Electrically Conducting Polymers

D J Walton

Department of Applied Physical Sciences, Coventry Polytechnic, Priory Street, Coventry CV1 5FB.

Abstract
Electrically.conducUng polymers are relatively recently discovered rnater/ais that possess not only electronic conductivity
variable over many orders of magnitude but other properties including ion.transport, junction effects and electrode effects
allied to polymeric physical properties. Because of this they are exciting considerable research interest and under investigation
for a wide range of applications within the electronics industry.
This review concerns basic properties of these materiaLs with respect to significant applications. Recent developments
will be addressed and the implications towards further advances are considered. The opportunities for chemical manipulation
of these materials, an important aspect of their technology, will be discussed with regard to both processability and
functionalisation; the effects so produced will be discussed.

Introduction

Plastics are renowned as insulators throughout the

electronics industry, but recently new polymers have
been discovered that have considerable electronic
conductivities. Quite an extensive range of these
polymers is now known and the maximum conductivity
so far obtained is only a single order of magnitude below
that of metallic copper. These polymers can also be
obtained in or converted to non-conductive forms and
therefore a single sample of material may display conductivity across a span of some fifteen orders of
magnitude. Figure ] gives conductivity ranges of several
conducting polymers compared to conventional metals,
semiconductors and insulators. Apart from conductivity
the structural features of these materials give rise to
properties of ion-transport, redox behaviour, electrochemical effects, electrooptic and electronic junction
effects; which are allied to lightweight, flexibility, nonmetallic surface behaviour and other polymeric physical
properties.
This range of properties has resulted in considerable
research interest, both industrial and academic, and a
considerable number of practical applications are under
investigation, including non-metallic conductors, EMI
shielding and anti.static electronic junction devices,
electro.chromic displays, opto-electronic systems, semiconductor protection, information storage, capacitors,
ion-release systems, anti-corrosion, and bioactive
devices, among others. The extend of this effort is
demonstrated by the production during the last four
years alone of over 1500 papers in the academic press
and over 800 patent applications.
It is not possible to describe all aspects of this
endeavour and this review will concern only the basic
properties of these materials and their applications,
together with some emphasis upon the opportunities
for chemical manipulation of these materials, a
beneficial aspect of organic systems, and how this has
been exploited to enhance processability and to induce
functionalisation of these polymers.
Further details of these materials may be found in

142

Polypyrrole
&
Polythiophene Polyacetylene

Copper. "106
Iron. 04
Mercury.

GermaniumS(doped)

Polyphenylene

02
0
0-2

Silicon ,10-4

.10-6
trans-PA

10-8
10-10
.10 -12
i

Polythene- . 10-14

cis-PA

Nylon.10 -16

PPP

PPy
PTh

Polystyrene- .10-18
Conductivity
(S crn-1 )

F~al

Comparison o f conducUvity ranges for several

conducting p o l y m e r s y s t e m s compared with
conventional materials

numerous recent in-depth reviews~17) towards which the

reader is directed. In addition the proceedings of the
biennial International Conference on Science and
Technology of Synthetic Metals are very extensively
reported,m) and th e journal 'Synthetic Metals' is
dedicated to these materials.
Structures
Metals conduct electricity through mobile electrons in
the conduction band that travel across atoms in the
lattice. The equivalent situation in organic materials is

0261-3069/90/030142-11 1990 Butterworth-Heinemann Ltd

MATERIALS & DESIGN Vol. 11 No. 3 JUNE 1990

Cis-polyacetylene

45C
H
(b) Polypyrrole

-7

Conductivity: trans= 10 S/cm ( insulative I

...... -,,s,cm

Oxidation (-e-)

Noo \

04

0 "~Reduction (+e-)

(a) Trans-polyacetylene
C

Na

C10~

(d) Polythiophene

(c)

Poly (p-phenylene)

F g3

CH=CH-(e) Polyphenylene vinylene

Fig 2

' P e r c h l o r a t e - D o p e d ' { c a t i o n i c chain)

C o n d u c t i v i t y about 100 S/crn
(conductive)

NH-(f) Polyaniline

Polymer structures

provided by delocalised 7r-electrons, but conventional

insulative polymers do not possess electrons in suitable
orbitals. Thus the backbone of polyethene comprises
sp3-hybridised carbon with valence electrons confined
to ~.bonding between adjacent atoms, while the 7relectrons in the pendant aromatic rings of polystyrene
are unavailable for travel along the chain. Electricallyconducting polymers have in common a significant overlap of deiocalised ~r-electrons along the polymer chain,
and several suitable structures are shown in figure 2.
The simplest structure with the required alternation
of single and double bonds is polyacetylene (2a), and
this was the first conducting polymer to be characterised. It remains the archetype and has been the subject
of most theoretical analysis although its properties are
not as simple as might be imagined and are complicated
by cis/trans isomerism. In practical applications polyacetylene has been somewhat superseded by polymers
of the polypyrrole (2b) type, on grounds of stability and
ease of procedure. Two important polymers similar to
polypyrrole are shown, polythiophene (2d) and polyaniline (2f); while polyphenylene (2c) and polyphenylene vinylene (2e) show similarities to polyacetylene. All
conducting polymers are unique, but the definition of
a 'polypyrrole class' has some merit, since a large
number of polymers have now been prepared exhibiting
common principles.

