Abstract

Many desirable characteristics of polymers arise from the method of polymerization and structural features of their repeat units, which typically are responsible for the polymer’s performance at the cost of processability. While linear alternatives are popular, polymers composed of cyclic repeat units across their backbones have generally been shown to exhibit higher optical transparency, lower water absorption, and higher glass transition temperatures. These specifically include polymers built with either substituted alicyclic structures or aromatic rings, or both. In this review article, we highlight two useful ring-forming polymer groups, perfluorocyclobutyl (PFCB) aryl ether polymers and ortho-diynylarene- (ODA) based thermosets, both demonstrating outstanding thermal stability, chemical resistance, mechanical integrity, and improved processability. Different synthetic routes (with emphasis on ring-forming polymerization) and properties for these polymers are discussed, followed by their relevant applications in a wide range of aspects.

Highlights

  • The design and development of polymers with beneficial and distinctive properties is critical for advanced technologies including nanomaterials, composites, photonics, microelectronics, and energy transformation [1,2,3,4,5]

  • An inexpensive micro-transfer molding technique was employed for the PFCB copolymers and their use as polymer waveguides and optical clad layers in microphotonics has been demonstrated [42]

  • The polymerization of BODA monomers by Bergman cycloaromatization produces highly reactive diradicals that react in a non-selective manner, leading to non-linear irregular structures

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Summary

Introduction

The design and development of polymers with beneficial and distinctive properties is critical for advanced technologies including nanomaterials, composites, photonics, microelectronics, and energy transformation [1,2,3,4,5]. The preparation of polymers containing aromatic rings or alicyclic structures has attracted much attention because tremendous increase in chemical, mechanical, and thermal resistance is anticipated for such polymers [7,8]. Fluoropolymers are classified as high-performance materials owing to their unique blend of complementary properties including chemical and thermal stability, mechanical durability, low surface energy, high insulation, and low refractive index [16]. These characteristics can all be linked to electronegative fluorine atoms and the strength of the resulting C–F and C–C bonds in fluoropolymers. CytopTM (perfluorovinyl ether cyclopolymer) and TeflonTM AF (tetrafluoroethylene and perfluorodioxole copolymer) are leading examples

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