Polymer-Plastics Technology and Engineering

ISSN: 0360-2559 (Print) 1525-6111 (Online) Journal homepage: http://www.tandfonline.com/loi/lpte20

Synthesis and Spectroscopic Studies of

DGEBAGrafted Polyaniline
C. H. Teh , R. Rozaidi , D. Rusli & H. A. Sahrim
To cite this article: C. H. Teh , R. Rozaidi , D. Rusli & H. A. Sahrim (2008) Synthesis and
Spectroscopic Studies of DGEBAGrafted Polyaniline, Polymer-Plastics Technology and
Engineering, 48:1, 17-24, DOI: 10.1080/03602550802539106
To link to this article: http://dx.doi.org/10.1080/03602550802539106

Published online: 17 Dec 2008.

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Date: 31 May 2016, At: 23:53

Polymer-Plastics Technology and Engineering, 48: 1724, 2009

Copyright # Taylor & Francis Group, LLC
ISSN: 0360-2559 print/1525-6111 online
DOI: 10.1080/03602550802539106

Synthesis and Spectroscopic Studies of DGEBAGrafted

Polyaniline
C. H. Teh1, R. Rozaidi1, D. Rusli2, and H. A. Sahrim1
1

Downloaded by [Cochin University of Science & Technolog y] at 23:53 31 May 2016

School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia,
Bangi, Selangor, Malaysia
2
School of Chemical Sciences and Food Technology, Faculty of Science and Technology,
Universiti Kebangsaan Malaysia, Bangi, Selangor, Malaysia

A polymer blend of PANI=epoxy resin system was

found to have various applications, such as conductive
adhesive material[1], electrical conductive resin[2,4], and
electromagnetic interference (EMI) shielding materials[8].
The presence of acidic doping in PANI=epoxy resin polymer blends enhances the thermal and electrical properties
in the composite products. Recently, Lu and co-workers[9]
reported that PANI=epoxy composites that synthesized via
in situ polymerization have a high value of dielectric
constant and thus can be applied as embedded capacitor
material.
In general, polymer blends are a very common technique
in processing PANI=epoxy resin composites. Although
polymer properties can compensate each other via this
technique, synergistic effects, such as compatibility and
dispersion of PANI filler in the epoxy matrix, are another
factor to consider as they affect final properties of the
composites. Therefore, other routes to prepare the PANI
with epoxy resin are desirable.
Modification of PANI with epoxy resin via chemical
synthesis may bring some interesting findings; recently,
the addition of other functional groups in an epoxy resin
system shows promising results[10,11]. Better mechanical,
thermal, and electrical properties can be obtained from
the composites of designated epoxy resin with other functional groups. There are several reports showing that PANI
and epoxy resin can be prepared chemically using as
emulsion polymerization[5], in-situ polymerization[9], and
interfacial polymerization[12].
Graft copolymerization can also be used to improve the
properties of PANI in epoxy resin. It has been reported
that graft copolymerization can be carried out through ring
opening polymerization of epoxide via N-alkylation reaction[1316]. Evers and co-workers[13] used sodium hydride
(NaH) to produce N
polyanion from the NH group of
polybenzimidazole. Thus, these N
polyanions caused ring
opening polymerization of the epoxide. The N-alkylation

N-grafted polyaniline with diglycidyl ether bisphenol A

(DGEBA) was synthesized via anionic copolymerization technique.
Metalation reaction was performed to cause grafting to occur
between DGEBA with emeraldine salt polyaniline (PANI-ES) and
leucoemeraldine base polyaniline (PANI-LEB), respectively. Fourier
transform infrared (FTIR), 13C-nuclear magnetic resonance (NMR),
and 1H-NMR spectroscopies and gel permeation chromatography
(GPC) were performed to characterize the PANI-EB-g-DGEBA
and PANI-ES-g-DGEBA copolymers. The gel content of the resultant copolymers was determined by Soxhlet extraction. Results of
spectroscopic studies showed that grafting took place together with
the side reaction, cross-linking, and DGEBA homopolymerization.
Oxidation states of PANI were found to influence the gel content
and molecular weight distribution of copolymers produced.
Keywords Anionic copolymerization;
Polyaniline

DGEBA;

Grafting;