Conducting forms ('Doping')

coating (cf fig 1). Conductivity ensues from the redox
perturbation of the polymer chain. Thus oxidation, the
most common procedure, produces an electron-deficient
'undoped" This is because the delocalised ~r-electron
structure is insufficient for conductivity, and in this
context neutral polyphenylene is used as an insulative
coating (cf fig 1). Conductivity ensues from the redox
perturbation of the polymer chain. Thus oxidation, the
most common procedure, produces an electron-deficient
polycationic chain, requiring the presence of anions
from the oxidising medium for charge compensation.
Conducting polymers are therefore ionomeric in their
conductive forms, and are often termed 'doped', with
the counterion classed as 'dopant'. This terminology
should be distinguished from the conventional use of
'dopant' in semiconductor physics. Considerably higher
concentrations of dopant are employed in conducting

MATERIALS & DESIGN VoI. 11 No. 3 JUNE 1990

'Sodium Doped ~ (anionic chain)

C o n d u c t i v i t y about 100 S/crn
{conductive)

Oxidation or reduction of polyacetylene to

produce conducting forms (hydrogen atoms
omitted for clarity)

polymer systems.
A marked distinction between polyacetylene and
polypyrrole is that while polypyrrole can only be
oxidatively-doped, p o l y a c e t y l e n e can also be
reductively-doped to a conducting polyanionic electronrich chain, compensated by cations. The doping
processes leading to the conducting forms of polyactylene are shown in figure 3.

Syntheses and properties

Polyacetylene
The impetus for the recent interest in conducting
polymers came from development of the 'Shirakawa'
route to reproducible thin films of polyacetylene ,<9~and
the discovery that these could become highly conductiveJ 1) In the preparation a conventional ZieglerNatta polymerisation catalyst system is employed, and
following exposure to acetylene gas the polymer forms
a lustrous flexible skin across the surface of the catalyst
solution. Alteration of catalyst concentration and other
factors can lead to fine powders.
Polyacetylene is insoluble and infusible and is
unstable to air, since exposure to oxygen produces
carbonyl and other oxygenated functionalities with
concomitant loss of mechanical properties. Temperature.dependent isomerisation is exhibited, with the cis
form only stable if prepared and held at low temperature
(-70C), becoming the trans form if prepared at or
exposed to temperatures towards 170C.
Two conductivity values are given to 'undoped'
polyacetylene in figure 1, since although the cis form
is a typical non-conductive polymer the trans form
possesses a degenerate ground state which allows the
formation of neutral solitons which effectively contain
unpaired electrons. These have been detected by
electron spin resonance (ESR) and are considered the
origin of the significantly-enhanced conductivity. Only
a symmetrically-substituted polymer chain can exhibit
the two-fold degeneracy necessary for this phenomenon
and only polyacetylene to date amongst conducting
polymers fulfils this criterion. This behaviour of transpolyacetylene is shown in figure 4.
Polyacetylene is usually prepared in an uncharged
non-conducting form, and the films have an open
fibrillar morphology which facilitates the necessary iontransport during doping to the conductive form.
Isomerisation to the thermodynamically stable transstructure accompanies the doping process.
The conductive doped forms of the polymer possess

143

i)

~C/C~C/C~C/C

or ~ / ~

C~'C~C~

Two-fold degeneracy of trans-polyacetylenechain

H
(R12)

ii)

Fig 6

I
L

~Xf
[i~2)

I
J

Ae

Heteroaromatic polyers - Structural manipulations

Soliton Formation (note inversionof double bonds)

Fig 4

Soliton formation in trans.polyacetylene

(hydrogen atoms omitted for clarity)
H

114

Conductive oxidised polymer

Mechanism of formation

Oxid,tion

Proton loss

H
Radical cation

H H

Fig 5

Repeat
oxidationPolymer
H

coupling
etc.

Polypyrrole formation

poorer mechanical properties than the undoped ones,

and are quite intractable. This latter feature is in
common with most, if not all conducting polymers, and
efforts to improve processability characterise a large
proportion of applications-oriented research into
these materials. For polyacetylene, copolymerisation
techniques and the development of an ingenious
processable.precursor route have shown some success
and are discussed later.
The maximum polymeric conductivity obtained to
date, 105S cm -1, concerns iodine-doped polycetylene
prepared by a variation of the Shirakawa route n. The
enhanced conductivity is tho6ght to be due to
diminution of sp 3 carbons, crosslinks, and other
defects; and enhanced air-stability is also claimed.

