J Polym Environ (2010) 18:539–544
DOI 10.1007/s10924-010-0188-x
ORIGINAL PAPER
Synthesis of Alkyd Resin from Non-Edible Jatropha Seed Oil
M. N. Satheesh Kumar • Zahira Yaakob •
Siti Maimunah • Siddaramaiah • S. R. S. Abdullah
Published online: 4 May 2010
Ó Springer Science+Business Media, LLC 2010
Abstract The kinetics of polyesterification of glycerol,
phthalic anhydride and jatropha oil leading to the formation
of alkyd resins were studied. A series of alkyd resins
having different amount of jatropha oil viz., 40–80% have
been prepared by employing two stage alcoholysis-poly-
esterification process. The extent of reaction and average
degree of polymerisation were calculated from the end
group analysis of the reaction mixture withdrawn at regular
intervals of time. The initial reaction rates followed the
second order kinetics and thereafter deviations were
observed. An appreciable degree of conversion was noticed
from the extent of the reaction which lies in the range of
49.5–62.5%. The average degree of polymerisation calcu-
lated in the region of deviation from second order sug-
gested the occurrence of chain branching at relatively
shorter intervals along the polymer chain. The second
order rate constants were found to be of the order of
10-5 g (mg KOH)-1 min-1.
Keywords Jatropha seed oil  Polyesterification 
Alkyd  Kinetics  Acid value
M. N. Satheesh Kumar (&)  Z. Yaakob  S. Maimunah 
S. R. S. Abdullah
Department of Chemical and Process Engineering, Faculty
of Engineering and Built Environment, National University
of Malaysia (UKM), 43600 Bangi, Selangor, Malaysia
e-mail: satheeshnag@gmail.com
Siddaramaiah
Department of Polymer Science and Technology,
Sri Jayachamarajendra College of Engineering,
SJCE Campus, Mysore, India
Introduction
The utilisation of renewable resource is expected to unhook
the dependency on fossil fuels and reduce the green house
gas emission. The vegetable oils such as soybean oil [1],
linseed oil [2], castor oil [3], tall oil [3], palm oil [4], etc.
have been employed for the preparation of alkyd resins to
impart certain properties like flexibility, compatibility with
solvents, control of solubility, durability, and to provide
cross linking ability [5]. The utilisation of renewable and
non-edible oils [6–9] for the manufacture of industrial
products is expected to reduce the dependency on edible
oils for industrial applications and hence helps to reduce
the global food demand [10].
Alkyd resins have gained importance in coating and
paint industries due to its low cost because of relatively
inexpensive raw material usage in the formulation and high
solubility in less expensive solvents. Alkyd resins are
employed commonly in decorative paints, air drying and
stoving paints, industrial paints, inks, machine toll finishes,
and marine topside and weather work paints [11–13].
The utilisation of an alcohol and acid for the preparation
of alkyd resin resulted the name ‘alkyd’. Alkyd resins are
typically made through condensation polymerisation of
natural oils or fatty acids with polyhydric alcohols such as
pentaerythritol, glycerol or trimethylol propane and dibasic
acids such as phthalic anhydride and isophthalic acid.
Alkyd resin is a highly branched polymer with polyester
backbone. The structure of typical alkyd resins is shown in
Fig. 1 [14]. Since the natural oils and fatty acids are
renewable raw materials, alkyd resin obtained from these
natural oils can be classified as green binder compared to
acrylic binders whose building blocks stem from mineral
oil. The main environmental problem with alkyd resins is
thus that they are typically used in diluted form in organic
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Fig. 1 Typical structure
of an alkyd resin
solvents. The possible routes to minimise the problem
associated with the use of solvents for the dilution of al-
kyds may be by minimising the solvent content to make
high solid resins or emulsifying the alkyd in water to make
alkyd emulsions.
The formulation composition and the process variation
during the synthesis of alkyd resins can have the significant
effect on the application properties of alkyd resins. Hence
it becomes important to have the kinetic treatment data to
