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Chemical Engineering Department, Faculty of Engineering, Nnamdi Azikiwe University, Awka, Nigeria.
*E-mail: cf.uzoh@unizik.edu.ng
Received September 14, 2017, Accepted March 7, 2018
Self-cured alkyd resin was synthesized from avocado seed oil (ASO) via a two way alcoholysis-
polycondensation method. The raw ASO was evaluated for its physical and chemical properties and fur-
ther epoxidized, hydroxylated dehydrated to obtain a desaturated ASO. The fatty acids present in the raw
ASO were evaluated with GC–MS while structural composition of the raw ASO, desaturated ASO and
ASO based alkyd resin were evaluated with FTIR analytical technique. A surrogate kinetic model was
used to approximate the acid functional group conversion in the alkyd reactor. FTIR and GC–MS results
confirmed that the oil was predominantly saturated. The oil content of avocado seed is found to be 55%
wt which justifies its availability as an industrial crop. The FTIR result further confirmed esterification
reaction of the oil with acid anhydrides. The results of iodine values show that the unsaturation level of
the oil increased significantly. The alkyd resin C produced met the requirements of standard drying test
(ASTM 1640-D) in presence of nano-ZnO pigment at 32 C; exhibit excellent adhesion, abrasion and
chemical properties. The kinetic study further discloses that conversion (82%), viscosity (269 cP) and
molecular weight average (4434 g/mol) were within the desired value in the state variable space.
Keywords: Avocado seed oil, Non-drying oil, Desaturation, Alkyd resin, Surface coating
Bull. Korean Chem. Soc. 2018 © 2018 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 1
Article BULLETIN OF THE
ISSN (Print) 0253-2964 | (Online) 1229-5949 KOREAN CHEMICAL SOCIETY
flowering plant family Lauraceae. Avocado. They have a and for export has the capacity of generating about 1 billion
green-skinned, fleshy body that may be pear-shaped, egg- USD on annual basis.17 The industrial use of avocado can
shaped, or round. They possess high commercial value and lead to reduction of pressure on conventional raw materials
are grown in tropical Mediterranean climates all over the such as groundnut, beniseed, and other oil seeds used for
world. The avocado seed constitute 16% wt of the entire vegetable oil production. It also has capacity for enhancing
fruit. As of today, USA produce more than 350 million ton the development of pharmaceutical and cosmetic industries
of avocado per year, with the seeds weighing 56 million in the country.17 In this research, therefore, an attempt was
tons. The oil content of avocado seed is 40–56% wt.6–9 made to develop a self-cure alkyd resin from inedible, non-
The oil content is very substantial and compares satisfacto- drying ASO. The polycondensation kinetics study was
rily with other seed oils from different plants such as Hevea enhanced by a surrogate model developed in Ref. 18.
brasiliensis (51% wt), Hematostaphis berter (54.5% wt),
Jatropha curcas (30–50% wt), Sapindus mukorossi (51% Materials and Methods
wt), Mellia azadirachta (33–45% wt), and 55–65% wt for
Simarouba glauca.10 Considering the oil content and avail- Materials. The avocado pears were purchased from the
ability, avocado seed is economically viable for industrial Eke-Awka market in Anambra State. The Avocado pear
applications, since any oil bearing seed that can produce up seeds were sun dried for 1 week after consuming the edible
to 30% oil are regarded as sustainable.11 Currently, there is mesocarp (Figure 1). The dried avocado seeds were milled
no report that avocado seed consumption is safe6–8; in this and the oil extracted by solvent method using a soxhlet
context, therefore, avocado seed oil is considered inedible. extractor. Analytical grade glacial acetic acid, H2SO4,
In most part of the world, the seed is a waste that is dis- phthalic anhydride, maleic anhydride, acetic acid, sodium
posed when the mesocarp has been consumed as food. bicarbonate, lithium oxide, and glycerol were obtained from
Avocado seed oil is a “non-drying” oil meaning that the commercial sources (Merck Chemicals, BDH Chemical
unsaturated group in its chemical structure that would Limited, Poole, UK and May and Baker Limited, Dange-
enable it to be polymerized or cured (harden) when suitable ham, UK) and used without further purification.
conditions are provided. This is a major impediment for
their use in alkyd resin production. The process of alkyd Methods
resin formulation should begin with the question, “what are Chemical Modification of the ASO. The raw ASO was
the intended applications of the resin?” The application dic- desaturation according to the method described in Ref. 19
tates property requirements, such as solubility, viscosity, as shown in Figure 2.
drying characteristics, compatibility, film hardness, film
flexibility, acid value, water resistance, chemical resistance,
and environmental endurance. Therefore, the only way avo-
cado seed oil can be polymerized is by desaturation and
attaching appropriate chosen functional group to the oil
molecule that changes its behavior and structure; converting
it from non-curable to curable product.
