DELHI TECHNOLOGICAL UNIVERSITY

REVIEW

CONDUCTING AND SEMI CONDUCTING POLYMERS.

ADITYA PRATAP GUPTA (2K18/PS/005)

Department of Chemical Engineering, Delhi Technological University (DTU)

 RECEIVED : 1 S EPTEMBER,2020 , SUBMITTED: 6 NOVEMBER,2020, RE-SUBMITTED: 17

NOVEMBER,2020

Abstract: The conducting polymer field has continued its rapid expansion since the discovery that
an organic polymer, polyacetylene, could be doped to the metallic regime. A number of new
conducting polymers have since been synthesized and many chemical, structural and physical
studies have helped in elucidating the doping processes and electronic and magnetic properties of
these materials; however, an adequate understanding of many fundamental phenomena will only be
attained by further research. Such understanding will be assisted by the synthesis and study of new
types of conducting polymers and composites. The first significant signs of technological
applications of these polymers now appearing are expected to stimulate even more basic and
applied research in this field in the future. The early problems associated with the stability and
solubility of such conducting polymers have largely been overcome using chemical intuition and
experimentation. A fairly wide range of interesting applications based on these polymers is
emerging; some of these are highlighted in this article.
 Introduction
Most organic polymers are insulators by nature. Most of the polymers are
used for electrical insulation, as they are bad conductor of electricity.
Since these polymers do not possess large number of free electrons,
they do not conduct electricity. Conductivity in polymers is observed
because of different reasons. Accordingly they can be categorized into
different types.
Conducting polymer research dates back to the 1960s, when Pohl,
Katon, and their coworkers, first synthesized and characterized
semiconducting polymers . The discovery of the high conductivity of
polysulfurnitride (SN), a polymeric material containing interesting
electrical properties, was a step forward for research in conducting
polymers.

The beginning of conducting polymer research started around 40 years

ago, when films of polyacetylene were found to exhibit profound
increases in electrical conductivity when exposed to halogen vapor. J.
Heeger, H.Shirakawa and G.MacDiarmid discovered conjugated
conducting polyacetylene when monomer of acetylene was doped with
bromine and iodine vapor; the resulting electrical conductivity was 10
times higher than the undoped monomers. They were awarded Nobel
Prize in Chemistry, 2000, for their discovery.
 Conductivity in Conducting Polymers

After their discovery, research papers dealing with polyconjugated

systems were very extensive and systematic. The trend was to
understand the chemical and physical aspects, either in neutral
(undoped) state or charged (doped) states. According to Scifinder,
almost 40,000 scientific papers were published in this field of research
since 1977. This previously underestimated family of macromolecular
compounds turned out to be extremely interesting, from both the basic
research and application points of view. The polymer was produced by
the exposure of the polyacetylene to dopant compounds: oxidizing or
reducing agents; electrondonor or electron-receptor of electrons.
 CONDUCTING POLYMERS

Electrical conductivities are shown by few polymers because of it

fundamental characteristics. Such polymers are known as intrinsically
conducting polymers. However, intrinsically conducting polymers (ICPs)
have alternating single and double bonds along the polymer backbone
(conjugated bonds) or that are composed of aromatic rings such as
phenylene, naphthalene, anthracene, pyrrole, and thiophene which are
connected to one another through carbon-carbon single bonds.

Examples of conducting polymers

These polymers can be easily oxidized or reduced as they have low
ionization potentials and high electron affinities. Their conductivities can
be increased by creating positive or negative charge on polymer
backbone by oxidation or reduction. The poor conductivity of polymers is
also explained by the band theory. This theory says that the energy
levels of electrons can occupy are grouped in allowed bands and may
have energy levels of electron that are forbidden, denominated band gap.
The lowest bands are called valence bands and are inert on an electrical
perspective. On the other hand, the highest bands, which participate in
the electric conduction, are called conduction bands.

Different types of band structures for different materials, (a)conductors,

(b)divalent metals, (c)insulators, (semiconductors)

Other conductors, such as divalent metals represented in b), can have an

overlap of the empty conductive band with a totally filled valence band.
For semiconductor and insulators, represented in d) and c) respectively,
the valence electrons must cross the band gap in order to result a
conduction. The difference is a semiconductor has a relatively smaller
band gap energy than insulators have .

