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<p>Reactive flame-retardant polymer resins have emerged as a robust alternative to conventional additive-type systems, providing enhanced resistance to migration and improved compatibility within the polymer matrix. While the role of phosphorus oxidation states has been previously explored in core–shell particulate systems, the influence of oxidation state and substituent architecture within linear acrylic resins requires further investigation. This study focuses on the effects of phosphorus oxidation states and, more importantly, the structural differences between aliphatic and aromatic substituents in determining the fire performance of a series of phosphorus-containing linear acrylic resins. Three distinct phosphorus-based methacrylate monomers, <b>DPMA</b> (+ 1 oxidation state), <b>DPOMA</b> (+ 5 oxidation state, aromatic), and <b>DEPMA</b> (+ 5 oxidation state, aliphatic), were synthesized and incorporated into acrylic backbones via free-radical solution polymerization. The results demonstrate that at the same + 5 oxidation state, the substituent type plays a decisive role in determining condensed-phase efficiency. Specifically, the aliphatic system (<b>PR-DEPMA</b>) exhibited significantly enhanced charring capability compared to its aromatic counterpart (<b>PR-DPOMA</b>). At a 50 wt% loading, <b>PR-DEPMA-50</b> achieved a remarkable 66% reduction in the maximum average rate of heat emission (MARHE). This enhanced performance is attributed to the synergistic effect of higher phosphorus atom density and the increased structural flexibility of the aliphatic chains. Unlike the rigid aromatic groups, the flexible aliphatic segments facilitate the effective rearrangement and reaction of phosphorus moieties, triggering timely dehydration and cross-linking during the early stages of decomposition. These findings establish a clear structure–property relationship in linear acrylic resins, highlighting that tailoring the substituent environment in the + 5 oxidation state is a key strategy for maximizing condensed-phase flame-retardant efficiency.</p> Graphical abstrcat <p></p>

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Synthesis and flame retardancy of phosphorus-containing acrylic resins: influence of oxidation state and substituent flexibility on condensed-phase efficiency

  • 期刊论文

  • 发表日期：

    2026年7月14日

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  • Suhyeon Jo,
  • Jimin Yun,
  • Changwoo Lee,
  • Kyungbeom Kim,
  • Minhyuck Seo,
  • Jong-Min Kim,
  • Nam-Suk Lee,
  • Ka Yeon Ryu,
  • Se Hyun Kim,
  • Hoyoul Kong

摘要

Reactive flame-retardant polymer resins have emerged as a robust alternative to conventional additive-type systems, providing enhanced resistance to migration and improved compatibility within the polymer matrix. While the role of phosphorus oxidation states has been previously explored in core–shell particulate systems, the influence of oxidation state and substituent architecture within linear acrylic resins requires further investigation. This study focuses on the effects of phosphorus oxidation states and, more importantly, the structural differences between aliphatic and aromatic substituents in determining the fire performance of a series of phosphorus-containing linear acrylic resins. Three distinct phosphorus-based methacrylate monomers, DPMA (+ 1 oxidation state), DPOMA (+ 5 oxidation state, aromatic), and DEPMA (+ 5 oxidation state, aliphatic), were synthesized and incorporated into acrylic backbones via free-radical solution polymerization. The results demonstrate that at the same + 5 oxidation state, the substituent type plays a decisive role in determining condensed-phase efficiency. Specifically, the aliphatic system (PR-DEPMA) exhibited significantly enhanced charring capability compared to its aromatic counterpart (PR-DPOMA). At a 50 wt% loading, PR-DEPMA-50 achieved a remarkable 66% reduction in the maximum average rate of heat emission (MARHE). This enhanced performance is attributed to the synergistic effect of higher phosphorus atom density and the increased structural flexibility of the aliphatic chains. Unlike the rigid aromatic groups, the flexible aliphatic segments facilitate the effective rearrangement and reaction of phosphorus moieties, triggering timely dehydration and cross-linking during the early stages of decomposition. These findings establish a clear structure–property relationship in linear acrylic resins, highlighting that tailoring the substituent environment in the + 5 oxidation state is a key strategy for maximizing condensed-phase flame-retardant efficiency.

Graphical abstrcat