Polymerization:

Polymerization in supercritical fluids, and in particular carbon dioxide continuous to be an active area
as CO2 is an attractive alternative to organic solvents as polymerization media. It can be easily removed after
polymerization, and there is minimal chain transfer in radical polymerizations if the medium is CO 2. Since
polymers are in general not soluble in CO2 except for amorphous fluoropolymers and polysiloxanes, majority
of polymerizations in CO2 are heterogeneous in nature. They involve either precipitation or dispersion
polymerizations. When appropriate stabilizers (which are often based on fluoropolymers or silicones) are
used, dispersion polymerizations lead to uniform size particles that are tunable in size and morphology. In
dispersion polymerizations, polymerization starts at initially homogeneous conditions, when monomer and
the dispersants are fully soluble in the in the solvent medium, but with progress of polymerization, when the
polymer chains reach a threshold length, they become immiscible in the medium and phase separation occurs,
leading to the polymer particles that are stabilized with the dispersant that is in the system. Dry polymers may
be obtained by simple depressurization of the vessel after polymerizations. The low viscosity of the medium,
high mass transfer and high diffusivity reduce the likelihood of the Trommsdorf effect which can lead to
localized heating and runaway conditions. Often higher molecular weight polymers are produced with higher
conversions and improved kinetics. From the foregoing, it is important to emphasize that the low solubility of
polymers in supercritical carbon dioxide does not prevent conducting polymerizations in CO2 as is the case
with dispersion polymerizations as long as the presence of added stabilizers in the final polymer that is
produced can be tolerated. Other approaches to improve the miscibility often employ carbon dioxide that is
modified with an organic solvent as the polymerization medium.
Traditionally, majority of polymerizations in supercritical CO2 have been carried out by free‐radical
polymerizations. In radical polymerizations control over molecular structure is however not easy because of
the high reactivity of the radical intermediates which have short lifetimes (< 1s) prior to termination.
Furthermore, the growing active polymer radicals can react with another (either by radical combination or
disproportionation) and lead to polymers with broad molecular weight distributions. New developments in
radical polymerizations are centered on controlled radical polymerizations (CRD) which is also known as
reversible deactivation radical polymerization (RDRP). This mode of polymerization involves multiple
reversible radical deactivation steps which inserts periods of dormancy (of about 1 min) after short periods of
activity (about 1 ms activity), extending the life‐time of a propagating chain from about 1s to much longer
times [9]. CRD permits synthesis of copolymers with controlled molecular weights and structure, which is
otherwise not possible with conventional free radical polymerizations that would lead to only random
copolymers. A range of controlled radical polymerization schemes have emerged over the years among which
are RAFT (reversible addition‐fragmentation chain transfer polymerization), ATRO (atom transfer radical
polymerization), NMP (nitroxide‐mediated polymerization), ITP (iodine transfer polymerization) and RTCP
(reversible chain transfer catalyzed polymerization) [37]. These all have their positives and negatives. For
example, ITP is considered to be a robust method that does not use metals and can be used with a wide range
of polymerizable monomers (such as fluorinated, phosphonated monomers), but does not allow high control
of molecular weight distribution. If block copolymerizations are conducted in supercritical CO 2 via RAFT‐
controlled dispersion polymerization, the results display greater blocking efficiency.
An excellent review by Boyere [7] summarizes all the CO2‐based polymerizations including (1) step‐
growth polymerization (where melt‐phase polycondensation in CO2 becomes valuable alternative because of
the plasticization effect of CO2 which reduces the viscosity for more effective stirring; and for extraction of side
products with CO2); (2) chain growth polymerizations by ATRP (polymerization of fluorinated (meth)acrylates;
block copolymers of poly(acrylic acid) and styrene), RAFT (polymerization of methyl methacrylate using
fluorinated macro‐RAFT agents as stabilizers ) and NMP (of styrene using PDMS‐b‐PMMA copolymer
stabilizers) , and controlled ring opening polymerization (ROP). These are either (a) homogenous (as in the

