Toughening of a Soft Polar Polythiophene through Copolymerization with Hard Urethane Segments

Polar polythiophenes with oligoethylene glycol side chains are exceedingly soft materials. A low glass transition temperature and low degree of crystallinity prevents their use as a bulk material. The synthesis of a copolymer comprising 1) soft polythiophene blocks with tetraethylene glycol side chains, and 2) hard urethane segments is reported. The molecular design is contrary to that of other semiconductor‐insulator copolymers, which typically combine a soft nonconjugated spacer with hard conjugated segments. Copolymerization of polar polythiophenes and urethane segments results in a ductile material that can be used as a free‐standing solid. The copolymer displays a storage modulus of 25 MPa at room temperature, elongation at break of 95%, and a reduced degree of swelling due to hydrogen bonding. Both chemical doping and electrochemical oxidation reveal that the introduction of urethane segments does not unduly reduce the hole charge‐carrier mobility and ability to take up charge. Further, stable operation is observed when the copolymer is used as the active layer of organic electrochemical transistors. A soft polythiophene with tetraethylene glycol side chains is copolymerized with hard urethane blocks. The copolymer exhibits improved ductility and stiffness, owing to a reversible network formed through hydrogen‐bonding between urethane segments, while electrical and electrochemical properties are retained to a great extent. The hydrogen‐bonded network reduces the degree of swelling of the copolymer as compared to the homopolymer.