Semiconducting polymers

Semiconducting polymers are described in terms of the energy bands

that originate from the bonding and anti-bonding energy levels
associated with the s-bonds between adjacent carbon atoms (formed
from the sp2 wavefunctions and the orthogonal p-bonds that originate
from the pz wavefunctions. The s-bonds hold the structure together, but
the p-bonds are the origin of the properties that characterize conjugated
polymers as semiconductors

The thin film diode first described in 1987 provides a simple example of a
semiconductor device: the metal–semiconductor– metal (MSM) structure
comprised of a single layer of semiconducting polymer cast from solution
and sandwiched between metal contacts with different work functions
operates as a diode with relatively high rectification ratio.
 Molecular structures of the more important First and Second generation
Semiconducting polymers

Mechanism
Conducting polymers are responsible for flow of electricity because of
their conjugation in pie bond system. Due to delocalization of electrons in
molecule the conjugated double bands allow to flow of more number of
electron. Delocalization is the condition in which pie bonding electrons
are spread over a number of atoms rather than localized between 2
atoms. This condition permits electrons to travel more easily making the
electrically conducting polymers.
 Conjugation and movement
of pie bond

The conductivity of
non-doped, conjugated
polymers such as
polyacetylene is due to the
existence of a conducting
band similar to a metal. In a
conjugated polymer three
or the four valence electrons form strong σ bonds through
sp2 hybridization where elctrons are strongly localized. The remaining
unpaired electron of each carbon atom remains in a pz orbital. It overlaps
with a neighboring pz orbital to form a pie bond. The pie electrons of
these conjugated pz orbitals overlap to form an extended pz orbital
system through which electrons can move freely (delocalization of pie
electrons).
 Different types of conugation

The process of doping of conductive polymers becomes easier due to

these conjugated bonds. In this process, defects and deformations in the
polymeric chain are formed. An electron-deformation pair, or also an
electron-photon cloud pair, is called polarons, which is responsible by the
conductivity in polymers. Bipolarons and solitons, other types of quasi-
particles, also participates in the conductivity mechanism. The type of
soliton, bipolaron, or polaron formed depends on the dopant used.
Only when an electron is removed from the valence band by oxidation (p-
doping) or is added to the conducting band by reduction (n-doping) does
the polymer become highly conductive. The four main methods of doping
are

 Redox p-doping: Some of the π-bonds are oxidized by treating the

polymer with an oxidizing agent such as iodine, chlorine, arsenic
pentafluoride etc.

 Redox n-doping: Some of the π-bonds are reduced by treating the

polymer with a reducing agents such as lithium, and sodium
naphthaline.
  Electrochemical p- and n-doping: Doping is achieved by cathodic
reduction (p) or by anodic oxidation (n).

 Photo-Induced Doping: The polymer is exposed to high energy

radiation that allows electrons to jump to the conducting band. In
this case, the positive and negative charges are localized over a few
bonds.

Doping increases. Values as high as 102 - 104 S/m have been reported.

Another method to increase conductivity is mechanical alignment of the
polymer chains. In the case of polyacetylene, conductivities as high as
105 S/m have been found which is still several magnitudes lower than the
conductivity of silver and copper (108 S/m) but more than sufficient for
electronic applications such as polymer-based transistors, light-emitting
diodes and lasers.

When the I2 oxidative dopants is added, it takes away an electron from

the pie backbone of the polyacetylene chain and creates a positive
charge (hole)on one of the carbon, now positively charged ,is termed as
a radical cation or polaron. The lone electrons of pie bond, from where an
electron was taken, can travel easily. As a moment the double bond
moves along the molecule. A bipolaron is formed on further oxidation.
 Conductivity comparison between conductive polymers and other
materials

If the polyacetylene chain is heavily oxidized, polarons condense

pair-wise into socalled solitons. Mobile charged solitons which
enable “spineless” conductivity are unique to polyacetylene.
Here, conducting polymers Poly (acetylene) & Polyaniline are
taken as example to show principle of conduction mechanism.
By showing the uniqueness property of unevenness of the poly
(acetylene) in ground state, two corresponding polyene chains R
and L are interconverted through the involvement of a mobile
charge carrier, a soliton. The solitons are mobile charged or
neutral defect, or a “kink” in the poly(acetylene) chain that spread
down the chain and thus decrease the barrier for inter
conversion.
The conductivity of a conductive polymer is also temperature dependent,
because as the temperature increases the molecules becomes farther
from each other. Thus, the doping effect is more effective and,
consequently, the amount of charges, which is the doping level of the
polymer is greater, increasing the conductivity. Moreover, as the
temperature increases, the energy of an electron is related with the
temperature by the Boltzmann relationship. Because of that, the greater
the temperature, the greater is the energy of the electrons, and,
consequently, the easier is to excite the electron to the conduction band.
The actual conductivity not only depends on the structure and
morphology of the polymer but also on the type of dopant and its
concentration.

