玉米秸秆木质素的去甲基化/羟乙基化复合改性研究

doi:10.3969/j.issn.1673-5854.2022.02.002

生物质化学工程 ›› 2022, Vol. 56 ›› Issue (2): 9-13.doi: 10.3969/j.issn.1673-5854.2022.02.002

玉米秸秆木质素的去甲基化/羟乙基化复合改性研究

张凯鑫, 于亚兰, 段宇婷, 吴长炜, 薛磊, 霍鹏飞()

东北林业大学材料科学与工程学院, 黑龙江哈尔滨 150040

收稿日期:2021-02-02 出版日期:2022-03-30 发布日期:2022-03-25
通讯作者: 霍鹏飞 E-mail:huopengfei@nefu.edu.cn
作者简介:霍鹏飞, 副教授, 硕士生导师, 研究领域: 天然高分子改性与利用; E-mail: huopengfei@nefu.edu.cn
张凯鑫(1996—), 女, 黑龙江双鸭山人, 硕士生, 主要从事木质素材料研究工作
基金资助:
东北林业大学大学生国家级创新训练计划项目(202010225133)

Demethylation/Hydroxyethylation Combined Modification of Corn Straw Lignin

Kaixin ZHANG, Yalan YU, Yuting DUAN, Changwei WU, Lei XUE, Pengfei HUO()

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

Received:2021-02-02 Online:2022-03-30 Published:2022-03-25
Contact: Pengfei HUO E-mail:huopengfei@nefu.edu.cn

摘要/Abstract

摘要：

利用亚硫酸钠和乙二醛对玉米秸秆木质素进行去甲基化/羟乙基化复合改性, 以提高木质素的羟基含量和反应活性。通过FT-IR、TG、DSC以及乙酰化滴定等技术研究了木质素复合改性效果。结果表明: 经过去甲基化/羟乙基化复合改性后的玉米秸秆木质素具有优异的活性, 其总羟基质量分数较原料木质素提升了88.33%, 酚羟基提升了14.70%, 反应活性得到明显增强。FT-IR表征发现: 复合改性从多方面提升了木质素的羟基含量, 对羟基含量的增加有着较为显著的效果。热重和DSC表征发现: 复合改性木质素(G-DL)相较于原料木质素降解得更加彻底, 其放热峰出现在77 ℃, 放热量达459.82 J/g, 反应活性较去甲基化木质素(DL)和原料木质素更高。

关键词: 玉米秸秆木质素, 复合改性, 羟基含量, 反应活性

Abstract:

The corn straw lignin was modified by demethylation/hydroxyethylation with sodium sulfite and glyoxal, to further improve the hydroxyl content and activity of lignin. The combined modification effect on lignin was characterized by Fourier transform infrared spectroscopic(FT-IR), thermogravimetric, differential scanning calorimetry(DSC) and acetylation titration. The results showed that the corn straw lignin modified by demethylation/hydroxyethylation had excellent activity. The total hydroxyl mass fraction of the modified lignin was 88.33% higher than that of the original lignin, and the phenolic hydroxyl group increased by 14.70%, which indicated that the reaction activity was significantly enhanced. Microscopic characterization by Fourier tansform infrared spectroscopy showed that the hydroxyl content of lignin was increased in many ways by combined modification, which had a significant effect on the increase of hydroxyl content. It was found by thermogravimetric and differential scanning calorimetry (DSC) analysis characterization that compared with the original lignin, the combined modified lignin(G-DL) degraded more thoroughly, with an exothermic peak at 77 ℃ and an exothermic value of 459.82 J/g. The activity of the reaction was higher than that of demethylated lignin(DL) and raw lignin.

Key words: corn straw lignin, combined modification, hydroxyl content, reactivity

中图分类号:

TQ35
O636.2

张凯鑫, 于亚兰, 段宇婷, 吴长炜, 薛磊, 霍鹏飞. 玉米秸秆木质素的去甲基化/羟乙基化复合改性研究[J]. 生物质化学工程, 2022, 56(2): 9-13.

Kaixin ZHANG, Yalan YU, Yuting DUAN, Changwei WU, Lei XUE, Pengfei HUO. Demethylation/Hydroxyethylation Combined Modification of Corn Straw Lignin[J]. Biomass Chemical Engineering, 2022, 56(2): 9-13.

图/表 5

图1

表1

图2

图3

图4

参考文献 15

1	邱学青. 工业木质素的改性与应用研究进展[J]. 中华纸业, 2016, 37 (7): 56- 59.
2	MA H, LI T F, WU S B, et al. Effect of the interaction of phenolic hydroxyl with the benzene rings on lignin pyrolysis[J/OL]. Bioresource Technology, 2020, 309: 123351[2021-01-20]. https://doi.org/10.1016/j.biortech.2020.123351.
3	MA X Z , LUO Q , QIN D D , et al. Lignin-based polyurethane[J]. Progress in Chemistry, 2020, 32 (5): 617- 626.
4	闫磊. 木质素的化学改性与高效利用研究进展[J]. 绿色科技, 2016, (12): 196- 200. doi: 10.3969/j.issn.1674-9944.2016.12.077
5	VENKATESAGOWDA B . Enzymatic demethylation of lignin for potential biobased polymer applications[J]. Fungal Biology Reviews, 2019, 33, 190- 224. doi: 10.1016/j.fbr.2019.06.002
6	WANG H L , PU Y Q , RAGAUSKAS A , et al. From lignin to valuable products-strategies, challenges, and prospects[J]. Bioresource Technology, 2019, 271, 449- 461. doi: 10.1016/j.biortech.2018.09.072
7	LI J J, ZHANG J Z, ZHANG S F, et al. Fast curing bio-based phenolic resins via lignin demethylated under mild reaction condition[J/OL]. Polymers, 2017, 9: 428[2021-01-20]. https://www.researchgate.net/publication/319597572.DOI: 10.3390/polym9090428.
8	CHEN Y C , ZHANG H , ZHU Z D , et al. High-value utilization of hydroxymethylated lignin in polyurethane adhesives[J]. International Journal of Biological Macromolecules, 2020, 152, 775- 785. doi: 10.1016/j.ijbiomac.2020.02.321
9	PODSCHUN J , SAAKE B , STVCKER A . Structure-function relationships in the phenolation of lignins from different sources[J]. ACS Sustainable Chemistry and Engineering, 2015, 3 (10): 2526- 2532. doi: 10.1021/acssuschemeng.5b00705
10	FERHAN M, YAN N, SAIN M. A new method for demethylation of lignin from woody biomass using biophysical methods[J/OL]. Journal of Chemical Engineering & Process Technology, 2013, 4: 160[2021-01-20]. http://dx.doi.org/10.4172/2157-7048.1000160.
11	WANG H, EBERHARDT T L, WANG C P, et al.Demethylation of alkali lignin with halogen acids and its application to phenolic resins[J/OL]. Polymers, 2019, 11: 1771[2021-01-20]. https://www.researchgate.net/publication/336853972.DOI: 10.3390/polym11111771.
12	CHEN Y C , FU S Y , ZHANG H . Signally improvement of polyurethane adhesive with hydroxy-enriched lignin from bagasse[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2020, 585, 124- 164.
13	于亚兰, 邸明伟. 玉米秸秆木质素的去甲基化改性研究[J]. 现代化工, 2020, 40 (7): 109- 112.
14	王森, 来雅赟, 于亚兰, 等. 玉米秸秆木质素的羟乙基化改性[J]. 化学与生物工程, 2017, 34 (9): 24- 28.
15	任世学, 姜贵全, 屈红军. 植物纤维化学实验教程[M]. 哈尔滨: 东北林业大学出版社, 2008: 27- 52.

样品 sample	总羟基质量分数/% total hydroxyl content	总羟基增加量/% percentage increase of total hydroxyl content	酚羟基质量分数/% phenolic hydroxyl mass fraction	酚羟基增加量/% percentage increase of phenolic hydroxyl content
木质素lignin	10.45		3.13
DL	16.41	57.03	3.75	19.81
G-DL	19.68	88.33	3.59	14.70

玉米秸秆木质素的去甲基化/羟乙基化复合改性研究

Demethylation/Hydroxyethylation Combined Modification of Corn Straw Lignin

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 5

参考文献 15

相关文章 1

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们