Journal
MACROMOLECULES
Volume 40, Issue 7, Pages 2303-2307Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma062735f
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Various poly(propylene carbonate)s (PPC)s with different head-to-tail linkages (from similar to 60% to 93%) could be synthesized by the copolymerization of racemic propylene oxide (rac-PO) and CO2 with chromium Salen complexes as catalyst. The axial X group and the Salen ligand framework of the chromium complexes and the properties of cocatalyst significantly affect stereochemistry of the resulting polymer. Continuous determination of a polymer chain end group (initiating and chain growth species) at various times was achieved by in situ electrospray ionization mass spectrometry (ESI-MS), which in combination with the terpolymerization of CO2 with R-PO and cyclohexene oxide (CHO) gave us an insight into the mechanistic understanding of CO2/PO copolymerization and polycarbonates stereochemistry control. Apart from the effect of the ligand set of the chromium Salen complexes on polymer stereochemistry, a polymer chain-end control mechanism also significantly affects the stereochemistry of the resulting polycarbonates.
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