As a component of printed circuit substrate, copper clad laminate (CCL) needs to meet the performance requirements of heat resistance, flame retardancy, and low coefficient of thermal expansion (CTE), which, respectively, affects the stability, safety, and processability of terminal electronic products. In this paper, benzocyclobutylene (BCB)-functionalized phosphorus−oxygen flame retardant composites were prepared through introducing the BCB groups, and the performance was researched by thermogravimetric analysis, microcombustion calorimetry, and thermomechanical analysis. The research results show that these phosphorus oxide compounds containing BCB groups show good thermal stability and low total heat release (THR) after thermal curing, and the more BCB groups on the phosphorus oxide monomers, the better the thermal stability and flame retardancy of cured resins. The T d5 and THR of the composite (M3) are as high as 443 °C and 23.1 kJ/g, respectively. In addition, the CTE of M3 is as low as 16.71 ppm/°C. Introduction of BCB groups which can be crosslinked through heat to improve the thermal stability, flame retardancy, and reduced CTE of traditional organophosphorus flame retardant materials. These materials are expected to be good candidates for CCL substrates for electronic circuits.

Based on the excellent physical properties and flexible molecular modifiability, modified silicone resins have received favorable attention in the field of microelectronics, and recently a number of modified silicone resins have appeared while few breakthroughs have been made in low dielectric constant (low-k) materials field due to the limitations of structure or the curing process. In this work, functional silicone resin with different BCB contents was prepared with two monomers. The resins showed low dielectric constant (k = 2.77 at 10 MHz) and thermal stability (T5% = 495.0 °C) after curing. Significant performance changes were observed with the increase in BCB structural units, and the functional silicone obtained does not require melting and dissolution during processing because of good fluidity at room temperature. Moreover, the mechanical properties of silicone resins can be also controlled by adjusting the BCB content. The obtained silicone resins could be potentially used in the field of electronic packaging materials.