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Progress in Chemistry 2020, Vol. 32 Issue (10): 1547-1556 DOI: 10.7536/PC200225 Previous Articles   Next Articles

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: Revised: Online: Published:
  • Contact: Xin Hu, Ning Zhu
  • About author:
    **e-mail:(Xin Hu)
    (Ning Zhu)
  • Supported by:
    National Natural Science Foundation of China(22078150)
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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
Fig.1 Precursor of lignin monomer[5]
Fig.2 Coordination-insertion mechanism
Fig.3 Enzymatic ring-opening polymerization mechanism[43]
Fig.4 Nucleophilic monomer activation mechanism
Fig.5 Electrophilic monomer activation mechanism
Fig.6 Chain-end activation mechanism
Fig.7 Bifunctional activation mechanism
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
Fig.8 TBD catalytic synthesis of lignin graft copolymer[54]
Fig.9 Three methods for synthesizing lignin graft copolymer[63]
Fig.10 Grafting modification of dodecylated lignin via ROP of LA [61]
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
Fig.11 TBD catalytic synthesis of BBL-g-PCL[74]
Table 3 The other cyclic monomers for grafting modification
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