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Article BULLETIN OF THE

DOI: 10.1002/bkcs.11444 C. F. Uzoh and O. D. Onukwuli KOREAN CHEMICAL SOCIETY

Self-cured Alkyd Resin Using Non-Drying Avocado Seed Oil as a


Material of Regenerative Resource
C. F. Uzoh* and O. D. Onukwuli

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

Introduction Consequently, there is an enhanced zeal and motivation to


develop coatings that uses inexpensive and sustainable
Special attention has risen to the forefront to the use of oils material in the coating industry.
that do not constitute food source and are substantially The use of seed oil as a material of regenerative
available for materials synthesis and their applications. Sur- resource is proliferating by the day in the chemical indus-
face coating materials are no exception. Surface coating is tries. This observation is as a result of consideration for
a general description for any material that can be applied as renewability, sustainability, and environmental friendli-
a continuous film to a surface. Alkyd resin is the major ness.3 Seed oils such as palm oil, groundnut oil, soya bean
ingredients of most surface coating materials. Their wide oil, and coconut oil etc., have been widely used for both
application as coating materials is as a result of their versa- edible and industrial applications. The dual usage of some
tility and capability of being engineered to give a wide of these oils has tremendous adverse effect in their avail-
brand of acceptable properties in terms of usage in coating ability; thus leading to relatively higher price of crops like
industries.1 Alkyd resin contains agro (50–70%) and petro- soya beans. Moreover, numerous locally available seeds
leum (25%) base raw materials as compared to commercial that are potential sources of industrial oil are mostly under-
resin containing 50–70% petroleum based products, which utilized.4,5 Some of the traditional oils employed in the
are imported. The alkyd resin can be made hydrophilic; alkyd resin synthesis are linseed, soybean, safflower, etc.,
hence it can be used in emulsion polymer synthesis. Vola- while those of non-traditional oils are neem oil, tobacco
tile organic compound (VOC) content of conventional seed oil, nahor oil, kamala oil, babool oil, etc.1 There is a
alkyd resin is 40% while the new alkyd resin was 14%.2 dire need, therefore, to investigate for more seed oil for
The cost of novel alkyd resin is less than the commercial, industrial applications and enlarge the current vegetable oil
as it uses more agro based products and less energy. More- supplies, especially in Nigeria. The sole aim is to alter seed
over, advantages of alkyd resins include agro based, energy oil that constitutes food sources with non-edible ones that
efficient, eco-friendly, low cost, controlled polymerization, reduce the problem of food shortage. There are many
low risk of batch failure and less volatile organic compo- potential oil crops waiting to be harnessed. Avocado seed
nents.2 The high cost, the environmental impact, and the oil (ASO) is one of such under-utilized non-edible seed oil
fear of depletion fossil resources for the manufacturing of with potential significance.
surface coating, are generating a lot research concerns in The avocado (Persea americana) is a tree that is native
different industrial field for alternate raw materials. to South Central Mexico, categorized as a member of the

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Article BULLETIN OF THE
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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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Article Self-cured Alkyd Resin Using Non-Drying Avocado Seed Oil KOREAN CHEMICAL SOCIETY

Figure 2. Proposed modification of a section of ASO triglyceride


chain.

