Malaysian Polymer Journal, Vol 4, No.

1, p 42-49, 2009
Available online at www.fkkksa.utm.my/mpj

42
A Study of the Effect of Pal m Oil on the Properties of a New Alkyd Resin

Issam A. M.* and Cheun C.Y.

School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia.


ABSTRACT: A new alkyd resin was synthesized by reacting glycerol, phthalic anhydride
and mono fatty acid (palm oil) (Alkyd-P) in the presence of calcium oxide as a catalyst. At
the first stage, palm oil was converted to monoglycerides as a polyol by alcoholysis.
Esterification process was held at the second stage by adding phthalic anhydride and
xylene in the mixture. FT-IR was used to detect the chemical structure of ester links
present from the condensation reaction. Physical properties of the alkyd resins were
studied in terms of viscosity, drying time and solubility. Mechanical properties of the alkyd
resins were also investigated by means of pendulum hardness, adhesion and impact
strength. The analysis showed that the alkyd resin based on palm oil had difficulty in
drying with the absence of a drying agent. However it exhibited excellent adhesion, which
indicated better protection to the substrate (aluminium).

Keywords: palm oil, alkyd resin, physical properties, mechanical properties, adhesion.



1.0 INTRODUCTION

Alkyd resins are widely used in the coatings and paints industry and they have
become indispensable raw materials that are used for the production of industrial and
household finishes [1]. The principal raw materials involved in the preparation of these
alkyd resins are polyhydric alcohols (polyols) and dibasic acids (or corresponding
anhydrides) together with the modifying oils (mono fatty acids such as soya bean, castor,
coconut and cotton-seed) [2, 3].

Palm oil is one of the most widely used plant oils in the world, which is grown in
mass plantation in tropical countries. The competitive environment of the industry provides
the drive needed to develop coatings that utilize less expensive material. Palm oil differs
from its major competitors (soybean, sunflowerseed, and rapeseed oil) in that it is
obtained from a perennial tree crop and drought impacts are less severe in comparison to
oilseed crops. Palm oil which contains significant amount of saturated bonds that
presumably contribute to the non drying property of the resin synthesized. The non-drying
alkyds have made tremendous improvement in quality of nitrocellulose lacquers [4].

Preparation of the alkyd resin from non-drying palm oil may expand the application
of the oil in various areas as environment-friendly materials, because of its abundance
and renewability. There is no study reported on the synthesis of alkyd resin based on
palm oil so far. However, the use of petroleum based monomers in the manufacture of
polymers is expected to decline in the coming years because of spiraling prices and the
high rate of depletion of the stocks. This has inspired the technologists all over the world
to investigate renewable natural materials as an alternate source of monomers for the
polymer industry as substitute for the petroleum-based monomers to manufacture of
polymers [5]. In this study, the effects of palm oil on the properties of alkyd resin
compared with common alkyd resin based on the soya oil (Alkyd-S) are evaluated.
_______________

*Corresponding author:
E-mail: issam@usm.my (Issam A.M.)
Issam and Cheun, Malaysian Polymer Journal, Vol 4, No.1, p 42-49, 2009
43

2.0 EXPERIMENTAL

2.1 Materials
Nur Suria pure palm oil was supplied by Soon Leong Enterprise. Phthalic
anhydride with assay and purum 97% was purchased from Fluka Chemical whereas
glycerol was from R&M Chemicals. Calcium oxide was supplied by Hamburg Chemical
Gmbh with assay 96% and xylene was supplied by Mallinckrodt Chemical with assay
99.7%. Cobalt was used as a drier, supplied by Euro Chemo-Pharma Sdn. Bhd.

2.2 Method
Palm oil and 0.1% calcium oxide (based on oil) were placed in the reaction flask.
The composition prepared in this study is presented in Table 1. The mixture was heated
up to 235
o
C using a heating mantle and nitrogen was allowed to flow in swiftly. Glycerol
was then added into the flask. The solubility of the product formed was monitored after
two hours. Phthalic anhydride and 10% xylene (based on weight) were placed in the
reaction flask which was fitted with dean-stark trap. The temperature was controlled
between 180
o
C~220
o
C for 3 to 4 hours using a laboratory temperature controller.

Table 1: Synthesis of Alkyd-P
a
Equivalent weight (E), (E=W / e =M / F)
b
Weight (W)
Total equivalents present at start of reaction
c
Number of acid equivalents
d
Number of hydroxyl equivalents
e
Functionality (M / E =e / m)
Number of moles (m)
f
Total moles present at start of reaction


2.3 Testing

2.3.1 Dryi ng ti me
Aluminum plates were cleaned by ethanol to make sure that there are no
contaminants present to affect the test result. A hand coater with different fixed coating
thickness was used to evenly coat the resin on the surface of the testing plates.

