Journal
MACROMOLECULES
Volume 54, Issue 20, Pages 9427-9436Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.1c01324
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Funding
- Zhejiang Provincial Natural Science Foundation of China [R21B040004]
- National Natural Science Foundation of China [51973186, 91956123]
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The carbonylative polymerization of epoxides using bifunctional organoboron-cobalt catalysts provides a promising strategy for synthesizing valuable PHA oligomers. The method demonstrates high polyester selectivity and a fundamentally different mechanism for the preparation of PHAs compared to traditional methods, extending the range of catalytic systems available for copolymerizing CO with epoxides.
The carbonylative polymerization of epoxides provides a promising but challenging strategy to synthesize polyhydroxyalkanoates (PHAs) which are of high commercial value in the field of biomedical materials and engineering plastics. Herein, a suite of well-defined bifunctional organoboron-cobalt catalysts, featuring simple preparation, high yields, and low metal content, are exploited for the carbonylative polymerization of epoxides to PHA oligomers. The organoboron-cobalt-mediated carbonylative polymerization exhibits high polyester selectivity (over 95%, four epoxide examples), and the obtained PHAs have more than 99% ester linkages on the polymer main chain. Detailed investigations based on in situ reactIR and H-1 NMR analyses first found the concurrence of the direct alternating copolymerization of epoxides/CO, the ring expansion carbonylation of the epoxides to afford beta-lactones, and the in situ homopolymerization of beta-lactones under a single catalyst. This rare discovery provides a fundamentally different mechanism in the preparation of PHAs from CO/epoxides, extending the arsenal of catalytic systems that can copolymerize CO with epoxides.
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