USE OF SUPERCRITICAL FLUIDS IN ENHANCEMENT OF

POLYMERIZATION PROCESS (REVIEW).

CHINMAY P TIWARI
DEPARTMENT OF CHEMICAL ENGINEERING
L.D. COLLEGE OF ENGINEERING
AHMEDABAD
chinmaytiwari15@gmail.com

Abstract
Our review paper is about one of the recent
advancement in the polymerization process
and discussing the methodology of
supercritical polymerization using the fluids in
their supercritical state for the process to take
place. Supercritical fluids are having
temperature and pressure higher than the
critical temperature. Major examples of fluids
used in supercritical state are CO2 and
Propane. Use of supercritical fluids in polymer
processing increases the rate of reaction and
thus decreases the reaction time which is
helpful. Supercritical fluids provides higher
mass transfer coefficients as compared to
liquid phase and hence they provide higher
value of overall rate of reaction in
polymerization process.

AKSHAY G CHOTHANI
DEPARTMENT OF CHEMICAL ENGINEERING
L.D. COLLEGE OF ENGINEERING
AHMEDABAD
akshaychothani1995@gmail.com

an SCF because, under all circumstances,

such a fluid will occupy the full volume of its
container, demonstrating the typical behavior
of a gas. Nevertheless, such a fluid is usually
not called a high-pressure gas but a
supercritical fluid. The reason is that one
cannot liquefy such a fluid under any
pressure once it is heated above its critical
temperature (it should be noted, how- ever,
that it can still be solidified at extremely high
pressures). No phase separation occurs for
any substance at pressures or temperatures
above its critical values. In other words, the
critical
point
represents
the
highest
temperature and pressure at which gas and
liquid can coexist in equilibrium. However, it
is very important to note that this definition is
for a pure substance.
Polymerization process is to react monomer
molecules together to form a polymer chain or
a 3-D network.

Keywords
Supercritical polymerization, fast polymer
processing.
Introduction
Supercritical fluids (SCFs) have unique
properties that may enhance many types of
chemical
processes.
An
additional
advantage of using SCFs stems from the
fact that they may replace many
environmentally harmful solvents currently
used in industry. In particular, SCFs
represent an attractive alternative to organic
solvents for use as additives in polymer
processing. For example, supercritical
carbon dioxide (scCO2), which is by far the
most widely used SCF, is relatively cheap,
nontoxic, and non-flammable and has zero
ozone-depletion potential. Moreover, the fact
that CO2 is a gas under ambient conditions
makes its removal from the polymeric
product very easy, avoiding for example, the
costly processes of drying or solvent
removal, which is very important in the
processing of polymer based materials.
But what are the properties of an SCF? A
supercritical fluid is defined as a substance
above its critical pressure and temperature.
However, there is still no apparent
distinction between a high-pressure gas and

An example of alkene polymerization, in

which each styrene monomer's double bond
reforms as a single bond plus a bond another
styrene monomer. The product is polystyrene.
Polymers can be synthesized and/or
modified in a supercritical medium. Most
polymers show some solubility, plasticization,
or swelling in supercritical fluid media.
Depending on the choice of polymer-SCF
medium, the degree of solubilization,
plasticization, or swelling varies.
Properties of Supercritical CO2 and its
effects on the polymerization process
CO2 is used in majority as a supercritical
fluid as its cheaper, non-poisonous and easily
available and its critical properties are easily
attainable with respect to others as seen from
the phase diagram of CO2.

USE OF SUPERCRITICAL FLUIDS IN ENHANCEMENT OF

POLYMERIZATION PROCESS (REVIEW).
CHINMAY P TIWARI
DEPARTMENT OF CHEMICAL ENGINEERING
L.D. COLLEGE OF ENGINEERING
AHMEDABAD
chinmaytiwari15@gmail.com

There have been many application of

different spectroscopic methods and other
new techniques at molecular level to identify
for the first time specific molecular
interactions between CO2 and polymers
that may be responsible for the
plasticization of glassy polymers. The
changes in IR spectra of CO2 incorporated
into various