Conductivity comparison of some common conjugated polymers

 Classification

One can distinguish between three types of conducting polymers:

 Electron conducting polymers
 Proton conducting olymers
 Ion conducting polymers

Poly(acetylene)s
The first conducting polymer synthesised was poly(acetylene). The first
reports on acetylene polymers date back to the last century. Cuprene, a
highly crosslinked and extremely irregular product of acetylene
polymerisation in the presence of copper- containing catalysts being a
typical example for the initial efforts. Poly(acetylene) is the simplest
conjugated polymer. In its linear form it precipitates as a black, air
sensitive, infusible and intractable powder out of solution and can not be
processed. Ant et al. were the first to polymerise acetylene in hexane
using a mixed catalyst of alkyl aluminium and titanium tetraalkoxides:

The inherent insolubility and infusibility of poly(acetylene) coupled with its

sensitivity to air imposes a barrier to the processability of the polymer. As
a result considerable research efforts have been directed towards
obtaining processable poly(acetylene) by means of polymer analogous
transformation. Two syntheses are of particular importance.
Property advantages of poly(acetylene) prepared by precursor routes:
 Continous solid films with densities of 1.05 -1.10.
 Controlled morphology ranfe, amorphous ,semi
crystalline,crystalline.
 Films can be stretched during or prior to conversion.

The conductivity of all substituted poly(acetylene) analogues reported to

date is significantly lower than that for poly(acetylene) itself. The
reduction in conjugation length is attributed to steric repulsions between
adjacent side groups which causes the polymer chains to twist (rotation
barrier single bond: 6 kcal/mol). Grubbs showed that monosubstituted
cyclooctatetraenes can be “ROMPed” to give partially substituted
poly(acetylene)s) that are both soluble and highly conjugated.

Oxidative doping of polyacetylene by iodine

(Polaron and its delocalization)
 Poly(phenylene)s
Four synthetic routes have been employed for the preparation of
poly(phenylene)s. Oxidative coupling, organometallic coupling,
dehydrogenation of poly(cyclohexylene)s and cycloaddition reactions.

Oxidative coupling

The structural features (meta or ortho linkages) and physical properties

of the polymer prepared by oxidative coupling depend to a large extend
on the nature of the tilized reagent. Ortho linkages can be introduced
by using more substituted benzenes rather than the parent compound.
Polymers substituted in the para position are in general more difficult to
process, i.e. they are more ordered and thus π stacking is more efficient.

Organometallic coupling

Ullmann and Wurtz-Fittig reactions have been tilized for the synthesis of
phenylene oligomers but these methods can not be applied to the
synthesis of poly(phenylene)s since yields are low.
Dehydrogenation of poly(cycohexylene)s

Diester derivatives of 5,6-dihydroxy-1,3-cyclohexadiene have been

tilized ed radically after which the resulting poly(cyclohexylene)s were
converted to poly(phenylene)s by pyrolysis. Best results were obtained
with methyl carbonate derivatives. The dihydroxy monomer precursor is
accessible through enzymatic oxidation of benzene. An environmentally
friendly route to conjugated/conducting polymers.

Cycloaddition reactions

1,4-cycloadditions of bis-cyclopentadienones with bisacetylenes can yield

high molecular weight polymers which contain approximately equal
amounts of meta and para substituted phenylene units.

Suzuki coupling of p-bromophenyl boronic acid offers another convenient

route to poly(phenylene) although substituted analogues require
elaborate syntheses of monomer units. An interesting extension of this
methodology is the synthesis of hyperbranched poly(phenylene)s from an
AB2 monomer. In general branching improves solubility and processibility
compared to the linear parent polymer, which is also true in the case of
highly conjugated polymers such as poly(phenylene)s.
 Poly(phenylene vinylene)s
Poly(phenylene vinylene) (PPV) possess a chemical structure which is
intermediate between that of poly(acetylene) and poly(phenylene).
Oriented PPV is highly crystalline, mechanically strong and
environmentally stable. Early attempts distilized dehydrohalogenation or
Wittig condensation reactions which resulted in the formation of
intractable oligomeric powders. The Wessling-Zimmermann precursor is
water-soluble PPV prepolymer (cf. Durham route) which allows the
reproducible formation of high molecular weight free standing films.

