Industrial Crops and Products 64 (2015) 194–200

Contents lists available at ScienceDirect

Industrial Crops and Products

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

Waterborne polyurethane dispersions synthesized from jatropha oil

Sariah Saalah a,b,∗ , Luqman Chuah Abdullah a,c , Min Min Aung c,e , Mek Zah Salleh d ,
Dayang Radiah Awang Biak a , Mahiran Basri e , Emiliana Rose Jusoh c
a
Department of Chemical and Environmental Engineering, Faculty of Engineering, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia
b
Chemical Engineering Department, Faculty of Engineering, Universiti Malaysia Sabah, Jalan UMS, 88400 Kota Kinabalu, Sabah, Malaysia
c
Institute of Tropical Forestry and Forest Products, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia
d
Radiation Processing Technology Division, Malaysian Nuclear Agency, 43000 Kajang, Selangor, Malaysia
e
Department of Chemistry, Faculty of Science and Technology, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia

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

Article history: A series of waterborne polyurethane dispersions derived from jatropha oil-based polyol (JOL) with dif-
Received 25 August 2014 ferent OH numbers ranging from 138 to 217 mgKOH/g, were successfully prepared. Jatropha oil-based
Received in revised form 17 October 2014 polyols were synthesized by epoxidation and oxirane ring opening using methanol. The JOLs produced
Accepted 24 October 2014
were then used to prepare jatropha oil based waterborne polyurethane (JPU) dispersions by reaction
Available online 16 November 2014
with isophrene diisocyanate (IPDI). Dimethylol propionic acid (DMPA) was used as an internal emulsifier
to enable the dispersion of polyurethane in water. The influence of the OH number, DMPA content and
Keywords:
hard segment content on the stability of the wet JPU dispersions, as well as the physical, mechanical
Jatropha oil
Polyurethane dispersion
and thermal properties of the dry JPU films were investigated. The results reveal that with increasing OH
Renewable polyol number, the DMPA content and hard segment content significantly decrease the particle size from 1.1 ␮m
Waterborne coating to 53 nm, indicating increasing stability of the dispersions. JPU films exhibit the stress–strain behavior
of an elastomeric polymer with a Young’s modulus ranging from 1 to 28 MPa, a tensile strength of 1.8
to 4.0 MPa and elongation at break ranging from 85 to 325%. The polyurethane dispersions synthesized
in this work possess good pendulum hardness, water repellence and thermal stability with promising
application as a binder for wood and decorative coatings.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction strength, high elasticity, a range of hardness, excellent abrasion

Many of the commercial polyurethane adhesives and coatings
are known to contain a significant amount of organic solvents and
some also contain volatile isocyanate which is harmful to human
health as well as the environment. Increasing concern on this issue
has pressured the urethane industry to move toward water based
systems. Waterborne polyurethane (PU) dispersion is a recent class
of binder that is easily diluted with water and air-dried, stoved or
crosslinked to produce volatile organic component (VOC) compli-
ant coatings (Athawale and Nimbalkar, 2011). As with their solvent
based counterparts, waterborne PU dispersions find application
mainly in the ink, surface coating and adhesive industries. Poly-
mers derived from waterborne PU dispersions exhibit an excellent
combination of physical properties such as high tensile and tear
∗ Corresponding author at: Department of Chemical and Environmental Engi-
neering, Faculty of Engineering, Universiti Putra Malaysia, 43400 Serdang, Selangor,
Malaysia. Tel.: +60 3 89466288.
E-mail address: s sariah@ums.edu.my (S. Saalah).
resistance, good resistance to chemicals and good low temperature
stability (Davies and Some, 1990).
Waterborne PU dispersions can be prepared by adding water to a
segmented polyurethane ionomer containing a very small amount
of solvent as a diluent agent. Ionomers which contain hydrophilic
groups are incorporated into the side chain or backbone of the
polymer to enable dispersibility of water-insoluble polyurethane.
The ionomer could be an anionic or cationic type but an anionic
type such as dimethylol propionic acid (DMPA) is commonly used.
The DMPA acts as an emulsifier to provide dispersion stability for
longer storage of the waterborne PU dispersion. The hydrophilicity
of ionic groups in the DMPA is reported to improve the mechanical
properties, but tends to make the dispersion film more sensitive
to water and chemicals (Bullermann et al., 2013). Therefore, the
amount of DMPA should be controlled to be as low as possible in
the polyurethane prepolymer.
Currently, most waterborne PU dispersions are derived from
petroleum based polyol which is non-renewable. As consumers are
becoming more aware of environmental issues, they are changing
their preference toward bio-based products. In addition, people

