chapter -3

Conducting polymers (MScE5 307)
Chapter Three
Syntheses and Processing of CPs
School of Mechanical Chemical and Materials

Engineering
Materials Science and Engineering Department
Prepared by : Wegene Lelisa
Date : …………………….
12/28/2023 Conducting polymers 1

3. Syntheses and Processing of CPs
OUTLINE
3.1. Electrochemical Polymerization.
3.2. Chemical Polymerization.
3.3. Dopants and Alternative Doping Techniques.
3.4.Composites
3.5.True Copolymerizations.
3.6.In Situ Polymerization.
3.7.CP Blends.
3.8. Bulk and Commercial Production.
3.9. Solubility and Processing of CP.


 Electrochemical Polymerization Mechanisms.
 Generic Electropolymerization Mechanism.
 All electrochemical polymerizations of CPs (which are nearly always oxidative

polymerizations) appear to follow a generic reaction pathway.
 This pathway shows the following common features or follow three step
of polymerization: For example for poly pyrrolle P(py).
1. The initiation step, (monomer) radical generation, via electrochemical

oxidation.


 Electrochemical Polymerization Mechanisms.
Step 1. The initiation step, (monomer) radical generation, via electrochemical

oxidation.
Or
Both of the way of representing pyrrole/reaction is same


Step 2a. Propagation :-Radical–radical recombination is take place and loss of

two protons from the radical–radical intermediate species, generating the dimer or
bi-pyrrole .
Step 2b. Propagation electrochemical oxidation of the dimer, generating

another, “oligomeric” radical;combination of this or similar oligomeric radicals
with monomer radicals form trimmer pyrrole.


Step 2. Propagation electrochemical oxidation of the dimer, generating another,
“oligomeric” radical;combination of this or similar oligomeric radicals with
monomer radicals form trimmer pyrrole.


 By repeating step 2a and step 2b we building up the polymer.
 The radical coupling between oligomeric pyrrole species is favored

since the oxidation potential of oligomeric or polymeric pyrrole species
is lower than that of the monomer.


 3.Termination:-via exhaustion of reactive radical species in the vicinity of

the electrode and accompanying oxidative or other chain termination
processes.
 Once the chain length of the oligomers exceeds the solubility limit of the
solvent, precipitation of PPy occurs.


 Other generic mechanism of CPs
 Once the initiating electrochemical potential is applied, the population of
radical cations is likely to far exceed that of neutral monomer in the vicinity of
the electrode surface.
 Electron transfer kinetics for electro-
oxidation of the monomer is rapid.
 Whereas in Chemical polymerization, the

concentration of monomer far exceeds that
of radical, and thus radical– monomer
combination (generating another radical) is
more likely to be the next propagation step
after radical generation.

 Factors Favoring Polymerization and No Polymerization.
 Electropolymerization :-Is a nearly generic technique usable for quick

and rapid production of CPs.
 Not all organic monomers undergo electropolymerization.
 The keys to why certain monomers electropolymerize at all to yield CPs

lies in a combination of factors those are:-
 Stability of the radical ions generated in the first step and
 The oxidation potentials for generation of these polymers.

 Carbazole, furan, and indole whose radical cations are less well stabilized
compared to pyrrole produce poorly formed polymers with low conductivity
on electropolymerization.


 The oxidation potential of indole is comparable to that of pyrrole (in

acetonitrile +0.9 V, +0.8 V vs. SCE) and that of furan comparable to that of
thiophene\ (+1.85 V vs. +1.6 V vs. SCE).
 The electrooxidation of benzene, to produce poly( p-phenylene), requires a
very high potential normally effected only in media such as HF or liquid SO2
, and thus chemical polymerization is preferred for this CP.


 Steric crowding by the large macrocycles can also hinder
electropolymerization or yield polymers of low conductivity.


Table :-Solvents and electrolytes used for Poly(pyrrole) polymerization. The list
is representative and by no means exhaustive.


 Proton removal renders the dihydro-dimer or dihydro-oligomer formation.
 Therefore ,proton acceptors including water, bases such as pyridine or

lutidine, and other nucleophiles enhance electrochemical polymerization.
 Limitation:-Excess water may however lead to premature oxidative

termination of the propagating polymer chain.
 As chain length increases, oxidation potential decreases. Thus ,the dimers and
subsequent oligomers produced invariably have oxidation potentials lower
than (more negative of) that of the monomer.


