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Phosphorus-Containing Acrylate-Based Core−Shell Polymers:

Synthesis and Flame-Retardant Properties
Youngeun Park, Suhyeon Jo, Xuancheng Tie, Woo Geun Kim, Geon Hui Lee, Ka Yeon Ryu,*
Sang-Hyun Pyo,* and Hoyoul Kong*
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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
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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.

1. INTRODUCTION (e.g., melamine, melamine cyanurate), primarily act in the

Polymeric materials are inherently flammable, which restricts condensed phase by promoting char formation and releasing
their widespread applications in electronics, construction, and inert gases,18−20 while silicon-containing systems (e.g.,
transportation.1−5 Halogenated flame retardants, especially polyhedral oligomeric silsesquioxanes, siloxane copolymers)
brominated and chlorinated compounds, have been widely enhance thermal stability and hydrophobicity by forming
used for decades owing to their high efficiency and low cost.6−9 ceramic-like protective layers on the surface during combus-
However, they release toxic and corrosive gases upon tion.21−23 Despite these benefits, many organic systems still
combustion and persist in the environment, raising serious demand relatively high loadings and may exhibit limited long-
health and ecological concerns.10 With the tightening of global term stability.
regulations such as REACH and RoHS, the development of Among various alternatives, phosphorus-containing flame
halogen-free flame retardants (HFFRs) has become a critical retardants (P-FRs) have attracted particular attention because
research direction. of their high efficiency and versatile mechanisms.24−30
In recent years, the development of HFFRs has advanced Depending on the oxidation state and bonding environment,
significantly, encompassing inorganic, organic, and phospho- phosphorus can operate either in the gas phase by quenching
rus-based systems.11,12 Among inorganic HFFRs, magnesium free radicals (typical of low oxidation state species such as
hydroxide (MH) and aluminum hydroxide (ATH) are widely
utilized due to their ability to suppress smoke and absorb heat Received: September 1, 2025
through endothermic decomposition during combustion.13−15 Revised: December 8, 2025
However, achieving effective flame retardancy typically Accepted: December 18, 2025
requires relatively high loadings, which can significantly
compromise mechanical properties and processability.16,17
Organic HFFRs, including nitrogen-based flame retardants
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phosphinates and phosphites with P−C or P−Ph bonds) or in phinic chloride (98%), diphenyl phosphoryl chloride (99%),
the condensed phase by promoting char formation (typical of styrene (ST, ≥99%), butyl acrylate (BA, ≥99%), allyl
high oxidation state species such as phosphates with P−O−C methacrylate (AMA, 98%), methyl methacrylate (MMA,
bonds).6,32,35,36 Recent studies on unsaturated polyester resins, 99%), and sodium dodecyl sulfate (SDS, ≥98.5%). Triethyl-
epoxy systems, and vinyl ester resins have confirmed this amine (TEA, 99%), ethyl acrylate (EA), and sodium persulfate
trend:31−36 P (+1) or P−C structures mainly act in the gaseous were obtained from DAEJUNG Chemicals (Korea). Dichloro-
phase, whereas P (+5) or P−O−C structures predominantly methane (DCM, 99.5%) and potassium hydroxide (KOH
enhance condensed-phase activity. However, most of these assay, ≥95.0%) were supplied by Samchun Chemical (Korea).
investigations incorporated P-FRs directly into bulk matrix, 4-(Dimethylamino)pyridine (DMAP) was purchased from
often leading to issues of poor dispersion, leaching, and Novabiochem. Dowfax 2A1 (surfactant) was kindly provided
property imbalance. by PROCHEM Co., Ltd.