understand the physical characteristic changes of the
reaction during the preparation of alkyd resins. Aigbodion
et al. [15, 16] have obtained the kinetic treatment data for
the preparation of alkyd resins from rubber seed oil and
African locust bean oil. The authors have found that, the
initial stages of the reaction followed a second order
kinetics with a rate constant in the order of 10-5 g (mg/
KOH/min) and deviates thereafter. Though few literatures
have been reported on the kinetic analysis of the prepara-
tion of alkyd resins from vegetable oils, the literature lacks
the information on the kinetic analysis of alkyd resin
preparation using jatropha oil.
Jatropha oil appears to have a significant potential as a raw
material for the industrial applications as because it is
renewable and non-edible. The cost competitiveness of
jatropha oil compared to other oils such as soya, rapeseed,
etc. [17] has attracted the industrialist and academicians to
explore this material as a material for the production of alkyd
resins. The present study is aimed to understand the rate of
polyesterification, time of gelation (that is the beginning of
cross linking of molecules) during the preparation of jatro-
pha oil based alkyds. The effects of coating thickness on the
drying performance of alkyd resins have been investigated.
Experimental
Materials
Jatropha oil seeds were obtained from Bionas Sdn. Bhd.,
Kuala Lumpur, Malaysia. The seeds were dried and cru-
shed before the oil extraction. The oil was extracted from
the crushed seeds using hexane as a solvent in a Soxhlet
extractor. The laboratory reagent grade phthalic anhydride,
glycerol, calcium carbonate and benzoic acid were used as
received in the reaction.
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J Polym Environ (2010) 18:539–544
Techniques
The properties of the jatropha seed oil were evaluated using
standard test methods [18]. In order to evaluate the drying
performance of the alkyd resins, the films were casted on
an aluminium plate. The aluminium plate was cleaned
using ethanol prior to casting to ensure that the plate is free
from any contaminants. A hand coater with different fixed
coating thickness was used to obtain an even coating of the
resin on the surface of the testing plates. The total drying
time of the prepared alkyd resin solution containing 0.75%
cobalt naphthenate dryer was determined according to
ASTM D 1640-69 at both indoor and outdoor conditions.
The prepared alkyd resins were formulated into white
gloss paints and their drying characteristics were evaluated.
The weight percentage composition of the gloss paint
formulation is; alkyd resin 50, talc powder 21, turpentine
15, titanium dioxide 13 and cobalt naphthenate 0.75.
Alkyd Resin Preparation
A series of alkyd resins having different amount of oil
content viz., 40–80% have been prepared using two stage
alcoholysis-polyesterification methods [19]. The alkyd
resins containing different amount of jatropha oil viz., 40,
50, 60 and 80% were labelled as JAL1, JAL2, JAL3 and
JAL4, respectively (Table 1).
In a typical reaction, to obtain alkyd resin, a known
quantity of jatropha seed oil was heated to a temperature of
225–235 °C. The glycerol and calcium carbonate were
added into the heated jatropha oil by maintaining the
temperature at 235 °C. The formulations of alkyd resins
having different quantities of oil content are given in
Table 1. The first stage alcoholysis reaction was monitored
by drawing the samples of reaction mixture at regular
intervals of time (5 min). The drawn samples were mixed
with anhydrous methanol in a 1:1 ratio. The completion of
alcoholysis reaction was confirmed by the formation of a
clear solution in anhydrous methanol [20]. After the
completion of first stage (alcoholysis) process, a known
quantity of phthalic anhydride and benzoic acid were added
into the reaction medium while maintaining the tempera-
ture at around 240 °C. Benzoic acid inclusion in the alkyd
resin formulation is expected to serve two purposes; (i)
being mono-functional it can acts as a chain terminating
J Polym Environ (2010) 18:539–544
Table 1 Formulation of
Ingredients (g) Alkyd resins with different oil content
different alkyd resins
