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ISSN 18112382, Polymer Science, Ser. C, 2014, Vol. 56, No. 1, pp. 144153. Pleiades Publishing, Ltd., 2014.
Original Russian Text Zh.A. Boeva, V.G. Sergeyev, 2014, published in Vysokomolekulyarnye Soedineniya, Ser. C, 2014, Vol. 56, No. 1, pp. 153164.

Polyaniline: Synthesis, Properties, and Application

Zh. A. Boeva* and V. G. Sergeyev
Faculty of Chemistry, Moscow State University, Moscow, 119991 Russia
*email: [email protected]
Received September 23, 2013

AbstractThe methods of synthesis and the properties of polyanilinea representative of the family of con
ducting polymersare reviewed briefly. It is shown that variation in the conditions of aniline polymerization
makes it possible to synthesize polymer materials with the desired structures and properties and, thus, to pro
vide for the use of polyaniline in various fields of science and engineering. Special attention is given to the
matrix synthesis of polyaniline as the main approach to obtain electroactive and conducting composite mate
rials. The use of polyaniline and the related composite materials in polymer electronics is analyzed briefly.
DOI: 10.1134/S1811238214010032

INTRODUCTION ductors, because they feature conductivity, low density,

Conducting polymers belong to a peculiar family of and easy processability. Polyaniline (PANI)a repre
compounds composed of monomer units with conju sentatives from the family of conducting polymersis
gated chemical bonds that, under certain conditions distinguished by easy synthesis and high environmental
(doping), ensure the electron conductivity of the poly stability.
mer. From the commercial viewpoint, these polymers
show promise for the production of materials for vari Polyaniline consists of monomer units built from
ous applications; they can replace metals and semicon reduced (y) and oxidized (1y) blocks:

H H
* N N N N * ,
y 1y
x

where 0 y 1.
The redox state of the polymer is determined by the value of y, which may vary continuously from zero to unity.
At y = 0.5, polyaniline occurs in the form of emeraldine; = 0 corresponds to the fully oxidized form, pernigra
niline, while = 1 corresponds to the fully reduced form, leucoemeraldine [1]. Pernigraniline and emeraldine may
occur as either salts or bases [2, 3]:
A A A A
+4HA
* N N N N * N N N N
4HA H H H H n
n
Blue pernigraniline base Blue pernigraniline salt
2e +2e 2e +2e
2HA +2HA 2HA +2HA

A A
H H +2HA H H
* N N N N * * N N N N *
2HA
n n
Violet emeraldine base Green emeraldine salt
+2e 2e
2e +2HA 2HA +2e
2HA +2HA

H H H H
* N N N N *
n
Colorless leucoemeraldine

144
 POLYANILINE: SYNTHESIS, PROPERTIES, AND APPLICATION 145

The forms of PANI have different colors, stabili tron conductivity of the polymer. The electron con
ties, and conductivities. Leucoemeraldine is a color ductivity of polyaniline in the form of emeraldine
less substance characterized by an absorption band at depends on its protonation and increases by ten orders
343 nm (in Nmethylpyrrolidone) [1]. Since this poly of magnitude as the degree of protonation is increased
mer contains only benzene and amino groups, leucoe from 0 to 20% [6]. Note that this behavior is typical for
meraldine slowly oxidizes in air and is not electrically polyaniline solely. The delocalization of PANI cation
conducting. Leucoemeraldine may be oxidized in an radicals may occur not only via the intramolecular
acidic medium to the conducting emeraldine salt mechanism but also via the intermolecular mecha
(p doping). Pernigraniline is composed of alternating nism. In this case, chains of the conducting polymer
aminobenzene and quinonediimine fragments. should be oriented in one direction so that the transfer
Because the quinonediimine group is unstable in the of electrons from one polymer chain to another is
presence of nucleophiles, specifically water, pernigra ensured [7]. This process occurs as a rule via van der
niline and its salts readily decompose in air. The emer Waals interactions between benzene and quinoid rings
aldine salt of PANI is formed during protonation of of PANI ( stacking) [8, 9]. The electron conductivity
the emeraldine base with organic and inorganic acids. of such a structured polyaniline may be as high as
As a rule, this process is referred to as doping. When (1.11.2) 103 S/cm [9].
PANI in the form of the emeraldine base is treated
with acids, protons primarily interact with the imine
atoms of nitrogen; as a result, polycations appear [4]. USE OF POLYANILINE IN ORGANIC
Because positive charges localized on neighboring ELECTRONICS
nitrogen atoms increase the total energy of the poly
mer system, electron density tends to undergo redistri The use of polyaniline in various areas of electron
bution; as a consequence, unpairing of the lone ics and engineering is limited because its conductivity
electron pair of nitrogen atoms occurs without any is unstable at neutral pH and temperatures above
change in the amount of electrons in the system [5]. In 150 owing to dedoping of polymer chains. However,
a chain, cation radicals appear; they are delocalized in closed systems PANI may be used as an electrode
over a certain conjugation length and provide the elec material.