To overcome these limitations, the core−shell particle 2.2. Synthesis of Phosphorus-Containing Methacrylate
strategy has emerged as an effective approach that offers Monomers (DPMA and DPOMA)
unique advantages and multiple benefits for enhancing the
overall performance of polymeric materials. The core−shell DPMA and DPOMA were synthesized by reacting 2-HEMA
architecture improves the intrinsic properties of polymeric with diphenylphosphinic chloride and diphenyl phosphoryl
materials by preventing phase separation and structural chloride, respectively. The procedures were adapted from
distortion.61 In addition, this morphology control provides reported methods.31,34
several benefits, including enhanced dispersion stability, 2.2.1. Synthesis of DPMA (Diphenylphosphinyl
reduced additive migration, and potential multifunctionality Methacrylate). DPMA was synthesized by the reaction
in waterborne systems.62 Recent advances in core−shell between 2-HEMA and diphenylphosphinic chloride. In a
emulsion systems have demonstrated that incorporating nitrogen-purged 250 mL three-neck round-bottom flask
flame-retardant moieties into either the core or the shell can equipped with a mechanical stirrer and a dropping funnel, 2-
simultaneously enhance both flame-retardant efficiency and HEMA (5.00 g, 0.04 mol), TEA (4.28 g, 0.04 mol), and
material stability.61−64 Nevertheless, studies on phosphorus- DMAP (0.14 g, 0.001 mol) were dissolved in 30 mL of DCM.
containing methacrylate monomers with a core−shell config- The solution was cooled to 0 °C using an ice bath with
uration remain limited, and the influence of the phosphorus constant stirring. Diphenylphosphinic chloride (9.09 g, 0.04
oxidation state under such morphology-controlled conditions mol) was dissolved in 15 mL of DCM and added dropwise
has not yet been systematically investigated. Therefore, this over 1−1.5 h through the dropping funnel. After addition, the
study aims to elucidate how the oxidation state of phosphorus reaction mixture was allowed to warm to room temperature
affects the flame-retardant behavior of core−shell structured and stirred for an additional 16 h. Upon completion, the
acrylic polymers. To this end, phosphorus-based flame- mixture was sequentially washed with 1 M HCl, deionized
retardant monomers (P-FRs) were selectively introduced water, and brine. The organic layer was dried over anhydrous
into the shell region so that the flame-retardant moieties MgSO4, filtered, and concentrated under reduced pressure.
could be localized at the thermal degradation interface. The crude product was purified by silica gel column
In this work, two methacrylate monomers with distinct chromatography (eluent: hexane/ethyl acetate, 3:1) to yield
phosphorus oxidation states were designed and synthesized: DPMA as a viscous colorless liquid in 92% yield. 1H NMR
diphenylphosphinyl methacrylate (DPMA, + 1 oxidation state, (300 MHz, CDCl3): δ 7.88−7.73 (m, 4H), 7.60−7.36 (m,
P−Ph bond) and diphenylphosphoryloxy methacrylate 6H), 6.13 (dt, J = 1.6, 1.0 Hz, 1H), 5.59 (p, J = 1.6 Hz, 1H),
(DPOMA, + 5 oxidation state, P−O−C bond). These 4.47−4.34 (m, 2H), 4.34−4.21 (m, 2H), 1.94 (dd, J = 1.6, 1.0
monomers were selectively incorporated into the shell of Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 167.06, 135.87,
core−shell polymers through seeded emulsion polymerization. 132.35, 132.31, 132.06, 131.70, 131.56, 130.24, 128.69, 128.52,
The resulting particles exhibited uniform size distributions and 126.18, 77.50, 77.28, 77.08, 76.66, 63.56, 63.46, 62.59, 62.51,
well-defined morphologies. More importantly, their flame- 18.29. 31P NMR (162 MHz, CDCl3): δ 32.96, 32.79, 32.74,
retardant behaviors revealed a clear dependence on the 32.73, 32.72, 32.67, 32.57, 32.54, 32.52, 32.45, 32.43, 32.42,
oxidation state of phosphorus: DPMA favored gas-phase 32.41, 32.40, 32.39, 32.37, 32.36, 32.35, 32.34, 32.33, 32.11,
radical inhibition, whereas DPOMA promoted condensed- 29.09. FAB-MASS calcd. for C18H19O4P: m/z 331.32 ([M +
phase char formation. By correlating the oxidation state, H]+), found: m/z 331 ([M + H]+).