JAL1
(40% oil content)
Jatropha seed oil 54.9
Glycerol 23.4
CaCO3 0.4
Phthalic anhydride 50
Benzoic acid 9.6
agent to prevent the tendency of gelling and (ii) reduces the
drying time during its application [21]. In all the reactions,
nitrogen was used to blanket the surface of the reaction
mixture. The acid value of the reaction mixture was
determined by withdrawing the samples frequently (every
30 min). The reaction mixture was quenched by immersing
the reaction vessel in cold water when the acid value was
10.
Extent of Reaction and Average Degree
of Polymerisation
Using the acid value of the reaction determined, the extent
of reaction P was calculated using the equation [22, 23],
P ¼ ðC0  Ct Þ=C0
where C0 and Ct are the acid value at zero reaction time
and after time t respectively. Using the P value, the average
degree of polymerisation can be calculated using the
equation,
DP ¼ 1=ð1  PÞ
Results and Discussion
The physico-chemical properties of jatropha seed oil in
comparison with linseed and rubber seed oil is given in
Table 2. The linseed and rubber seed oil are the known
materials employed for the synthesis of alkyd resins. The
obtained jatropha oil yield was 50–55% by weight of the
seed. The specific gravity of jatropha oil is lower than that
of linseed and rubber seed oil. The iodine value (an indi-
cation for the presence of unsaturation levels) of the
jatropha oil is lower than that of rubber seed and linseed
oil. The low iodine value indicates that the jatropha oil
alone may not be capable to produce dry and hard films
through auto oxidation process and needs some cross
linking agents. The acid value of jatropha seed oil is higher
than that of linseed oil but lower than that of rubber seed
oil. The acid and saponification value of jatropha oil is
541
JAL2 JAL3 JAL4
(50% oil content) (60% oil content) (80% oil content)
85.9 67.8 169.6
23.4 11.7 11.7
0.4 0.2 0.2
50 25 25
9.6 4.8 4.8
higher as compared to linseed oil but lower compared to
rubber seed oil.
The important fatty acids of jatropha oil in comparison
with linseed and rubber seed oil is given in Table 3. The
jatropha oil found to have low level of unsaturation as
compared to rubber seed and linseed oil due to the absence
of linolenic acid which has three double bonds. This may
also be the reason for the low iodine value of jatropha oil.
The presence of linolenic acid in the oil may cause yel-
lowing due to the formation of chromophoric groups
through conjugation. The films produced with the oil
having higher amount of linolenic acid may be less sus-
ceptible for the use in the off-colour coatings.
The relationship between the presence of oil content in
ð1Þ the formulation and the completion of the first stage alco-
holysis reaction is shown in Fig. 2. The redistribution of
molecular fractions between the triglycerides and glycerol
can be expected with the alcoholysis reaction. The alco-
holysis reaction time varied from 65 to 100 min for the
resin formulation containing the oil content in the range
ð2Þ 40–80%. The alcoholysis reaction time found to increase
with increasing the oil content in the formulation. A similar
behaviour was noticed by Ogunniyi and Odetoy [10] in
case of tobacco seed oil and Ogunniyi and Njikang [18] in
case of castor oil.
The plot of acid value as a function of polyesterification
reaction time for the resin formulation having different
amount of jatropha oil is shown in Fig. 3. The acid value
found to reduce as the reaction progressed. The reduction
in acid value found to be more rapid during the initial
stages of the reaction as compared to the later stages. The
initial rapid reduction in acid value may be due to the
reaction of primary hydroxyl groups of glycerol which
reacts faster than the secondary hydroxyl groups [24]. The
reduction in acid value at the later stage may be due to the
reaction of secondary hydroxyl groups. The cross linking
of alkyd chains can be expected when the reduction in acid
value is less rapid at the later stages of polyesterification
reaction. The viscosity of the reaction increased with
increasing the reaction time. This can be attributed to the
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Table 2 Comparison of the

