosity are therefore important parameters when castor oil is used
381
Industrial Crops & Products 107 (2017) 378385
without modication in key commercial applications, since often hy-
droxyl functionality determines the reactivity of castor oil while visc-
osity dictates the processing conditions used for castor oil polyol.
Camelina oil has signicant amount of unsaturation with an iodine
value about 151 g I2/100 g oil. It was hypothesized that hydroxylation
of a dened portion of the unsaturates to hydroxyl functionality would
yield a product similar to castor oil. In addition, it would be possible to
manipulate the hydroxyl functionality and the viscosity by varying the
fraction of unsaturates in the camelina oil that are modied. These
castor oil replacement polyols were developed and produced from ca-
melina oil via a 2-step process. First, a controlled degree of epoxidation
was performed using performic acid and this was followed by hydro-
xylation due to epoxy ring opening by alcohols.
3.1. Controlled epoxidation of camelina oil
Controlled partial epoxidation of camelina oil was carried out using
in-situ generated performic acid from formic acid and hydrogen per-
oxide. For the epoxidation of camelina oil, the molar ratio of camelina
oil: formic acid: H2O2 used was 1.0: 1.25: 7.5, respectively. This means
that for every mole of double bonds in camelina oil there will be
0.25 mol of formic acid and 1.5 mol of H2O2. This is because the
double bond functionality (i.e. the average number of double bonds per
camelina oil triacylglycerol (TAG)) of camelina oil is 5.0, estimated
from the fatty acid prole of camelina oil and taking the average mo-
lecular weight of camelina oil as 893 g/mol. Although the limited
amount of acid slows the epoxidation reaction down, this condition is
desirable to avoid epoxy ring opening by the acid and acid generated
nucleophile (Omonov et al., 2016). An excess of H2O2 is desirable, in
part to compensate for any loss or decomposition of peroxide during the
epoxidation at elevated temperatures. Several batches of ECamO were
prepared, diering in their OOC and consequently also diering in their
remaining iodine value. As an example, Fig. 2 shows a plot of the
measured IV against changes in OOC for p-ECamO. Note that these
experimental points represent dierent batches of p-ECamO.
As expected, progress in the epoxidation reaction leads to a corre-
sponding decrease in the iodine value. The IV of the p-ECamO with an
OOC of about 4.2, is roughly the same as the IV of castor oil. Therefore,
it is reasonable to expect that after hydroxylation, a polyol can be
produced from this product with a similar viscosity to castor oil, as-
suming a similar inuence of hydroxyl functionality on viscosity. Thus,
p-ECamO with OOC 4.2 is considered as a starting point to produce
polyol with a similar viscosity to castor oil. However, from the known
fatty acid proles of camelina oil and using methanol as epoxy ring
opening agent, it can be readily predicted that p-ECamO with OOC of
Fig. 2. Change of IV and OOC for the camelina oil over epoxidation time. Dashed line
shows the target IV of the castor oil.
T.S. Omonov et al.
4.2 will not yield the targeted hydroxyl value. As a result, epoxides with
the higher OOC were also produced from camelina oil in order to be
able to make polyols with hydroxyl functionality matching those of the
castor oil, even if these resulting polyols have lower IV than castor oil.
3.2. Camelina oil polyols
Polyols were produced by hydroxylation of p-ECamO through epoxy
ring opening reactions with an alcohol in the presence of acidic catalyst
as described in the 2.2. Procedures section. The basic chemistry of the
epoxy ring opening reactions by variety of nucleophiles including al-
cohols is well described elsewhere in literature (Carey, 2000; Omonov
and Curtis, 2016). Examples of typical structures of biobased polyols
obtained via epoxy ring opening reactions of plant oil epoxides by al-
cohols have also been described (Curtis et al., 2015a; Petrovic et al.,
2002). It can be seen from Scheme 2 that the COROL polyol produced
from camelina oil has a similar structure to castor oil. However, the
location of the hydroxyl functionalities in COROL will vary (i.e. at C9,
C12 or C15) depending on the epoxide precursors. Moreover, formation
of isomers of these structures can also be expected. A series of fully
hydroxylated polyols were prepared from camelina oil which was
partially epoxidized to various degrees. These dier in their OHV and
viscosities. Fig. 3 demonstrates the change of the hydroxyl value with
the change of OOC in the input p-ECamO. The target OHV of castor oil,
which is about 177 mg KOH/g, is also shown as horizontal dashed line.
