Abstract

Vitrimers are a new class of cross-linked materials that are capable of network topology alternation through the associative dynamic bond-exchange mechanism, which has recently been invented to solve the problem of conventional cross-linked materials, such as poor recyclability and healability. Thus far, the concept of vitrimers has been applied to various commercial polymers, e.g., polyesters, polylactides, polycarbonates, polydimethylsiloxanes, polydienes, polyurethanes, polyolefins, poly(meth)acrylates, and polystyrenes, by utilizing different compatible bond-exchange reactions. In this review article, the concept of vitrimers is described by clarifying the difference from thermoplastics and supramolecular systems; in addition, the term “associative bond-exchange” in vitrimers is explained by comparison with the “dissociative” term. Several useful functions attained by the vitrimer concept (including recyclability and healability) are demonstrated, and recent molecular designs of vitrimers are classified into groups depending on the types of molecular frameworks. This review specifically focuses on the vitrimer molecular designs with commercial polymer-based frameworks, which provide useful hints for the practical application of the vitrimer concept.

Highlights

  • Cross-linking is a method used to link polymers to form a 3D network

  • The results indicate that the bond exchange progressed re-processability, healability, recyclability, and self-adhesion, are introduced on the basis of the sufficiently between different surfaces of therepresentation vitrimers, and of new bonds were newly formed across report by the author.the

  • The results indicate that the bond exchange progressed sufficiently between the different surfaces of the vitrimers, and new bonds were newly formed across the surfaces

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Summary

Introduction

Cross-linking is a method used to link polymers to form a 3D network. Various physical properties of polymeric materials (e.g., thermal/mechanical properties and solvent resistance) can be modified or enhanced by cross-linking. On the basis of the abovementioned background, a special type of covalent bond been developed with the capability of dissociation and re-association under external stimuli. The networks constructed from such dynamic covalent bonded cross-links are referred the bond. In 2005, Bowman et al reported the preparation of novel cross-linked materials that exhibited useful functions, such as plasticity and shape changes, without residual stress [22] These functions were achieved by the incorporation of exchangeable bonds into the network on the basis of radical addition–fragmentation upon exposure to light. The materials constructed from an associative dynamic covalent bond are termed “vitrimers,” and many molecular designs with unique useful functions, such as recyclability and healability, have been under development. As far as the author knows, this is the first review article of vitrimers that are designed based on the frameworks of commercial polymers, which can give some hints to the practical application of the vitrimer concept

Characteristics of the Bond Exchange Mechanism of Vitrimers
Examples
Characteristics of the Physical Properties of Vitrimers
Representative Useful Functions of Vitrimers
Representative
Polyesters
Polylactide
Polycarbonates
Polydimethylsiloxanes
Polydienes
13. Molecular
Polyolefins
Findings
Summary
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