Combination effect of zinc borate in intumescent polybutylene succinate systems: Study of the carbonaceous structures using solid-state NMR

Abstract

Inspired by the concept of intumescence, this research proposed and exemplified a strategy for reinforcing the carbonaceous structures to improve the fire retardancy of intumescent polybutylene succinate (PBS). Herein, intumescent PBS formulations were fabricated by incorporating ethylenediamine phosphate (EDAP) and melamine (MEL) or melamine cyanurate (MCA) as well as zinc borate (ZnB) into PBS at a relatively low loading (10 wt%). The reaction to fire of PBS formulations were assessed by mass loss calorimeter (MLC) and the reinforcement mechanism of the condensed phase was investigated by solid-state NMR technique. Compared to PBS/EDAP&MEL(5:1,10%) and PBS/EDAP&MCA(5:1,10%), the synergistic combination of ZnB and EDAP&MEL (or EDAP&MCA) significantly reduced the peak of heat release rate (pHRR) of PBS/EDAP&MEL(5:1,8%)/ZnB(2%) and PBS/EDAP&MCA (5:1,8%)/ZnB(2%) by 61% and 53%, respectively, exhibiting high degrees of intumescence. Meanwhile, the fire growth rate index (FIGRA) were reduced by 48.8% and 39.5%, respectively, and the maximum average rate of heat emission (MARHE) decreased by 47.9% and 53.3%, respectively. Moreover, the flameout time increased by 428 s (from 507 to 935 s) and 444 s (from 509 to 954 s), respectively. Those phenomena suggested a synergistic flame retardant effect of ZnB and intumescent additives on PBS. Solid-state NMR of 11B, 13C and 31P of the top and bottom of chars after MLC test demonstrated the strengthening of the protective char by the formation of borophosphate and other phosphate glasses, limiting cracking and increasing the char cohesion.