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通过高效的CaI/1,3-双[三(羟甲基)甲氨基]丙烷催化剂由末端环氧化物可持续合成环状碳酸酯。

Sustainable Synthesis of Cyclic Carbonates from Terminal Epoxides by a Highly Efficient CaI/1,3-Bis[tris(hydroxymethyl)-methylamino]-propane Catalyst.

作者信息

Liu Kuan-Ting, Chuang Jia-Yu, Jeng Ru-Jong, Leung Man-Kit

机构信息

Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan.

Institute of Polymer Science and Engineering, National Taiwan University, Taipei 10617, Taiwan.

出版信息

ACS Omega. 2021 Oct 8;6(41):27279-27287. doi: 10.1021/acsomega.1c04086. eCollection 2021 Oct 19.

Abstract

The nonstopping increment of atmospheric carbon dioxide (CO) concentration keeps harming the environment and human life. The traditional concept of carbon capture and storage (CCS) is no longer sufficient and has already been corrected to carbon capture, utilization, and storage (CCUS). CCUS involves significant CO utilization, such as cyclic carbonate formation, for its cost effectiveness, less toxicity, and abundant C1 synthon in organic synthesis. However, the high thermodynamic and kinetic stability of CO limits its applications. Herein, we report a mild, efficient, and practical catalyst based on abundant, nontoxic CaI in conjunction with biocompatible ligand 1,3-bis[tris(hydroxymethyl)-methylamino]-propane () for CO fixation under atmospheric pressure with terminal epoxides to give the cyclic carbonates. The Job plot detected the 1:1 Ca/ binding stoichiometry. Furthermore, formation of a single crystal of the 1:1 Ca/ complex was confirmed by single-crystal X-ray crystallography. The bis(cyclic carbonate) products exhibit potentials for components in the non-isocyanate polyurethanes (NIPUs) process. Notably, this protocol shows attractive recyclability and reusability.

摘要

大气中二氧化碳(CO₂)浓度的持续增加不断危害着环境和人类生活。传统的碳捕获与封存(CCS)概念已不再充分,现已修正为碳捕获、利用与封存(CCUS)。CCUS涉及大量的CO₂利用,例如环状碳酸酯的形成,因为其具有成本效益、低毒性以及在有机合成中丰富的C1合成子。然而,CO₂的高热力学和动力学稳定性限制了其应用。在此,我们报道了一种温和、高效且实用的催化剂,该催化剂基于丰富、无毒的CaI₂与生物相容性配体1,3-双[三(羟甲基)甲氨基]丙烷(TMAP)结合,用于在大气压下将CO₂与末端环氧化合物固定以生成环状碳酸酯。Job曲线检测到Ca²⁺/TMAP的结合化学计量比为1:1。此外,通过单晶X射线晶体学证实了1:1 Ca²⁺/TMAP配合物单晶的形成。双(环状碳酸酯)产物在非异氰酸酯聚氨酯(NIPUs)工艺中显示出作为组分的潜力。值得注意的是,该方案具有吸引人的可回收性和可重复使用性。

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