Reactive & Functional Polymers 47 (2001) 125139

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Preparation, properties and applications of polypyrroles

Lin-Xia Wang a , Xin-Gui Li a , *, Yu-Liang Yang b
a
Department of Polymer Materials Science Engineering, College of Materials Science and Engineering, Tongji University,
1239 Siping Road, Shanghai 200092, People s Republic of China
b
Department of Macromolecular Science, Key Laboratory of Molecular Engineering of Polymers, Fudan University, Shanghai 200433,
People s Republic of China

Received 21 August 2000; received in revised form 30 November 2000; accepted 10 December 2000

Abstract

Polypyrrole (PPY) is one of the most promising materials for multifunctionalized applications. Preparation, characteriza-
tion, properties and applications of PPYs are reviewed in this paper. In addition, the PPY composites are described in detail
according to the synthetic methods and their applications. At the same time, effects of various parameters such as doping
anions, additives, and oxidant, on the PPY properties are also concerned. The PPY films and membranes used for ion
exchange, pervaporation, and gas separation are mentioned. In this review, ion exchange membranes are highlighted.
Moreover, the further investigation of PPY composite membranes for oxygen enrichment is predicted. A total of 117
references are cited. 2001 Elsevier Science B.V. All rights reserved.

Keywords: Polypyrrole; Oxidatively chemical polymerization; Electrochemical polymerization; Conductive polymer; Gas separation
membrane; Oxygen enriching membrane

1. Introduction capacitor [8,9], electrochromic windows and

In recent years, intrinsic conducting polymers
with conjugated double bonds have been at-
tracted much attention as advanced materials.
Among those conducting polymers, polypyrrole
(PPY) is especially promising for commercial
applications because of its good environmental
stability, facile synthesis, and higher conduc-
tivity than many other conducting polymers.
PPY can often be used as biosensors [1,2], gas
sensors [3,4], wires [5], microactuators [6],
antielectrostatic coatings [7], solid electrolytic
*Corresponding author.
E-mail address: lixingui@citiz.net (X.-G. Li).
displays, and packaging, polymeric batteries,
electronic devices and functional membranes,
etc. [1012]. PPY coatings have an excellent
thermal stability and are good candidate for use
in carbon composites [13]. Furthermore, the
electrochemical process parameters affecting the
properties of the PPY coatings are also investi-
gated [14]. PPY can be easily prepared by either
an oxidatively chemical or electrochemical
polymerization of pyrrole. However synthetical-
ly conductive PPY is insoluble and infusible,
which restricts its processing and applications in
other fields. The problem has been extensively
investigated and new application fields have
also been explored in the past several years. For

1381-5148 / 01 / $ see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S1381-5148( 00 )00079-1
126 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139
example, PPY-based polymers can be used to
load and release drugs and biomolecules [15].
PPY-based polymer blends can protect the
corrosion of metals [16]. Because of the strong
adhesion of PPY to iron or steel treated with
nitric acid, PPY polymers can be used as good
adhesives [17]. In a recent report [18], PPY-
modified tips for functional group recognition
are applied in scanning tunneling microscopy.
However, there are no systematical publications
on PPY as far as we know. The aim of this
review not only introduces what have been
done, but also prospects the new development
of PPYs.
2. Syntheses, properties and applications of
polypyrrole
In the past decade, many reports about PPY
have been published [14]. As a conducting
polymer, the conductivity and other electrical
properties were attracted most interests. At the
same time, the relationships between the prop-
erties and the polymerization conditions (i.e.
protein-binding capacity, pH value [19]) were
also studied. Additionally, thermal stability and
mechanical properties of PPY have been given
much concern. In 1994, Biswas and Roy [20]
studied the thermal, stable, morphological, and
conductive characteristics of the PPY prepared
in aqueous medium. The results showed that the
PPY exhibits a spongy texture, the initial de-
composition temperature at 1802378C, glass-
transition temperature at 1601708C, and con-
ductivity below 3 S cm 21 . Furthermore, all
results depended on the FeCl 3 / pyrrole feed
composition. In a recent report, PPY films with
a thickness of 34 mm have been obtained by
chemical oxidation of pyrrole at the interface of
chloroform and water with an oxidant
(NH 4 ) 2 S 2 O 8 [21]. The films prepared were
compact and could be removed with a solid
plate. The quality and compositions of these
films varied with the molar ratios of the mono-
mer to oxidant of the reaction systems. Structur-
al studies of PPYs through an ab-initio evalua-
tion of bonding [22] and a Monte Carlo growth
approach to the branch formation have been
reported [23]. The energy differences of differ-
ent types of structures suggest that a great deal
of branching is probable. The approximate
probability function generated in this manner is
used in a statistical mechanical approach to
estimate the extent of bonding involving b
carbons as well as branching in PPYs [22]. The
statistical analysis of the growth process shows
that the branching occurs even at very short
chains. The extent of the branching does not
depend on the chain length but it is a slowly
varying function of the temperature [23]. The
surface morphology of PPY film has also been
studied through atomic force microscopy
(AFM) [24,25]. The surface morphology of
electrogenerated PPY films of various thick-
nesses and with different dopant anions such as
chloride, sulfate, perchlorate and dodecylsulfate
was discussed, as well as films both as-prepared
and after potential dynamic cycling in various
supporting electrolytes. The AFM data show
that the characterization of surface roughness
with one common parameter (RMS, roughness
factor or R a ) is not justified. In general, two
types of surface globules with different heights
are present on the film surface, independent of
film thickness and dopant nature [24]. Inter-
action energy anisotropy of the pyrrole dimer
has been discussed using ab-initio theoretical
method [26]. The influence of selected geometry
variations on the interaction energy components
was investigated. The results show that any
structure variation connected with the external
attraction energy is more than compensated for
by the repulsion energy.