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case of homogenous free radical polymerization to synthesize fluoropolymers), or (b) precipitation (as in the
case of vinyl hydrocarbon monomers like styrene or acrylonitrile), (c) dispersion polymerizations of monomers
that are miscible (but polymers not miscible) with CO2 using fluorinated or non‐fluorinated stabilizers (as in
synthesis of PMMA or poly (vinyl acetate), (e) suspension polymerizations of monomers that are not soluble in
CO2 (such as the polymerization of N‐ethyl acrylamide or the ring opening polymerization of lactide), (f)
emulsion polymerization which is typically conducted in biphasic water/organic solvent mixture in the
presence of a surfactant to form micelles is adopted to carbon dioxide in water or water in carbon dioxide
emulsion using dedicated surfactants ( to polymerize hydrophilic and CO2‐insoluble monomer). In water‐in‐
CO2 systems, (as in the polymerization of acrylamide using functionalized perfluoropolyether as stabilizer ),
CO2 is the continuous phase and the surfactant forms micelles with an aqueous core containing the hydrophilic
monomer, where polymerization of the monomer leads to particles suspended in supercritical CO 2. The CO2‐
philic segment of the stabilizer extends into the CO2 continuous phase to prevent aggregation of the polymer
particles by steric stabilization. In the CO2‐in‐water emulsions, (as in the polymerization of acrylamide, or ionic
liquid monomers using fluorinated glycosurfactants), water is the continuous phase, the CO 2‐phillic segment of
the stabilizer stabilize droplets of CO2 dispersed in water. In this case the polymerization of the water soluble
monomer in the water phase is templated by CO2. The removal of CO2 at the end of polymerization leads to
formation of a porous polymer matrix. When the dispersed CO2 phase constitutes more than 74 % of the total
volume, the end results is a highly porous network with interconnected pores and is referred to as poly(HIPE).
The use of fluorinated stabilizers are however limited due to their cost and also due to their toxicity which
puts further limitations for these porous materials for biomedical applications. The review article by Yao [38])
reviews the free‐radical polymerizations in supercritical carbon dioxide to produce fluorinated
poly(meth)acrylates, among which are copolymerization of 11, dihydroperfluorooctyl acrylate with methyl
methacrylate, styrene, butyl acrylate.
It is no surprise that majority of the polymerization studies carried out in CO2 published in 2014
employed controlled polymerization techniques. Combination of polymerization with other CO 2 driven
phenomena such as foaming is noted as a new trend towards forming highly porous structures [5]. Generation
of hybrid materials by conducting polymerization of a second monomer in the pores of a first polymer are also
explored. Among the specific polymers that have been prepared in supercritical CO2 in 2014 are poly(vinyl
esters) such as poly(vinyl acetate) [39‐41], polylactide and polyglycolide [42‐45], poly(N‐isopropylacrylamide)
[46], copolymers of perfluoroalkyl methyl methacrylate and styrene [47‐48], and molecularly imprinted
polymers [49]. These activities are described below.

References:
5. F. Picchioni, Supercritical carbon dioxide and polymers: an interplay of science and technology,
Society of Chemical Industry 63 (2014) 1394‐ 1399.
7. C. Boyere, C. Jerome, A. Debuigne, Input of supercritical carbon dioxide to polymer synthesis: An
overview, European Polymer Journal, 61(2014) 45‐63.
9. K. Matyjaszewski, N. V. Tsarevsky, Macromolecular engineering by atom transfer radical
polymerization, Journal of the American Chemical Society, 136 (2014) 6513‐6533.
37. J. Jennings, M. Beija, J. T. Kennon, H. Wilcock, R. K. O’Reilly, S. Rimmer, S. M. Howdle, Advantages
of block copolymer synthesis by RAFT‐controlled dispersion polymerization in supercritical carbon dioxide,
Macromolecules 46 (2013) 6843‐6851.
38. W. Yao, Y. Li, X. Huang, Fluorinated poly(meth)acrylate: Synthesis and properties, Polymer (55
(2014) 6197‐6211.
39. M. T. Islam, Y. Haldorai, V. H. Nguyen, M. N. Islam, C. S. Ra, J. J. Shim, Controlled radical
polymerization of vinyl acetate in supercritical CO2 catalyzed by CuBr /terpyridine, Korean Journal of Chemical
Engineering, 32 (2014) 1088‐1094.

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 40. M. N. Islam, Y. Haldorai, V. H. Nguyen, J. J. Shim, Synthesis of poly(vinyl pivalate) by atom transfer
radical polymerization in supercritical carbon dioxide , European Polymer Journal, 61 (2014) 93‐104.
41. Q. L. Pham, Y. F. Haldorai, V. H. Nguyen, C. K. Kang, J. J. Shim, Reversible addition fragmentation
chain transfer polymerization of vinyl acetate and vinyl pivalate in supercritical carbon dioxide, Korean Journal
of Chemical Engineering 31 (2014) 2101‐2107.
42. C. Schmidt, M. Behl, A. Lendlein, S. Beuermann, Synthesis of high molecular weight polygycolide in
supercritical carbon dioxide, RSC Advances, 4 (2014) 35099‐35105.
43. S. Zhan, J. Ren, W. Wang, Q. Zhao, J. Zhau, Precipitation polymerization of PLGA with Sn(Oct)2
/BuOH in supercritical carbon dioxide, Polymer Engineering and Science (2014) 704‐710; DOI
10.1002/pen.23618.
44. R. Ferrari, C. M. Pecoraro, G. Storti, D. Moscatelli, A green route to synthesize poly(lactic acid)
based macromonomers in sc CO2 for biodegradable nanoparticle production. RSC Advances 4 (2104) 12795-
12804.

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