PPVs were originally synthesised via the popular Gilch route which uses
the bis(chloromethyl)benzene precursor monomer in THF in the
presence of t-butoxide as non-nucleophilic base. The reaction leads to a
rather defined product with limited conjugation length and defects along
the polymer backbone. The precursor sulfonium electrolyte is prepared in
aqueous solution (Wessling route to PPV, less defects, longer
conjugation, milder) by the base induced polymerisation of the
appropriate bis-sulfonium monomer.

The polymerisation is quenched by addition of dilute acid and the

reaction mixture is then dialysed against water to separate the high
molecular weight fraction as well as the sodium and chloride ions. A
study of the polymerisation mechanism revealed the existence of a
quinoid intermediate during the early stages of the polymerisation. An
alternative radical mechanism has been considered but ruled out by the
experimental evidence.
 Oligomers
Drawn PPV films were analysed by X-ray diffraction and NMR. The
results demonstrated that the average tilt of the phenylene ring relative to
the chain axis was 7.7o, close but not exactly equal to the 9.2 o predicted
for a trans-stilbene-like structure. Highly oriented PPV shows high
electrical conductivity upon vapour-phase doping with AsF5 but iodine
doped films show only modest conductivities.

PPV oligomers have been synthesised by the Wittig reaction in order to

obtain model compounds for physical characterisation studies aimed at a
more detailed understanding of the conduction mechanism present in
doped conjugated polymers.
 Ladderpolymers
Poly(thiophene)s
Heteroaromatic polyarylenes can be prepared employing similar
synthetic strategies as those described for poly(phenylene)s and
poly(phenylene vinylene)s. Not only has the heteroatom an influence on
the chemical and physical properties of the polymeric product, it also has
to be taken into account when preparing the required monomer (aromatic
heterocycles lectures).

Polythiophene like many other linear polyaromatic compounds is

insoluble in organic solvents (rigid backbone) and substitution in the 3
and/or 4 position is necessary to render the polymer soluble.

With the introduction of 3-substituents, a number of different

regioisomers are possible. These are head-to-head, tail-to-tail and head-
to-tail. and random configurations. The issue of regioregularity pervades
all of polymer chemistry and is present even in simple linear polymers
such as polystyrene and poly(methyl methacrylate). Potentially any olefin
is prone to polymerise to yield all of these regiochemical variations. Thus
it is a significant challenge to find polymerisation reactions and/or
reaction conditions to allow to control the sequence of regioisomers at
will.

Studies on regioregular poly(thiophene)s, that have become accessible

recently via a number of elegant routs, have shown that crystallinity
increases with stereoregularity and that the possibility of sidechain
crystallinity is essential for the development of optimal properties. For
regiorandom polymers the optimal chain length for properties like
conductivity and optical non- linearities has been determined to be in the
range of 7-9. In contrast doped regioregular 3-substituted poly(thiophene)
reaches
its optimal conductivity (1000 S/cm) with an dodecyl sidechain (octyl for
the regiorandom polymer (20 S/cm)). 3,4- disubstitution reduces
conductivity in the case of methylene groups (loss of coplanarity)
because of steric hindrance. This can be overcome by substituting the
methylene group with an oxygen.

Oxidative coupling to poly(thiophene)s using FeCl 3 has also been shown

to produce regioregular polymers with up to 94% HT.

An interesting and intriguing property of substituted poly(thiophene)s is

the temperature dependence of the UV absorption. An increase in
temperature causes the maximum wavelenght to shift to shorter
wavelengths. This thermochromism arises from the conformational
change in the aromatic backbone as a result of an increased disorder of
the alkyl sidechains. Two distinct structures are possible depending on
solvent and temperature; a predominantly coplanar structure in an
aggregated form in a poor solvent (or low temperatures) and a
conformationally disordered non-planar structure in a good solvent (high
temperature).

The synthesis of poly(pyrrole)s is very much related to that of

poly(thiophene)s. However there is one distinct difference and that is the
reactive nitrogen-hydrogen bond. Thus protection of the amine is
required to prevent sidereactions such as crosslinking to occur. As in so
many cases in polymer chemistry the t-Boc group serves well as stable
protecting group which subsequently can be removed easily through
acidic or thermal deprotection.