Property Rubber Linseed Jatropha
properties of jatropha seed oil
seed oil oil seed oil
with linseed and rubber seed oil
Specific gravity at 27 °C 0.921 0.931–0.936 0.912–0.916
Saponification value (mg KOH/g) 192 175 178
Iodine value (g I2/100 g) 155 188 130
Acid value (mg KOH/g) 24.5 1.0 9.9
Free fatty acid (% as oleic acid) 11.29 – 1.03

Table 3 Comparison of the

Fatty acid No of carbon Composition (%)
fatty acid composition of
atoms/double
jatropha seed oil with linseed Rubber Linseed Jatropha
bonds
and rubber seed oil seed oil oil seed oil

Oleic C18/1 20.00 13–19 41–43

Linoleic C18/2 36.00 15–31 34–35
Palmitic C16/0 7.6 – 13–14
Palmitoleic C16/1 – – 1–1.5
Stearic C18/0 10.7 – 6–7
Linolenic acid C18/3 23.5 44–54 –

Fig. 2 Oil content versus alcoholysis reaction time

formation of three dimensional cross linked networks of
alkyd chains.
The rate for mono and poly condensation reactions is
expressed as second order rate [25]. These condensation
reactions are considered to be equivalent as the reaction
takes place between the functional groups.
ð1  PÞ1 ¼ C0 k t þ 1
where C0 is the initial concentration of the reactants, t is the
time of the reaction, P is the extent of reaction and k is the
rate constant. In the present study, concentration was
substituted by acid value. The plots of (1 - P)-1 versus
time as per the Eq. 3 must be linear if k is constant
throughout the reaction. The plots of (1 - P)-1 versus time
for different alkyd samples are shown in Fig. 4. From the
Fig. 3 Plots of acid value versus the reaction time for different alkyd
resins
figure, it can be observed that, the plots are not linear
throughout the reaction. The initial portion of the plots are
linear up to a certain point and deviated thereafter from
linearity. Aigbodion and Okieimen have made a similar
observation in the polyesterification of rubber seed [22]
ð3Þ
and African locust bean seed oil [23]. The formation of
linear molecules can be expected in the initial linear por-
tion of the curve and the crosslinking of alkyd chains are
expected after the point of deviation from linearity.
The calculated average degree of polymerisation and the
extent of reaction for different alkyd resins (at the point of
deviation from linearity) are given in Table 4. From the
table, it can be observed that, the extent of reaction varied

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Fig. 5 Drying performance of prepared alkyd resin formulated into

gloss paint

Fig. 4 Plots of (1 - P)-1 as a function of reaction time for different from 49.3 to 62.5% for alkyd resins having different
alkyd resins amount of oil content in the formulation viz., 40–80%. The
alkyd resin formulation having 50% oil content has showed
the highest degree of polymerisation. But these values are
still lower than the range 75–80% observed in the poly-
Table 4 Calculated average degree of polymerisation, extent of
reaction and second order rate constant (k) for different alkyd resins at
esterification reaction between phthalic anhydride and
the point of deviation from the linearity glycerol [26]. The observed low degree of polymerisation
as compared to typical polyesterification reaction may be
Parameter JAL1 JAL2 JAL3 JAL4
due to the presence of low molecular weight species at the
Time (min) 60 60 90 120 point of deviation from linearity. The second-order rate
Average degree of polymerisation 2.03 2.66 2.34 1.97 constant (k) calculated from the linear portions of the
Extent of reaction (%) 50.9 62.5 57.2 49.3 curves are given in Table 4. The k values lie in the range
k 9 105 (g/mg KOH/min) 2.1 3.35 2.15 2.37 2.1–3.35 9 105 g/mg KOH/min. The alkyd formulation
having 50% oil content has showed the highest k value.
The k value suggested that the rate of alkyd production
Table 5 Total drying time of alkyd resin solution (out door temp
depends on the ratio of reactants used in the formulation.
35 °C) The total drying characteristics of the alkyd resin
solution containing 0.75% by weight cobalt naphthenate
Alkyd resin sample code Drying time (h)
(drying agent) are given in Tables 5 and 6. The drying
20 lm 40 lm performance of alkyd resins formulated into white gloss
JAL1 1.3 1.5 paint is shown in Fig. 5. It can be noticed that, the drying
JAL2 1.8 2.0
time was shorter for out door as compared to indoor. This
JAL3 2.1 2.2
may be due to high temperature at the outdoor. The
JAL4 2.2 2.4
observed drying time without cobalt naphthenate dryer was
very long. The drying time was found to increase with
increase in the oil content and the thickness of coating. The
low extent of polymerisation in case of alkyd resins having
high oil content may be the reason for higher drying time.
Table 6 Total drying time of alkyd resin solution (indoor temp
25 °C) The neat alkyd resin and pigmented formulations have
exhibited the drying performance as similar to the results
Alkyd resin sample code Drying time (h)
reported elsewhere [10].
20 lm 40 lm

JAL1 1.5 1.6

Conclusions
JAL2 2.1 2.2
JAL3 2.3 2.4
An investigation has been made on the utilisation of
JAL4 2.4 2.5
jatropha seed oil for the preparation of alkyd resins. The

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presence of linoleic acid revealed that, the jatropha oil
bears semi drying nature and suitable for the preparation of
alkyd resins. The kinetics of polyesterification reaction of
alkyd resin preparation followed a second order reaction
with a rate constant in the order of 10-5 g (mg KOH-1).
The polyesterification reaction found to reach an appre-
ciable level before the deviation from the second-order rate
law. The alkyd resin with 50% oil content has showed the
highest degree of polymerisation. The drying performance
of the investigated alkyd resins can be further enhanced by
blending with fast drying resins.
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