Progress in Organic Coatings 38 (2000) 187192

Preparation, analysis and applications of rubber seed

oil and its derivatives in surface coatings
A.I. Aigbodion
a,
, C.K.S. Pillai
b
a
Rubber Research Institute of Nigeria, P.M.B. 1049, Benin City, Nigeria
b
Polymer Section, Regional Research Laboratory (CSIR), Thiruvananthapuram 695 019, India
Received 6 September 1999; accepted 14 March 2000
Abstract
Rubber seed oil (RSO) and its derivatives, heated rubber seed oil (HRSO) and alkyd resins were evaluated as binders in air drying solvent
and waterborne coatings. HRSO was obtained by heating RSO at 3005

C until the desired viscosity. Acid value of RSO (53) is somewhat

high. The major saturated fatty acids are palmitic (10.2%) and stearic (8.7%) while the main unsaturated fatty acids are oleic (24.6%),
linoleic (39.6%) and linolenic (16.3%). Naturally, RSOis semi-drying and heating enhances its drying ability. GPCanalysis reveals that RSO
consists of a rather high molecular weight fraction that is rarely found in commonly known vegetable oils. The average molecular weight
of RSO is higher than that of HRSO with the latter narrower in molecular weight distribution. Low molecular weight species constitute
greater proportion of the alkyds and their number average molecular weights range between 1379 and 3304 which are comparable to those
of commercial alkyds. The narrower the size distribution the better the quality of these alkyds as binders. Physico-chemical properties of
solvent-borne alkyds vary with oil length (OL) and they are optimum at 50% OL. Water-borne alkyds investigated show that the sample
with lower oil content contains lower volatile organic content. All the alkyd samples and HRSO are fairly resistant to water and alkali
while they are virtually unaffected by acid and salt solutions. However, samples IV and V (water-borne alkyds) are more resistant than
their solvent-borne counterparts (samples IIII) but exhibited lower scratch/gouge pencil hardness. 2000 Elsevier Science S.A. All rights
reserved.
Keywords: Rubber seed oil; Alkyd resin; Volatile organic content; Solvent-borne coatings; Water-borne coatings
1. Introduction
Despite the predominance of petroleum-based products in
the last few years, vegetable oils are increasingly being used
in edible as well as non-edible applications such as surface
coatings including paints, printing inks, rubber/plastic pro-
cessing, pharmaceuticals, lubricants, cosmetics, chemical in-
termediates and diesel fuel substitute/extender [112]. These
diverse elds of applications have resulted in increase in the
demand for vegetable oils. There is thus a compelling reason
to explore low priced and unconventional sources such as
rubber seed oil (RSO) to supplement available sources. Ex-
ploration of such inexpensive sources of vegetable oils has
become imperative in countries like Nigeria where there is
competitive use of presently available vegetable oils for both
edible and non-edible purposes thereby leading to scarcity
and high price [13,14].

Corresponding author.
E-mail address: carmel@alpa-linkserve.com (A.I. Aigbodion)
Rubber seed is obtained in high yield as a by-product of
Hevea cultivated primarily for its latex. Its traditional use is
as planting material. However, research has shown it to be
a rich source of oil that is comparable in quality to dry oils
commonly used in surface coatings [1517]. RSO is there-
fore considered as an attractive candidate for development to
supplement current supply of vegetable oils in the country.
In this study, RSO has been used in the manufacture of alkyd
resins (both solvent- and water-borne) which were evaluated
as binders in air-drying surface coatings. Also, RSO was
modied by heating and evaluated as binders in surface coat-
ings. Heating confers drying ability on the crude rubber seed
oil that is naturally semi-drying. Water-borne RSO alkyds
seem promising in production of low volatile organic com-
ponent (VOC), non-polluting and environmentally friendly
coatings. These represent new areas of application of RSO
which hitherto have been largely wasted. Importantly, de-
velopment of water-borne RSO alkyds is consistent with the
global trend aimed at reduction of VOC of coatings. Sim-
ilarly, heated vegetable oils are currently being favored for
use as printing ink vehicle in comparison to petroleum-based
0300-9440/00/$ see front matter 2000 Elsevier Science S.A. All rights reserved.
PII: S0300- 9440( 00) 00086- 2
188 A.I. Aigbodion, C.K.S. Pillai / Progress in Organic Coatings 38 (2000) 187192
vehicles [2,3]. It is hoped that the result of this study will
open new avenues of application of RSO, enhance the rev-
enue accruable to natural rubber farmers and consequently
boost the agricultural sector of the Nigerian economy.
2. Experimental
2.1. Materials
RSO was obtained from M/s Kathivel and Bros., India.
Technical grade phthalic anhydride (PA), glycerol (GLY),
and xylene were obtained from New India Chemical Enter-
prise (NICE), Cochin, India while laboratory grade trimethy-
lol propane (TMP) was obtained from Aldrich.
2.2. Method
2.2.1. Analysis of RSO
Analysis of RSO was carried out according to IUPAC
standard method [18].
2.2.2. Gas liquid chromatography
Fatty acid composition of RSO was determined by gas
liquid chromatography (GLC) using its methyl esters pre-
pared by AOCS method Ce 266. The GLC consists of a
Hewlett-Packard (HP) Series II, Model 5890 equipped with
hydrogen ame ionizer and an integrator, HP, 3394. The
coiled column (dimension: 3.0 m0.35 mm) was packed
with polyethylene glycol on cross-linked FFAP. The oper-
ation conditions are: oven temperature=180

