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Studies on copra oil self-cured ester as a sustainable material for surface

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DOI: 10.1080/22243682.2015.1040835

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Studies on copra oil self-cured ester

as a sustainable material for surface
coatings
a a a
Chigozie F. Uzoh , Okey D. Onukwuli , Joseph T. Nwabanne &
a
Stone R. Odera
a
Chemical Engineering Department, Faculty of Engineering,
Nnamdi Azikiwe University, Awka, Nigeria
Published online: 22 Jun 2015.

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 Journal of the Chinese Advanced Materials Society, 2015
http://dx.doi.org/10.1080/22243682.2015.1040835

Studies on copra oil self-cured ester as a sustainable material

for surface coatings
Chigozie F. Uzoh*, Okey D. Onukwuli, Joseph T. Nwabanne and Stone R. Odera

Chemical Engineering Department, Faculty of Engineering, Nnamdi Azikiwe University, Awka,

Nigeria
(Received 4 March 2015; revised 6 April 2015; accepted 10 April 2015)

In this paper, synthesis, characterization, and optimization of a copra oil self-cured

ester have been studied. The oil was first analyzed to examine the physico-chemical
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properties (iodine value, viscosity, refractive index, acid value, and specific gravity)
and subsequently neutralized and dehydrated. The synthesis of self-cured ester was
accomplished by reduction of the triglycerides in the oil by alcoholysis and functional
group modification with phthalic anhydride and styrene via free radical co-
polymerization reaction. Structural elucidation of the resin was enhanced by the
Fourier transform infrared (FT-IR) spectroscopic technique. The response surface
methodology (RSM) based on a central composite rotatable design (CCRD) involving
30 experiments of four process variables at five levels was employed for the
optimization study as an economical way of obtaining an optimal response with
fewest number of experiments. The studied process parameters were reaction
temperature, reaction time, catalyst concentration, and phthalic anhydride-to-
monoglyceride oil (PA:MGO) ratio. A predictive model describing the fractional
conversion in terms of process variables was derived from multiple regression
analysis. An optimum fractional conversion of 96.55% was predicted at a reaction
temperature of 241.94
C, reaction time of 124.2 min, catalyst concentration of 0.1%
and PA:MGO ratio of 0.38:1, for the process. The extent of reaction at 135 min of
polycondensation of the monomers was more than 85%. A model validation
experiment shows a good agreement between the actual (97.19%) and predicted
(96.55%) values. Physico-chemical properties and performance characteristics of the
ester indicate its suitability in surface coating applications.
Keywords: copra oil; central composite rotatable design; multi-objective-optimization;
polymerization; free radical co-polymerization

1. Introduction
The high costs, the environmental impact, and the decrease in fossil resources are main
reasons behind attracting a great deal of attention of the research community towards
searching for alternative raw materials in different industrial fields. Copra oil, extracted
from a dried kernel or the meat of a matured coconut palm (Cocos nucifera), is a versatile
oil compared with other unsaturated vegetable oils. It is used by medical, food, oil, chem-
ical, and cosmetic industries. Recently, its production has been intensified due to the pos-
sibility of its use as biodiesel. Most vegetable oils can be used in alkyd resin formulation,
among them the most common are palm oil, palm kernel oil, and coconut oil. Utilization
of palm oil and a palm kernel in alkyd resin formulation has been reported in Uzoh et al.

*Corresponding author. Email: [email protected]

Ó 2015 Chinese Advanced Materials Society

 2 C.F. Uzoh et al.

[1, 2] The use of dry oil is not only costly, but also the alkyds are susceptible to yellowing
due to the high unsaturation level of dry oil.
The production of alkyd resin used in the manufacture of paints and other protective
coating materials from non-drying palm oil involves a two-phase esterification process of
the glyceride oil. Coconut oil is a “non-drying oil”, meaning that its chemical structure
lacks the unsaturated group that would enable it to be polymerized or cured when appro-
priate conditions are provided. Therefore, the only way coconut oil can be polymerized is
by attaching a suitably chosen functional group to the coconut oil molecule that alters its
behavior and structure, converting it from a non-curable to a curable product. The first
phase known as alcoholysis involves the transesterification reaction of glycerol and the
triglyceride of the oil in the presence of a catalyst to obtain monoglyceride oil, while in
the second phase (esterification) the monoglyceride oil generated from the early phase
reacts with phthalic anhydride (PA) to form glyceride phythalate (resin). It is noted that
the application of vegetable oils for the manufacture of resins is generally bedeviled by
the presence of some dissolved non-oil substances such as caroten, chlorophyll, gossypol,
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and other impurities such as phosphatides, oxidation metals, trace metals, and traces of
soaps in the crude samples.[3] In a similar vein, other studies have also shown that the
interactions of some identified system parameters such as reaction time, temperature,
molar ratio of phthalic anhydride to glyceride oil, and catalyst concentration on the poly-
esterification process may equally affect the quality of the product. Hence, to ensure that
highquality alkyd resin of good commercial value with acceptable drying quality, appear-
ance, and other desired coating properties is produced from this process, the unwanted
dissolved substances must be separated from the actual oil sample, and the reaction condi-
tion monitored to control the effects of these influential process parameters. These objec-
tives are achieved through the characterization and optimization of the polyesterification
process presented in this paper. The necessary and usual first tasks involve applying a
standard refining protocol to the raw sample such that an oil product with appropriate
physico-chemical properties (such as photometric color, refractive index, specific gravity,
moisture content, free fatty acid (FFA) content, and iodine value) as stated in the AOCS
standard needed for the production of alkyd resin may be processed. In view of the advan-
tages related to the energy savings and laboratory preference, the chemical (alkaline)
refining method which essentially involves degumming, neutralization, washing, bleach-
ing, and dehydration was chosen for this purpose instead of the distillation process that is
gaining wider popularity in industrial refining due to some advantages associated with the
reduced operation steps and material cost. This is followed by the polyesterification pro-
cess which must be carried out within a predetermined space of the controllable factors
that are known to have considerable effects on the system response. The characterization
(or screening) of these major contributing variables to the process response was achieved
through design-of-experiment (DOE) and analysis of variance (ANOVA), while the con-
trol and optimization tasks were accomplished using the well-known response surface
methodology (RSM). The experimental design was based on a full-factorial central com-
posite rotatable design (CCRD) that guarantees a reduced number of experimental runs.
The experimental analysis enhanced the characterization of the full effects of the four fac-
tors at five distinct settings. The global design matrix of Equation (1) written in coded
notations recommends 16 experimental runs at 24  full factorial distinct points, 8 runs at
the 8-unique axial points, and 6 repeated runs at the center point which give rise to a total
of 30 experimental runs. This sequence of experiments were performed in the equivalent
natural units of the controllable factor space and the extents of reaction (or fractional con-
version) were recorded in terms of the measured percentage drop in acid value of the
 3

