Two phosphorus-containing organosilicon compounds (PCOCs) with similar structure but different phosphorus-containing groups (phenyl phosphate group, PCOC1; phenylphosphoryl group, PCOC2) were synthesized. They were used to modify ammonium polyphosphate (APP), and the products obtained were coded as MAPP1 and MAPP2. Then MAPP1 and MAPP2 were respectively incorporated into low-density rigid polyurethane foam (LD-RPUF). The pyrolysis behavior of these two kinds of MAPP was investigated. Results showed that PCOC2, with the phenylphosphoryl group, induced the decomposition of APP, leading to early and rapid decomposition of MAPP2 with the release of NH3 in a short time and the formation of crosslinked structure quickly. Simultaneously, the phosphorus of MAPP2 was all retained in the condensed phase. In contrast, PCOC1, with the phenyl phosphate group, also induced the decomposition of APP. However, not all the phosphorus-containing groups of MAPP1 were retained in the condensed phase; some of the phosphorus was released into the gas phase in the form of PO2· and PO· free radicals. Evaluation of the flame-retardant effect by means of the cone calorimeter test demonstrated that MAPP2 had better flame-retardant properties in the LD-RPUF system, including the reduction of peak heat release rate, total heat release, and total smoke release. Moreover, the char yield of LD-RPUF/MAPP2 was more than that of LD-RPUF/MAPP1. Macro and micro photographs showed that MAPP2 can promote the LD-RPUF matrix to form an intumescent char layer with more complete and stable foam during the combustion process compared with MAPP1. Finally, a possible flame-retardant mechanism of MAPP1 and MAPP2 in LD-RPUF is proposed.
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