As expected, the OHV of the nal polyol depends on the OOC of the
starting epoxides, so that epoxides with higher OOC yield polyols with
higher hydroxyl functionalities.
The OHV of polyol made from the p-ECamO with an OOC of about
5.6% is very similar to the OHV of castor oil. It can be seen from Fig. 3
that the p-ECamO with an OOC of about 4.2% yields a polyol with OHV
of 140 mg KOH/g, which is somewhat below the OHV of castor oil.
However, we predicted that the viscosity of this polyol would be similar
to that of castor oil since the IV of the input p-ECamO was identical to
that found in castor oil. The viscosities of the polyols prepared as above
with dierent hydroxyl functionalities were measured using a rhe-
ometer and are shown in Fig. 4.
This gure shows that the viscosity of the polyol with a OHV of
140 mg KOH/g is indeed similar to that of castor oil, at 0.63 Pa.s. This
suggests that the IV of the p-ECamO did not decrease during hydro-
xylation and that the inuence of OHV on viscosity is less signicant.
On the other hand, the OHV of this polyol is smaller than the hydroxyl
value of castor oil, which alters the reactivity of the COROL compared
with castor oil. The COROL with a similar OHV to castor oil (177 mg
KOH/g) has a somewhat higher viscosity at about 2.0 Pa.s.
Furthermore, the ECamO with the highest OOC content tested
Fig. 3. Dependence of OHV of polyols on the OOC of epoxidized oils. Horizontal dashed
line shows the target OHV of the castor oil.
382
Industrial Crops & Products 107 (2017) 378385
Fig. 4. Viscosity of the polyols with dierent amount of hydroxyl functionalities.
Diamond symbol () represents the hydroxyl value and viscosity of the castor oil.
(5.9%) resulted in a polyol with a higher OHV (195 6 mg KOH/g),
which could be useful in certain applications where higher hydroxyl
functionality is required. Although the viscosity of this polyol (2.5 Pa.s)
is also signicantly higher than that of castor oil (Fig. 4), it is still low
compared with other biopolyols and some types of petrochemical
polyols. In summary, the data presented in Figs. 2-4 shows that polyols
from non-food camelina oil can be produced with a wide range of
viscosities and hydroxyl functionalities. The ability to adjust these
parameters oers a signicant advantage over castor oil.
3.3. GPC of polyols
It is highly desirable to produce polyols having a monomeric
structure with the uniform distribution of molecular weight (low
polydispersity index). This is because polyols produced via epoxy ring
opening reactions can also undergo oligomerization processes (Curtis
et al., 2015a), for example, due to reactions of epoxidized oils with the
hydroxylated derivatives that are newly formed during the ring opening
reactions. If such reaction occurs, the formation of polyol with low
hydroxyl functionality and increased viscosity is unavoidable.
To circumvent the formation of oligomeric compounds during the
hydroxylation process, we have attempted to isolate epoxides by the use
of an excess of methanol, the ring opening alcohol. Based on the fatty
acid composition of camelina oil, the average molecular weight of fully
epoxidized camelina oil is close to 976 g/mol. Also, fully epoxidized
camelina oil should have about 5 oxirane groups per epoxidized TAG
molecule, so could potentially react with 5 molecules of methanol (i.e.
160 g methanol per mole ECamO). However, it has been reported that
epoxidized vegetable oil has limited solubility in methanol. In parti-
cular, the solubility of epoxidized soybean oil is reported to be 65 g per
100 g of methanol at a temperature of 64 C, while soybean based
polyol has unlimited solubility at this temperature (Petrovic et al.,
2002). In our experiments a 1.0: 1.0 w/w mixture of ECamO and me-
thanol was used. Under such conditions the methanol acts as a reactive
solvent which dissolves the co-reactant (ECamO), is miscible with the
product (polyol) and participates in the epoxy ring opening reactions.
