The Effect of a Polymeric Flame Retardant Containing Phosphorus–Sulfur–Silicon and a Caged Group on Unsaturated Polyester Resin

Currently, the issue of natural flammability of unsaturated polyester resin (UPR) severely restrains its application. In this study, polymeric flame retardant poly methyl vinyl di (1-thio-2,6,7-trioxal-1-phosphabicyclo [2.2] octane-4-methoxy) silane (PMVDOS) with P–S–Si-based cage unit was synthesized. The UPR/PMVDOS composites were prepared by adding different ratios of PMVDOS into UPR. The flame-retardant properties and the char layer structure of UPR samples were evaluated via the limiting oxygen index (LOI), vertical burning test, cone calorimeter test, scanning electron microscopy, laser Raman spectroscopy, and X-ray photoelectron spectroscopy. The results showed that UPR/PMVDOS composites reached the UL-94 V-0 rating with the LOI value of 27.8%, and the carbon residue increased from 4.9% for pure UPR to 14.9% when the content of PMVDOS was 18 wt%. The peaks of heat release rate, total heat release, and total smoke production were comparatively reduced. The flame-retardant mechanism of PMVDOS mainly acted on the condensed phase. The surface of the matrix was covered with the polymer containing phosphorous and silicon dioxide particles, preventing the escape of flammable volatiles and isolating the exchange of oxygen and heat, thus, the degradation of the matrix could be inhibited. This research provides a solution to improve the flame retardancy of UPR.