Polypyrrole
The great advantage of the polypyrrole class of polymers
is that they can be prepared directly in a doped
polycationic form by oxidation of the monomer. The
reaction involves initial formation of the radical cation
and is not a simple polymerisation since protons are lost
from the ot ring positions, as shown in figure 5. The
polymers can be reduced ('dedoped') to uncharged nonconductive forms provided certain criteria regarding ion.
transport are satisfied, but cannot be further reduced
to negatively-charged chains.
Pyrrole may be chemically oxidised to an insoluble
powder by ferric and other transition metal salts,
persulphate anions, and others in a wide range of
oxidants. The polymer is found doped with CI-,
FeCl 4- o r other species derived from the oxidant. This

144

procedure is significant if processable composites with

conventional polymers are required, further discussed
below.
A feature of this general class of polymer is that
electrochemical oxidation may be employed. Not only
may oxidising power be independently varied but a wide
range of anions may be used in the electrolyte. In
addition polypyrrole tends to form free-standing and
mechanically-cohesive films that can be peeled from
the electrode. These films are black, have a paper-like
consistency when dry but are tougher and more flexible
when wet and have a relatively dense morphology. The
polymer is markedly stable to air at room temperature
in its oxidised as-obtained form (although the less
common reduced neutral form is quite air-unstable).
Conductivities of - 100A cm -1 are typical.
Polypyrrole is tolerant of electrolyte, electrode
material and solvent during preparation, and can even
be prepared from aqueous solution, surprisingly for such
a process involving reactive cationic species.
Acetonitrile, propylene carbonate, alcohols and cyclic
ethers are commonly-used organic solvents, with
p-toluene sulphonate an anion that produces films with
enhanced mechanical integrity. Platinum, steel,
transparent indium-tin oxide coated glass, semicon.
ductor surfaces, other conducting polymers and carbon
fibres are examples of the many effective electrode
materials. In the simplest instance an acceptable film
can be obtained from stainless steel electrodes powered
by a battery, using a beaker open to the air, and in this
respect polypyrrole is the most 'user friendly' conducting
polymer. In general, good quality free-standing films are
the province of polypyrrole and its simple derivatives.
'Hetero-aromatic polymers' - structural
manipulations

A feature of the polypyrrole class, often termed the

'hetero-aromatic' conducting polymers, is the range of
manipulations that can be performed to vary the
properties of the resultant polymer. This is shown
diagrammatically in figure 6. Thus the monomer ring
may be changed, for example to thiophene, (where X
-- sulphur). 5-membered heterocycles are not exclusive
and aniline, certain phenols, pyrazines and a range of
other monomers will produce oxidatively-formed conductive electrode coatings.
Substituent groups (R), may be introduced, altering
conductivity, morphology and other properties, or
introducing specific functionalities. Alternatively the
dopant (A) may be varied, and may also introduce
functionality. Again pyrrole derivatives produce the most
striking tolerance towards functionalisation routes, and
are further discussed below. However, despite the greater

MATERIALS & DESIGN VoI. 11 No. 3 JUNE 1990

facility of pyrrole systems, for many applications

polythiophenes and polyanilines seem more suitable,
having conductivities of a similar order but differing in
other properties.
Copolymers may be formed in several ways, such that
Y is a different species linking the polymer chain; and
for example in the case of polythienylene vinylene
(similar to figure 2 structure e, where an o~o~~ linked
thiophene replaces the benzene ring), Y need not be
a ring system at all. Additionally the polymer may be
blended, laminated or otherwise incorporated into a
composite, either with another polymer or even with
inorganic materials.
Finally the dopant ratio (l/N) may be varied.
Polypyrrole is typically found with N = 3 to 4 over a
wide range of anions and electrolysis conditions, while
polythiophene tends to N = 5 to 6. Both are maximum
values since attempts to overoxidise (reduce N) usually
result in chemical breakdown of the polymer. However,
reduction towards the neutral polymer (N --oo) is
important.
Redox

properties

Charge~discharge ('Doping/dedoping')
The ability to charge and discharge a conducting
polymer sample resulted in the early examination of
these materials as battery electrodes. Polyacetylene,
which can be both oxidised and reduced to conducting
forms offers a range of half-cell reactions, but particularly interesting is the concept of the 'all plastic'
battery using conducting polymer as anode and
cathode, with suitable electrolyte. The cell reaction
might be as follows:-

and shelf life are important parameters requiring

optimisation. For polypyrrole a half-cell reaction in only
one sense is available. However, various prototype
batteries employing conducting polymers are now
developed.(l~a)
The change of conductivity with doping level for
polyacetylene is given in figure 7, which shows a
characteristic shape, and is a composite of typical
results. The polymer changes from semi-insulating to
metallic-like conduction, and the amount of dopant, for
example a maximum of one iodine per 5 CH units for
iodine doping, represents a considerable build-up of
charge in the polymer. Different regimes have been
identified, based on ESR measurements of electron
spin, temperature behaviour, optical measurements and
similar; whilst in the reductive cationic doping process
staging has been observed comparable to that in
graphite intercalation systems.
Both oxidative and reductive doping of polyacetylene
may be carried out chemically, e.g. by iodine and
sodium naphthalide respectively or alternatively by
electrochemical means, which allow a wider range of
counterions such as BF4- or Bu4N respectively. Many
redox reagents and dopants have been found to be
suitable and considerable study has been made of these
redox processes; the ensuing results and conclusions
are thoroughly discussed in a recent review.~5~

