Ethylene free radical polymerization in supercritical

ethylene/CO2 mixture†

Polymerization of ethylene via radical pathways involving high temperatures and pressures (>200
°C, >2000 bar) is the current process of choice to produce low-density polyethylene (LDPE). Here
we report ethylene free radical polymerization in supercritical CO2/ethylene mixture as a reaction
medium without any addition of organic solvent and under milder conditions (<100 °C, <300 bar).
The effect of CO2 pressure on the yield and the molar masses of the polyethylenes (PE)
produced is substantial and depends on the chosen initiator. The three selected initiators
(AzobisIsoButyroNitrile, lauroyl peroxide, and benzoyl peroxide) all yield PE, with Mw up to
∼20 000 g mol−1, confirming the non-transferring nature of CO2. We also investigated the
divergences in initiation/transfer/termination for these 3 compounds embedded within the
functionalities borne by the polyethylene chains, and in particular the influence of CO2 over the
polymerization. No CO2-derived moieties could be evidenced within the PE chains, neither for
AIBN nor lauroyl peroxide. On the contrary, benzoic ester moieties could be identified within the
produced PE when benzoyl peroxide was employed. This study paves the road towards
functionalization of PE via radical processes.

Polymer chemistry is a sub-discipline of chemistry that focuses on the chemical synthesis,

structure, chemical and physical properties of polymers and macromolecules. The principles and
methods used within polymer chemistry are also applicable through a wide range of other
chemistry sub-disciplines like organic chemistry, analytical chemistry, and physical
chemistry Many materials have polymeric structures, from fully
inorganic metals and ceramics to DNA and other biological molecules, however, polymer
chemistry is typically referred to in the context of synthetic, organic
compositions. Synthetic polymers are ubiquitous in commercial materials and products in
everyday use, commonly referred to as plastics, and rubbers, and are major components
of composite materials. Polymer chemistry can also be included in the broader fields of polymer
science or even nanotechnology, both of which can be described as encompassing polymer
physics and polymer engineering.
The chemist Hermann Staudinger first proposed that polymers consisted of long chains
of atoms held together by covalent bonds, which he called macromolecules. His work expanded
the chemical understanding of polymers and was followed by an expansion of the field of
polymer chemistry during which such polymeric materials as neoprene, nylon and polyester were
invented. Before Staudinger, polymers were thought to be clusters of small molecules (colloids),
without definite molecular weights, held together by an unknown force. Staudinger received
the Nobel Prize in Chemistry in 1953. Wallace Carothersinvented the first synthetic
rubber called neoprene in 1931, the first polyester, and went on to invent nylon, a true silk
replacement, in 1935. Paul Flory was awarded the Nobel Prize in Chemistry in 1974 for his work
on polymer random coil configurations in solution in the 1950s. Stephanie Kwolek developed
an aramid, or aromatic nylon named Kevlar, patented in 1966. Karl Ziegler and Giulio
Natta received a Nobel Prize for their discovery of catalysts for the polymerization
of alkenes. Alan J. Heeger, Alan MacDiarmid, and Hideki Shirakawa were awarded the 2000
Nobel Prize in Chemistry for the development of polyacetylene and related conductive
polymers.[8] Polyacetylene itself did not find practical applications, but organic light-emitting
diodes (OLEDs) emerged as one application of conducting polymers.

Polymers and their properties

Polymers are high molecular mass compounds formed by polymerization of monomers. The
simple reactive molecule from which the repeating structural units of a polymer are derived is
called a monomer. A polymer can be described in many ways: its degree of
polymerisation, molar mass distribution, tacticity, copolymer distribution, the degree of branching,
by its end-groups, crosslinks, crystallinity and thermal properties such as its glass transition
temperature and melting temperature. Polymers in solution have special characteristics with
respect to solubility, viscosity, and gelation. Illustrative of the quantitative aspects of polymer
chemistry, particular attention is paid to the number-average and weight-average molecular

weights and , respectively.

The formation and properties of polymers have been rationalized by many theories
including Scheutjens–Fleer theory, Flory–Huggins solution theory, Cossee-Arlman
mechanism, Polymer field theory, Hoffman Nucleation Theory, Flory-Stockmayer Theory, and
many others.