In the series of conducting polymers, consid-
erable attention has been drawn to the poly-
pyrrole family prepared by electrochemical oxi-
dation such as PPY, poly (N-methyl pyrrole) and
their copolymers for their application in solid
state devices. Several investigations [27,28]
have been performed to observe the effect of
various parameters such as solvent, electrolyte
 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139 127

choice of monomer, polymerizing temperature,
annealing temperature, etc., on the mechanical
strength, stability, and conductivity of the films
prepared. Surface morphology studies suggest
3D-type growth and it is found that there is no
change in conductivity and good handling
strength after a certain annealing time [28]. A
one-step synthesis of adherent PPY films on
zinc electrodes is achieved by electrooxidation
of pyrrole in aqueous oxalate solution [29].
In chemical polymerization, the oxidants used
generally are as follows: (NH 4 ) 2 S 2 O 8 , H 2 O 2
and many kinds of salts containing transition
31 21 61
metal ions, for example, Fe , Cu , Cr ,
41 31 71
Ce , Ru and Mn . When only (NH 4 ) 2 S 2 O 8
is used as the oxidant [30], the addition of
anionic surfactants caused moderate increases in
the yields and great decreases in the conduc-
tivities (see Table 1). In addition, it took a very
long time to filter the resultant polymers for the
formation of fine colloidal particles. These
phenomena were caused by interaction between
(NH 4 ) 2 S 2 O 8 and the surfactant PPY doped with
sulfonate, since the dissociation of the anionic
surfactant is prevented due to the presence of
the highly concentrated and strongly electrolytic
oxidant, the undissociated molecules of the
surfactant appear to be thickly absorbed on the
PPY surface in the polymerization process so
that it may act as the steric stabilizer. The
presence of the steric stabilizer led to the
increase in yield, and the decrease in particle
size and conductivity of PPY, as Aldissi et al.
mentioned [31]. The relationship between time
and yield was also discussed as well as the
effect of the temperature [30]. The results
showed that the addition of the surfactant
accelerated the polymerization reaction and
PPY also showed a small dependence of room-
temperature conductivity on the polymerization
temperature.
PPY prepared by chemical polymerization
using aqueous solution containing Fe 2 (SO 4 ) 3
and anionic surfactant was also studied [30].
The combinations of Fe 2 (SO 4 ) 3 as an oxidant
and anionic surfactants, such as sodium
dodecylbenzenesulfonate (NaDBS), sodium
alkylnaphthalenesulfonate (NaANS) and sodium
alkylsulfonate (NaAS) brought about enhanced
conductivity as well as increased yield of re-
sultant PPY (see Table 1). The phenomena
resulted from the large-sized surfactant anions
being predominantly incorporated into the PPY
backbone. Although the concentration of sulfate
is more than an order of magnitude higher than
that of sulfonate in the polymerization solution,
the doping ratio of sulfate to whole dopant is
reversed. This result showed that the sulfate is
more difficult to incorporate into the PPY
backbone than sulfonate. This can be accounted

Table 1
Conductivity and yield of polypyrrole (PPY) prepared at various conditions a
Oxidant Additive Conductivity Yield Refs.
(mol dm 23 ) (mol dm 23 )b (S cm 21 ) (g)
(NH 4 ) 2 S 2 O 8 (0.1) 4.42 1.36 [30]
(NH 4 ) 2 S 2 O 8 (0.1) NaDBS (0.0225) 0.57 2.01 [30]
(NH 4 ) 2 S 2 O 8 (0.1) NaANS (0.024) 0.221 1.91 [30]
Fe 2 (SO 4 ) 3 (0.1) NaDBS (0.0225) 26.1 2.44 [30]
Fe 2 (SO 4 ) 3 (0.1) NaANS (0.024) 15.7 2.65 [30]
Fe 2 (SO 4 ) 3 (0.1) NaAS (0.022) 40.7 2.24 [30]
Fe 2 (SO 4 ) 3 (0.1) NaANS (0.04)
p-Nitrophenol (0.0375) 25.6 2.79 [32]
Fe 2 (SO 4 ) 3 (0.1) NaANS (0.04)
m-Nitrophenol (0.0375) 23.9 2.73 [32]
Fe 2 (SO 4 ) 3 (0.1) NaANS (0.04)
p-Cyanophenol (0.0375) 22.2 2.86 [32]
a 23 3
Polymerization time 60 min, temperature 258C, pyrrole monomer concentration 0.375 mol dm , solvent 200 dm of deionized water.
b
NaDBS, sodium dodecylbenzene sulfonate; NaANS, sodium alkylnaphthalene sulfonate; NaAS, sodium alkylsulfonate.
128 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139
for as follows: (1) in order for each divalent
sulfate to be incorporated into PPY as the
dopant, two close cation sites have to be
prepared in the intrachains or interchains of the
PPY backbone. (2) the incorporation of divalent
and the small-sized sulfate probably produce a
distorted PPY backbone. The latter can also
explain why PPY doped with sulfate shows low
conductivity. Kudoh et al. [32] studied the
properties of chemically prepared PPY with an
aqueous solution containing Fe 2 (SO 4 ) 3 and a
phenol derivative. PPY obtained under the
coexistence of a sulfonic surfactant and a
phenol derivative with an electron-withdraw
group has high conductivity (see Table 1) and
superior environmental stability. These favor-
able properties seemed to be caused by the
surfactant anion being selectivity incorporated
into the PPY backbone as the dopant and the
electron-withdrawing substituent of the phenol
derivative interacting with pyrrole monomer so
as to improve the regularity of the PPY back-
bone. The oxidative matrix polymerization of
pyrrole by Fe(III), Cu(II) etc. in the presence of
polyacrylic acid (PAA) was also studied [33].
