Precise Synthesis of Block and Miktoarm Star‐Branched Polymers Containing Polythiophene Segments with Low Dispersity by Combination of Living Anionic Polymerization and Catalyst‐Transfer Polycondensation Systems

Abstract

In this Talent article, the synthesis of well‐defined block and miktoarm star‐branched polymers is described by the combination of living anionic polymerization (LAP) and Kumada catalyst‐transfer polymerization (KCTP), mostly focusing on poly(3‐alkylthiophene) (P3AT)‐based block copolymers and miktoarm star‐branched polymers. The two synthetic methodologies are introduced as follows: (a) a chain‐extension method using chain‐end‐functional polymers via site transformation reaction, and (b) a linking reaction method between two polymer building blocks. The most promising method (b) can further be divided into four different approaches, (b‐1) direct addition reaction of living anionic polymers with chain‐end‐functional P3HT; (b‐2) “Click” reaction between two chain‐end‐functional polymers; (b‐3) direct coupling reaction of living anionic polymers with chain‐end‐functional P3HT; and (b‐4) ionic bond formation of chain‐end‐functional polymers. Based on the recent progresses in synthetic methodologies, versatile block copolymers and miktoarm star‐branched polymers have been successfully produced, well controlling the molecular weights (MW) and dispersities (ÐM). image