Designed Monomers and Polymers

ISSN: (Print) 1568-5551 (Online) Journal homepage: https://www.tandfonline.com/loi/tdmp20

Electrochemical synthesis and characterization

of the conducting copolymer poly(aniline-co-o-
anisidine-co-o-toluidine)

D.D. Borole , U.R. Kapadi , P.P. Mahulikar & D.G. Hundiwale

To cite this article: D.D. Borole , U.R. Kapadi , P.P. Mahulikar & D.G. Hundiwale (2004)
Electrochemical synthesis and characterization of the conducting copolymer poly(aniline-
co-o-anisidine-co-o-toluidine), Designed Monomers and Polymers, 7:4, 337-349, DOI:
10.1163/1568555041475266

To link to this article: https://doi.org/10.1163/1568555041475266

Published online: 02 Apr 2012.

Submit your article to this journal

Article views: 96

View related articles

Citing articles: 9 View citing articles

Full Terms & Conditions of access and use can be found at

https://www.tandfonline.com/action/journalInformation?journalCode=tdmp20
Designed Monomers and Polymers, Vol. 7, No. 4, pp. 337 – 349 (2004)
 VSP 2004.
Also available online - www.vsppub.com

Electrochemical synthesis and characterization

of the conducting copolymer
poly(aniline-co-o-anisidine-co-o-toluidine)

D. D. BOROLE, U. R. KAPADI, P. P. MAHULIKAR and D. G. HUNDIWALE ∗

School of Chemical Sciences, North Maharashtra University, Jalgaon-425 001 (M.S.), India

Abstract—Copolymerization of aniline, o-anisidine and o-toluidine was achieved electrochemically

in aqueous solution containing H2 SO4 as supporting electrolyte. The copolymer compositions can
be altered by varying the monomer feed ratios during electrosynthesis. The films were electropoly-
merized in solution containing monomers in various ratios (0.025 to 0.1 M) and 1 M sulphuric acid
as electrolyte by applying a sequential linear potential scan rate of 50 mV/s between −0.2 to 1.0 V
versus Ag/AgCl electrode. The copolymers were characterized by cyclic voltammetric, conductiv-
ity measurement, UV-Vis spectroscopy, differential scanning calorimetry (DSC), thermogravimetric
analysis (TGA), CHN elemental analysis and optical microscopy photographs.

Keywords: Conducting polymers; electrochemical polymerization; copolymer.

1. INTRODUCTION
Polymers are generally used as insulators. However, the discovery that organic
polymers can also have conductivities comparable to metals and semiconductors
has revolutionized this area of research, especially in the electronics industry. The
prospective utility of these conducting polymers or synthetic metals in electronic
displays, telecommunication, electrochemical storage systems, biosensors and
molecular electronics, etc., has further enhanced the interest in this important field
[1– 5]. Considerable research efforts are currently being devoted to electrochemical
studies on conducting polymers [6]. Among conducting polymers, polyaniline and
its derivatives have attracted much attention due to its ease of synthesis, good
stability in the presence of oxygen/water, interesting electrochemical properties,
including a unique conduction mechanism, and interesting electrical, optical and

∗ Towhom correspondence should be addressed. Tel.: (91-257) 225-2187-90, Ext. 415; Fax: (91-
257) 225-2183; e-mail: ddborole@indiatimes.com
338 D. D. Borole et al.

