Excellent flame resistance is supposed to be taken into consideration for electronic packaging materials due to the spontaneous combustion of short circuits, except for good mechanical and dielectric properties. Herein, a hyperbranched polyborosiloxane (HPSiB) flame retardant was synthesized via a simple one‐pot transesterification as a multifunctional additive for cyanate ester (CE) resin. The HPSiB with many active terminals features good compatibility with the resin matrix, while catalyzing the curing reaction that conducts at a lower temperature. With as little as 2 wt% HPSiB incorporated, the HPSiB/bisphenol A cyanate ester (BADCy) resin achieves a UL‐94 V0 rating and 32.4% LOI value, and its peak heat release and total smoke production are simultaneously reduced. Its flexural strength and impact strength were significantly enhanced by 30.0% and 85.4%. Besides, the minimum values of dielectric constant and loss can reach 2.77 and 0.0024 at 10 GHz, which are, respectively, reduced by 7.9% and 88.5%. The integration of unique hyperbranched SiOB backbone of HPSiB with CE crosslinked network was responsible for the enhanced overall performance. This work paves a facile strategy to develop multifunctional flame retardant as a promising candidate for the high‐performance electronic packaging materials.Highlights
A novel hyperbranched polyborosiloxane flame retardant was synthesized.
HPSiB shows good compatibility and catalyzes the curing reaction of CE resin.
HPSiB/CE resin with significantly enhanced flame retardancy was obtained.
Simultaneously high toughness and low dielectric loss were achieved.
Hyperbranched structure containing SiOB chains led to the great enhancement.