Origin
Polymers can be subdivided into biopolymers and synthetic polymers according to their origin.
Each one of these classes of compounds can be subdivided into more specific categories in
relationship to their use and properties.
Biopolymers are the structural and functional materials that comprise most of the organic matter
in organisms. One major class of biopolymers are proteins, which are derived from amino
acids. Polysaccharides, such as cellulose, chitin, and starch, are biopolymers derived from
sugars. The polynucleic acids DNA and RNA are derived from phosphorylated sugars with
pendant nucleotides that carry genetic information.
Synthetic polymers are the structural materials manifested in plastics, synthetic
fibers, paints, building materials, furniture, mechanical parts, and adhesives. Synthetic polymers
may be divided into thermoplastic polymers and thermoset plastics. Thermoplastic polymers
include polyethylene, teflon, polystyrene, polypropylene, polyester, polyurethane, Poly(methyl
methacrylate), polyvinyl chloride, nylons, and rayon. Thermoset
plastics include vulcanized rubber, bakelite, Kevlar, and polyepoxide. Almost all synthetic
polymers are derived from petrochemicals.
Viscosity[edit]
As polymers get longer and their molecular weight increases, the viscosity of polymers in their
dissolved and liquid states also tend to increase. Thus, the measured viscosity of synthesized
polymers can provide valuable information about the average length of the polymer, the progress
of reactions and in what ways the polymer branches.[10]

History of polymer science[edit]

The first modern example of polymer science is Henri Braconnot's work in the 1830s. Henri,
along with Christian Schönbein and others, developed derivatives of the natural
polymer cellulose, producing new, semi-synthetic materials, such as celluloid and cellulose
acetate. The term "polymer" was coined in 1833 by Jöns Jakob Berzelius, though Berzelius did
little that would be considered polymer science in the modern sense. In the 1840s, Friedrich
Ludersdorf and Nathaniel Hayward independently discovered that adding sulfur to raw
natural rubber (polyisoprene) helped prevent the material from becoming sticky. In 1844 Charles
Goodyear received a U.S. patent for vulcanizing natural rubber with sulfur and heat.Thomas
Hancock had received a patent for the same process in the UK the year before. This process
strengthened natural rubber and prevented it from melting with heat without losing flexibility. This
made practical products such as waterproofed articles possible. It also facilitated practical
manufacture of such rubberized materials. Vulcanized rubber represents the first commercially
successful product of polymer research. In 1884 Hilaire de Chardonnet started the first
artificial fiber plant based on regenerated cellulose, or viscose rayon, as a substitute for silk, but
it was very flammable.[1] In 1907 Leo Baekeland invented the first synthetic plastic,
a thermosetting phenol–formaldehyde resin called Bakelite.[2]
Despite significant advances in polymer synthesis, the molecular nature of polymers was not
understood until the work of Hermann Staudinger in 1922.[3] Prior to Staudinger's work, polymers
were understood in terms of the association theory or aggregate theory, which originated
with Thomas Graham in 1861. Graham proposed that cellulose and other polymers
were colloids, aggregates of molecules having small molecular mass connected by an unknown
intermolecular force. Hermann Staudinger was the first to propose that polymers consisted of
long chains of atoms held together by covalent bonds. It took over a decade for Staudinger's
work to gain wide acceptance in the scientific community, work for which he was awarded
the Nobel Prize in 1953.
The World War II era marked the emergence of a strong commercial polymer industry. The
limited or restricted supply of natural materials such as silk and rubber necessitated the
increased production of synthetic substitutes, such as nylon[4] and synthetic rubber.[5] In the
intervening years, the development of advanced polymers such as Kevlar and Teflonhave
continued to fuel a strong and growing polymer industry.
The growth in industrial applications was mirrored by the establishment of strong academic
programs and research institute. In 1946, Herman Mark established the Polymer Research
Institute at Brooklyn Polytechnic, the first research facility in the United States dedicated to
polymer research. Mark is also recognized as a pioneer in establishing curriculum and pedagogy
for the field of polymer science.[6] In 1950, the POLY division of the American Chemical
Society was formed, and has since grown to the second-largest division in this association with
nearly 8,000 members. Fred W. Billmeyer, Jr., a Professor of Analytical Chemistry had once said
that "although the scarcity of education in polymer science is slowly diminishing but it is still
evident in many areas. What is most unfortunate is that it appears to exist, not because of a lack
of awareness but, rather, a lack of interest."[7]