C, injection
temperature=250

C and detector temperature=300

C. Ni-
trogen gas was used as the carrier gas at a ow rate of
20 cm
3
/min. The methyl esters were identied and quanti-
ed by comparing the retention times and areas under the
peaks of the unknown with those of standard methyl esters.
2.2.3. Heating of rubber seed oil
RSOwas heated with stirring at 3005

Cuntil the desired

viscosity [19].
2.2.4. Preparation of the alkyds
Samples IIII containing 40, 50 and 60% oil, respectively,
were formulated as solvent-borne while samples IV and V
of 40 and 50% oil content, respectively, were formulated as
water-borne alkyds as per the formulation in Table 1. All the
alkyds were formulated to the same alkyd constant of 1.02.
They were all initially prepared as conventional alkyds to
acid value below 10 mg KOH/g employing the alcoholysis
technique with lead (II) oxide as catalyst and xylene (10%
v/w) as the azeotropic solvent according to the method re-
ported previously [20]. Samples IV and V were processed
further to yield water-thinnable alkyds by reacting with
additional PA at temperature 230

C to acid value between

60 and 80 mg KOH/g. Then, it was allowed to cool to 70

C
Table 1
Composition of the alkyds
Ingredients (moles) Alkyd samples
I II III IV V
RSO 0.456 0.575 0.702 0.283 0.342
PA 0.778 0.652 0.531 0.470 0.421
GLY 0.657 0.307 0.328
TMP 0.400 0.332
Alkyd constant (k) 1.02 1.02 1.02 1.02 1.02
and the calculated amount of TEA added to neutralize the
free acid functionality [21,22]. The solution of the alkyds in
2-methyl propan-2-ol (60% w/w) was made slightly alka-
line (pH 8.0) by neutralizing with 25% ammonia solution.
Driers were added followed by addition of de-ionized water
(73% v/w) and surfactant and then agitated vigorously. All
the alkyd samples were evaluated for their physico-chemical
properties in accordance with ASTM 2689-73 techniques.
Performance characteristics of the alkyds and HRSO
were determined thus: viscosity (ASTM D1725-62), dry-
ing schedule (ASTM D1640-69), pencil hardness (ASTM
D3363-74) and resistance (ASTM D1308-57).
2.2.5. Gel permeation chromatography
Gel permeation chromatography (GPC) was used to es-
timate the molecular weight averages of RSO, HRSO and
the alkyd samples. GPC was performed on a Hewlett-
Packard 1081 BHPLC with refractive index detector consist-
ing of three Styragel HT3 columns (dimension: 300 mm
75 mm) of porosity 100 500 and 1000 A (Water Associa-
tion) arranged in series. Tetrahydrofuran of HPLC grade
was used as the mobile phase. 200 l of sample solution
(2% w/v) was injected into the column at 40

C. The ow
rate was 1 cm
3
/min. Propylene glycol of various molecular
weights were used as internal standard. The chromatograms
and integrated data were recorded with a Chromatopac
C-R 3A processor (Shimadzu) using Waters Associates
Programming Version 3.0.
3. Results and discussion
3.1. Properties of RSO and HRSO
The physico-chemical properties of RSO and HRSO de-
termined are given in Table 2. Acid value of 53 indicates that
RSO is highly acidic. Its iodine value is lower than that of
linseed oil but similar to that of soy bean oil which is most
commonly employed in surface coatings [23]. The fatty acid
composition of RSO given in Table 3 shows that it con-
sists essentially of 18.9% saturation comprising mainly of
palmitic and stearic acids; and 80.5% unsaturation compris-
ing mainly of oleic, linoleic and linolenic acids. The lower
linolenic acid (triene) content of RSO than that of linseed
oil (4454%) makes it semi-drying.
A.I. Aigbodion, C.K.S. Pillai / Progress in Organic Coatings 38 (2000) 187192 189
Table 2
Physico-chemical properties of RSO and HRSO
Properties RSO HRSO
Colour Dark Dark
Specic gravity (30