Up to 16% of the methanol is consumed during the ring opening re-
actions of fully epoxidized camelina oil and the remainder eectively
dissolves the polyol product. As a result, this use of excess methanol
favors formation of monomeric polyol structures and prevents forma-
tion of the oligomeric compounds. Several batches of COROL polyols
were analyzed in order to follow the formation of oligomers using gel
permeation chromatography.
Fig. 5 shows the GPC chromatograms of a dierent batches of
COROL polyols as well as castor oil and camelina oil. Note that the GPC
T.S. Omonov et al.
Fig. 5. GPC chromatograms of the camelina oil, castor oil and dierent batches of the
COROL polyols.
trace labeled COROL 1 corresponds to the polyol with lowest hydroxyl
functionality (140 mg KOH/g) while COROL 6 is the polyol with the
highest hydroxyl value (195 mg KOH/g).
It can be seen from Fig. 5 that the COROL polyols contain only small
amounts of dimers and no higher oligomers. The dimer content of the
polyols is found to be less than 10% on a peak area basis. It is also
evident from Fig. 5 that the GPC monomer peak for the COROL polyols
is indistinguishable from that of castor oil, whereas the starting came-
lina oil has a lower molecular weight and elutes at a slightly longer
retention time. Although, the GPC chromatograms showed a similar
MW distribution for COROL polyols and castor oil, the reactivity of
these products may dier due to the dierences between their struc-
tures. These dierences include the location of the hydroxyl groups,
double bonds and the presence of methoxy side chain on COROL (see
Scheme 2). Also, unlike castor oil which contains 90% of a single
fatty acid, camelina contains much wider distribution of fatty acids
(Table 1) resulting in a corresponding distribution of polyol products.
The properties and reactivity of a COROL polyol will reect this
overall polyol distribution. The reactivity of the hydroxyl groups in
COROL towards other reactive components determines its applicability
as drop-in replacement for castor oil, to be used without process
modication. Hence, the reactivity of COROL polyols and castor oil
were tested in a polyurethane application.
3.4. Polyurethanes
A variety of polyurethanes from COROL polyols and castor oil were
produced using p-MDI. The ratio of the hydroxyl functionality of polyol
to the isocyanate functionality of p-MDI was 1.0: 1.2. The excess of the
isocyanate from its stoichiometric ratio was selected to match that used
with castor oil in certain PU coatings applications. PU from castor oil
and COROL were produced under identical curing conditions to allow
direct comparisons. The diagram in Fig. 1 demonstrates the PU sample
preparation protocol for real-time rheological experiments. Real-time
rheological experiments upon curing of PU were carried out to de-
termine and compare the gelation times of the systems, while DSC ex-
periments were carried out to measure the thermo-mechanical
383
Industrial Crops & Products 107 (2017) 378385
Fig. 6. Viscoelastic properties of the castor oil and select COROL polyol cured iso-
thermally at 70 C. The vertical dashed line highlights the tgel of the system. The boxed
patterns correspond to the PU sample preparation time outlined in the protocol in Fig. 1.
properties of the nal polyurethanes after complete curing.
Fig. 6 demonstrates the typical viscoelastic properties (storage
moduli G and loss moduli G) of a selected COROL polyol (with OHV of
166 mg KOH/g) and castor oil based PUs as a function of curing time.
Note that the curing time (x-axis) in Fig. 6 was corrected for the sample
preparation and equilibration time in the rheometer before isothermal
curing. These times are shown in Fig. 6 as various patterned boxes on x-
axis which corresponds to the times shown in the sample preparation
protocol in Fig. 1. Also, the y-axis results are presented on logarithmic
scales to allow the entire process to be presented.
As shown in Fig. 6, the overall trend in a viscoelastic behavior of
castor PU and COROL PU during curing are fairly similar. For both
systems, at initial stages of the curing the viscous behavior dominates
the elastic behavior (G > G) which is typical for thermoset polymers.
The trend in Fig. 5 also shows that the PU prepolymer formation in
castor based PU starts at early stages of mixing which is indicated by
the higher storage and loss modulus compared with COROL PU. This
means that the castor oil is more reactive towards isocyanates under
these conditions.
