FULLERENE POLMERS

A SEMINAR

UNDER THE GUIDENCE OF

Dr. S. SAMI KANNU
(Reader in chemistry)

Presented by
k.vijay benadict raj
19-03-07
 Background
Fullerene- The fullerene is a spheroidal or polyhedra
shaped carbon molecule.
The Fullerene was discovered in 1984 by Harry Kroto at
Rice University. For many years diamond and graphite
were believed to be the only carbon allotropes. Kroto
and his colleagues were studying carbon clusters and
came upon some heavier molecules that added up to
exactly 60 carbon atoms. The discovery was called a
buckminsterfullerene. It was called this because of the
resemblance to the polyhedra structures that Buckminster
Fuller had known so well in architecture. The carbon
molecule very closely resembles the soccer ball shape.
View of the molecule

C60
  

Laser vaporization
The graphite is hit with a laser and extreme
temperatures are created.

The carbon breaks apart and reforms into fullerenes

and other carbon molecules when blasted with inert
gasses to cool it.

When the graphite is impregnated with metal atoms

endohedral fullerenes form.

Endohedral fullerenes are fullerenes filled with an

atom of another element. They are also termed
dopyballs.
 DISCOVERY

Fullerene is a third allotrope of carbon.

The first fullerene was discovered in 1985 richard
smalley and robert curl of the united states and
harold kroto of the united kingdom.
The fullerene thus obtained is composed of 60 carbon
atoms are joined to together by single or double
bonds to form a hollow sphere.
They contain 12 pentagonal and 20 hexagonal faces a
design that resembles a soccer ball.
Fullerene derive their name from the american
architect r. buckminister fuller, whose geodesic dome
design is similar to the molecular structure of C60. .
 CLASSIFICATION

One or more metal or noble gas atoms can be

trapped inside the molecules its called
exohedral fullerenes.

One or more metal or noble gas atoms can be

trapped outside the molecules its called
endohedral fullerenes.
PROPERTIES

C60 is not “superaromatic “.

C60 behaves like an electron

deficient alkene,and react
readily with electron rich
spices.

The C60 molecule is known to

rotate very rapidly at room
temperature while it is in the
solid state. This presents a
liquid like behavior that is very
strange for a solid.
SOLUBLITYS

fullerene are sparingly

soluble in many solvents.
Commen solvents for the
fullerenes include toluene
and carbon di sulphide.
Some fullerenes are not
soluble.

Fullerenes dissolved in non-

polar solvents create unique
colors like a red-wine color
to deep purple for C60 and
C70 molecules in benzene.
 More Uses for Fullerenes
Antioxidants
Fullerenes are powerful antioxidants, reacting readily and at a high
rate with free radicals, which are often the cause of cell damage or
death. Fullerenes hold great promise in health and personal care
applications where prevention of oxidative cell damage or death is
desirable, as well as in non-physiological applications where
oxidation and radical processes are destructive (food spoilage,
plastics deterioration, metal corrosion).

Biopharmaceuticals
Major pharmaceutical companies are exploring the use of fullerenes
in controlling the neurological damage of such diseases as
Alzheimer’s disease and Lou Gehrig's disease (ALS), which are a
result of radical damage. Drugs for atherosclerosis, photodynamic
therapy, and anti-viral agents are also in development. They can be
used for recognition of HIVP.
Polymer Electronics and Bulk Polymers
Fullerenes are chemically reactive and can be added to polymer
structures to create new copolymers with specific physical and
mechanical properties. They can also be added to make
composites. Much work has been done on the use of fullerenes
as polymer additives to modify physical properties and
performance characteristics. Currently, the record efficiency for
a polymer solar cell is a fullerene/polymer blend, where the
fullerene acts as the n-type semiconductor. Polymer transistors
and photodetectors have also been developed using the n-type
semiconducting properties of fullerenes.
Fullerene polymers
Cllassification
 1.Sidechain fullerene polymer
The first fullerene side chain fullerene polymer was
prepared by WUDL.

They first prepared a low molecular weight bi

hydroxy functional fullerene derivative and then
obtained the c60 containing polyester or
polyurethane by polycondensation.

GECKLER AND HIRSH prepared the first true side

chain fullerene polymer..
 
 Inorder to overcome the influence of the fullerene of
steric hinderence of the c60 moiety on the oilymer
molecular weight, they prepared the aminopolymer
first,and then reacted with fullerene to tbtain the side
chain fullerene polymer(4)
 
HAWKER prepared a linear polymer with pendent c60
moieties by nitrogen bridging (5)
In this reaction azide groupe can control the
reaction..
For example , using group transfer polymerization
allyl methacrylate and methyl acrylate copolymeras
were synthesized; then the pendent allyl groups in
copolymer were hydrobrominated, followed by
reaction with NaN3
And finally with fullerene by addtion reaction(6)..
 Main chain fullerene polymer

The first main chain fullerene was prepared by beni nori

via electrochemical polymerization.
 
a well defined main chain fullerene polymer was
prepared by “OLEAMURA”.
 