solution over the reaction periods using the method given below [4, 5]:

AVi ¡ AVj Vi ¡ Vj
Yn D D (1)
AVi Vi

To study all standard effects of these process variables on the responses analyticaly
often requires fitting an appropriate predictive model usually obtained from regression
analysis of the resulting data on which detailed statistical analysis and optimization exer-
cises are based. Preliminary data analysis conducted using the steepest ascent method
showed that curvature effects exist. In view of the curvature, a reduced order quadratic
model (ROQM) was fitted over the resulting data, as shown below:

X
k XX
k XX
k
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Y D b0 C b i Xi C bij Xi Xj C dij Xi Xj C e (2)

iD1 i< jD2 iD1jD1

where Y is the measured system response (fractional conversion) of the glyceride oil
based esterification process. The first term on the right side of the equation, b0 , is the
model intercept, the second term characterizes the main linear effects of individual pro-
cess variables, the third term incorporates the interaction effects between the variables,
while the fourth term represents the main quadratic effects, and e is the random error of
experimentation. Xij represents the matrix of the uncoded process variables.
Equation (2) serves as the global predictive equation from which a specific solution
may be derived. The determination of the unknown coefficients of b0 ; bi ; bij ; and dij is
accomplished via regression analysis implemented on the statistical analysis software
Design-Expert Version 8.1.7.1 (trial) from Stat-Ease, Inc. using the data recorded from
the investigation.
A critical review of the existing literature on alkyd resin reveals that the few studies
on palm kernel oil and coconut oil can be attributed to kinetics, extent of reaction, and
degree of polymerization.[6, 7] Momodu et al. [8] carried out a similar study using walnut
seed oil. However, all these studies have neglected the interaction effect among process
variables and their effect on process or product characteristics. In this study, we investi-
gated the viability of synthesizing a self-cured alkyd resin from coconut oil from an
approach devoid of guesswork, luck, experience, and intuition.
DOE facilitates systematic, efficient, cost-effective planning and analysis of experi-
mental studies.[8–11] Numerous investigations in other fields have efficiently used such
studies to get an optimal blend of product or process characteristics.[1214] Thus, exper-
imental investigations based on simultaneous variation of composition (process variables)
rather than an OFAT (one factor at a time) approach are needed to get more insight into
the study of air drying of non-drying oil modified alkyd resins.[15] In this study an
attempt was also made to develop a mathematical model for novel self-cure alkyd resin
synthesis based on the DOE technique. The reaction temperature, reaction time, weight
ratio, and weight % of catalyst were chosen as process parameters and their effect on the
acid value was investigated. An optimization problem was then formulated such that both
these responses should fall within a given range for better product quality and
productivity.
 4 C.F. Uzoh et al.

2. Materials and methods

2.1. Materials
Dried coconut oil (copra) was obtained in crude form from an oil mill at Nise, Anambra
State. A rotary evaporator equipped with a digital thermometer, rotatable round bottom
flask, condenser, and water were also used. Other equipment includes an electronic
weighing balance, heating mantle, magnetic stirrer, and general laboratory glassware.
Phthalic anhydride (C6 H4(CO)2O) with minimum assay > 97%, glycerol (C3H8O3)
with assay > 99%, and sodium bisulfate (NaHSO4) with assay 97.5% were purchased
from BDH Chemicals Ltd, Poole, England. Diethyl ether, ethanol, xylene, anhydrous
methanol, sodium hydroxide (NaOH) with assay 96% were supplied by Wharefedale Lab-
oratories, Yorkshire, England. Analytical grade styrene, litharge, benzoyl peroxide, and
nano-zinc drier were obtained from Sigma-Aldrich. The chemicals purchased were of
highest purity. The oil was characterized using standard methods.
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2.2. Methods
2.2.1. Neutralization of copra oil
Neutralization of the crude copra oil was carried out according to AOCS standard.[16] An
amount of 200 g of the crude sample (copra oil) was heated in a flask to 60
C, then strong
2N NaOH was added to neutralize the FFA content through constant stirring. The chemi-
cal reaction involved in this process is as follows:

R-COOH C NaOH ! RCOONa C H2 O

The neutralization progress was monitored using a phenolphthalein indicator. At the

end of the neutralization process, sodium chloride solution was added to the mixture to
ensure adequate salting or graining out the soap stock produced. Subsequently, the mix-
ture was poured into a separating funnel. Three hours later, the mixture separated into
two distinct layers. The lower layer containing the FFA rich soap stock was drained out,
while the upper layer containing the neutralized oil was then washed with hot water to
remove any traces of soap. The washing was carried out until the color of the phenol-
phthalein indicator did not change to pink.

