Perfectly Alternating Copolymerization of CO and Epoxides to Aliphatic Polyester Oligomers via Cooperative Organoboron–Cobalt Complexes,Macromolecules

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Perfectly Alternating Copolymerization of CO and Epoxides to Aliphatic Polyester Oligomers via Cooperative Organoboron–Cobalt Complexes
Macromolecules ( IF 5.1 ) Pub Date : 2021-10-15 , DOI: 10.1021/acs.macromol.1c01324
Yao-Yao Zhang ₁ , Li Yang ₁ , Rui Xie ₁ , Guan-Wen Yang ₁ , Guang-Peng Wu ₁

Affiliation

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 ¹H NMR analyses first found the concurrence of the direct alternating copolymerization of epoxides/CO, the ring expansion carbonylation of the epoxides to afford β-lactones, and the in situ homopolymerization of β-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.

中文翻译：

CO和环氧化物通过协同有机硼-钴配合物完美交替共聚为脂肪族聚酯低聚物

环氧化物的羰基化聚合为合成在生物医学材料和工程塑料领域具有很高商业价值的聚羟基链烷酸酯（PHA）提供了一种有前途但具有挑战性的策略。在此，一套定义明确的双功能有机硼-钴催化剂具有制备简单、产率高和金属含量低的特点，可用于环氧化物羰基化聚合为 PHA 低聚物。有机硼-钴介导的羰基化聚合表现出较高的聚酯选择性（超过 95%，四个环氧化物实例），并且获得的 PHA 在聚合物主链上具有超过 99% 的酯键。基于原位反应IR和^1的详细调查H NMR 分析首先发现了环氧化物/CO 的直接交替共聚、环氧化物的扩环羰基化得到 β-内酯以及β-内酯在单一催化剂下的原位均聚的并发性。这一罕见的发现为从 CO/环氧化物制备 PHA 提供了一种根本不同的机制，扩展了可将 CO 与环氧化物共聚的催化系统的库。

更新日期：2021-10-26

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