CHAPTER - I

INTRODUCTION
AND
LITERATURE REVIEW
1.00 INTRODUCTION AND LITERATURE REVIEW

1.01 Historical background

As a class of materials, polymers have had a late

beginning. They have come to play a vital role in the materials
field since the enunciation of the macromoI ecu Iar concept about
them by stau^dinger. Over the past six and seven decades, the
developments that have taken place in the area of polymer science,
technology and engineering, both in diversity and in depth are
viewed as phenomenal and spectacular.
Polymerization processes, leading to formation of
polymer molecules of different sizes, shapes and complexities
combine as much science as art. The molecular engineering
approach leads to tailor made synthesis of polymer molecules of
any preset structural pattern or sequence starting with simple
monomeric molecules (separately or in selected combinations)
through chain growth or step growth synthetic routes using
appropriate catalysts under specified conditions of time,
temperature and pressure and in the presence or absence of
selected additives.
It is also a common experience that a new range of
physical and chemical properties may be infused in or derived from
a preformed polymer simply by modifying it differently, chemically
or even physically, employing different chemical agents and
4> 5 4$
different physical agencies including heat , Iijht ' , high energy
7 &
radiations , mechanical shear and by judicious thermomechanical
treatments.
In the ear Iy phase of deveIopments, new poIymeric
materials were synthesized and diverse applications for them were
developed through a number of approaches covering, (a) new
monomers (b) copolymerization giving random, alternate, block and
graft copolymers (c) incorporation of a host of additives for
imparting extra plasticity or flexibility, additional stiffness,
higher mechanical strength, higher environmental stability and

1
economic advantage, (d) thermomechanical treatment enabling
accompIishment of some desired patterns and degrees of
organization of molecular aggregates of the material systems for
improved and wider application prospects, (e) chemical
modifications of the available polymers through (i) incorporation
of new functional groups in the chain molecules, (ii) modification
of the existing functional groups or their removal (iii)
cross I inking, and finally (f) blending of two or more polymers.
Multidirectional chain extension leading to the
formation of network structures through cross I inking of the chain
molecules of the polymer system may be viewed as a stabilization
process. Cross I inking makes a polymer usually more resistant to
heat, light and other physical agencies imparting to it a higher
degree of dimensional stability, mechanical strength and chemical
Zi.
and solvent resistance . The effect of cross I inking on physical
properties of polymers are primarily influenced by the nature of
the cross Iinking agent, degree of cross Iinking, regularity of the
networks formed and crystaI Iizing tendencies of the polymer
systems24.
The prospect of obtaining new polymers using new monomer
systems appears to have crossed its height. The compounding
approach is more versatile and in fact, compounding often holds
the key to higher performance and longer life of the polymers
employed in plastic, elastomeric, adhesive and coating
applications. In many systems use of low doses of selected
cross!inking agents or curatives are an important controlling
feature about compound design. For most of such systems,
cross I inking or curing is accomplished in the final stage of the
processing steps. Prospects of finding new material systems
meeting new processing demands and property ranges through
adoption of compounding and cross Iinking approaches with higher
sophistications in processing equipments are rated very high.

2
1.02 Polymerization

Polymerization of a vinyl and related monomers can be

4 g 7
readily activated by heat , light' or high energy radiations ;
the process is more conveniently accomplished using a selected
catalyst or initiator ' ' . Polymerization of vinyl and related
monomers is characterized by a chain growth mechanism and the
process and the nature of the polymer formed depend upon catalyst
systems used, nature of the monomer including its purity and
3 22
presence of specific additives etc. ' . The chain carriers may be
2 3 22
free radicals, cations or anions'' . For the present thesis,
the centre of attention will be free radical polymerization only.
Where two monomers are used together the product is a copolymer
usually characterized by a random sequence of the two monomer
units in the chain molecules of the polymer. The polymerization of
a monomer in the presence of a free radical initiator (I), may
3
proceed by a reaction scheme given below :

(a) Initiator decomposition or radical generation

I --------► 2R (D
followed by chain initiation,

r” + M --- ---- - R - Ml ( 2)