2.2.2. Bleaching/filtration/dehydration of neutralized oil

The neutralized washed oil was introduced in a cylindrical vessel equipped with an agita-
tor called “bleacher” and then heated up to 90
C with steam under vacuum pressure. The
moisture from the oil thus evaporated and the oil became dry. The dried oil was then
treated with 5% by mass of a bleaching agent (mixture of fuller’s earth and carbon at a
1:1 ratio) to enhance the adsorption of the residual color. The process was allowed to con-
tinue for about 45 min with constant agitation. After which the resulting mixture was fil-
tered through a standard plate and frame press to enhance separation to obtain clear oil
very much lighter in color than the neutralized oil. The oil charge was dehydrated under
vacuum to avoid any further deterioration due to oxygen. The bleached dehydrated oil
was weighed to calculate the oil loss and the FFA content was determined. The character-
istics of the crude oil and neutralized oil were determined according to the AOCS stan-
dard.[16]
 5

Production of crude oil from copra

Neutralization with caustic soda (NaOH) at 600C

and salting with NaCl

Dehydration with NaHSO4

Alcoholysis, polyesterificaon and styrenaon

of COMG

Addion of pigments
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Figure 1. Process flow diagram for alkyd resin synthesis.

2.2.3. Synthesis of copra oil self-cured alkyd resin

Copra oil modified alkyd resin was prepared with the dehydrated oil, glycerol, and
phthalic anhydride using NaOH as a catalyst, as shown in Figure 1 and Table 1. Medium
oil length copra oil modified alkyd was prepared in a three-necked flask fitted with Dean
and Stark under reflux and azeotropic conditions. Under the same setup and conditions,
copra oil modified self-cured ester was prepared by post-free radical co-polymerization
of copra oil modified polyester obtained at the condition of process parameters by adding
and heating styrene (14 wt% of copra oil) and benzoyl peroxide (initiator).The alkyd
was thinned with xylene, then an appropriate amount of a nano-zinc pigment was added,
and then applied as thin films on glass panels and air-dried. The alkyd was evaluated for
its physico-chemical and coating properties using ASTM methods.
In the synthesis of the self-cured alkyd resin, the following three stages were involved:

(1) Alcoholysis. In this stage, monoglyceride was first synthesized by reacting the oil
with glycerol. Alcoholysis of oil was carried out with a 0.2% (by wt) NaOH cata-
lyst. In the alcoholysis reaction, the oil was heated with an agitation speed of
700 rpm to 230
C. Glycerol and selected catalysts were added and alcoholysis
reaction occurred at 230240
C. The reaction was continued until a sample of
the reaction mixture became soluble in 24 volume of anhydrous methanol. After
alcoholysis was completed, the reaction mixture was cooled to 140
C before the
commencement of esterification.
Table 1. Quantity of reagents utilized for alkyd resin synthesis.

Raw material Weight (g) Weight %

Dehydrated copra oil 115 58.08

Phthalic anhydride 48 24.24
Glycerol 35 17.68
Total 198 100
 6 C.F. Uzoh et al.

(2) Esterification. At this stage, phthalic anhydride was added to the monoglyceride
mixture. The temperature of the mixture was maintained in the range of 230 to
240
C. The reaction progress was monitored by a periodic determination of the
acid value. The second stage reaction was continued at the elevated temperature
and long-chain molecules were formed which contained the excess hydroxyl
group. At this state, water was released. The removal of water from the mixture
was facilitated by a solvent extraction method. The mixed vapor generated was
then condensed and collected. By choosing the exact solvent (xylene) that does
not mix with water in liquid phase, the mixture was demarcated into two layers.
Xylene was chosen for this process since it has a suitable boiling point and low
water solubility. When the acid value dropped to a value somewhat below 8, the
reaction was stopped. The acid values of the alkyd resin were determined and the
chemical resistance measured.
(3) Styrenation. Using the setup above, resin obtained by the implementation of the
statistical optimization paradigm was co-polymerized with styrene (14wt% of
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the oil) and benzoyl peroxide (0.5wt% of styrene) as initiators, under reflux at
120
C and cure using a nano-zinc pigment (see Figure 2).

Figure 2. Three-phase polymerization reactions of the monoglyceride process. First stage: alcohol-
ysis; second stage: esterification; third stage: styrenation.
 7

2.2.4. Physico-chemical test

2.2.4.1. Spectral analysis. The chemical composition of alkyd resin was confirmed by
Buck M530 Fourier transform infrared (FT-IR) spectroscopy. The FT-IR equipment was
operated with a wavelength range of 4000 to 500 cm¡1.

2.2.4.2. Adhesion. The dried films were cut by a crosshatch and the coatings were
cleaned using a brush. A scotch tape was adhered on to the film and then peeled off
quickly at 180
angle. The peeled-off grid areas on the tape were observed by a magnifier.

2.2.4.3. Solubility. The solubility of the synthesized palm oil modified resin was tested
in different solvents  xylene, benzene, toluene, DMF, acetone, ethanol, and methanol.

2.2.4.4. Chemical resistance. The chemical resistance of the alkyd was determined in
two media, distilled water and strong NaOH in solution.
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2.2.4.5. Abrasion resistance test. The test is useful in determining the resistance of
organic coatings to a falling abrasive.

