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含动态硼酸酯键的木质素基可重塑型材料,具有固有光转化性能和优异的光热重塑性。

Lignin-based vitrimer containing dynamic borate ester bonds with intrinsic photoconversion and excellent photothermal remoldability.

机构信息

Key Laboratory of Bio-based Material Science & Technology (Northeast Forestry University), Ministry of Education, Harbin 150040, China.

College of Material Science and Engineering, Northeast Forestry University, Harbin 150040, China.

出版信息

Int J Biol Macromol. 2024 Oct;278(Pt 2):134754. doi: 10.1016/j.ijbiomac.2024.134754. Epub 2024 Aug 14.

Abstract

The development of photoresponsive shape memory materials based on the photothermal conversion properties of lignin and the low activation energy of the dynamic covalent borate bond is of great importance. In this paper, a kind of lignin-based vitrimer polymer (LBP) containing dynamic boronic ester bonds was prepared by a "sulfhydryl-epoxy" click reaction and etherification reaction. The results show that the rigid segment EP-EL (lignin-based epoxy resin) and BDB (2,2'-(1,4-phenylene)-bis-[4-mercapto-1,3,2-dioxaneborane]) with benzene ring structure can impart tensile strength (20.8 MPa) to the LBP, while the flexible segment PEG imparts good elongation at break (15 %). The dynamic binding and dissociation exchange mechanism of the boronic ester bonds enables LBP to exhibit thermal remodelling properties (up to 36.2 %) and water-assisted self-healing properties at room temperature (up to 49.0 %). In addition, LBP exhibits excellent thermal and light-responsive shape memory properties due to its own photothermal conversion performance (photothermal conversion efficiency up to 18.2 %) and the dynamic boronic ester bond thermal activation bond exchange mechanism. The insulating properties of LBP make it suitable for use in high temperature protection circuit devices and light-responsive circuit devices. This study provides new insights into the design and application of Vitrimer and photoresponsive shape memory polymers, and also offers a new avenue for high-value utilization of lignin.

摘要

基于木质素的光热转换特性和动态共价硼酸酯键的低活化能,开发光响应形状记忆材料具有重要意义。本文通过“巯基-环氧”点击反应和醚化反应,制备了一种含动态硼酸酯键的木质素基 vitrimer 聚合物(LBP)。结果表明,具有苯环结构的刚性段 EP-EL(木质素基环氧树脂)和 BDB(2,2'-(1,4-亚苯基)-双-[4-巯基-1,3,2-二氧杂环丁硼烷])可为 LBP 提供拉伸强度(20.8 MPa),而柔性段 PEG 则赋予其良好的断裂伸长率(15%)。硼酸酯键的动态键合和解离交换机制使 LBP 具有热重塑性能(高达 36.2%)和室温下的水辅助自修复性能(高达 49.0%)。此外,由于其自身的光热转换性能(光热转换效率高达 18.2%)和动态硼酸酯键热激活键交换机制,LBP 还表现出优异的热光响应形状记忆性能。LBP 的绝缘性能使其适用于高温保护电路器件和光响应电路器件。本研究为 Vitrimer 和光响应形状记忆聚合物的设计和应用提供了新的思路,也为木质素的高值化利用提供了新途径。

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