(b) Chain propagation

R - M4 + M RM„

R - + M rm5 ( 3)

R - Mn_* + M RMr

3
 (c) Chain termination

h.
RMn + RMro Dead polymer (4)

The basic reaction steps involved in the polymerization

reactions are :

(a) Decomposition of the initiator into radicals followed by

chain initiation.
(b) Chain propagation and (c). Chain termination, usually by
bimolecular mechanism.

i.02. 1 Chctin trans/er

Besides the three above basic steps, many practical

polymerizations also involve additional reactions known as chain
transfer reactions2'3'22. Chain transfer usually leads to lowering
of the average degree of polymerization of the polymer being
formed without materially disturbing the rate of polymerization;
the major consequence of chain transfer is an increase in the
number of polymer molecules for a given conversion under a given
3 22
set of conditions of time and temperature ’ . A chain transfer
reaction and the reinitiation reaction that follows may be
represented by the following equations :

Hr
M + XA MX + A (5)

A + M AM ( 6)

A chain transfer reaction may take place between the

V
chain radicals (M ) and any other species in the polymerization
system, viz., the monomer (M) present, the initiator (I) used, the
solvent (S) taken and the polymer (P) being formed.

4
 Chain transfer with the polymer being formed leads to
3 22
varied degrees of branching and cross Iinking ' . For chain
transfer with a preformed polymer having repeat units different
from those of the polymer being formed, one may readily obtain a
graft copolymer in which the newly formed polymer chains get
23-40
chemically linked to the preformed polymer usecf

1.03 Polymer modification

Modification of known and existing polymers is a very

interesting and challenging field of modern polymer research. It
is a common experience that no known polymer can satisfy diverse
property demands without selective and appropriate modifications,
41-5P
which can be accomplished either by physical means or by
. . , <so-ao
chemical means

i .03. i Hocii/icext ion fey physical means

Mixing together of a host of chemical additives to a

&4-G4.
poIymer4* 53 or bI ending of two or more different poIymers
81
together and spinning and drawing of suitable polymers to fibres
bring about physical modifications of the polymer molecular
systems and they are in practice for many years and are still in
the process of further developments for different applications. In
fact, polymers of any class, particularly that meant for plastics
and rubber applications, are seldom used in the pure/virgin form.
In many cases, they are mixed and compounded with selected
compounding ingredients before moulding, forming and coating etc.
The processing itself, covering mixing of the compounding
82**fi7
ingredients is dependent on the melt rheology of the base
polymer and the gross rheological behaviour of the mix. As for
blends of two or more different polymers the technology is
still in the developing stage and the scope for further
development appears very high indeed, if not unlimited. Elastomers
are being used to flexibilize rigid plastics and to improve impact

5
resistance of brittle piasticsBO,£>e 102; on the other hand rigid

plastics are being used for stiffening of elastomers. Conductive

fillers such as selected metal powders, flakes and whiskers,
conducting carbon blacks, carbon fibers and graphite powders are
also being used as fillers to make semiconducting and conducting
eIastomers . Many adhesives , seaI ants ,
110
coatings and composites have been prepared based on
blends of polymers; yet it is being realized that the polymers are
123 124
basically incompatible ' with one another.
Simple mixing together or blending of two incompatible
125—12?
polymers through melt mixing or by coagulation of mixtures
of their lattices result in products that are morphologically
120—144
characterized by phase heterogeneity . Many gross properties
of polymer blends such as tensile strength, elongation at break,
105—ISO
modulus and hardness etc. usually lie between those of the
constituent polymers, even though some synergistic or
antisynergistic behaviours are not altogether uncommon. The
molecular properties such as melting point (Tw) and glass
transition temperature (Tg) of the constituent polymers in blends
are often readily identified or distinctly indicated during
135 195 I9p
appropriate testing and evaluation of blends ' ' . It is far
from simple to appreciate whether or not the constituent polymers
fully retain their distinct or separate identities in the blends
or whether they undergo variable degrees of chemical interlinking
during thermomechanical treatments at the time of melt mixing.
Extraction of only one constituent polymer from a binary blend by
a selective solvent is not only difficult but it is often far from
complete, more so, if the constituent polymers are transformed
into interpenetrating polymer network (IPN)14° 104 systems. The
IPNs may be semi IPNs if only one of the constituent polymers in
the blend is cross I inked or full IPNs if both the constituent
polymers are separately cross I inked either simultaneously or
, . . , i.48-l.S4
sequentially

