Progress in Organic Coatings 75 (2012) 569578

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Progress in Organic Coatings

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Synthesis, characterization and properties of a castor oil modied biodegradable

poly(ester amide) resin
Sujata Pramanik a , Kalpana Sagar b , Bolin Kumar Konwar b , Niranjan Karak a,
a
b

Advanced Polymer and Nanomaterial Laboratory, Department of Chemical Sciences, Tezpur University, Napaam, Sonitpur 784028, Assam, India
Department of Molecular Biology and Biotechnology, Tezpur University, Napaam, Sonitpur 784028, Assam, India

a r t i c l e

i n f o

Article history:
Received 19 January 2012
Received in revised form 5 May 2012
Accepted 22 May 2012
Available online 9 June 2012
Keywords:
Poly(ester amide)
Castor oil
Rheology
Biodegradation

a b s t r a c t
A biodegradable poly(ester amide) resin was synthesized from N,N-bis(2-hydroxy ethyl) fatty amide of
castor oil with maleic anhydride, phthalic anhydride and isophthalic acid (100:30:35:35 mole ratio) by
the polycondensation process. The fatty amide of the oil was obtained for the rst time with 95% yield.
The chemical structure of the synthesized resin was characterized by spectroscopic techniques like FTIR,
1
H NMR and 13 C NMR. Various physical properties such as acid value, saponication value, iodine value,
specic gravity and viscosity of the resin were also determined. Further the rheological behavior, studied
in the steady shear mode showed shear thinning behavior of the resin. The epoxy cured poly(ester amide)
thermoset using poly(amido amine) hardener exhibited better properties than with the cycloaliphatic
amine hardener cured system. TGA studies also revealed higher thermal stability of the former system
than the latter. In vitro-biodegradation study of the poly(ester amide) thermoset using Pseudomonas
aeruginosa and Bacillus subtilus bacteria revealed superior biodegradability of the thermoset using the
former bacterial strain. Excellent chemical resistance against various chemical media including alkali was
observed for epoxy-poly(amido amine) cured poly(ester amide) resin over epoxy-cycloaliphatic amine
one. The epoxy-poly(amido amine) cured poly(ester amide) thermoset thus has the potential to be used
as surface coating material.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The need of greener materials to overcome the ecological challenges and the uctuating petroleum prices have instigated the
industrial and scientic fraternities to switch over from petroleum
to renewable resources [13]. In this context, vegetable oils offer
many advantages apart from their renewability. The ample availability with versatility in structure and compositions, ease of
handling and inherent biodegradability [4,5] make them industrially attractive and feasible. Moreover a wide variety of monomers
and polymers can be obtained from them by applying appropriate
knowledge of chemistry [6]. Among the different types of traditional and non-traditional vegetable oils, non-edible castor oil,
Ricinus communis is proved to be a unique feedstock for the synthesis of the polymeric materials because of its many advantages
including the presence of a very high percentage (9095%) of ricinoleic acid, a 12-hydroxy oleic acid [7].
Recently, poly(ester amide)s with a combination of aliphatic and
aromatic moieties have generated signicant interest in biomedical
and environmental applications due to their apt biodegradability,

Corresponding author. Tel.: +91 3712 267009; fax: +91 3712 267006.
E-mail addresses: karakniranjan@yahoo.com, nkarak@tezu.ernet.in (N. Karak).
0300-9440/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.porgcoat.2012.05.009

biocompatibility and favorable physical properties [810]. The special structure arises due to the regular enchainment of ester and
amide linkages in the same polymer chain resulted in synergism
of the properties of the polyesters and polyamides. The rigidity
due to the double-bond character of the amide group coupled with
extensive hydrogen bonding inuences the ordering of poly(ester
amide) and consequently enhances the mechanical and thermal
stability [10]. In addition to the above, the presence of ester groups
in the structure renders poly(ester amide) biodegradable [11]. Consequently the synthesis of castor oil [12] based poly(ester amide)
with desirable properties is a valuable proposition.
Vegetable oil based poly(ester amide) resin can be prepared
from the polycondensation of N,N-bis(2-hydroxy ethyl) fatty
amides obtained by base catalyzed aminolysis of various oils viz.,
linseed [13], pongamia glabra [14], Nahar (Mesua ferrea) [15] and
others with different dibasic acid moieties such as phthalic anhydride, adipic acid, tartaric acid, maleic anhydride, etc. Although the
synthesis of poly(ester amide) from dehydrated castor oil using
dibasic acids has been reported in literature [16], but there is no
report on the direct utilization of castor oil in the synthesis of
the same. Further, the above study resulted in the synthesis of a
poly(ester amide)s with poor performance characteristics [16].
Thus in the present communication the authors wish to report
the synthesis of poly(ester amide) resin from N,N-bis (2-hydroxy

