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 Td5 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.
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