6
1.03.2 Modification £>y chemical means

The primary objective of a chemical modification of a

polymer is to preserve the ready-made or built-in structure of the
molecular chains, while modifying their chemical structures,
thereby incorporating changes or improvements in the material
properties to suit specific application needs. Chemical
modification of polymers may, however, involve varied degrees of
chain scission/chain degradation with or without different degrees
of cyclization of chain molecules or some changes in their
functional group patterns. To obtain the most desired product,
keeping particular application prospects in view, it is necessary
to control the overall condition of the modification reaction
meticulously.
Thus, nitration, sulphation, etherification and
esterification of cellulose give us products having properties
completely different from cellulose itself. Cellulose is
commonly insoluble and infusible but when chemically modified as
above, it becomes soluble and melt processable and consequently
its applicability is significantly widened and diversified,
similarly, special purpose rubber based products can be prepared
by different degrees of halogenation, cyclization etc. of diene
rubbers1O0,4jP. Polystyrene finds wide application as ion exchange
resin by sulphonation or ch I oromethy I at i on1G£,,1<*° and subsequent
quaternization with suitable amines. Polyethylene, a major
thermoplastic, is transformed into an elastomeric product commonly
known as "Hypaion” in the trade when suitably treated with
chlorine and sulfur dioxide (by su I foch I or i nat i on)i<M,1<a. Some
conjugated polymers***9 such as polyacetylenes, po I yd i acety I enes,
polyaniIines, polypyrroles and some poIyaromatics change from near
insulating to semiconducting or from semiconducting to conducting
characters when appropriately doped with suitable dopants.

7
1.04 Copoiymerization

The modification of a polymer by introducing a second

monomer during the polymerization process has long been used to
alter its physicochemical and mechanical properties and sometimes
<$2~<S<S,1<S4~4<S7
to achieve improved processing characteristics
Incorporation of a second monomer structure as repeat units in the
polymer (i.e. copolymer) molecules reduces overall molecular
symmetry leading to a lowering in the degree of crystallinity,
168-170
mechanical strength and softening temperature
Copolymerization is therefore viewed as a case of internal
plasticization. There is practically unlimited scope for variation
of polymer structure and hence polymer properties through
variation of feed monomer ratios in copolymerization. Besides
having random or alternate sequence of the two monomer units in a
binary copolymer, it is also possible to recognize and synthesize
copolymers having at least two other types of different sequences
23
and they are commonly termed as block or graft copolymers' .
The probability of finding a very long sequence of a
given monomeric unit in an ordinary random copolymer is usually
very remote except in the trivial case where one of the
constituent monomers is used in large excess. Methods of synthesis
of polymers containing long sequences of more than one specific
monomer unit are of great interest since they often lead to
polymers with properties widely different from those of the two
homopolymers or corresponding random copolymers or their selective
blends. Polymers with long sequences of two monomers (A and B) can
have two distinctive arrangements of chain sequences viz. (i)
22 164
Block copolymers ' (where the two different long sequences
follow one another along the polymer chain axis) and

AAA BBB - AAA - BBB - AAA - BBB -

(Schematic representation of a block copolymer)

8
 €5<$ <S6
(ii) Graft copolymers ' ' where long and short sequences of
monomer units of one kind appear as grafted on or pendant chains
I inked to the backbone of a long sequence of the other monomer.

- AAA - AAA - AAA -

I I I
B B B
B B B
B B B
I I I

(Schematic representation of a graft copolymer)

The ultimate aim of synthesis of a block or graft

copolymer is to obtain a desired copolymer free from the
corresponding homopolymers as far as practicable. Although the.
copolymer structures resulting from a graft and block
copolymerization processes are quite different, the former being a
chain branching process and the latter being a chain extension
process, each may be considered as a chain modification process
differing only in direction. Reactive groups according to their
presence as end groups or as side groups along the chain may lead
to formation of block and graft copolymers respectively.
Polymei—Polymer reaction through selected functional groups
present in them may also lead to the formation of block and graft
copoIymers.

