American Chemical Science Journal

15(2): 1-7, 2016, Article no.ACSJ.26431

ISSN: 2249-0205

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www.sciencedomain.org

Synthesis and Characterization of Oil-Modified

Alkyd Resin from Epoxidized Neem Oil
I. R. Jack1, A. U. Anya2*, and O. F. Osagie1
1
Department of Chemistry, Rivers State University of Science and Technology (RSUST),
Port Harcourt, Nigeria.
2
National Research Institute for Chemical Technology (NARICT), Zaria, Kaduna State, Nigeria.

Authors’ contributions

This work was carried out in collaboration between all authors. All authors read and approved the final
manuscript.

Article Information

DOI: 10.9734/ACSJ/2016/26431
Editor(s):
(1) T. P. West, Department of Chemistry, Texas A&M University-Commerce, USA.
Reviewers:
(1) Nikesh B. Samarth, Institute of Chemical Technology, Mumbai, India.
(2) Rachna Jain, Research and Development, Tata Steel limited, India.
(3) Rajarshi Nareshkumar Patel, Sardar Patel University Affiliated institute, APMS, India.
(4) C. O. Akintayo, University of Ado Ekiti, Ado-Ekiti 4418, Nigeria.
Complete Peer review History: http://sciencedomain.org/review-history/15257

th
Received 17 April 2016
th
Original Research Article Accepted 8 June 2016
Published 2nd July 2016

ABSTRACT

The aim and objective of this work is to synthesize a greener alkyd resin by substituting petroleum
based epoxides in alkyd resin modification. Chemical transformation of the existing functional
group present in neem oil via epoxidation, epoxy functionality was inserted and used as substitute
to petroleum based epoxide. Epoxidization of neem oil was carried out with per-acetic generated
in-situ at 50°C. Alkyd resin with oil-length of 64.5% was synthesized from the epoxidized neem oil
ENO. Polyesterification reaction of the oil was carried out using glycerol and phthalic anhydride at
250°C to synthesize epoxidized neem oil alkyd resin ENOMAR. The resin where cured using
methyl ethyl ketone peroxide MEKP and 12% cobalt naphthalate in toluene; this was applied
uniformly on a different glass plate substrate and heated in an oven at 80°C and 120°C
respectively at different time intervals. Films properties such as drying time, set to touch time and
chemical resistance of the resins were determined. Minimum drying and set to touch time was
recorded at 15 and 9 hrs at 120°C for 120 mins, while minimum value of 17 and 11 hrs was also
recorded at 80°C for 120 min. Chemical resistance of the resin show good resistance in 10% HCl
and distilled water. The resin also shows relatively good resistance in 1% NaCl and a poor result in

_____________________________________________________________________________________________________

*Corresponding author: E-mail: anyauzo023@gmail.com;

 Anya et al.; ACSJ, 15(2): 1-7, 2016; Article no.ACSJ.26431

1% NaOH. Infrared analysis result of the resin shows broad and sharp peaks at 1732 cm-1, 2928
-1 -1
cm and 3465 cm . Assessments of the properties show that epoxidized neem oil modified alkyd
resin ENOMAR has film properties that are characteristic of good alkyd resins.

Keywords: Alkyd resin; chemical resistance; drying properties; infrared analysis.