catalytical properties [7– 11]. However, their properties depend on the synthesis
conditions such as type of supporting electrolyte, reagent concentration, applied
potential, type of solvent and pH of polymerization bath [12– 14].
With regard to polyaniline-based copolymers, pioneering work has been done by
Wei and co-workers [15, 16] who showed that aniline could be copolymerized with
o-toluidine to control conductivity in a broad range. Dao et al. [17] have reported
electrosynthesis of copolymer of aniline and N-butylaniline with good conductivity
and solubility in common organic solvents. Successful copolymerization of aniline
with N-methylaniline [18], 3-aminophenyl-boric acid [19] and o-aminobenzonitrile
[20] has also been reported. Optical and electrical properties of soluble terpolymers
of pyrrole, thiophene and 3-decylthiophene have also been studied [21]. All these
reports reveal that the electrochemical synthesis of copolymers is a convenient
method to prepare new conducting materials with desired properties different from
individual homopolymers. When polymer is synthesized by anodic oxidation (of
monomer), the anions of supporting electrolyte function as doping ions (anions)
and in turn influence overall properties of conducting polymers.
In continuation of our work on conducting homopolymers and copolymers
[22– 25], poly(aniline-co-o-anisidine-co-o-toluidine) (PA-co-POA-co-POT) films
were synthesized by changing the mol ratio of monomers and characterized by
cyclic voltammetry, UV-Vis spectroscopy, conductivity measurements, differential
scanning calorimetry (DSC), thermogravimetric analysis (TGA), CHN elemental
analysis and optical microscopy photographs.

2. EXPERIMENTAL
The monomers aniline, o-anisidine and o-toluidine were distilled twice before use.
The thin films of poly(o-anisidine) (POA), poly(o-toluidine) (POT) and a copolymer
(PA-co-POA-co-POT) were synthesized electrochemically on platinum substrates
under cyclic voltammetric conditions in a single compartment glass cell. A
three-electrode geometry was employed during the electrochemical polymerization
in which platinum substrate as working electrode (1.5 cm2 ), carbon as counter
electrode and Ag/AgCl as the reference electrode. The reference electrode was
kept in close proximity to the working electrode to minimize the electrolytic
ohmic drop. The films were electropolymerized in solution containing monomers
(various mol ratios) and 1 M supporting electrolyte (sulphuric acid) by applying
sequential linear potential scan rate of 50 mV/s between −0.2 to 1.0 V versus
Ag/AgCl electrode. The cyclic voltammetric conditions were maintained using
Potentio-Galvano Stat-30 (Metrohm Autolab Electrochemical Instrument with 663
VA Stand). The homopolymer and copolymer films were deposited with 20 cycles
for the polymerization and their voltammograms were recorded on a PC. After
deposition, the films were rinsed with the solution of 0.2 M supporting electrolyte.
Throughout the studies, anaerobic conditions were maintained with nitrogen gas
atmosphere.
 Synthesis and characterization of the conducting copolymer PA-co-POA-co-POT 339

The optical absorption study of all synthesized films was carried out using UV-
Visible spectrophotometer (Simadzu, UV-1601). The UV-Vis spectra were obtained
ex situ in DMSO. All the spectra were recorded in the wavelength range 300–1100
nm. The conductivity was measured on a platinum electrode, 4 mm in diameter
and 1 µm thick. The thickness of polymer thin films was measured using a digital
micrometer. After the synthesis, films were washed thoroughly using 0.2 M solution
of the respective supporting electrolyte and then the films were immersed in the
solution for 24 h. Finally, the films were dried at 50 ◦ C for 2 h. The dried films
were used for the determination of conductivity at constant current of magnitude
of 10 mA. The electrical conductivity of the films was measured using four probe
techniques. Differential scanning calorimetry (DSC) studies were carried out on a
DuPont 2100 calorimeter with a standard heating rate of 20 ◦ C/min in a nitrogen
atmosphere. A temperature range from 25 ◦ C to 200 ◦ C was selected for each
scan. Thermogravimetric analysis (TGA) was studied in a nitrogen atmosphere
with a temperature range from 40 ◦ C to 700 ◦ C with a heating rate of 20 ◦ C/min in
a nitrogen atmosphere. The elemental analysis of the thin films was done using a
Perkin Elmer Analyser CHNS series II 2400. The surface morphology of the thin
films was carried out by optical microscopy using AN Olympus STM RE-5 at 500×
magnification.