1.05 Conducting polymer system

Most common polymers are good thermal and

electrical17* 17<S insulators and they are useful because of their
insulating character. The electrical conductivity range of good
insulators are very low and it ranges between 10 1 -104°0hm1cm1
or siemen/centimeter (S/cm). However, many metals and metal alloys
show high conductivities; highly conducting metals are
characterized by conductivities > 10 S/cm. In between the

9
insulators and good metallic conductors, there are a few metals or
some metalloids, some varieties of carbon black and graphite, and
special type of conjugated polymers or polymeric charge transfer
comp I exes, which may be cI assified as semiconductors. The position
of some insulators, semiconductors and conductors on the
conductivity scale is schematically shown in fig. 1.
The interest in the field of organic semiconductors
stems from the suggestion that the transfer of electron from
mo I ecu Ie to mo I ecu Ie may pI ay an important role in fundamentaI
physical processes in living organ isms17**. Single crystals of
purified anthracene and other condensed aromatic ring systems form
interesting objects of preliminary study of the fundamental
behaviour of charge carriers introduced into them; however, such
molecular crystals showing some degrees of electrical
conductivity, would be prominently brittle, low melting and easily
soluble. It is, therefore, obvious that a high polymeric system
obtained in a semiconducting and conducting form by virtue of its
intrinsic quality or consequent to dispersion of some conducting
fillers in them would combine the interesting electrical property
of molecular crystals of condensed polynuclear aromatic compounds
with the useful range of mechanical and thermal properties and
corrosion resistance of organic high polymeric systems.
A conducting polymer system as conceived above would be
a much desired product for use as corona shields or as a separate
layer on an insulator system in film, filament or sheet form
designed to prevent corona discharge and providing a conducting
177
surface for electroplating non conductors , Gas separation
1?B ±7P,iBO 181
membranes' eIectronic devices photovoltaic devices
. . . 182,183 184.
chemical/gas sensors , Iight emitting d i odes' and
185-187
batteries etc.
Highly conducting poIymer for use as high qua Iity
coatings, strong films and filaments are still in the process of
deveIopment. A practicaI or more obvious method invoIves
incorporation of metailic powders, flakes, whiskers or other
conducting fillers such as conducting carbon blacks, graphite etc.

10
 Copper—«f!0'
Iron
Mercury •1CT
102
Doped _
Germanium
4*10
1 cf2 Fbly acetylene
Fbly aniline
Silicon •io“4
156 Poly(P-
^gphenylene) Poly pyrrole
FblyCp-phenylene
1010 sulfide)

10-12

Polyethylene • 10"14
Nylon
10"16
10"18
Polystyrene'
tf.Scm -1

Fig. 1. Conductivity range of some selected insulating,

semiconducting and conducting materials.
into useful ranges of ptastomers and elastomers10*140. However,
such filled conducting compositions wouId have their own
limitations. Despite infusion of conductivity through
incorporation of conducting filler particles, the prominent
insulation or resistance character of the matrix polymer generates
heat during passage of electricity. Accumulation of heat and
consequent rise in temperature and thermal expansion finally cause
the conducting filler particles in such filled polymer systems
move further apart thereby leading to a dropping trend in
electrical conductivity with time100.
As for synthesis of inherently conducting polymers
(ICPs), two developing trends can be identified,
(a) Synthesis of conjugated polymers1**3
(b) Preparation of poIymeric charge transfer
, 187-100
complexes
The first approach i.e. synthesis of conjugated polymers
in offering good level of conducting character is based on the
fact that the electron delocalization favourably occurs as the
molecular system becomes more conjugated. Likewise, in charge
transfer (CT) complexes, a partial electron transfer occurs from
the donar site to the acceptor site of the molecule such as in a
crystalline structure of quinoline with tetracyanoquinodimethane
(TCNQ) which shows a room temperature conductivity of the order of
1 S/cm. By complexation of this nature in a high polymeric system,
a conductivity level in the upper side of the semiconducting range
can be readily achieved.

