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Non-carbon Skeletal Polymers — Polyphosphazenes (PPZs) (Inorganic Rubber)

A Promising Smart Inorganic-based Material

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Abstract

Poly(dichlorophosphazene), [NPCl2]n (helical structure) consisting of the unsaturated −NPC12− group (as the repeating unit), was discovered by H. N. Stokes in 1897. It is elastomeric (i.e. rubber-like property) and thermally stable and is known as inorganic rubber. However, rapid hydrolysis of this so-called inorganic rubber in moist air precluded its commercial and technical use. Due to this drawback, scientists tried to modify this rubber-like material to impart hydrolytic stability. It was found by Allcock et al. in 1965 that the high-molecular-weight poly(dichlorophosphazene) linear polymer without cross-linking, produced by controlled thermal ring-opening polymerisation (ROP) of cyclic trimer [NPCl2]3, was completely soluble in benzene and other organic solvents. The chloro groups of this soluble polymer could be completely replaced by other substituents (macromolecular substitution) to yield the inorganic-organic hybrid polymeric products [NPR2]n of good hydrolytic stability maintaining the elastomeric property. In fact, a lot of modification has been done on the actual polymer (inorganic rubber) for practical application. It is important to note that the flexible PNP group in the helical structure of inorganic rubber is isoelectronic with the SiOSi group of silicone rubber, another inorganic-based important polymeric material.

These inorganic-organic hybrid polymers having the noncarbon skeletal possess unique properties like thermal and chemical stability, easily controlled synthesis, versatile and tuneable functionalities (e.g. biostability to biodegradability, superhydrophobicity to hydrophilicity, etc.), advanced architectures of polymer networks including various types of copolymers, etc. Because of these attractive features, polyphosphazenes (PPZs) have emerged as promising inorganic-based smart materials and find versatile applications in industrial, technical and biomedical fields such as plastics, elastomers and fibres.

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12 Acknowledgements

Facilities provided by Visva Bharati University are thankfully acknowledged. The authors are thankful to Prof. Abhishek Dey (Editor) for meticulously reading the text and making some constructive suggestions to make the article more readable and informative.

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Authors and Affiliations

  1. School of Chemical Sciences, Indian Association of Cultivation for the Science, Kolkata, 32, India

    Ankita Das

  2. Department of Chemistry, Visva Bharati, Santiniketan, 731 235, India

    Asim K. Das

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  1. Udita Das
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Correspondence to Ankita Das or Asim K. Das.

Additional information

This article is dedicated to Prof. Harry R. Allcock, Evan Pugh Professor of Chemistry at Pennsylvania State University, United States, for making a significant and pioneering contribution to the development of polyphosphazenes (inorganic rubber) as a useful and promising, smart inorganic-based material.

Udita Das, a DST INSPIRE Scholar, is now a PG student (chemistry) at Visva Bharati University, Santiniketan.

Ankita Das works as a DST INSPIRE Research Fellow in computational chemistry at the Indian Association for the Cultivation of Science, Kolkata.

Asim K. Das is currently a Senior Professor at the Chemistry Department, Visva Bharati, Santiniketan. He is interested in thermodynamic and kinetic aspects of metal-ligand interactions and has authored some advanced-level inorganic chemistry textbooks for undergraduate and postgraduate students.

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Das, U., Das, A. & Das, A.K. Non-carbon Skeletal Polymers — Polyphosphazenes (PPZs) (Inorganic Rubber). Reson 28, 1523–1548 (2023). https://doi.org/10.1007/s12045-023-1689-y

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