Valorization of polycaprolactone for the production of nylon-6 monomers†

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Green Chemistry Pub Date : 2024-03-18 DOI:10.1039/d3gc05118h

Hui Zhang , Yanfei Zhao , Yusi Wang , Rongxiang Li , Minhao Tang , Wei Zeng , Ying Wang , Xiaoqian Chang , Buxing Han , Zhimin Liu

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Abstract

Upcycling biodegradable polyester waste into value-added chemicals can not only avoid CO₂ emissions but also achieve sustainable carbon recycling. Herein, we report a one-pot catalytic process to deconstruct polycaprolactone into 6-aminocaproic acid (EACA) and caprolactam (CPL), two monomers of nylon-6, using aqueous ammonia and Ru catalysts. No additional hydrogen is required, and the total yield of EACA and CPL could reach 90.2% using a ternary catalyst, Ru/CeO₂/RGO, at 140 °C. It is verified that 6-hydroxyhexanoic acid and 6-hydroxyhexanoamide are the initial intermediates resulting from polycaprolactone decomposition, which undergo dehydrogenation, amination and re-hydrogenation to transform into EACA and 6-aminohexanoamide over the Ru catalyst. The hydrolysis of 6-aminohexanoamide produces EACA, and the reverse reaction between dehydration of EACA and hydrolysis of CPL results in their coexistence. The protocol demonstrated here provides a novel route to recycle polycaprolactone to valuable chemicals.

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聚己内酯在生产尼龙-6 单体中的价值评估

将可生物降解的聚酯废料转化为高附加值化学品不仅可以避免二氧化碳排放，还能实现可持续的碳循环。在此，我们报告了一种使用水氨和 Ru 催化剂将聚己内酯解构为 6-氨基己酸（EACA）和己内酰胺（CPL）（尼龙-6 的两种单体）的一锅催化工艺。使用 Ru/CeO2/RGO 三元催化剂，在 140 ℃ 条件下，无需额外氢气，EACA 和 CPL 的总产率可达 90.2%。实验验证了 6-hydroxyhexanoic acid 和 6-hydroxyhexanoamide 是聚己内酯分解产生的初始中间产物，它们在 Ru 催化剂上经过脱氢、胺化和再氢化转化为 EACA 和 6-aminohexanoamide。6-aminohexanoamide 的水解生成 EACA，而 EACA 的脱水和 CPL 的水解之间的反向反应导致它们共存。这里展示的方案提供了一条将聚己内酯回收为有价值化学品的新途径。

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来源期刊

Green Chemistry 化学-化学综合

CiteScore

16.10

自引率

7.10%

发文量

677

审稿时长

1.4 months

期刊介绍： Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.