Electrochromism

Heteroaromatic polymers are reduced from their

oxidised forms towards the neutral polymers, a process
in which conductivity and morphological changes are
accompanied by inter alia, changes in colour. For
polypyrrole the green/black yellow transformation is in(CH)x+ .nClO4- + (CH)xn- .nLi+-(CH)x + nLiCl04 + (CH)x appropriate on colour grounds and also because the airinstability of the neutral forms affects cycle life. The
Stability, reversibility, cycle life, charge/discharge rates blue/red change of polythiothene is more useful,
particularly since this polymer is relatively stable in both
its oxidised and neutral forms, and is thus suitable for
electrochromic display elements. Furthermore a
bisthienyl bibenzyl (figure 12, structure j), produces a
polymer with a green doped form, allowing a red/green/
blue colour element system to be based on thiophene
polymers. (12a)Polyanilines are also attracting interest as
electrochromicsJ~2b)
T

200

Ion bind~release

uo

100

0
0.

0.1

0.2

D o p i n g level ( D o p a n t per CH u n i t )

Fig7

Effect of doping level upon conductivity of

trans-polyacetylene

MATERIALS & DESIGN Vol. 11 No. 3 JUNE 1990

A corollary of change in the polymer charge is that ions

must travel for compensation, and in principle for the
reduction of for example oxidised polypyrrole either the
existing anion migrates out of the polymer or a cation
migrates in from the reduction medium. The actual
process which occurs will depend on the nature of the
polymer, the anion present, the cation in the system,
solvent, reduction parameters and others. Externallycontrolled ion-release has been demonstrated for
release of the bioactive anion glutamate from doped
poly 3-methoxy thiophene;/~31 and other 'active' anions
may be proposed.

pH-sensitive switching
Polyaniline, unlike other heteroaromatic polymers, can
exist in forms that are interconverted by pH as well as
by redox processes. Several forms of polyaniline are

145

given in figure 8. The highly-conductive emeraldine

form is interconverted with emeraldine base by proton
exchange, a reaction described as a doping process
which unlike other doping processes in conducting
polymers does not involve change in the number of
electrons associated with the polymer chain.( TM
Conventional redox conversion from fully reduced forms
is also available to this polymer, and several structural
units so derived are given in figure 8.

-2.Se,-2H*[ - ~
H /~X H ~ H
/-~ H ]
NH2 a%Uec~U'-----~L-~-N.~_~ N-J~_~. A%~/~N~_J

( ~

Emeraldine [green, conductive)

.'1 LOH-

Emeraldine base (blue)

Micro-electrochemical devices
Redox switching between conductive and insulative
forms has been exploited in micro-electrochemical
transistors and signal amplification has been demonstrated at frequencies exceeding l OOHz for gold or
platinum micro-electrode arays connected by a redox
polymer which is also part of an electrochemical ceil.
Poly 3-methyl thiophene and polyaniline have been used
successfully, among others.oda) In a variation of this
system, poly 3-methyl thiophene in such a device is
platinised electrochemically to yield an electrocatalytically-active polymer that produces a chemicallyresponsive microelectrochemical transistor that senses
for hydrogen, oxygen, or pH. <'db).
Further developments in this technology would seem
promising, but for the drawback of relatively slow
response speeds. However, a recent paper has shown
that redox switching of polyaniline can be faster than
previously described, and that this result may also apply
to the redox rates of other conducting polymers,< '7)
with benefit to any application involving redox cycling
processes.

1/4

I14

Various repeat units (via proton transfer or redox reactions}

Oxidised unprotonated

Reduced

N__

Oxidised monoprotonated

Fig 8

N-

Oxidised diprotonated

Polyaniline

Uncharged
H

-~-;

Polaron
H

~+e-

F-H

,~L=

Undoped

"~

n_l-

gipolaron

H
I

FH

H
I

"~

H
I

Itigh doping

Conduction mechanisms and electronic

structures

Fig 9

Considerable effort has gone into the understanding of

conductivity in conducting polymers since key
applications may hinge on the correct exploitation of
mechanistic differences between these materials and
conventional conductors and semiconductors. The
situation is complex since a polymer that can exhibit
conductivity across a range of some fifteen orders of
magnitude may involve different mechanisms within
different regimes. Much careful work has been
performed to correlate conductivity with other
properties and system parameters over a wide range
of conditions; but it should be noted that since
conducting polymers are generally insoluble and
interactable they are not amenable to conventional
methods of purification and characterisation, and some
discrepancy and apparent irreproducibility may originate
from changes in preparation procedures that are
sufficient to alter the exact nature of the polymer under
study. Several recent reviews have described the status
of results and theory. (],2,5)
However, a qualitative summary is as follows:The majority of conducting polymers possess
cationic chains, and the discovery that highly-conducting
forms with high charge concentrations showed only low
concentrations of free spins suggested the existence of
spinless positive charge-carders, termed bipolarons. This
is shown pictorially for polypyrrole in figure 9, where the
quinonoidal section between the two positive charges