3. RESULTS AND DISCUSSIONS

There are three ways to carry out electrochemical oxidative polymerization: (i) to
control the anodic current, (ii) to hold the applied potential at certain value and (iii)
to scan the applied potential within a certain potential region. Only the third method,
cyclic voltammetry, resulted in the formation of better homo- and copolymer thin
films of aniline, o-anisidine and o-toluidine.
Figures 1 and 2 show the cyclic voltammograms (CVs) recorded during the syn-
thesis of PA, POA, POT and PA-co-POA-co-POT films in aqueous solutions con-
taining 0.1 M respective monomer(s) and changing the concentration of monomer(s)
in 1 M H2 SO4 as electrolyte at room temperature. The overall observations and re-
sults based on CVs are concluded as follows.
• Three peaks (A, B and C) are observed in repetitive cycling. The redox potentials
and current densities corresponding to these peaks are summarized in Table 1.
• The height of the CV curves increases with the number of cycles for all
supporting electrolytes, indicating the formation of conducting polymer films in
each case. It signifies that the oxidation potential depends on the concentration
of monomer.
• The highest current densities corresponding to the anodic peaks are observed
for the copolymerization of 0.1:0.1:0.1 (mol/mol) ratio of aniline, o-anisidine
and o-toluidine in 1 M H2 SO4 . The current densities observed during CVs are
summarized in Table 1.
340 D. D. Borole et al.

(a) (b)

(c) (d)
Figure 1. Cyclic voltammograms recorded during the synthesis of (a) PA, (b) POA, (c) POT and
(d) PA-co-POA-co-POT films in aqueous solution containing 0.1 M of the respective monomer(s)
and 1 M H2 SO4 as electrolyte.

• Two redox peaks were observed for the polymerization of aniline in H2 SO4 . The
redox peaks observed for aniline in H2 SO4 are similar to those reported by Trivedi
and Dhawan [26]. In the case of o-anisidine polymerization, two redox peaks are
observed in H2 SO4 as supporting electrolyte. The CV result for poly o-anisidine
is in good agreement with the result of Lacroix et al. [27]. The redox peaks for
the polymerization of o-toluidine are three in H2 SO4 as supporting electrolyte.
The redox peaks of o-toluidine carried out in H2 SO4 are similar to those reported
by Wei et al. [15], while in case of copolymerization of aniline, o-anisidine
and o-toluidine at various concentration of monomer ratios three redox peaks are
observed.
• In the reverse scan, as the applied potential decreased from 1 to −0.2 V versus
Ag/AgCl, the film became reduced, which was seen by an increase in the cathodic
current.
Thus, the CVs clearly revealed the formation of electroactive polymer films in all
supporting electrolytes. The anodic peaks A and/or C are assigned to the oxidation
of polymer deposited on the electrode surface, which corresponds to the conversion
of amine units into radical cations [28]. Peak B in the CVs is due to adsorption
of quinone/hydroquinone, generated during the growth of polymer film which is
 Synthesis and characterization of the conducting copolymer PA-co-POA-co-POT 341

(a) (b)

(c) (d)

(e) (f)
Type
a b c d e f
Polymer PA-co- PA-co- PA-co- PA-co- PA-co- PA-co-
POA-co- POA-co- POA-co- POA-co- POA-co- POA-co-
POT POT POT POT POT POT
Concentration of monomer (M)
Aniline 0.025 0.05 0.075 0.05 0.075 0.025
o-Anisidine 0.05 0.025 0.05 0.075 0.025 0.075
o-Toluidine 0.075 0.075 0.025 0.025 0.050 0.05

Figure 2. Cyclic voltammograms recorded during the synthesis of PA-co-POA-co-POT films in an

aqueous solution of H2 SO4 as electrolyte.
 342

Table 1.
Redox potentials and current densities at the redox peaks, UV-Vis spectra and electrical conductivity of PA, POA, POT and PA-co-POA-co-POT films in
aqueous solutions of H2 SO4 as supporting electrolyte