C) 0.910 0.946
Acid value (mg KOH/g) 53.09 4.16
Free fatty acid (% as oleic acid) 26.00 2.09
Saponication value (mg KOH/g) 206.20 181.41
Iodine value (g I
2
/100 g) 135.36 21.34
Bulk viscosity (P) 0.42 152.00
3.2. Molecular weight analysis
GPC chromatograms of RSO, HRSO and the alkyds are
shown in Figs. 1 and 2. Chromatograms of RSO and HRSO
in Fig. 1 contain four peaks each with the fourth peak (d)
more prominent in the chromatogram of HRSO. It can be
seen that while peaks a and b attenuate, peaks c and d in-
crease. Comparison of Fig. 1 with GPC chromatograms of
a series of vegetable oils investigated by Husain et al. [24]
and by White and Wang [25] shows that the presence of the
fourth peak in the chromatogram of RSO seems to be a rare
occurrence in vegetable oils. Such comparison shows that
peak a represents low molecular weight fraction consisting a
mixture of free fatty acids and monoglycerides, peak b cor-
responds to diglycerides and peak c corresponds to a mixture
of triglycerides and oligometric triglycerides. Peak d repre-
senting fraction with rather high average molecular weight
(>38801) is thought to originate from poly-isoprene present
in natural rubber latex. This assertion is reinforced by the
reported presence of tocotrienol found in latex in RSO [26].
The relative peak percent and average molecular weights
of the different fractions are shown in Table 4. The percent
free fatty acid of 20 is in reasonable agreement with the value
of 26 obtained from chemical analysis in Table 2. Similarly,
the equivalent weight of 272.4 estimated from saponication
value also compares well with the value of 249 from GPC.
GPC chromatograms of the alkyds shown in Fig. 2 de-
pict broad size distribution. It is evident from this gure that
proportion of high molecular weight fraction decreases with
Table 3
Major fatty acid composition of RSO
Fatty acid Composition (%)
Saturated
C
16:0
palmitic acid 10.2
C
18:0
stearic acid 8.7
Total 18.9
Unsaturated
C
18:1
oleic acid 24.6
C
18:2
linoleic acid 39.6
C
18:3
linolenic acid 16.3
Total 80.5
Others 0.6
Fig. 1. GPC chromatograms of RSO (1) and HRSO (2).
Fig. 2. GPC chromatograms of rubber seed oil alkyd samples IIII.
190 A.I. Aigbodion, C.K.S. Pillai / Progress in Organic Coatings 38 (2000) 187192
Table 4
Peak percent and average molecular weights of the various fractions of
RSO obtained from GPC
Peak Average molecular weight Percent
a 249 20
b 1460 25
c 9066 45
d >38801 <1
Table 5
Number average molecular weight (Mn) and weight average molecular
weight (Mw) of RSO, HRSO and the alkyd samples
Average molecular weight Polydispersity (Mw/Mn)
Mn Mw
RSO 7393 13076 1.77
HRSO 475 599 1.26
Alkyd samples
I 3234 6186 1.91
II 1379 2147 1.56
III 3304 8406 2.54
increase in oil content. This is probably due to the large
amount of monobasic fatty acid acting as chain terminator
in the alkyd with higher oil content [1]. The average molec-
ular weights determined for RSO, HRSO and the alkyds are
presented in Table 5. While average molecular weight of
RSO is larger than that of HRSO, the latter is narrower in
size distribution wherein it is inferred that the more homo-
geneous the more the drying ability of the oil. On the other
hand, average molecular weight of the alkyds vary in the or-
der III>I>II. The polydispersity indices are 1.91, 1.56 and
2.54, respectively, for samples I, II and III.
3.3. Properties of the alkyds and HRSO
Table 6 contains the physico-chemical properties of the
alkyds and HRSO. The dark colour of the binders is due to
the dark colour of RSO used in their preparation. Acid value
of each sample is lower than 10 mg KOH/g while the higher
saponication value of the alkyds than that of pure RSO
is attributable to their being composed essentially of ester
groups. Heating reduces the saponication value of RSO.
The level of unsaturation of the alkyds as indicated by their
iodine value shows that this property varies with formulation
Table 6
Physico-chemical properties of HRSO and the alkyd samples
Properties HRSO Alkyd samples
I II III
Colour Dark Dark Dark Dark
Acid value (mg KOH/g) 4.10 8.27 9.85 4.70
Saponication (mg KOH/g) 181.41 391.94 530.40 493.92
Iodine value (g I
2
/100 g) 21.34 48.81 66.12 78.78
Table 7
Performance characteristics of HRSO and of alkyd samples
Properties HRSO Alkyd samples
I II III
Specic gravity (at 30