Poly(pyrrole)s
Poly(pyrrole) are prepared by the Stille coupling/thermolysis sequence.
 Poly(aniline)s
Oxidation of aniline is the most widely employed synthetic route to
polyaniline and can be performed either electrochemically or
chemically. The reaction is usually carried out in acidic medium
with a chemical oxidising agents such as ammoniumpersulfate.
Branching or even crosslinking during polymerisation occurs
through the formation of radicals at the 2 and 6 position.

Polyaniline can occur in a number of well-defined oxidation states.

The different states range from the fully reduced leucoemeraldine
via protoemeraldine, emeraldine and nigraniline to the fully
oxidised pernigraniline. Unlike most other polyaromatics, the fully
oxidised state in polyaniline is not conducting as are all the others
too!. Polyaniline becomes conducting when the moderately
oxidised states, in particular the emeraldine base, are protonated
and charge carriers are generated. It is this process, generally
called protonic acid doping, which makes polyaniline so unique.
No electrons have to be added or removed from the insulating
material to make it conducting.
The different oxidation states of polyaniline can also be generated
by doping with oxidants such as iodine but the resulting
conductivity is lower than that obtained via protonic acid doping.
The conduction mechanism is believed to involve polarons. In the
case of the protonated emeraldine a delocalised
poly(semiquinone radical cation) is the polaronic carrier.

The conductivity is affected by the water content. Completely dry

samples are five times less conductive than samples containing
some water.

Self-doped polyaniline, containing sulphonic acid substituents has

been synthesised by sulphonation of the emeraldine base.

A different approach to the production of polyaniline (instead of

long alkyl sidechain e.g.) is the use of n-alkyl sulphonic acids as
proton donor (and ionically anchored aliphatic sidechains).

Stable thin films of polyaniline that can be processed out of

solution are prepared from the emeraldine base with
camphorsulphonic acid as dopant. m-Cresol as cosolvent is
essential to obtain a chiral crystalline structure.

Each polymer type has already found widespread use in many,

mainly optical and electronic applications such as batteries,
displays, plastic wires, optical signal processing, information
storage, solar energy conversion, etc..
 APLLICATIONS

Conducting polymers have an immense advantage of being

simple to synthesis, with their chemical structure tailored to alter
their physical properties, such as their band gap. They exhibit an
extensive rangeof electrical conductivity and can exhibit metallic
to insulator property(105- 10-9 S/cm). The properties that make
these conductors attractive include a wide range of electrical
conductivity, which can be achieved with various doping levels,
while maintaining mechanical flexibility and high thermal stability.
Further to theirease of synthesis and with lower cost, they are
known to have low poisoning effects. So that they have many
application Even for rugged applications including LED lighting
and electrical supercapacitors, conducting polymers have
advantages over other materials candidates such as conductive
metal oxides. In this special issue of Interface, conducting
polymers and their applications are featured.

Some common applications are:

Storage Batteries • Biosensors • Displays • Mechanical Actuators
• EMI Shielding • Conductive Textiles • Antistatic Films/Fibers •
Neutron Detection • Non-linear optics • Electroluminescence ●
Biosensors and medical devices ● Biocompatible electrodes
Field-Effect Transistors
Field-effect transistors (FETs) were among the first
semiconductor-based devices fabricated with a conducting
polymer. A FET is a simple device composed of three contacts
(source, drain, and gate), a dielectric layer, and a semiconducting
layer (Fig. 1a). FETs act essentially as electronic valves, by
modulating the semiconductor channel conductance via the gate
field. In this device structure the current flow between the source
and the drain electrodes is controlled by the application of two
independent biases, one between the source and the drain (Vd)
and one between the source and the gate (Vg). For the TFT the
current flows throughout a conducting polymer (CP) that its
conductivity produced from the reaction with the analytes and/or
by the electric fields. So, it can be said that the response signal
depends on two things; the work function and the conductivity of
the Conducting Polymer.

Light-Emitting Diodes
In 1990 the Cambridge group led by Richard Friend reported the
emission of light from a semiconducting polymer sandwiched
between two contacts and connected to a battery. The discovery
of electroluminescence (EL) in conjugated polymers, i.e., the
emission of light upon electron-hole recombination as the result of
an electric current flown, has provided a new impetus for the
development of polymer light-emitting diodes (PLEDs). These
elements are fundamental for display and other applications. In
PLEDs and in OLEDs (organic LEDs), the latter being their small
molecule-based equivalents, the holes and electrons injected
from the device contacts recombine and produce luminescence
with a wavelength (color) dictated by the energy difference
between the molecular excited and ground states.

