含1,3,4-噻二唑环聚合物的合成及应用研究进展

doi:10.11896/j.issn.1005-023X.2018.11.017

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Abstract  As a new type of functional aromatic heterocyclic polymers, 1,3,4-thiadiazole ring-containing polymers have attracted a great deal of attention in recent years due to their unique energy storage, electrocatalytic activity and electron-rich properties. In the past two decades, the uninterrupted research over 1,3,4-thiadiazole ring-containing polymers has been mainly focused on the electrochemical synthesis and structural characterization of these polymers as well as their applications in cathode materials for rechar-geable lithium batteries, biochemical sensors, clinical diagnosis and pharmacology and other related fields.
    Electrochemical synthesis method is favorable to the preparation of self-supporting membrane with controllable thickness and easy modification for electrodes, but nevertheless presents many defects such as electrolyte contamination, high cost and unsuitability for large-scale production. Some researchers have made attempts to synthesize 1,3,4-thiadiazole ring-containing polymers via chemical oxidative polymerization, though merely obtained some complexes or coordination polymers except 2,5-dimercapto-1,3,4-thia-diazole polymers, yet the environmental friendly and large-scale synthesis methodology represent the general trend. There are scanty means available for the structural characterization of 1,3,4-thiadiazole ring-containing polymers because of the solubility limitation, and the main characterization methods are X-ray photoelectron spectroscopy and infrared or Raman spectroscopy. The features of high energy density and high specific capacity have recommended 2,5-dimercapto-1,3,4-thiadiazole polymers to global researchers in seeking for the secondary lithium battery cathode materials, but they also suffer some weaknesses such as slow charge-discharge rate and rapid decline in the capacitance. Besides, the sensors constructed based on 1,3,4-thiadiazole ring-containing polymer modified electrodes have displayed potential for highly sensitive and highly selective detection of a rich variety of bio-related molecules, but the stability of these electrodes needs improvement.
    Among all 1,3,4-thiadiazole ring-containing polymers, poly-2-amino-1,3,4-thiadiazole (PAT), poly-5-amino-1,3,4-thiadiazole-2-thiol or poly-5-amino-2-mercapto-1,3,4-thiadiazole (PAMT) and poly-2,5-dimercapto-1,3,4-thiadiazole (PBT) have been synthesized through electrochemical method, while PBT has also been synthesized via a chemical oxidative synthesis method under green conditions, offering a reference for the synthesis of other 1,3,4-thiadiazole ring-containing polymers. Furthermore, our group also has successfully synthesized PAT, PAMT and poly-2-mercapto-1,3,4-thiadiazole (PTT) through chemical oxidative polymerization. So far, with respect to cathode material for secondary lithium ion battery, the PBT with a theoretical specific capacity of up to 362 mAh/g has been the most studied. Researchers have combined PBT with conductive polymers such as polypyrrole, polyaniline or water-soluble sulfonated graphene to further enhance the specific capacity and the stability of the electrode and accelerate the charge-discharge process. Meanwhile impressive strides have been made in fabricating the biochemical sensors based on 1,3,4-thiadiazole ring-containing polymers modified electrodes for the purpose of detection and content measurement of active ingredients in natural pro-ducts, drugs or metabolites in blood and body fluids of human/mammals or in the drug injections, the pesticide residues in Chinese herbal medicine or food, and heavy metal ions in aqueous solutions. Combining 1,3,4-thiadiazole ring-containing polymer with perf-luorosulfonic acid binder and multi-walled carbon nanotubes would facilitate to reduce polymer loss, thus enhancing the stability of the electrode and prolonging the service life.
    This review mainly concerns the worldwide research over 1,3,4-thiadiazole ring-containing polymers. It introduces the synthesis, structure characterization and application of 1,3,4-thiadiazole ring-containing polymers, and discusses the problems confronting the 1,3,4-thiadiazole ring-containing polymers and their application prospects. It is expected to provide a reference for the preparation technology and function extension of this species of polymers.

Key words： 1,3,4-thiadiazole ring-containing polymers synthesis cathode materials for rechargeable lithium battery sensors

Published: 20 July 2018

CLC number:

TB324

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	LI Chao
	MA Chengzhang
	HUANG Shaojun
	MIN Chungang
	HUANG Qiuling
	SUN Xiaodong

Cite this article:

LI Chao,MA Chengzhang,HUANG Shaojun, et al. Advances in the Synthesis and Application of 1,3,4-Thiadiazole Ring-containing Polymers[J]. Materials Reports, 2018, 32(11): 1891-1902.

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http://www.mater-rep.com/EN/10.11896/j.issn.1005-023X.2018.11.017 OR http://www.mater-rep.com/EN/Y2018/V32/I11/1891

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