一步法高效合成异山梨醇基聚碳酸酯的可调原生离子液体催化剂

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引用次数: 0

摘要

使用二氧化碳衍生的碳酸二甲酯(DMC)代替碳酸二苯酯(DPC)作为合成生物基聚碳酸酯的羰基源,是一条绿色环保、经济高效的路线。然而,与 DPC 相比,DMC 的反应性和选择性较差,因此通过 DMC 路线合成高性能聚碳酸酯仍具有挑战性。在此,我们设计了一系列高活性原生离子液体(PIL)催化剂,用于从 DMC 与 ISB 合成聚异山梨醇碳酸酯(PIC)。系统研究了阴阳离子结构对 PIL 催化活性的影响。与已报道的烷基惰性离子催化剂相比,PILs 中阳离子特有的活性氢能与 DMC 的羰基形成较强的氢键作用,从而使 DMC 的羰基碳具有更高的反应活性。此外,阴离子的亲核性可以通过调节 pKa 值进行调节,从而有效地实现了 ISB 中外-OH 和内-OH 反应性差异的平衡。其中,[DBUH][Im] 的催化活性最高,PIC 的重均分子量(Mw)和玻璃化温度分别达到 55,700 g/mol 和 160 ℃。结合核磁共振分析和 DFT 计算,提出了阴阳离子对 DMC 和 ISB 聚合作用的协同催化机理。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Tunable protic ionic liquid catalysts for the efficient one-step synthesis of isosorbide-based polycarbonates

Tunable protic ionic liquid catalysts for the efficient one-step synthesis of isosorbide-based polycarbonates

Using CO2-derived dimethyl carbonate (DMC) instead of diphenyl carbonate (DPC) as a carbonyl source for synthesizing bio-based polycarbonates is a green and cost-effective route. However, the synthesis of high-performance polycarbonates via the DMC route remains challenging due to the poor reactivity and selectivity of DMC compared to DPC. Herein, we designed a series of highly active protic ionic liquid (PIL) catalysts for the synthesis of poly(isosorbide carbonate) (PIC) from DMC with ISB. The influences of the structures of anion and cation on the catalytic activity of PILs were systematically studied. Compared with the reported aprotic IL catalysts, the unique reactive hydrogen of the cation in PILs could form a strong hydrogen bond interaction with the carbonyl group of DMC, resulting in higher reactivity of the carbonyl carbon of DMC. Moreover, the nucleophilicity of the anion could be easily tuned by adjusting the pKa value, which effectively realized the balance of the reactivity difference between exo-OH and endo-OH in ISB. Among them, [DBUH][Im] showed the highest catalytic activity, and the weight-average molecular weight (Mw) and glass transition temperature of PIC reached 55,700 g/mol and 160 °C, respectively. Combined with NMR analyses and DFT calculations, the mechanism that exhibited the synergetic catalytic effect of anion-cation for the polymerization of DMC and ISB was presented.

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