INTRODUCTION
Research involving the combination of properties of
polyaniline (PANI) with epoxy resin has been developed
for decades. There are several ways to impart the properties
of PANI into epoxy resin in order to achieve desired
properties, such as polymer blends[14], emulsion polymerization[5], electrochemical[6,7], and other reliable methods.
Each method employed determines the application routes
of the PANI=epoxy resin systems. For example, PANI=
epoxy resin systems that are prepared via electrochemical
methods can be applied as corrosion coatings materials
for steel[6,7] because uniformity of film thickness can be
produced from this method. This behavior is important
for organic coatings and electronic application.
Address correspondence to C. H. Teh, School of Applied
Physics, Faculty of Science and Technology, Universiti
Kebangsaan Malaysia, Bangi 43600, Selangor, Malaysia. E-mail:
atinc_ch@yahoo.com

17

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18

C. H. TEH ET AL.

reaction has also been employed by Wang et al.[14] to

synthesize poly(ethylene glycol) (PEG)-grafted polyaniline
(PANI) copolymer, which has better solubility in common
organic solvents and water.
Recently, Yamaguchi and co-workers[15,16] described
the synthesis and the chemical, optical, electrochemical,
and thermal properties of PANI grafted with glycidyl
phenyl ether (GPE) by utilizing ring opening graft copolymerization of epoxide. They reported that chemical and
physical properties of N-grafted polyaniline copolymers
can be controlled and tuned from the degree of grafting
and length of grafted side.
In this work, we apply and use the anionic copolymerization technique to carry out grafting on polyaniline via
ring opening polymerization of epoxide on diglycidyl ether
bisphenol A (DGEBA). Grafting of DGEBA on PANI
with different oxidation states, particularly in emeraldine
salt polyaniline (PANI-ES) and leucoemeraldine base
polyaniline (PANI-LEB), was studied. Both PANI-LEBg-DGEBA and PANI-ES-g-DGEBA copolymers were
characterized by Fourier transform infrared (FTIR) and
nuclear magnetic resonance (NMR) spectroscopies to
determine the grafting section and identify the molecular
structure of the copolymers. Gel permeation chromatography (GPC) was also conducted to determine the molecular weight distribution of the copolymers, and gel content
of the copolymers was determined by Soxhlet extraction.
EXPERIMENTAL METHOD

was followed by drying in an oven at 80C for 24 h. The

PANI-ES was later neutralized with excess amount of
1.0 M ammonium hydroxide aqueous solution and washed
with excess water followed by methanol to obtain the emeraldine base polyaniline (PANI-EB). Methanol was used to
remove the impurities and oligomers formed in PANI-ES
polymerization. The reduced form polyaniline, leucoemeraldine base (PANI-LEB), was prepared by using hydrazine
monohydrate, and 5 g of PANI-EB was added in the three
neck reactor containing 50 ml of hydrazine monohydrate.
The reaction was carried out under nitrogen atmosphere
for 5 h. The light blue precipitate was washed thoroughly
with distilled water and methanol followed by drying in
an oven for 1 h at 80C. The molecular structures of general
form PANI and oxidation states PANI-ES, PANI-EB, and
PANI-LEB are summarized in Fig. 1.
Graft Copolymerization of PANI with DGEBA
The copolymer was designed and modified via Yamaguchi
and co-workers ring opening graft copolymerization
method[16,17]. The copolymerization process was initiated
by a solution of sodium methylsulfinyl carbanion in
DMSO (40 ml) prepared from sodium hydride (190 mg,
7.95 mmol) in a three neck reactor. The reaction flask
was kept under nitrogen atmosphere throughout the subsequent reactions by a constant flow of nitrogen gas. The
mixture was stirred at 75C for 24 h until all the sodium
hydride was completely dissolved. This was followed
by addition of PANI-LEB (650 mg, 6.99 mmol) and the