2.2.5. Formulation of design matrix

The determination of the unknown coefficient of Equation (2) applies the design matrix of
Table 3, formulated by judicious transformation of the actual values of the four control
variables at various levels over which the experiments were executed to their coded
equivalents using 1 and C1 notations to designate low- and high-level factor settings
and “§a” and “0” for axial and center points, respectively. It has been shown that work-
ing with the coded variables enhances matrix transformation and helps in result analyses.
A useful value of a is evaluated from the general expression a D f 1=n (D2), where f is
the number of factorial points (D16) and n is the number of factors (D4) or for two-level
designs a D 2n=2 .
The coded values of the independent variables for the DOE for alkyd resin synthesis
are given in Table 2. For statistical analysis, the variables Xi (i D 1, 2,…,4) were coded A,
B, C, and D.
The data given in Table 2 were used to formulate a global design matrix shown in
Table 3 based on which further analyses were carried out.
Y is the measured fractional conversion (or extent of reaction of PA) across the vari-
ous experimental runs, expressed as a percentage drop in acid value of the reaction mix-
ture during the esterification process of copra oil modified alkyd resins. Equation (2) was
fitted to the experimental data presented in Table 3 to obtain the final predictive equation
for the reaction progress in terms of the coded variables.

Table 2. Experimental range and level of independent process variables for alkyd resin synthesis.

Range and level

Independent variable ¡a ¡1 0 1 a

Temperature (
C) (A) 220 230 240 250 260

Time (minutes) (B) 30 60 90 120 150
Molar ratio (C) 0.1:1 0.2:1 0.3:1 0.4:1 0.5:1
Catalyst concentration (wt%) (D) 0.02 0.04 0.06 0.08 0.10
 8 C.F. Uzoh et al.

Table 3. Full factorial CCRD matrix in coded notations for alkyd resin production from glyceride
oil of copra oil.

Independent variable
Response
Std. Run A B C D Y

21 1 0 0 2 0 58.3
10 2 1 1 1 1 76.2
26 3 0 0 0 0 69.5
1 4 1 1 1 1 30.7
6 5 1 1 1 1 67.2
28 6 0 0 0 0 78.5
11 7 1 1 1 1 66.7
19 8 0 2 0 0 46.2
4 9 1 1 1 1 75.0
23 20 0 0 0 2 57.0
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14 11 1 1 1 1 79.0
8 12 1 1 1 1 88.5
29 13 0 0 0 0 69.0
7 14 1 1 1 1 93.3
18 15 2 0 0 0 90.4
25 16 0 0 0 0 77.4
24 17 0 0 0 2 72.2
13 18 1 1 1 1 47.5
16 19 1 1 1 1 81.2
27 20 0 0 0 0 72.5
5 21 1 1 1 1 37.1
30 22 0 0 0 0 72.4
12 23 1 1 1 1 75.0
17 24 2 0 0 0 66.5
9 26 1 1 1 1 40.1
2 27 1 1 1 1 45.3
15 28 1 1 1 1 74.1
3 29 1 1 1 1 56.0
22 30 0 0 2 0 67.4

2.2.5.1 Process analysis. The transesterification process is analyzed for the different
interaction effects of the process variables on the responses based on solutions derived
from Equation (2) at some assumed experimental conditions so as to reveal possible
routes to optimum fractional conversion. The popular surface response methodology was
suitably utilized for this exercise. The Design-Expert analysis and optimization tool func-
tions provided all the necessary computational assistance. The results were presented as
response surface contours.

3. Results and discussion

3.1. Characteristics of crude, neutralized, and dehydrated copra oil
The characteristics of crude, neutralized, and dehydrated copra oil are shown in Table 4.
From Table 4, it can be seen that the neutralization process can reduce the FFA content of
 9

Table 4. Characteristics of the crude, neutralized, and dehydrated copra oil.[17]

Characteristics Crude oil Neutralized oil Dehydrated oil

Free fatty acid (%) 10.7 1.2 1.2

Colour, photometric Brown Light brown 
Refractive index  1.499 
Viscosity (25
C) (stoke) 4.6 4.7 1.8
Iodine value 62 62 92
Specific gravity 0.9673 0.9618 0.940
Set to touch time (h)   4.5
Drying time (h)   4.5

crude copra oil from 10.7 to 1.2, with a refractive index of 1.499. The refined oil now pos-
sesses a specific gravity of 0.9618, while the viscosity and iodine values were nearly the
same as the crude samples. Although the neutralization technique reduces significantly
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the FFA content in the oil sample, it had a slight effect on the specific gravity, viscosity,
and iodine values. The iodine and viscosity values control the extent of reaction, and set
to touch time and drying time show the drying properties of the dehydrated sample. The
drying time and set to touch time gave satisfactory results. Therefore, this dehydrated oil
sample was acceptable to prepare oil modified self-cured alkyd resin.
The alcoholysis reaction is usually completed within an hour or two after the batch
has reached the operating temperature.[18] Table 5 shows the solubility of the alcoholysis
in anhydrous methanol carried out for several hours using an NaOH catalyst.
In the esterification reaction, it was observed that the longer the reaction, the more vis-
cous the mixture is. In this stage, adequate agitation was necessary for complete mixing of
monoglyceride mixture and phthalic anhydride. Unless there is adequate mixing in this
stage, an unqualified alkyd resin would result. So the agitation speed of the rotatable flask
was increased from 500 to 700 rpm. Xylene was also introduced to form azeotrope with
water. The liberated water of esterification was carried off in the xylene, normally result-
ing in a significant increase of heat and mass transfer of the chemical reaction. The extent
of reaction at 135 min of polycondensation of monomers was more than 85%.[17]

