Issue 16, 2023

Preparation of functionalized diene-elastomers upon top-down pyrolysis of their vulcanizates via dynamic covalent polymerization

Abstract

Decorating diene rubbers with functional handles through copolymerization with polar monomers or post-modification of the chain backbone still struggles with some stubborn problems, including the dependence on specific catalytic systems, inescapable side reactions and poor tunability. Herein, we pioneer a brand-new methodology to rationally design functionalized diene rubbers with tunable chain structures. More specifically, by adopting the disulfide/polysulfide linkages in vulcanizates as reactive substrates, these linkages can be cleaved into active sulfur radicals upon solvothermal pyrolysis, which not only enable network disintegration but initiate the direct insertion of functional vinyl monomers into the rubber skeleton through a dynamic covalent polymerization mechanism. Accordingly, the local polarity of the functionalized chain segments increases, which reduces compatibility with the pristine components and hence facilitates the high-yield separation (∼98 wt%) of these functionalized rubbers from the network architecture. The chain structure of the obtained functionalized rubbers can be facilely tuned by regulating the pyrolysis conditions (time and temperature) and monomer content. More importantly, it is demonstrated that this methodology is versatile for obtaining functionalized rubbers with desired handles from various vulcanizates and vinyl monomers. Therefore, we envision that the present methodology will have important scientific and economic significance, since it exploits a feasible alternative for custom-made functionalized rubbers that will have broad application prospects, such as functional coupling agents, and self-healing and shape memory materials.

Graphical abstract: Preparation of functionalized diene-elastomers upon top-down pyrolysis of their vulcanizates via dynamic covalent polymerization

Supplementary files

Article information

Article type
Paper
Submitted
27 Jan 2023
Accepted
27 Feb 2023
First published
28 Feb 2023

J. Mater. Chem. A, 2023,11, 8647-8655

Preparation of functionalized diene-elastomers upon top-down pyrolysis of their vulcanizates via dynamic covalent polymerization

X. An, S. Wu, S. Xiong, S. Yu, Z. Tang, B. Guo and L. Zhang, J. Mater. Chem. A, 2023, 11, 8647 DOI: 10.1039/D3TA00478C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements