微波辅助木质素脱甲基化改性及结构表征

doi:10.3969/j.issn.0253-2417.2016.02.009

林产化学与工业 ›› 2016, Vol. 36 ›› Issue (2): 57-63.doi: 10.3969/j.issn.0253-2417.2016.02.009

微波辅助木质素脱甲基化改性及结构表征

夏成龙¹, 许玉芝^1,2,3, 刘晓欢⁴, 王春鹏^1,2

1. 中国林业科学研究院林产化学工业研究所;生物质化学利用国家工程实验室;国家林业局林产化学工程重点开放性实验室;江苏省生物质能源与材料重点实验室, 江苏南京 210042;
2. 中国林业科学研究院林业新技术研究所, 北京 100091;
3. 车用生物燃料技术国家重点实验室, 河南南阳 473000;
4. 浙江农林大学工程学院, 浙江临安 311300

收稿日期:2015-03-09 出版日期:2016-04-25 发布日期:2016-04-26
通讯作者: 许玉芝(1974—),女,副研究员,博士,主要从事生物质基材料及胶黏剂研究;E-mail:xuyuzz@163.com。 E-mail:xuyuzz@163.com
作者简介:夏成龙(1989—),男,山东德州人,硕士生,从事生物基高分子材料研究;E-mail:xiasanjiao@163.com
基金资助:
林业公益性行业科研专项(201404604);国家自然科学基金资助项目(3120048);车用生物燃料技术国家重点实验室开放基金资助项目(KFKT2013011)

Preparation and Characterization of Demethylated Lignin Assisted by Microwave Irradiation

XIA Cheng-long¹, XU Yu-zhi^1,2,3, LIU Xiao-huan⁴, WANG Chun-peng^1,2

1. Institute of Chemical Industry of Forest Products, CAF;National Engineering Lab.for Biomass Chemical Utilization; Key and Open Lab.of Forest Chemical Engineering, SFA;Key Lab.of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China;
2. Research Institute of Forestry New Technology, CAF, Beijing 100091, China;
3. State Key Laboratory of Motor Vehicle Biofuel Technology, Nanyang 473000, China;
4. School of Engineering, Zhejiang A&F University, Lin'an 311300, China

Received:2015-03-09 Online:2016-04-25 Published:2016-04-26

摘要/Abstract

摘要： 为提高木质素的反应活性,采用微波辅助加热方式,在HBr/十六烷基三正丁基溴化磷(HBr/TBHDPB)体系下对木质素进行脱甲基化改性。考察了HBr用量、反应温度、反应时间和催化剂用量对木质素改性反应的影响。通过紫外光谱(UV)、核磁共振氢谱(¹H NMR)、傅里叶变换红外光谱(FT-IR)、凝胶渗透色谱(GPC)和元素分析等手段研究了木质素改性前后的官能团及分子质量变化,并由羟甲基化反应和曼尼希反应分析了木质素改性前后的活性变化。结果表明:木质素在微波辅助加热条件下,HBr用量为20 mmol/g,催化剂TBHDPB用量为木质素质量的2%,95 ℃反应1 h,制备的改性木质素含酚羟基为4.95%,相比原料木质素提高了32.71%,甲氧基为6.11%,相比原料木质素降低了20.44%。与甲醛反应的活性提高了18.15%,胺基侧链增加了7.54%。UV、¹H NMR 和FT-IR分析也表明,改性木质素的酚羟基含量增加,甲氧基含量降低。

关键词: 木质素, 微波加热, 脱甲基化, 结构

Abstract: In order to improve the reaction activity of lignin, the demethylation modification was carried out with aid of microwave heating in the presence of hydrobromic acid and (HBr)-hexadecyltributylphosphonium bromide (TBHDPB). The effects of HBr dosage, temperature, time and dosage of catalyst TBHDPB on reaction were investigated. Structural and molecular weight of starting purified lignin and modified lignin were characterized by ultraviolet spectrum(UV), nuclear magnetic resonance hydrogen spectrum (¹H NMR), Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatograph (GPC) and elemental analysis. The reaction activities of lignin before and after modification were evaluated by hydroxymethylation and Mannich reaction. The results showed that the content of phenolic hydroxyl group of modified lignin was 4.95%, which increased by 32.71%. When the acid reacted with the purified lignin at the dosage of 20 mmol/g at 95 ℃ for 1 h with TBHDTB (2% to Lignin) under microwave irradiation, the content of methoxyl group was 6.11%, which decreased by 20.44%. The reaction activity with formaldehyde increased by 18.15%, whereas the amino side chain increased by 7.54% compared with the starting lignin. The analyses of UV, ¹H NMR and FT-IR confirmed the increase of the contents of phenolic hydroxyl group and methoxyl group.

Key words: lignin, microwave heating, demethylation, structure

中图分类号:

TQ35

夏成龙, 许玉芝, 刘晓欢, 王春鹏. 微波辅助木质素脱甲基化改性及结构表征[J]. 林产化学与工业, 2016, 36(2): 57-63.

XIA Cheng-long, XU Yu-zhi, LIU Xiao-huan, WANG Chun-peng. Preparation and Characterization of Demethylated Lignin Assisted by Microwave Irradiation[J]. Chemistry and Industry of Forest Products, 2016, 36(2): 57-63.

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微波辅助木质素脱甲基化改性及结构表征

Preparation and Characterization of Demethylated Lignin Assisted by Microwave Irradiation

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