represents the bipolaron. At lower charge concentrations

a polaron is envisaged, which has a positive charge at
one end, a free electron at the other and has a
measurable spin. An equilibrium exists for the coalescence of polarons into bipolarons with increasing charge
density. Other species such as a charged solition (cation)
are also implicated in conduction mechanisms.
Conductivity is influenced by a variety of factors,
including polaron length (the number of rings or double
bands spanned), the conjugation length (the extent of
delocalisation along the chain before a defect is
encountered), the overall chain length (which also
affects other physical properties of the polymer), and
importantly by the case of charge transfer to adjacent
molecules. This latter involves interchain hopping within
a fibril or polymer particle and finally interparticle
hopping. The complexity of processes in charge transport is shown pictorially in figure 10.
The most widely-applied theoretical approach to the
electronic structures of conducting polymers is the
valence-effective Hamiltonian (VEH) technique, which
gives good agreement with experiment for band gaps
and ionisation potentials and also predicts band widths.
A detailed account with data is provided in the chapter
on electrically-conductive polymers in reference 3, and
references therein. Experimental band-gaps for several

146

Formation of polaron and biopolaron along a

polypyrrole chain

MATERIALS & DESIGN Vol. 11 No. 3 JUNE 1990

substitution at the 3.position enhances solubility of the

undoped polymers, particularly for polythiophenes, while
!
/ /
longer-chain alkyl groups (eg octyl, structure 12a)
impart solubility to both neutral undoped and
B /
conductive doped forms of thiophene and pyrrole
polymers. (2,21~Alkoxy-substitution also produces solubility of conductive forms of polythiophenes, (221 (for
example where R = CH2OCH2CH2OCH2CH2CH2OCH3,
structure 12b, and others). Solution-processable
conducting polymers are now available, although some
loss of conductivity is found upon redeposition.
When the substituent side-chain contains a sulphonate group (eg fig 6, R = -CH2CH2CH2CH2SO3e/,
structure 12c) the polymers so obtained are watersoluble in the conducting state./23.24~ These polymers,
termed 'self-doped' because the dopant anion is
attached to the ring, act as cation-exchangers during
Fig 10 Conductivity network of a conducting polymer redox.~25~
Polyanilines soluble in water and other solvents have
with A indicating intrachain transport of charge;
B indicating interchain transport; C indicating also been prepared, (26~and polyaniline systems are now
interparticle transport and arrows showing path attracting considerable interest.
In general, substituted monomers lead to polymers
of a charge carrier migrating through the
material (reprinted from reference 3 with with lower conductivities than those from the
unsubstituted parent monomer. The possibility that
permission)
interference with the polymerisation process may
produce enhanced solubility because of the formation
of
shorter chains has been demonstrated by the use of
conducting polymers are: trans-polyacetylene 1.4eV,
chain-stoppers
to end-cap and solubilise oligomers of
polyphenylene 3.4eV, polypyrrole 3.0eV, and polythiopolypyrroles.~27,28~
phene 2.0eV. Comparisons have been made between
Fusibility of simple heteroaromatic conducting
conducting polymers and typical semiconductors such
polymers
is less well-established, and is generally
as silicon, in electronic junction devices such as fieldinduced
by
the formation of composites, further
effect transistors, and optoelectronic systems. ~8,~9a~
described
below.
The use of polymeric sulphonic acids
Results have been sufficiently successful for patent
(figure
1
2,
structure
a) as dopants in polypyrrole affords
application. 09b~Further exploitation of these principles
a
measure
of
heat
processability.
~29/
is anticipated.
A significant enhancement in the fabrication of these
devices was provided by processing improvements in
polyacetylene production; and this emphasises an
important area of conducting polymer development,
namely the inducement of processability.
The inherent flexibility of approach to organic
systems is shown by the range of different strategies
employed in this endeavour, described below.

Precursor route synthesis

Since the origin of intractability is the conjugated
conducting-polymer chain, this strategy demands a
synthesis involving a precursor polymer that is nonconjugated, and therefore soluble and processable. This
precursor is then converted to the conductive form after
the necessary processing stages. Three precursor-route
syntheses are given in figure 11.