Supramolecular structure of PANI:

Globules, nanotubes, fibrils

Properties

Electron Semiconducting Electrical activity

conductivity properties

Use

Transparent Solar batteries

antistatic Organic field transistors
coatings

Flexible electrodes
Conducting fibers Electrochromic glass

Electromagnetic Anticorrosive coatings

screens
Catalysts
Actuators
Supercapacitors
Storage devices

POLYMER SCIENCE Series C Vol. 56 No. 1 2014

146 BOEVA, SERGEYEV

For example, fibrillar PANI was used to design a sulfonic acid) [22] surpass the known polymer analogs
rechargeable battery [10] with a specific energy of in terms of performance characteristics and stability
280 (W h)/kg. On the basis of the composite material, the because of the high chemical stability of the material.
secondary current source ZnPANIgraphite with a Polyaniline doped with camphorsulfonic acid has
specific energy of 160 (W h)/kg was developed [11]. In found use as an element of an electrically programma
terms of specific energy, these current sources surpass ble permanent storage device [27] whose performance
commercial analogs. However, their main drawback is mechanism is similar to that of a fuse.
low stability during recharging; that is, on average, batter Polyaniline deposited on tin fluoroxide is used
ies lose 0.15% specific energy per cycle owing to degrada instead of platinum as an internal electrode in photo
tion of polyaniline and passivation of zinc. The advan electric cells (solar cells) [28, 29]. The replacement of
tages of PANIbased batteries are their reprocessability metal with the conducting polymer results in a gain in
and relative environmental compatibility during utiliza the photoelectric conversion coefficient of a photo
tion in comparison to those of traditional current electric cell to 7% (6% in the case of platinum) owing
sources. to a more effective reduction of iodine on the elec
Composite materials based on PANI are used more trode surface [30]. The employment of nanostructured
frequently to manufacture supercapacitors, owing to PANI in these systems makes it possible to increase
the high specific capacitance of the material, 450 the efficiency of photoelectric cells to 11% [31], and
900 F/g [1214], and the stability during recharging the manufacture of electrodes based on graphite and
(up to 1000 cycles). Graphene or carbon nanotubes, PANI makes it possible to reduce the cost of solar bat
which increase the capacitance characteristics of the teries without any decrease in their performance [32].
material, are used as the second component of these
composite materials [15, 16]. Note that electrodes When PANI is used as a component of an elec
composed of PANI electrochemically deposited on tronic device, special conditions of synthesis or modi
steel, as well as composite materials based on manga fication of this conducting polymer are used to impart
nese oxide, likewise possess high capacitance and can the desired properties to it.
endure a large number of recharging cycles [17, 18].
Another application area of PANI in organic elec SYNTHESIS OF POLYANILINE
tronics includes the design of photochromic devices WITH THE DESIRED SUPRAMOLECULAR
with modulated conductivity [19], organic field tran STRUCTURE AND PROPERTIES
sistors [20, 21], and polymer light diodes [2224]. The
use of composite materials based on conducting poly Polyaniline is, as a rule, prepared via the chemical
mers for the manufacture of transistors is often limited or electrochemical polymerization of aniline in the
by the low mobility of charge carriers and the grain presence of dopants. Depending on the synthesis pro
boundary effect. Nevertheless, the available tech cedure; the temperature and time regimes; the types of
niques make it possible to prepare materials with a oxidant, dopant, and solvent; the voltage applied on
high mobility of charge carriers (up to 3 cm2/(V s)) the electrode; etc., polyaniline featuring different
and a high ratio of switchon/switchoff currents propertiesnamely, the structure, morphology, and
(above 104) [21, 25]. A technique of vacuum deposi redox statemay be prepared.
tion of oligomeric PANI and fullerenes to create
organic field transistors was developed. For this pur
Electrochemical Polymerization
pose, an insulator layer composed of oligomeric PANI
over which a fullerene layer functions as a semicon It is commonly believed that the electrochemical
ductor is evaporated on an aluminum gate electrode. synthesis gives rise to the purest product, which is free
Aluminum evaporated over the fullerene layer serves as of admixtures and does not need special procedures
a drain and a source of such transistor configuration. for the purification of polyaniline from the solvent and
The asprepared organic field transistors feature unreacted monomer and initiator molecules. The
highly reproducible characteristics; however, the ratio polymerization of aniline occurs on an electrode made
of switchon/switchoff currents of the device is of inert conducting material. The electrochemical
~500 [26]. polymerization of aniline is most often conducted in
The efficiency of polymer lightemitting diodes con aqueous solutions containing background electrolytes
taining PANI as conductive or emission layers depends and an acid [33].
on the method of preparing the conducting polymer. For In the case of the electrochemical synthesis of
example, lightemitting diodes based on PANI stabi polyaniline, potentiostatic, galvanostatic, and poten
lized in organic solvents owing to the use of a low tiodynamic methods are applied [34]. In the first case,
molecularmass dopant possess relatively low efficiency the potential has a fixed value on the order of 0.7
in comparison to that of organic semiconductors based 1.2 V (against a saturated calomel electrode) [35]; in
on poly(3,4ethylenedioxythiophene) [24]. the last case, the potential varies in a cyclic mode from
In contrast, lightemitting diodes designed with the 0.2 to 0.71.2 V (against a saturated calomel elec
use of the graft copolymer PANIpoly(4styrene trode). In the galvanostatic regime of aniline polymer

