Use of supercritical fluids in

enhancement of polymerization
process.
Prepared by :Chinmay Tiwari
Akshay Chothani
Chemical Engineering
LD College of Engineering
Ahmedabad.

Table of contents
Introduction of supercritical fluids
Properties and effects of supercritical carbon dioxide on polymerization
Illustrations of enhancement in polymer processing using supercritical
fluids
1. Decomposition of waste plastics in supercritical water
2. Polymer clay nano-composites

Introduction of supercritical fluids

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
(toluene, methyl-chloride..etc.)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.

 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 SCF because, under all circumstances, such a
fluid will occupy the full volume of its container, demonstrating the typical
behaviour 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, however, that it can still be solidified at extremely high pressures).
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.

Properties and effects of supercritical carbon dioxide on polymerization

CO2 is used in majority as a supercritical fluid as its cheaper,
non-poisonous and easily available and its critical properties
(critical temperature (304.25 K) and critical pressure (72.9atm
or 7.39MPa))are easily attainable with respect to others as seen
from the phase diagram of CO2.

 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.

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.

 Elevated pressure CO2 is known to swell and plasticize glassy polymers.

The increase in the polymer inter-chain distance upon 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.
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.
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 fluids
Decomposition of Waste Plastics in Super critical Water
Property of super critical water
(variation in density linking to dielectric constant values, ion-product Kw value increase at sc state acting as acid solution
catalyst)

Hydrolysis of plastic in super critical water

(condensation polymers having ether , ester and isocyanate bond can be decomposed using sc-water , eg. PET decompose
to ter-pthalic acid and ethylene glycol )

Pyrolysis of plastic in super critical water

(using sc-water thermal decomposition of plastic takes place giving oil,gas and char as a product)

Application off super critical water in waste plastic treatment field

 When the waste material which is composed of the condensation

polymerization plastic and the addition polymerization plastic, is treated in
the super critical water, the former one is selectively decomposed to their
monomer in short time, that is the chemicals, and at this time latter one is
not decomposed.
The addition polymerization polymer, however, is continuously converted
to oil following to the monomerization of the condensation polymerization
plastic.
The technology on this decomposition of plastics in the super critical water
is expected as the novel waste material treatment process.

Polymer clay nanocomposites

Research has shown that soaking commercial clays in supercritical CO2,

followed by a rapid depressurization can produce significant clay
dispersion without any additional modification of the clays or their
modifiers.

The scCO2-processed samples have been benchmarked with solution

blended and melt-compounded PS(polystyrene) nanocomposites .

 The results suggest that the supercritical CO2-processing 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.

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, non-flammable gas like carbon
dioxide easy separations plus higher rate of reaction due to formation of
microcellular structure takes place.

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.

References
http://www.kannangroup.com/nanocomposites.html
http://infohouse.p2ric.org/ref/26/japan/Waste-187.html
http://www3.imperial.ac.uk/vibrationalspectroscopyandchemicalim
aging/research/intermolecular/polymerprocessing
https://workspace.imperial.ac.uk/.../public/reviewscf.pdf
eckert.chbe.gatech.edu/pdf/polymer.pdf
Journal on supercritical Carbon-Dioxide for Sustainable Polymer
Processes - Maartje Kemmere
Polymer Processing with Supercritical Fluids-S. G. Kazarian

THANK YOU