Induction‐Proximity Strategy of Aromatic Ring‐Embedded Cross‐Linked Networks to Prepare Intrinsically High Thermal Conductivity Epoxy

The low thermal conductivity (TC) of epoxy resin limits its application in thermal management. Introducing liquid crystal units into the polymer can improve the TC. The significant restriction of molecular chain mobility, in the cross‐linked system, combined with the weak π‐π interactions between liquid crystal units and the large interlayer spacing of molecular chains, leads to severe phonon scattering, making it difficult to achieve a substantial increase in TC (through‐plane TC<0.4 W m −1 K −1 ). Herein, we employed an aromatic ring induction‐proximity strategy by bonding naphthalene into the resin cross‐linked network. This approach leverages the π – π interaction between naphthalene rings and liquid crystals to reduce layer spacing between molecular chains, further enhancing TC. The introduction of naphthalene rings can also reduce phonon scattering along the molecular chains. Simultaneously, dynamic ester bonds were introduced to improve the degradability. The resulting resin exhibits high intrinsic thermal conductivity (in‐plane TC 1.05 and through‐plane TC 0.45 W m −1 K −1 ), high glass transition temperature (T g >220 °C), excellent thermal stability (T 5% = 342.7 °C), and good water degradability. Molecular dynamics simulations confirmed that naphthalene ring embedding reduces both interlayer spacing and phonon scattering. This work presents a novel strategy for developing epoxy resins with intrinsically high TC and degradability.