E n h a n c e m e n t of processabllity

Polyacetylene
The most widely-established precursor system is the
'Durham' route to polyacetylene discovered by Feast and
Edwards and developed in collaboration with BP.~31~
(scheme 1). This was exploited to facilitate the fabrication of polyacetylene-based transistors. ~19~ The
precursor of polymer is prepared by conventional
metathesis reaction; it is subsequently converted to
neutral polyacetylene by heat, with loss of hexafluoroxylene in a retro-Diels-Alder reaction. Several other
sophisticated chemical processes leading to conjugated
polymers have been proposed by the Durham group.
The neutral polymer requires doping as usual for
conductivity and there are subtle differences between
'Durham' and 'Shirakawa' polyacetylene particularly
relating to morphology and properties thus influenced.
An important aspect of the Durham route is that by
application of a suitable stretching process during the
procedure oriented films of polyacetylene can be

Because in their doped conductive forms simple

conducting polymers are insoluble, infusible and
intractable there has been considerable effort towards
improved processability. Varying success has been
achieved by diverse routes which include:- i) the use of
functionalised monomers, ii) the development of
syntheses employing processable precursor polymers,
iii) the use of copolymerisation or the formation of
composites and blends, iv) by other chemical processes.
Enhanced processability is an aim for a host of
conducting polymer applications, but particular effort
has gone into EMI shielding, anti-static and conductive
coatings.

Functionalised monomers
Heteroaromatic polymers will tolerate substituents in
ring positions of the monomer that are not involved in
the polymerisation process (cf figure 6). Simple alkyl-

MATERIALS & DESIGN Vol. 11 No. 3 JUNE 1990

147

Scheme 1 Polyacetylene (PA)

CF 3

CF 3

CF 3

CF3

CF 3

CF3

rl

soluble, processable
precursor

Scheme 2 Polyphenylene Vinylene (PPV)

CH 3

CI e

CH 3

+ (CH3)2S+HCl
water-soluble precursor
polymer
Scheme 3 Polyphenylene (PPP)
O
II

HO

OH

OxidationBaCteria~I

CH 3 CO

PPV

II

It

OCCH 3

CH 3CO

Esterificatin~ ~ P l y m e r i s a t i n

O
II

OCCH 3

E( ~

+ 2 CH3COOH
n

PPP

Precursor polymer

Fig 10 Precursor routes to conducting polymers

produced with draw ratio > 20 and marked anistropy

in conductivity and optical properties. Normally polyacetylene and most other conducting polymers are
obtained in relatively isotropic forms, even as thin films.
It is worth noting here that recent advances in the
physics of conducting polymers have followed the
production of reproducible anisotropic materials. Polyacetylene has also been prepared in an oriented form
in Shirakawa polymerisations, by growing films on a
polypropylene substrate and then stretching to give a
25-fold conductivity anistropy/32~ or by the use of a
liquid-crystalline solvent in polymerisation.~ 33~
Polypyrrole is oriented by stretching solvent-swollen
films ~34~ and also by the formation of LangmuirBlodgett films of long-chain alkyl-substituted pyrrole
derivatives.~3s~

in which a genetically-manipulated variant of the

organism pseudomonas putida is used to convert
benzene to 5, 6 dihydroxy cyclohexa-1, 3 diene, which is
then esterified and polymerised conventionally to the
processable precursor polymer, which is converted to
polyphenylene product by heat treatment.

Copolymers, composites and blends

Considerable effort has been placed towards this
approach, evidenced by a particularly large number of
patent applications in the literature. Considerable
development in processability and mechanical and
physical properties have variously been obtained, but
the 'dilution' of a conducting polymer with a nonconducting one also produces a loss of conductivity.

Polyacetylene
Polyphenylene uinylene
Scheme 2 shows a route to this polymer using a soluble
sulphonium.salt precursor ~36~ with a similar benefit
towards orientation and fabrication procedures. In
addition, very highly-oriented thin films with a conductivity anisotropy of 10 s have been obtained by
Langmuir-Blodgett deposition of the polysulphonium
precursor prior to final conversion to the conducting
polymer structure.W~

Polyphenylene
Scheme 3 shows an ingenious route to this polymer,
developed by ICI.~38~ This employs a bio-organic stage

148

In general studies on polyacetylene have concerned

copolymerisation methods, and have recently been
reviewedJ 39~ Both block and graft copolymerisations
have been employed, and for example block copolymers
of acetylene and isoprene are soluble in toluene,~ 4~as
are graft copolymers of acetylene and butadiene.141~

Heteroaromatic polymers
The oxidative polymerisation mechanism does not lend
these polymers to conventional copolymerisation techniques; and here strategies have involved composites,
laminates and blends. A diversity of methods have been
employed and the references given are simply typical

MATERIALS& DESIGNVoI.11 No. 3 JUNE1990

~C8H17

Other chemical processes

This is a relatively undeveloped area, but one which
exploits the facility for the chemical manipulation of
conducting polymers, not only before and during but
also after preparation. This is particularly significant for
polymers that are produced in neutral forms, which are
usually more chemically-reactive than the doped
conductive ones. Thus polyacetylene reacts with tosyl
methyl isocyanide to give j3-1inked pyrrole units, (46) with
dichloromaleic anhydride to give a fusible derivative128~
and with chlorosulphonyl isocyanate leading to a
hydrophilic material. ~28~These studies are part of the
considerable effort into these materials undertaken at
BASF laboratories.

