Preventing Benzoquinone‐Based Catalyst Aggregation Enables the One‐Step Synthesis of Highly Conductive Poly(benzodifurandione) without Post‐Reaction Purification

Abstract Conductive polymers have become crucial in advancing various electronic applications. While p‐type materials like poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) are widely used and produced at scale, the development of high‐performance n‐type polymers has lagged due to challenges in synthesis and scalability. In this work, a novel method is introduced to synthesize the highly conductive n‐type polymer poly(benzodifurandione) (PBFDO) using α‐tocopherylquinone (α‐TQ) as a catalyst. This approach eliminates the need for post‐reaction dialysis, a major obstacle to large‐scale PBFDO production. By preventing catalyst aggregation, high electrical conductivity (>1320 S cm −1 ) is achieved, which remains stable in air for over 180 d, significantly simplifying the process. The α‐TQ‐synthesized PBFDO also exhibits excellent thermoelectric properties, with a power factor exceeding 100 µW m −1 K −2 , placing it among the highest‐performing n‐type thermoelectric polymers. Additionally, residual α‐TQ acts as a plasticizer, reducing the elastic modulus by over tenfold while maintaining high conductivity, making this material suitable for mechanically compliant electronics. Similarly, residual α‐TQ lowers the thermal conductivity of PBFDO by more than an order of magnitude. The process is scalable, as demonstrated by producing high‐conductivity ink in a 20 L reactor. This work presents an efficient and sustainable approach for large‐scale n‐type polymer production.