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S. Pramanik et al. / Progress in Organic Coatings 75 (2012) 569578

ethyl) fatty amides of castor oil. The rheological behaviors of the oil,
methyl ester and fatty amide of the oil along with the resin were
investigated. The curing study of the resin was performed using
conventional curing system comprising of methyl ethyl ketone peroxide (MEKP), cobalt octoate (Co-octoate) and styrene, and epoxy
based curing systems with poly(amido amine) and cycloaliphatic
amine hardener, separately. The physical, mechanical, chemical
and thermal properties of the cured resins were also delved into.
Further the biodegradability of the epoxy-poly(amido amine) cured
thermoset was carried out by the broth culture technique using
Pseudomonas aeruginosa and Bacillus subtilus bacterial strains for 6
weeks.

anhydride and isophthalic acid as dibasic acids together with

diethanol amide of the castor oil at mole ratio 35:35:30:100 and
in the presence of catalytic amount of sodium methoxide (0.8 wt%
with respect to the fatty amide). The reaction was initially heated
at 150 C for 1 h, followed by 185 C for another 1 h and nally
at 220225 C for 3045 min with continuous mechanical stirring
under the nitrogen atmosphere, until a viscous mass was obtained.
The yield obtained in this process was about 75%. A part of the synthesized resin was puried by dissolving it in THF and precipitating
in a non-solvent such as cold distilled water for structural analysis.

2. Materials and methods

The synthesized resin was cured by using three curing systems as stated earlier. In rst system, the resin was mechanically
mixed with BPA based epoxy resin (at 60:40 weight ratio) followed by sonication for 1520 min and then hand mixing with
50% poly(amido amine) hardener (weight with respect to epoxy
resin). In the second system, the resin was cured with BPA based
epoxy resin (at 60:40 weight ratio) and cycloaliphatic amine hardener (25 wt% with respect to epoxy resin as higher weight percent
resulted in brittle material) by the similar process as above. While in
the third system, the resin was homogeneously mixed with 30 phr
of styrene as the reactive diluent, 4 phr of MEKP as the initiator
and 2 phr Co-octoate as the activator by sonication. The mixtures
were then cast on mild steel plates (150 mm 50 mm 1.60 mm)
and glass plates (75 mm 25 mm 1.75 mm) under ambient conditions, degassed under vacuum and then baked in a furnace at a
denite temperature for specied period of time. The cured systems
were designated as PEA1, PEA2 and PEA3 for epoxy-poly(amido
amine), epoxy-cycloaliphatic amine and conventional curing systems respectively.

2.1. Materials
Castor oil (Sigma Aldrich, India), diethanol amine (Merck,
India), phthalic anhydride (Merck, India) and isophthalic acid
(Sisco Research Laboratory Pvt. Ltd., India) were used after drying under vacuum at 50 C for overnight. Maleic anhydride (Merck,
Germany) was used after drying in a vacuum desiccator for 2
days. Metallic sodium (E-Merck, India) and methanol (Merck,
India) were used for preparation of sodium methoxide. The
solvents like DMAc and THF (Merck, India) were used after distillation. The bisphenol-A-based epoxy resin (BPA, Araldite LY
250) (epoxy equivalent:180190 g/equiv. and density: 1.16 g/cc
at 25 C), poly(amido amine) hardener ((HY 840) Hindustan Ciba
Geigy Ltd., India) and cycloaliphatic amine hardener (Asian Paints
(I) Ltd., India) were used as received. Methyl ethyl ketone peroxide (MEKP) and cobalt octoate (Co-octoate, Kumud Enterprise,
India) were used as received. Styrene (Merck, India) was used
after purication by the conventional technique. The P. aeruginosa
strain (MTCC 7814) and Bacillus subtilis strain (MTCC 441) were
obtained from the Department of Molecular Biology and Biotechnology, Tezpur University. All other reagents used in the study were
of reagent grade.
2.2. Preparation of resin
2.2.1. Preparation of methyl ester of castor oil
1 mmol of castor oil with 10 mmol of super dry methanol was
reuxed in the presence of sodium methoxide (1 wt% with respect
to oil) as catalyst for 45 h under the blanket of nitrogen. The
excess methanol was evaporated using a rotor evaporator. The
crude product was then extracted with 30 mL of petroleum ether
(b.p. 6080 C) in a separating funnel to separate the product from
glycerol. The product was washed with NaCl solution and dried over
anhydrous sodium sulfate. The petroleum ether used for extraction
of the crude product was then distilled off. The yield of the product
obtained was found to be 95%.
2.2.2. Preparation of diethanol amide of castor oil
A nitrogen-ushed two-necked reactor vessel equipped with
a mechanical stirrer was charged with methyl ester of the oil
and diethanol amine at mole ratio of 1:1.2 in the presence of
0.5 wt% sodium methoxide (with respect to the methyl ester) as
the catalyst. The reaction mixture was heated to 110115 C for 4 h
with constant stirring. The crude product was washed with water
to remove the excess diethanol amine. The yield of N,N -bis(2hydroxy ethyl) fatty amide of castor oil obtained by this technique
was about 95%.
2.2.3. Preparation of poly(ester amide) resin
The poly(ester amide) resin was synthesized by the solution polymerization technique using maleic anhydride, phthalic