Synthesis of ASO-modified Alkyd Resin. Four different


alkyd resins were synthesized from ASO using lithium
hydroxide as catalyst according to the recipes shown in
Table 1. Resin-A was prepared from the refined unmodified
ASO, Resin-B was prepared from modified ASO and phtha-
lic anhydride (PA) only while resins-C to D were prepared
from the modified ASO with varying concentration of
phthalic anhydride and maleic anhydride (MA) (Table 1).
The reactions were conducted in a three necked round
bottom flask titled with a motorized stirrer, a dean-stark
trap titled with water-cooled condenser and nitrogen in let
tube at a temperature of 215–255  C. Xylene was used as
an azeotropic solvent. In the course of alcoholysis, the tri-
glycerides of ASO were transformed into monoglycerides
by reaction with glycerol at 180–200  C. PA, glycerol, and
xylene were then added, and polymerization was carried
out at 215–255  C for more than 5 h as shown in Figure 3
(a). An appropriate amount of MA was then added to com-
plete the reaction (Figure 3(b) and (c)). The concentrations Figure 3. (a) Alcoholysis. (b) Esterification: First stage-Reaction
of alkyd solutions were determined and finally diluted to with Phthalic anhydride (PA). (c) Esterification: Second stage-
70–75% by addition of xylene. The progress of reaction reaction with maleic anhydride (MA).
was monitored by measuring the evolved water of reaction
mechanical and chemical properties by standard methods.20
and checking the acid number by titration specific interval
Infrared spectra of the alkyds were also recorded on the
of time. The fatty acid of the raw ASO was determined
FTIR spectrometer. The dry time test was repeated when
with a Thermo Finnigan Trace GC/Trace DSQ/A1300
nano ZnO pigment was included in the prepared resin.
(San Jose, California), according to a method described in
A surrogate model of the form:
Ref. 18. The chemical compositions of the raw ASO, modi-
fied ASO and ASO modified alkyd resin were also evalu-
cðt Þ = 1 − e − ½k F ðt Þ + ψ 
*

ated with SHIMADZU FTIR-84008 (Kyoto, Japan). ð1Þ


Viscosity was confirmed by Brookfield viscometer (Mid-
dleboro, MA USA), RVT Model (#Spindle 3, RPM 22). was used to approximate the motion and the trajectory of
The physical and chemical properties of the raw and modi- the polyesterification reaction process such that the desired
fied ASO were determined by standard methods (ASTM, properties were kept within specification.18 The terms of
1973). The synthesized alkyd resins were thinned with the linear integral conversion model (Eq. (1)) k* and ψ
xylene and coated as thin panels on an aluminum plate of which describe the reaction path represent the universal
55 × 55 × 0.1 mm3 dimension according to ASTM D kinetic constant and the integration constant, respectively.
1640. The dried films were equally evaluated for k* and ψ could be obtained (for the linear integral conver-
sion model) from the gradients and the intercept, respec-
tively, of the linear plot of − ln(1
Ð − c) against F(t).
Table 1. Formulation of the ASO-modified alkyd resin.
Where the integral F ðt Þ = f ðt Þ dt≔ 32 t + 2ωcos ðωt − ϕÞ
Oil length Glycerol LiOH − ωsin2ðωt − ϕÞ. c is conversion.
Resin type (%) (g) (g) PA (g) MA (g)
Resin-A 50 50 1 50 —
Results and Discussion
Resin-B 50 50 1 50 —
Resin-C 50 50 1 25 25
Characteristics of Crude and Modified ASO. The physi-
Resin-D 50 50 1 15 35
cal and chemical properties of crude and modified ASO are

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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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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

weak drying rate but color retentive. ASO, therefore, if


structurally modified, can give alkyd resin with a more sat-
isfying performance. In Figure 5, the spectrum of the
unmodified ASO, 3714 and 3487 cm−1 correspond to the
hydroxyl group (O H) of the unsaturated fatty acid in the
oil. The carboxyl group (C O) is indicated at 1954 cm−1.
The straight chain of CH stretch in aliphatic compound
is located at the band 2934 cm−1. Alkene group (CH CH)
is ascribed to the band of 1677 cm−1. The FTIR spectra of
crude ASO shows the peak value at 1123 cm−1, and
1239 cm−1 which correspond to cyclic ester of saturated
oil. However, for the dehydrated ASO, an apparent reduc-
tion in the O H stretching vibration was noticed in
Figure 4(c) (3109 cm−1), which shows an increase of unsa-
turation as the ASO pass through the various processes of
the modification. The peaks of the epoxidized ASO were
similar to the crude samples while those due to the hydrox-
ylated ASO were similar to the dehydrated samples.