2.3.2 Vi scosi ty
HAAKE Rotary Viscometer PK 100 was used in this test at 25
o
C.
Raw
Materials

Amount
Charged
(g)
E
a

(g/eku)
e
0
(W/E)

b

e
A
c
e
B
d
F
e
M
o
f

Palm Oil 55 256 0.2154 0.2154 1 0.2154
Phthalic
anhydide
31 74 0.4180 0.4180 2 0.2090
Glycerol 14 31 0.4497 0.6651 3 0.2217
Total 100g 0.6334 0.6651 0.6461
Issam and Cheun, Malaysian Polymer Journal, Vol 4, No.1, p 42-49, 2009
44

2.3.3 FT-IR spectra anal ysi s
The chemical composition of Alkyd-P and Alkyd-S were confirmed by Nicolet FT-
IR Avatar 360. The FT-IR equipment was operated with wavelength range of 4000 400
cm
-1
.

2.3.4 Adhesi on
The dried films were cut by cross hatch cutter and the coating flakes were cleaned
using a brush. A scotch tape was adhered onto the film and peeled of quickly at 180
o

angle. The peeled off grid of areas on the tape were observed by a magnifier.

2.3.5 Impact strength
The dried films in various thicknesses on separate aluminium testing plates were
tested using Tubular Impact test machine.

2.3.6 Pendulum hardness
Hand coater of different fixed thicknesses was used to coat the resin on glass
testing plates. The dried film was tested using Pendulum Hardness machine.

3.0 RESULTS AND DISCUSSIONS

3.1 Physi cal properti es
Figure 1 shows drying rate of alkyd resin based on palm oil (Alkyd-P) with different
thickness applied and amount of cobalt employed. Palm oil categorized as non-drying oil
which containing fatty acids that are higher portion in saturated chains than other types of
oil. Non-drying oil alkyds do not readily form films without catalyst. Thicker films (120 m)
required much more time to dry compare with thinner films (30 m). The drying
mechanism of thicker films necessitates higher amount of cobalt to cross-link between the
chains. When the concentration of catalyst was decreased, a less dense cross-linked
network was formed [6]. The drying time of the thicker films alkyd can dramatically
accelerate the oxygen uptake either at the double bonds or at the methylene groups as
the increasing presence of driers [7].

Figure 1: Drying time of Alkyd-P

The alkyd resin based on palm oil and soya oil showed about the same solubility in
different types of solvents. The solvents used include benzene, toluene, xylene, DMF,
acetone, ethanol and methanol. The solvent molecules increases the distance between
0
2
4
6
8
10
12
14
16
4% 5% 6%
D
r
y
i
n
g

T
i
m
e

(
D
a
y
s
)
Cobalt (%)
30 m
120 m
Issam and Cheun, Malaysian Polymer Journal, Vol 4, No.1, p 42-49, 2009
45

the molecular chains of the resin. The spaces between long chains with pendant side
groups of resins are invaded by the solvent molecules as they fill the spaces made
available by chain movements. When movement brings two chains close into proximity,
short range attractive forces are therefore established resulting in restricted chain
movement and thus the formation of a viscous system [8, 9]. Solvents are added to deal
with the problem of high viscous of resin which is an obstacle in substrates wet ability.

The measured viscosity of control sample, alkyd resin based on soya oil (Alkyd-S)
is 7793 cP which is more viscous than that of 4432 cP of Alkyd-P. This is due to the fact
that viscosity is highly dependent on amount of cross linking in polymer. Viscosity
increases with the amount of cross-links, which means the formation of longer and
branched polymer chains. Slight decrease in the cross-linking density of the coating
results in low porosity of the coating [10]. The extent of polymerization directly affects the
viscosity of polymers. Palm oil is classified as non drying oil which contains higher
proportion of saturated bonds and leads to lower degree of polymerization [11]. However,
the high molecular weight of the resin also causes the resin to have an unsuitably high
viscosity, thereby necessitating low-solids formulations for coating applications [12]. In
many paint systems, low viscosity is a desirable attribute in spraying lacquers and
penetrating sealers and stains [11]. Low viscosity entailed their penetrative ability while
concomitant with binding or consolidation of the substrate surface [8, 9].

The FT-IR spectrum of Alkyd-P is shown in Figure 2. Carbonyl group (C=O)
indicated at 1747 cm
-1
. Detection of aromatic C=C is at 1599 cm
-1
and 1580 cm
-1
. The
straight chains of CH stretch in aliphatic compounds found at the bands of 2854 cm
-1
.
Alkene group (CH=CH) is attributed to the band of 3069 cm
-1
. Figure 3 shows the
absorption bands of Alkyd-S by FT-IR, which are quit similar to the absorption bands of
Alkyd-P.



