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Thus, the
present work was focused on the improvement of known and the development of
new catalytic systems. The main intention was not only to optimise the properties
of the polymer and the polymerisation efficiency, but also to determine a model
for the reaction mechanism. The prior insufficient understanding of the
mechanism, and further more the inefficiency of the available catalysts prevented
the production of attractive aliphatic polycarbonates in industrial scale. Today,
the amplified understanding of mechanistic details enables the synthesis of
improved catalysts and led to the development of new concepts for the formation
of aliphatic polycarbonates.
The alternating copolymerisation of CO
2
and propylene oxide (PO) is of high
interest for the industry because it enables an excellent technique for the
application of cheap and industrially available building blocks. The utilisation of
cheap monomers is, in addition to highly active catalysts, an essential factor for
the realisation of industrial fabrication.
The reaction of carbon dioxide with metal complexes has been extensively
studied, revealing potential pathways for catalytic reactions. However, the
thermodynamic stability of CO
2
has hindered its convenience as a reagent for
chemical synthesis. To overcome this limitation, reactions applying CO
2
with very
reactive reagents have been investigated. Especially the catalytic coupling with
heterocycles has received extensive attention over the past three decades.
43,44,45
Reactions of carbon dioxide are dominated by nucleophilic attacks on the
carbon, which result in bending the O-C-O angle to approx. 120. Generally,
energy must be supplied to drive the desired conversion. Thus, high
temperatures, high pressures, extremely reactive reagents, electricity or the
energy from photons may be exploited to carry out carbon dioxide reactions.
from General
Electric and Calibre
However, a
comparable alternative low-energy pathway was detected as soon as reactions
between chromium(III)-salophen-carbonate complex and a second metal centre
carrying an activated epoxide were allowed. In the productive step, the
carbonate group was transferred from one metal centre to the epoxide carbon
atom carried by the other. During this formal chain- or metal-exchange process
the epoxide undergoes ring-opening and is incorporated into the polymer chain
leading to an alkoxy group at the second metal centre. The process is depicted
in Figure 6.