http://dx.doi.org/10.1016/j.indcrop.2014.10.046
0926-6690/© 2014 Elsevier B.V. All rights reserved.
 S. Saalah et al. / Industrial Crops and Products 64 (2015) 194–200
in industry are constantly looking for alternatives as the price of
fossil oil is typically increasing. Recently, the synthesis of water-
borne PU dispersions derived from vegetable oil such as soybean oil,
castor oil, rapeseed oil and linseed oil have been reported (Chang
and Lu, 2012, 2013; Lu and Larock, 2008; Ni et al., 2010). How-
ever, to the best of our knowledge, no research has been reported
concerning jatropha oil regarding its promising properties to pro-
duce waterborne dispersions. In Malaysia, jatropha become one of
the most important crop after palm oil and rubber, mainly planted
for biodiesel production. BATC Development Berhad was actively
engaged in jatropha plantation and bio-fuel industry since 2007. Up
to 2011, about 600,000 acres planted areas, 3.3 million areas land-
banks and more than 300 nurseries and collection centers were
reported in Malaysia (Bionas, 2011).
Jatropha oil (JO) which is extracted from the seeds of the jat-
ropha fruit is a promising candidate for chemical purposes as it
contains 78.9% unsaturated fatty acids, mainly of oleic acids (43.1%)
and linoleic acid (34.4%) (Sarin et al., 2007). This high degree of
unsaturation provides a broad alternative for chemical modifica-
tion to produce polymers with various properties. Furthermore, it
is an advantageous to use jatropha oil because it is a non-edible
oil and thus its usage will reduce the consumption of edible oils
for chemical purposes (Rios et al., 2013). Previous researches have
revealed the potential of producing alkyd resin (Boruah et al., 2012),
polyurethane coatings (Sugita et al., 2012), polyurethane adhesive
(Aung et al., 2014) and polyurethane elastomer (Hazmi et al., 2013)
from jatropha oil. In this research, an attempt is made to produce a
waterborne PU dispersion using a jatropha oil-based polyol.
The aim of this study is to investigate the effect of the polyol
OH number, DMPA content and hard segment content on the sta-
bility of the wet jatropha oil-based polyurethane (JPU) dispersion
and the physical, mechanical and thermal properties of the dry JPU
films. The stability of the dispersion was investigated by particle
size analysis, pH and viscosity measurement. On the other hand, the
physical properties of the JPU films were determined by pendulum
hardness and water contact angle analysis. Tensile test and thermo-
gravimetric analysis (TGA) were used to determine the mechanical
and thermal properties of the JPU films. These properties will have
an influence on the practical design of products as the PU disper-
sion can be used as a standalone coating or as a binder in wood and
decorative coatings.
2. Materials and methods
2.1. Materials
Crude jatropha oil was supplied by BATC Development Berhad,
Kuala Lumpur, Malaysia. The hydrogen peroxide 30% and methanol
were supplied by Merck, Germany. Isophrene diisocyanate (IPDI),
dimethylol propionic acid (DMPA), n-methyl pyrollidone (NMP),
2-hydroxyethyl methacrylate (HEMA), phtalic anhydride and
dibutyltin dilaurate (DBTDL) were purchased from Sigma–Aldrich.
Ethyl methyl ketone (MEK), triethylamine (TEA), formic acid, mag-
nesium sulphate anhydrous, pyridine, and sodium hydroxide were
supplied by Systerm. All chemicals were reagent grade, and were
used as received.
2.2. Preparation of epoxidized jatropha oil (EJO)
The reactions were carried out in a 1000 mL four neck flask
equipped with a mechanical stirrer, condenser, a thermometer sen-
sor and an isobaric funnel. The reaction temperature was controlled
by placing the flask in a water bath. Jatropha oil (200 g) and formic
