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用于环氧丙烷CO辅助水合反应的可膨胀有机-无机杂化聚合物的制备

Fabrication of Swellable Organic-Inorganic Hybrid Polymers for CO-Assisted Hydration of Propylene Epoxide.

作者信息

Dang Lulu, Yuan Huixia, Wang Binshen, Zhang Jingshun, Wang Ziyi, Gao Guohua

机构信息

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663 North Zhongshan Road, Shanghai 200062, China.

Institute of Eco-Chongming, 20 Cuiniao Road, Shanghai 202162, China.

出版信息

ACS Appl Mater Interfaces. 2023 Mar 29;15(12):16017-16025. doi: 10.1021/acsami.2c23332. Epub 2023 Mar 20.

Abstract

Swelling is a very common phenomenon in organic substances. However, the swelling behaviors of inorganic substances had rarely been reported. In this study, a new type of swellable organic-inorganic hybrid polymer (PIL@CHT) was designed and successfully synthesized through free-radical copolymerization of polymerizable phosphonium ionic liquid monomer and vinyl-functionalized hydrotalcite (CHT). The swelling behaviors of PIL@CHT in various solvents with a wide range of Hansen solubility parameters (δ) were investigated, and PIL@CHT exhibited excellent swellable capacity in the solvents with δ > 24.4 MPa. The swollen state of the hybrid PIL@CHT in water presented a network structure with a diameter of approximately 8-12 μm, and CHT particles were well dispersed to the channel of PIL. PIL@CHT was applied to catalyze the CO-assisted hydration of propylene oxide (PO), in which a cascade reaction including the cycloaddition of CO and PO and the subsequent hydrolysis of propylene carbonate (PC) occurred. PIL@CHT, combining the active sites of PIL and CHT, synergistically catalyzed this cascade reaction and achieved a high yield (93.0%) and selectivity (98.2%) of 1,2-propanediol (1,2-MPG) under a low HO/PO ratio of 1.5/1. Moreover, the catalyst could be recycled seven times without any significant loss of catalytic activities and had good substrate generality.

摘要

溶胀是有机物质中非常常见的现象。然而,无机物质的溶胀行为鲜有报道。在本研究中,通过可聚合膦离子液体单体与乙烯基官能化水滑石(CHT)的自由基共聚,设计并成功合成了一种新型的可溶胀有机-无机杂化聚合物(PIL@CHT)。研究了PIL@CHT在具有广泛 Hansen 溶解度参数(δ)的各种溶剂中的溶胀行为,PIL@CHT 在 δ > 24.4 MPa 的溶剂中表现出优异的溶胀能力。杂化聚合物 PIL@CHT 在水中的溶胀状态呈现出直径约为 8 - 12 μm 的网络结构,CHT 颗粒很好地分散在 PIL 的通道中。PIL@CHT 被应用于催化环氧丙烷(PO)的 CO 辅助水合反应,其中发生了包括 CO 与 PO 的环加成以及随后碳酸丙烯酯(PC)水解的串联反应。PIL@CHT 结合了 PIL 和 CHT 的活性位点,协同催化该串联反应,在低 HO/PO 比为 1.5/1 的条件下,1,2 - 丙二醇(1,2 - MPG)实现了高产率(93.0%)和高选择性(98.2%)。此外,该催化剂可以循环使用七次,催化活性没有任何显著损失,并且具有良好的底物通用性。

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