Materials
Diglycidyl ether bisphenol A (DGEBA) with trade name
EPIKOTETM Resin 828 was supplied by the ASA Chem.
This product is a medium viscosity liquid epoxy resin with
epoxy values of about 0.53 mol=100 g and epoxy equivalent
of 187 g=equivalent. Aniline, ammonium peroxydisulphate
(APS), and hydrazine monohydrate were analytical grade
supplied by Alfa Aesar. Both hydrochloric acid and
ammonium hydroxide were provided by Tedia Company,
Inc. Sodium hydride was supplied by BDH Chemical,
and DMSO was made in Lab Scan Analytical Science.
Aniline was distilled at 182C until colorless prior to use.
All other reagents were used as received.
Synthesis of Polyaniline in Different Oxidation States
Emeraldine salt polyaniline (PANI-ES) was synthesized
via chemical oxidation method similar to the report by
Zeng and Ko[17] but with APS as the oxidation agent,
and 10 ml of aniline and 24.5 g of APS were prepared separately in 150 ml of 1.0 M hydrochloric acid aqueous solutions. The APS solution was added dropwise to the stirred
solution of aniline hydrochloride after 30 min of stirring in
an ice bath. After 3.5 h, the greenish black precipitate was
filtrated and washed with excess water and methanol. This

FIG. 1. Molecular structures of PANI, PANI-ES, PANI-EB, and

PANI-LEB.

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DGEBAGRAFTED POLYANILINE

reaction was allowed to continue for 24 h at 40C. The

metalation reaction was expected to occur between
PANI-LEB with the sodium methylsulfinyl carbanion
solution[18]. The dark blue solution was cooled to 30C
before adding DGEBA (8.37 g, 44.81 mmol) into it. The
reaction was allowed to continue for another 24 h. The
distilled water was poured into the reaction flask, under
vigorous stirring to precipitate the copolymer. The gel
formed black precipitation and was recovered by using
vacuum filtration and washed excessively with distilled
water and methanol. The black precipitate was later dried
in an oven at 80C for 48 h. The product obtained was
labeled as PANI-LEB-g-DGEBA copolymer. The same
procedure was employed to prepare the PANI-ES-gDGEBA copolymer by replacing the PANI-LEB with
PANI-ES (1 g, 10.75 mmol).
Characterization
All samples used for characterization were in powder
form. The FTIR spectra were recorded on a GX model
Perkin-Elmer Infrared Spectrometer using KBr discs. The
spectra were recorded in the range of 4,000 cm
1 to
370 cm
1. The 1H and 13C NMR spectra were obtained
through the ECP 400 model Jeol FT-NMR spectrometer
using deuterated chloroform (CDCl3) as solvent. The molecular weight distribution of copolymer was determined by
Waters 2410 gel permeation chromatography with polystyrene as standard and toluene as eluent. Approximately
0.3 g of each sample were weighed exactly and placed in a
thimble, which later underwent Soxhlet extraction for
24 h using THF as solvent. After the extraction, the thimble
was dried in an oven at 90C until constant weight was
achieved. The gel content was calculated as follows:
Gel content %

Weight after extraction

 100
Initial weight

RESULTS AND DISCUSSION

Copolymerization of Polyaniline (PANI) with DGEBA
Samples of PANI with two different oxidation states
were used to study the grafting and cross-linking behavior
with DGEBA. The metalation reaction on PANI was carried out in the sodium methylsulfinyl carbanion solution,
which was prepared using sodium hydride in DMSO. The
metalation reaction was as illustrated (Scheme 1a).
This mechanism was used by Evers et al.[13] and
Yamaguchi et al.[15,16] to produce N
polyanion from the
NH groups. Yamaguchi and co-workers[16] described that
sodium methylsulfinyl carbanion solution in DMSO
caused deprotonation of NH groups and produced an
anion N
on PANI backbones chains. This anion later
promotes b-scission of DGEBA followed by epoxide ring

19

SCHEME 1. (a) Metalation reaction of PANI with sodium methylsulfinyl carbanion solution followed by (b) epoxide ring opening of DGEBA
grafting on polyaniline backbones.