3.2. Performance characteristics

3.2.1. Chemical resistance
The resistance of the alkyd was determined in three media, distilled water, NaOH solu-
tion, and acid, as shown in Table 6. It was observed that there was no effect on the alkyd
film after immersion in distilled water for 18 h. When the alkyd film was immersed in a
strong alkali solution, 3N NaOH and acid, the film got a whitening after an immersion

Table 5. First stage alcoholysis reaction.[17]

Alcoholysis catalyst Catalyst % (wt) Reaction time (h) Completion of alcoholysis reaction

NaOH 0.1 4 Not complete

0.2 4 Not complete
0.3 2 Complete

Note: It was determined by testing the solubility of the alcoholysis mixture in anhydrous methanol.
 10 C.F. Uzoh et al.

Table 6. Chemical resistance of the alkyd resin film.

Media Immersion time (h) Appearance of film

Distilled water 18 No effect

8 Whitening
3N NaOH 20 Blistering
36 Removal
8 Whitening
Acid 20 Blistering
36 Blistering

Note: It was examined after the film was dried for 30 min.

time of 8 h, blistering after an immersion time of 16 h, and removal after an immersion

time of 36 h for the alkali solution, while there was no removal in the acid even after 24
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h. This could be as a result of masking of the ester linkages of the polyester from alkali
hydrolysis. This result therefore shows that coconut oil modified alkyd resin has high
chemical resistance.

3.2.2. Abrasion resistance

All coatings are subject to abrasive forces after being applied to a surface. The synthe-
sized resin was found to be quite resistant to abrasion. This indicates that the synthesized
resin was tough and durable. The abrasion resistance was 16.7/mm.

3.2.3. Adhesion
A coating must adhere well in order to protect the surface of the substrate and for long time
durability. The adhesion of the resin on both glass and metal surfaces was found to be very
strong and the adhesion ratings were found to be the highest, 5B. No flaking or ribboning
occurred after making cuts and applying the adhesive tape. The hydroxyl groups and sty-
rene in the structure of the resin further improved the adhesion to the substrates.

3.2.4. Solubility
The alkyd resin based on copra 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 increase in number with the distance between the
molecular chains of the resin. The spaces between long chains with a pendant side group
of resin are “invaded” by solvent molecules as they fill the space made available by chain
movements. When movements bring two chains close to proximity, short range attractive
forces are therefore established, resulting in restricted chain movement and thus the for-
mation of a viscous system.[27, 28] Solvents are added to deal with the problem of high-
viscous resin which is an obstacle in substrate’s wetability.

3.2.5. Gloss
The specular gloss values of the resins applied both on glass and metal substrates were
measured at three different angles of incidence. The results are tabulated in Table 7. If
the gloss value of a coating measured at 60
is higher than 70, it is said to be in high gloss
 11

Table 7. Specular gloss of the resin at different angles of incidence and on different substrates.

Resin Substrate/Angle 20
60
85

CO Glass 113.8 126.0 83.0

Metal 88.0 116.2 77.2

range. Therefore, it can be said that all of the resins showed high gloss property. The gloss
values of the resins on metal substrates came out to be less than the gloss values on glass
substrates since glass substrates reflect the diffracted light, yielding higher gloss values
(between 116.2 and 126) on both substrates at 60
. At 20
, the gloss values on the glass
substrate were much higher than on the metal substrate. The gloss values measured at 60

were higher than the values at 20
and 85
.

3.2.5. Drying rate

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Figure 4 shows the drying rate of self-cured alkyd resin based on different thicknesses of
copra oil applied and the amount of nano-ZnO employed. This oil is classified as non-dry-
ing, containing fatty acids that are higher in saturated chains than other types of oil. Non-
drying oil alkyds do not readily form films without modification.[22] However, modifica-
tion and addition of pigments yield resins that form films at normal atmospheric conditions.
Thicker films (120 mm) require much more time to dry compared to thinner films (30 mm).
The drying mechanism of thicker films necessitates the use of ZnO of nanoscale to cross-
link between chains. This is informed by the fact that the material size to the nanoscale
leads to increase in the ratio of surface area to volume and this changes effects of the
behavior of an atom on the surface of particles in isolation or their interaction with other
materials. When the concentration of a catalyst decreased, a less dense cross-linked net-
work was formed.[29] The drying time of the thicker film alkyd can dramatically accelerate
the oxygen uptake either at the double bond or at the methylene group with increasing pres-
ence of pigments.[30] It was observed that the ability of the resin to air dry is due to
phthalic anhydride modification in a definite proportion, amount of styrene, and the pig-
ment that causes the resin to cross-link. The higher the presence of phthalic anhydride, sty-
rene, and the pigment, the longer the chain length and a highly cross-linked dense resin
through condensation polymerization. The resin becomes denser, viscous, and more com-
pact, conferring self-curing tendency. This also confirms that addition of co-polymers and
driers increases film formation and reduces the drying time by an entanglement of chains
through condensation polymerization. Chemical potential is a thermodynamic quantity
which expresses the incremental energy content of a system. Addition of styrene increases
the chemical potential, hence, leading to higher chemical activity and spontaneous reaction.