1.06 Carbon black filled polymer composites

Among the filled conducting polymer composites those

based on the use of different grades of conducting carbon black as
fillers100'10** have grown more in importance in respect of their
physical, mechanical, conducting and noncorrosive property
balance. Investigations over recent years have led two important
revelations regarding their electrical conductivity level, trends
of change in the same with variations in loading level and role of
other physical factors that influence their conducting
. . 101-103
character
,■ At low loading of carbon black, the conductivity of a
relevant polymer composite is essentially that of the matrix
dielectric medium itself. As the conducting carbon black loading
is increased, a percolation threshold or in other words, a
critical loading level or zone is reached wherefrom the
conductivity level begins to increase sharply as a function of
loading. In the lower loading zone, from or above which the
electrical conductivity shows a sharp increase or jump, the
conductivity is hindered or restricted by barriers to passage of
charge carriers (electrons) in the form of gaps between one carbon
black particle and another. As the loading is gradually increased,
the conducting carbon black particles draw closer though remaining
short of touching one another; electrons made to move through the
conducting composite must acquire enough energy to overcome the
potential barrier to jump out of carbon black aggregates and get
across the gap to be carried to the neighbouring carbon black
aggregates and so on. It has been further proposed that electron
passage in such systems is due to tunneling400.
Tunneling takes place almost exclusively between closely
neighbouring carbon bIack aggregates with little conduction
between aggregates which are separated by somewhat Iarger gaps and
as such the tunneling current has been shown to be an exponential
. 10E,104,1£«
function of gap width
At ordinary and at elevated temperatures polymer
compounds with normal loadings of carbon blacks show a decrease in
conductivity with increase in temperature which is believed to be
a consequence of increase in gap width between the conducting
carbon black aggregates while compounds with very low loadings
show the opposite behaviour.
The resistivity of polymers commonly used is very much
Iarger than that of the dispersed carbon black phase in the

12
(conducting) carbon black filled composites. The resistivity ratio
is in the order of 1010. As a consequence, minor differences in
resistivities between various types of carbon blacks are of little
consequence to the resistivity of the dispersion or the filled
composites. Thus, any change in electrical resistivity of the
carbon bIack filled composites upon variation of externa I
conditions must result from a change in average distance between
the carbon black agglomerates and hence form a change in carbon
black distribution.
In general, the degree of agglomeration of the carbon
black particles or aggregates decreases on rising temperature. The
deagglomeration may be viewed as a consequence of two factors :
(i) increased Brownian (particle) motion due partly to enhanced
thermal energy as the temperature rises; but it is primarily due
to (ii) significantly enhanced motion of the chain segments and
the branch units of the matrix polymer. It is also important that
in crystalline polymers, volume expans i on10<S is more significant
on melting. For carbon black composites from crystalline polymers,
the carbon black particles are restrictiveIy located in the
amorphous phase and hence a major rearrangement and redistribution
of the carbon black particles will expectedly occur over the
melting range as the crystalline phase disappears and the matrix
becomes homogeneous.

1.07 Rheology of carbon black filled composites

The rheological behaviour of carbon black loaded polymer

407—204
composites has been studied by different workers and it is
reported to be a very complex property, particularly at high
filler loadings. The factors100 that contribute to enhancement in
electrical conductivity may also lead to development of high melt
viscosity. Enhancements in both electrical conductivity and melt
viscosity are reported to be related to volume loading of the
20S
filler . The differences in melt viscosity at a given melt