2.3. Curing of poly(ester amide) resin

2.4. Measurements
FTIR spectra of oil, methyl ester, fatty amide and the poly(ester
amide) resin of castor oil were recorded by FTIR spectroscopy
(Impact-410, Nicolet, USA) using KBr pellet. 1 H and 13 C NMR spectra of the oil, intermediate products and the resin were recorded
with 400 MHz FTNMR (JEOL, Japan) spectrometer by using CDCl3 as
the solvent and TMS as the internal standard. Ultrasonic processor
(UP200S, Hielscher, Germany) was used at 60% amplitude and half
cycle for sonication.
The rheological studies of the castor oil, methyl ester of the oil,
diethanol amide and the resin were carried out using a rheometer,
CVO100 (Malvern, UK) with a parallel plate of 20 mm diameter.
Gel permeation chromatography (GPC) was performed by a Waters
Associates GPC unit at 25 C using THF as the eluent and at the ow
rate of 1 mL/min. The instrument was used after standardization
with polystyrene standard.
Thermogravimetric (TG) analysis was carried out in Shimazdu
TGA 50 thermal analyzer at a nitrogen ow rate of 30 mL/min and at
the heating rate of 10 C/min. The differential scanning calorimetry
(DSC) analysis was done by DSC 60, Simadzu, Japan under the nitrogen ow rate of 30 mL/min by repeated heating and cooling of the
samples. The samples were initially heated from 25 C to 100 C at
the rate of 10 C/min, and then cooled to 25 C and nally heated
up to 300 C at the rate of 3 C/min.
The tensile strength and elongation at break (as per the ASTM
D 412-51 T) of the cured thermosets were measured with the help
of a Universal Testing Machine of model Zwick Z010 (Germany)
by a 10 kN load cell and at 40 mm/min jaw separation speed. The
gloss, scratch hardness and impact resistance of the cured lms
were measured as per the standard methods [17]. The scratch
hardness test (ASTM D5178/1991) of the cured lms was performed by a scratch hardness tester (Sheen instrument Ltd., UK).

S. Pramanik et al. / Progress in Organic Coatings 75 (2012) 569578

The front impact resistance test was carried out by applying falling
ball method using an impact tester (S.C. Dey Co., Kolkata) with a
maximum test height of 100 cm. In this test a weight of 850 g is
allowed to fall on the lm coated on a mild steel plate from minimum to maximum falling heights. The maximum height was taken
as the impact resistance up to which the lm was not damaged.
The gloss characteristics of the cured lms were measured using
a mini glossmeter (Sheen instrument Ltd., UK) at an angle of incidence of 60 . The hardness of the samples was measured by using a
Shore A durometer model SHR-MARK-III as per the standard ASTM
D 676-59 method.
The bending tests and chemical resistance of the cured lms
in different chemical environments were investigated by using the
standard techniques [18]. The surface morphology of the thermoset
was studied by a JEOL scanning electron microscope of model JSM6390LV SEM after platinum coating on the surface.
2.5. Biodegradation by broth culture technique
A nutrient salt broth medium was prepared for culture by dissolving 2.0 g (NH4 )2 SO4 , 3.61 g KH2 PO4 , 1.75 g MgSO4 7H2 O, 0.2 g