Synthesis of ASO-modified Alkyd Resin. During the


polyesterification reaction, the synthesis of alkyd macro-
mer, was monitored by checking of the acid number of the
reaction mixture at definite interval of time. Polyesterifica-
tion was carried out by heating a mixture of monoglyceride
mixture and phthalic anhydride/and maleic anhydride
according to the defined recipe and the product obtained
from the alcoholysis step until the acid value reduced to
about 10.22 This shows that the acid value reduces slowly
with time. Utilization of maleic anhydride as a polybasic
acid introduces an additional complexity to the formulation
of alkyd resins. Due to its olefinic unsaturation it produces
extra compounds with the unsaturated fatty acids (for
example adduct of Diels-Alder synthesis) which become
part of alkyd composition along with the common esterifi-
cation of the two acid groups with a polyhydric alcohol.23
The necessary task involved in predicting the reaction pro-
gress and product quality basically requires that the conver-
sion of acid functional group at any time during the
reaction is first evaluated. Figure 5 describes the dynamics Figure 4. (a) FTIR spectra of unmodified avocado seed oil.
of the reaction. The entire results in terms of the predicted (b) FTIR of spectrum of epoxidized avocado seed oil. (c) FTIR
state parameter suggest that the reaction was relatively fast spectrum of dehydrated avocado seed oil.

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1 resin A and resin B. It was equally noticed that there is no


conversion

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)

have a perfect resistance to the alkali solution. However,


Model
Linear fit alkyd C has the best chemical resistance in alkali solution
0
0 100 200 300 400 500 relative to alkyd A, B, and D, because it takes longer time
F(t) before its film got whitening. The result shows that alkyd C
Figure 5. Approximation of conversion, viscosity and molecular has a very good chemical resistance.
weight average (MWA), for the studied batch reactor. The resins A to D were each, applied on the surface of
the four different aluminum plates by hand coating. The
molecular weight average (4434 g/mol) which were within surfaces were cleaned with an ethanol to make sure that the
the desired value in the state variable space was obtained surfaces of the aluminum plates were free from impurities
(Figure 5). which might alter the drying test conducted on it. The
Performance Evaluation of ASO-modified Alkyd Resin. results of the drying time of the resins A to D at indoor
The performance of ASO modified alkyd resin was evalu- temperature of 32  C  2 are shown in Figure 5.
ated in terms of their physical, chemical, and mechanical It can be seen that a tremendous improvement was obvi-
properties (drying schedule, chemical and abrasion resis- ous in both set to touch, surface dry, and dry through time
tance, adhesion, impact, and scratch hardness test). Table 4 from resin C to D. Specifically, resin C and D have a better
shows the chemical resistance of the four different medium drying schedule compared to the resin A and B, respec-
oil length ASO-modified alkyd resins determined in three tively. It can be concluded from these results, therefore, that
media; distilled water, 0.1 mol of sodium hydroxide, and alkyd C and D could be used as a binder in surface coating
0.1 mol of hydrochloric acid. From the table, it was formulations as it showed comparable coating characteris-
observed that the resins C and D have good chemical resis- tics (drying time) to other reported oil modified alkyd.24
tance properties in the three media when compared to the The acid value and carboxyl functionality (F-COO) have

Table 4. Chemical resistance of the alkyd films.


Alkyd resin Resin A Resin B Resin C Resin D
Immersion
Media time (hours) Appearance of the film Appearance of the film Appearance of the film Appearance of the film
Distilled water 6 4 4 4 4
12 4 4 4 4
18 1 4 4 4
0.1 mol NaOH 6 1 and 2 1 4 4
12 3 2 1 1
18 3 3 1 3
0.1 mol HCl 6 1 4 4 4
12 2 1 4 1
18 3 3 1 2
1 = Whitening; 2 = Blistering; 3 = Removal; 4 = No effect.