acid were poured into the flask and heated to 40 ◦ C, before adding
hydrogen peroxide dropwise over a period of 30 min. The molar
195
ratio of the oil double bond to formic acid and hydrogen peroxide
was 1:0.6:1.7. The reaction temperature was then increased and
maintain at 60 ◦ C. The reaction was quenched after a prescribed
time by cooling the reaction mixture to room temperature. The mix-
ture was then transferred to a 500 mL separating funnel to allow
phase separation. The aqueous phase was removed, and the oil
layer was washed successfully with distilled water to remove the
remaining acid. The oil layer was then dried using magnesium sul-
phate. Four samples of EJO were prepared by varying the reaction
time.
2.3. Preparation of jatropha oil-based polyols (JOL) by the oxirane
ring opening method
The reactions were carried out in a four neck flask, as mentioned
in Section 2.2. A calculated amount of methanol and water was
charged into the flask followed by adding sulphuric acid and heat-
ing to 64 ◦ C, and then added with EJO. The reaction was kept at
64 ◦ C for 30 min, and sodium bicarbonate was added to quench the
reactions. After being cooled to room temperature, the deposit was
discarded. Methanol and water were removed by vacuum distilla-
tion at 60 ◦ C for 30 min, followed by 80 ◦ C for 10 min. The resulted
clear golden yellow polyol was analyzed for OH number according
to ASTM D4274-99 (Test Method C-Reflux Phtalation). By using the
same hydroxylation procedure for different EJO, a series of jatropha
oil based polyols (JOL) with different OH numbers were prepared
and coded as JOL 138, JOL 161, JOL 188 and JOL 217. The numbers
represent the OH number of the polyol in mgKOH/g.
2.4. Preparation of jatropha oil-based polyurethane (JPU)
dispersion
The JOL and DMPA (dissolved in NMP) were added to a four-
necked flask equipped with a mechanical stirrer, nitrogen inlet,
condenser, and thermometer. The mixture was heated to 70–80 ◦ C
and stirred for 30 min to obtain a homogeneous mixture. IPDI was
then added dropwise for 30 min followed by adding a few drops of
dibutyltn dilaurate as a catalyst. MEK was added batch by batch to
reduce the viscosity of the system. After an additional 3 h of reac-
tion, HEMA was added until the NCO peak at 2270 cm−1 of Fourier
transform infrared (FTIR) spectra disappeared, showing that all the
diisocyanate had been consumed. The reactants were then cooled
to 40 ◦ C and neutralized by adding TEA (1.2 equiv. per DMPA), fol-
lowed by dispersion at high speed with distilled water to produce
the JPU dispersions with a solid content of ∼25 wt.% after removal
of the MEK under vacuum. The reaction scheme for this method is
shown in Fig. 1. The formulation for waterborne JPU dispersion is
shown in Table 1. The “JPU 138” designation indicates that the OH
number of the polyol used for the JPU preparation is 138 mgKOH/g.
For all formulation, the molar ratio between the polyol (JOL), IPDI,
DMPA and HEMA was fixed which led to JPUs with an increase in
the hard segment and DMPA content. The corresponding JPU films
were obtained by casting the JPU dispersions into a Teflon mold,
and drying at room temperature for 7 days, followed by drying in
a vacuum oven at 60 ◦ C for 12 h. The JPU films were stored in a
desiccator at room temperature.
2.5. Characterization
The attenuated total reflectance Fourier transform infrared
(ATR-FTIR) spectra were recorded on a Perkin-Elmer Spectrum
2000 spectrometer which collects mid-infrared scattered radiation
using a single-beam improved Michelson interferometer. The spec-
tra were recorded in the range of 4000–500 cm−1 with a nominal
resolution of 4 cm−1 .
196 S. Saalah et al. / Industrial Crops and Products 64 (2015) 194–200