Poor processibility of PPY due to its in-
solubility and infusibility has retarded further
investigation on the structure and structure-
physical properties. To improve the processibili-
ty, many researchers have been engaged in the
development of soluble or swollen PPY and
dispersible fine-powdered PPY. At the same
time, the electric properties and / or stability of
chemically prepared PPY have also been in-
vestigated at many laboratories because the
stability of conducting polymers seems to be the
main limiting factor in their practical applica-
tions. A review has been reported the long and
fruitful history on processibility of conducting
polymers [34]. Several methods for PPY were
introduced in that review. For example, several
kinds of soluble PPY have been synthesized,
such as poly (3-alkylpyrrole) with an alkyl
group equal to or greater than a butyl group
[35]. Poly (3-alkylpyrrole) is easily soluble in
common solvents or soluble in water when the
substituents bear hydrophilic groups, such as
SO 3 H, giving conducting ranging from 10 22 to
10 1 S cm 21 depending on the bulkiness of the
alkyl group. However, the main problem of this
method is the complicated synthesis of 3-substi-
tuted pyrrole monomer. And poly (N-substituted
pyrroles) have much lower conductivity due to
greatly suppressed conjugation along the poly-
mer chains by the substituents on nitrogen
[36,37]. At the same time, they are only partly
soluble in some organic solvents even with long
alkyl groups on the nitrogen of pyrrole rings.
Although recently, a facile synthesis of 1,2,3-
trisubstituted pyrrole from the reaction of chlo-
rocarbons with 1-azabuta-1,3-dienes is reported
[38]. The structure is shown as follows:
Where Ar5phenyl, 4-toluyl, 4-Cl-phenyl, R1 5
methyl and benzyl, R2 5phenyl and methyl.
Development of classical and modern methods
of synthesis of arypyrroles is summarized by
Korostova et al. [39]. An emphasis is made on a
new simple and effective procedure for prepara-
tion of arylpyrroles by the Trofimov reaction
from alkyl aryl ketone oximes and acetylene.
Compared to the substitution method to pre-
pare soluble poly (3-substituted pyrrole) and
poly (N-substituted pyrrole), doping is simple
for PPY which may give comparable conduc-
tivity to poly (3-substituted pyrrole), but much
higher than poly (N-substituted pyrrole). For
instance, PPY doped by p-dodecylbenzene sul-
fonic acid (DBSA) with a high conductivity of 2
S cm 21 dissolves in m-cresol or chloroform in
the presence of an extra amount of DBSA [40].
The later research [41,42] by Lee et al. has been
found that there is a critical concentration range
of the oxidant at a given polymerization tem-
perature to obtain soluble PPY. When O / M,
 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139
0.2 (oxidant / monomer) and D/ M,1.0 (dopant /
monomer), PPY obtained was partially soluble
in m-cresol or NMP. Its solubility decreases as
the increase of O / M. When O / M was greater
than 0.2, the polymer obtained was totally
insoluble in any solvent [42]. Shen and Wan
studied the solubility in m-cresol, room-tem-
perature conductivity, morphology and thermal
stability of PPY synthesized by in situ doping
polymerization in the present of sulfonic acid
[43]. It was noted that good solvating ability of
sulfonic acid, such as DBSA and BNSA (5-
butylnaphthalene), renders PPY soluble, while
sulfonic acids only having large molecular size,
such as CSA (camphor sulfonic acid) and
MBSA ( p-methylbenzenes sulfonic acid or p-
toluene sulfonic acid), fail to make PPY soluble.
The nature of sulfonic acid also has an influence
on morphology of the resulting PPY. The im-
ages of PPY doped with CSA, DBSA and
MBSA have typical granular morphology but
PPY doped with NSA (b-naphthalene) is fibril-
lar. And it was also observed that PPY doped
with NSA and BNSA are thermostable based on
the measurement of weight loss. But it has been
found that doping PPY with mixed acid con-
taining CSA and DBSA could get soluble
conductive PPY with room temperature con-
ductivity (218 S cm 21 ) [44] (Table 2). Pres-
sure effects on the electrical conductivity of
doped PPY have been studied [45]. The pres-
sure dependence has characteristics of a phase
Table 2
Conductivity of polypyrrole (PPY) in situ doped with different sulfonic acids
Sulfonic acid
p-Methylbenzene sulfonic acid (MBSA)
p-Hydroxybenzene sulfonic acid (HBSA)
p-Dodecylbenzene sulfonic acid (DBSA)
b-Naphthalene sulfonic acid (NSA)
5-n-Butylnaphthalene sulfonic acid (BNSA)
5-Sulfo-isophthalic sulfonic acid (SIA)
8-Hydroxy-7-iodo-5-quinoline sulfonic acid
(QSA)
Alizarin red acid (ARA)
Camphor sulfonic acid (GSA)
a
IS, insoluble; SS, slightly soluble; S, soluble.
129
transition and is interpreted as a conformational
wit-rod transition. The pressure effect should be
considered in experiments with PPY gas sen-
sors. The pressure and temperature dependences
of the electric condition of thin films composed
of doped PPY microtubules are also measured
[46]. In addition, it was found that the con-
ductivity of PPY electrochemically polymerized
in acrylamide solution is lower that of PPY
prepared in the absence of acrylamide [47]. The
difference is attributed to the insulating effect of
acrylamide. Besides above, synthesis of nano-
structures composed of PPY can enhance in
electronic conductivity compared to analogue
polymer bulk conductivity [48].