571

CaCl2 2H2 O, 2.0 g Na2 HPO4 , 50 mg FeSO4 7H2 O, 1 mg CuSO4 7H2 O,

50 g MnSO4 5H2 O, 70 g ZnSO4 7H2 O, 10 g H3 BO3 5H2 O and
10 g MoO3 in 1.0 L of MilliQ water. 10 mL of the above prepared
liquid culture media was poured into 100 mL conical asks and was
sterilized using autoclave machine at 121 C and 15 lb pressure for
15 min. The cured lms were immersed in 10 mL of sterilized media
in conical asks inside laminar air hood under sterile condition. P.
aeruginosa and B. subtilis bacterial strains were used in the present
study. Media containing no polymer lm was considered as the
negative control.
Each of the bacterial strain was cultured separately in the
above mineral media for two days at 37 C. The conical asks were
incubated with 200 mg of poly(ester amide) resin under sterile
condition at 37 C for the degradation study. Each of the conical
asks containing 100 mL of culture medium was inoculated with
1 108 mL1 microbes. The extent of biodegradation was studied
from the measurement of weight loss of the poly(ester amide) resin
based on the following equation:

Wt =

W0 Wt
100
Wt

Scheme 1. Synthesis of poly(ester amide) resin from castor oil.

(1)

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S. Pramanik et al. / Progress in Organic Coatings 75 (2012) 569578

where Wt (%) is the percent weight loss after time t week of incubation, W0 is the original weight of the poly(ester amide) resin
incubated and Wt is the weight of the degraded poly(ester amide)
resin after t time period of incubation.

3. Result and discussion

3.1. Synthesis of intermediates and poly(ester amide) resin
The quantitative yield of the intermediates like methyl ester and
fatty amide of the oil was obtained in the present study. This is
mainly due the use of appropriate reaction conditions and compositions of the reactants including catalyst. The 1:1.2 mole ratio
of methyl ester of the oil to the diethanol amine together with
the removal of methanol formed, helped drive the transamidation
reaction to completion and yield 95% diethanol amide.
The polycondensation reaction of the diethanol fatty amide
of the oil with the dianhydrides/diacids resulted the desired
poly(ester amide) resin (Scheme 1). The DMAc solvent provided
good homogeneity of mixing of the reactants because of its polar
nature and thereby facilitating the esterication reaction. The solvent was subsequently removed from the product by evaporation
under the used reaction conditions and thus the resin was obtained
with high solid content. The formation of ester-amide linkages in
the polycondensation reaction was conrmed by the FTIR study.
The hydroxyl group of the diethanol amide reacted with carboxyl
ester group of the anhydride and diacid to form the poly(ester
amide) resin. The use of sodium methoxide has advantages over
the other conventional catalysts in enhancing the polyesterication rate. The mole ratio of 30:70 unsaturated to saturated
anhydrides/diacids was used in the reaction to control the gelation.
The aromatic diacid, isophthalic acid has the highest dissociation
constant and is the most hydrophobic of all the anhydrides/diacids
used in the reaction thereby enhancing the hydrolytic stability and
durability of the synthesized resin. The fatty amide with the long
hydrocarbon chain imparted exibility into the structure whereas
the presence of the aromatic moieties contributed to the thermal
stability of the thermosets.
3.2. Physical properties of poly(ester amide) resin
The physical properties of the resin like color, acid value, saponication value, iodine value, density etc. are shown in Table 1. The
moderate acid value of the resin supports its moderate reactivity
for different binder applications. The saponication value of the
resin endorses the formation of a sufcient number of ester linkages in the resin which is further conrmed by the FTIR spectrum
of the resin [18]. The lower value of inherent viscosity indicated
formation of relatively low molecular mass of the resin and hence
it is useful for its different applications. The weight-average molecular weight (Mw ) and polydispersity index (PDI) of the poly(ester
amide) resin obtained from GPC data are summarized in Table 1.

Fig. 1. FTIR spectra of (a) castor oil, (b) methyl ester, (c) diethanol amide and (d)
poly(ester amide) before curing, and (e) epoxy-poly(amido amine) cured poly(ester
amide) and (f) epoxy cycloaliphatic amine cured poly(ester amide).

The molecular weight of the resin was found to be 2793 g/mol with
PDI 1.93.
3.3. FTIR study
The FTIR spectra of the castor oil, methyl ester, diethanol amide
of the oil and the poly(ester amide) resin are shown in Fig. 1. The
sharp absorption band at around 1736 cm1 (Fig. 1b) conrmed the
formation of the ester linkages in the methyl ester of the oil. The
various literature reports [1315] on the FTIR spectra of the fatty
amide of the oil showed the carbonyl amide band together with a
small carbonyl ester band at around 1736 cm1 . Authors here take
the opportunity to report the synthesis of fatty amide of castor oil
for the rst time with high yield (95%) and with non-occurrence of
carbonyl ester FTIR band (Fig. 1c). The disappearance of the band
for carbonyl ester and the appearance of a carbonyl amide band
at around 1620 cm1 afrmed the formation of the fatty amide
of the oil (Fig. 1c). Further, the appearance of both the carbonyl
ester and amide FTIR bands (Fig. 1d) conrmed the formation of
the ester and amide linkages in the synthesized resin. In addition to
the above bands, the OH absorption band appeared at 3420 cm1 ,
C O (ester) at 1177 cm1 , C N at 1070 cm1 , CH2 asymmetrical
and symmetrical stretching at 2926 cm1 and 2857 cm1 respectively, which conrmed the presence of important linkages in the
structure of the resin [13].
3.4.

1H

and 13 C NMR studies

1 H NMR of methyl ester, fatty amide of oil and poly(ester

amide) resin using CDCl3 are shown in Fig. 2a, b and c respectively.

Table 1
Physical characterization of castor oil, methyl ester, diethanolamide and poly(ester amide) resin.
Property

Castor oil

Methyl ester

Diethanol amide

Poly(ester amide)

Color
Acid value (mg KOH/g)
Saponication value (mg KOH/g)
Iodine value (g I2 /100 g)
Specic gravity
Mw (g/mol)
PDI
Viscositya

Light yellow
0.32
180
82.3
0.95

0.06

Yellowish white
2.5
175
81.3
0.90

0.05

Yellowish brown
2.5

80.5
0.96

0.07

Light brown
2.55
145
96.4
0.98
2793
1.93
0.09

ninherent in 0.2% THF at 25 C.

S. Pramanik et al. / Progress in Organic Coatings 75 (2012) 569578

Fig. 2.

573

H NMR spectra of (a) methyl ester, (b) diethanol amide and (c) poly(ester amide).

The singlet peak at around = 0.850.89 ppm occurred due to terminal methyl group of the fatty acid portion, whereas a broad
singlet peak for the internal CH2 groups was observed at around
1.221.25 ppm. The chemical shift value around 1.311.45 ppm and
2.2 ppm observed in the spectra are attributed to the beta () CH2
protons of the OH group of the fatty acid part and the CH2
protons between the CH and C C respectively. In the spectra, the shift value observed at around 5.45.5 ppm and 5.3 ppm
were assigned to the CH CH and OH protons of the fatty
acid part, respectively. The peaks observed at 2.63 ppm, 2.7 ppm,
7.4 ppm and 7.5 ppm are due to the presence of the protons of
maleic anhydride, OH attached to the CH2 of the fatty amide,
phthalic and isophthalic moieties respectively in the structure of
the resin. On one hand the CH proton attached to the OH group
of ricinoleic acid and CH2 protons attached to the OH of the
fatty amide group were found at 3.5 ppm and 3.9 ppm respectively.
On the other hand, when those OH peaks were substituted by
ester moieties then the peak values shifted to 3.7 ppm and 4.4 ppm
respectively [19,20]. Thus the integration ratio of the substituted to
the sum of the substituted and unsubstituted indicated the extent of

substitution of the OH in the resin. The observed integration ratio

was 1.91, which indicated that out of three OH groups 1.91 OH
groups were only substituted. This integration ratio signied that
the molecular architecture of the synthesized resin is linear since
the integration value of more than two results in the formation of
branched structure.
13 C NMR methyl ester, fatty amide of oil and poly(ester amide)
resin are shown in Fig. 3ac. The shift value () at 14 ppm and
22.631.8 ppm were ascribed to the carbon of the CH3 group
and CH2 of fatty acid chain respectively. The peaks at 125.4 ppm,
132.8 ppm, 174 ppm and 175 ppm are attributed to the aromatic
carbon, ring carbon attached to COOCH2 group of resin, C O of
ester and amide groups respectively [21].
3.5. Rheological behavior
The poly(ester amide) resin showed shear thinning behavior
in steady shear mode. The shear viscosities of the oil, poly(ester
amide) resin and its intermediates were determined at room temperature under controlled rate and steady strain of 20 Pa (Fig. 4a).

