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The pyrolysis and flame retardancy of a bisphenol A polycarbonate/silicon rubber/bisphenol A bis(diphenyl phosphate) (PC/SiR/BDP) blend were investigated and compared to those of PC/BDP and PC/SiR. The impact modifier SiR consists mainly of poly(dimethylsiloxane) (PDMS > 80 wt %). The pyrolysis of PC/SiR/BDP was studied by thermogravimetry (TG), TG–FTIR to analyze the evolved gases, and a Linkam hot stage cell within FTIR as well as 29Si NMR and 31P NMR to analyze the solid residue. The fire performance was determined by PCFC, LOI, UL 94, and a cone calorimeter under different external irradiations. The fire residues were studied by using ATR-FTIR as well as the additional binary systems PC + PDMS, PC + BDP, and BDP + PDMS, focusing on the specific chemical interactions. The decomposition pathways are revealed, focusing on the competing interaction between the components. Fire retardancy in PC/SiR/BDP is caused by both flame inhibition in the gas phase and inorganic-carbonaceous residue formation in the condensed phase. The PC/SiR/BDP does not work as well superimposing the PC/SiR and PC/BDP performances. PDMS reacts with PC and BDP, decreasing BDP's mode of action. Nevertheless, the flammability (LOI > 37%, UL 94 V-0) of PC/SiR/BDP equals the high level of PC/BDP. Indeed, SiR in PC/SiR/BDP is underlined as a promising impact modifier in flame-retarded PC/impact modifier blends as an alternative to highly flammable impact modifiers such as acrylonitrile–butadiene–styrene (ABS), taking into account that the chosen SiR leads to PC blends with a similar mechanical performance.
The pyrolysis of polycarbonate (PC) and PC/acrylonitrile-butadiene-styrene (PC/ABS) with and without arylphosphates (triphenylphosphate TPP, resorcinol-bis(diphenyl phosphate) RDP and bisphenol A bis(diphenyl phosphate) BDP) is investigated by thermal analysis as key to understanding the flame retardancy mechanisms and corresponding structure-property relationships. The correspondence between the decomposition temperature range of arylphosphates and PC is pointed out as prerequisite for the occurrence of the reaction between arylphosphate and structures that are typical for the beginning of PC decomposition. Resulting cross-linking enhances charring in the condensed phase and competes with the alternative release of phosphate in the gas phase and thus flame inhibition. Flame inhibition was identified as the main flame retardancy mechanism. The additional condensed phase mechanisms optimise the performance.