Synthesis of Bottlebrush Polymers with Spontaneous Self-Assembly for Dielectric Generators

Cross-linked bottlebrush polymers received significant attention as dielectrics in transducers due to their unique softness and strain stiffening caused by their structure. Despite some progress, there is still a great challenge in increasing their dielectric permittivity beyond 3.5 and cross-linking them to defect-free ultrathin films efficiently under ambient conditions. Here, we report the synthesis of bottlebrush copolymers based on ring-opening metathesis polymerization (ROMP) starting from a 5-norbornene-2-carbonitrile and a norbornene modified with a poly­(dimethylsiloxane) (PDMS) chain as a macromonomer. The resulting copolymer was subjected to a postpolymerization modification, whereby the double bonds were used both for functionalization with thiopropionitrile and subsequent cross-linking via a thiol–ene reaction. The solutions of both bottlebrush copolymers formed free-standing elastic films by simple casting. DMA and broadband impedance spectroscopy revealed two glass transition temperatures uncommon for a random copolymer. The self-segregation of the nonpolar PDMS chains and the polynorbornane backbone is responsible for this and is supported by the interfacial polarization observed in broadband impedance spectroscopy and the scattering peaks observed in small-angle X-ray scattering (SAXS). Additionally, the modified bottlebrush copolymer was cross-linked to an elastomer that exhibits increased dielectric permittivity and good mechanical properties with significant strain stiffening, an attractive property of dielectric elastomer generators. It has a relative permittivity of 5.24, strain at break of 290%, elastic modulus at 10% strain of 380 kPa, a breakdown field of 62 V μm–1, and a small actuation of 5% at high electric fields of 48.5 V μm–1. All of these characteristics are attractive for dielectric elastomer generator applications. The current work is a milestone in designing functional elastomers based on bottlebrush polymers for transducer applications.