AKSHAY G CHOTHANI
DEPARTMENT OF CHEMICAL ENGINEERING
L.D. COLLEGE OF ENGINEERING
AHMEDABAD
akshaychothani1995@gmail.com

plasticization by CO2 is accompanied by the

enhanced mobility of polymer segments,
similar to the plasticizing effect by ordinary
solvents. One of the differences between
common liquid plasticizers and CO2 is that
CO2 is easily removable from the processed
polymers, and thus may be used for solventfree incorporation of additives. It is possible to
change the degree of plasticization and
swelling of such a polymer, and consequently
its free- volume, merely by changing the
density of the CO2.
The motivation for using SCFs in polymer
processing stems not just from the
environmental impetus for their use as the
benign (not harmful) solvents. As explained
above, SCFs have a number of unique
properties that could be utilized for polymer
synthesis in these media.

polymers indicate a specific interaction

between CO2 and polymer functional
groups. Increased polymer segmental
mobility has also been observed, indicative
of the plasticization phenomenon.

Fig. Visualization of the relative effort required for polymerization and

solvent recovery in conventional catalytic polymerization processes
based on organic solvents. Thus polymerization with supercritical
fluids is preferred.

Supercritical fluids, mainly supercritical CO2,

have been widely applied in the chemistry
and processing of polymers. Elevated
pressure CO2 is known to swell and
plasticize glassy polymers. The increase in
the polymer inter-chain distance upon

In addition, it is the molecular structure of

some specific fluids, primarily supercritical
CO2 that plays a major beneficial role in
polymer-processing. The sorption of scCO2
into polymers results in their swelling and
changes the mechanical and physical
properties of the polymers. The most
important effect is the reduction of the glass
transition temperature (Tg) of glassy polymers
subjected to scCO2, often simply called
plasticization. The plasticization of polymers
induced by scCO2 has an impact on many
polymer-processing operations, These
include viscosity reduction for polymer
extrusion and blending, enhancement of the
diffusion of additives through polymer matrices
for impregnation and extraction, enhancement
of monomer diffusion for polymer
synthesis, foaming of polymers, and
changes in polymer morphology due to
induced crystallization.

Illustrations of enhancement in polymer

processing using supercritical fluid
Decomposition of Waste Plastics in
Super critical Water

USE OF SUPERCRITICAL FLUIDS IN ENHANCEMENT OF

POLYMERIZATION PROCESS (REVIEW).
CHINMAY P TIWARI
DEPARTMENT OF CHEMICAL ENGINEERING
L.D. COLLEGE OF ENGINEERING
AHMEDABAD
chinmaytiwari15@gmail.com

AKSHAY G CHOTHANI
DEPARTMENT OF CHEMICAL ENGINEERING
L.D. COLLEGE OF ENGINEERING
AHMEDABAD
akshaychothani1995@gmail.com

1. Property of super critical water

Water, most important solvent in nature, has
fascinating properties as a reaction solvent in
its super critical condition. The super critical
water is the fluid that is over the critical point
of vapour-liquid coexistence state. The critical
temperature and critical pressure of water are
647K and 22MPa, respectively. The density of
super critical water can continuously be
controlled between gas like and liquid like
values by varying its pressure and
temperature. The value of dielectric constant
that is one of the parameter estimating the
fig2. Ion product of water
solvent polarity, increase with increasing
At super critical condition, for example at 573K
density. The relation between dielectric
and 34.5MPa, the value of ion product is 10-11.
constant and density is shown in figure 1.
This value means hydrogen ion concentration
of super critical water is almost 3*10-7 and this
value means that the super critical water at this
condition acts the role as acid solutions
catalyst.
2. Hydrolysis of plastic in super critical
water
By the fascinating properties of super critical
water, the substance with ether, ester and
isocyanate bond which are the condensation
polymerization plastic can easily be
decomposed to their monomer when super
fig1. Dielectric constant of water
critical water is used as reaction solvent. It is
experienced that the PET (Polyethylene
At super critical condition, the values of the
terephthalate) is decomposed to their monomer
constant between 5 to 25 can be obtained.
This corresponds to the dielectric properties of in the super critical water by the batchcontinuous apparatus. Fig.3 shows the relation
polar organic liquids under normal condition.
between the recovery yield of monomer and
This property partially explain its ability to
reaction temperature at 25MPa and 30MPa.
dissolve nonpolar organic compounds.
The recovery yield of TPA (Ter-phthalic acid)
At standard conditions, water dissociates
reaches almost 100% over 350K of the
slightly into hydrated hydrogen and hydroxyl
temperature. However, yield of EG (Ethylene
ions: the "ion product" (Kw) of their
glycol) is about 30% at the same temperature.
concentrations is about 10-14(mol/1)2. The ion It seems that this due to effect of acid catalyst
product of water is strongly dependent on
of recovered TPA in super critical water.
density and weakly dependent on
temperature. This is shown in figure 2

