The Electrochemical Synthesis of Crosslinked Polycarbosilane

ABSTRACT Polysilynes, also known as crosslinked polysilanes or polycarbosilanes (PCS), are widely used to produce polymer‐derived ceramics (PDCs). A novel highly crosslinked PCS polymer was synthesized from an alternative monomer with a unique microstructure, enabling direct non‐oxide ceramic production without the need for Kumada rearrangement—an additional crosslinking step required for traditional linear polysilanes such as SMP‐10. Unlike SMP‐10 and similar polyalkylsilanes, which typically require further post‐synthetic modification to achieve the desired ceramic yield and structure, our new PCS precursor features a highly crosslinked backbone from the outset. Comprehensive characterization of this polymer was performed using UV/visible spectroscopy, gel permeation chromatography (GPC), ATR‐FTIR, 1 H‐NMR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Subsequent pyrolysis yielded a PDC, analyzed by optical microscopy, SEM, ATR‐FTIR, Raman spectroscopy, and X‐ray diffraction (XRD). The results demonstrate the successful synthesis and characterization of a novel PCS and its subsequent transformation into SiC ceramic, highlighting the potential of this PCS for enhanced ceramic yield and microstructural control.