Recent advances on the structure–properties relationship of multiblock copolymers

Abstract

Multiblock copolymers represent a fascinating class of materials that sits at the very heart of industrial applications and fundamental polymer science. They are most often made of a linear succession of incompatible “soft” and “hard” segments that microphase separate at room temperature while they can be easily re‐homogenized upon heating. This thermoreversible character provides them with decisive advantages with respect to other rubber‐based materials such as vulcanized elastomers, making them indispensable for the development of a more sustainable polymer industry. Beyond practical opportunities, tailoring the multiblock copolymers morphology has a pivotal role to play in the fundamental understanding of the structure–properties relationship of polymer‐based systems. It notably serves to comprehend complex materials such as semicrystalline homopolymers and nanocomposites. Aside from the thorough work developed on well‐defined diblock copolymers for half a century, this article review aims to guide the reader into the more intricate world of multiblock copolymers by providing him/her quantitative tools to connect chemical nature, microstructure and mechanical properties.

Bio-Based Upcycling of Poly(ethylene terephthalate) Waste for the Preparation of High-Performance Thermoplastic Copolyesters

“…Thermoplastic copolyesters (TPCs) constitute a materials class with commercial relevance, employed in demanding engineering applications 30 where the combination of thermal stability, chemical and abrasion resistance, and mechanical strength are critical. The molecular microstructure is described by the alternation of immiscible hard and soft segments (i.e., blocks) linked with ester bonds.…”

Discrete Giant Polymeric Chain with Precise Sequence and Regio-configuration: A Concise Multiblock Model System

“…One of the most well-known examples is a block copolymer consisting of chemically distinct chains . It has been widely recognized that an AB diblock copolymer can spontaneously form diverse ordered structures simply by tuning the composition and interaction. , Introducing additional blocks greatly increases the molecular complexity and offers extra handles to regulate phase formation and transition. − Precise manipulation of molecular parameters such as the block sequence, regio-configuration, chain architecture, and molecular symmetry provides alluring opportunities to generate exquisite structures and achieve advanced properties. , For example, it has been recently demonstrated that rationally adjusting the relative block length of multiblock copolymers affords access to rich unconventional phases otherwise unattainable. − …”

“…5−8 Precise manipulation of molecular parameters such as the block sequence, regioconfiguration, chain architecture, and molecular symmetry provides alluring opportunities to generate exquisite structures and achieve advanced properties. 9,10 For example, it has been recently demonstrated that rationally adjusting the relative block length of multiblock copolymers affords access to rich unconventional phases otherwise unattainable. 11−16 The vastly expanding design space of multiblock copolymers, however, is both an opportunity and a challenge.…”

Fully biobased triblock copolymers generated using an unconventional oscillatory plug flow reactor

“…2,3 The properties can therefore be tuned by preparing products with different relative block lengths and different block sequences. 4,5 However, each individual target composition typically requires a separate synthesis, which can be quite elaborate depending on the architecture. [6][7][8][9] This is nearly always carried out in batch reactions with each block made sequentially, which is especially necessary with mechanistically incommensurate monomers/repeating units.…”