Nobel prizes related to polymer science[edit]

2005 (Chemistry) Robert Grubbs, Richard Schrock, Yves Chauvin for olefin metathesis.[8]
2002 (Chemistry) John Bennett Fenn, Koichi Tanaka, and Kurt Wüthrich for the development of
methods for identification and structure analyses of biological macromolecules.[9]
2000 (Chemistry) Alan G. MacDiarmid, Alan J. Heeger, and Hideki Shirakawa for work
on conductive polymers, contributing to the advent of molecular electronics.[10]
1991 (Physics) Pierre-Gilles de Gennes for developing a generalized theory of phase transitions
with particular applications to describing ordering and phase transitions in polymers.[11]
1974 (Chemistry) Paul J. Flory for contributions to theoretical polymer chemistry.[12]
1963 (Chemistry) Giulio Natta and Karl Ziegler for contributions in polymer synthesis. (Ziegler-
Natta catalysis).[13]
1953 (Chemistry) Hermann Staudinger for contributions to the understanding of macromolecular
chemistry.[14]

Subdisciplines
This science comprises three main sub-disciplines:

 Polymer chemistry or macromolecular chemistry is concerned with the chemical synthesis

and chemical properties of polymers.
 Polymer physics is concerned with the bulk properties
of polymer materials and engineering applications.
 Polymer characterization is concerned with the analysis of chemical structure, morphology,
and the determination of physical properties in relation to compositional and structural
parameters.

Steps of chain-growth polymerization[edit]

Typically, chain polymerization must contain chain initiation and chain propagation. Chain
transfer and chain termination do not always happen in a chain-growth polymerization.

Chain initiation[edit]
Chain initiation is the process of initially generating a chain carrier (chain carriers are some
intermediates such as radical and ions in chain propagation process) in a chain polymerization.
According to different ways of energy dissipation, it can be divided into thermal initiation, high
energy initiation, and chemical initiation, etc. Thermal initiation is a process that obtained energy
and dissociated to homolytic cleavage to form active center by molecular thermal motion. High
energy initiation refers to the generation of chain carriers by radiation. Chemical initiation is due
to chemical initiator.

Chain propagation[edit]
IUPAC defined chain propagation as an active center on the growing polymer molecule, which
adds one monomer molecule to form a new polymer molecule which is one repeat unit longer
with a new active center.

Chain transfer[edit]
The polymerization process does not have to undergo chain transfer. Chain transfer means that
in a chain polymerization, the active center of the polymer A takes an atom from B molecule and
terminates. The B molecule produces a new active center instead. It can happen in free radical
polymerization, ionic polymerization and coordination polymerization. Generally, chain transfer
will generate by-product.[5]
An example of chain transfer

Chain termination[edit]
Chain termination refers to in chain polymerization process, active center disappears, resulting in
the termination of chain propagation. It is different from chain transfer. During the chain transfer
process, the active point only shifts to another molecule but does not disappear.

Classes of chain-growth polymerization[edit]

Radical polymerization[edit]
Based on definition from IUPAC, radical polymerization is a chain polymerization in which the
kinetic-chain carriers are radicals. Usually, the growing chain end bears an unpaired electron.
Free radicals can be initiated by many methods such as heating, redox reactions, ultraviolet
radiation, high energy irradiation, electrolysis, sonication, and plasma. Free radical
polymerization is very important in polymer chemistry. It is one of the most developed method in
chain-growth polymerization. Currently, most polymers in our daily life are synthesized by free
radical polymerization, such as polyethylene, polystyrene, polyvinyl chloride, polymethyl
methacrylate, polyacrylonitrile, polyvinyl acetate, styrene butadiene rubber, nitrile rubber,
neoprene, etc.