POLYMER SCIENCE Series C Vol. 56 No. 1 2014

 POLYANILINE: SYNTHESIS, PROPERTIES, AND APPLICATION 147

Aniline
pH < 3
Hard template Monomer adsorption
on hard template

Oxidant

Hard template Oxidation of monomer

with adsorbed monomer polymerization

PANI adsorbed on template

final product

Anilinium cation, Partially negative charge,

Oxidized anilinium cationreactive species,

polyaniline.

Scheme 1.

ization, the fixed value of current density does not the presence of this oxidant, polyaniline is formed
exceed 10 mA/cm2 [36]. with the highest yield (90%); it features high conduc
The electrochemical polymerization of aniline, tivity (~1.2 S/cm) and intrinsic viscosity in Nmeth
whose most important aspects are considered in detail ylpyrrolidone (1.17 dL/g).
in reviews [37, 38], makes it possible to synthesize In order to prepare polyaniline in the form of the
polyaniline with different properties and morpholo emeraldine salt, polymerization is conducted in an
gies. PANIbased composite materials prepared elec acidic medium (1 < pH 3) with the use of various
trochemically have found use in organic field transis acids or buffer solutions.
tors [39, 40] and rechargeable batteries [10, 11]. The chemical synthesis of polyaniline is the simplest
way to prepare conducting polymers with various physic
Chemical Polymerization ochemical properties and supermolecular structures.
Note that the conducting polymer may be applied on any
The chemical polymerization of aniline is con substrate (matrix). This circumstance gives chemical
ducted with the use of various oxidants, among which synthesis an indisputable advantage over electrochemical
ammonium persulfate is most commonly used [41]. In synthesis, in which a substrate must be a conductor.

