期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 20, 期 47, 页码 15499-15504出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201404147
关键词
carbon dioxide; NMR spectroscopy; onium salts; porphyrinoids; ring-opening polymerization
资金
- Bundesministerium fur Bildung und Forschung [033RC1015C]
Cobalt(III) tetraphenylporphyrin chloride (TPPCoCl) was experimentally proved to be an active catalyst for poly(propylene carbonate) production. It was chosen as a model catalyst in the present work to investigate the initiation step of propylene oxide (PO)/CO2 copolymerization, which is supposed to be the ring opening of the epoxide. Ring-opening intermediates (1-7) were detected by using H-1 NMR spectroscopy. A first-order reaction in TPPCoCl was determined. A combination of monometallic and bimetallic ring-opening pathways is proposed according to kinetics experiments. Addition of onium salts (e.g., bis(triphenylphosphine) iminium chloride, PPNCl) efficiently promoted the PO ring-opening rate. The existence of axial ligand exchange in the cobalt porphyrin complex in the presence of onium salts was suggested by analyzing collected H-1 NMR spectra.
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