The long-term stability of the electrical con-
ductivity of PPYs is a crucial property from an
application point of view. It has been shown
that the conductivity and the aging behavior of
PPYs can be altered by treatment with acid or
base [49]. Properties of PPYs obtained by
electrochemical polymerization were studied
[50]. With NaOH, conductivities smaller than
that of the initial sample can be obtained
whereas an H 2 SO 4 treatment leaves the con-
ductivity nearly unchanged. Both procedures
result in an increase in the long-term stability of
the conductivity at least at 808C and 1408C.
Using elemental analysis and energy dispersive
X-ray spectroscopy it was shown that the
chemical treatment has an effect on ion ex-
change properties of the polypyrrole salt film
Conductivity Solubility
(S cm 21 ) in m-cresol
16.0 IS a
11.0 SS a
2.0 Sa
18.0 S
0.5 S
3.0 SS
3.0 SS
8.0 SS
18.0 IS
130 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139
such as conductivity, weight, thickness, and
oxygen permeability closely related to the coun-
terions. It was found that exposure of the film to
0.1% NaOH, which reduced the conductivity
only slightly, improved the stability quite sig-
nificantly. The electrical properties of PPY can
be also drastically modified by a strong base or
acid, as well as upon treatment with various
anions. Zhang et al. [51] studied the surface of
pristine and surface-modified PPY films (modi-
fied with acrylic acid or sodium salt of 4-
styrenesulfonic acid). The results showed that
the density of surface grafting decreased with
ozone pretreatment. Surface grafting of the two
polymeric acids also gives rise to a self-proton-
ated surface structure. A substantial proportion
of the grafted protonic acid groups at the
surface remains free for further surface func-
tionalization. Kudoh et al. have reported that
electropolymerized PPY doped with a large-
sized anion [52], for example, alkylnaphthalene
sulfonate, has excellent thermal and moisture
stabilities. Recently, Ghosh et al. [53] have
studied the electrochemical oxidative degrada-
tion of PPY, known as overoxidation, in aque-
ous media by using Raman and FT-IR spec-
troscopies. It was noted that PPY degrades at
potentials as low as 10.5 V versus the saturated
calomel electrode, in the presence of chloride
ions. The rate of overoxidation of PPY is higher
potential and at higher pH. Furthermore, PPY
prepared with surfactants in chemical polymeri-
zation also showed high thermal and moisture
stabilities in air at 1258C, and at 858C and 85%
RH (relative humidity) [30]. The study of Shen
and Wan indicated that PPY doped by CSA or
DBSA showed similar thermal stability [44].
Both samples begin to lose weight at about
2178C, but PPYCSA decomposes more rapid-
ly. PPY doped with NSA or BNSA is more
thermostable. Weight loss of these PPY samples
begins at 3178C [44]. Thin films of a substituted
PPY synthesized via the chemical oxidation of a
chloroform solution of 5-acetamido-4,5,6,7-
tetrahydro-2H-benzol pyrrole have established
their long-term stability as floating monolayer
[54].
In practical applications, the mechanical
properties of PPY are also important. As a
result, a lot of interest has put on the studies on
the mechanical properties of PPY. In general,
PPY showed a much larger Youngs modulus
but lower tensile strength in the doped state
compared with the undoped material.
Fukuyama et al. [55] have studied the effect
of monosubstituted phenol additives on some
mechanical properties of PPY. Both properties,
tensile strength and elongation, were higher than
those in undoped PPY films. Zinger et al. [56]
reported that PPY prepared electrochemically in
aqueous solutions containing perchlorate salt as
an electrolyte exhibits a high conductivity and
superior mechanical properties. For example,
when concentration of phthalate was 0.05 M,
the elongation of the film was 3.6%, maximal
strength was 50.4 MPa, modulus of elasticity
was 0.075 GPa, and the conductivity was as
high as 33.4 S cm 21 (before stretching) and
45.0 S cm 21 (after stretching) (Fig. 1). Murray
et al. have studied the in situ mechanical
properties of PPY doped with pTS (tosylate) in
a range of electrolytes and at different applied
potentials [57]. A brittle-ductile transition was
observed when the polymer was reduced at low
Fig. 1. Variation of tensile properties of PPY films with phthalate
concentration.
 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139
potentials. The brittleness in the oxidized state
was found to be due to the ionic crosslinking
between charged polymer chains and the coun-
terion species present in the polymer structure
(Fig. 2). Compared the two systems, it can be
found that the mechanical properties of PPY/
phthalate films, such as tensile strength, are
better than the properties for PPY/ pTS films
prepared in organic solutions (Figs. 1 and 2).
Polypyrrole films and fibers are proved to have
highly sensitive electromechanical effects so
that they are useful as artificial valves, chemical
valves, actuators and chemomechanical materi-
als [58].
The research by Kaynak et al. [59] proved
that the electrical conductivity of the doped
films has a significant effect on transmission,
reflection, and absorption of microwaves.
Heavily doped, conducting films were highly
reflective, whereas lightly doped, semiconduct-
ing films had very high transmission. Inter-
mediate conductivity PPY samples were highly
absorptive. Shielding effectiveness of PPY films
was also discussed.
Electron spin resonance (ESR) was carried
out at atmosphere as well as low pressures to
find any relation between paramagnetic species
and the charge carriers in pyrrole-based electric
conducting polymers [60]. ESR spectrum sug-
Fig. 2. Variation of tensile properties of PPY/ pTS with applied
potentials.
131
gests that there is no link between the para-
magnetic centers and bipolarons which serve as
the major charge carriers in these materials.
ESR measurements at low temperatures for
pyrrole-based polymers show that most of the
polymers obey CurieWeiss law in terms of
increase in spin populations.