They heated PsTEMPO, which was prepared by nitroxyl-
mediated ‘living’ radical polymerization at 145 0C.
 
 The C60 derivatives thus obtained 60-80% yield were
found to be predominately A1,,D1, dipolystyryl
dihydro fullerenes.
 
It is retained the redox properties of original C60.
 
Another reactive fullerene polymer allowed the
incorporation of fullerene units into the polymer
backbone of polysiloxanes. (scheme 17)
 
Similarly, C60 pearl-necklace polymer, poly(4, 49,
carbonyl bisphenylene-trans 2-fullerenobiscaetamide)
was synthesized by direct poly condensation of trans
fullerene bisacetic acid with 4, 49,
diaminobenzophenone in the presence of large excess
of triphenyl phosphate and pyridine. (scheme(18)).
Fullereo dendrimer
Wooleyet al prepared dendritic fullerene by
attachment of poly(aryl ether) based dendrimer to
phenol functionalized fullerenes(scheme-20).
The benzylic bromide moiety of the fourth generation
dendrimer reacts with rhe phenolic groups attached
to fullerene , and thus two dendrimer building blocks
copule with one fullerene to give the fullerene based
dendrimer.
Using cycloaddtion reaction of azides with fullerenes,
wooley et al prepared a new type of fullerene
dendrimer based on the benzylic bromid moiety of
the fourth generation dendrimer.
The final products contained mono and bi addtion
products.
But no higher addition products.
The failure to obtain tri or multisubstitution may be
due to steric hindrence around the c60.
Nucleus and unfavourable electronic conditions after
the biaddtion .
Rio et al used a m poly(aryl ether) dendrimerTo
obtain a series of fullerodendrimers. 
Systametic changes in yhe photophysical properties
properties in thre series suggest increasing
interaction betwee n the poly(aryl ether) dendritic
wedges and the cntral chromophore from yhe
exterior.
Rio et al areincorporated there fullero dendrimers in
to mesoporous silica glasses , and showed that there
matrials posses efficient optical limiting properties.
Star shaped fullerene polymer
 Star shaped fullerene
polymers
1. Many papers have been published on radical polymerization of the
presence of C60.
2.  Chen and Lin gave a detail description.
3.  They conducted radical polymerizations of styrene in the presence
of C60 at 900C in benzene using benzoyl peroxide (BPO) as the
initiator.
4. However, the number of polystyrene chains added to C 60 increases
with polymerization time. Scheme2.
5. They polymerization process was followed by monitoring BPO
concentration, C60 content and polymerization time. It was found
that C60 acts like a radical absorber, which multiply absorbs
primary radicals of BPO and the propagating polymer radicals. At
be beginning of the reaction, chain propagation is restricted by the
radical absorbing effect of C60.
Direct fulleranation of polycarbonate (PC), a commercially important
optical polymer, can yield. Star shaped fullerene polymers.

By simply irradiating a solution of PC and C60 at room temperature

using a conventional Ar lamp, or by warming a C60/PC solution to
600C in the presence of AIBN, tangetdl star shaped fullerene PC
polymers.

Living free radical technique (iniferter) He etal. Scheme 31

synthesised starlike C60 bonding polymers.

The used C60 with pendent N,N diethyldithiocarbanate groups (C60-

SR) as a polyfunctional photoiniferter.

Photopolymerization proceeded by living radical mechanism and

gave soluble polyfunctional polymers.
 Fullerene endcapped polymers
The first fullerene c60 end capped polystyrene were prepared
by reaction of amino terminated polystyrene with c60.
 
GU prepared mono c60 end capped oligovinylene
(scheme33)
 
Mono and bi c60 end capped poly ethylene oxide were
prepared using the reaction with azide group with c60.

 They are exhibiting good photo conductivity..

 
   CLOUTEL reported here c60 end capped star
polymer(scheme-35)
 Cross linked fullerene polymers