1. INTRODUCTION reaction with polybasic acid and other chemicals

used in resin modification, this produce tough
Alkyd resins are polyester that is derived from and chemically resistance coatings. The curing
the polymerization reaction of polyhydric alcohol process takes place either between the epoxide
and poly-functional acid or polybasic acid molecules themselves or by the reaction
modified with fatty acid or their triglyceride [1]. between the epoxy group and other reactive
Alkyd resin was also defined by [2] as the molecules with or without the help of the catalyst
products of poly-condensation reaction between [8]. The aim of this work is to synthesize a
polybasic acid and polyhydric alcohol modified greener alkyd resin by substituting petroleum
with fatty acid or drying oil. Presently, alkyd based epoxides through chemical transformation
resins are typically manufactured from acid of the existing functional group present in neem
anhydrides such as phthalic anhydride with oil via epoxidation. The drying process of alkyd
polyols like glycerine and are modified with resin takes place when atmospheric oxygen
unsaturated fatty acids to give them air drying oxidizes the unsaturated bond present in the fatty
properties. About 60-70% of an alkyd resin acid.
constituents are made-up of biologically derived
or biodegradable raw materials and the rest are 2. MATERIALS AND METHODS
non biodegradable [3]. Resins can either be
produced with drying oil or chemically modified 2.1 Materials
non-drying oils and are referred to as oil-modified
alkyd resins and contribute to about 70% to the The neem seed oil was obtained, pretreated and
conventional binders used in surface coating. extracted in national research institute for
Some vegetable oil have the tendency to dry or chemical technology (NARICT) Zaria, Nigeria.
form films in their natural form, this characteristic Nitrogen gas and analytical grade reagents of
is directly related to their fatty acid composition hydrogen peroxide (30%), acetic acid, wijs
and is an inherent characteristic of vegetable oil solution prepared by dissolving 16.2 g iodine
with high percentage of unsaturated fatty acid, monochloride in 1 litre of glacial acetic acid,
thus such vegetable oil are referred to as drying carbon tetrachloride, sulphuric acid (98%),
oil. Non-drying vegetable oil such as neem seed sodium thiosulphate, potassium iodate, phthalic
oil that has low percentage of un-saturation, can anhydride, glycerol, styrene, sodium hydroxide
be utilized for alkyd resin synthesis by and other reagents were all from BDH chemical
incorporation of a suitable functional group like limited. The glassware and equipment used were
epoxide in the vegetable oil backbone through 500ml three neck round bottom flask, dean and
chemical reaction to transform. It has been stark flask, water bath, glass plates, mechanical
reported by [4] that fatty acids from vegetable oil stirrer, thermometer, reflux condenser, heating
contained suitable functionalities in their mantle and FTIR-8400S SHIMADZU.
backbone such as esters, triple and double Characterization of neem oil was carried out
bonds either conjugated or non-Conjugated and using American oil chemical society (AOCS) test
other functional groups that undergoes several methods. Table 2 depicts the result obtained from
chemical modifications. The functional group it characterization.
transformation of un-saturated bonds in non-
drying oil to epoxide via epoxidation can be 2.2 Methodology
carried out; this will add value to it by changing
the drying characteristic of the resin synthesized 2.2.1 Epoxidation of neem oil
from it and enhance its use as alkyd resin
feedstock. Epoxidation of neem oil was carried About 300 g of neem oil was introduced into 500
out with per-acetic acid formed in-situ according ml three necked round bottom flask fitted with
to a method reported in the literature by [5,6] and reflux condenser and mechanical stirrer and
[7]. Epoxides functionality undergo curing placed in a water bath. The temperature was

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 Anya et al.; ACSJ, 15(2): 1-7, 2016; Article no.ACSJ.26431

Table 1. Percentage composition of fatty acids in some vegetable oil

Veg oil Palmitic Stearic Oleic Linoleic Linolenic Other %US %S

Rapsed [9] 4.1-6.1 1.2-2.0 57.5-68.9 16.0-23.9 5.5-11.3 ----- ----- -----
Soy bean [10] 10.57 4.09 22.98 54.51 7.23 0.62 84.72 14.66
Rubber seed 8.78 6.15 38.96 42.12 2.38 0.90 83.70 15.61
[11]
Cotton seed [12] 24.40 2.20 17.20 55.00 0.30 1.20 72.20 26.60
Jatropha [13] 14.1-15.3 3.7-9.8 34.3-45.8 29.0-44.2 0.0-0.3 ----- ----- -----
Neem [14] 16-34 6-24 25-58 6-17 ----- ----- ----- -----
%US= Percentage un-saturation,
%S= Percentage saturation

