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Progress in Chemistry 2021, Vol. 33 Issue (12): 2188-2202 DOI: 10.7536/PC201119 Previous Articles   Next Articles

• Review •

Metal Coordination Polyurethanes

Jinke Wu1, Jianjun Wang1(), Lixing Dai1, Donghao Sun1, Jiajia Chen2()   

  1. 1 College of Chemistry, Chemical Engineering and Materials Science, Soochow University,Suzhou 215123, China
    2 College of Chemistry and Chemical Engineering, Xiamen University,Xiamen 361005, China
  • Received: Revised: Online: Published:
  • Contact: Jianjun Wang, Jiajia Chen
  • Supported by:
    the National Natural Science Foundation of China(21975211); the Fundamental Research Funds for the Central Universities(20720190035); and the Nanqiang Young Top-notch Talent Fellowship from Xiamen University.
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Metal coordination polyurethanes (MCP) are the aggregates of metal-polyurethane complexes that form between a zero-dimensional metal ion or ionic cluster center with the surrounding array of one-dimension ligand polyurethanes (PU). Those metal-polyurethane complexes exhibit interesting physical characteristics, including thermoplasticity, elasticity, electrical conductivity, fluorescence, etc. The coordination interactions between metal ions and PU lead to formation of supramolecular aggregates, which endow the PU with advanced functionalities at high structural hierarchies across disciplinary boundaries such as self-repair, memory, antibacterial, luminescent, and so on. The orthogonal metal-polymer self-assembly is an ongoing theme in coordination chemistry, and thus brings MCP widely attention from various research areas in recent years. However, there has been not yet a review on this related topic of MCP. Herein, this review summarizes the ways and methods of the interaction between PU and metals from the molecular compositions and structures, and provides a comprehensive discussion on the coordination structures, as well as the related properties and applications. Finally, the prospective on the future development and application of MCP is presented.

Contents

1 Introduction

2 Alkali earth metal coordination polyurethanes

3 Transition metal coordination polyurethanes

4 Rare earth metal coordination polyurethanes

5 Other metal coordination polyurethanes

6 Conclusion and outlook

Key words: polyurethanes, coordination, metal ions, dynamically reversible
Fig.1 Three typical preparation methods and six general structures of MCP
Table 1 Diols and diamines of metals chelated by carboxylates
Structures Notes ref
a M = Mg2+, Ca2+, Mn2+, Co2+, Cu2+, Zn2+, Cd2+, Hg2+ or Pb2+;
R = (CH2)2, (CH2)4, (CH2)5, (CH2)2O(CH2)2;		 12,13, 18~28,30~40
b 14,15
c 29
d 17
e 16
Fig.2 Schematic representation of ionic aggregates in PU ionomers
Fig.3 Schematic of PU with pendant pyridine group[41]
Fig.4 Schematic shows the Ca2+ coordinated by coordination groups on the surface of polyurethane membranes[42]. Copyright 2015, Wiley
Fig.5 Preparation of Ca2+ coordination polyurethanes by coordination of Ca2+ with terminal catechol groups[44]. Copyright 2019, Wiley
Fig.6 Structures of (a) hard segment of the sulfonated PU[48⇓~50], and (b) coordination between carboxylate in PU and Ni2+, Cu2+, Zn2+ [51]
Fig.7 Coordination structures of (a) Fe3+, (b) Zn2+ and (c) Tb3+ with diamidopyridine. (d~f) Healing properties of PU containing Fe3+-diamidopyridine coordination structure[65]. Copyright 2019, Wiley
Fig.8 Chemical structures of PU with (a) terpyridine ligand[68] and (b) 2,6-bis(1,2,3-trizol-4-yl)pyridine ligand[70,71] in main chain
Table 2 Transition metal coordinated Schiff base diol or diamine
Structures Notes ref
a M = Cu2+, Co2+, Ni2+ 72~74
b m = 7, 10, 12 75
c M = Cu2+, Ni2+, Pb2+, Zn2+ 76
d M = Cu2+, Co2+, Ni2+ 77
e M = Cu2+, Zn2+;
R = >C S, >C O		 78, 79
f M = Mn2+, Co2+, Ni2+;
R = >C S, >C O
g / 80
h M = Ni2+, Zn2+ 81
i M = Ni2+, Zn2+ 82
Fig.9 Constructing self-healing and stretchable electronics with Cu2+ coordination dimethylglyoxime-extended PU (Cu-DOU-PU)[83]. Copyright 2019, Wiley
Fig.10 The number of pendant catechol groups coordinated with Fe3+ is regulated by pH[85]
Fig.11 Structures of pyrazole-based coordination polyurethanes[87]
Fig.12 Possible coordination junction points of PU[104,105]
Fig.13 Schematic for the synthesis of MCP through the coordination of hydroxyl and carbonyl in PU with Mn2+、Zn2+、Ni2+ [106, 107]
Table 3 The rare earth chelates of carboxylate for preparing rare earth metal coordination polyurethanes
Structures ref
a 110
b 111
c 112
d 114
e 115
Fig.14 (a) Schematics of the coordination structure of Ln3+ with terpyridine, and (b) luminescent behavior of rare earth coordination polyurethanes with different molar ratio of Eu3+ and Tb3+ under ultraviolet radiation[116]. Copyright 2020, American Chemical Society
Fig.15 Coordination structure of β-diketone with Eu3+ [118]
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