Sr. No. Concentration of monomer (M) PA-co-POA-co-POT

Aniline o-Anisidine o-Toluidine Redox potential (mV) Current density (mA/cm2 ) Electrical UV-Vis spectroscopy (nm)
conductivity
A B C A B C (S/cm) Peak Shoulder
1 0.1 — — 191 474 — 1.12 1.01 — 0.0972 810 416
2 — 0.1 — 230 388 — 2.15 4.52 — 0.0275 826 426
3 — — 0.1 239 441 663 1.76 2.95 2.25 0.0563 802 410
4 0.1 0.1 0.1 247 410 703 3.53 3.54 4.03 0.0591 816 420
D. D. Borole et al.

5 0.025 0.050 0.075 227 398 684 2.55 2.40 2.89 0.0453 804 410
6 0.050 0.025 0.075 230 403 676 2.67 2.64 3.11 0.0479 806 410
7 0.075 0.050 0.025 222 385 694 2.89 2.61 4.09 0.0509 810 413
8 0.050 0.075 0.025 235 386 674 3.46 3.19 4.04 0.0423 813 418
9 0.075 0.025 0.050 217 383 694 2.72 2.57 3.96 0.0531 808 411
10 0.025 0.075 0.050 245 401 664 3.26 3.64 2.99 0.0384 811 416
 Synthesis and characterization of the conducting copolymer PA-co-POA-co-POT 343

Figure 3. Optical absorption spectra of (a) PA, (b) POA, (c) POT and (d) PA-co-POA-co-POT films
synthesized electrochemically under cyclic voltammetric conditions in aqueous solutions containing
0.1 M respective monomer(s) and 1 M H2 SO4 as electrolyte.

strongly adsorbed in the polymer matrix [29]. The appearance and intensity of peak
B is highly dependent on the electrolytic medium. The CV of copolymer PA-co-
POA-co-POT differs (A, B or C peaks) from that of individual homopolymers PA,
POA and POT, clearly supporting the formation of a copolymer.

3.1. UV-Vis spectra of the homo- and copolymers

The peak values of optical absorption spectra of PA, POA, POT and PA-co-POA-
co-POT films deposited in presence of sulphuric acid under identical experimental
conditions are summarized in Table 1 and the nature is visualized in Figs 3 and 4.
The UV-Vis spectra are obtained ex situ in DMSO and peaks appearing at about
802–826 nm with a shoulder at 410–426 nm are for emeraldine salt (ES) phase of
PA, POA, POT and PA-co-POA-co-POT in sulphuric acid as electrolyte.

3.2. Conductivity of the homo- and copolymers

The conductivity of PA, POA, POT and PA-co-POA-co-POT films prepared in a
solution containing 0.1 M monomer(s) and 1 M H2 SO4 , are 0.0972, 0.0275, 0.0563
and 0.0591 S/cm, respectively. The conductivity of these films prepared in a solution
containing different ratio of monomer(s) in 1 M H2 SO4 are as shown in Table 1.

3.3. Differential scanning colorimetery (DSC)

The thermal properties of PA, POA, POT and PA-co-POA-co-POT prepared in
H2 SO4 as electrolyte were measured by DSC. The graphs of temperature ( ◦ C)
versus heat flow (W/g) are shown in Fig. 5. The peak values (melting) for PA,
POA, POT and PA-co-POA-co-POT are observed at 82.11 ◦ C, 46.56 ◦ C, 64.38 ◦ C
and 70.64 ◦ C, respectively. Since a single peak is obtained for the copolymer on
the DSC thermogram it confirms the formation of copolymer and not the layers of
individual homopolymer.
344 D. D. Borole et al.