Ionic polymerization[edit]
Based on IUPAC, ionic polymerization is a chain polymerization in which the kinetic-chain
carriers are ions or ion pairs. It can be further divided into anionic polymerization and cationic
polymerization. Ionic polymerization is widely used in our daily life. A lot of common polymers are
generated by ionic polymerization such as butyl rubber, polyisobutylene, polyphenylene,
polyoxymethylene, polysiloxane, polyethylene oxide, high density polyethylene, isotactic
polypropylene, butadiene rubber, etc. Living anionic polymerization was developed since the
1950s, the chain will remain active indefinitely unless the reaction is transferred or terminated
deliberately, which realizes the control of molar weight and PDI.[6]

Coordination polymerization[edit]
Based on definition from IUPAC, coordination polymerization is a chain polymerization that
involves the preliminary coordination of a monomer molecule with a chain carrier. The monomer
is firstly coordinated with the transition metal active center, and then the activated monomer is
inserted into the transition metal-carbon bond for chain growth. In some cases, coordination
polymerization is also called insertion polymerization or complexing polymerization. Advanced
coordination polymerizations can control the tacticity, molecular weight and PDI of the polymer
effectively. In addition, the racemic mixture of the chiral metallocene can be separated into its
enantiomers. The oligomerization reaction produces an optically active branched olefin using an
optically active catalyst.[7]

Living polymerization[edit]
Living polymerization was first introduced by Michael Szwarc in 1956. Based on definition from
IUPAC, it is a chain polymerization from which chain transfer and chain termination are absent.
As there is no chain-transfer and chain termination, the monomer in the system is consumed and
the polymerization is stopped when the polymer chain remains active. Once the new monomer is
added, the polymerization can proceed. Due to the low PDI and predictable molecular weight,
living polymerization is at the forefront of polymer research. It could be further divided into living
free radical polymerization, living ionic polymerization and living ring-opening metathesis
polymerization, etc.
Ring-opening polymerization[edit]
According to definition from IUPAC ring-opening polymerization is a polymerization in which a
cyclic monomer yields a monomeric unit which is acyclic or contains fewer cycles than the
monomer. Generally, the ring-opening polymerization is carried out under mild conditions, and
the by-product is less than the polycondensation reaction and the high molecular weight polymer
is easily obtained. Common ring-opening polymerization products includes polypropylene
oxide, polytetrahydrofuran, polyepichlorohydrin, polyoxymethylene, polycaprolactam and
polysiloxane.[8]

Reversible-deactivation polymerization[edit]
IUPAC stipulates that reversible-deactivation polymerization is a kind of chain polymerization,
which is propagated by chain carriers that are deactivated reversibly, bringing them into active-
dormant equilibria of which there might be more than one. An example of a reversible-
deactivation polymerization is group-transfer polymerization.

Comparison to other polymerization methods[edit]

Previously, based on the difference between condensation reaction and addition
reaction, Wallace Carothers classified polymerization as condensation polymerizations and
addition polymerizations in 1929. However, Carothers’ classification is not good enough in
mechanism aspect, as in some case, addition polymerizations shows condensation features
while condensation polymerization shows addition features. Then the classification was
optimized as step-growth polymerization and chain-growth polymerization. Based on IUPAC
recommendation, the names of step-growth polymerization and chain-growth polymerization
were further simplified as polyaddition and chain polymerization.

Step-growth polymerization[edit]
polyamides and polyethers. It is sometimes confused by condensation previous definition of
condensation polymerization. Polyaddition is a type of step-growth polymerization of which chain
growth is based on addition reaction between two molecules of various degree of polymerization.
The typical example for polyaddition is the synthesis of polyurethane. Compared to chain-growth
polymerization, where the production of the growing chaingrowth is based on the reaction
between polymer with active center and monomer, step-growth polymerization doesn’t have
initiator or termination. The monomer in step-growth polymerization will be consumed very
quickly to dimer, trimer or oligomer. The degree of polymerization will increase steady during the
whole polymerization process. On the other hand, in chain-growth polymerization, the monomer
consumed steadily but the degree of polymerization could be increased very quickly after chain
initiation. A step-growth reaction could happened between any two molecules with same or
different degree of polymerization, usually monomers will form dimers, trimers, in matrix and
finally react to long chain polymers. The mechanism of step-growth reaction is based on their
functional group. Step-growth polymerization includes polycondensation and polyaddition.
Polycondensation is a kind of polymerization whose chain growth is based on condensation
reaction between two molecules with various degree of polymerization. The typical example are
polyesters,[9] Compared to step-growth polymerization, living chain-growth polymerization shows
low PDI, predictable molecular mass and controllable conformation. Some researchers are
working on the transformation of two polymerization methods. Generally, polycondensation
proceeds in a step-growth polymerization mode. Substituent effect, catalyst transfer and biphasic
system could be used for inhibiting the activity of monomer, and further prevent monomers from
reacting with each other. It could make polycondensation process go in a chain-growth
polymerization mode.