3.3. Spectral analysis of copra oil based resin and raw copra oil
The IR spectra of raw copra oil and the corresponding resin are shown in Figure 3. In the IR
spectrum of copra oil, the small shoulder, 3600 cm¡1, corresponds to the hydroxyl (O–H) of
the unsaturated fatty acid in copra oil. The carboxyl group (CDO) is indicated at 1747 cm¡1.
The straight chain of the CH stretch in an aliphatic compound is found at a band of 2854
cm¡1. The alkene group (CHDCH) is attributed to the band of 3000 cm¡1. The IR spectrum
of the prepared resin exhibits a characteristic straight chain ester band at 1738.64 cm¡1 and
an aromatic (CDC) ring ester at 1730.09 cm¡1. The presence of ODCOC also exhibits a
 12 C.F. Uzoh et al.
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Figure 3. FT-IR spectroscopy of raw copra oil and copra oil based alkyd resin.

characteristic ester band at 1125.62 cm¡1. The absorption band at 3008.99 cm¡1 is character-
istic of alkenes.[19, 20] The appearance of a ring ester band at 1730.09 cm¡ 1 confirms the
esterification of copra oil monoglyceride with phthalic anhydride.

3.4. Optimization
The response obtained for the various experimental runs executed in the equivalent natu-
ral units of the process variables as prescribed in the full factorial CCRD is presented in
Table 3. The experiments were carried out at 24 distinct and 6 homogenous factor set-
tings, giving a total of 30 experimental runs following the procedure described earlier in
Section 2.4, and the fractional conversion of the manufactured copra oil modified alkyd
resins designated with Y was estimated in terms of the measured reduction in acid value
(AV) over the reaction periods. The responses recorded for the different runs were sub-
stantially unique which shows that the factors have significant effects. The deductions
from the characterization, control, and optimization protocol implemented for the
manufacturing processes are discussed in what follows.

3.4.1. Statistical analysis/factor screening

The process characterization (or factor screening) was carried out to evaluate the system
variables which provide the most important effects in tune with the research objectives.
The necessary computational tasks were aided with the ANOVA function of the statistical
 13

9
120 m
30 m
8
Poly. (120 m)
7 Poly. (30 m)

5
s

4
y = 0.0573x2 - 1.0457x + 8.1398
R² = 0.974
3
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2
y = 0.0101x2 - 0.5723x + 5.9145
R² = 0.9874
1

0
0 2 4 6 8 10
Nano-ZnO (%)

Figure 4. Effect of nano-ZnO on styrenated copra oil modified resin.

software Design-Expert Version 8.1.7.1. In view of the curvature, a reduced order qua-
dratic model of the general form given in Equation (2) was appropriate for predicting the
overall process characteristics. The ANOVA results derived from the predictive model
show that the main linear effects due to individual control factors, temperature ðX1 Þ, time
ðX2 Þ, molar ratio ðX3 Þ, and catalyst concentrationðX4 Þ, coded A; B; C; and D, respectively,
are all significant process variables indicated with the observed p-values < 0.05 in the
numerical analyses. This is equally true with the linear interaction effects between tem-
perature and time ðABÞ, and time and catalyst concentration ðBDÞ . The quadratic effects
of temperature, time, and molar ratio denoted by A2 , B2 ; and C 2 , respectively, are signifi-
cant while the quadratic effect of catalyst concentration D2 is insignificant. The data
obtained for specific investigations were reffited with a modified model obtained by
excluding the non-significant variables from the general predictive equation, and the
results of statistical analyses obtained for the sequence of experimentations are summa-
rized in Table 7. The coefficients of determination R2 values of 0.9523 obtained for the
copra oil based esterification process show that more than 95% of the overall system vari-
ability can be explained by the empirical models of Equation (3) which are specific cases
of the general predictive equation derived for the investigations from the multivariate
regression analyses implemented on Design-Expert.

Y D 78:97 C 8:73A C 8:67B C 3:07C C 5:62D ¡ 3:90AB ¡ 2:66BD

¡ 3:70A2 ¡ 2:77B2 ¡ 3:54C 2 (3)
 14 C.F. Uzoh et al.

where Y is the predicted value of the dependent variable (i.e. fractional conversion). The
coefficients of A; B; C; and D are main linear effects of the independent process variables:
temperature, time, molar ratio, and catalyst concentration, respectively, in coded units.
AB; BD; and CD represent the linear interaction effects between temperature and time,
time and catalyst concentration, and mole ratio and catalyst concentration, respectively.
A2 ; B2 ; C 2 ; and D2 are the quadratic effects of the respective process variables. The
“Predicted R-squared” of 0.8679 is in reasonable agreement with the “Adjusted R-
squared” of 0.9308; and the Model F-value of 44.35 further indicates that the model is
significant. There is only a 0.01% probability that the “Model F-value” this large could
occur due to noise. p-value less than 0.05 indicates model terms are significant.
“Adequacy precision” measures the signal-to-noise ratio (S/N). A ratio greater than 4 is
desirable. An S/N value of 24.621 indicates an adequate one.
The diagnostics analyses completed via normal probability plots of residuals for the
investigations are presented in Figure 5. A visual inspection of the graphs is sufficient to
say that the residuals follow a normal distribution. A picture of points which interlock a
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straight line with some moderate scatter is expected with normal data.

3.4.2. Process analysis

The esterification processes for the production of CO modified alkyd resins are analyzed
based on the various solutions obtained at possible reaction conditions from the model
predictive equations (3). The well-known RSM is considered appropriate owing to its
flexibility in navigating the design space. These equations were solved for the various
interaction effects on alkyd resin conversion, considering at any instance the interactions
between two factors only, assuming the other variables are set at their mean coded value
of 0. The analyses and optimization exercises are completed accordingly using the

Figure 5. Normal probability plots of residuals obtained from copra oil data analysis.
 15
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Figure 6. Response surface contour for interaction on copra oil modified alkyd resin production
between temperature and time.