C) 0.940 0.956 0.944 0.966

Viscosity (P) 60% solution (w/v) 4.89 3.11 7.46 2.54
Solid content (%) 60.36 69.21 74.03 64.76
Drying time surface dry (min) 150 150180 120 210
Dry through (h) 24 24 12 24
Pencil hardness
Scratch F H HB 2B
Gouge 2H 3H F HB
and seems to increase with increase in the amount of oil used.
Heating drastically reduces the level of unsaturation. This is
due to thermal polymerization of the oil during heating at
such temperature.
3.4. Performance evaluation of the alkyds and HRSO
These properties are presented in Tables 7 and 8. Although
all the alkyds were formulated with the same alkyd constant
of 1.02 they differ in properties. In Table 7, specic grav-
ity of the alkyds ranges from 0.944 for sample II to 0.966
for sample III, while that of HRSO is 0.940. Sample II has
the highest viscosity of 7.46 P and sample III has the low-
est viscosity of 2.54 P. Their solid contents (%) vary in the
order II>I>III consistent with variation in viscosity. Sample
II also exhibited the fastest drying rate. This is likely due
to the balance in the ability of this alkyd sample to dry by
evaporation of solvent and autoxidation. The scratch/gouge
pencil hardness exhibited by alkyd samples IIII and HRSO
lms were F/2B, H/3H, HB/F and 2B/HB, respectively.
Results in Table 8 show that samples IV and V are lighter
in colour than samples IIII. Both samples have the same
specic gravity. However, sample IV is about six times
more viscous than sample V and it is also of lower VOC.
Another important property of both alkyds critical to their
application in air-drying coatings is their drying schedule.
It was observed that on application of aqueous solutions of
Table 8
Physico-chemical properties and performance characteristics of alkyd sam-
ples IV and V
Properties Sample
IV V
Colour Dark brown Dark brown
Specic gravity (at 30

C) 0.940 0.940
Viscosity (P) 60% solution (w/v) 6.38 1.13
VOC (g/l) 308 338
Dry through time (h) 24 24
Pencil hardness
Scratch 2B 4B
Gouge HB 3B
A.I. Aigbodion, C.K.S. Pillai / Progress in Organic Coatings 38 (2000) 187192 191
Table 9
Resistance of alkyd and HRSO lms
a
Type of coating Medium
Distilled water Alkali (N/10 KOH) Acid (N/10 KOH) Salt (5% w/v NaCl)
Alkyd samples
I 4 6 1 1
II 5 3 1 1
III 5 6 1 1
IV 2 2 1 1
V 1 1 1 1
HRSO 2 6 1 1
a
No effect=1, whitening of lm=2, slight shrinkage of lm=3, little blisters=4, lm softened=5 and lm removed=6.
samples IV and V as thin layer, their lms initially cloudy
became clearer and transparent after some time. This phe-
nomenon has been referred to as setting resulting from
coalescence of the latex particles [2730]. The time for this
occurrence is much earlier for sample IV than sample V.
However, both samples tend to exhibit slower drying rate
than their solvent-borne counterparts. This is likely due to
the need for the aqueous medium to evaporate before the
on-set of drying of the alkyd lm by the process of autox-
idation in a similar fashion to conventional alkyds [31,32].
The scratch/gouge pencil hardness for samples IV and V is
2B/HB and 4B/3B, respectively.
3.5. Resistance of alkyd and HRSO lms
It can be seen from the results in Table 9 that the lms are
affected to various degrees by these media and resistance
tends to depend on the OL. Samples IIII are more suscep-
tible to water and alkali than samples IV and V. They are
unaffected by acid and salt media. HRSO lm also shows
a similar trend in its resistance. Sample IV is less resistant
than sample V. Both are more resistant than samples IIII
in these media.
4. Conclusion
RSO, a by-product of Hevea and its derivatives, HRSO
and alkyd resins have been investigated for use in surface
coatings. RSO, which is a renewable resource material is
naturally semi-drying, while heating at 300

C for 6 h con-
fers reasonable drying ability on it. They are constituted
mainly of low molecular weight species and number average
molecular weight ranges from 1379 for sample II to 3304 for
sample III. The narrower the molecular weight distribution
the better its performance as a binder. Although alkyd sam-
ples IIII and HRSO exhibit faster drying rate than samples
IV and V they are less resistant. Generally, the alkyds and
HRSO are susceptible to water and alkali and are virtually
unaffected by acid and salt. All the alkyd samples and HRSO
exhibit reasonable degree of scratch/gouge pencil hardness.
Properties of the alkyds vary with oil content and they are
optimum at 50% OL. Results of this study indicate that RSO
is an attractive domestic substitute for imported drying oils
in the manufacture of alkyd resins including those contain-
ing low VOC for non-polluting coatings.
Acknowledgements
The authors wish to express their gratitude to Dr. G.V.
Nair, Director, Regional Research Laboratory, Thiruvanan-
thapuram, India, for providing laboratory facilities for this
work. This work was funded by Council of Scientic and
Industrial Research (CSIR), Government of India and Third
World Academy of Science (TWAS), Italy.
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