 The oligomer, once produced, is rapidly oxidized at the electrode to its
radical cation. It then is more likely to react with monomeric radical cations,
which are in abundance, rather than other oligomer radical cations.
 Note that:- Attempts to electropolymerize dimers or trimers directly, e.g.,

bipyrrole or terpyrrole impossible but, polymerize these oligomeric pyrroles in
the presence of monomer but at a potential at which the monomer is not
oxidized.
 A surfeit of monomer radical cation appears to be necessary for successful
electropolymerization.


 Solvents and Electrodes
 The solvent of electropolymerization is an important factor governing not only

the quality of the CP obtained, but also its conductivity, morphology, and
subsequent electrochemical and chemical behavior.
 Acetonitrile is one of the most versatile polymerization solvents for several

reasons:
i) Good nucleophilicity, facilitating proton removal in the polymerization
ii) poorer solubility or insolubility of nearly all CPs as well as of oligomers; and
iii) relative dryness, with sufficient water content for effective polymerization
without early termination


 Solvents such as propylene carbonate (PC), for instance, exhibit high

solubility of oligomers and of reduced polymer and very high water
content; thus poly(diphenyl amine) will electropolymerize in acetonitrile but
not in PC.
 Solvents may also be too nucleophilic: Besides its high solvation capability
for even doped CPs, dimethylformamide (DMF) is also a poor
electropolymerization solvent due to high nucleophilicity; if this is reduced with
addition of protic solvents, electropolymerizations are observed.






 If the monomer had poor solubility in the solvent even in an ideal solvent like
acetonitrile then mixed solvents are used primarily to facilitate solubility.
 Mixed acetonitrile + aqueous HCl solvents have been used for polymerization
of the aromatic amine 4-amino-biphenyl.


 Hydrocarbons such as toluene may be mixed with acetonitrile to facilitate
solution of monomers such as pyrene.
 Selection of Working electrode
 Any electrode which does not undergo oxidation at a potential equal to or less
than the oxidation potential of the monomer can be used,
 Several electrodes are preferred for specific applications.
1) For electrochromic and initial characterization studies, a transparent

electrode such as indium tin oxide (ITO) or Au/Pt on glass is preferred.


2) For purely electrochemical characterizations, Pt wires, on which adhesion of

nearly all CPs is excellent, are preferred.
3) For preparation of freestanding films:-graphite, special (e.g., basal-plane or

pyrolytic graphite), or glassy carbon may be preferred.
4) Stainless steel electrodes have been used for corrosion studies, and
5) n-Si for semiconductor applications


 Adhesion to such electrodes can be improved by using standard
“semiconductor rinses,” e.g., soap water, DI water, acetone, methanol, and
acetonitrile.
 Selection of Counter electrode
 Pt coil or flag electrodes is frequently used for electrochemical

characterization studies Cu electrodes are used in some cases.
 Three-electrode mode is used in most electrochemical work, while a two-

electrode mode finds use in bulk syntheses or emulation of
electrochromic or other end-use devices.


 Potentiostatic, Cyclic, and Galvanostatic Polymerizations and
Threshold Concentrations.
 A potentiostatic (constant potential) deposition mode generally yields

polymer with the most consistent morphology.
 Repeated potential cycling, typically to a few hundred mV beyond the

monomer oxidation potential, is also commonly used, yielding CP films almost
comparable to potentiostatic deposition.
 Constant current, i.e., galvanostatic, deposition can be used when control of

charge (e.g., for thickness) is desired, but it is almost universally accepted that it
yields polymer of poorer morphology, conductivity, and general quality.


 Typical monomer concentrations taken during electropolymerization range

from as low as 1 mM to as much as 1 M.
 Dopant electrolyte concentrations must be from at least 2 X to up to 1000
X monomer concentration. E.g,Typical values are 50 mM monomer and 200
mM dopant electrolyte.


 The galvanostatic polymerization data show that threshold concentrations
for polymerization can vary substantially for different monomers but are
generally above ca. 1.0 mM.
Fig. Galvanostatic
electropolymerization data for
thiophene and bithiophene


Dopants
 During a typical electropolymerization, the net charge transfer is a little in
excess of that indicated stoichiometrically, due to the additional oxidation
(and doping) that occurs during electrochemical preparation of CPs.
 For example, while P(Py) and poly(azulene) both stoichiometrically require two
electrons per monomer for electropolymerization.
 Experimentally a charge of the order of 2.3 electrons per monomer is found to
be consumed.
 The excess 0.3 is used to effect a 30% doping of the polymer.


Dopants
 It is best to incorporate the final dopant to be used during electropolymerization
itself.
 Dopants can also cause a substantial shift in redox potential of a CP.
 For example, poly(4-amino-biphenyl) P(4-ABP) with perchlorate dopant has
a redox potential of +0.6 V vs. +0.0 Ag/AgCl (in acetonitrile), which shifts to
+1.1 V vs. Ag/AgCl with tosylate dopant.