H3CO OH
O

O OH OCH3 H3C CH3 CH3 O

OCH3 CH3
+ + HO H2C C CH2 OH + H2C OH
O O C N O
N C O COOH
O OH CH3
O IPDI DMPA
HEMA
O
JOL
DBTDL ( catalyst )

O H O
O H N O CH2
N O O O N O
H3CO O N H CH3
H O
O O
O OH
O O OCH3
OCH3
O CH2 CH3
N TEA
O O CH3 CH2 CH2 CH3

O H O
O H N O CH2
N O O O N O
H3CO O N H CH3
H O
O O COO
NH
O O OCH3
OCH3
O

O O

Water

Jatropha oil-based waterborne PU (JPU) dispersion

Fig. 1. Reaction scheme for synthesis of waterborne polyurethane dispersions.

The particle size of the polyurethane dispersions was mea-
sured by a Zetasizer Nano-S (Malvern Instruments). Approximately
0.1 mL of the polyurethane dispersion was diluted with 3 ml dis-
tilled water and measured at 25 ◦ C. The Zetasizer Nano ZS was
also applied for zeta potential measurements using electrophoresis
principle.
The viscosity of the polyurethane dispersion was determined
according to ASTM D4878-03 using a Brookfield Viscometer (RV
DV-II+ Pro) with spindle number 40. The measurement was con-
ducted at temperature 25 ◦ C.
The pendulum hardness was determined according to ASTM
D4366-82. The JPU dispersions were applied on a glass plate with a
wet film thickness of 120 ␮m using a hand bar coater. After 72 h of
drying at room temperature the pendulum hardness was measured
using a Byk pendulum hardness tester.
The mechanical properties of the dispersion cast films were
analyzed using a tensile tester (Strograph R1 Toyoseiki), accord-
ing to ASTM D638-03 Type V specifications. The crosshead speed
was 10 mm/min with 1 kN load cell. The stress and strain measure-
ments data were analyzed for Young’s modulus, tensile strength,
and elongation at break. The values were reported as the average
of a minimum of five measurements for each sample. The mea-
surement was carried out at room temperature and 50% relative
humidity.

Table 1
The formulation of jatropha oil-based polyurethane (JPU) dispersions.

Sample designation JOL OH number Molar ratio DMPA (wt.%) HSa (wt.%)

(mg KOH/g) JOL (OH) DMPA (OH) HEMA (OH) IPDI (NCO)

JPU 138 138 1 0.38 0.2 1.25 4.1 34.2

JPU 161 161 1 0.38 0.2 1.25 4.6 38.0
JPU 188 188 1 0.38 0.2 1.25 4.9 40.6
JPU 217 217 1 0.38 0.2 1.25 5.4 45.0
a
Hard segment content [HS = Mass (IPDI + DMPA + HEMA + TEA)/Mass (Polyol + DMPA + IPDI + HEMA + TEA)].
 S. Saalah et al. / Industrial Crops and Products 64 (2015) 194–200
Fig. 2. FTIR spectra of jatropha oil-based polyol (JOL) and polyurethane (JPU) film.
The contact angle between a water drop and the surface of the
sample was measured using a contact-angle meter (FACE, Japan).
The drop of water was mounted on the surface of the films using a
microsyringe and the contact angle was measured. A high value of
contact angle indicates a good hydrophobic nature of the coating,
while a low value indicates that the water wets the surface. The
angle measurements were done in triplicate on different parts of
the films.
Thermogravimetric analysis (TGA) was performed using a
TGA/SDTA851e, Mettler Toledo, Switzerland. The films were heated
from 25 to 600 ◦ C at a rate of 10 ◦ C/min under a nitrogen atmo-
sphere.
3. Results and discussion
3.1. FTIR analysis
The IR spectra of jatropha oil-based polyol and water-borne
polyurethane (JPU) films are shown in Fig. 2. It can be seen that the
broad absorbance at 3454 cm−1 in the polyol shifted to 3334 cm−1
in the JPU implying that the OH group was converted to a hydrogen
bonded NH group. There is no peak at 2270 cm−1 indicating that the
isocyanate group ( NCO) had fully reacted. In addition, the absorp-
tion band corresponding to C O of urethane linkage (hydrogen
bonded) of the PU components can be observed at 1710 cm−1 while
the absorption bands at 2923 cm−1 , 2853 cm−1 and 1461 cm−1 cor-
respond to the C H stretching of the CH2 and CH3 groups. It is
also worth mentioning that there was a minimum side reaction to
form urea as no absorption band of the carbonyl group (C O) at a
range of 1645–1635 cm−1 was observed.
3.2. Particle size of the JPU dispersions
Particle size and zeta potential analysis are important meth-
ods to predict the stability of the dispersion. A stable dispersion
is generally recognized by a smaller particle size and high abso-
lute value of the zeta potential. The results (Table 2) indicate a
significant reduction in particle size from 1167 to 53.3 nm when
the OH number increases from 138 to 217 mgKOH/g. The parti-
cle size distribution of the JPU188 dispersion is shown in Fig. 3.
One particle distribution peak was observed at 164 nm and the
197
polydispersity index (PDI) of 0.219 indicated that the dispersion
exhibited a homogeneous composition.
According to Table 1, when the OH number of the polyol
increases, the amount of diisocyanate and DMPA also increases to
maintain a constant molar ratio between the NCO and OH groups.
However, increasing the amount of IPDI and DMPA in the PU
formulation results in a higher hard segment content as well as
DMPA content. As shown in Fig. 4, as the amount of hard segment
increases in the PU formulation, the particle size decreases due to
the decrease in the soft segment content, which is more hydropho-
bic as it is derived from vegetable oil. The ionic stabilization of
the dispersion particles by an ionomer is well documented. Gen-
erally, the hydrophobic component forms the core of the particles
while the ions are on the surface which creates an electrochemical
double layer consisting of COO− from the DMPA and counter ions
of NH(Et3 )+ from the neutralization with TEA (Bullermann et al.,
2013).
The particle size reduction as a result of increasing the DMPA
content is clearly shown in Fig. 5. The decreasing trend of particle
size as the OH number increases is due to a combination of high
hard segment content and a sufficient amount of DMPA in the JPU
formulation. The results are supported by the Zeta potential data
suggesting that JPU dispersions synthesized from JOL with a high
OH number are more stable, which is indicated by a high absolute
value for the zeta potential. From the point of view of colloidal
15
10
Volume (%)
5
0
0.1 1 10 100 1000 10000
Parcle diameter (nm)
Fig. 3. Particle size distribution of JPU 188 dispersion.
198 S. Saalah et al. / Industrial Crops and Products 64 (2015) 194–200

