Small change, big impact: Simply changing the substitute on Si atom towards significant improvement of flame retardancy and toughness of epoxy resins.

Enhancing simultaneously the flame retardancy and mechanical properties of polymer materials is a good expectation but always a tough challenge. In this work, two multifunctional compounds: phosphaphenanthrene/vinylsiloxane (DDVS) and phosphaphenanthrene/phenylsiloxane (DDPS) were synthesized, and both effectively improved the flame-retardant properties, toughness and UV shielding performance of epoxy resins (EPs) with high transparency. It was further found that the flame retardancy and toughness of EPs were greatly affected by simply changing the substituents from phenyl to vinyl groups on Si atom. Compared with DDPS, DDVS with vinyl group on Si showed more efficiency in improving flame retardancy (higher LOI value), self-extinguishing properties (higher UL 94 grade) and higher quality retention (more carbon residue) in EP. For example, DDVS was added in two-thirds of the amount of DDPS to make EPs achieve UL94 V-0 rating. This attributed to the high-temperature self-crosslinking of unsaturated carbon-carbon double bonds in DDVS, which can increase the charring ability of EPs and form more high-temperature stable char residues. Meantime, this also inhibited the release of volatile phosphorus-containing pieces from DDVS decomposition and retained more P in condense phase, thus improving the compactness and graphitization degree of char layers. The introduction of unsaturated bonds strengthened the condense-phase flame-retardant function of DDVS in EP, while retaining the original gas-phase flame-retardant actions of DOPO groups. The mechanism of gas-phase and condensed-phase mechanisms cooperated with each other, obtaining better flame retardant effect. Meanwhile, DDVS possessed greater efficiency than DDPS in increasing the fracture toughness of matrix due to the difference of steric hindrance between the substituents on silicon. Furthermore, the introduction of DDVS and DDPS did not significantly affect the transparency of EPs and the high visual transparency of materials was still maintained. In brief, the coordination design of phosphaphenanthrene and vinylsiloxane groups provided a theoretical basis to simultaneously improve the flame retardancy and toughening of EPs without losing glass transition temperature, while maintaining the high visual transparency of EPs with good UV shielding performance. [ABSTRACT FROM AUTHOR]