文献类型：期刊文献

中文题名：木质素基环氧聚合物的构建及其光热转化应用

英文题名：Fully biobased epoxy resin with structure-controlled lignin as a light-absorbing material for enhanced photothermal conversion efficiency

作者：何娟[1] 章亚琼[1] 黄曹兴[2] 黄晨[3] 蒋峰[1] 汪钟凯[1]

第一作者：何娟

机构：[1]安徽农业大学材料与化学学院,合肥230036;[2]南京林业大学化学工程学院,南京210037;[3]中国林业科学研究院林产化学工业研究所,南京210042

年份：2025

卷号：10

期号：5

起止页码：91-103

中文期刊名：林业工程学报

外文期刊名：Journal of Forestry Engineering

收录：;北大核心:【北大核心2023】；

基金：国家重点研发计划(2022YFD2200802);安徽省自然科学基金(2208085QC90)。

语种：中文

中文关键词：植物油;木质素;化学修饰;热固性高分子;光热响应材料

外文关键词：plant oil;lignin;chemical modification;thermosetting polymers;photothermal-responsive materials

分类号：O636.2;TQ645

摘要：为进一步扩展木质素在高分子材料中的应用,将木质素引入植物油基环氧高分子中,制备具有热响应性的生物基环氧复合材料。首先,利用十一烯酰氯和油酸酰氯对木质素羟基官能团进行梯度修饰,采用核磁共振确定了酯化木质素的化学结构,通过凝胶色谱确定了酯化木质素的分子量。研究发现:十一烯酰氯和油酰氯以酯键形式修饰在木质素的羟基位置,其中油酰氯的酯化接枝率较高为38.1%,酯化木质素上仍然保留少量羟基和羧基活性官能团。将酯化木质素和植物油环氧聚合物进行溶液共混制备热固性环氧树脂,通过相容性观察分析,发现油酰氯修饰的木质素更适于构建均相的环氧复合材料。通过差示扫描热量仪确定油酰氯修饰型木质素/植物油基环氧树脂的固化温度及时间,采用热重分析仪和动态力学分析仪等对该类复合材料的力学和热力学性能进行了测定与分析。结果表明:酯化木质素中残余的活性官能团可以参与环氧聚合物的固化行为,增强了环氧树脂的力学和热力学性能。通过近红外激光及红外热成像仪对该复合材料的热响应性进行了表征与分析发现,木质素/植物油基环氧聚合物具有良好的热响应性,可在20 s内迅速从环境温度上升至140℃,且在100 s内表现出良好的持续性光热转换效率。
Nowadays,sustainable epoxy resins with permanent cross-linking networks synthesized from renewable resources are garnering significant attention.Biomass resources,particularly plant oils,contain multiple reactive groups that enable the formation of highly cross-linked epoxy resins.However,the inherent flexibility of these materials often leads to suboptimal mechanical properties,thereby limiting their applications.This study aimed at enhancing the mechanical properties of epoxy composites by incorporating lignin into plant oil-based epoxy polymers,specifically targeting improvements in rigidity and modulus.This research explored the potential applications of these epoxy composites and highlighted the role of lignin in polymer materials.The initial step involved modifying the hydroxyl functional groups of lignin using 10-undecylenoyl chloride and oleic acid chloride.Nuclear Magnetic Resonance(NMR)spectroscopy and gel chromatography were employed to ascertain both the chemical structure and molecular weight of the modified lignin samples.It was determined that both 10-undecylenoyl chloride and oleyl chloride successfully modified lignin via ester bonds at their hydroxyl positions.The esterification grafting rate for oleyl chloride was found to be 38.1%,while a small number of active hydroxyl and carboxyl functional groups remained intact post-modification.Various thermosetting epoxy resins were synthesized by blending esterified lignin with plant oil-based epoxy polymers.Notably,oleyl chloride-modified lignin exhibited greater compatibility in forming homogeneous epoxy composites compared to lignin modified with 10-undecylenoyl chloride.The curing temperature and time for the oleyl chloride-modified lignin/plant oil-based epoxy resin were established using differential scanning calorimetry(DSC),indicating an optimal curing condition at 100℃ for 7 h for complete curing of epoxies containing 10%modified lignin.The mechanical and thermodynamic properties of these composites were evaluated through thermogravimetric analysis(TGA)and dynamic mechanical analysis(DMA).The results indicated that the residual active functional groups present in the modified lignin could participate in the curing behavior of the epoxy polymer,thereby enhancing both the mechanical and thermodynamic properties of the resulting resin.The thermal response characteristics of lignin/plant oil epoxy composites were assessed using the near-infrared laser technology in conjunction with infrared thermal imaging techniques to investigate potential thermal responsiveness attributed to lignin.Findings revealed that these polymers exhibited excellent thermal responsiveness,capable of rapidly increasing from ambient temperature to 140℃within just 20 s,while also demonstrating commendable sustained photothermal conversion efficiency over 100 s.This study presents an effective approach for developing adjustable epoxy composites with enhanced mechanical properties and increased thermal responsiveness.