POLYMER SCIENCE Series C Vol. 56 No. 1 2014

148 BOEVA, SERGEYEV

Aniline
pH < 3
Sorption or solubilization of the
Soft template monomer by surfactant micelles
surfactant micelles Oxidant

Growth of PANI chains

Growth of PANI chains into the Entanglement near polar groups,
hydrophobic cores of the micelles of micelles by PANI chains inversion of micelles

Anilinium cation, Partially negative charge

or partially negative group
Oxidized anilinium cationreactive species

Polyaniline

Scheme 2.

Matrix (template) polymerization. Matrix (tem not only the polymer occurring in the common phase
plate) polymerization [42] implies the chemical trans with the monomer but also a solid substrate exhibiting
formation of monomers or oligomers into macromole template effects. Therefore, templates are divided into
cules in accordance with the structuralchemical infor two kinds: hard and soft. Hard templates are inorganic
mation derived from the sequence of macromolecular substrates than can interact with the monomer and
units of the template present in the reaction system. change both the parameters of the polymerization pro
During the template polyreaction, organization of the cess and the morphology of the resulting polymer. Tem
monomer with the template occurs via various interac plate polymerization occurs at the interface between the
tions (hydrogen bonds, Coulomb interactions, covalent hard template and the monomer and initiator solution.
bonds, hydrophobic interactions); as a result, template Soft templates imply surfactants and polymers [44].
effects appear. Thus, template polymerization makes it
possible to control the composition and arrangement of Hard templates. The general scheme of aniline poly
chemical units, the degree of polymerization, and the merization in the presence of a hard template (carbon
isomeric composition of a daughter macromolecule and nanotubes, graphite, inorganic oxides) includes adsorp
to change the kinetics of the polyreaction [43]. In the tion of the monomer or aniline cation radical on the
modern literature devoted to PANI, template implies matrix surface and polymerization (see Scheme 1).

POLYMER SCIENCE Series C Vol. 56 No. 1 2014

 POLYANILINE: SYNTHESIS, PROPERTIES, AND APPLICATION 149

NH2 NH2
+.
Cl NH3 NH2
Oxidant
NH2
H
N
Oxidant
+
polyelectrolyte
template H H
N N

H H
N N
N N
H H
SO3 O3S
SO3 SO3
O3S O3S
O3S
SO3
SO3
SO3
O3S O3S
SO3
SO3
O3S SO3

Scheme 3.

The use of inorganic materials as templates makes around micelles of the surfactant once its first or sec
it possible to obtain composites in situ that combine ond critical micelle concentration is attained [43].
such properties of PANI as electron conductivity and The polymerization of aniline with the participation of
reactivity with respect to acidbase and redox interac a surfactant as a soft template, which includes the
tions with mechanical characteristics of the template interaction of an aniline monomer or a cation radical
[45, 46]. This approach is the most suitable when with surfactant micelles and the formation of PANI,
PANI is used in the form of electrochromic glass [47], may be schematically presented as follows (see
supercapacitors and secondary cells [48], sensors [49], Scheme 2).
and anticorrosive coatings [50]. Moreover, aniline may be solubilized by micelles
The employment of anodized aluminum oxide or [58]. In both cases, the structure of the micelles deter
vanadium oxide [5152] as a hard template offers a mines the morphology of the resulting conducting
way to obtain composite materials with the fibrillar polymer. For example, the use of cetyltrimethylam
morphology of PANI and to use these materials in monium bromide in the polymerization of aniline ini
field emitters [51, 52] and lithiumion batteries [54]. tiated by ammonium persulfate leads to the formation
of PANI nanofibils with diameters of 6090 nm and
If the chemical synthesis of polyaniline is per
lengths of ~1 m [59]. Along with cationic surfactants,
formed in the presence of amorphous carbon, the
compounds able to function as both dopants and
resulting composite material may be used as an indica
structuring agents are used in the chemical polymer
tor electrode suitable for determining various organic
ization of aniline. For example, PANI nanotubes and
compounds [49].
nanofibrils with controlled diameters may be prepared
With the use of hard template, such as carbon nan with the use of naphthalenesulfonic acid [60].
otubes [55] and graphene and their derivatives formed For the synthesis of polyaniline soluble in organic
as a result of oxidation and chemical modification [12, solvents and/or aqueous media, it is possible to use 4
13, 15, 16, 56] in the chemical polymerization of dodecylbenzenesulfonic acid [6163]which serves
aniline, composite materials with high capacitance simultaneously as a dopant and a counterion to pro
characteristics were produced [12, 13] and sensors vide for solubility of PANIas well as sodium dodecyl
were manufactured on their basis [57]. sulfate [6466], bis(ethylhexyl) sulfosuccinate, tet
Soft templates. Polyanilinesurfactant polymer col radecyltrimethylammonium bromide [67], and dode
loid complexes. In the presence of a soft template cyltrimethylammonium bromide [66] in combination
(a surfactant), the polymerization of aniline occurs with hydrochloric acid, sulfuric acid, ptoluene

