Phosphorus-Containing Acrylate-Based Core–Shell Polymers: Synthesis and Flame-Retardant Properties
Park, Youngeun ; Jo, Suhyeon ; Tie, Xuancheng ; Kim, Woo Geun ; Lee, Geon Hui ; Ryu, Ka Yeon ; Pyo, Sang-Hyun LU
and Kong, Hoyoul
(2026)
In ACS Omega
11(2).
p.2917-2929
- Abstract
- To address the flammability issues limiting polymer applications, phosphorus-containing flame retardants have received increasing attention as halogen-free alternatives. In this study, two phosphorus-containing methacrylate monomers, diphenylphosphinyl methacrylate (DPMA, +1 oxidation state, P–Ph bond) and diphenylphosphoryloxy methacrylate (DPOMA, +5 oxidation state, P–O–C bond), were synthesized and selectively incorporated into the shell of core–shell polymers via seeded emulsion polymerization. The resulting particles were uniform, spherical, and low polydispersity (PDI < 0.07). The flame-retardant behavior was strongly affected by the oxidation state of phosphorus. When 70 wt % of each monomer was placed in the shell, PA-DPMA70... (More)
- To address the flammability issues limiting polymer applications, phosphorus-containing flame retardants have received increasing attention as halogen-free alternatives. In this study, two phosphorus-containing methacrylate monomers, diphenylphosphinyl methacrylate (DPMA, +1 oxidation state, P–Ph bond) and diphenylphosphoryloxy methacrylate (DPOMA, +5 oxidation state, P–O–C bond), were synthesized and selectively incorporated into the shell of core–shell polymers via seeded emulsion polymerization. The resulting particles were uniform, spherical, and low polydispersity (PDI < 0.07). The flame-retardant behavior was strongly affected by the oxidation state of phosphorus. When 70 wt % of each monomer was placed in the shell, PA-DPMA70 reduced the peak heat release rate (pk-HRR) by 44% and showed a significant decrease in the fire growth index (FGI) and average effective heat of combustion (av-EHC), indicating a dominant gas-phase inhibition. In contrast, PA-DPOMA70 reduced the pk-HRR by 19% but greatly increased the residual char yield, producing a dense and highly graphitized structure with an ID/IG ratio of 1.56, which is characteristic of condensed-phase protection. These findings clearly demonstrate that the oxidation state of phosphorus determines whether gas-phase radical quenching or condensed-phase char formation governs the flame-retardant mechanism. In addition to earlier reports on incorporating phosphorus methacrylates into bulk matrices or silicone–acrylic adhesives, this work establishes a shell-specific localization strategy that clarifies the oxidation state mechanism relationship and offers guidance for the rational design of next-generation halogen-free flame-retardant polymers. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/6ee6ef0d-a44e-4f3d-9316-40fa8a89bdc0
- author
- Park, Youngeun
; Jo, Suhyeon
; Tie, Xuancheng
; Kim, Woo Geun
; Lee, Geon Hui
; Ryu, Ka Yeon
; Pyo, Sang-Hyun
LU
and Kong, Hoyoul
- organization
- publishing date
- 2026-01-20
- type
- Contribution to journal
- publication status
- published
- subject
- in
- ACS Omega
- volume
- 11
- issue
- 2
- pages
- 2917 - 2929
- publisher
- The American Chemical Society (ACS)
- ISSN
- 2470-1343
- DOI
- 10.1021/acsomega.5c09027
- language
- English
- LU publication?
- yes
- id
- 6ee6ef0d-a44e-4f3d-9316-40fa8a89bdc0
- date added to LUP
- 2026-01-03 15:49:06
- date last changed
- 2026-01-30 08:51:12
@article{6ee6ef0d-a44e-4f3d-9316-40fa8a89bdc0,
abstract = {{To address the flammability issues limiting polymer applications, phosphorus-containing flame retardants have received increasing attention as halogen-free alternatives. In this study, two phosphorus-containing methacrylate monomers, diphenylphosphinyl methacrylate (DPMA, +1 oxidation state, P–Ph bond) and diphenylphosphoryloxy methacrylate (DPOMA, +5 oxidation state, P–O–C bond), were synthesized and selectively incorporated into the shell of core–shell polymers via seeded emulsion polymerization. The resulting particles were uniform, spherical, and low polydispersity (PDI < 0.07). The flame-retardant behavior was strongly affected by the oxidation state of phosphorus. When 70 wt % of each monomer was placed in the shell, PA-DPMA70 reduced the peak heat release rate (pk-HRR) by 44% and showed a significant decrease in the fire growth index (FGI) and average effective heat of combustion (av-EHC), indicating a dominant gas-phase inhibition. In contrast, PA-DPOMA70 reduced the pk-HRR by 19% but greatly increased the residual char yield, producing a dense and highly graphitized structure with an <i>I</i><sub>D</sub>/<i>I</i><sub>G</sub> ratio of 1.56, which is characteristic of condensed-phase protection. These findings clearly demonstrate that the oxidation state of phosphorus determines whether gas-phase radical quenching or condensed-phase char formation governs the flame-retardant mechanism. In addition to earlier reports on incorporating phosphorus methacrylates into bulk matrices or silicone–acrylic adhesives, this work establishes a shell-specific localization strategy that clarifies the oxidation state mechanism relationship and offers guidance for the rational design of next-generation halogen-free flame-retardant polymers.}},
author = {{Park, Youngeun and Jo, Suhyeon and Tie, Xuancheng and Kim, Woo Geun and Lee, Geon Hui and Ryu, Ka Yeon and Pyo, Sang-Hyun and Kong, Hoyoul}},
issn = {{2470-1343}},
language = {{eng}},
month = {{01}},
number = {{2}},
pages = {{2917--2929}},
publisher = {{The American Chemical Society (ACS)}},
series = {{ACS Omega}},
title = {{Phosphorus-Containing Acrylate-Based Core–Shell Polymers: Synthesis and Flame-Retardant Properties}},
url = {{http://dx.doi.org/10.1021/acsomega.5c09027}},
doi = {{10.1021/acsomega.5c09027}},
volume = {{11}},
year = {{2026}},
}