~._~CH20(CH2) 20(CH2)2OCH3

H
a)

b)
(CH2JqSO3K+

c)

d)

--

--

(CH2)3 NHC(CH2)5NHC
e)

Fe

(iH2)6

(~H2)6

cj)

i)

Functionalisation
This last section concerns certain selected applications
of these materials and how chemical manipulations have
been employed to promote specific opportunities.
Though some substituted polyacetylenes have been
studied the greater toluence of the heteroaromatic
systems has led to their wider investigation. A series of
functionalised monomers are given in figure 12, while
functionalised dopants anions are given in figure 13.

h)

j)

Fig 12 Functionalised monomers leading to heteroaromatic polymers

examples. Thus the monomer may be imbibed into the
carrier polymer, which might be a polyester, and then
this is exposed to a gaseous oxidant, or to an oxidant in
solution. 42~Alternatively the oxidant is imbibed into the
polymer and is exposed to a liquid monomer, or
monomer vapour. 431 In addition polymerisation may
take place within latex particles. 44~Also inorganic fillers
have been coated. Appreciable conductivities are
claimed for some composites (eg :> 0.1 Scm -1) and
also semitransparency. Toughness and strength are
significantly improved, and the composite may be meltprocessable and mouldable.
For thin film systems electropolymerisation is still
feasible; and for example a composite with PVC is
obtained if the PVC is first spin-coated onto the electrode
before electrolysis. ~451
in summary a range of pyrroles, thiophenes, anilines
and similar have been found to produce composites with
a number of conventional polymers.

MATERIALS& DESIGNVoI.11 No. 3 JUNE1990

Microelectrochemical and electronic junction devices

Systems employing simple polymers have already been
described, but a further development concerns a
polypyrrole containing a pendant viologen group. ~47~
The polymer from 1-hydro-l' (6 pyrrol-l-yl) hexyl-4, 4'
bipyridinium bis hexafluorophosphate (structure 12d)
is significant, not only because it is the viologen group
that acts as the channel in the transistor device, and
because pH-sensitivity is observed, but also because this
work shows clearly the astonishing tolerance of pyrrole
towards complex functionality in substituent groups.
Even when a suitable homopolymer cannot be prepared
from such a monomer, it is often found that
copolymerisation with unsubstituted and unhindered
pyrrole will produce a polymer with significant functional
activity. Given the increasing number of substituted
monomers now available it is evident that a plethora of
potential systems are awaiting further investigation in
this and other applications.

Sensors
Sensing capabilities have been demonstrated for a range
of polymer types. Heteroaromatic polymers can act as
gas and solution sensors. Simple polypyrroles and
polythiophenes show conductivity changes upon
exposure to both oxidising gases (eg nitrogen dioxide)
and reducing ones (eg ammonia); 148,49) and there is a
reproducible response in solution to the sensing of the
anion used as dopant. ~5) More sophisticated are the
chemFETS described above, and even more sophisticated are the biosensors obtained by the immobilisation
of an enzyme and a suitable mediator in a polypyrrole
system.lS~ Thus polymerisation of pyrrole in the
presence of glucose oxidase and ferrocene carboxylate
as electron relay produces a glucose sensor in which
the enzyme still operates satisfactorily.~52~A ferrocene
group may also be attached directly to the polypyrrole
chain by use of a monomer such as structure 12e. ~53~

149

ICH2 H2
H12(PW12040)
a) Sulphonated polystyrene

b) 'Keggin type' polyacid

copper phthalocyanine derivative obtained from an

aqueous/alcohol preparation medium show surprising
cohesiveness and mechanical properties and are also
purple in colour suggesting that the optical properties
of the polymer system are influenced by the anion.too)
Porphyrins, ferricyanide and other complex anions have
also been used as dopants in polypyrrole.

Chiral recognition and optical activity

N" ~

-o,s..,~

This is an important aim, and asymmetrical functionalisation has been employed in heteroaromatic systems.
Thus the chiral thiophene monomer (strucuture 12g)
produces a polymer that can entantioselectively recognise the chiral dopant anion camphor sulphonic acid
(structure 1 3d).ml)