POLYMER SCIENCE Series C Vol. 56 No. 1 2014

150 BOEVA, SERGEYEV

sulfonic acid, camphorsulfonic acid [68], or sulfosali When template polymerization is performed under
cylic acid [69] as dopants. In the case of 4dodecyl homogeneous conditions, the sizes of particles of the
benzenesulfonic acid, a product soluble in both water PANIPSS complex depend on the molecular mass of
[61] and chloroform [70] was isolated. The composite the used polyanion and the selected concentration
materials based on polyaniline and surfactants have regime. For example, in the presence of PSSNa with
been used in solar cells [71, 72]. Mw > 6800, the average diameter of particles of the inter
Polymerization of aniline in the presence of poly polymer complex is 23 nm at [aniline] = [PSSNa] <
meric templates: Macromolecular templates. PANI 4.5 102 mol/L. If the concentration of the compo
with the desired morphology is synthesized via tem nents is above this value, fibrillar aggregates with
plate polymerization in the presence of macromolec diameters of 7090 nm and lengths from 200 nm to
ular templatespolyanions capable of undergoing 1 m form. As the molecular mass of PSSNa is
electrostatic interactions with PANIand watersol decreased, polymerization yields particles with diam
uble polymers that can form hydrogen bonds [73, 74]. eters of 100130 nm that likewise consist of aggre
The polyelectrolyte template (a polyacid) serves as a gated small particles [90].
highmolecularmass counterion that not only stabi When the concentration of aniline is less than 4.5
lizes polyaniline particles in a solution but also dopes 10 2 mol/L, but polymers capable of hydrogen bond
polyaniline, thereby providing for the formation of ing are present, the resulting PANIs have different
the watersoluble conducting product [75] (see morphologies that depend on the types of polymer and
Scheme 3). dopant. For example, the template polymerization of
When this template is used as a dopant, the thermal aniline performed at the presence of polyvinylpyrroli
stability of conductivity improves because the high done and hydrochloric acid gives rise to a complex of
molecularmass dopant, as opposed to the low the granular morphology composed of particles with
molecularmass dopant, is removed at elevated tem diameters of 50150 nm [91]. If the polymerization of
peratures only during decomposition [76]. If water aniline is conducted at the presence of poly(vinyl alco
soluble polymers are used as templates, PANI is syn hol) and hydrochloric acid, extended structures con
thesized in the presence of lowmolecularmass acids sisting of aggregated PANI particles with sizes of
in order to obtain stable conducting dispersions. ~200300 nm arise. If hydrochloric acid is replaced
Ammonium persulfate is usually used as an oxi with ptoluenesulfonic acid, spherical particles of the
dizer of aniline in the template polymerization [74]. In interpolymer complex with an average diameter of
addition, in the polymerization of aniline, it is possible 300 nm form, while after addition of ()camphor10
to use hydrogen peroxide, whose oxidation is cata sulfonic acid, a PANIPVA complex of a needle
lyzed by hemoglobin [77] or peroxidases [73, 78, 79], shaped structure forms [79].
as well as oxygen dissolved in the reaction mixture. In Depending on the polyelectrolytetemplateto
the latter case, the oxidation of the substrate is cata aniline ratio in the reaction medium, stoichiometric
lyzed by laccases [80]. Polymerization is performed as PANIpolyelectrolyte complexes, which are isolated
a rule in the presence of strong polyacids, such as as an individual phase [84, 92], or nonstoichiometric
poly(4styrenesulfonic acid) and poly(2acrylamido watersoluble complexes, in which polyaniline occurs
2methyl1propanesulfonic acid) [8183], as well as in the conducting state, form [93]. At [aniline] : [PSS
weak polyacids, such as poly(vinylphosphonic acid) Na] = 4 : 1, the formed complex is isolated as an indi
[84] and poly(acrylic acid) [85]. Along with polyelec vidual phase in the form of flakes. In accordance with
trolytes, polymers able to form hydrogen bonds with the elementalanalysis data, N : S = 2.3 in this prod
polyaniline, poly(vinyl alcohol) [86], polyvinylpyri uct; that is, charges of the template are fully neutral
dine, polyvinylpyrrolidone [87], polyacrylamide [88], ized by protonated quinonediimine nitrogen atoms of
hydroxypropyl cellulose [74], etc., in combination PANI [92].
with dopantslowmolecularmass acidsare used The conductivity of the complex formed during
as templates. template synthesis is practically independent of the
Template polymerization is conducted both under nature and strength of the polyacid. In most cases, this
homogeneous conditions and at the interface. During parameter is ~103101 S/cm.
the interfacial polymerization, aniline is dissolved in The composite materials synthesized with the use
the organic phase, while a polysalt (e.g., sodium of polymer soft templates may be modified in an
poly(4styrenesulfonate) (PSSNa)) and ammonium appropriate manner in order to solve practical prob
persulfate are dissolved in the aqueous phase. Polya lems. For example, the precipitation of platinum and
niline formed at the interface is complexed with poly ruthenium particles on a net composed of PANIPSS
aniline PSS and gradually diffuses into the aqueous fibrils makes it possible to prepare a material with elec
phase. Depending on the [aniline]to[polysalt] ratio, trocatalytic properties useful for the oxidation of
polymerization yields spherical particles of the methanol [94].
PANIpolyanion complex ([aniline] : [polysalt] < 1) Solid polymer templates. Polymer films and mem
or extended structures composed of aggregated parti branesfor example, polyethyleneterephthalate,
cles of the complex ([aniline] : [polysalt] > 1) [89]. polyethylene, polypropylene, polystyrene, or polya