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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

Figure 6. Drying characteristics of alkyd resins a to D.

effect on drying time of the resin. As seen from Figure 6,


resins C and D which have relatively small acid value when
compared to resins A and B have the best drying properties.
Figure 7. FTIR spectrum of alkyd resin from avocado seed oil.
Figure 6 further discloses that none of the resin samples
were able to dry hard overnight. However, on addition of
nano-Zinc oxide (ZnO) pigment to all the resins, resin C
was able to dry hard overnight (9 h). The drying time FTIR Spectra of the ASO Alkyd Resins. The FTIR spec-
reduction of the alkyd film may be due to the increased trum of the ASO alkyd resin is shown in Figure 7. The IR
chemical potential attributable to the nano-ZnO pigment. spectrum of the synthesized resin exhibits a unique straight
Contribution of surface energy to total energy content of chain ester band at 1851 cm−1 and aromatic (C C) ring
nano-material, positively influence its chemical energy/ ester at 1974 cm−1. The reduction of the intensity of the
reactivity; invariably, leads to extensive acceleration of OH groups and appearance of carbonyl groups of esters
chemical reactions.25 (RCOOR’) signal at 1825 cm−1 confirm esterification reac-
From Table 5, it was observed that the four medium oil tions; this signal is conspicuously absent in the raw ASO
length ASO-modified alkyd resin produced exhibits varying and the modified ASOs (Figure 4(a)–(c)). Around 1355 and
mechanical properties when subjected to impact, adhesion, 1571 cm−1, overtones seem to appear, which are assigned
and scratch hardness test. Resins A and D show poor, to C C stretching of aromatic rings. The absorption
impact, hardness, and adhesion properties while C and D band at 1678 cm−1 is characteristic of alkenes.29,30
passed all the tests. The good hardness and impact proper-
ties of the resins C and D could be as a result of the aro- Conclusion
matic moiety presence in phthalic anhydride, while
adhesion is ascribed to the polar ester bond.26–28 No flak- Alkyd resin has been synthesized from nondrying avocado
ings or ribboning was noticed after making cuts and apply- seed oil as environmental friendly material of regenerative
ing the adhesive tape. The maleic anhydride on the resource. Epoxidation, hydroxylation, and dehydration pro-
polymer backbone improves adhesion. The hydroxyl cesses were confirmed to have major improvements in
groups (OH) in the structure of the resins also promotes the introducing unsaturation in the pendant chain of the ASO.
adhesion to the substrates. These results suggest the poten- The synthesized alkyd resins possess very good physical,
tial of the formulated alkyd resins as surface coating chemical, and mechanical properties. The study further
materials. showed that inclusion of nano-pigments gave a faster dry-
ing resin. The FT-IR spectrum confirmed the chemical
structures of both the raw oil and their corresponding resins
Table 5. Mechanical properties of the resin A–Resin D. with the functional ester groups present. The polycondensa-
Mechanical test tion reaction was adequately approximated by a known acid
function group conversion model. Therefore, it can be con-
Impact Adhesion
cluded that modified ASO offers an excellent potential
Alkyd resins test test Scratch hardness test
applications for surface coating purposes.
Alkyd resin A Failed Poor H Failed, −
Acknowledgment. The authors would like to pay their
Alkyd resin B Passed Fair H Passed, 2H Failed
most profound gratitude to the Tertiary Education Trust
Alkyd resin C Passed Good H Passed, 2HPassed
Fund (TETFUND), Nigeria, for the hefty research grants
Alkyd resin D Passed Good H Passed, 2HPassed
extended for the accomplishment of this research activity.