Dopants

 Electrochemical Monitoring of Polymerization
 Electrochemical monitoring of electropolymerizations is most effectively

done using cyclic voltammetry (CV) and yields useful mechanistic information,
which can be applied to interpretation of electrochemical and electrochromic
behaviour of new CPs .
 Simple case of preparation of a CP film via potential cycling, using a slow

sweep rate.
 On the first anodic (to (+) potential) scan, the predictable oxidation peak,
corresponding to production of the radical monomer cation, is observed.

 On the reverse, cathodic (to (-) potential) scan, the reduction peak
corresponding to the radical cation is rapidly consumed in a subsequent
(chemical) reaction.
 The oxidation peak progressively diminishes and shifts to higher potential

on subsequent scans, indicating that monomer is rapidly depleted in the
vicinity of the electrode and converted to radical cation.
 Thereafter its oxidation is limited by diffusion of monomer from bulk solution.

Fig:-Representative electropolymerization via potential

cycling, here for a poly(aromatic amine).


Fig:-Scan rate dependence of

cyclic voltammograms Scan rate:
(a) 10, (b) 5.0, (c) 1.0, and (d) 0.2
V/s .

High scan rate

 In above Fig (a), at a fairly high scan rate of 10 V/s, the first few anodic
scans show the expected monomer oxidation peak, ca. +0.65 V (the most
positive peak), corresponding to generation of the radical cation and
steadily diminishing with each scan.
 The reverse cathodic scans however also show the corresponding peak for the
reduction of the radical cation, at ca. +0.55 V.
 At this scan rate this species is not depleted rapidly enough to not be
detected.

3.2. Chemical Polymerization
 Condensation polymerization mostly Chemical Polymerization also called

step growth polymerization.
 Addition polymerization Mostly Electrochemical Polymerization and some is

chemical polymerization also called chain growth polymerization.
 Facts, In the bulk of the reaction environment, where the radical initiators are
generated, the concentration of monomer is in excess, unlike in
electrochemical polymerizations:

 The more common typical chemical polymerization is relatively simple, involving

monomer and an oxidant (usually also the dopant) in a suitable solvent medium,
frequently aqueous, and temperatures in the region of 20 C to +80 C.
Typical example
 Monomer – Aniline 0.5 M

 Oxidant - ammonium peroxydisulfate ((NH4)2 S2O8)
 Dopant - Aqueous p-toluene sulfonic acid solution
 Temperature – Room temperature
 Reaction time – 2 h
 As reaction temperature rises, the reaction bath is cooled with an ice bath.


Typical example
 Finally, the polymer is filtered, washed with dopant electrolyte solution, and
dried in vacuum at 60oC.
 The polymer is then neutralized with 2 M NH4OH to yield the emeraldine base
form of P(ANi).
 Limitation :
 Control of morphology, conductivity, doping, and related factors is however a little
more difficult in chemical polymerizations,
 with slight changes in temperature, concentration, and other factors yielding
substantial differences in polymer properties and even identical synthetic
procedures never yielding exactly the same polymer each time.

Chemical doping
 Chemical doping can be used to incorporate new dopants not present in the
original synthesis into the CP.
For example,
 P(ANi) in its emeraldine oxidation state is convertible into Cl- , SO4 2- and
acetate doped P (ANi) by simply soaking for 6 h. in the corresponding dilute (ca. 1
N) acid solution.
 Poly(3-bu-thiophene), chemically polymerized in its near-neutral state, can be

chemically doped by I3 via simple immersion in methylene chloride solvent
containing excess iodine and by SbF6 via simple immersion in a nitromethane
solution of nitrosyl SbF6.
 Optimization in Solution Polymerizations
 The effect of solvent and of the redox potential of the polymerization

medium on CP quality and morphology can be very strong.
 Chemical synthesis of P(Py) using anhydrous FeCl3 as oxidant-cum-dopant

in various solvents they found that while methanol appeared to be the best
solvent for optimal conductivity and morphology.
 Equilibrium redox potential of the solution, controllable via the relative

concentrations of the monomer and oxidant.

 For example addition of FeCl2 as oxidant was a more important determinant

of polymer quality.
 It found that at a redox potential of +0.5 V vs. SCE, optimal polymer of
conductivity 220 S/cm as showed in Fig.
 The polymer so produced also showed a more ordered, fibrillar morphology,
and stretched films showed greater tensile strength and high flexibility.