3. Preparation, properties and applications
of PPY-based composites
The formation of polymer blends, alloys or
composites can prepare new polymeric materi-
als with interesting combinations of physical
properties. When a comparison is made among
the three conducting polymers (polyani-
line(PAN), polythiophene(PTP) and PPY), PPY
can form blends easily with the insulating
polymers, whereas PAN-based absorbents had
the ability to be deposited onto reinforcing
textiles and polyalkylthiophene had excellent
solubility and melting properties that were more
difficult with other conducting polymers. As for
PPY, it has high conductivity and good en-
vironmental stability, but poor mechanical prop-
erties. This has been overcome to some extent
by use of composite structures, for example,
combination of the PPY film with the good
mechanical properties of insulating polymers
such as poly-N-vinyl-carbazole [61,62], poly-
styrene (PS) [63], poly(N-vinylimidazole) (PVI)
[64], polyvinylphosphate (PVP) [65], polyvinyl
alcohol (PVA) [6668], poly(vinyl-methyl
ketone) (PVMK) [69] and so on. The conduct-
ing composite films are prepared either by
electrochemical polymerization of pyrrole on an
electrode substrate whose surface is coated with
an ordinary insulating polymer film [70], or by
exposing a polymer film containing an oxidizing
agent such as ferric or cupric chloride to pyrrole
vapor [71,72]. In every case conducting compo-
site films are obtained whose mechanical prop-
erties are considerably improved compared to
the brittle PPY. The effect of low temperature
132 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139
conditions on the electrochemical polymeriza-
tion of PPY-hexafluorophosphate (PPY-PF 6 )
films has been researched [73]. An electro-
chemism of the composite film of ethylene-
vinyl alcohol copolymer and PPY has been
reported [74], too.
Tieke and Gabriel studied pyrrolepolyimide
(PPYPI) composite films [75]. It reported that
the composite films had high electrical con-
ductivity with thermal stability. The composite
films were prepared either by electrochemical
polymerization of pyrrole on a PI coated elec-
trode (type I) or by exposing PI films containing
ferric chloride as an oxidizing agent to pyrrole
vapor (type II). Type I films consist of a
sequence of three layers with the PI sandwiched
between two layers of PPY. The maximum
conductivity is about 10 S cm 21 . Type II films
consist of PI containing finely dispersed PPY
particles of 10 to 500 nm in diameter. The
composite films are thermally stable up to
3508C. The choice of the matrix PI is crucial for
the preparation of the composite films. Conven-
tional PIs are insoluble after imidization and
therefore do not swell enough in organic sol-
vents in order to allow the pyrrole monomer to
penetrate the film and to become polymerized
with the film or at its electrode side. Conductive
pyrrolepolystyrene sulfonate (PPYPSS) was
chemically prepared using FeCl 3 as an oxidant
[76]. The chemical formula proposed for con-
ductive PPYPSS is [(C 4 H 3 N) x1 C 8 H 7
SO 23 .y(H 2 O)] n , where x denotes the degree of
oxidation,and y takes into account some hydra-
tion of ionic species. The method is based on
the different precipitation rates of the two PPY-
based polymers: PPYPSS and PPYCl. In
general, chemical synthesis of PPY yields a
conducting polymer that incorporates the anion
of the oxidant salt as counterion. But by choos-
ing a short reaction time (a few minutes), pure
PPYPSS, free of conductive PPYCl, can be
obtained after filtration. The presence of meta-
hydroxy benzoic acid in the reaction medium
allows shorter reaction times to be used, and
higher yield values of conductive material to be
obtained. Rueda et al. [77] also reported on the
chemical polymerization of PPY on the sul-
fonated surface of polyethylene films (PPY
PES) using FeCl 3 . Another conducting compo-
site of PPY and poly(tetramethylbisphenol A
carbonate) (TMPC) had been prepared electro-
chemically [78]. The method is that monomers
of conducting element diffuse into the insulating
polymer coated on an electrode and start poly-
merization in the interface between the elec-
trode surface and the host polymer film. This
kind of conducting polymer synthesis not only
improves the poor mechanical and physical
properties of heterocyclic polymers but also
retains the conductivity to a desirable value.
Intrinsically conducting hot melt adhesives
(ICHMAs) have been developed, based on PPY
blends, for use in electronic and telecommunica-
tion applications requiring shielding against
electromagnetic interference (EMI) [79]. These
advanced materials have been formulated to
exhibit significant EMI shielding effectiveness
(SE) while retaining the superior properties of
conventional hot melt adhesives. The fabrication
of a PPY-Heparin composite film modified
electrode in pyrrole with coexistence of heparin
was investigated [80]. The PPY-Heparin modi-
fied electrode was easy to make and very stable,
which can be used for the detection of calcium
in childrens hair and the results of detection
was satisfactory.
A recent work indicated that PPY could be
also blend or composite with other conducting
polymers. Sacak et al. prepared PPY/ PAN
(polyaniline) (or inverse order) films on platium
foil electrodes by sequential electrode sides of
the films [62]. It was found that depending upon
conditions, either the second polymer was in-
corporated into the initially coated layer or a
double-layer film was formed with a well-de-
fined interface. Electrolysis of pyrrole and
aniline monomer mixtures having molar ratios
of pyrrole over aniline greater than 0.12 gave
films rich in pyrrole. Because of the layered
structure with each layer having distinctly dif-
ferent electronic, optical and other physico-
 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139
chemical properties, these block copolymers
could be used to fabricate electronic devices,
selective membranes and biosensors. Kojima et
al. studied PPYPTP double layers prepared by
electrochemical polymerization of pyrrole in
presence of thiophene [81]. At a constant cur-
rent, only pyrrole is electrochemically polymer-
ized in the electrolytic solution containing
pyrrole and thiophene in the present experi-
ments. The resulting double layers showed good
rectification characters dependent on thickness.