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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.
References 18. C. F. Uzoh, O. D. Onukwuli, South African J. Chem. Eng.
2016, 21, 11.
1. S. K. Tiwari, M. Saxena, J. Sci. Ind. Res. 2002, 61, 110. 19. T. E. Odetoye, D. S. Ogunniyi, G. A. Olatunji, Prog. Org.
2. Gogte, B. B., Dabhade, S.B.. Alkyd based on non-edible oils Coat. 2012, 73, 374.
karanja oil (Pongamia glabra), Paint India, pp. 3–5, 1981. 20. Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd ed.,
3. M. A. Meier, R. Metzger, J. O. Schubert, Chem. Soc. Rev. Interscience Publishers, New York, 1966, p. 851 (Vol. 1) and
2007, 36, 1788. p. 388 (Vol. 7).
4. D. S. Ogunniyi, T. E. Odetoye, Bioresour. Technol. 2008, 21. C. F. Uzoh, O. D. Onukwuli, R. S. Odera, S. Ofochebe, J.
99, 1300. Environ. Chem. Eng. 2013, 1, 777.
5. F. E. Ezeagu, K. J. Petzke, E. Lange, C. C. Metges, JAOCS 22. N. N. Hlaing, O. Mya, World Acad. Sci. Eng. Technol. 2008,
1998, 75, 1031. 24, 115.
6. http://www.nutritionmyths.com/is-avocado-seed-edible/ 23. O. M. Musa, Handbook of Maleic Anhydride Based Materials
(05.5.2017) Syntheses, Properties and Applications, Springer, Switzer-
7. E. Barbosa-Martín, L. Chel-Guerrero, E. González- land, 2016, p. 151.
Mondragón, D. Betancur-Ancona, Food Bioproducts Process. 24. G. L. Marshall, Eur. Polym. J. 1986, 22, 217.
2016, 100, 457. 25. H. Abd El-Wahab, J. Macromol. Sci. A Pure Appl. Chem.
8. L. N. Henry, U. Y. Mtaita, C. C. Kimaro, Global Sci. Res. 2017, 54, 271.
2015, 3, 192. 26. E. H. Pryde, J. A. Rothfus, Industrial and non-food users of
9. W. B. Storey, California Avocado Society 1973–74 Yearbook, vegetable oils. In Oil Crops of the World, G. Robbelen, R. K.
1974, Vol. 57, p. 70. Downey, A. Ashri Eds., Mc Graw-Hill, New York, 1989,
10. E. W. Eckey, Vegetable fats and oils. American Chemical p. 87.
Society Monograph Series no. 123, Reinhold Publishing Cor- 27. C. F. Uzoh, O. D. Onukwuli, J. Coat. Technol. Res. 2017,
poration, New York, 1954. 14, 607.
11. P. N. Okolie, A. E. Ajekwene, E. Uaboi, World J. Agric. Sci. 28. S. Ataei, R. Yahya, S. N. Gan, Prog. Org. Coat. 2011,
2012, 8, 359. 72, 703.
12. A. M. Issam, C. Y. Cheun, Malaysian Polym. J. 2009, 4, 42. 29. J. G. Grasselli, S. E. Mocadlo, J. R. Mooney, Applied Poly-
13. M. Boruah, P. Gogoi, B. Adhikari, S. K. Dolui, Prog. Org. mer Analysis and Characterization, Analysis of Polymer by
Coat. 2012, 74, 596. Fourier Transform Infrared Spectroscopy (2), Oxford Univer-
14. http://www.dainet.de/fnr/ctvo/paint/2_workshop/ull.doc sity Press, New York, NY, 2000.
(23.04.2014) 30. S. R. Sanler, Polymer Synthesis and Characterization: A Lab-
15. M. R. Islam, M. D. H. Beg, S. S. Jamari, Procedia Eng. oratory Manual, Academic Press. A Division of Harcourt
2013, 90, 78. Brace and Company, San Diego, California, USA, 1998.

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Graphical abstract

Self-cured Alkyd Resin Using Non-Drying Avocado Seed Oil as a Material of Regenerative
Resource

C. F. Uzoh,* and O. D. Onukwuli

• 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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