13
temperature consequent to different levels of loading with carbon
black for a given polymer system follows a diminishing trend with
increase in rate of shear ' . With highly conducting
particulate carbons which are also highly porous, the volume
percent loading may prove to be illusive because of absorption and
accommodation100 of the matrix polymer into the pores of the
filler particles, more so at higher rates of shear. Different
carbons with different porosity level are expected to impart
different levels of dependence of melt viscosity and conducting
character of re Ievant poIymer composites on variation of Ioading
i i10D
I eve I
Some rubber-carbon black compositions have been reported
to exhibit strong thixotropic200,207 behaviours in contrast to
much different behaviours for the gum rubber.
For the rubber processing industry, a knowledge of the
flow properties of the compounded rubber is more important than a
knowledge of the same for the pure elastomer. In many studies, gum
elastomers compounded with only one additive are commonly
considered for assessment of their process rheology with special
reference to the role and influence of the particular additive in
modifying the said property of the base polymer (elastomer). Such
studies have revealed that incorporation of the reinforcing
fillers, particularly carbon black, results in (i) an increase in
apparent v i scos i ty1P7,2°a,20<>, (i i) prominent development of
thixotropic character200'207, (iii) reduction in die swell and
240
extrudate distortion , (iv) some enhancement in yield value at
high filler loadings and (v) increasing trend in
wall slippage210. The rheological features of elastomeric systems
may get complicated due to structural changes as a result of
mechanochemical and thermomechanical degradation of the filler
particles and of elastomer scorching, particularly in the
presence of curatives, and reduction in porosity of filler
particles due to occlusion of matrix polymer (elastomer) during
melt processing.

14
1.08 Inherently conducting polymers

Inherently conducting polymers (ICPs) also commonly

known as synthetic metals possess the electrical, electronic,
magnetic and optical properties of a metal while at the same time
exhibiting the physical and mechanical properties, rheological
features and processibiIity characteristics associated with a
24.7 21G
polymer. The applicability of the concept of "doping" ' is
the unifying theme that distinguishes the inherently conducting
polymers (ICPs) from all others. Addition of electron donors or
acceptors and sometimes protonic aci22<s causes doping
that results in dramatic changes in the electronic and magnetic
properties of ICPs; A notable increase in the electrical
conductivity level approaching the metallic conductivity range
then follows. Doping is commonly reversible; removal of dopants or
dedoping produces the original (base) polymer, usually, without
degradation of the polymer backbone.

i.08.1 Polyacetylene and s“ubsti txit&d polyacetylens

A simplistic approach to synthesis of an inherently

conducting poIymer is to remove one hydrogen atom from each carbon
atom in the chain molecules of polyethylene, leaving one spare
electron on each carbon atom constituting the chain backbone; the
electrons can be made to flow through the polymer mass so that the
hyphotheticaI polymer intermediate can be called a 'metallic
polymer’. A material of this kind can be synthesized by
227
polymerization of acetylene . In polyacetylene (PA), a
conjugated polymer, the spare electrons are held by formation of
alternate single and double bonds in the polymer structure.

nCH = CH------- CH = CH (CH = CH)n_z - CH = CH -

Acetylene polyacetylene (PA)

15
 The conjugated structure of PA makes it behave like a
semiconductor and not as a typical insulator, some of the «
electrons can be thermally activated giving rise to a small
electrical conductivity.
PA may exist in the following geometrical isomeric
forms :

Cis-transoid ( Cis-PA)
(Relatively unstable)

Trans-Cisoid
(Meta stable)

Trans-transoid (Trans-PA)
(Relatively s table)

Polymerization of acetylene catalyzed by Z \ g I ei—Natta

227 228 220
type catalysts , metal carbonyls , metal acetyl acetonate
280
complexes and glow discharge have been reported, The poIymer
can be obtained in powder, gel or film form. It is common Iy
insoluble and intractable having as well some degrees of

16
cross I i nk i ng284'232. As it is formed, it does not exhibit well
defined melting point. It decomposes gradually at elevated
temperatures and reacts readily with oxygen to give oxygenated
233
products
Doped derivatives of PA are ionic in nature and its
doping is viewed as a redox reaction247'23*. The net step in
doping is oxidation or reduction of PA molecules to polycations or
polyanions :

_ + Reductant , Oxidant ,+
-(-CH=CH—)- (Reductant) *---------------------------------------------
*'-{-CH=CH4' (Oxidant)
n n n