Utilization of drying oil in the alkyd resin synthesis is
not only costly, but also the resins are prone to yellowing
due to the extreme unsaturation level of the dry oil. There
is a paradigm shift on the use of non-drying oil in the alkyd
resin synthesis. Issam et al. observed in their work that
without using drying agent, the curing process of non-
drying palm oil found difficulties, but using drying agents,
the produced resins showed satisfactory adhesion onto alu-
minum surface as a substrate.12 In previous works, non-
drying palm oil, palm kernel oil, and coconut oil have been
utilized in alkyd resin synthesis by attaching an appropriate
chosen functional group to the oils molecules that changes
its behavior and structure.12–14 In another account, Muham-
mad et al.15,16 also synthesized an alkyd resin from non-
drying palm oil by increasing the unsaturation content and
incorporation of carbon nanotubes. Apparently, there is no
report on the use of ASO in the alkyd resin synthesis. ASO
was chosen for alkyd resin synthesis in terms of its avail-
ability, renewability, biodegradability, and inedibility. The
development of avocado in Nigeria for industrial utilization Figure 1. Avocado pear seed.
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Table 2. The characteristics of the crude and modified avocado seed oil (ASO).
Crude Neutralized Epoxidized Hydroxylated Dehydrated Dehydrated
Properties ASO ASO ASO ASO ASO palm oil (17)
Free fatty acid value (%) 1.85 1 — — 1 0.98
Color Light yellow Golden yellow Whitish yellow Whitish yellow Dark brown —
Refractive index (25 C) 1.431 1.450 — — — —
Specific gravity (25 C) 0.893 0.899 0.9393 0.9456 0.9012 0.970
Viscosity (pa s) 3.336 3.392 — — 3.486 1.69
Saponification 38.22 — — — 140.41 —
value (mgKOH/g)
Acid value (mgKOH/g) 3.90 — — — 6.20 —
Iodine value (gI2/100 g) 34.9 — — — 125 127
Set to touch (h) — — — — 4 3.5
Drying time (h) — — — — 7 4.5
Oil content (wt %) 55 — — — 44 —
Physical state (25 C) Liquid Liquid Liquid Liquid — —
Ash content (%) 5 — — — — —
shown in Table 2. It is observed that the neutralization pro- unsaturation (Figure 1) of the aliphatic chain by ring-open-
cess reduced the free fatty acid (FFA) content of crude ASO ing, addition and elimination reactions, respectively.
from oil from 1.85 to 1, with a refractive index of 1.450 Evidently, it can be established from the results shown in
from 1.431. In the neutralization process, the free fatty acid Table 2 that modified ASO is quite acceptable in alkyd
content of oil was converted to oil soluble soaps. Traces of resin preparation. Specifically, its degree of unsaturation
impurities like proteins and /or proteins fragments, phospho- will accommodate the cross-linking reactions for alkyds to
tides, and gummy or mucilaginous substances were also form dry, hard solid film.20 The set to touch time and dry-
removed by the neutralization process. The acid value ing time show the drying properties of the dehydrated ASO
increases from 3.90 to 6.20 mg KOH/g. Specifically, it was sample. The saponification values of crude and dehydrated
observed the characteristics of the oil changed as it passed ASO were 38.22 and 140.41 mg KOH/g, respectively. The
through the various modification procedures (epoxidation, saponification value reveals average molecular weight of
hydroxylation, and dehydration) to obtain a chemically fatty acids of triglyceride present in ASO. The iodine value
modified oil. At first, there was increase in the density and viscosity of the dehydrated ASO were within limit of
through epoxidation and hydroxylation, but a seemingly ASTM standard. The drying time and set to touch time
decrease in density after dehydration. The increase in den- gave acceptable result. Therefore, these dehydrated oil sam-
sity during epoxidation and hydroxylation indicates increase ples were acceptable to prepare alkyd resin. Effort to add
in mass per unit volume of the ASO sample which could be comparative data for other non-drying oils in Table 2
attributed as a result of the decrease of low molecular overtly from earlier works found in the literature did not
weight free fatty acid content in the ASO and addition of provide much desired result. This is because epoxidation-
oxygen atom in the fatty acid structure. The increase in acid hydroxylation-dehydration paradigms of production of
value and the decrease in density of the ASO may be attrib- alkyd resins with non-drying oil have not received suffi-
uted to loss of water molecules. Moreover, the acid value cient research attention. However, there is a lot of similari-
increase during the chemical modification step may be as a ties between the results of current study and that of an
result of competing side reactions such as hydrolysis of tri- earlier study,21 where non-drying palm oil were expressly
glycerides to free fatty acids due to presence of mineral acid dehydrated as shown in Table 2.
