高反应性木质素的高效提取及其制备生物聚氨酯泡沫

doi:10.3969/j.issn.1673-5854.2024.01.004

摘要/Abstract

摘要：

为了解决木质素参与聚氨酯泡沫反应存在结构复杂、纯度低、分子质量大、反应性较低等问题，本研究以天然竹粉为原料，利用氯化胆碱（ChCl）和草酸六水合物（Oad）制备低共熔溶剂（DES）作为提取溶剂，结合超声波辅助技术提取高活性酚羟基木质素，并将其作为反应单体替代部分石化多元醇，通过全水发泡法制备木质素聚氨酯泡沫（LPUF），并对其化学结构、微观形貌和力学性能进行分析。研究结果表明：基于DES超声波辅助处理未破坏木质素的基本结构，LPUF成功制备；较优的提取工艺条件为提取温度80 ℃、超声波作用时间0.5 h、超声波功率70 W，此条件下木质素含酚羟基8.8%、提取率高达87.8%。当木质素与聚乙二醇200（PEG-200），聚乙二醇400（PEG-400）和六亚甲基二异氰酸酯（HDI）的质量比为1∶84∶23∶155，所制备的木质素聚氨酯泡沫LPUF-2，平均孔径261.66 μm，弹性模量3 MPa，经1 000次压缩循环，LPUF-2最大应力为22.26 kPa，仍能保持初始应力的84%以上，显示出优异的力学性能及稳定性。

关键词: 酚羟基木质素, 低共熔溶剂, 超声波, 木质素聚氨酯泡沫, 全水发泡, 回弹性

Abstract:

In order to solve the problems of lignin involved in bio-polyurethane foam reaction due to its complex structure, low purity, large molecular weight, and low reactivity, phenolic lignin with high activity was extracted from natural bamboo powder by deep eutectic solvent(DES) prepared by choline chloride(ChCl) and oxalate hexahydrate(Oad) combined with ultrasonic assisted technology. It was used as a reaction monomer to partly replace petroleum-based polyols to prepare lignin-based polyurethane foam(LPUF) via all water foaming method, and the chemical structure, micromorphology and mechanical properties were analyzed. The results showed that the optimal process conditions were the ultrasonic temperature of 80℃, ultrasonic action time of 0.5 h, and ultrasonic power of 70 W. Under these conditions, the content of phenolic hydroxyl groups of the extracted lignin was 8.8%, and the lignin extraction rate reached to 87.8%. The basic structure of lignin was not destroyed by DES ultrasonic assisted treatment, and LPUF was successfully prepared. When the mass ratio of lignin: polyethylene glycol 200(PEG-200): polyethylene glycol 400(PEG-400): hexamethylene diisocyanate(HDI) was 1:84:23:155, the average cell size of the prepared lignin polyurethane foam(LPUF-2) was 261.66 μm, and the elasticity modulus reached to 3 MPa. After 1 000 compression cycles, the maximal stress of LPUF-2 still maintained initial 84%, reached 22.26 kPa, showing excellent mechanical properties and mechanical stability.

Key words: phenolic lignin, deep eutectic solvent, ultrasound, lignin-based polyurethane foam, all water foaming, resilience

中图分类号:

TQ35

陈阳柳, 王邓峰, 龚秀金, 刁梦媛, 刘琳. 高反应性木质素的高效提取及其制备生物聚氨酯泡沫[J]. 生物质化学工程, 2024, 58(1): 27-34.

Yangliu CHEN, Dengfeng WANG, Xiujin GONG, Mengyuan DIAO, Lin LIU. Efficient Extraction of Highly Reactive Lignin and Its Preparation of Bio-polyurethane Foam[J]. Biomass Chemical Engineering, 2024, 58(1): 27-34.

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样品 sample	木质素/g lignin	PEG-200/g
PUF	0	22.50
LPUF-1	0.1	16.69
LPUF-2	0.2	16.88
LPUF-3	0.3	14.06

处理条件 process conditions		酚羟基/% phenol hydroxyl	提取率/% extraction rate
温度 temperature	60 ℃	4.9	59.9
	70 ℃	7.4	67.8
	80 ℃	8.7	87.3
	90 ℃	6.5	74.1
功率 power	60 W	8.5	74.6
	70 W	8.8	87.1
	80 W	7.8	68.9
	90 W	7.4	64.7
时间 time	0 h	6.7	64.6
	0.5 h	8.8	87.8
	1 h	8.0	80.2
	1.5 h	7.7	77.8
	2 h	7.3	66.8

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