60

50

Konig Hardness (s)

40

30

20

10

0
JPU 161 JPU 188 JPU 217

Fig. 6. Pendulum hardness of JPU films.

Fig. 4. Effect of soft segment content on particle size of a JPU dispersion.

Generally, greater transparency of a dispersion indicates a greater

1400
amount of DMPA in the formulation and consequently the dis-
1200 persion is more hydrophilic. In the present study, all JPU samples
were physically dried after evaporation of water except for JPU 138,
Particle size (d, nm)

1000 which formed a soft and tacky surface. This may due to insufficient
800 amount of hard segment content which is responsible for the dry
film formation of the PU dispersion.
600

400 3.4. Pendulum hardness of JPU films

200 The pendulum hardness of jatropha oil-based waterborne

0 polyurethane films is reported in Fig. 6. The hardness of the
4 4.2 4.4 4.6 4.8 5 5.2 5.4
DMPA content (wt%)
Fig. 5. Effect of DMPA content on particle size of a JPU dispersion.
stability, the ideal particle size for polymer dispersions should be
around 100 nm and below (Tielemans et al., 2006). However, the
intended application is another aspect to be considered as relatively
larger particles are preferred in surface coatings for rapid drying,
while smaller sizes are desirable when the deep penetration of the
dispersion into a substrate is essential (Asif et al., 2005).
3.3. Characteristics of the JPU dispersions
The solid content, viscosity, pH, acid value and color of the
JPU dispersions are reported in Table 2. All samples show a rel-
atively low viscosity in the range 7–80.4 mPa s at a solid content
of 24.2–26.9 wt.%. The viscosity information is very important in
deciding a suitable application method of dispersion on a substrate.
A lower viscosity is generally required for spray and brush applica-
tion. The reported pH of 7.0 is in the range of the pH of commercially
available polyurethane dispersions. All samples had the same pH
even though the acidity value varied from 4.80 to 8.60 mgKOH/g.
In terms of appearance, the JPU dispersions were milky white to
yellowish in color and turned to transparent and glossy films as
they dried. Similar observations were reported by Ni et al. (2010)
for waterborne PU dispersions derived from soy bean oil, while
Lu and Larock (2008) obtained clear and slightly blue dispersions.
5.6 polyurethane increased as a high OH number for the polyol was
used in the PU formulation. This is due to the high functionality of
the polyol to incorporate a greater amount of diisocyanate as a hard
segment component, thus contributing to a higher crosslinking
density of the polyurethane. The results are higher than those for a
waterborne polyurethane wood coating derived from rapeseed oil
fatty acid methyl ester, hardened by the addition of polyisocyanate
with a hardness in the range of 17–27 s (Philipp and Eschig, 2012).
It is interesting to note that the JPU films were produced solely by
evaporation of water and without any additional curing or chemi-
cal crosslinking agent. The hardness of JPU 217 was comparable to a
linseed oil based coating, with a reported hardness of 46 s, air dried
by slow oxidation polymerization in the presence of metal drier
(Chang and Lu, 2012). The hardness of the PU dispersions could be
improved by introducing chemical crosslinking structure by radi-
ation curing such as electron beam and ultraviolet (Chang and Lu,
2012).
3.5. Tensile properties of JPU films
Fig. 7 shows the stress–strain curves of JPU films, demonstrat-
ing an elastomeric behavior of the films. Tensile properties of the
JPU films are given in Table 3. The tensile strength and Young’s
modulus increased and the elongation at break decreased with
increasing OH number of the polyol. This is related to an increasing
functionality of the polyol with increasing OH number, and increas-
ing hard segment content to provide more crosslinking sites for
the formation of hydrogen bonding in the hard segment chain.