Photovoltaic Cells
Two years after the PLED breakthrough at Cambridge, the Santa
Barbara group reported the first results on polymer-based
photovoltaic cells,of which the principles can be regarded as the
inverse of the EL process. In photovoltaic (PV) devices, bound
electron hole pairs (excitons) are created upon illumination. To
convert the absorbed light into electricity, the excitons must first
dissociate into the separate charges which then have to be
collected at the device contacts (holes at the anode and electrons
at the cathode). This process is possible thanks to the use of
contacts with different work functions enabling the formation of a
built-in potential field within the device.

Polymer solar cell

Polymer solar cells have attracted broad research interest
because of their advantageous solution processing capability and
formation of low-cost, flexible, and large area electronic devices.
However, the efficiency of polymer solar cells is still low compared
to that of inorganic solar cells. Therefore, it is a challenge to find a
polymer that has all the required properties for high efficiency
devices, such as strong and broad absorption, high carrier
mobility, and appropriate energy levels. One possible solution to
avoid the strict material requirements is to stack two or more
devices with different spectral responses, which enables more
efficient utilization of solar energy. A typical example of the
usability of organic semiconductors is the dye-sensitised solar cell
which owes its first demonstration Gratzel and his co-workers.
Conducting polymers (CP’s) could be utilized as discriminating
layer in a sensor or to be the transducer itself. Therefore, for
instance, change in conductivity of a Conducting Polymer as it is
exposed to a gas is the mechanism of sensing in a chemiresistor
or field effect transistor characteristic.

CHEMISTOR
A Chemiresistor is simply formed by two electrodes as contact
points with the conducting polymer (CP) put onto an insulate
substrate. When applying a constant current, the probable
difference occurs on the electrodes represents the response
output signal.

Corrosion
Conducting polymers of various forms will be electrodeposited
onto oxidisable metals and electrochemical and environmental
means will be used to access their applicably for corrosion
protection.
Polyaniline (Pani) and its derivatives are among the most
frequently studied CPs used for corrosion protection. In addition,
the use of PANI for corrosion protection of metals has been of
wide interest since the works by (DeBerry 1988; Mengoli et al.
1981) reporting that electro active coatings of the Pani could
provide adequate protection against corrosion of stainless steels
and iron sheets, respectively. Ever since, numerous studies have
been published in which various CPs in different configurations
were evaluated for corrosion protection of different metals and
alloys: mild steel.

Conclusion
Conducting polymers have, thus, come a long way from purely
laboratory curiosity to a class of materials that can find end use in
a wide variety of commercial products, ranging from batteries to
biosensors. Such a development is a classic example that serves
to illustrate the wide range of expertise, starting from chemists,
physicists, biologists and technologists, that is required to take
some invention in the laboratory to the market place.
 References
https://ir.ua.edu/handle/123456789/6713
https://www.tandfonline.com/doi/abs/10.1080/10601325.2013.784546
https://link.springer.com/article/10.1007/s10008-008-0561-z
https://pubs.rsc.org/en/content/articlelanding/2011/cs/c0cs00194e/unauth#!divAbstract
https://d1wqtxts1xzle7.cloudfront.net/54536286/AndersonDavidson_-
_Conducting_Polymers_4-25-2013.pdf?1506393322=&response-content-
disposition=inline%3B+filename
%3DConducting_Polymers.pdf&Expires=1604611659&Signature=WDLmNvj3IwgyTpjY
N~v2O4nksoGki~XM8LVdq8sVFDFPaeIkWEFjOojtiHGQ847WoB~eGBpZC4Ia~mdoTv
p55sijvSY5onJpDOafG9AT46DPRJKNqGLq3lKzkQ0fNsZ9DuBDY6oowqQqjLDkdLlZyb
x2Np6ycdJdko8FKHPvaFChJb9j7CdRPc06tW9LFCIaeBFr0mTvWIDM6fuX26fqb2uPip
BQB8L3OYZnNW60h7hfV4z8cxkaTH6RwY5Ke5ynhzFOVjDO0G6Ncfrhyw5PNlp0e7ec
mmFOG62a8opFZCFEFBrVexCm~Chm~fAcR4SAx6~kMrN4cQMRlr0KiBWrxA__&Key-
Pair-Id=APKAJLOHF5GGSLRBV4ZA