Zarbin et al. have successfully obtained two
glass I conducting polymer by in situ oxidative
polymerization of pyrrole and aniline inside the
pores of Porous Vycor Glass (PVG) [82].
Biswas and Roy studied variable properties of
PPY after chemical modification [83,84]. PPY
can be prepared in ether and in aqueous medium
as modified by polycondensation with phthalic
anhydride (PA) and pyromellitic dianhydride
(PMDA) in presence of Friedel-Crafts catalysts
such as anhydrous zinc chloride and anhydrous
ferric chloride at high temperature. Previous
work by Biswas and Roy [20,61] indicated that
PPY prepared in aqueous medium possesses
appreciably higher conductivity than the same
obtained in ethereal medium. Furthermore, PPY
produced by aqueous polymerization of pyrrole
in FeCl 3 exhibits fairly well-defined crystalline
peaks in contrast to PPY produced in ether
(FeCl 3 , catalytic mount) which is totally amor-
phous. Structural characterization was studied
by IR, X-ray diffraction and SEM. The SEM for
PPYPA reveals, in general, the formation of
larger particles of spherical shapes and lesser
agglomeration tendency. The base polymer
(PPY) appeared to be rendered crosslinked
through intrachain as well as interchain incorpo-
ration of the anhydride moieties [83]. Polymers
modified PA and PMDA showed interesting
improvements in thermal stability and dielectric
behavior, but the conductivity is somewhat
deteriorated relative to the unmodified PPY
[84]. The overall thermal stability is in the order
PPY,PPYPA,PPYPMDA, which may be
rationalized in terms of intra- and intermolecu-
133
larly cross-linked structures of the polyconden-
sates. Both PPYPA and PPYPMDA exhibit
high dielectric constants (200 and 125) at low
frequency (10 3 Hz), which fall monotonically
with increasing frequency, suggesting the possi-
bility of interfacial polarization. These modified
polymers exhibit frequency-dependent dielectric
behavior, which is a feather that is totally absent
in the unmodified PPY. The conductivity values
of PPYPA and PPYPMDA are in the range
10 24 10 23 S cm 21 , which are obviously lower
than that for unmodified PPY (2.5). This is due
to the adverse effect of increasing temperature
on the PPY chain stability, whereby structural
conjugation and eventually conductivity will be
affected.
Classical conducting polymers are usually
insoluble and infusible materials. Beside the
methods mentioned above, another attempt to
improve their processability is the synthesis of
block and graft copolymers containing conven-
tional and conducting sequences, where conven-
tional sequences increase the solubility of the
resultant block and graft copolymer. Nazzal et
al. [85] were successful in electrochemical
grafting of pyrrole onto a polystyrene backbone
while Hallensleben et al. [86] described the
preparation of poly[(methyl methacrylate)-co-
(2-N-pyrrole / ethyl methacrylate)] which con-
tains pyrrole moieties in the side chains. Further
study described the chemical synthesis of graft
copolymers from poly(methyl methyacrylate)
containing pyrrole moieties in the side chains
via several routes [8688]. Recently, the syn-
thesis of conducting H-type polysiloxane-poly-
pyrrole block copolymers was reported [89]. A
conducting interpenetrating polymer network
(IPN) was prepared by sequential crosslinking
of tetra-ethyl orthosilicate (TEOS) with acrylic
acid grafted styrene-isoprene-styrene triblock
copolymer (SIS) and PPY doped with DBSA
[90]. The resulting IPN has good condition and
exhibits far superior thermal stability. Poly(ani-
line-co-pyrrole) has also been successfully syn-
thesized by Wei et al. [91]. The polymerization
process is neither the classical step nor the
134 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139
Scheme 1. Polymerization of block copolymer of pyrrole and aniline.
classical chain polymerizations but something
in-between, which can be called tentatively the
non-classical chain polymerization or the re-
activated chain polymerization, because before
every growth step the chain ends would have to
be oxidized (i.e. reactivated) to give the
electrophilic species that will attack incoming
monomers. A typical process is illustrated in
Scheme 1 for the preparation of a bilayered
block poly(aniline-co-pyrrole). The copolymers
having the properties of both homopolymer
blocks were obtained.
4. Formation and liquid separation of PPY
membranes
PPY can not only be used as conductive
films, but also be used as functional membranes.
Conducting electroactive polymer membranes
such as PPY membranes have attracted much
interest over the past decade because of their
dynamic chemical / electrochemical properties.
Electrochemically controlled transport of ionic
species across conducting electroactive polymer
membranes has been reported [9294]. The
transport of ionic species across the membrane
can be switched on and off by mean of applica-
tion of an appropriate electrical potential. In
addition, the rate of transport and the selectivity
of the membrane can be dynamically controlled
in situ by application of different electrical
potential waveforms. Furthermore, membranes
synthesized using different counterions show a
remarkable influence not just on the electrical
conductivity, mechanical property and elec-
troactivity of the membrane, but also on the
transport and dynamic control transport prop-
erties. Zhao et al. [95] produced asymmetric
membranes based on conducting polymers. A
free-standing conducting polypyrrole membrane
can be electrochemically synthesized according
to the following reaction:
where, C 2 is the counterion. Two layers of
different PPY films (PPY-p-toluene sulphonate
and PPY-dodecyl sulfate) were electrodeposited
onto an electrode to form a sandwich or layer
structure. The results showed that the films had
sufficiently good mechanical properties to be
used as free-standing membranes in simple
experiments. In mixtures of simple salts such as
KCl and NaCl, it was possible to derive some
reasonable selectivity between cations with
selectivity of K 1 : Na 1 in ratios up to 4.5:1.