USE OF SUPERCRITICAL FLUIDS IN ENHANCEMENT OF

POLYMERIZATION PROCESS (REVIEW).
CHINMAY P TIWARI
DEPARTMENT OF CHEMICAL ENGINEERING
L.D. COLLEGE OF ENGINEERING
AHMEDABAD
chinmaytiwari15@gmail.com

Fig.3 Relation between recovery yield of TPA from

PET and reaction temperature at 25, 30MPa

3. Pyrolysis of plastic in super critical

water

AKSHAY G CHOTHANI
DEPARTMENT OF CHEMICAL ENGINEERING
L.D. COLLEGE OF ENGINEERING
AHMEDABAD
akshaychothani1995@gmail.com

fig.4

Polymer clay nanocomposites

(illustration 2)

When the super critical water is used as

reaction solvent, the temperature of water
used as reaction medium is over the pyrolysis
condition of plastics. The addition
polymerization plastic is converted to the oil in
the super critical water.

4. Application off super critical water in

waste plastic treatment field

CO2 has a readily accessible critical point and

is a relatively inexpensive, non-toxic, and
When the waste material which is composed
of the condensation polymerization plastic and environmentally friendly solvent. Our research
has shown that soaking commercial clays in
the addition polymerization plastic, is treated
supercritical CO2, followed by a rapid
in the super critical water, the former one is
depressurization can produce significant clay
selectively decomposed to their monomer in
dispersion without any additional modification
short time, that is the chemicals, and at this
of the clays or their modifiers. Clay dispersion
time latter one is not decomposed. The
has been achieved with a variety of different
addition polymerization polymer, however, is
clays, with and without the presence of polymer
continuously converted to oil following to the
monomerization of the condensation
The extent of dispersion is characterized by a
polymerization plastic. The technology on this
wide range of characterization tools, such as
decomposition of plastics in the super critical
WAXD (wide-angle X-ray diffraction), SEM
water is expected as the novel waste material
(scanning electron microscope), TEM
treatment process.
(Transmission electron microscopy), rheology,

USE OF SUPERCRITICAL FLUIDS IN ENHANCEMENT OF

POLYMERIZATION PROCESS (REVIEW).
CHINMAY P TIWARI
DEPARTMENT OF CHEMICAL ENGINEERING
L.D. COLLEGE OF ENGINEERING
AHMEDABAD
chinmaytiwari15@gmail.com

tensile and permeability testing.

The scCO2-processed samples have been

benchmarked with solution blended and
melt-compounded PS nanocomposites. The
results suggest that the supercritical CO2processing produces significant dispersion
and improves polymer-clay interactions. The
low-frequency modulus of scCO2-processed
PS/clay melts are more than an order of
magnitude better than those prepared by
solution blending and melt compounding, for
the same clay loading.

AKSHAY G CHOTHANI
DEPARTMENT OF CHEMICAL ENGINEERING
L.D. COLLEGE OF ENGINEERING
AHMEDABAD
akshaychothani1995@gmail.com

Conclusion
These theories shows that conventional
processes for polymerization mainly uses
liquids as solvents which has its own
demerits while using supercritical fluids
has its own merits. In using liquid solvents
for polymerization their revival from the
reaction mixture is costlier whereas it may
sometime contaminate the product by its
presence but by using non-toxic, nonflammable gas like carbon dioxide easy
separations plus higher rate of reaction
due to formation of microcellular structure
takes place as illustrated in below figure.

References
http://www.kannangroup.com/nanoco
mposites.html
http://infohouse.p2ric.org/ref/26/japan
/Waste-187.html
http://www3.imperial.ac.uk/vibrational
spectroscopyandchemicalimaging/res
earch/intermolecular/polymerprocessi
ng
https://workspace.imperial.ac.uk/.../pu
blic/reviewscf.pdf
eckert.chbe.gatech.edu/pdf/polymer.p
df
Journal on supercritical CarbonDioxide for Sustainable Polymer
Processes - Maartje Kemmere
Polymer Processing with Supercritical
Fluids-S. G. Kazarian