Photochemical addition of c60 to furan derivatives

has been used to prepare crosslinked furan
containing polymer.
Poly(2hydroxy ethylmethacrylate) with 2- furoic
chloride an d then 1122 tetra cholora ethana solution
polymer was exposed to visible light in the presence
of c60.
Thje solution turned to gel after 10h and solidified
completely. Ethylene diene norborene with c60 was
prepared by jiang.
A highly uniform photo condutive film can be
obtained from the solution..(scheme 37)
Polymer derivatives of fullerene.
All fullerene polymers
 All fullerene polymers.
Fullerene cages are directly connected covalently. 
I n 1993 rao et al first reported that solid c60 film
undergoes a phototransformation when exposed to
visible or uv light yield toluene insoluble species ,
which were characterized as all fullerene polymer4s
formed by2+2 cycloaddtion between neighbouring
c60 molecules. 
Ma and co wor4kers synthesized high molecular
weight. Plyfullerenes by fullerene by photochemical
reactions of c60.
Clusters in carefully de oxygenated tolune –
acetonitrile soultons at room temperature. 
   Morita etal considered that the strong lattice interaction is
the one dimensional system would dramatically modify
and distort the conjuctedpolymer system, and
thatP+orBP+ formed.
Therefore the density of states in the upper energy range
of the valence band would be decreased, resulting in
suppression of the interband absorption, especially in the
lower energy range.
Fig 3 which shows that transfer of free electrons between
the rigid bands of C60 and PAT is nearly impossible since
charge transfer (CT) requires positive energy C,T = 0.1to
0.2ev.
However, charge transfer from polymer to C60 may occur
if polaronic effects are taken in to account, both in the
polymers. (P+ level approximately 0.2ev while BP+
approximately 0.7ev above the valance band to P) and in
C60 molecules.
In C60 a shape deformation effect will lead to splitting of three fold
degenerate LUMO of C60 in the ionic state due to polaronic
distortion; in other words john teller distortion will occur.
In latter case, the t1u level should split into three levels of different
symmetries as sketched figure 3 and the transferred electron
should occupy the lowest split-level. Moreover, it has been reported
that in weak doping with slightly positive CT energy, the coulomb
attraction of the P+ polaron and the dopant can additionally
stabilize the charge transfer due to the creation of polarons P + in
the ground state with C60.
LESR providence evidence that C60 is formed upon photoexitation
figure 4 shows two spin signals in which the g approximately equal
to 2.000 spin with deltaHFWHM approximately equal to 4 G us
assigned to the P3…….. polaron radical (donor cation radical), and
the g approximately equal to 1.9935 spin with deltaHFWHM
approximately equal to 3.7 G is assigned to C60- anion radical.
Recently Marumoto etal studied regioregular PAT/ C 60 composite is
used.
Application
They found that the C60 moieties were bonded to the pendant
benzene ring of PMPS by Friedel-crafts reaction and incorporated
into the main chain by direct copolymerization.
Doping this compound in to PVK, long etal found much higher
photoconductivity than could be obtained by doping with pure C 60.
C60 can enhance the photoconductivity of non-conductivity as well
as conducting polymers.
Another system is C60 containing styrene acrylamide copolymer in
which the maximal C60 content
­ in the polymer is 1.45wt% good
conductivity.
PVK/MDDA(didecylaminemodified MWNT) blend showed good
photoconductivity. However the PVK/MVNT exhibited little
photoconductivity (figure 15).
Fluorescence studies indicated the MDDA can act as an electron
acceptor in either the ground state or excited while PVK is electron
donor.
 Photodiodes
Bulk heterojunction polymer photovoltaic devices and
photodiodes have been constructed with composite films of
semiconducting polymer as electron donors and fullerene
derivatives are electron acceptor.
NAVA et al prepoared fullerene containing polyester by
polycondensation of bifunctional fullerene adducts with
tetraethyleneglycol or polyethylene glycol (scheme46a,b)
Oligo (p phenyl vinylene) fullerene dyads were prepared by
several research groups in order to avoid the incompletely and
macrophase separation problem of regular fullerene based
photovoltaic devices.
WANGet al fabricated a multiplayer organic lightemitting device
by mixing together a c60 based poly(phenylvinylene)dyad and
an emmisive conjugated polymerPMPV(scheme-49).
Their primary study showed that the PPVc60 dyad can improne
the light emiting performance..
 Optical limiting
One of the most attractive NLO properties of
fullerene is optical limiting.
optical limiting occurs when the optical transmission
of a material decreases with increasing laser fluence,
a property that is desirable for protection sensors
and human eyes from intensc laser beam radiation.
For laser radiation at 532 nm,C60 and its derivative
are among the best material showing optical limiting
properties.
SUN et al prepared linear polystyrene bound c60
(scheme-50 )in fullerene cages are covalently
attached to polystyrene chains, in primarily pendant
linkages by a friedel kraft type reaction using alcl3
catalyst.
These soluble pendant c60 ps polymers have better
defind structure than the copolymers reported by
KOJIMA et al. 
At the optical limiting of the polystyrene bound c60
at 532 nm is not as good as that of pristine c60 in
solution.
LU et al synthesized copolymers of
benzylaminofullerene with methylmethaacrylate by
free radical polymerization.
These polymers have relatively good solubility in thf.
Although benzylamino fullerene homopolymer shows
optical limiting of all the copolymersm is much
weaker.
 Conclusion
The development of fullerene organic chemistry ,
many low molecular organic reactions can be used ib
polymeric modification of fullerene.
By controlling the functional groups in polymers and
reaction conditions, many welldefined fullerene
polymers,such as side chain fullerene polymers,
mainchain fullerene polymers,dendritic fullerene
polymers, starshaped fullerene polymers, fullerene
end capped polymers and so on.
At the same time many LIVING POLYMERIZATION
method can be introduced.
By anionic polymerization, well defined six arm star
shapped fullerene polymers can be obtained.