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purity, and quality of these materials will continue to reactions has been demonstrated in many studies.9
expand as more products are commercialized. The phase What is more interesting is that polymer molecular
behavior of the solute species in the supercritical fluid weight and molecular weight distribution, as well as
must be known precisely for reliable process design, and microstructure and morphology, can be controlled in
the considerable effort in this area is likely to continue. these reactions. Supercritical fluids such as CO2 also
However, there will be an increasing need for mass- lower the glass transition temperature of the polymer,
transfer, process design, and simulation studies for which can facilitate the impregnation of the polymer by
these supercritical processes. Moreover, the need for additives, drugs, dyes, and other polymers. The viscosity
acceptance of these sometimes “new” products by the of the polymer in the molten or dissolved states can be
consumer will determine their commercial success. lowered in the presence of supercritical fluids, which
can lead to new methodologies for the production of
Solvent Replacement and Green Chemistry polymer films, coatings, fibers, foams, membranes,
composites, and porous structures.10 Finally, supercriti-
A significant amount of research on supercritical cal fluids also offer the potential for the processing of
fluids has been devoted to their use as alternative inorganic materials, via synthesis reactions or from
solvents that are environmentally benign. In particular, decomposition of soluble precursors. Thin metal films,
the use of water and CO2 as solvents for traditional magnetic oxides, silicon nanowires, and other materials
organic syntheses is receiving and will continue to have been produced by deposition, microemulsion, and
receive much attention. The design of new chemical sol-gel techniques using supercritical fluids.11
pathways using these and other supercritical solvents
will also be of much interest. The potential for exploiting Analytical Applications
the “tunable” nature of the properties of supercritical
solvents (with and without cosolvents) will probably be The use of supercritical fluids as mobile phases in a
realized commercially in applications other than the chromatograph was demonstrated almost 40 years ago.
oxidation of organic wastes in supercritical water.4 Since then, commercial chromatographs have been
Supercritical fluids are promising media for homoge- marketed and supercritical fluid chromatography has
neous as well heterogeneous reactions. In particular, found its place as an analytical technique in many
reactions in near-critical and supercritical fluids will be applications.12 Furthermore, supercritical fluid extrac-
able to exploit the enhanced rates, improved mass tion is extensively used in sample preparation. There
transfer, increased selectivity and yield, and ease of is an extensive literature on the development of pack-
separation of reaction products.5,6 The technical feasibil- ings, columns, modifiers, detectors, and methods, dis-
ity of phase-transfer catalysis, selective oxidations, cussion of which is beyond the scope of this brief
cycloadditions, enzymatic reactions, and enantioselec- commentary. It is sufficient to note here that research
tive syntheses has already been demonstrated and will and development in this area will continue to flourish
likely be exploited in commercial applications in the in the future.
future.
Other Applications
Particle Production
Mechanisms by which molecules are solubilized in
The manufacture of uniform-sized organic and inor- supercritical CO2 have been studied extensively and are
ganic particles using the RESS process has already been being increasingly understood. It has been demon-
commercialized on a pilot-plant scale. The supercritical strated that fluoroalkanes, fluoroethers, poly(dimeth-
antisolvent process (and its many variations including ylsiloxane), and even carbonates offer special opportu-
GAS, SAS, PCA, SEDS, etc.) has also been the subject nities for CO2-philicity.13 This can be exploited in the
of many studies to make uniform particles.7 These synthesis of fluorochemicals and fluoropolymers and in
processes are of considerable interest in the pharma- the design of amphiphilic molecules specifically for
ceutical, paint, and polymer industries. Supercritical supercritical CO2. The latter include surfactants to
fluids offer a wide range of possibilities in the making promote water/CO2 macro- and microemulsions that
of particles. Active fragrance and flavor agents, as well offer many opportunities to do aqueous chemistry in the
as drugs, can be microencapsulated within a coating of supercritical phase. As a result, bioreactions involving
protective material using RESS. The supercritical pro- enzymes, peptides, and proteins can now be carried out
cess eliminates the potential for solvent contamination in supercritical CO2. These techniques can also be used
and is able to microencapsulate many materials that to make chelating agents to recover metal atoms, to
are difficult to treat with existing techniques. It has also carry out heterogeneous reactions such as phase-
been demonstrated that morphology can be controlled transfer catalysis and biphasic chemistry in fluorous
by adjusting nucleation and growth during the synthesis systems, and to develop new synthesis routes for na-
of nanoparticles of inorganic materials in supercritical nomaterials in supercritical CO2.
fluids,8 and this is an area that is likely to receive much Finally, investigations are underway to use super-
attention in the future. critical CO2 to improve the uniformity, purity, and
feature size of microelectronic devices. These investiga-
Materials Processing tions include the use of chemical fluid deposition from
CO2-soluble precursors to make thin metal films and
Processing in supercritical fluids offers routes to core-shell materials for magnetic recording.
“novel” materials, especially in the case of polymeric It has been suggested that the future of supercritical
materials, where properties such as morphology can be fluid processing depends on the technology going beyond
tailored to specific applications. The use of supercritical these niche markets and into mainstream processing.2
fluids as polymerization media to replace conventional The argument is that this technology would never
organic solvents and as reactants in polymerization gain acceptance in chemical manufacturing until it was
4444 Ind. Eng. Chem. Res., Vol. 39, No. 12, 2000
applied to high-volume products with low capital costs. (6) Brennecke, J. F.; Chateauneuf, J. E. Homogeneous Organic
Although we would welcome such applications, it seems Reactions as Mechanistic Probes in Supercritical Fluids. Chem.
more likely that the “niche” markets described in this Rev. 1998, 99, 433-452.
commentary will make up a significant fraction of the (7) Debenedetti, P. G.; Tom, J. W.; Yeo, S.-D.; Lim, G. B.
manufacturing sector in the future. Supercritical fluids Application of Supercritical Fluids for Production of Sustained
Delivery Devices. J. Controlled Release 1993, 24, 27-34.
have already made inroads into these markets, and
their contributions are likely to continue to increase. (8) Hakuta, Y.; Adschiri, T.; Hirakoso, H.; Arai, K. Chemical
Equilibria and Particle Morphology of Boehmite in Sub- and
The variety of these “niche” applications and the in- Supercritical Water. Fluid Phase Equilib. 1999, 158-160, 733-
creasing amount of research devoted to understanding 739.
the mechanisms of supercritical processes attest to the (9) DeSimone, J. M.; Maury, E. E.; Menceloglu, Y. Z.; McClain,
“maturing” of this technology and to the increasing J. B.; Romack, T. J.; Combes, J. R. Dispersion Polymerizations in
likelihood that it will be a significant contributor to Supercritical Carbon Dioxide. Science 1994, 265, 356-357.
manufacturing in the future. (10) Watkins, J. J.; Rao, V. S.; Pollard, M. A.; Russell, T. P. In
Phase Transitions in Polymer Blends and Block Copolymers
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