Small change, big impact: Simply tailoring the substitution position towards significant improvement of flame retardancy

The use of conventional flame-retardant elements such as Cl, Br, P for carbon-based polymers usually leads to the deterioration of smoke and toxic gas release, and possesses serious environmental and ecological issues. Herein, we proposed a facile strategy to largely improve the flame-retardant efficiency of an eco-friendly flame-retardant method. By simply tailoring the substitution position of the functional polymerization monomer, the corresponding copolymer exhibited extremely high flame retardancy, including a 59% lower peak heat release rate (pHRR), a 48% lower smoke density, a high limiting oxygen index (LOI) of 30%, and passed the UL-94 V-0 rating without dripping. More importantly, the para-substitution copolymer showed a much higher flame-retardant efficiency than the meta-substitution copolymer, for which the monomer content needed for UL-94 V-0 rating, high LOI value, and low smoke and toxic gas release largely decreased by 25%. The detailed mechanism and the different performance between the two copolymers were comprehensively investigated. The results first confirmed the “end-group-capturing” mechanism, then revealed that the different flame-retardant efficiency was owing to the different thermal rearrangement capability of the two functional monomers. The molecular-level mechanism revealed here provided a novel thinking for designing flame-retardant polymers.