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化学进展 2020, Vol. 32 Issue (5): 617-626 DOI: 10.7536/PC190901 前一篇   后一篇

• 综述 •

木质素基生物质聚氨酯

马晓振1,2, 罗清1, 秦冬冬1,3, 陈景1,**(), 朱锦1, 颜宁4,**()   

  1. 1.中国科学院宁波材料技术与工程研究所 宁波 315201
    2.中国科学院大学 北京 100049
    3.天津大学化工学院 天津 300350
    4.多伦多大学化学工程和应用化学系 多伦多 M5S 3B3
  • 收稿日期:2019-09-02 修回日期:2019-11-29 出版日期:2020-05-15 发布日期:2020-02-20
  • 通讯作者: 陈景, 颜宁
  • 基金资助:
    国家重点研发计划(2017YFE0102300); 多伦多大学(加拿大)OCE计划(29983); 国家自然科学基金项目(51503218)
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Lignin-Based Polyurethane

Xiaozhen Ma1,2, Qing Luo1, Dongdong Qin1,3, Jing Chen1,**(), Jin Zhu1, Ning Yan4,**()   

  1. 1.Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201,China
    2.University of Chinese Academy of Sciences, Beijing 100049, China
    3.Chemical Engineering Institute, Tianjin University, Tianjin 300350, China
    4.Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto M5S 3B3, Canada
  • Received:2019-09-02 Revised:2019-11-29 Online:2020-05-15 Published:2020-02-20
  • Contact: Jing Chen, Ning Yan
  • About author:
    ** e-mail: (Jing Chen);
    (Ning Yan)
  • Supported by:
    National Key Research and Development Program of China(2017YFE0102300); OCE Project #29983 from University of Toronto(Canada)(29983); National Natural Science Foundation of China(51503218)

聚氨酯材料是由多元醇与异氰酸酯经过聚加成反应得到的一种多功能性的高分子材料,在涂料、弹性体、胶黏剂、泡沫等领域具有非常广泛的应用。但是多元醇与异氰酸酯都来源于石油,随着石油资源的消耗以及环境问题的加剧,寻求可再生原料成为研究热点。目前对于生物基聚氨酯的报道,大多都是针对多元醇的生物质替代,其中利用最多的是植物油和木质素。木质素作为储量丰富的天然有机碳资源,当前利用效率极低,大多被作为燃料而浪费。与植物油相比,在合成聚氨酯方面木质素不存在“与人争粮”问题并且相关产品性能优越,但是木质素的利用仍存在一定缺陷,如分离困难、均一性差、易聚集、位阻大和活性低等,这让木质素的直接利用或改性利用成为关键。本文主要介绍了木质素在生物基聚氨酯合成中的发展现状和最新研究进展。最后,在此基础上展望了木质素基聚氨酯材料在不同领域的发展前景。

关键词： 聚氨酯, 木质素, 改性, 未改性, 弹性体, 泡沫

Polyurethane(PU), one of the most multifunctional polymers, is produced by polyaddition reaction of polyols and isocyanates. It has found wild applications in coatings, elastomers, adhesives, foams. However, one of the problems related to the production of PU is its dependence on petroleum-based resources. With the consumption of petroleum resources and the destruction of environment, the searching for renewable raw materials has become a research hotspot. At present, most reports are based on biobased polyols replacing petroleum-based polyols to prepare polyurethane, among which vegetable oil and lignin are the most used. Lignin, a natural organic carbon resource with abundant reserves, is low value-added and wasted as fuel at present. Compared with vegetable oil, lignin does not compete with human for food and the performance of related products is superior. However, the utilization of lignin has some problems, such as isolation, heterogeneity, aggregation, steric hindrance and low activity. These disadvantages make the unmodified utilization and modified utilization of lignin become the key problem. This paper introduces the development status and latest research progress of lignin in bio-based polyurethane synthesis. Finally, the development prospects of lignin-based polyurethane materials in different fields are prospected.

Contents

1 Introduction

2 Lignin

3 Lignin bio-based polyurethane elastomer

3.1 Preparation of bio-based polyurethane elastomers from unmodified lignin

3.2 Preparation of bio-based polyurethane elastomers with modified lignin

4 Lignin bio-based polyurethane foam

4.1 Preparation of bio-based polyurethane foams from unmodified lignin

4.2 Preparation of bio-based polyurethane foams from modified lignin

5 Conclusion and outlook

Key words: polyurethane, lignin, modified, unmodified, elastomer, foam
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图1 酶解木质素以及其结构
Fig. 1 Enzymatic lignin and structure
图式1 木质素单体结构:1香豆醇;2松柏醇;3芥子醇
Scheme 1 Structures of monolignols;1. Coumarol alcohol; 2. Coniferyl alcohol; 3. Sinapyl alcohol
图式2 木质素单体共振式
Scheme 2 Lignin unit resonant type
图2 聚乙二醇/甘油液化木质素多元醇
Fig. 2 Polyethylene glycol/glycerol liquefied lignin polyol
图3 未改性木质素制备高性能聚氨酯弹性体[70]
Fig. 3 Preparation of high performance polyurethane elastomers from unmodified lignin[70]
图式3 木质素羟基改性的四种方式
Scheme 3 Four methods of lignin hydroxyl modification
图4 季铵盐改性木质素-二氧化硅复合材料[18]
Fig. 4 Quaternary ammonium salt modified lignin-silica composite[18]
图式4 RAFT-点击化学制备自修复木质素基聚合物[78]
Scheme 4 Preparation of self-healing lignin-based polymers in RAFT-click chemistry[78]
图式5 木质素基热塑性聚氨酯[80]
Scheme 5 Lignin-based thermoplastic polyurethane[80]
图式6 环碳酸酯代替环氧乙烷改性木质素[102]
Scheme 6 Cyclocarbonate replaces ethylene oxide to modify lignin[102]
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木质素基生物质聚氨酯