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S. Pramanik et al. / Progress in Organic Coatings 75 (2012) 569578

Fig. 3.

13

C NMR spectra of (a) methyl ester, (b) diethanol amide and (c) poly(ester amide).

All of them showed Newtonian-type behavior. The methyl ester of

the oil has lower dynamic viscosity as compared to the oil. This is
expected due to the formation of methyl ester of the fatty acids
which has lower molecular mass than the oil. However, the resin
exhibited the highest viscosity among the studied systems. The viscosity of a material is related to the dynamic extension and the
segment density within the volume of a material and intermolecular chain entanglement. The increment in viscosity of the resin may
be attributed to the entanglements among molecular chains [22],
and the presence of intermolecular interactions among different
functionalities like amide and hydroxyl groups.
The effect of shear rate on the shear viscosity of the resin
together with the intermediates and the oil are shown in Fig. 4b.
The decrease of viscosity of poly(ester amide) with the shear rate
(2100 s1 ) indicated shear thinning behavior, while all others
intermediates showed Newtonian like behavior i.e. their shear viscosity was independent of shear rate. The shear thinning nature of
the resin implied that the owability of the resin increased with
the increment in the rate of shear. This behavior of the resin can be

related to the fact that the polymer chains became progressively

aligned with the increase shear rate in the direction of applied force
[23]. This shear thinning behavior also signied good processability of the resin. In other words, instead of the relatively random
intermingled state which exists when the uid is at rest, the major
axes were brought into line with the direction of ow. The shear
viscosity continued to decrease with the increase of apparent shear
rate until no further alignment along the streamlines was possible
and subsequently the ow curve became linear [24].
The temperature sensitivity of the shear viscosity has a profound
effect on the choice of processing conditions which is shown in
Fig. 4c. The gure showed that the shear viscosities of the samples decreased with the increase of temperature in the range of
25100 C at shear stress of 20 Pa, indicating that the increase of
temperature improved the ow behavior of the system. This observation may be attributed to the increase in the molecular motion
or kinetic energy of the polymeric chains which is directly related
to the decrease of viscosity. Also it has been found that the temperature sensitivity of shear viscosity was higher in lower shear rate

S. Pramanik et al. / Progress in Organic Coatings 75 (2012) 569578

575

Fig. 4. Variation of (i) Shear viscosity as a function of time, (ii) Shear viscosity as a function of shear rate and (iii) Shear viscosity as a function of temperature for (a) castor
oil, (b) methyl ester, (c) diethanol amide and (d) poly(ester amide).

region and dropped at higher shear rates. This phenomenon was in

agreement with the fact that elevating shear rate was accompanied
by a rapid decrease of the entanglement of macromolecules and its
viscosity [25].

3.6. Curing study of the resin

The curing study of the poly(ester amide) resin using the three
different curing systems revealed that it was not cured by the
conventional MEKP curing system, though it was found to be
cured by epoxy curing systems using poly(amido amine) as well as
cycloaliphatic amine as hardeners. The lms were baked at temperatures between 150 and 200 C for different time periods to
obtain optimum baking temperature and time by monitoring the
swelling value (Table 2). Over baking of the resin resulted in the loss
of gloss and embrittlement of the lms. The optimum temperature
of baking of the poly(ester amide) resins was found to be 185 C
for the specied time as given in Table 2. There is a prospect of the
occurrence of crosslinking reaction between the hydroxyl groups
of the fatty acid part of the resin along with the amido group of the
hardener with the epoxide groups of the epoxy resin in the presence of the amine hardener, which also acts as an active base and
thus aids in the curing process. The FTIR study of PEA1 and PEA2

