Polymer Synthesis with More Than One Form of Living Polymerization Method

Abstract

Controlled radical polymerization (CRP) or controlled/living radical polymerization has revolutionized the polymer industry as a tool for the preparation of a wide variety of polymers. This process enables the preparation of polymers with good control of molecular weight, narrow polydispersity, and a range of architectures including block and graft copolymers, star polymers, and other functional polymers. The mechanistic transformation reaction provides a great opportunity to tune chemical and physical properties of copolymers. It can be applied to combine different homopolymers using post‐modification techniques or by the use of a dual initiator, allowing the combination of mechanistically distinct polymerization reactions. This review will cover CRP transformations including the synthesis of block copolymers with both linear structures (AB, ABA, (AB) n , multiblocks, etc.) and branched macromolecular architectures (graft, miktoarm star, and dendritic‐like), which are obtained by a combination of more than one form of living polymerization reaction.

Polystyrene Chain Growth Initiated from Dialkylzinc for Synthesis of Polyolefin-Polystyrene Block Copolymers

“…The synthesis of block copolymers has been a topical issue in the field of polymer science and chemistry [1]. Conventionally, block copolymers are synthesized by controlled living anionic or radical polymerizations [2,3]. A typical example is polystyrene-block-polybutadiene-block-polystyrene (SBS), which is industrially produced by controlled living anionic polymerization at a large scale.…”

Amphiphilic tri- and tetra-block co-polymers combining versatile functionality with facile assembly into cytocompatible nanoparticles

“…Importantly, the adoption of bifunctional initiators provides additional opportunities to produce biodegradable copolymers with hybrid architectures by using the ω-functionality in a second synthetic step, such as ATRP or RAFT polymerisations, or Michael addition reactions. 28 In this work we report the synthesis of a small library of mixed-polyester-polycarbonate materials with potential applications in polymer therapeutics (Fig. 1).…”

Versatile, Highly Controlled Synthesis of Hybrid (Meth)acrylate–Polyester–Carbonates and their Exploitation in Tandem Post‐Polymerization–Functionalization

“…The demand for novel materials such as these throughout the pharmaceutical field makes it imperative to develop simple techniques for their synthesis, requiring minimal use of toxic catalysts, non‐stringent reaction conditions, and simple purification steps . It is also desirable to minimize side‐reactions to ensure the integrity and purity of the final structure of the materials to optimize the efficiency of further modification steps, minimize subsequent separation procedures, and retain any additional properties, such as bioenvironment responsiveness …”