bonding environment, and particle morphology, this study 2.2.2. Synthesis of DPOMA (Diphenylphosphoryloxy
establishes a shell-specific localization strategy using core−shell Methacrylate). DPOMA was synthesized under conditions
phosphorus-containing microspheres as model systems to similar to those used for DPMA. In a nitrogen-purged 250 mL
investigate oxidation-state-dependent flame-retardant behavior, three-neck round-bottom flask equipped with a mechanical
thereby providing new insights and design principles for next- stirrer and a dropping funnel, 2-HEMA (5.00 g, 0.04 mol),
generation halogen-free flame-retardant acrylic coatings and TEA (4.28 g, 0.04 mol), and DMAP (0.14 g, 0.001 mol) were
adhesives. dissolved in 30 mL of DCM and stirred at 0 °C. Diphenyl
phosphoryl chloride (10.3 g, 0.04 mol) dissolved in 15 mL of
2. EXPERIMENTAL SECTION DCM was then added dropwise over 1−1.5 h under
continuous stirring. The mixture was subsequently stirred at
2.1. Materials room temperature for 16 h. The workup procedure was
All chemicals used in this study were of analytical grade and identical to that used for DPMA. The organic layer was washed
employed without further purification unless otherwise noted. successively with 1 M HCl, deionized water, and brine, then
The following reagents were purchased from Sigma-Aldrich: 2- dried over anhydrous MgSO4 and concentrated under reduced
hydroxyethyl methacrylate (2-HEMA, 97%), diphenylphos- pressure. The crude product was purified by column
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chromatography to yield DPOMA as a clear, slightly yellow using a Bruker Avance Neo 400 MHz Nanobay spectrometer
viscous liquid in 97% yield. 1H NMR (300 MHz, CDCl3): δ under identical solvent conditions. All NMR spectra were
7.39−7.28 (m, 4H), 7.25−7.13 (m, 6H), 6.11 (p, J = 1.0 Hz, collected at room temperature.
1H), 5.57 (p, J = 1.6 Hz, 1H), 4.52−4.43 (m, 2H), 4.38 (ddd, J Fourier-transform infrared (FT-IR) spectra were recorded
= 6.6, 3.6, 1.7 Hz, 2H), 1.91 (t, J = 1.3 Hz, 3H). 13C NMR (75 on a Thermo Scientific Nicolet iS5 FT-IR spectrometer in
MHz, CDCl3): δ 166.99, 150.49, 150.39, 135.66, 129.83, attenuated total reflectance (ATR) mode over the range 500−
126.43, 125.48, 125.46, 120.07, 120.00, 77.47, 77.25, 77.05, 4500 cm−1.
76.62, 66.71, 66.63, 63.06, 62.97, 18.21. 31P NMR (162 MHz, Molecular weights of the monomers were verified by high-
CDCl3): δ −11.75, −12.00, −12.04, −12.09. FAB-MASS calcd. resolution fast atom bombardment mass spectrometry (FAB-
for C18H19O6P: m/z 363.32 ([M + H]+), found: m/z 363 ([M MS) using a JEOL JMS-700 instrument.
+ H]+). The solid content (SC) and conversion yield (CY) of the
2.3. Emulsion Polymerization emulsions were determined according to a previously reported
method by Li et al.,38 using the following relationship:
Core−shell polymers were synthesized via seeded emulsion
polymerization, following a previously reported method37 with Dry solid(g )
slight modifications. All polymerizations were performed under SC(%) = × 100
Mlatex (g )
nitrogen atmosphere in a 300 mL double-jacketed glass reactor
equipped with a reflux condenser and an overhead mechanical
(SC × Mlatex ) NPF
stirrer operated at 300 rpm. The total reaction mass was 150 g, CY(%) =
and the resulting emulsion had a solid content of M mon
approximately 31%.