(Fig. 1e and f) showed the presence of hydrogen bonding between

epoxy cured poly(ester amide) resin with the poly(amido amine)
and cycloaliphatic amine hardeners. Fig. 1e and f showed blue shifting together with the decrement in intensities of the FTIR band of
the hydrogen bond (HB) in the poly(ester amide). The HB so formed
due to the associated blue shifting is known as the weak HBs. In
the above cured systems, the epoxy cured poly(ester amide) acts as
a HB donor (X H) and both cycloaliphatic amine and poly(amido
amine) as HB acceptors (Y). The above blue shifting was attributed
to the increased percentage of s character in the X H moiety when
Table 2
Film properties of PEA1 and PEA2 resins.
Physico-mechanical property

PEA1

PEA2

Curing time (h)

Gel fraction (%)
Scratch hardness (kg)
Hardness (Shore A)
Flexibility (mm)
Impact resistance (cm)
Gloss at 60
Tensile strength (MPa)
Elongation at break (%)
Tg ( C)

3
78.57
8
65
1
100
90
8.67
114
20

2.5
86.14
6
68
3
100
82
7.3
98
22

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S. Pramanik et al. / Progress in Organic Coatings 75 (2012) 569578

Scheme 2. Possible curing mechanism of PEA1.

the Y approached H atom. The X H bond contraction is ascribed

to a weak hyperconjugation to * orbital of donor moiety. There
appeared a loss of electron density between H and Y and this depletion of electrons resulted due to the tendency to attract electrons
by X in the presence of Y, which in turn increased the attraction between X and H causing X H bond to contract [26]. Since
cycloaliphatic amine is more basic (strong HB acceptor) compared
to the poly(amido amine), the former tends to attract the electron
density of X H bond toward itself more than the latter. Consequently the X H bond contraction was less in the former compared
to the latter. Thus the blue-shifting was more in PEA1 than PEA2. All

such possible interactions of the poly(ester amide) resin with the

epoxy and cycloaliphatic amine and poly(amido amine) hardeners
are shown in Schemes 2 and 3 respectively.

3.7. Morphological study

The representative SEM micrograph of the poly(ester amide)
thermoset (shown in Fig. 5) exhibited uniform surface morphology. This is indicated good miscibility of the components, with no
segregation that is formation of a single phasic system.

Scheme 3. Possible curing mechanism of PEA2.

S. Pramanik et al. / Progress in Organic Coatings 75 (2012) 569578

Fig. 6. DSC thermograms of PEA1 and PEA2 thermosets.

Fig. 5. TGA thermograms of PEA1 and PEA2 thermosets.

3.8. Physical and mechanical properties of poly(ester amide)

thermoset
The performance characteristics like gloss, impact resistance,
scratch hardness, tensile strength and elongation at break of PEA1
and PEA2 systems are shown in Table 3. The gloss values of the
cured poly(ester amide) thermosets reected the good compatibility of the poly(ester amide) with epoxy resin and the hardener,
and the lms have good dimensional stability and smooth surface
texture. However the lower gloss value of the PEA2 compared to
the PEA1 may be attributed to the lower dimensional stability of
the epoxy-cycloaliphatic amine cured thermoset compared to the
epoxy-poly(amido amine) cured thermoset. Also the cycloaliphatic
amines are low molecular weight and hygroscopic in nature and
thus have a tendency to react with atmospheric carbon dioxide and
moisture to form an ammonium carbamate thereby causing blushing or blooming problems, which may contribute to the low gloss
value of the PEA2 thermoset.
The high impact resistance of both PEA1 and PEA2 thermosets
reected optimum crosslinking together with exibility due to the
presence of long hydrocarbon chain of the castor oil. Better scratch
hardness of PEA1 thermoset over PEA2 thermoset may be due to
enhanced combined effect of strength and exibility of the former than the latter. The long aliphatic chain of poly(amido amine)
hardener imparted exibility to the resin together with strength.
The tensile strength of PEA1 thermoset was found to be higher
compared to the PEA2 which may be attributed to the optimum
crosslinking (as evident from the percent gel fraction) in the former than in the latter. However, higher elongation at break and
exibility of the former thermoset than the latter may be due to
the better plasticizing effect of the poly(amido amine) hardener
used in PEA1 than cycloaliphatic amine used in PEA2. The Shore A
hardness of the PEA2 was found to be higher compared to PEA1.
This may be due to the higher extent of crosslinking as resulted by
gel fraction value of the former than the latter.
The changes of mass of the cured lms in various chemical environments kept for 30 days are shown in Table 3. Overall chemical