Type
a b c d e f
Polymer PA-co- PA-co- PA-co- PA-co- PA-co- PA-co-
POA-co- POA-co- POA-co- POA-co- POA-co- POA-co-
POT POT POT POT POT POT
Concentration of monomer (M)
Aniline 0.025 0.05 0.075 0.05 0.075 0.025
o-Anisidine 0.05 0.025 0.05 0.075 0.025 0.075
o-Toluidine 0.075 0.075 0.025 0.025 0.050 0.05

Figure 4. Optical absorption spectra of PA-co-POA-co-POT films in an aqueous solution of H2 SO4

as electrolyte.

Table 2.
Elemental analysis (C, H, N) of PA, POA, POT, PA-co-POA, PA-co-POT, POA-co-POT and PA-co-
POA-co-POT in H2 SO4

Sr. No. Polymer % of C, H, N in polymer

C H N Total
1 Polyaniline (PA) 66.71 6.03 14.71 87.45
2 Poly(o-anisidine) (POA) 61.13 6.24 8.29 75.66
3 Poly(o-toluidine) 69.44 7.21 12.87 89.52
4 PA-co-POA-co-POT 65.74 6.55 10.19 82.48

3.4. Thermogravimetric analysis (TGA)

The thermal stability of PA, POA, POT and PA-co-POA-co-POT prepared in H2 SO4
as electrolyte was measured by TGA. The graphs of temperature ( ◦ C) versus weight
loss (%) are shown in Fig. 6. Thermal stability for PA, POA, POT and PA-co-
POA-co-POT is observed up to 407.41 ◦ C, 287.85 ◦ C, 320.81 ◦ C and 333.49 ◦ C,
respectively. This study shows that the stability of copolymer lies in between the
values for the corresponding homopolymers.
 Synthesis and characterization of the conducting copolymer PA-co-POA-co-POT 345

(a)

(b)
Figure 5. DSC thermograms. (a) PA in H2 SO4 , (b) POA in H2 SO4 , (c) POT in H2 SO4 and
(d) PA-co-POA-co-POT in H2 SO4 .
346 D. D. Borole et al.

(c)

(d)
Figure 5. (Continued).
 Synthesis and characterization of the conducting copolymer PA-co-POA-co-POT 347

Figure 6. TGA of PA, POA, POT and PA-co-POA-co-POT in H2 SO4 .

PA POA

POT PA-co-POA-co-POT
Figure 7. Optical microscopy photographs of PA, POA, POT and PA-co-POA-co-POT in H2 SO4 .
348 D. D. Borole et al.

3.5. CHN elemental analysis

The percentages carbon (C), hydrogen (H) and nitrogen (N) present in PA, POA,
POT and PA-co-POA-co-POT films prepared in H2 SO4 as electrolyte were mea-
sured by elemental analysis. The % values of C, H and N are shown in Table 2.

3.6. Optical microscopy

The surface morphology of the PA, POA, POT and PA-co-POA-co-POT thin films
was studied by optical microscopy and the photographs are shown in Fig. 7. All
thin film surfaces of PA, POA, POT and PA-co-POA-co-POT coatings are uniformly
covered. PA coatings have smooth surface morphology. In case of POA and PA-co-
POA-co-POT coatings clearly indicate smooth surface morphology characterized
by the presence of small grains, while in POT coating clearly indicates as smooth
surface morphology and it is characterized by presence of empty islands.

4. CONCLUSIONS
The following conclusions can be drawn from the present study:
1. The cyclic voltammetric investigation clearly indicated the formation of elec-
troactive PA, POA, POT and PA-co-POA-co-POT films prepared using various
monomer feed ratio in sulphuric acid as electrolyte.
2. It is observed that the anodic current densities of polymerization of PA, POA,
POT and PA-co-POA-co-POT films are greatly influenced by the concentration
of monomer in the bath.
3. The optical absorption spectroscopy results also show that UV-Visible spectra
for copolymer lies in between individual homopolymers. However, the optical
absorption varies with the changing the concentration of monomer.
4. In general, the electrical conductivity depends on monomers and its concentra-
tion.
5. The formation of copolymer has been confirmed by DSC studies.
6. Thermogravimetric analysis suggests that stability of copolymer lie in between
their individual homopolymers.
7. All thin film surfaces of PA, POA, POT and PA-co-POA-co-POT coatings are
uniformly covered.

