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碳酸钾作为一种低成本且高活性的固体碱催化剂用于聚碳酸酯的低温甲醇解反应

Potassium Carbonate as a Low-Cost and Highly Active Solid Base Catalyst for Low-Temperature Methanolysis of Polycarbonate.

作者信息

Lin Tzu-Ming, Anggo Krisbiantoro Philip, Sato Miyu, Chang Yu-Chia, Atayde Eduardo C, Liao Weisheng, Kamiya Yuichi, Otomo Ryoichi, Wu Kevin C-W

机构信息

Department of Chemical Engineering, National Taiwan University, Taipei, 10617, Taiwan.

Molecular Science and Technology Program, Taiwan International Graduate Program, Academia Sinica, Taipei, 11529, Taiwan.

出版信息

ChemSusChem. 2025 Jan 14;18(2):e202401676. doi: 10.1002/cssc.202401676. Epub 2024 Oct 30.

Abstract

As the demand for polycarbonate (PC) plastic increases over the years, the development of a chemical recycling system to produce virgin-like-quality monomers is indispensable not only to attain completely sustainable cycles but also to contribute to the decrease in global plastic pollution. Herein, potassium carbonate (KCO) was used as a low-cost, readily available, and highly active solid base catalyst for low-temperature PC methanolysis in the presence of THF as a solvent, producing highly pure and crystalline bisphenol A (BPA) and with a catalytic performance higher than group IIA metal oxides (MgO, CaO, and SrO) and some group IA metal carbonates (NaHCO, KHCO, and NaCO). THF was the best solvent in aiding the reaction owing to it having a similar polar parameter (δ) to that of PC according to Hansen solubility parameters. By the reaction over the catalyst, 100% PC conversion, 97% BPA yield, and 86% dimethyl carbonate yield were achieved within just 20 min at 60 °C. The catalyst possessed an apparent activation energy (E) of 52.3 kJ mol, which is the lowest value so far for heterogeneous catalysts, while the mechanistic study revealed that the reaction proceeded via the methoxide pathway. The reusability test demonstrated that the catalyst was reusable at least four times. Furthermore, this catalytic system was successfully applied to actual post-consumer PC wastes and polyesters, including polyethylene terephthalate (PET) and polylactic acid (PLA).

摘要

随着多年来对聚碳酸酯(PC)塑料需求的增加,开发一种化学回收系统以生产类似原始质量的单体不仅对于实现完全可持续的循环至关重要,而且有助于减少全球塑料污染。在此,碳酸钾(KCO)被用作低成本、易于获得且高活性的固体碱催化剂,用于在四氢呋喃(THF)作为溶剂存在下的低温PC甲醇解反应,生产高纯度和结晶性的双酚A(BPA),其催化性能高于IIA族金属氧化物(MgO、CaO和SrO)以及一些IA族金属碳酸盐(NaHCO、KHCO和NaCO)。根据汉森溶解度参数,THF是辅助该反应的最佳溶剂,因为它具有与PC相似的极性参数(δ)。通过在该催化剂上进行反应,在60℃下仅20分钟内就实现了100%的PC转化率、97%的BPA产率和86%的碳酸二甲酯产率。该催化剂的表观活化能(E)为52.3 kJ·mol,这是迄今为止非均相催化剂的最低值,而机理研究表明该反应通过甲醇盐途径进行。可重复使用性测试表明该催化剂至少可重复使用四次。此外,该催化系统成功应用于实际消费后的PC废料以及聚酯,包括聚对苯二甲酸乙二酯(PET)和聚乳酸(PLA)。

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