resistance in all the media were found to be satisfactory in both

the cases. The good alkali resistance of the resin was attributed
to the presence of stable amide moiety and adequate amount of
crosslinking in the structure. However, PEA1 showed slightly better resistance against different chemical media compared to PEA2.
This may be due to the optimum curing of PEA1.
It is seen from Table 2 that the epoxy-poly(amido amine) cured
thermoset showed superior performance properties together with
good chemical resistance compared to the cycloaliphatic amine
cured one.
3.9. Thermal behavior
Both PEA1 and PEA2 showed a two step degradation pattern
(shown in Fig. 6) with initial degradation temperature (decomposition onset) around 250 C and 220 C respectively. The rst
degradation peak is due to the chain scission through the ester linkages of the polymer. While the second step degradation is due to the
presence of thermally stable aromatic moiety and amide linkages
in the polymeric backbone. The increase in the thermal stability of
the PEA1 resins was attributed to the adequate crosslinking. The
TGA thermogram of PEA1 exhibited 50 wt% loss at 400 C and a
char residue of 3% at 700 C. This resulted due to the strong interaction between the epoxy-poly(amido amine) hardener system
and poly(ester amide), which restricted the motion of the polymer
chains.
It is evident from the cooling curves of DSC (Fig. 7) that the glass
transition temperature (Tg ) of PEA1 appeared at lower temperature

Table 3
Chemical resistance of PEA lms.
Type of media

Distilled water
5% aq. HCl
10% aq. NaCl
3% aq. NaOH

577

Weight changes (g)

PEA1

PEA2

1.7 102
2.5 102
5 103
1 102

3.9 102
4.1 102
1 102
3 102

Fig. 7. SEM micrograph of PEA1.

578

S. Pramanik et al. / Progress in Organic Coatings 75 (2012) 569578

conrmed the formation of the poly(ester amide) resin. The study

showed that the nature of the curing system has a profound
effect on the properties of the thermoset. The epoxy-poly(amido
amine) cured thermoset exhibited better scratch hardness, gloss
and chemical resistance and enhanced thermal behavior than
the epoxy-cycloaliphatic amine cured one. The former thermoset
exhibited biodegradation post 6 weeks of inoculations by broth
culture technique using P. aeruginosa. Thus studied epoxy cured
poly(amido amine) thermoset has good prospective to be explored
as biodegradable thin lm material.
Acknowledgements

Fig. 8. Biodegradation of poly(ester amide) resin using Pseudomonas aeruginosa and

Bacillus subtilis bacterial strains.

than the PEA2 thermoset. This observation may be attributed to the

greater plasticizing effect of the poly(amido amine) hardener used
in the former as compared to the cycloaliphatic amine used in the
latter. Hence PEA1 thermoset showed better thermal behavior than
PEA2.
3.10. Biodegradation
The biodegradations of PEA1 thermoset against P. aeruginosa
and B. subtilus bacterial strains are shown in Fig. 8. From this gure it was found that the lms were deteriorated to a signicant
extent post 6 weeks of inoculations. This was indicative of the fact
that the bacteria used the polymer (carbon source) as its catabolite.
The differences in the biodegradation as evident from the weight
loss prole of poly(ester amide) resin using two different bacterial strains showed microbial specicity for the polymer substrate.
However the B. subtilus bacterial strain exhibited comparatively
lower degradation rate compared to the P. aeruginosa bacterial
strain. P. aeruginosa possesses higher biosurfactant activity and
high cell surface hydrophobicity (CSH) than the B. subtilis [27]. The
former thus colonises the polymeric surface and grows faster than
the latter bacterial strain which in turn aids in the biodegradation of
the poly(ester amide). Also P. aeruginosa is a gram negative bacteria
while B. subtilis is a gram positive bacteria and the differences in
their cell wall structures, which acts as an active barrier is supposed
to control the degradation of the polymer substrate.

The authors express their gratitude and thanks to the research

project assistant given by DRL, India, through the grant no.
DRL/1047/TC, dated 2nd March, 2011, SAP (UGC), India through
grant no. F.3-30/2009(SAP-II) and FIST program-2009 (DST), India
through the grant no. SR/FST/CSI-203/209/1 dated 06.05.2010. Dr.
M.A. Laskar, HoD, Biotech. Dept., St. Anthonys College, Shillong
is gratefully acknowledged for his advice and suggestions for the
biological study.
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