DesignExpert Version 8.1.7.1 trial application and the graphical solutions are presented as
response surface contour diagrams.
The interaction effects on the process response between temperature ðx1 Þ and time
ðx2 Þ in their natural units associated with the resins produced are presented in Figure 6.
As expected for a typical batch process, the fractional conversion of the CO modified res-
ins generally increases readily with reaction time, approaching 70% at 100 min even at a
low-level temperature setting of about 230
C following first-order reaction kinetics in
sufficient monoglyceride oil, while towards the completion of the reactions, the responses
assume a second order. Such observations conform to a large extent with the results of lit-
erature.[23] A significant curvature is identified with the response as the temperature is
adjusted through its range. The responses increase as the temperature setting shifts from
220
C to 240
C and begins to show depreciating values at higher isotherms above 250


C. This may be associated with the reversible nature of the esterification process and
possible existence of a critical factor setting that guarantees optimun conversion of high-
grade resin with desired polymerization properties under atmospheric conditions and an
adequate economic value that may justify the efforts on experimental design and optimi-
zation study.
The observed interaction effects on the responses between temperature ðx1 Þ and molar
ratio ðx3 Þ are recorded in Figure 7. The quadratic effect of molar ratio is identified with
smooth curves on the reference surface contour. The process responses are all maximized
in a similar fashion as the phthalic anhydride-to-oil ratio is increased from a low value of
0.1:1 to mean values between 0.3:1 and 0.45:1. Transition to the optimum fractional con-
version of CO modified resins may be achieved with the molar ratios 0.44:1 as obtained
from the optimization solution.
Figures 8, 9, and 10 display the responses for the interactive factors: temperature ðx1 Þ
vs catalyst concentration ðx4 Þ, time ðx2 Þ vs molar ratio ðx3 Þ, and time ðx2 Þ vs catalyst ðx4 Þ
concentration, respectively . The 3D response surface plots show that the best results on
alkyd resin conversion are obtained at a reaction time in the range of 95120 min using a
catalyst concentration not less that 0.08% and a reaction temperature between 240 and
 16 C.F. Uzoh et al.
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Figure 7. Response surface contour for interaction on copra oil modified alkyd resin production
between temperature and molar ratio.

250
C. The response surface contours report that allowing a short reaction time of 30 min
at a low concentration of pthalic anhydride leads invariably to low fractional conversions
and non-viscous products. The obvious reason for this has to do with non-completion of
reaction: essentially abundant hydroxide (OH) group of the monoglyceride oil is react-
ing with only scanty molecules of pthalic anhydride within some time substantially less
that the optimum, giving rise to a poor yield of alkyd resin with a relatively high acid
value > 15.[21] This type of product is not desirable for coating processes where the

Figure 8. Response surface contour for interaction on copra oil modified alkyd resin production
between temperature and catalyst concentration.
 17
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Figure 9. Response surface contour for interaction on copra oil modified alkyd resin production
between time and molar.

Figure 10. Response surface contour for interaction on copra oil modified alkyd resin production
between time and catalyst concentration.
 18 C.F. Uzoh et al.

curing duration must be minimized. Alkyd resins with acid number < 15 are preferable
for improved polymerization properties at atmospheric conditions.[22] Evidently, the
responses are maximized as the ratio of phthalic anhydride to glyceride oil in the mixture
is increased to some value above the mean, allowing the reaction to progress uninterupted
for about two hours (120 min). However, operating at an extreme condition of time >
130 min and molar ratio > 0.45 invokes decreasing responses. This explains the tendency
that the available OH group from monoglyceride oil may be used up towards the end of
effective reaction time, causing the equillibrium of the system to adjust in a manner as to
allow unreacted or excess glycerol in the mixture to form an additional but undesirable
product (glyceryl pthalate) which is insoluble in the wanted product (oil-acid glyceryl
pthalate) and the unreacted glyceride oil.[21] It is further observed that the response on
copra oil based alkyd resin continues to show some discrepancies as the response
increases uniformly with catalyst concentration all through and follows a swift curvature
as the temperature is reviewed upwards (see Figure 6). This indicates that the optimum %
conversion is associated with a mean esterification temperature of 260
C and maximum
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catalyst concentration in the sample. A comparable result has been reported for the manu-
facture of alkyd resin from castor oil in Hlaing et al. [23] where 97.72% of the esterifica-
tion reaction was completed at about 240
C within the allowed 150 min of the reaction
using pre-determined weights of phthalic anhydride and the catalyst. The reaction was
terminated after this duration to avert gelation.
The response surface plot of Figure 11 reveals that interactive effects between these
two factors are important in the three processes and need to be controlled. It is evident
from the figure that increasing catalyst concentration within the design space at a fixed
setting of pthalic anhydride-to-oil molar ratio invariably leads to an increased fractional

Figure 11. Response surface contour for interaction on copra oil modified alkyd resin production
between molar ratio and catalyst concentration.
 19

conversion. Such response is desired but the best results under this condition are achiev-
able at an optimal molar ratio and moderate catalyst concentration. By and large, it is pos-
sible to achieve up to 87% fractional conversion in a CO product even at a lowest molar
ratio setting and high catalyst concentration. However, such solution may not be of any
economic or manufacturing importance as it would lead to relatively high consumption
of catalyst and poor yield of alkyd resin. The necessary detail on optimization analysis
and results is given below.