Figure 2: FT-IR spectrum of alkyd resin based on palm oil
Issam and Cheun, Malaysian Polymer Journal, Vol 4, No.1, p 42-49, 2009
46


Figure 3: FT-IR spectrum of alkyd resin based on soya oil

3.2 Mechanical properties
The cross-hatch test was carried out to determine the adhesion of the coatings.
Classification of the adhesion and testing method is in accordance with ASTM D 3359-78
standard [14]. There are six different classifications of the results of this test. There are;

5B 0% area removed
4B less than 5% area removed
3B 5-15% area removed
2B 15-35% area removed
1B 35-65% area removed
0B greater than 65% area removed

The results shown in Table 2 clearly indicated that the coating had very good
adhesion properties. No delamination or detachment of films at the edges and within the
square lattice was observed on thickness of 30m and 60m of Alkyd-P. While only
detachment of small flakes of the films observed at the intersections of the cuts on
thickness of 90m and 120m of Alkyd-P. The good adhesion to the substrate is
attributed to the inherent chemical structure and flexibility of the alkyd resin [13]. Certain
polar groups in a film such as carboxylic groups (COOH) are very active promoters of
adhesion, due to their attraction to the substrate, or by their influence in improving the
wetting properties. Good initial wetting of a surface by a coating and the maintenance of
wetting during the process of film formation are essential for good film adhesion [11].




Issam and Cheun, Malaysian Polymer Journal, Vol 4, No.1, p 42-49, 2009
47

Table 2: Adhesion in different thickness
Thi ckness Al kyd-P Al kyd-S
30 m 4B (2%) 3B (6%)
60 m 4B (1%) 4B (2%)
90 m 4B (1%) 3B (6%)
120 m 4B (3%) 3B (8%)

During assembly operations or service life a finished part may be subjected to
single blows of varying intensity or repeated impacts of constant intensity. Figure 4
demonstrates that higher impact strength in thicker film possesses ability to resist the blow
of force. This proves that thickness of film affecting the value of adhesion which due to the
impact tests is differentiated according to the resin thickness; as it can be expected, those
corresponding to the higher thickness have lower stress values [15]. Alkyd-S showed
higher impact strength compare with Alkyd-P. The ability of alkyd films to resist the blow of
force is directly influenced by the chains flexibility. A highly flexible coating will prevent the
paint films from cracking and flaking, creating the enamel possesses higher impact
strength.

Figure 4: Impact strength on different thickness of alkyd films

Pendulum hardness of alkyd resins at different thicknesses; 30 m, 60 m, 90 m
and 120 m were studied. Thicker films produced significant hardness compared with thin
films as shown in Figure 5. Alkyd-P had lower film hardness compare with Alkyd-S. Good
hardness of the coating is related to the good cross-linking of the resin as reported by
Shailesh K.D et al. [13]. Cross-linked films generally are harder, tougher and more durable
[16, 17]. The cross-linked films will produce a high molecular weight in polymer, creating
the polymer as hard, as tough and as durable suitable in various applications.

0
500
1000
1500
2000
2500
3000
30m 60m 90m 120m
I
m
p
a
c
t

s
t
r
e
n
g
t
h

(
J
/
m
)
Thickness (m)
Alkyd-P
Alkyd-S
Issam and Cheun, Malaysian Polymer Journal, Vol 4, No.1, p 42-49, 2009
48


Figure 5: Pendulum hardness on different thickness of alkyd films

4.0 CONCLUSION

Alkyd resin based on palm oil (Alkyd-P) was synthesized and characterized
successfully. FT-IR spectrum confirmed the chemical structures of both Alkyd-P and
Alkyd-S with the functional ester groups present. The studies established that the
excellent adhesion of Alkyd-P compare with Alkyd-S. Alkyd-P and Alkyd-S showed about
the same solubility among the eight types of solvents tested. The hardness, impact
strength and viscosity of Alkyd-P was lower compare to Alkyd-S, thus showed its
insufficiency to produce a hard film, however, suitable to produce a film which required
high wet ability such as sealer. Drying time of Alkyd-P cannot be determined unless a
drier is added. The drying rate increased directly with the amount of drier employed. It was
observed that increasing the thickness of alkyd film will affect the properties of the resin
due to the inherent chemical structure of palm oil and reactions that took place during the
production alkyd.

5.0 ACKNOWLEDGEMENT
The authors would like to thank Universiti Sains Malaysia for the financial support.

6.0 REFERENCES
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nd
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& hall London.

[3] Saunders, K.J . (1988), An Introduction To the Organic Chemistry or Adhesives,
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nd
Edition, Chapman & hall London.

[4] Williams, R. C. (2000), Advances in alkyd resins, Applied Polymer Science: 21st
Century, pp. 471-481.
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[16] Turner, G.P.A. (1988), Introduction to Paint Chemistry and Principles of Paint
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rd
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nd
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