(H2SO4) during the epoxidation process. The color of the The fatty acid composition of the crude ASO and FTIR
ASO became whitish yellow from golden yellow after the spectra of the crude and modified ASO are shown in
epoxidation and hydroxylation but changed to brown after Table 3 and Figure 4 (a–c), respectively. The fatty acid pro-
dehydration as a result of the relatively high temperature at file as analyzed by gas chromatography–mass spectrometry
which the reaction was conducted. The viscosity of the oil (GC–MS) showed abundance of palmitoleate (31.94% wt)
also increases slightly during the process of the modifica- and arachidic acid (17.16% wt). The most abundant unsatu-
tion. The iodine value showed a reasonable increase (34.9 g rated and saturated fatty acids were palmitoleate (31.94%
I2/100 g to 125 g I2/100 g) showing the increase in the level wt) and methyl stearate (14.22% wt), respectively. The oil
of unsaturation after the chemical modification process. This contains 50.86% saturated fatty acid and 49.10% unsatu-
observation is expected since epoxidation, hydroxylation, rated fatty acid. The high saturation in ASO shows that if it
and dehydration reactions actually took place at the point of is used in the synthesis of alkyd resin, it will form alkyd of
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Article Self-cured Alkyd Resin Using Non-Drying Avocado Seed Oil KOREAN CHEMICAL SOCIETY
Table 3. Fatty acid composition of avocado seed oil. in the early stage of batch operation approaching 80% con-
Concentration version within the first 100 min of the reaction, but gradu-
Carbon molecules Name (ppm) % wt ally slows down as the reaction progresses towards
gelation. Desired conversion (82%), viscosity (269 cP) and
C10 Capric acid 0.1415 1.27
C11 Undecyclic acid 1.1689 10.49
C12 Lauric acid 0.6686 6.00
C20:2 Arachidic acid 1.9122 17.17
C14 Myristste 0.5115 4.59
C16:1 Palmitoleate 3.5592 31.95
C17 Magaric acid 0.5393 4.84
C18 Methyl stearate 1.5846 14.23
C25 Pentacosylic acid 0.4123 3.70
C30 Melissic acid 0.6407 5.75
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0.5
change on resins C and D after immersion on distilled
Experimental
Model water and 0.1 mol of HCl for a period of 18 h unlike resin
0
0 100 200 300
A whose film got whitening after immersion on distilled
water after 18 h. Furthermore, the film of the resins A and
MWA (g/mol.) Viscosity (cP)
400
B got whitening after 6 and 12 h, respectively, when
200 immersed in 0.1 mol of HCl. When the four alkyd resins
Experimental
0
Model
were immersed in 0.1 mol of NaOH, resins A and B films
0 100 200 300 got whitening after 6 h whereas resins C and D films got
10000 whitening after immersion period of 12 h. Resin C showed
Experimental
5000 Model superior resistance than other resin samples. Resin based on
PA only (resin B) showed excellent resistance for NaOH
0
0 100 200 300 solution and fairly resistivity to HCl solution. This might
1 be as a result of the presence of aromatic functional group.
Experimental MA-based resin (resin D) gave fair and poor resistance to
Chi
0.5 Model
the alkali and acid solution, respectively. The poor alkali
0
0 100 200 300 resistant may be ascribed to ester linkages in the alkyd
5
Time (Mins) resins which are known to be prone to alkaline hydrolysis.
From the results, it can be inferred that none of the alkyds
-ln(1-c)
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Set-to-touch
80
70
60
Time (hrs)
50
40
30 dry through…
20 Dry through
10 Surface dry
Set-to-touch
0
Alkyd-A Alkyd-B Alkyd-C Alkyd-D
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The state of the art research facilities provided by the 16. M. R. Islam, M. D. H. Beg, S. S. Jamari, Engineering 2015,
Nnamdi Azikiwe University, Awka is also highly 9, 499.
appreciated. 17. RMRDC, Avocado Utilisation: Its Industrial and Economic
Potential, Raw Materials Research and Development Council
Publication, Abuja, Nigeria, 2012, 76.
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Graphical abstract
Self-cured Alkyd Resin Using Non-Drying Avocado Seed Oil as a Material of Regenerative
Resource
• An alkyd resin has been synthesized from non-drying avocado seed oil (ASO).
• The synthesis was enhanced by epoxidation-hydoxylation-dehydration paradigm.
• The ASO modified alkyd resin show excellent physico-chemico-mechanical properties.
• Overall, a dry through alkyd was obtained with nano-ZnO pigment within 8.3 h.
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