A cysteine derivative-enabled ultrafast thiol-ene reaction for scalable synthesis of a fully bio-based internal emulsifier for high-toughness waterborne polyurethanes
A cysteine derivative-enabled ultrafast thiol-ene reaction for scalable synthesis of a fully bio-based internal emulsifier for high-toughness waterborne polyurethanes
复制标题
半胱氨酸衍生物超快硫醇烯反应可大规模合成高韧性水性聚氨酯的全生物基内乳化剂
DOI：
10.1039/d0gc02213f
复制
发表时间：
2020
期刊：
影响因子：
9.8
通讯作者：
Zhang Chaoqun
中科院分区：
文献类型：
--
作者：
Wang Xiao;Liang Haiyan;Jiang Jizhou;Wang Qingwen;Luo Ying;Feng Pengju;Zhang Chaoqun
虽然人们已经做出了巨大的努力来将植物油转化为增值化学品，但大多数已知的协议仍然需要繁琐的原料制备程序，温度高，反应时间长，伴随着沉重的经济成本和低的能源效率。本文报道了一种简单、可扩展、超快速合成全生物基内乳化剂的方法。以半胱氨酸衍生物和蓖麻油为原料，采用流动化学的方法在室温下实现了光点击、硫醇-烯反应。转化率可达92.0%，内乳化剂NaCO的生产效率可达360.0 g h−1。将该全生物基内乳化剂进一步应用于以典型多元醇为原料合成水性聚氨酯。这些水性聚氨酯的生物含量可高达90.0wt%。此外，由水性聚氨酯制备的薄膜具有比已知的溶剂型和石油基聚氨酯薄膜更好的热物理和机械性能。通过光点击硫醇-烯化学制备的新型乳化剂，连接了天然材料(氨基酸衍生物和蓖麻油)和基于化石的产品；这为水性聚氨酯的合成提供了一种绿色和可持续的策略，将减少我们对化石资源的化学依赖。
Although tremendous attempts have been made to transform vegetable oils into value-added chemicals, most of the known protocols still require cumbersome preparation procedures for the raw materials, high temperatures, and long reaction times, accompanied with encumbering economic costs and low energy efficiency. In this manuscript, a simple, scalable, and ultrafast method for the synthesis of fully bio-based internal emulsifiers is reported. Flow chemistry was applied to achieve a photo-click, thiol–ene reaction at room temperature by using a cysteine derivative and castor oil as natural raw materials. Conversion rates up to 92.0% were obtained, and the productivity of the internal emulsifier NACCO could reach 360.0 g h−1 with a custom flow chemistry setup. The fully bio-based internal emulsifier was further applied to synthesize waterborne polyurethanes with typical polyols. The bio-content of these waterborne polyurethanes could be as high as 90.0 wt%. Moreover, the films derived from waterborne polyurethanes exhibit superior thermophysical and mechanical properties to known solvent- and petroleum-based polyurethane films. The novel emulsifier, prepared via photo-click thiol–ene chemistry, bridges natural materials (amino acid derivatives and castor oil) and fossil-based products; this affords a green and sustainable strategy for the synthesis of waterborne polyurethanes, which will decrease our chemical dependence on fossil resources.