POLYMER SCIENCE Series C Vol. 56 No. 1 2014

 POLYANILINE: SYNTHESIS, PROPERTIES, AND APPLICATION 151

mide6are used as templates as well [9597]. Note tion of synthesis procedures is largely determined by
that the majority of these composite materials are syn the tasks and application of polyaniline in a given area
thesized on the basis of amorphous or partially crystal of organic electronics. Owing to a wide spectrum of
line polymers [98]. This circumstance is due to the fact properties, polyaniline is used as a material for sensors
that the synthesis of polymer composites via in situ and actuators, fuel cells, solar batteries, lithiumion
polymerization involves swelling of a polymer matrix batteries, supercapacitors, fieldeffect transistors, and
in a monomer [99]. Highly crystalline polymers can many other purposes. With the use of the methods of
not absorb considerable amounts of organic com template synthesis of polyaniline, various composite
pounds, because sorption predominantly occurs materials combining mechanical and physicochemi
toward amorphous regions; as a result, the use of these cal properties of the template and PANI (pH sensitiv
polymers is confined. Composite materials based on ity, electron conductivity, various kinds of chromism,
PANI and crystalline polymers are usually synthesized and the ability to absorb electromagnetic radiation in
with the use of membranes, while the polymerization a wide wavelength range) may be synthesized.
of aniline is performed in pores [98]. Note that the
morphology of PANI synthesized in polymer tem
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