 Oxidation potential/conductivity relationship

in poly(pyrrole) synthesis. Open circles
show the conductivity of prepared
poly(pyrrole) when the oxidation potential of
the solutions was controlled by changing
solvents.
(1) DMA, (2) DMP, (3) ethylene glycol, (4)

MeOH, (5) Et-OH, (6) water, (7) pentanol, (8)
octyl alcohol, (9) 0.7 M Fe(ClO4)3, (10)
benzene, (11) acetone, (12) acetonitrile, and
(13) chloroform

 Synopsis of Chemical Syntheses.
 A representative chemical syntheses of CPs to impart an idea of the very

wide variety of synthetic methods used.
 Perhaps the greatest variety of methods has been applied to the synthesis of
poly (acetylenes) (P(Ac)) and poly(diacetylenes) (P(DiAc)).
 The most well known is the Shirakawa method, which is an adaptation of

Ziegler–Natta polymerization used for stereospecific polymers.
 Stereospecific polymerization involves directing the monomers in their

approach to the growing polymer chain by using catalyst.

 In a typical synthesis, a solution of Ti(OBut)4-Al(Et)3 (4:1) is used to coat a

reaction flask cooled in dry ice/methanol (78 oC), with controlled thickness.
 Acetylene is introduced and removed at the end of the preselected reaction

time.


 One of the simplest precursor routes to P(Ac) is illustrated in Fig below is the
precursor in this case being soluble, processible poly(chloroethylene).
Fig:-Typical dehydrochlorination routes to poly(acetylene)
 Condensation polymerization route for synthesis of P(Ac) and P(DiAc) is

not successful so – nearly all methods are variants of addition
polymerization.

 Unique Chemical Polymerization Methods
 There are various unique polymerization techniques available, depending

on the researcher’s creativity, novelty/innovation arises every now and then
 Photo-polymerization of photosensitized polymerization of pyrrole by

Ru(bpy)3 3+ carried out using a 490 nm dye laser in a matrix of Nafion, which
also served as the dopant.

Fig:- Example of direct, photosensitized polymerization of pyrrole.

 A variation of the optimization of the equilibrium redox potential of the

polymerization solution can be achieved by using solvent evaporation to
change this potential (as solvent evaporates, concentration of oxidant and
electrolyte change, thereby changing redox potential).
 A polymerization solution (monomer, electrolyte, oxidant, solvent) can be cast
onto an appropriate substrate, and as the solvent evaporates, polymerization
occurs, usually indicated by a remarkable color change.


Examples:
1) FeCl3 polymerization of pyrrole in a poly(vinyl acetate) (PVAc) matrix in

methanol solvent, yielding a P(Py)/PVAc composite with a claimed
conductivity of 10 S/cm at P(Py) proportions of only 5%.
2) Spin coated P(Py)/phosphomolybdate films on insulating substrates

(phosphomolybdic acid (12 MoO3  H3PO4 ) as the dopant-cum-oxidant in THF),
yielding ca. 100 nm thick P(Py) films with claimed conductivities in the 15–30 S/cm
range.

3.3. Dopants and Alternative Doping Techniques
 Common Dopants.
 In electrochemical doping, tetrafluoroborate or perchlorate can be

introduced as Li+ or tetraethyl ammonium Et4N+ salts used as
electrolyte, while in a chemical polymerization, copper (II)
tetrafluoroborate CuBF4 may be used.
 AsF6 - will be introduced as AsF5 vapor for chemical polymerization

(e.g., for poly(acetylene)), while for electrochemical polymerization,
LiAsF6 would be used as the electrolyte salt.

 Common Dopants
 FeCl4 is invariably introduced chemically in solution as FeCl3 ,

functioning as dopant as well as oxidant.
 In the case of several poly(aromatic amines) such as P(ANi), dopants

such as sulfate, chloride, and hydrosulfate are invariably introduced
during electrochemical or chemical synthesis in the corresponding
acids; in such cases, when an additional dopant electrolyte (such as
perchlorate) is present, co-doping occurs, with the proportion of dopants
closely related to their initial concentrations.


Table 31.3 Common dopants studied in prior work with CPs.


Table 31.3 Common dopants studied in prior work with CPs.

 Uncommon or Unusual Dopants

 Novel dopants into CP systems imparts special or unusual properties to
them.
Examples:
1) Doping of P (ANi) with phospho tungstic acid (using the conventional persulfate
oxidation in phosphotungstic acid), yields interesting complexes with W (VI) active
groups.
 While the CP is shown to have catalytic activity, it is poorer than that of the
dopant alone, and the CP’s conductivity, stability, and other properties are poorer
than that of P(ANi) with a more conventional dopant.

