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Abstract Polyimides (PIs), known for their thermal resistance, chemical stability, and mechanical properties, are often considered challenging materials to process, resulting in limited commercial availability of PIs for melt extrusion, injection molding, and fused filament fabrication (FFF). Currently, material and knowledge gaps prevent the ability to rapidly produce parts from PIs that can be used in high strength and elevated temperature applications. To address this, a novel, fully aromatic PI with thermotropic liquid crystalline properties (LCPI) is successfully synthesized. The synthesized LCPI exhibits better solvent tolerance and thermal stability than commercially available counterparts. The LC phase is confirmed by thermal analysis, wide angle X‐ray scattering, and polarized optical microscopy. Rheological behavior clearly demonstrates that the LC phase reduces melt viscosity. These properties enable the LCPI to be processed into both drawn fibers and filaments for FFF, which is demonstrated alongside an injection molding process. The properties of the printed parts rivaled those made with Ultem 1000, exhibiting an average elastic modulus of 4.16 GPa. The injection molding process resulted in tensile moduli as high as 8.59 GPa and tensile strengths as high as 124.70 MPa. The LCPI polymer demonstrates the desired properties required for aerospace applications via melt processing techniques. 

Abstract A new class of high‐temperature dipolar polymers based on sulfonylated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SO₂‐PPO) was synthesized by post‐polymer functionalization. Owing to the efficient rotation of highly polar methylsulfonyl side groups below the glass transition temperature (T_g≈220 °C), the dipolar polarization of these SO₂‐PPOs was enhanced, and thus the dielectric constant was high. Consequently, the discharge energy density reached up to 22 J cm⁻³. Owing to its highT_g , the SO₂‐PPO₂₅sample also exhibited a low dielectric loss. For example, the dissipation factor (tan δ) was 0.003, and the discharge efficiency at 800 MV m⁻¹was 92 %. Therefore, these dipolar glass polymers are promising for high‐temperature, high‐energy‐density, and low‐loss electrical energy storage applications.