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化学进展 2020, Vol. 32 Issue (10): 1547-1556 DOI: 10.7536/PC200225 前一篇   后一篇

• 综述 •

开环聚合接枝改性木质素

秦国富1, 刘一寰1, 尹帆1, 胡欣2,**(), 朱宁1,**(), 郭凯1   

  1. 1.南京工业大学生物与制药工程学院 材料化学工程国家重点实验室 南京 211800
    2.南京工业大学材料科学与工程学院 南京 211800
  • 收稿日期:2020-02-24 修回日期:2020-05-19 出版日期:2020-10-24 发布日期:2020-09-02
  • 通讯作者: 胡欣, 朱宁
  • 基金资助:
    国家自然科学基金项目(22078150)
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Grafting Modification of Lignin via Ring-Opening Polymerization

Guofu Qin1, Yihuan Liu1, Fan Yin1, Xin Hu2,**(), Ning Zhu1,**(), Kai Guo1   

  1. 1. College of Biotechnology and Pharmaceutical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211800, China
    2. College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211800, China
  • Received:2020-02-24 Revised:2020-05-19 Online:2020-10-24 Published:2020-09-02
  • Contact: Xin Hu, Ning Zhu
  • About author:
    **e-mail:(Xin Hu)
    (Ning Zhu)
  • Supported by:
    National Natural Science Foundation of China(22078150)

作为自然界储量丰富的生物质资源之一,木质素尚未得到充分利用,成为掣肘生物化工发展的挑战。利用木质素丰富的功能基团进行接枝聚合改性,已成为木质素高值化利用的一个重要途径。开环聚合是一种温和、高效的聚合方法,可以将脂肪族聚酯链段引入到木质素中,提高材料的溶解性、相容性和可降解性,拓展木质素的应用范围。本文关注多催化条件下丙交酯、己内酯等环状单体通过开环聚合对木质素进行接枝改性的研究进展,同时对木质素改性材料的性能、应用以及发展前景进行了探讨。

关键词： 木质素, 开环聚合, 接枝改性, 环状单体

As one of the most abundant biomass resources in nature, lignin has not been fully utilized, which has become a challenge to the development of biochemical industry. As an important strategy to achieve high-value utilization of lignin, grafting modification of lignin has been paid much attention. Ring-opening polymerization is a mild and efficient polymerization method, which can introduce aliphatic polyester segments into lignin. Compared to the pristine lignin, graft polymers show improved solubility, compatibility and degradability. This paper focuses on the progress of grafting modification of lignin via ring opening polymerization by using varied catalysis. Lactide, caprolactone and other cyclic monomers are summarized. The performance and applications of lignin grafted polymers are discussed as well as the challenges and opportunities.

Contents

1 Introduction

2 Catalysis for ring-opening polymerization

2.1 Metal-catalyzed ring-opening polymerization

2.2 Enzymatic ring-opening polymerization

2.3 Organocatalyzed ring-opening polymerization

3 Lactide as monomer

3.1 Synthesis of lignin grafted polylactide

3.2 Effect of lignin's structure and lactide's chirality

3.3 Application of lignin grafted polylactide

4 Caprolactone as monomer

4.1 Synthesis of lignin grafted polycaprolactone

4.2 Application of lignin grafted polycaprolactone

5 Other monomers

5.1 Oxazoline

5.2 Cyclic carbonate

5.3 β-Butyrolactone

6 Conclusion and outlook

Key words: lignin, ring-opening polymerization, graft modification, cyclic monomer
()
图1 木质素单体的前驱体[5]
Fig.1 Precursor of lignin monomer[5]
图2 配位-插入型开环聚合机理
Fig.2 Coordination-insertion mechanism
图3 酶促开环聚合机理[43]
Fig.3 Enzymatic ring-opening polymerization mechanism[43]
图4 亲核单体活化机理
Fig.4 Nucleophilic monomer activation mechanism
图5 亲电单体活化机理
Fig.5 Electrophilic monomer activation mechanism
图6 链末端活化机理
Fig.6 Chain-end activation mechanism
图7 双官能团活化机理
Fig.7 Bifunctional activation mechanism
表1 不同催化剂制备木质素接枝聚丙交酯
Table 1 Preparation of Lignin-g-PLA with different catalysts
Catalysts Sn(Oct)2 DBU TBD DMAP CaH2
Lignin Alkali lignin Dodecylated lignin Lignin(Indulin AT) Alkaline lignin Pyrolitic lignin
Tem(℃) 130 25 130 80 110
Time(h) 24 24 4 24 10
Mn(kg/mol) 10.4~16.4 1.3~28.2 0.2~11 4.1 2.8
PDI 1.25~2.41 1.23~1.41 none 1.58~1.61 none
ref 36 61 54 59 64
图8 TBD催化合成木质素接枝共聚物[54]
Fig.8 TBD catalytic synthesis of lignin graft copolymer[54]
图9 三种合成木质素接枝共聚物的方法[63]
Fig.9 Three methods for synthesizing lignin graft copolymer[63]
图10 烷基化木质素对PLA材料进行增韧[61]
Fig.10 Grafting modification of dodecylated lignin via ROP of LA [61]
表2 引发己内酯开环聚合的不同木质素
Table 2 Different lignins as the initiators for ROP of CL
Type of lignin Hydroxyl content
(mmol/g lignin)		 Mn
(g/mol)		 ref
Aliphatic Phenolic
soda lignin 2.94 1.67 1120 73
organic solvent
lignin		 3 5 1600 65
kraft lignin 7.93 2.16 970 75
biobutanol lignin 5.62 876 74
图11 TBD催化合成生物丁醇木质素接枝聚己内酯[74]
Fig.11 TBD catalytic synthesis of BBL-g-PCL[74]
表3 用于木质素开环聚合接枝改性的其他单体
Table 3 The other cyclic monomers for grafting modification
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摘要

开环聚合接枝改性木质素