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Download fileHeterotrinuclear Ring Opening Copolymerization Catalysis: Structure–activity Relationships
journal contribution
posted on 29.11.2021, 14:37 authored by Alex J. Plajer, Charlotte K. WilliamsHeteronuclear complexes are highly
active catalysts in alternating
ring opening copolymerizations (ROCOP) of cyclohexene oxide (CHO)/carbon
dioxide or CHO/phthalic anhydride (PA). In this contribution, a series
of new trinuclear complexes is investigated through a structure activity
study that reveals the influences of ligand electronic properties
and metal selection over the catalytic activity and linkage selectivity.
The fastest catalyst shows high activity for CHO/CO2 ROCOP
at low pressure (1 bar CO2 pressure) and features the ligand
coordinated to two Zn(II) centers and with inexpensive and abundant
Na(I) (TOF = 1084 h–1, catalyst/CHO 1:4000, 1 bar,
100 °C). High CHO/PA copolymerization activity is achieved with
the combination of two Mg(II) and one Na(I) center (TOF = 142 h–1, catalyst/PA/CHO 1:200:4000, 100 °C); further
the catalyst undergoes “switchable” epoxide/anhydride
ROCOP and epoxide ring opening polymerization (ROP), allowing for
controlled polyether block formation. Polymerization kinetic investigations
reveal the influences of the ligand electronics, complex stability
and metal–metal separation, and their influences over the retention
of high activity throughout the catalysis. The findings should help
in guiding future polymerization catalyst design, facilitate block
polymer production, and inspire other CO2 utilization processes.
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Keywords
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