Clearly, COROL polyol has a lower reactivity with isocyanates
compared with castor oil characterized by the lower values of G and G
over the course of experiments. As the crosslinking reaction progressed,
the G and G values of both systems started to increase. At a certain
point (14 min for castor PU and 25 min for COROL PU), the elastic
behavior of the system prevailed (G G). This point, where a cross-
over of the viscous and elastic components of the moduli occurs, is
considered to be the gelation time for the system (Chambon et al., 1986;
Omonov and Curtis, 2014), as indicated by the dashed lines in Fig. 6.
Note that the tgel of the curing system could also be determined from the
change of viscosities during curing experiments (e.g. Fig. 7). In an ideal
case, after gelation, the viscosity of the reactive mixture should tend
toward innite values (Omonov and Curtis, 2014), and an extrapolation
of the viscosity to the time axis (x-axis) should give a similar value for
gelation time. The viscosities of the PU upon curing and the gelation
times are discussed below.
It can be concluded that camelina based COROL polyols react with
polymeric isocyanate signicantly slower than castor oil does, most
likely due to dierences in their structures, such as due to the steric
hindrance imposed by the adjacent methoxy side chains. This could
have a negative impact on applications where the COROL is expected to
be as a drop-in replacement of castor oil. However, it was found that to
adjust the reactivity of the COROL to castor oil a small amount of
commonly used amine catalyst (Dabco 33-LV, a 33 wt% solution of
triethylenediamine in dipropylene glycol) can be added. Thus, similar
T.S. Omonov et al.
Fig. 7. The change of the complex viscosity of the castor oil PU, COROL PU without
catalyst and COROL PUs at dierent loads of the catalyst. The values of tgel of dierent
systems are shown in the gure near respective curves.
real-time curing reactions of the COROL polyols with the addition of
dierent amounts of catalysts were carried out in the rheometer to
establish the optimum amount of the catalyst to match the tgel of the
castor oil in making PU. Fig. 7 demonstrates the complex viscosities of
the castor PU, COROL PU and COROL PU at dierent concentrations of
catalyst. The established gelation times of dierent systems are shown
in the gure near respective curves.
It can be seen from Fig. 7 that the tgel for castor oil PU was about
14 min, while the tgel of COROL PU without catalyst was about 25 min,
which is nearly identical to that determined from Fig. 6. However, the
addition of a small amount catalyst signicantly reduces the time ne-
cessary for gelation of COROL PU. After addition of 0.3 wt% catalyst
the gelation of COROL PU occurs at about 13 min, earlier than the tgel of
castor oil.
Thus, it can be concluded that the curing process of COROL polyols
with isocyanates can be accelerated by an addition of catalyst to match
those of castor oil. However, it is also necessary to examine the inu-
ence of the catalyst on the nal mechanical performance of the PU.
3.5. Glass transition temperature
In order to investigate how the amount of catalyst added might
eect the glass transition temperature (Tg) of the polyurethanes pro-
duced, DSC experiments were carried out on the PU samples prepared
with various loads of catalyst. The experiments showed that the Tg
range for the PUs at dierent loads of catalyst were all within the likely
experimental error range of 2 C. For example, the PU from the
COROL with the lowest hydroxyl functionality (147 mg KOH/g) at
catalyst loads of 0.20, 0.25 and 0.30% had measured Tg values of 11.6,
11.8 and 11.8 C, respectively. Similarly, the PU made from the COROL
with the highest hydroxyl functionality (195 mg KOH/g) and using
0.10, 0.15 and 0.20% catalyst had measured Tg values of 39.7, 43.4 and
42.4 C, respectively. Therefore, the inuence of the catalyst amount on
the nal thermo-mechanical properties of The PU can be considered as
negligible. After a series of real-time curing experiments of COROL
polyols with isocyanates, the optimum amount of catalyst for each
COROL to produce PU with similar gelation times to castor oil were
established. It should be noted that the maximum amount of catalyst
required to adjust the reactivity of COROL was found to be 0.30 wt%
and this amount depends on the hydroxyl functionality of the polyol.