Table 2
Some properties of the JPU dispersion with different OH numbers.

Sample pH Acid value (mg KOH/g) Solid content (wt.%) Viscosity (mPa s) Color Average particle size (d nm) Zeta potential (MV)

JPU 138 7.0 8.63 24.8 30.0 Milky white 1167.0 −46.37
JPU 161 7.0 4.80 24.2 7.3 Milky white 670.4 −46.7
JPU 188 7.0 7.93 26.9 80.4 Milky white 165.9 −68.23
JPU 217 7.0 6.23 26.5 78.2 Yellowish 53.3 −66.4
 S. Saalah et al. / Industrial Crops and Products 64 (2015) 194–200 199

12 100.00
JPU 217
JPU 217
10 80.00 JPU 188
JPU 188 JPU 161

8 JPU 161

Weight (%)
60.00
Stress (MPa)

6 40.00

4
20.00

2
0.00
0.00 100.00 200.00 300.00 400.00 500.00 600.00
0 Temperature (°C)
0 100 200 300 400
Strain (mm/mm) Fig. 9. TGA curves of JPU films.

Fig. 7. Stress–strain curve of JPU films.

217 which included 45.0% hard segment content. This was based
Table 3
on the contact angle data taken one minute after the water drop
Tensile properties of JPU films. was mounted on the surface of the samples. A contact angle of 90◦
or more indicates a nonwetting surface (Pathak et al., 2009). There-
Sample Young’s Tensile Elongation
Modulus (Mpa) Strength (Mpa) at break (%)
fore, the increased contact angle represents a lower level of wetting
of the coating films by water. It is worth noting that JPU 217 demon-
JPU 161 1.0 ± 0.3 2.4 ± 0.5 325.1 ± 46.8
strated a hydrophobic character even though the DMPA content is
JPU 188 8.7 ± 0.7 1.8 ± 0.0 145.5 ± 5.3
JPU 217 27.9 ± 2.5 4.0 ± 0.2 84.9 ± 4.0 the highest (Table 1). This reveals that the hydrophobicity of the
dry films is mainly governed by the high hard segment content,
and the increase in ionic content does not significantly increase
Increasing crosslinking density in the polyurethane reduces the the hydrophilicity. The results are comparable with PU coatings
mobility of chain segments, hence provides better resistance to derived from other vegetable oils such canola oil, sunflower oil,
externally applied extension forces which leads to higher tensile and camelina oil based PU (Kong et al., 2013) and also petroleum
strength and lower elongation at break (Hwang et al., 2011). The based PU dispersions (Negim et al., 2011).
increase in hard segment content also suppresses the soft segment-
hard segment phase separation, and results in decreased elongation
3.7. Thermal properties of JPU films
(Lee and Kim, 1995).
Investigation into the thermal degradation of polymers is impor-
3.6. Water contact angle of JPU films tant to determine the proper conditions for manipulation and
processing, and for obtaining high-performance products that are
The hydrophilicity of the JPU films was evaluated by measur- stable and free of undesirable by-products (Asif et al., 2005). The
ing the contact angle formed between the surface of the cast film TGA curves for the JPU films prepared using polyol with different
and a drop of distilled water. The results obtained are shown in OH numbers are shown in Fig. 9, and the thermal parameters are
Fig. 8. A remarkable difference in contact angle between compo- summarized in Table 4. The TG curves are similar for all samples,
sitions with different hard segment contents can be observed. The and two thermal degradation stages can be observed.
contact angle increased significantly from 66◦ for sample JPU 188 The onset of first degradation can be observed from 286.69 to
which included 34.2% hard segment content to 90◦ for sample JPU 296.38 ◦ C and peak temperatures (the maximum rate of mass loss)
from 313.92 to 321.6 ◦ C. This stage involves a loss of 28–37% of the
100 sample mass, which represents the decomposition of the urethane
linkage and the formation of isocyanates, alcohols, primary amines,
secondary amines, olefins, and carbon dioxide (Javni and Petrović,
90 2000).
Stage II exhibited similar onset temperatures from 361.18 to
Contact angle (degree)