N,~:::: N

, ~

-so

-O3SCH20
d) Camphor sulphonate
c) Tetrasulphonated phthalocyanine

COO-

CH2OH COO- H2COSO3- "7

o I s Oo
oo
OSO3

[
SO3-

OH

NHSO3j N

e) Heparin

Fig 13 Functionalised dopants employed in polypyrrole

Electrode applications and electrocatalysis
Polyacetylene has shown activity in the oxygen
reduction reaction and has also been employed as a
photoelectrode in photoelectrochemical systems. The
electrode properties of simple conducting polymer
systems show a variety and have been reviewed. ~54~
Enhanced catalytic activity can be induced by
functionalisation, particularly for heteroaromatic
polymers. Thus metallic platinum particles can be
spread through a polythiophene matrix by electroreductive post-treatment, ms~while polypyrrole containing active transition metal ions such as Cu(l) can be
prepared by polymerisation of the extremely complex
monomer (structure 12f), where the metal ion is bound
by the chelating agent 2, 9 diphenyl, 1, 10 phenanthroline. The polymer can be reversibly demetallated. <56~
Other studies have employed the attachment of
different complexing agents to the monomer.
The very bulky biocatalytic porphyrin ring-system has
been attached to a polymerisable aniline monomer. ~57~
Catalytic activity may originate from the dopant
anion, thus heteropolyanions that are oxygen reduction
catalysts, such as the Keggin-type 12-tungstophosphates
(structure 13b) have been inserted into several
heteroaromatic systems including polyaniline.mm This
latter is interesting because utnil recently large or
complex dopants have been restricted to polypyrrole.
Polypyrrole is tolerant of extremes of dopant
characteristics, for example the very large tetrasulphonated phthalocyanine anion (structure 13c) which is an
electrocatalytic and photoactive species. ~sgJFilms of the

150

Transparency
Polymers that are transparent in the conducting forms
are of great interest for optical switches and shutters,
electrochromic displays, information storage and other
electro-optic applications. Monomer structure in heteroaromatic systems influences the effective band-gap and
fused thiophene systems seem particularly effective.
Thus polymers from isothianaphthene (structure 12h)m21
and from dithieno (3, 4 . b:3'4'd) thiophene (structure
12i)m3~ possess this facility. Other systems including
substituted aminophenol derivatives produce polymers
with claimed transparency.m4~
Transparency is also claimed for many composites
of simple heteroaromatic polymers, more straightforward with regard to monomer availability. Thus a
popypyrrole/polyester composite reportedly possesses
sufficient characteristics of conductivity and transparency for use as electrostatic recording material in a
reprographic application, mS~

Bio.acUvity
The polypyrrole/enzyme sensor has been described;
another ingenious bioactive system employs herapin,
the natural anti-blood coagulant (structure 13e) as the
dopant anion in polypyrrole. ~46) Potential applications
include artificial nerves and the masking of metalimplant surfaces against blood clotting and rejection.

Other effects
Semiconductor protection/anticorrosion
Polypyrrole coatings have been shown to protect several
kinds of photoelectrode surface against photocorrosion,
of benefit to the application of semiconductors in solar
cells.m41
Conducting polymers have also shown effects in the
protection of metal surfaces against conventional
corrosion processes.m6)
There are considerable opportunities for functionalisation; for example the inducement of biocidal
properties in protective surface coatings, roT)

Switchable membranes ('ion gates')

Because the mobilities of ions are different in the
oxidised and neutral forms of a conducting polymer, thin
films may be exploited as 'ion-gates' to control the flow
of ions between two electrolyte solutions, mm

MATERIALS& DESIGNVol. 11 No. 3 JUNE 1990

Photoactivity
Conducting polymers have been found effective in the
production of active photovoltaic devices. A typical
study concerns a polypyrrole/rhodamine B two-layer
ce11.~69)
Other effects have been observed and potential
applications proposed.

8
9
10
11
11a
12a

Conclusion
Electrically-conducting polymers are versatile materials
that display a unique range of properties. They are
attracting considerable interest, not only from physicists
because of theoretical aspects and the opportunities
offered for practical physical devices; but also from
chemists keen to exploit the range of chemical manipulations available in these organic systems.
New developments proceed at such a pace that only
selected aspects have been addressed in this review, and
only representative references given. Little mention has
been made of the body of work relating to the
optimisation of preparation procedures (eg ~0~) though
this is of considerable practical importance. Fundamental studies tend to concern well-defined systems
whereas the production of relatively exotic materials is
so rapid that arguably a proper appreciation of the
properties of each lags behind, to the detriment of
potential applications.
Several problems associated with the early development of these materials, namely reproductibility, stability
and processability are being addressed, and a better
understanding of relevant principles supports the drive
towards the wide range of practical applications under
assessme nt.
Other recent advances of significance in this technology include the production of oriented materials and
of highly conducting samples; and also the development
of short-chain oligometric systems that have similar
band-gap energies to the parent polymers. These latter
are well-defined materials, easier to purify, and have
fewer defects than the polymers; and increased charge
carrier mobilities have been claimedF ~) These results
also imply that high molecular weights, responsible for
many disadvantageous physical properties, may not be
necessary for the production of desired electronic
effects.
The field is still expanding as recent advances are
transferred to practical applications. As a final example
of future potential, preliminary results have been disclosed concerning the photochemical disposition of
polypyrrole on to any types of surface in a photolithographic-type of process. ~72~ This impinges on many
electronic applications, and further developments are
awaited.

12b

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MATERIALS & DESIGN Vol. 11 No. 3 JUNE 1990

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60
61

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