Polycondensation[edit]
The chain growth of polycondensation is based on condensation reaction. Low-molar-mass by-
product will be formed during polymerization. It is a previous way to classify polymerization,
which was introduced by Carothers in 1929. It is still used currently in some case. The step-
growth polymerization with low-molar-mass by-product during chain growth is defined as
polycondensation. The chain-growth polymerization a with low-malar-mass by-product during
chain growth is recommended by IUPAC as “condensative chain polymerization”.[10]

Addition polymerization[edit]
Addition polymerization is also a type of previous definition. The chain growth of addition
polymerization is based addition reactions. There is no low-molar-mass by-product formed during
polymerization. The step-growth polymerization based on addition reaction during chain growth is
defined as polyaddition. Based on that definition, the addition polymerization contains both
polyaddition and chain polymerization except condensative chain polymerization we used now.

Application[edit]
Chain polymerization products are widely used in many aspects of life, including electronic
devices, food packaging, catalyst carriers, medical materials, etc. At present, the world's highest
yielding polymers such as polyethylene (PE), polyvinyl chloride (PVC), polypropylene (PP), etc.
can be obtained by chain polymerization. In addition, some carbon nanotube polymer is used for
electronical devices. Controlled living chain-growth conjugated polymerization will also enable
the synthesis of well-defined advanced structures, including block copolymers. Their industrial
applications extend to water purification, biomedical devices and sensors.[11]
 Bibliography
The following information is taken from Wikipedia.org and following
references can also be considered.

1. Penczek, Stanisław; Moad, Graeme (2008). "Glossary of terms related to kinetics,

thermodynamics, and mechanisms of polymerization (IUPAC Recommendations
2008)"(PDF). Pure and Applied Chemistry. 80 (10): 2163–2193. doi:10.1351/pac200880102163.
2. ^ R.J.Young (1983). Introduction to polymers. Chapman and Hall. ISBN 0-412-22170-5.
3. ^ Plastics packaging : Properties, processing, applications, and regulations (2nd ed.). Hanser Pub.
2004. ISBN 1-56990-372-7.
4. ^ Paul Flory (1953). Principles of polymer chemistry. Cornell University Press. ISBN 0-8014-0134-
8.
5. ^ Paul Flory (1953). Principles of polymer chemistry. Cornell University Press. ISBN 0-8014-0134-
8.
6. ^ Sawamoto, Mitsuo (January 1991). "Modern cationic vinyl polymerization". Progress in Polymer
Science. 16 (1): 111–172. doi:10.1016/0079-6700(91)90008-9.
7. ^ Kaminsky, Walter (1 January 1998). "Highly active metallocene catalysts for olefin
polymerization". Journal of the Chemical Society, Dalton Transactions (9): 1413–
1418. doi:10.1039/A800056E. ISSN 1364-5447.
8. ^ Hofsten, E. "Population growth-a menace to what?". Polymer Journal. ISSN 1349-0540.
9. ^ Aplan, Melissa P.; Gomez, Enrique D. (3 July 2017). "Recent Developments in Chain-Growth
Polymerizations of Conjugated Polymers". Industrial & Engineering Chemistry Research. 56 (28):
7888–7901. doi:10.1021/acs.iecr.7b01030.
10. ^ Herzog, Ben; Kohan, Melvin I.; Mestemacher, Steve A.; Pagilagan, Rolando U.; Redmond, Kate
(2013). "Polyamides". Ullmann's Encyclopedia of Industrial Chemistry. American Cancer
Society. doi:10.1002/14356007.a21_179.pub3. ISBN 978-3527306732.
11. ^ Sawamoto, Mitsuo (January 1991). "Modern cationic vinyl polymerizatio