opening polymerization (Scheme 1b). Through this

method, both PANI-LEB-g-DGEBA and PANI-ES-gDGEBA copolymers can be obtained. In this work, we
found that samples of PANI with different oxidation states
used to prepare copolymers with DGEBA showed different
levels of cross-linking besides desired grafting and side
reaction, DGEBA homopolymerization. This shows that
anionic grafting techniques used in this work are unavoidable with the side reaction of cross-linking and homopolymer contamination as also reported by Noshay and
McGrath[19].
The PANI-LEB-g-DGEBA was found solidified in the
reactor before the reaction was quenched while PANIES-g-DGEBA was still in gel form after 24 h of copolymerization. This may explain why PANI-LEB, which has
additional benzenoid rings, was expected to change back
to typical PANI-EB due to oxidation and formed more
cross-linked sections as the PANI intermolecular Michael
reaction occurred[20] during metalation reaction. The
PANI-ES-g-DGEBA copolymer was expected to have
few partially cross-linked sections.
Gel Content and GPC Analysis
Both PANI-ES-g-DGEBA and PANI-LEB-g-DGEBA
were successfully produced from the anionic copolymerization method. Without using this method, both polymers
possibly become a polymer blend with no grafting section.
However, cross-linking will take place in this polymer
blend because PANI, which has amine functional groups,
will partially cure the DGEBA[2,4]. We found that the
PANI-ES-g-DGEBA copolymer has higher total monomer
conversion of DGEBA, which consisted of grafted sections
and DGEBA homopolymer and cross-linked section compared with PANI-LEB-g-DGEBA copolymer. As well,
THF was used in Soxhlet extraction because it will mostly

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20

C. H. TEH ET AL.

dissolve the oligoether side of the copolymer together with

the grafting section, leaving behind the cross-linked
residues. This can be determined from the IR spectra.
In this work, PANI-ES-g-DGEBA yielded 72.7% of
total monomer conversion of DGEBA compared with only
42.8% for PANI-LEB-g-DGEBA. Upon extraction using
th Soxhlet method, PANI-ES-g-DGEBA did not have
much cross-linked section found. The PANI-ES-g-DGEBA
yielded nearly 12% of gel content compared with PANILEB-g-DGEBA, which yielded 62.7% of gel content. The
gel content of PANI-LEB-g-DGEBA was found to be 5
times more than PANI-ES-g-DGEBA. This explained that
more cross-linked section was formed in the PANI-LEB-gDGEBA compared to PANI-ES-g-DGEBA.
Sodium methylsulfinyl carbanion solution was used to
increase the neucleophilicity of nitrogen by deprotonation
the NH groups. Thus, PANI-LEB, which has more benzenoid units compared with the PANI-ES, will form more
N
polyanion, which later caused epoxide ring opening
on DGEBA. Unfortunately, there were also cross-linked
sections formed in the PANI-LEB-g-DGEBA. Mikhael
and his coworkers[20] explained that the emeraldine anion
from PANI-ES or PANI-EB that has a halide anion was
unstable when left at room temperature. Therefore, it
formed cross-linked sections via the intermolecular
Michael reaction wherein the N
anion was added to the
CC of other quinoid rings. This side reaction can be
avoided by carrying out the reaction on the reduced form
of PANI as reported by Levon[21]. In this work, it was
expected that the PANI-LEB was oxidized to typical
PANI-EB during the metalation reaction, followed by
intermolecular Michael reaction on quinoid rings before
copolymerization conducted. This probably reduced the
grafting reaction between PANI-LEB and DGEBA.
From the GPC results, PANI-LEB-g-DGEBA had a
number average molecular weight (Mn) of 0.38  104 and
weight average molecular weight (Mw) of 0.50  104. The
index of polydispersity (PDI) of 1.55 explained that
PANI-LEB-g-DGEBA underwent additional polymerization and it terminated via a coupling reaction[22]. As for
PANI-ES-g-DGEBA copolymer, GPC did not show any
results. This possibly was due to the insolubility of
PANI-ES-g-DGEBA in toluene.
IR Analysis
The IR spectra of PANI-LEB-g-DGEBA and PANIES-g-DGEBA copolymer showed all characteristic bands
of PANI, respectively, at 1606 and 1607 cm
1 (assigned
as CC stretching of the quinoid rings), 1508 and
1509 cm
1 (CC stretching of benzenoid rings), 1292 and
1297 cm
1 (C-N stretching mode), 1182 and 1184 cm
1
(C-H bending of aromatic rings), and 828 and 830 cm
1
(C-H out of plane bending of p-disubstituted benzene ring).
These absorption peaks indicated the presence of the PANI