 Uncommon or Unusual Dopants
2) Unique HF2 (from H2 F2 /water) and chlorometallate (MCl4 , M = Al, Fe,

Tl, In, from LiCl/MCl3 /nitromethane) dopants have been reported for P(Ac).
etc.
 Alternative Doping Techniques
 The most common alternative doping techniques used have been
1. Ion implantation,
2. photochemical doping,
3. heat treatment,
4. solution doping, and
5. “dry doping.”


I. Ion implantation:-
 It is via bombardment of a substrate by high-energy ions which then implant in
the substrate’s lattice, forming covalent bonds there with, is a technique widely
used in the semiconductor and microelectronic fabrication fields.
For Examples
1) Benzimidazobenzophenanthroline-type ladder polymer, BBL, and the rigid-

rod polymers poly( p-phenylenebenzobisthiazole) (PBT) and poly( p
phenylenebenzobisoxazole (PBO) were bombarded with Kr+ ions of an energy of
200 keV and flux 4 x 1016 /cm2 , obtaining doped polymers with broad metallic
band behavior. Showed RT conductivity of 140 S/cm but poor environmental
stability.

Benzimidazobenzophenanthroline(BBL)

 Other examples of ion-implantation doping are in which P(ANi) was

bombarded with 100 keV Ar+ and 24 keV I + ions at fluences of ca. 1016/cm2 .
 While the Ar+ ions effected a low, “damage-induced” conductivity, the I+ ions
effected a “permanent,” environmental stable conductivity increase, from the
undoped polymer, of 12 orders in magnitude.

II.Photochemical doping:-
 involves treating a CP with a dopant which is initially inert but rendered an
active dopant by irradiation.
 These dopants are usable with common CPs.
For Examples
 Diphenyliodonium hexafluoroarsenate (in CH2Cl2 ) or triarylsulfonium salts

(in aqueous medium), both of which are rendered active by UV radiation.


III.Chemical solution doping:-
 Can be used to incorporate new dopants not present in the original synthesis
into the CP following polymerization.
For example
 P(ANi) in its emeraldine oxidation state is convertible into Cl- , SO4 2- and
acetate doped P(ANi) by simply soaking for 6 h. in the corresponding dilute (ca. 1
N) acid solution.
 P(ANi) has also been doped by such dopants as camphorsulfonic acid (CSA)
by simply mixing emeraldine base with CSA in m-cresol solvent.


IV.Heat Treatment Doping:-
 An interesting method of doping, that of heat treatment, has been applied

mainly to ladder-type CPs such as benzimidazobenzophenanthroline-
type ladder Polymer (BBL).
 When subjected to a heat treatment of 50 C increments lasting 2 min in a

calorimeter chamber, yielded a conductivity of ca. 10-8 S/cm with 100 C
treatment and a ca. 10-4 S/cm conductivity with 350 C treatment, reverting
again to ca. 10-8 S/cm at 600 C.


IV.Heat Treatment Doping:-
 The enhancement of conductivity by heating has been ascribed by the

authors to “improved structural order and thermally excited charge carriers”
but may also be due simply to “impurity doping”, i.e., the creation of oxidation
centers which then function as dopants (e.g., C=O or C + -O-bonds then
yielding oxide dopants).
Benzimidazobenzophenanthroline(BBL)

IV.Dry Doping:-
 It is similar to the photochemical doping described above, with heat used to

generate an active dopant from an inert species.
For example
 Dry doping of P(ANi) (used in photoresists) with amine triflate salts, which
are then thermally decomposed to yield the active dopant (triflate).

3.4. Composites
 A composite, as defined by polymer and materials scientists, is a combination

of two constituents, an adhesive matrix or resin base component and a
fiber-reinforcing component.
Examples of composites.
 Natural wood
 graphite-epoxy aircraft composites,

 and fiberglass (glass fibers in a
thermoplastic or adhesive matrix)

3.4. Composites
 The word “composite” is used freely by CP scientists to denote any
combinations of CPs and conventional polymers, which are in fact either
simple blends (mixtures), host–guest combinations (host polymer template with
guest CP deposited therein), or genuine(true) copolymers.
 Blends having a conductive component (e.g., a CP):-Admixed into a non-

conducting host matrix, as more of the conductive component is added, there is a
point at which the conductivity of the blend experiences a sudden rise, eventually
levelling off to a limiting or saturation value.
 This point is denoted as the percolation threshold.