Comparative studies have been reported on
diffusion behavior of electrochemically pre-
pared polythiophene and PPY, especially the
effect of ionic size of dopant [96].
Various methods have been used to induce
transport of ionic species across CP membranes.
 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139
Partridge [97] reported that continuous mono-
directional transport of cations through PPY
membranes could be achieved by applying a
potential gradient across the membrane. This
gradient was implemented by using 3-electrode
systems in both the feed and permeate compart-
ments, with the PPY membranes as the common
working electrode separating the two. Ehren-
beck and Juttner [98] reported a method, which
combines potential gradient induced transport,
using a 4-electrode system, with a more conven-
tional 3-electrode system to control the oxida-
tion state of the membrane. The combined effect
was to switch the membrane between a cation
and anion exchange material depending on the
oxidation potential applied to the membrane. In
essence, the membrane acted as an ion gate,
which could be either opened, closed or re-
versed depending on the magnitude and sign of
the applied potential. More recently, Partridge et
al. [99] also described the effect on cation fluxes
across a CP membrane of varying the physical
parameters used during the transport experi-
ment. The parameters included the concentra-
tion of the feed solution, the membrane orienta-
tion, the magnitude of the potential gradient and
the dopant type employed during fabrication of
the membrane. The results indicated that the
PPY membranes doped with a combination of
polystyrenesulphonate (PSS) and 1% dodecyl-
benzene sulfonate (DBS) (PSS / DBS 1%) dis-
played the best physical characteristics, in terms
of conductivity, strength and cation fluxes.
Partridge et al. [100] studied the effects of the
various parameters employed in the synthesis of
the membranes, on the physical characteristic
and cation transport properties of the resulting
membranes, including temperature, current den-
sity, dopant concentration, applied potential
gradient and growth time on flux. The results
indicated that the optimal membrane growth
was achieved when using a growth temperature
at or below 208C, a current density between 1
and 3 mA / cm 2 , and a dopant concentration of
0.1 M.
Electronically conducting polymers (ECPs)
135
for membrane-based separations, including gas
separation and pervaporation were also reported
[101]. Martin et al. used interfacial polymeri-
zation to synthesize thin films of the desired
electronically conductive polymer (e.g. PPY).
The interfacial polymerization yields thin film
composite membranes in which the microporous
support provides the requisite mechanical
strength and the conductive polymer provides
the chemical selectivity. ECPs provide a wealth
of opportunities for fundamental investigation
of the effects of molecular and supermolecular
structure on gas and vapor-transport in poly-
mers. Polymers with a large variety of chemical
structures and substituents can be easily syn-
thesized and the counterion in the doped form
can be charged at will. Pervaporation data were
listed in Table 3 for the uncoated hollow fiber
and for hollow fibers coated with PMPY and
PPY films. Because the interfacially polymer-
ized PPY films are porous, it is not surprising
that the selectivity data for the PPY-coated fiber
is only slightly different from that for the fiber
itself PMPY shows good selectivity for metha-
nol vs. MIBE (methyl-t-butyl ether) transport,
because PMPY is polycations and PMPY (inter-
facially polymerized) film is defect-free.
In recent years, composite membranes based
PPY were also studied [102,103]. Morita [102]
has reported the effects of applied potentials on
permselectivity of ions through PPY/ porous-
polypropylene composite membrane. The results
showed that the composite membrane worked
effectively as a functional separation membrane
to control the ionic permeability by potential
application. Using porogen-leaching techniques,
a series of porous membranes consisting of
Table 3
Pervaporation selectivity coefficient for methanol vs. methyl-t-
butyl ether (MTBE) transport through microporous hollow fibers
coated with PPY and PMPY
Polymer membrane Selectivity
coefficient
Uncoated hollow fiber 1.06
PPY 1.40
PMPY 3.90
136 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139
polymethyl methacrylate (PMMA) and PPY
were prepared [103]. The potential advantage of
the composite polymer membrane approach (as
opposed to a coated membrane) is that the PPY
can be dispersed throughout the entire pore
structure and yet the mechanical properties of
the host polymer can be used to advantage. This
can allow the membrane potential to be exerted
over the filtration medium through the entire
length of the pore (or the thickness of the
membrane) instead of being restricted to the
surface. The use of polypropylene glycol and
sodium chloride as porogens in developing
porous PMMAPPY composite membranes was
investigated. Porosity was introduced via the
use of a polymeric liquid porogen (PPG) or
sodium chloride powder. PPYPMMA compo-
site films have been prepared previously by
chemical polymerization followed by heating
[104] or by dipping PMMA film containing
pyrrole monomer into FeCl 3 [105]. However,
none of these methods obtained controlled
porosity films. The membranes could be made
to be permeable to small amino acid
(tryptophan) or large proteins (BSA, bovine
serum albumin). The membranes demonstrated
21
conductivities up to 19.8 S cm and with
further development may have applications in
bioseparations and other areas that require con-
trolled porosity conducting polymer composites.
5. Prospect of PPY membranes for gas
separation
In recent years, the use of conjugated poly-
mer membrane for gas separations has been
reported a lot. Why the ECPs can be used in
gas-transport lies in: (1) it was found that
polymers, which contain high concentrations of
fixed ionic sites can show exceptional gas-trans-
port selectivity; the doped forms of ECPs are
exactly such polymers [106]. (2) It is easy to
synthesize thin films of ECPs; this is important
because flux of permeate is inversely propor-
tional to film thickness in nearly all membrane-
based chemical separation. (3) ECPs can be
reversible switched between polyionic and
neutral forms [107]. This raises the interesting
prospect of reversibly switching the gas-per-
meability of a film between two well-defined
values. In 1986, Munstedt et al. have studied the
permeability for oxygen through PPY films
differently treated with acid and base. The main
properties of the film are shown in Table 4 [50].