main chain structure[17,23] in both copolymers. Upon

reduction to PANI-LEB from PANI-ES, the wave numbers of related absorption peaks and intensity shifted to
higher values.
Figure 2 shows the comparison of IR spectra of epoxy
resin (DGEBA) with both PANI-LEB-g-DGEBA and
PANI-ES-g-DGEBA copolymers. The DGEBA consists
of bisphenol A and diglycidyl ether moieties. The secondary
alcohol functional group in epoxy resin was represented by
the absorption peaks at 3492 cm
1 (OH stretching
vibration); 1430 cm
1 (in plane OH deformation vibration
coupled with CH wagging vibration); 1298 cm
1 (OH deformation vibration); 1132, 1108, and 1085 cm
1 (CO stretching); and 737 cm
1 (OH out of plane deformation
vibration). The CO stretching mode has multiple bands
due to the coupling with the nearby carbon[23].
Bisphenol A moiety, which has a C(CH3)2 group, exhibited absorption peaks at 2967 and 2872 cm
1 due to the CH3
asymmetrical and symmetrical stretching vibration, respectively. The methylene ether, OCH2, which linked the bisphenol A moiety with the epoxide group, showed 2 absorption
peaks at 2928 cm
1 (asymmetric CH2 stretching) and
2872 cm
1 (symmetric CH2 stretching). These two peaks
were reported to have the same intensity, but due to overlapping with the methyl groups, the peak at 2872 cm
1 was
found to have lower intensity compared with the asymmetric CH2. The deformation vibration modes of methyl group
were represented by the absorption peaks at 1456 cm
1
(asymmetric CH3), 1385 cm
1 (symmetric CH3), and
1346 cm
1 (symmetric CH3). The peak at 1362 cm
1 should
be due to the wagging vibration of the methylene group.
The skeletal vibration modes of aromatic ring can be
determined by the absorption peaks at 1607, 1582, 1511,
and 1456 cm
1. The step-type band at 1456 cm
1 showed

FIG. 2. IR spectra of (a) DGEBA, (b) PANI-LEB-g-DGEBA copolymer and, (c) PANI-ES-g-DGEBA copolymer.

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DGEBAGRAFTED POLYANILINE

that there are peaks of other functional groups on the

same band. The CH stretching vibration of aromatic rings
was represented by the peak at 3056 cm
1. The paradisubstituted benzene was determined by the absorption
peak at 831 cm
1. The peak at 1180 cm
1 corresponds to
the CH in plane deformation vibration of aromatic ring.
Methyl aromatic ether was found to have two strong bands
at 1247 and 1036 cm
1 due to asymmetric and symmetric
COC stretching vibration, respectively. The absorption
peaks at 1414 cm
1 (CH deformation vibration), 1158 cm
1
(CH2 twisting deformation vibration), 915 cm
1 (ring
deformation vibration), and 772 cm
1 (ring vibration) were
assigned to the epoxide ring.
Figure 2 shows the comparison of IR spectra of both
copolymers with the DGEBA. The IR spectra of copolymers were found to possess most of the absorption peaks
from the PANI and DGEBA counterpart. Due to only
15% of PANI used to prepare the copolymer, the IR spectra of the resultant copolymers was mainly influenced by
the DGEBA functional groups.
As shown in Fig. 3c, the CN stretching of secondary
aromatic amine functional group of PANI-LEB appeared
at 1376 cm
1. The grafting between PANI with DGEBA
was expected to raise a new absorption peak in the region
of 13801265 cm
1, which was attributed to the CN
stretching of the tertiary aromatic amine group. There were
reports showing that the reaction between secondary amine
with epoxide will produce a tertiary aromatic amine
group[24,25]. This new functional group was confirmed as
the formation of a grafted section between PANI and

FIG. 3. IR spectra of (a) PANI-LEB-g-DGEBA, (b) PANI-ESg-DGEBA, (c) PANI-LEB, and (d) DGEBA in the region of
1500500 cm
1.

21

FIG. 4. IR spectra of PANI-ES-g-DGEBA copolymer (a) before and

(b) after Soxhlet extraction.