3.4.3. Process optimization

As anticipated for a typical manufacturing process, the need for optimization arises where
products which provide some obvious advantages such as short drying time, reduced
material cost, improved color (appearance), and weight are desired. Of particular interest
is the drying time which is a critical issue highlighted in this paper. We may recall that a
major objective is to contrive a route to high-quality resins with good polymerization
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properties for industrial coating processes from a non-drying oil. Other avenues for pro-
cess optimization are through reduced reaction time and temperature which in effect min-
imize the overall cost of manufacturing simultaneously. The optimization problem may
be compounded when the process(es) pose multiple desired targets which may be a com-
bination of two or more of the above-stated conditions. This is actually the case with the
esterification processes and many other real systems for that matter. A standard approach
to this problem is to formulate global optimization criteria through which the necessary
trade-off may be effected so as to achieve what may be considered as the best combina-
tion to the desired result.
The optimization exercise for the manufacturing processes towards the production of
copra oil modified resins was conducted separately utilizing the flexibility of the Design-
Expert optimization tool function. Equation (3) was solved for the best solutions such
that the responses ðYn Þ are maximized within the design space. No unique solutions were
possible. A usual approach which involves selecting the best solution based on economic
considerations is adopted and the chosen optimal solutions are presented in Table 8.
Given that the various optimum reaction times and temperatures were not considerably
far separated from each other, the selection of the desired optimum solution of Table 9
was mainly influenced by the avalaibility and cost of reagents. An experiment was then
performed using the optimal result of the numerical optimization executed by Design-
Expert. Fractional conversion of 97.16% for CO obtained by experiment was in reason-
able agreement with that of the statistical model of Design-Expert.
Efforts to compare these solutions overtly with previous works found in literature did
not provide much desired result. This is because the production of alkyd resins via esteri-
fication processes of non-drying copra oil has not received adequate research attention it
deserves. However, it has been shown that a lot of similarities exist between the results of
current research and that reported by Hlaing et al. [23] where more than 97% of the esteri-
fication process of monoglyceride of castor oil and pthalic anhydride was completed
within the first 150 min of reaction at a temperature maintained between 230 and 240
C.
Although the Hlaing et al. [23] observation was based on close monitoring of the reaction
progress via continual evaluation of the product acid number, not on any formalized opti-
mization paradigm, yet it was able to show that the results of Table 8 are realistic and reli-
able. On the other hand, the observations contained in this essay are apparently different
from those reported in literatures: transesterification of vegetable oils with ethanol by
Giovannilton et al. [24] and Freedman et al. [25] for biodiesel production, and the
 20 C.F. Uzoh et al.

Table 8. ANOVA for the response surface reduced order quadratic model (RSROQM) in terms of
only the significant process variables.

Copra oil

Source F-value p-value

Model 44.35 <0.0001

A  temperature (
C) 127.39 <0.0001
B  time (min) 125.45 <0.0001
C  molar ratio 15.71 0.0008
D  catalyst concentration (w/w) 52.69 <0.0001
AB 16.94 0.0005
BD 7.89 0.0108
CD  
A2 26.65 <0.0001
B2 14.99 0.0010
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C2 24.36 <0.0001
D2  
Copra oil Std. Dev. 3.79 R-squared 0.9523
Mean 70.96 Adj R-squared 0.9308
C.V. % 5.34 Pred R-squared 0.8679
Press 795.44 Adeq precision 24.621

Note: DF: model D 9, residual D 20, total D 29.

Table 9. Optimum values of process parameters for maximum responses of copra oil based resin.
[17]

Process Parameters Optimum values

Fractional conversion (%) ðYn Þ 96.55

Temperature (
C) ðx1 Þ 241.94
Time (min) 124.21
Molar ratio ðx3 Þ 0.38:1
Catalyst concentration (wt%) ðx4 Þ 0.10
Desirability 1.00

transesterification study of cynara oil by Encinar et al.[26] This may be attributed to the
inherent high activation energy associated with the equilibrium of reaction between
phthalic anhydride and the glyceride oils to form alkyd resins.

4. Conclusion
Critical monitoring of the reaction progress in time indicates a rapid and linear transfor-
mation of the monomers to polymers in the parameter space at the early stage of the reac-
tion. This observation, however, changed at a later stage where the response showed a
certain degree of curvature with decreasing conversion rate. The decrease in acid value of
the alkyd was found to be rapid in the first 135 min of the polyesterification reaction. The
 21

extent of reaction at 135 min of the polycondensation of the monomer was more than
85%. This shows that a linear-type polymer was formed within this period. The RSM
based on a CCRD employed for the analysis and optimization of the polyesterification
process of the palm oil predicts optimum fractional conversion of 96.55% at a reaction
temperature of 241.94
C, time 124.21 min, catalyst concentration 0.1%, and PA:MGO
ratio of 0.38:1. Fractional conversion of 96.55% predicted by statistical analysis shows a
close enough agreement with the 97.19% fractional conversion obtained with the validat-
ing experiment perfomed at the predicted optimum conditions.

Nomenclature
ANOVA: D analysis of variance
AOCS: D American Oil Chemists Society
CCRD: D central composite rotatable design
D degree of freedom
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DF:
F-value: D test statistics of F distribution
FFA: D free fatty acid
MGO: D monoglyceride oil
p-value: D smallest level of significance that would lead to the rejection of the null
hypothesis in test statistics
PA: D phthalic anhydride
RSM: D response surface methodology
X: D coded independent system variables
Y: D dependent variables, predicted response
a: D axial point of factorial design
b: D constant coefficient of mathematical model
e: D random error of mathematical model

Disclosure statement
No potential conflict of interest was reported by the authors.

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