80 399.2 ◦ C and similar peak temperatures from 392.26 to 401.38 ◦ C,

JPU 161
with a 60–68% loss of sample mass due to dissociation of the soft
JPU 188 segment. Among all JPU films, JPU 161 demonstrated the highest
70
thermal stability with a low mass loss in the first stage degradation.
JPU 217
This is related to the low amount of urethane bond due to the low
60 OH number of polyol used for the synthesis of JPU. It is well known
that the urethane bond is weak at a decomposition temperature
50 of less than 300 ◦ C. However, there is an increasing trend for the
peak temperature as the OH number of the polyol increased which
indicated that higher crosslinking occurred in the films to compen-
40 sate with a high OH functionality. Based on these results, it can
0 2 4 6 8 10 12
Time (min) be concluded that the waterborne PU films derived from jatropha
oil have good heat resistance. These thermal properties of JPU are
Fig. 8. Water contact angle of JPU films as a function of time. comparable to those of waterborne PU derived from soybean oil (Lu
200 S. Saalah et al. / Industrial Crops and Products 64 (2015) 194–200
Table 4
The thermal properties of JPU films produced from polyol with different OH numbers.
Sample T1on (◦ C) T1max (◦ C) *w1 (%)
JPU 161 286.69 313.92 28.00
JPU 188 290.80 319.86 34.70
JPU 217 296.38 321.60 37.20
*w, mass loss (%).
and Larock, 2008; Ni et al., 2010) and petroleum based UV curable
PU-acrylate (Xu et al., 2012).
4. Conclusions
Environmentally friendly waterborne polyurethane dispersions
have been synthesized from jatropha oil-based polyols and IPDI.
Dispersions with a wide range of particle size from 53 nm to 1.1 ␮m
were obtained, and the trend demonstrated increasing JPU disper-
sion stability as the OH number, hard segment content and DMPA
content increased. Physically dried, tack free JPU films with pen-
dulum hardness ranging from 20 to 50 s were obtained by the
evaporation of water, which indicated good film formation. Water
contact angle analysis demonstrated that the hydrophobic char-
acter of the surface of the films is mainly related to the hard
segment content. The resulting JPU coating films for all formula-
tions demonstrated good thermal stability with a minimum onset
of degradation temperature at 286 ◦ C. On the other hand, the films
exhibited elastomeric polymer behavior with a Young’s modulus
ranging from 1 to 28 MPa, a tensile strength of 1.8 to 4.0 MPa and
elongation at break ranging from 85 to 325%. The polyurethane dis-
persion synthesized in this work possesses good properties with
promising application as a binder for wood and decorative coatings.
Acknowledgements
The authors gratefully acknowledge the Ministry of Higher Edu-
cations Malaysia for the financial support provided for this work.
The authors would also like to thank the Malaysian Nuclear Agency
for the use of their facilities and instruments.
References
Athawale, V.D., Nimbalkar, R.V., 2011. Waterborne coatings based on renewable oil
resources: an overview. J. Am. Oil Chem. Soc. 88 (2), 159–185.
Davies, W., Some, 1990. Property aspects of aqueous polyurethane ionomer disper-
sions. In: Kansa, D.R. (Ed.), Additives for Water-Based Coatings. The Royal Society
of Chemistry, Cambridge, pp. 181–209.
Bullermann, J., Friebel, S., Salthammer, T., Spohnholz, R., 2013. Novel polyurethane
dispersions based on renewable raw materials – stability studies by varia-
tions of DMPA content and degree of neutralisation. Prog. Org. Coatings 76 (4),
609–615.
Chang, C., Lu, K., 2013. Linseed-oil-based waterborne UV/air dual-cured wood
coatings. Prog. Org. Coatings 76 (7–8), 1024–1031.
T2on (◦ C) T2max (◦ C) *w2 (%) Residue at 600 ◦ C (%)