regulated to 40°C and the flask allow to stand for 2.3 Synthesis of Alkyd Resin from
5mins while stirring at constant speed of 500 rpm Epoxidized Neem Oil ENO
before adding about 0.1% v/w concentrated
sulphuric acid to oil weight. In a separate flask Alkyd resin having oil-length of 64.5% was
(conical flask); solution of per-acetic acid was prepared from the epoxidized neem oil ENO.
prepared by mixing 14.82 g of acetic acid and This was synthesized using two stage process
118.98 g of hydrogen peroxide. This solution was namely alcoholysis followed by polyesterification
added drop wise to the heated neem oil at a process. Table 4 shows the percentage
constant rate for a period of one hour. The composition of ENOMAR.
temperature was raised to 55°C while still stirring
at 500 rpm for fine dispersion. This was Table 3. Characteristic properties of
allowed to stand for 6hrs while maintaining epoxidized neem oil ENO
constant temperature of 55°C and stirring speed
of 500 rpm. During the reaction period, oxirane Properties ENO
oxygen content test OOC was periodically Iodine value (Cg/g) 12.73
carried out using American oil chemist society Oxirane content (%) 85.00
(AOCS) Cd 9-57 test method to ascertain the Specific gravity 0.959
degree of epoxidation. After having about 85% of Colour yellow brown
OOC test, the reaction was quenched and
transferred to a separating funnel where it was Table 4. Percentage composition of ENOMAR
allowed to stand for 24 hrs. The epoxidized neem constituents
oil ENO was separated by decanting off the
aqueous phase. The OOC is calculated as Raw materials Weight (gram) Weight
follows (%)
ENO 300 64.5
%OOC = (TV × N × 1.60)/ (Wt of sample) (1) Phthalic anhydride 95 20.4
Glycerol 70 15.1
TV = Titra value of hydrogen bromide Total 465 100
N = Normality of Hydrogen bromide
Weight of sample = weight of oil sample 2.3.1 Alkyd resin synthesis

Table 2. Physicochemical properties of neem 2.3.1.1 Stage 1; alcoholysis

seed oil
Monoglycerides were first prepared by reacting
Properties Values 300 g of ENO with 70 g of glycerol and 0.2%
NaOH (w/w) in a reactor equipped with reflux
Specific gravity 0.912
condenser, mechanical stirrer arrangement and
Colour Dark brown nitrogen in-let [15]. This was allowed to stir for 30
Physical state liquid min at agitation speed of 800 rpm at room
Acid value 16.83 mgKOH/g temperature in order to achieve good mixture.
Saponification value 173.06 mgKOH/g The oil was then heated to 250°C with agitation
Iodine value 84.69 cg/g speed of 700 rpm in the presence of N2 with
3
Peroxide value 1.42 mg/g sparging rate of about 0.05ft /sec. The reaction
continued until a sample of the reaction mixture

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 Anya et al.; ACSJ, 15(2): 1-7, 2016; Article no.ACSJ.26431

became soluble in one to three 1:3 volumes of The performance properties of ENOMAR under
anhydrous methanol and was cooled to 140°C. different chemical environment are given in Table
8. In each case, equal amount of the cure film
2.3.1.2 Stage 2; polyesterification via trans- was dipped into the solvent and allowed for 6hrs.
esterification After which the film is dried and the weight loss
measured. Increase in weight loss shows less
95 g of phthalic anhydride was added to the resistance of the resin to the respective solvent
monoglyceride mixture formed from ENO and vice versa.
produced from the alcoholysis process. The
temperature was increased to 250°C and Table 5. Characteristics properties of the
maintained at that temperature, while the alkyd resins synthesized
sparging rate of the N2 was increased to
0.1ft3/sec. Aliquots were withdrawn periodically Properties ENOMAR
from the reaction mixture to determine the drop Acid value (mgKOH/g) 12.54
in acid value using titrimetric method. The Iodine value (Cg/g) 21.15
reaction was quenched when the acid value Refractive index 1.49
dropped to 12.54 mgKOH/g. The acid value of in- Specific gravity 0.984
process samples were determined by titrating Colour Dark brown
with a 0.1 M KOH solution to the phenolphthalein
end point after dissolution in a mixture of toluene Table 6. Drying and set to touch time of
and ethanol 1:1. ENOMAR at 80°C