Appropriate Iy doped PA may show electrical

conductivities in the metal Iic range (10-103 s/cm). Substituted
235-23?
acetylenes (RiCsCRz, RCsCH) may also be polymerized by
initiation using free radical catalysts. Polymers of substituted
acetylenes are usually soluble in organic solvents and are
amorphous4*13. They also usually exhibit far I ower conductivities
than simple poIyacety I ene in both doped and undoped238'230 forms.
While PA is usually black, substituted poIyacety1enes are usual Iy
dL<S3
white or light yellow in colour . Unlike PA, substituted
240
poIyacetyIenes generally have high oxygen stability
Another interesting group of polymers are
poly(diacetyIenes) (PDA) which may be obtained in soluble form and
they have enabled casting of thin films from their
244—243
solution . In the solution cast form, the parallel packing
of the chain molecules of PDA crystal lattice is lost, thereby,
largely impairing the electrical conducting character of the PDA
films2**.

17
 Formation of poIy(diacetyIene) (PDA) from the
corresponding monomer is an example of a topochemical
polymerization in which a conjugate 1,4 addition of the 1,3 diyne
units occurs in the crystalline state on activation by heating or
irradiation of crystals using visible/UV light, ^-ray or x-ray.

R'
N
cf fr cw
/ * or R' c
c. c
v
/
A o
/*
heat or
I rrad iation
R' c
/V/
c
v <?
R
2?
/V
R“
V
R‘

The intense colour of PDA is attributable to the fully

conjugated linear C-backbone similar to PA with the difference
that the main chain of PDA comprises alternate double and triple
bonds interspaced with single bonds while that of PA comprises a
conjugated polyene structure. PDA crystals are not doped by all
conventional chemical dopants . The low doping efficiency in PDA
is a direct consequence of perfect, close packing of the PDA
crystal lattice that in a way restricts dopant diffusion. Solution
cast PDA films having less crystalline order allows a much deeper
penetration of dopant, whereby, electrical conductivity level as
high as 10 1 $/cm can be obtainedf84*'2*0.
Other than PA, the inherently conducting polymers shown
in Table - 1, such as poIy(ParaphenyIene) (PPP), PoIy(PhenyIene
vinylene) (PPV), Poly(Furan) (PFu), Polythiophene (PTh),
poly(phenylene sulfide) (PPs) and Poly(Pyrrole) (PPy) etc. also
undergo redox doping.

18
 Table - 1

Some Inherently conducting polymers

Name of Polymer Repeat Unit

/

Polyacetyle n e (PA) CH~C

Poly(iParaPhenylene)(PPP) *Ofc

PolyCPhenyleneV'mylen^PPV) V"
CH=CHt“
n

Poly Thiophene (PTh) r\

s n

Poly Pyrrole (PPy)

N
\H n

Poly Furan (PFu) r \

0 n

PolyCPhenylene Sutfide)(PPs) rys

n

Poly Ani line (PANI)

— H n
0-0

19
i.08.2 Polyaniline

The most important inherently conducting polymer from

the view point of high application potential ' is
polyaniline (PANI). It has drawn the attention of many workers in
recent years in respect of synthesis by chemical and electro-
1<S3 , .
chemical means and structural and electrical characterizations.
185
Its nonredox doping character is also an added attraction.
PANI's relatively low cost, ease of synthesis, processability in
dispersion forms and satisfactory environmental stability are also
some advantageous features204.
The base form of polyaniline (PANI) has the general
formuI a,

255—257
consisting of reduced (I) and oxidized (II) repeat units
The average oxidation state (1 —y) may vary from zero (to give
completely reduced polymer characterized only by the repeat unit
I) to 0.5 (to give the "half oxidized" polymer characterized by
1 : 1 alternating sequence of I and XI) to one (to give y=0 and
completely oxidized polymer characterized by the repeat unit U
only200207). For the presence of 1 : 1 alternating sequence of I
and II repeat units in PANI, the polymer is called emeraldine. The
imine nitrogen atoms can be protonated in full or in part to give
the respective salts, the degree of protonation being dependent on
J255—257
oxidation state and pH of the aqueous (acid) medium usecT
The partly protonated emeraldine hydrochI oride salt is
prepared readily in the form of dark green precipitate by