3.4. Composites
 Percolation thresholds for CP blends generally lie in the 5–15% (w/w) region
 e.g., a blend of P(ANi) and nylon 12 shows a percolation threshold of 5%

(w/w) P(ANi) with conductivity at 20% approaching that of pure P (ANi), values
that are typical.
 These thresholds are generally lower than corresponding thresholds for

“traditional” conductive polymer blends, i.e., those using carbon or metal
as the conductive component, which are usually in the 15–30% w/w range.

3.4. Composites
 CP composites may be prepared via chemical or electrochemical

polymerization.
 Chemical polymerizations are usually in situ, with a host conventional polymer,

such as poly(ethylene terephthalate) (PET)
 Typically used to sorb monomer vapors, e.g., of pyrrole, then exposed to
oxidant, e.g., FeCl3, which results in polymerization of the sorbed monomer.
 Catalytic in situ chemical polymerizations, with, e.g., a transition metal catalyst

sorbed into the host polymer and then exposed to monomer vapor, are used
primarily for P(Ac) composites.

3.4. Composites
 Electrochemical polymerizations:-usually involve polymerization from

monomer solution into a host polymer that is adsorbed or coated onto a
standard metal electrode such as Pt.
 True copolymers :Are synthesized via conventional polymer and organic

synthetic techniques.
 Usually incorporate a CP monomer and the monomer of a conventional
polymer (e.g., ethyl methacrylate or styrene) one solvent and then follow
conventional synthesized techniques to develop a composite conventional
polymer and CPs .

3.5.True Copolymerization
 Copolymers can be synthesized using electrochemical or chemical

methods using a mixture of several monomers rather than a single monomer.
For Example:
1) A good example of true copolymers is acetylene/ethylene copolymers prepared by

the common Ziegler–Natta route described above but using mixtures of varying
proportions of ethylene and acetylene as the starting monomers.
 At a 20% acetylene composition, these yield CPs with conductivities of 10-3 S/cm.

2) poly(methyl-methacrylate/acetylene) copolymers were synthesized by using

methyl methacrylate monomer but using Na-doped poly(acetylene) as the
initiator for anionic polymerization.
3) Copolymer of acetylene and isoprene which is castable from solution and

dopable to ca. 5 S/cm.
4) Block copolymers of styrene and acetylene which are soluble but poorly
conducting have been prepared again using Ziegler–Natta catalysts.

 Pyrrole–styrene graft copolymers was synthesized using a polystyrene
derivative
 (1) derivatized with a pendant pyrrole group
 (2), and the derivative then copolymerized electrochemically with pyrrole monomer,
yielding the final “graft copolymer.”
 Conductivities, as high as 0.4 S/cm, and acceptable mechanical properties are

reported for these copolymers,
 In fact ,this example of a “template polymerization.


 It is an important method for processing of CPs as coatings.
 It is important because it is one of the few practical applications of CPs

implemented successfully on a commercial scale.
 In situ polymerization of CPs on varied substrates, ranging from individual textile

fibers and cloth to thermoplastics.
 Highly durable and uniform CP coatings on varied substrates, is in fact superior

to the many highly elaborate processing and solution methods.


 A good example of this practical implementation is the series of “Contex”-
trademarked P(Py)- and P(ANi)-coated textiles marketed by Milliken
Research Corp., a textile company.
 The basis of the deposition procedure is adsorption of monomer and/or dopant

and/or oxidant on the substrate surface, at which chemical polymerization then
occurs.
 By this process, highly conductive CP on the substrate of thickness 1μm is

obtained.

 The coating proceeds equally well on substrates ranging from rayon and cotton
to polypropylene, polyester (e.g., poly(ethylene terephthalate)), nylon,
Kevlar, and quartz fiber; coatings on all these substrates have been successfully
produced.
 The Milliken researchers postulate a mechanism in which the free radical
monomer or oligomers are the actual species adsorbed on the substrates but
provide little strong evidence for this.

 In one simple procedure for the production of P (ANi) coatings on glass fibers
of diameters in the region of 7–9 μm, after acid wash and rinse of the glass
fiber, it is kept for several hours with stirring in a solution of aniline, p-toluene-
sulfonic acid (dopant), and ammonium persulfate (oxidant) in aqueous HCl.
 The result, after washing and post-processing, is a CP-coated glass fiber

with CP thickness from 0.07 to 1.3 μm with surface resistivities from 1.4 to ca. 30
kΩ/square.
 Polymerization rates are controllable via concentration and time of addition of

oxidant, the former also being adjustable via addition of complexing agents
such as sulfosalicylic acid.
 It use of high dilutions (e.g., 0.02–0.04 M monomer and oxidant and
solution/substrate volume ratios of up to 50:1).
 The choice of doping agent also appears important; dopants such as methane
sulfonate, benzene sulfonate, naphthalene sulfonate, and anthraquinone
sulfonate yield progressively higher conductivities (1200–56 Ω/square)