DGEBA. Unfortunately, the absorption peaks of this

functional group were overlapped by the absorption peaks
of other functional groups, such as OH, C(CH3)2, and
OCH2 from bisphenol A and diglycidyl ether moiety (Refer
Fig. 3), so it was hard to determine. Although the grafting
between PANI with DGEBA was unable to be determined
from the IR spectra, there was a reaction between these two
polymers. Figures 3a and 3b show that the copolymers
exhibit two new absorption peaks at about 574 and
426 cm
1, and these peaks cannot be found in the IR spectra of DGEBA. It was believed that these peaks belonged
to the 1,2,4-trisubstituted benzene groups, and it was
stated as a cross-linked section due to the intermolecular
Michael reactions on the quinoid rings of PANI[20].
The IR spectra of PANI-ES-g-DGEBA before and after
Soxhlet extraction are shown in Fig. 4. As can be seen, the
peaks that correspond to the grafted section (1380
1265 cm
1) and epoxide rings (915 cm
1) disappeared
in the spectrum of PANI-ES-g-DGEBA after Soxhlet
extraction. This meant that Soxhlet extraction extracted
most of the grafted section and epoxide rings homopolymer. The gel content obtained after extraction was
actually a cross-linked section, which cannot be removed
by THF solvent. Therefore, the gel content gave us information about the percentage of cross-linked section formed
in the copolymers.
NMR Studies
Figure 5 shows the comparison of 13C-NMR spectra
of DGEBA, PANI-LEB-g-DGEBA, and PANI-ES-gDGEBA copolymers. There were three peaks with high
intensity that appeared in the range of dc 77.576.9 ppm,
which referred to the resonance peak of residual carbon
of deuterated chloroform (CDC13)[26,27].

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22

C. H. TEH ET AL.

FIG. 5. Comparison of 13C NMR spectra of DGEBA, PANI-LEBg-DGEBA, and PANI-ES-g-DGEBA copolymers.

The assignments of 13C-NMR spectra of copolymers

were characterized based on the works reported by other
research[13,16,2629]. The resonance peaks at dc 44.9 (C1),
50.4 (C2), and 68.9 ppm (C3) represented the carbon of
the glycidyl terminal groups. The aromatic carbon in copolymer was assigned by the resonance peaks at 156.5 (C4),
143.8 (C7), 127.9 (C6, C8), and 114.1 ppm (C5, C9). The
high intense peaks at dc 127.9 and 114.1 ppm indicated that
these aromatic carbons were bonded to the hydrogen atom,
and it can be found in the para-disubstituted benzene rings
in the copolymer. Meanwhile, low intensity peaks centered
at dc 156.48 and 143.8 ppm indicated that the aromatic carbon was bonded to another atom that has higher electronegativity than the hydrogen atom. The resonance peak at
31.2 ppm (C11) represented the methyl carbon, whereas

FIG. 6.

Assignment of

13

the quaternary carbon of bisphenol A moiety has an

intense peak at 41.9 ppm (C10).
Both PANI-ES-g-DGEBA and PANI-LEB-g-DGEBA
copolymers displayed similar 13C-NMR spectra. The grafting was expected to occur on the center and chain end of
the PANI structure. The epoxide ring opening on the
center of the PANI structure was represented by dc 63.9
(C12), 69.3 (C13), and 70.5 ppm (C14). Meanwhile, the grafting on the chain end of the PANI structure can be determined by the chemical shift at dc 41.1 ppm (C15). The
assignment of the 13C chemical shift on the copolymer
molecular structure is illustrated in Fig. 6. As for the
cross-linked section, the carbon resonance peaks for
1,2,4-trisubstituted benzene could not be identified because
the percentage of cross-linked formation were expected to
be much less. In addition, the resonance peaks were
possibly overlapped by the para-disubstituted benzene
from bisphenol A moiety and benzenoid rings of PANI
in the range of dc 100150 ppm.
Figure 6 also shows the assignment of 1H chemical shift
on the DGEBA-grafted PANI copolymer. According to
the reports[28,30,31], resonance peaks (f) and (g) at dH 7.1
and 6.8 ppm, respectively, were due to the aromatic
protons of bisphenol A moiety. The resonance peak (h)
at dH 1.6 ppm referred to the methyl proton. The protons
of the glycidyl terminal group were characterized by the
resonance peaks at dH 4.2 ppm (d), 3.9 ppm (e), 3.3 ppm
(c), 2.9 ppm (b), and 2.7 ppm (a). The aliphatic proton of
oligomers, which synthesized in low molecular weight
epoxy resin, was found to have a resonance peak at dH
4.0 ppm[30], and it was assigned as resonance peak (i).
Grafting between PANI with DGEBA was represented
by resonance peaks (k)(m). It was expected that the anion
N
on PANI backbones initiated the epoxide ring opening.
The grafting was found to occur at the center and chain
end of PANI backbones, and these were configured from
the 13C and 1H-NMR spectra. The terminal hydroxyl
hydrogen was observed at dH 1.8 ppm (k), and the peak
for ring opening was expected to appear at dH 3.4 ppm,
which was represented by resonance peak (l). Grafting on

C and 1H chemical shift of the DGEBA grafted PANI copolymer.