20
 2BB-2<Si
polymerization of aniline by oxidative coupling in aqueous
acid (HCI media) using such oxidizing agents as (NH^SzOb, FeClg
etc. as polymerization catalysts. It can also be prepared
electrochemical Iy from aniline. The following different
structures of fully protonated emeraldine may be obtained for use
of > 1 (N) HCI for doping :

Bipolaron (dication) Constitution

A separate Polaron form

(Poly semiquinone radical Cation)

From possible alternative resonance forms of the

separated radical cation structure, it follows that the overall
structure would have extensive spin and charge delocalization
resulting in a half filled polaron conduction band2*8. The
conductivity of PAN I increases with doping and the conductivity of
the doped polymers increases monotonicaI Iy with molecular weight
21G
up to a molecular weight of 1,50,000 . PAN I is reported to have
been produced in aqueous dispersion form through polymerization of
monomer aniline by oxidative coupling in aqueous acidic media
using the support of some water soluble polymers such as methyl
cellulose , poly (vinyl alcohol) , poly (acrylic acid) ,

21
 , , 267,2<Sfl „2<SO-272
poly (vinyl methyl ether) , poly (ethylene oxide)
etc. PAN I has application potential for electromagnetic
interference (EMI) shielding, in gas sensors, in molecular
electronics, in electrodes for rechargeable batteries and in
180,210,240-252,273
static charge dissipation etc.
Charge transport in inherentIy conducting polymers
(ICPs) is believed to occur through a combination of two primary
. . 274
mechanisms ,

(i) Propagation of charge along the polymer chain.

(ii) Hopping of charge between neighbouring chains.

To a large extent, the lengths of the conjugated chain

segments determine whether propagation along the polymer or
interchain hopping will be the dominant mechanism of charge
transport and hence electrical conductivity. A higher molecular
weight obviously favours enhanced charge propagation due to
lengthening of the segments of conjugation. The same may also be
accomplished in a way by stretching the conjugated polymer
segments thereby allowing enhanced order of charge transport.
248
Stretching of conducting polymers of a given range of molecular
weight often results in increase of electrical conductivity by one
order of magnitude. In the I CP system's, disruption of the
conjugation along the polymer backbone can inhibit charge
propagation and thereby reduce electrical conductivity.
275-200
The formation of blends and composites of
inherently conducting polymers (ICPs) in nonconducting polymer
matrix is also used to prepare modified polymeric materials. These
composites may appear more handy and of practical advantage over
the homogenous materials. They often demonstrate improved
204
environmentaI stabiIity , resistance to mechanicaI
loading and may even acquire good optical property with
transparency if appropriately constituted; often the advantages so
accrued will far outweigh a small decrease in conductivity level
on blending. Sometimes, uniform dispersion of an otherwise

22
 ' '«D _

intractable inherently conducting polymer in a nonconducting

stretchabIe poIymer matrix is readi Iy prepared2**8-87*; the smaI I
lowering in the conducting level due to the presence of the
nonconducting matrix may also be more than compensated on
application of stretching, that imparts an orientational effect248
and thereby causes a notable enhancement in electrical
conductivity.

i.08.3 Objective of the present thesis

The research work embodied in- the present thesis was

undertaken with the objective of making some studies relating to
polymerizations and polymer modifications, keeping synthesis or
preparation of some conducting polymeric systems in view.
The investigations were planned for implementation under
two major heads :

(i) preparation and physical, mechanical, rheological

and electrical characterization of conducting carbon black filled
elastomers based on ethylene-propylene diene monomer system (EPDM)
and ethylene vinylacetate (EVA) copolymer and,

(ii) synthesis and physical, chemical, structural,

morphological and electrical characterization of polyaniline
(PAN!) as an inherently conducting polymer in aqueous solution or
dispersion of high stability and easy processibiIity using the
support of a water soluble polymer, say polyacrylamide (PAAm) and
(NH4)zS20b .as the oxidant and catalyst.

23