3.7.CP Blends
 Blending of CPs implies simply blending already synthesized CP and host

polymer and
 Then using that liquid phase blend for further processing. It can be done
either in solution or in the melt phase.
 Two types of CP Blends :-
1. Melt Blending and
2. Blending in Solution
1. Melt Blending
 The most well-known example of melt blending of CPs is that of P(ANi) in the
molten state of host polymers such as PVC, nylon, poly(ethylene
terephthalate glycol) (PETG), and PMMA.

3.7.CP Blends
1. Melt Blending
 The molten form of the thermoplastic is blended with P(ANi) in its

commercial, “Versicon” form (now from Monsanto Co., formerly from Allied
Signal Corp.), which comes in fine-particulate, ready-to disperse, doped,
conductive form.
 Blending of Poly 3-octyl tiophen at near 200 oC with thermoplastics including

poly(ethylene vinyl acetate) (PEVA), poly(ethylene butyl acrylate) (PEBA),
PStyr, and PE.
 A special high-temperature blender cum twin-screw extruder is used.

3.7.CP Blends
1. Melt Blending
 After blending, films and sheets of the composite are made using standard
compression molding techniques at ca. 200oC and 100 bar pressure.
 The composite films are then doped via immersion in FeCl3 /nitromethane.
 PEVA and PE yield the best composites with P (3OT), with conductivities at
20 w/w% P(3OT) loading of 1.0 and 0.04 S/cm, respectively.
 The composites are also apparently easily stretched.

3.7.CP Blends
 P(ANi)/PVP composite (PVP= Poly(vinyl pyrrolidone), a hydrophilic plastic.
 Solutions of the emeraldine base (de-doped) form of P(ANi) and PVP were
prepared in NMP (N-methyl-2-pyrrolidone) with some sonication, stirring, and
filtering.
 Films of thickness ranging from 30 μm to 0.3 mm were cast directly from

solution.

3.7.CP Blends
 Films unfortunately retained ca. 20 w/w% NMP (a consistent problem with use
of this high boiling solvent) even after drying but had conductivities of up to 2
S/cm while showing no evidence of phase separation.
 Another simple example of solution blending is that of several poly( p-phenylene

vinylene) (PPVderiv) with host polymers such as poly(methyl methacrylate)
(PMMA, a very common, household thermoplastic), polycarbonate, a
common shatter-resistant thermoplastic, and poly (styrene).

3.8. Bulk and Commercial Production

 The dopability of P(PS) was understood, poly(aniline), and to a lesser
extent, some of the poly(3-alkyl-thiophenes), have been the major CPs
which have been bulk produced and marketed.
 Polyaniline chemically polymerized, proprietary-sulfonate-doped CP was

marketed under the tradename Versicon.
 Originally produced by the Allied Signal Corp,based in Morristown, NJ, USA .

.
 The product line was taken over in the mid-1990s by the High-Performance
Materials division of Monsanto Co., St. Louis, MO, USA.

 Around April 1998, Monsanto sold the product line to

Ormecon Chemie, a subsidiary of Zipperling Kessler,
based in Ammersbek (near Hamburg), Germany.

 Until 1996 the CPs produced by Monsanto company was in pilot

scale.
 Versicon were compacted powder conductivity 4 S/cm, moisture

4% w/w, particle size 3–100 μ, density 1.36 g/cc, and surface area 5–20 m2/g.
 Soluble P(ANi),” a green liquid which is a blend of 50% colloidal P(ANi), 40%
xylenes, and 10% butyl cellulose.
 Neste Oy, Helsinki, Finland, and Hexcel Corp. also test marketed P(ANi)
and P(3AT) powders; for example, one of the product lines of Neste Oy
included poly(3-octylthiophene) chemically polymerized using FeCl3 and
with a weight-average MWt of ca. 89,000.

3.8. Bulk and Commercial Production.
 Several other companies have bulk produced CPs in house, to be marketed

as products:
 Milliken Research Corp, Spartanburg, SC, USA, P(Py)-coated textiles for

microwave absorption, electrostatic dissipation, and related uses.
 Echema Co. has produced conductive electrodes incorporating P(ANi)
 Bridgestone-Seiko, Japan, and Siemens, Germany, have attempted

unsuccessfully to market CP-based batteries;
 BASF, Ludwigshafen, Germany, also attempted unsuccessfully to market

several CP (P(Py), P(ANi)) products such as films, particulate fillers, and
batteries;

 Several other companies have bulk produced CPs in house, to be marketed

as products:
 Matsushita Co., Higashimita, Japan, apparently still markets

P(Py)-based Al-electrolytic capacitors. This appears to be the only
really successful marketing of a CP product thus far.