COROL versions with higher hydroxyl functionalities require lower
amounts of catalyst in order to adjust their reactivities to match castor
oil. COROL polyols with hydroxyl values of 147, 156, 166, 172 and
195 mg KOH/g were selected to produce PU. In each case, the amount
of catalyst used was adjusted to yield gelation times that are similar to
384
Industrial Crops & Products 107 (2017) 378385
Fig. 8. Glass transition temperatures (left y-axis) and the gelation times (right y-axis) of
PU from COROL polyols and castor oil. Vertical dashed line highlights the Tg and tgel of
castor oil.
that of castor oil. Both the COROL PU and castor oil PU (as a control)
were prepared in the same way, as described in the 3.4. Polyurethanes
section but with a curing time of 24 h at 70 C. The thermo-mechanical
properties of these nal PU samples were evaluated by DSC and their
glass transition temperatures were compared. Fig. 8 shows the Tg
measured by DSC and the tgel measured by rheometer, for these castor
oil and COROL PU samples.
It can be seen from the plot of the tgel vs OHV (bottom curve and
right y-axis) that all PUs have similar gelation times (adjusted by cat-
alyst amount), with an average value of 13.3 0.6 min. Castor PU
was found to have a Tg of 10.1 C (highlighted with vertical dashed line)
whilst the COROL PU made from the lowest OHV COROL was found to
have a Tg value of 11.8 C, i.e. just slightly higher than the value for
castor PU. It is also clear from Fig. 8 that the Tg of COROL based PU
varies with OHV (open circle data points and left-hand y-axis). The
COROL polyol with OHV above 150 mg KOH/g can give rise to PU at
similar gelation times to castor oil but with signicantly higher Tgs (up
to 30 C higher over the range of OHV tested), which could be benecial
in certain applications.
4. Concluding remarks
In this work, we have demonstrated a cost-ecient route to man-
ufacture a castor oil replacement polyol (COROL) from camelina oil via
controlled epoxidation followed by ring-opening of the partially epox-
idized camelina oil (p-ECamO) by an alcohol. The polyol produced
primarily has a monomeric structure with less than 10% dimers and is
free of trimers or higher oligomers. The hydroxyl functionalities of
these polyols can be tailored during synthesis to suit particular appli-
cations. However, the viscosity of a polyol depends on its OHV; to make
a polyol with a higher OHV requires a greater consumption of un-
saturates, resulting in a small increase in the viscosity of the polyol.
Nevertheless, the COROL polyol manufacturing process along with the
careful selection of oils with higher levels of unsaturates, can still
produce biopolyols with low viscosities (0.5-3.0 Pa.s).
It was also shown that the castor oil replacement polyols have
somewhat lower reactivity towards isocyanates compared with castor
oil, due to structural dierences. However, their reactivities are readily
enhanced by the addition of low amount of commonly used amine
catalysts. It worth pointing out that the reactivity of these oil-based
polyols could also be modied by including some primary hydroxyl
functionality, which is much more reactive. However, this creates a
polyol with a structure that is distinct from castor oil, and may not be
suitable for drop-in replacements. In cosmetics applications, where the
hydroxyl functionality and viscosity of polyols are the only signicant
parameters, COROL polyols can be used as is without catalyst or
T.S. Omonov et al.
modications.
We have demonstrated the overall manufacturing process of castor
oil replacement polyol using camelina oil. However, any plant oil with
the high amount of unsaturates, preferably linoleic acid (C18:2), are
suitable for this purpose. The plant oil with higher amount of un-
saturates and low content of saturated fatty acids such hempseed oil
(C18:2 5456%, C18:3 2426%), soybean oil (C18:2 4355%, C18:3
511%) and axseed oil (C18:2 1725%, C18:3 3560%) could be al-
ternative candidates to produce castor oil replacement polyols. Ideally,
a plant oil containing mainly linoleic acid should produce hydroxyl
value/viscosity balance matching castor oil. However, it is not feasible
to target selective epoxidation of linoleic acid only at the 12 position,
as well as nearly impossible to prevent the formation of hydroxyl group
isomers (Scheme 2(C)) during hydroxylation, so as to produce polyol
structurally closer to castor oil on the molecular level. Nonetheless, it is
clearly possible to produce polyol matching the overall hydroxyl
functionality, viscosity and reactivity in polyurethane applications, as
has been demonstrated in this work.
Funding
This work nancially supported by the Agriculture and AgriFood
Canada AgriInnovation Program (Project # AIP-P003) and Linnaeus
Plant Sciences (BC, Canada).
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