2.4 Alcoholysis and Polyesterification Time in ENOMAR ENOMAR set to

Reaction Involve in Alkyd Resin oven (min) drying touch (hour)
time (hour)
Synthesis
30 36 18
In the alcoholysis process, epoxidized neem oil 60 24 15
fatty acid triglyceride reacts with glycerol forming 90 19 14
a monoglyceride. This was followed by 120 17 11
polyesterification reaction involving phthalic
Table 7. Drying and set to touch time of
anhydride with the monoglyceride to form a
ENOMAR at 120°C
polyester alky resin as shown in Figs. 1 and 2.
Time in ENOMAR ENOMAR set
3. RESULTS oven (min) drying time to touch
Physicochemical properties of the synthesized (hours) (hours)
epoxidized neem oil modified alkyd resin 30 32 12
ENOMAR are presented in Table 5. An acid 60 22 11
value of 12.54 mgKOH/g was obtained after 90 16 10
reacting for 150 mins. 120 15 9

Scheme 1. Alcoholysis Scheme 2. Polyesterification

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 Anya et al.; ACSJ, 15(2): 1-7, 2016; Article no.ACSJ.26431

4. DISCUSSION ENOMAR is shown in Fig. 1. In the IR spectrum,

the small shoulder 3465.23 cm1, 3316.71 cm1
-1
The percentage composition of the alkyd resin and 3205.80 cm correspond to free isolated
constituents are listed in Table 4, while Table 5 hydroxyl (O-H) alcohol of the polymer. The strong
shows some of the physicochemical properties of broad band at 1732.13 cm-1 indicate the
the resin. The results of drying and set to touch presence of carbonyl group (C=O), while a
time of ENOMAR after heating in an oven set at medium band at 2928.04 cm-1 correspond to the
temperature of 80°c and 120°c at different time presence of olefins. The presence of several
intervals are listed in Tables 6 and 7 respectively. other bands are an indication of other functional
Minimum drying and set to touch group such ether, ester etc that comes as a
time was recorded at 17 and 11 hrs after heating result of ring opening of the epoxy group, thus
for 120 mins at 80°C, while the time of 15 and culminating to side reactions. Ring opening of
9hrs was recorded as the minimum drying and oxirane functional group during the process of
set to touch time after heating for 120 mins at synthesizing ENOMAR gives alkoxy and hydroxyl
120°C. Increase in temperature from 80°C to radicals. This radical are susceptible to other
120°C reduces the drying time and enhances the side reactions that form ester and ether. The
curing rate of the alkyd resin synthesized. This is drying process of alkyd resin takes place when
attributed to increase in cross-linkages of the unsaturated bonds present in fatty acids are
polymeric compound initiated by heat. The oxidized by atmospheric oxygen to give hydro-
results also show that increase in temperature peroxy groups as seen below.
from 80°C to 120°C reduces the drying time.
The drying process is based on reaction between -CH2-CH=CH- + O2 → HOOCH-CH=CH- (2)
oxygen from the epoxy functional group and (ROOH) Hydro-peroxy
unsaturation present in the oil [16]. [17] and [18]
as shown in equation 2 and 3. Table 8 shows the Decomposition of hydro-peroxy give alkoxy and
performance properties of the cured ENOMAR hydroxyl radicals
under different chemical environments. The
® ®
result shows that ENOMAR are highly resistant RO – OH → RO + OH (3)
to 10% hydrochloric acid solution and distilled
water but shows relatively poor resistance in The alkoxy, hydroxyl radicals are susceptible to
1% sodium hydroxide solution. The poor side reactions which results to ester and ether
resistance to alkaline solution by ENOMAR may formation. These radicals are form after the
be as a result of the presence of epoxy ring opening, thus exposing it to other side
alkali hydrolysable group. The IR-spectra of reactions.

Fig. 1. Infrared spectra of ENOMAR

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 Anya et al.; ACSJ, 15(2): 1-7, 2016; Article no.ACSJ.26431

Table 8. Chemical resistance of ENOMAR in different chemical environments

Alkyd type 10% HCl 1% NaOH 10% NaCl Distilled H2O

ENOMAR Very good Fair Very good Very good
Key; Very good = >70%, Good = 60-69%, fair = 50-59%, Poor= < 50%

5. CONCLUSION applications. ChemSusChem. 2009;2:136-

147.
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synthesize a greener alkyd resin by substituting K. Utilization of green seed canola oil for in
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that is characteristic of a good alkyd resin. Alkyd Science and Technology. 2002;(104):293-
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