3.9. Solubility and Processing of CPs
 Truly Soluble and Processible CPs.
 There are only few CPs truly soluble and processible in their doped state.
 Some ways to achieve solubility
1) Dissolution in highly specialized and frequently impractical solvents such as conc.

H2SO4 or AsF3
2) Processing of the soluble de-doped forms of the polymers followed by in situ re-
doping.
3) Dispersion of the CPs as colloids.

3.9. Solubility and Processing of CPs
 Truly Soluble and Processible CPs.
 Some ways to achieve solubility
4) Melt processing of powder-form CPs with thermoplastics,
5) Attachment of solubilizing groups such as urethane side chains which yield some
processibility at the strong expense of conductivity and other properties,
6) Attachment of water-soluble groups such as sulfonates which yield poor solubility in

the important protonated (conducting) forms of the CP, and
.
7) In-situ polymerization of adsorbed or otherwise preprocessed monomers.

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Conducting polymers (MScE5 307)

School of Mechanical Chemical and Materials

Prepared by : Wegene Lelisa

12/28/2023 Conducting polymers 1

12/28/2023 Conducting polymers 2

3.1. Electrochemical Polymerization.

 All electrochemical polymerizations of CPs (which are nearly always oxidative

1. The initiation step, (monomer) radical generation, via electrochemical

12/28/2023 Conducting polymers 3

3.1. Electrochemical Polymerization.

Step 1. The initiation step, (monomer) radical generation, via electrochemical

Both of the way of representing pyrrole/reaction is same

12/28/2023 Conducting polymers 4

3.1. Electrochemical Polymerization.

Step 2a. Propagation :-Radical–radical recombination is take place and loss of

Step 2b. Propagation electrochemical oxidation of the dimer, generating

12/28/2023 Conducting polymers 5

3.1. Electrochemical Polymerization.

12/28/2023 Conducting polymers 6

3.1. Electrochemical Polymerization.

 By repeating step 2a and step 2b we building up the polymer.

 The radical coupling between oligomeric pyrrole species is favored

12/28/2023 Conducting polymers 7

3.1. Electrochemical Polymerization.

 3.Termination:-via exhaustion of reactive radical species in the vicinity of

12/28/2023 Conducting polymers 8

3.1. Electrochemical Polymerization.

 Whereas in Chemical polymerization, the

12/28/2023 Conducting polymers 9

3.1. Electrochemical Polymerization.

 Factors Favoring Polymerization and No Polymerization.

 Electropolymerization :-Is a nearly generic technique usable for quick

 Not all organic monomers undergo electropolymerization.

 The keys to why certain monomers electropolymerize at all to yield CPs

12/28/2023 Conducting polymers 10

3.1. Electrochemical Polymerization.

 Factors Favoring Polymerization and No Polymerization.

12/28/2023 Conducting polymers 11

3.1. Electrochemical Polymerization.

 The oxidation potential of indole is comparable to that of pyrrole (in

 The electrooxidation of benzene, to produce poly( p-phenylene), requires a

, and thus chemical polymerization is preferred for this CP.

12/28/2023 Conducting polymers 12

3.1. Electrochemical Polymerization.

12/28/2023 Conducting polymers 13

3.1. Electrochemical Polymerization.

12/28/2023 Conducting polymers 14

3.1. Electrochemical Polymerization.

 Proton removal renders the dihydro-dimer or dihydro-oligomer formation.

 Therefore ,proton acceptors including water, bases such as pyridine or

 Limitation:-Excess water may however lead to premature oxidative

12/28/2023 Conducting polymers 15

3.1. Electrochemical Polymerization.

 Note that:- Attempts to electropolymerize dimers or trimers directly, e.g.,

12/28/2023 Conducting polymers 16

3.1. Electrochemical Polymerization.

 The solvent of electropolymerization is an important factor governing not only

 Acetonitrile is one of the most versatile polymerization solvents for several

12/28/2023 Conducting polymers 17

3.1. Electrochemical Polymerization.

 Solvents such as propylene carbonate (PC), for instance, exhibit high

12/28/2023 Conducting polymers 18

3.1. Electrochemical Polymerization.

12/28/2023 Conducting polymers 19