REFERENCES
1. T. A. Skotheim, Handbook of Conducting Polymers. Marcel Dekker, New York, NY (1986).
2. K. G. Neoh, H. W. Teo, E. T. Kang and K. L. Tan, Langmuir 14, 2820 (1998).
3. H. Okamoto, M. Okaomoto and T. Kotaka, Polymer 39, 4359 (1998).
4. M. Rethi, S. Ponrathnam and C. R. Rajan, Macromol. Rapid Commun. 19, 119 (1998).
 Synthesis and characterization of the conducting copolymer PA-co-POA-co-POT 349

5. T. P. Mcandrew, Trends Polym. Sci. 5, 7 (1997).

6. D. E. Stilwell and S. M. Park, J. Electrochem. Soc. 135, 2254 (1988).
7. D. Kmar, Eur. Polym. J. 35, 1919 (1999).
8. D. Macinnes and B. L. Funt, Synth. Met. 25, 235 (1988).
9. M. Leclerc, J. Guay and L. H. Dao, Macromolecules 22, 649 (1989).
10. Y. Cao and P. Smith, Polymer 34, 3139 (1993).
11. F. Lux, Polymer 35, 2915 (1994).
12. J. Lei, Z. Cai and R. C. Martin, Synth. Met. 46, 53 (1992).
13. E. L. Kupila and J. Kankare, Synth. Met. 55, 1402 (1993).
14. R. Stankovic, O. Pavlovic, M. Vojnovic and S. Jovanovic, Eur. Polym. J. 30, 385 (1994).
15. Y. Wei, W. W. Focke, G. E. Wnek, A. Ray and A. G. MacDiarmid, J. Phys. Chem. 93, 495
(1989).
16. Y. Wei, R. Hariharan and S. A. Patel, Macromolecules 23, 764 (1990).
17. J. Y. Bergeron and L. H. Dao, Polym. Commun. 32, 403 (1991).
18. S. K. Dhawan and D. C. Trivedi, Synth. Met. 60, 63 (1993).
19. J. J. Langer, Synth. Met. 35, 301 (1990).
20. T. L. Porter, G. Caple and C. Y. Lee, Synth. Met. 46, 105 (1992).
21. M. Sato, S. Yamanaka, J. Nakaya and K. Hyodo, Electrochim. Acta 39, 2159 (1994).
22. D. D. Borole, U. R. Kapadi, P. P. Kumbhar and D. G. Hundiwale, Mater. Lett. 56, 685 (2002).
23. D. D. Borole, U. R. Kapadi, P. P. Kumbhar and D. G. Hundiwale, Mater. Lett. 57, 844 (2002).
24. D. D. Borole, U. R. Kapadi, P. P. Kumbhar and D. G. Hundiwale, Polym. Plastic Technol. Eng.
42, 415 (2003).
25. D. D. Borole, U. R. Kapadi, P. P. Kumbhar and D. G. Hundiwale, Mater. Lett. 57, 3629 (2003).
26. R. B. Dabke, A. Dhanabalan, S. Major, S. S. Talwar, R. Lal and A. Q. Contractor, Thin Solid
Films 335, 203 (1998).
27. J. C. Lacroix, P. Garcia, J. P. Audiere, R. Clement and O. Kahn, Synth. Met. 44, 117 (1991).
28. W. S. Huang, B. D. Humphrey and A. G. MacDiarmid, J. Chem. Soc. Faraday Trans. 82, 2385
(1986).
29. S. K. Dhawan and D. C. Trivedi, J. Appl. Electrochem. 22, 563 (1992).