361.18 393.12 68.28 3.69
361.32 392.26 61.90 3.13
399.20 401.38 60.70 2.18
Chang, C., Lu, K., 2012. Natural castor oil based 2-package waterborne polyurethane
wood coatings. Prog. Org. Coatings 75, 435–443.
Lu, Y., Larock, R.C., 2008. Soybean-oil-based waterborne polyurethane disper-
sions: effects of polyol functionality and hard segment content on properties.
Biomacromolecules 9 (11), 3332–3340.
Ni, B., Yang, L., Wang, C., Wang, L., Finlow, D.E., 2010. Synthesis and thermal prop-
erties of soybean oil-based waterborne polyurethane coatings. J. Therm. Anal.
Calorim. 100 (1), 239–246.
2011. Bionas BATC Development Company Profile., pp. 1–26, Retrieved from
http://bionas-usa.com/file/BATC%20%20Company%20Profile.pdf
Sarin, R., Sharma, M., Sinharay, S., Malhotra, R.K., 2007. Jatropha–palm biodiesel
blends: an optimum mix for Asia. Fuel 86 (10–11), 1365–1371.
Rios, L., Echeverri, D., Cardeño, F., 2013. Hydroxylation of vegetable oils using acidic
resins as catalysts. Ind. Crops Prod. 43, 183–187.
Boruah, M., Gogoi, P., Adhikari, B., Dolui, S.K., 2012. Preparation and characterization
of Jatropha Curcas oil based alkyd resin suitable for surface coating. Prog. Org.
Coatings 74 (3), 596–602.
Sugita, P., Alim, Z., Poliuretan, A., Minyak, B., Pagar, J., Baru-baru, P., 2012. Synthesis
and application of jatropha oil based polyurethane as paint coating material 2,
134–140.
Aung, M.M., Yaakob, Z., Kamarudin, S., Abdullah, L.C., 2014. Synthesis and character-
ization of Jatropha (Jatropha curcas L.) oil-based polyurethane wood adhesive.
Ind. Crops Prod. 60, 177–185.
Hazmi, A.S.A., Aung, M.M., Abdullah, L.C., Salleh, M.Z., Mahmood, M.H., 2013. Pro-
ducing jatropha oil-based polyol via epoxidation and ring opening. Ind. Crops
Prod. 50, 563–567.
Tielemans, M., Roose, P., Groote, P.De, Vanovervelt, J.-C., 2006. Colloidal stability of
surfactant-free radiation curable polyurethane dispersions. Prog. Org. Coatings
55 (2), 128–136.
Asif, A., Shi, W., Shen, X., Nie, K., 2005. Physical and thermal properties of UV curable
waterborne polyurethane dispersions incorporating hyperbranched aliphatic
polyester of varying generation number. Polymer 46 (24), 11066–11078.
Philipp, C., Eschig, S., 2012. Waterborne polyurethane wood coatings based on rape-
seed fatty acid methyl esters. Prog. Org. Coatings 74 (4), 705–711.
Hwang, H.-D., Park, C.-H., Moon, J.-I., Kim, H.-J., Masubuchi, T., 2011. UV-curing
behavior and physical properties of waterborne UV-curable polycarbonate-
based polyurethane dispersion. Prog. Org. Coatings 72 (4), 663–675.
Lee, J.S., Kim, B.K., 1995. Poly(urethane) cationomers from poly(propylene) glycol
and isophorone diisocyanate: emulsion characteristics and tensile properties of
cast films. Prog. Org. Coatings 25 (4), 311–318.
Pathak, S.S., Sharma, A., Khanna, A.S., 2009. Value addition to waterborne
polyurethane resin by silicone modification for developing high performance
coating on aluminum alloy. Prog. Org. Coatings 65 (2), 206–216.
Kong, X., Liu, G., Qi, H., Curtis, J.M., 2013. Preparation and characterization of high-
solid polyurethane coating systems based on vegetable oil derived polyols. Prog.
Org. Coatings 76 (9), 1151–1160.
Negim, E-S.M., Bekbayeva, L., Grigory, A.M., Abilov, Z.A., Saleh, M.I., 2011. Effects of
NCO/OH ratios on physico-mechanical properties of polyurethane dispersion.
World Appl. Sci. J. 14 (3), 402–407.
Javni, I., Petrović, Z., 2000. Thermal stability of polyurethanes based on vegetable
oils. J. Appl. Polym. Sci. 77, 1723–1734.
Xu, H., Qiu, F., Wang, Y., Wu, W., Yang, D., Guo, Q., 2012. UV-curable waterborne
polyurethane-acrylate: preparation, characterization and properties. Prog. Org.
Coatings 73 (1), 47–53.