The rate and selectivity of gas transport in the
conductive, heterocyclic polymer, poly(N-
methyl pyrrole) (PMPY) have been studied
[108]. It showed that PMPY has interesting and
potentially useful gas-transport properties.
These two investigations of very different mem-
bers of the ECP family suggest that ECPs
warrant further investigations for potential ap-
plications in gas membrane-based separation. It
was also found that the thin films were essen-
tially defect-free and the permeability coeffi-
cient (P) values for all gases in the polycationic
form of PMPY are lower than the permeability
for the neutral form of this polymer. It is well
known that introduction of ionic groups into a
polymer lowers the available void volume
[109]. This decrease in void volume is un-
doubtedly responsible for the diminution in the
permeability values for PMPYNO 3 . The re-
sults showed that PMPYNO 3 has extraordinary
gas-transport characteristics. The oxygen over
nitrogen selectivity coefficient (aO 2 / N 2 ) of
PMPYNO 3 approached 7.9, and PO 2 was
Table 4
Oxygen permeability through polypyrrole (PPY) salt films treated
differently
Temperature Oxygen permeability
(8C) (10 216 mol / m s Pa)
Aa Ba Ca
23 1.34 0.60 0.44
40 4.02 1.94 1.41
60 20.2 11.89 7.20
80 88.07 50.55 27.24
a
A, an initial sample; B, treated with 10% H 2 SO 4 for 240 min;
C, treated with 10% NaOH for 240 min.
 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139 137

Table 5
Permeability and selectivity coefficient for gases through polymethylpyrrole (PMPY) and polyaniline (PAN) membranes
Membranes PO 2 PN 2 aO 2 / N 2 PCO 2 PCH 4 aCO 2 / CH 4 PH 2 aH 2 / N 2 Refs.
PMPYNO 3 1.26 0.16 7.9 2.82 0.17 16.2 [101]
PMPY 2.04 0.33 6.2 6.90 0.22 31.9 [101]
PANNO 3 0.129 0.0087 14.8 0.401 0.0073 54.9 [114]
PANCl 0.142 0.0096 14.7 0.462 0.0089 51.9 [114]
PAN 0.141 0.015 9.4 0.421 0.032 18.3 3.308 205.3 [113]
PAN d a / ud b 0.546 0.063 8.7 2.60 0.017 152.9 17.6 279.4 [113]
PAN as-cast 0.280 0.0382 7.3 1.44 [112]
PAN d / ud 0.172 0.00323 53 1.59 0.608 2.6 10.6 3281 [112]
PAN rd c 0.110 0.00253 43.5 0.732 ,0.005 146 [112]
a
d5doped.
b
ud5undoped.
c
rd5redoped.

l.26310 210 cm 3 (STP) cm / cm 2 s cmHg (or
5.63310 216 mol / m s Pa). PMPYNO 3 pro-
vides both high selectivity and high flux. But
generally, enhanced selectivity in a polymer
film can only be achieved at the expense of flux.
Musselman et al. studied the separation prop-
erties of poly(3-dodecythiophene) (PDDT)
membrane and found the results unsatisfactory
(aO 2 / N 2 52.23.0 [110]). But it was reported
that PAN films show significantly larger selec-
tivity coefficients than that for PMPYNO 3 and
also found that the rate and selectivity of gas
transport depend on doping level [111]. The
selectivity of the polyaniline emeraldine base
was reported by Kaner et al. [112,113],
Kawabata and Martin [114] and Pellegrino et al.
[115] to be quite high ((aO 2 / N 2 57.3 [112],
aO 2 / N 2 59.4 [113,114], aO 2 / N 2 57.2 [115]). Fur-
thermore, the selectivity was observed to in-
crease with chemically induced doping
(aO 2 / N 2 515 [111]). As for PPY membrane, the
same result was obtained. Martin et al. demon-
strated that as cast (aO 2 / N 2 56.2) and doped
with NO 3 (aO 2 / N 2 57.9) for poly(N-
methylpyrrole) as mentioned before [101].
Table 5 showed permeability and selectivity
coefficient of different gases. It can be found
that PAN films show higher selectivity coeffi-
cient, but lower permeability. However, PPY
films display relatively high permeability. It
suggests that a copolymer of pyrrole and aniline
should be a suitable material for gas separation,
especially for oxygen enrichment.
6. Conclusions
Polypyrrole and its derived polymers have
been discussed in detail. Polypyrroles can be
synthesized by many different and facile meth-
ods including electrochemical and oxidatively
chemical polymerization. Different methods to
improve the processability of PPYs were dis-
cussed. From the discussion, it is obvious that
PPY has excellent properties, including electri-
cal, thermal, and mechanical properties. Owing
to these properties, PPYs have been widely
studied and exhibit a wide potential application,
especially, in the studies of the PPY-based
membrane for the potential application in gas
separation [101]. Compared with three conduct-
ing polymers (PPY, PAN, PTP), in order to get
functionalized membranes with excellent per-
meability, selectivity, stability, as well as en-
hanced conductivity, the copolymers of pyrroles
and aniline derivatives have been investigated in
our laboratory [116,117].
Acknowledgements
This research was supported by (1) the
National Natural Science Foundation of China
138 L.-X. Wang et al. / Reactive & Functional Polymers 47 (2001) 125 139
(Grant No. 29804008); (2) the Foundation of
University Key Teacher by the Chinese Minis-
try of Education; (3) the Phosphor Plan of
Science Technology for Young Scientists of
Shanghai, China (Grant No. 98QE 14027); and
(4) the Key Laboratory of Molecular Engineer-
ing of Polymers of the Chinese Ministry of
Education.
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