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DGEBAGRAFTED POLYANILINE

the center of PANI backbones can be determined from the

resonance peak (m) at dH 3.0 ppm. Meanwhile, the resonance peak (n) at dH 2.6 ppm represented the chain end
grafting on PANI backbones. The resonance peak of methylene proton, which grafted, displayed a sharp singlet
pattern. This was due to the electrical quadrupole moment
of the nitrogen nucleus[27].
The 1H-NMR spectra for PANI-ES-g-DGEBA copolymer was assigned as follows: H aromatic, 7.16.8 (m); H
diglycidyl ether, 2.7 (dd), 2.9 (t), 3.3 (m), 3.9 (dd), and
4.2 (dd); C(CH3)2, 1.6 (s); N-CH2, 2.63.0 (m); CH(OH),
1.7 (s); and O-CH2, 4.1 (t). The 1H resonance peaks for
cross-linked sections were also found overlapped by the
resonance peaks from para-disubstituted benzene in the
range of dH 6.58.0 ppm. This can be explained by the 1H
found located in the same chemical environment in the
cross-linked section and under the same influence of
magnetic field as 1H of para-disubstituted benzene.

SUMMARY
We found that characterizing and evaluating a copolymer that synthesized by using graft copolymerization of
PANI with DGEBA was not easy. Various methods of
characterization were employed to determine and identify
the existence of the grafted section. However, the
formation of grafted section was unavoidable with its side
reactions, cross-linking, and DGEBA homopolymerization. From the IR spectra of copolymers, absorption peaks
of the grafted section can be found at the region of 1380
1265 cm
1, whereas absorption peaks of epoxide ring
homopolymer were found to appear at 915 cm
1. Both
574 and 426 cm
1 represented the cross-linked section
due to intermolecular Michael reaction on quinoid rings
of PANI. Upon Soxhlet extraction, the IR spectra of
copolymers shows disappearance of absorption peaks
corresponding with grafted section and epoxide rings
homopolymer. The cross-link residue was found insoluble
in THF. As a result, PANI-LEB-g-DGEBA exhibited
higher gel content compared with the PANI-ESg-DGEBA. In this work, we noticed that PANI-LEB used
for copolymerization was probably changed to PANI-EB
prior to oxidation. If the PANI-LEB remained unchanged,
the side reaction, such as the cross-linking, can be avoided.
The Soxhlet extraction and IR spectra were in agreement
with each other by the presence of cross-linked sections
in the copolymer.
Grafting between PANI and DGEBA will create a tertiary aromatic amine. The IR spectra were unable to prove
the existence of this functional group because it falls on the
region of 13801265 cm
1. These absorption peaks were
found overlapped by the absorption of other functional
groups from bisphenol A and diglycidyl ether moieties.
The formation of grafting was expected to occur on the

23

center and chain end of PANI backbones. The epoxide ring

opening on the center of the PANI backbones was represented by dc 63.9 (CHOH), 69.3 (CH2-N), and 70.5 ppm
(CH2-O). Meanwhile, the chain end grafting of PANI
backbones can be determined at dc 41.1 ppm (CH2-N).
This was also supported by the 1H-NMR spectra, where
(CH2-N) has 1H resonance peak at dH 3.0 ppm for the center grafting and dH 2.6 ppm for the chain end grafting. Both
PANI-ES-g-DGEBA and PANI-LEB-g-DGEBA have
similar resonance peaks for the grafted section. The grafted
section on this copolymer was important because it was
believed that the conductive properties of PANI could be
imparted into the epoxy resin system in order to produce
a conductive resin material.
ACKNOWLEDGEMENT
The authors would like to acknowledge the financial
support provided by the Ministry of Science, Technology,
and Innovation, Malaysia (MOSTI) under the IRPA
03-02-01-0124 PR 001 grant.
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