The reactor temperature was maintained at 85 °C under where SC is the experimentally determined solid content, Mlatex
continuous nitrogen purging. For seed formation, ST (0.36 g), is the weight of the latex, NPF is nonpolymeric solid fraction of
BA (0.36 g), SDS (0.03 g), and deionized water (51.0 g) were the sample, and Mmon is the weight of monomer charged into
charged into the reactor. Polymerization was initiated by the reactor.
adding sodium persulfate (7.7 wt % aqueous solution, 0.59 g), Particle size and polydispersity index (PDI) of the emulsions
and the reaction proceeded for 20 min. were measured with a Malvern Zetasizer Nano ZS at 25 °C.
Core formation was then carried out by continuously Samples were diluted to below 1 wt % in deionized water to
feeding a monomer emulsion containing ST (7.01 g), BA (7.01 minimize multiple scattering.
g), KOH (0.08 g), SDS (0.12 g), Dowfax 2A1 (0.11 g), Particle morphology was observed by field-emission
deionized water (21.9 g), and sodium persulfate (7.7 wt % scanning electron microscope (FE-SEM, JEOL JSM-7610F).
aqueous solution, 0.59 g) at a rate of 0.18 mL/min using a Prior to imaging, emulsions were diluted to below 0.1 wt %,
syringe pump (KD Scientific Legato 200−Infuse Only). After drop-cast onto carbon-coated glass slides, and dried at room
feeding was completed, the reaction was maintained for an temperature.
additional 30 min. TEM images were obtained using a Bio 120 kV transmission
An interlayer was subsequently introduced by feeding a electron microscope. The latex samples were diluted with
second emulsion containing EA (4.59 g), AMA (0.51 g), SDS deionized water to a concentration of 0.1 wt %, and a drop of
(0.02 g), Dowfax 2A1 (0.05 g), deionized water (5.83 g), and the diluted dispersion was placed onto a carbon-coated copper
sodium persulfate (7.7 wt % aqueous solution, 0.59 g) at a rate grid. The samples were then dried at room temperature for 24
of 0.26 mL/min. After completion of the feed, the mixture was h prior to imaging.
stirred for 15 min. Thermal stability of the polymer samples was assessed using
Finally, the shell layer was formed by feeding a third thermogravimetric analyzer (TGA, TA Instruments Q50).
emulsion consisting of BA (8.93 g), phosphorus-containing Approximately 5−8 mg of each sample was heated from 30 to
monomer (DPMA or DPOMA, 7.65 g), MMA (8.93 g), KOH 800 °C at 10 °C/min under nitrogen flow. Parameters
(0.06 g), SDS (0.10 g), Dowfax 2A1 (0.06 g), deionized water recorded included the onset decomposition temperature
(23.0 g), and sodium persulfate (11.8 wt % aqueous solution, (T5%), the maximum degradation rate temperature (Tmax),
0.62 g) at a rate of 0.26 mL/min. The reaction was continued and char yield at 700 °C (CY700). The heating program was 30
for an additional 1 h after the completion of feeding. °C → 150 °C → 30 °C → 800 °C.
Upon completion, the mixture was cooled to room Glass transition temperature (Tg) values were measured
temperature. The final emulsions were filtered through a using a Differential Scanning Calorimeter (DSC, TA Instru-
325-mesh sieve and stored in airtight containers. The resulting ments-Waters Ltd.) under nitrogen. Samples were scanned
flame-retardant emulsions were designated as PA-DPMAX and from −80 to 200 °C at 10 °C/min, and Tg values were
PA-DPOMAX, where X represents the weight percentage (30, obtained from the second heating cycle to eliminate thermal
50, 70, or 100 wt %) of the phosphorus-containing monomer history effects.
in the shell phase. A phosphorus-free reference emulsion (PA) The vertical burning test (UL-94) was performed using an
was also prepared under identical conditions, omitting the HVUL2 Horizontal Vertical Flame Chamber according to the
phosphorus-containing monomer. UL-94 standard. Test specimens were prepared with
dimensions of 125 × 13 × 2 mm3.
2.4. Characterization and Measurements Cone calorimetry tests (CCT) were carried out in
The structures of the synthesized phosphorus-containing accordance with ISO 5660 standards to evaluate combustion
monomers were confirmed using spectroscopic and mass behavior. Square specimens (100 × 100 × 3 mm3) were
spectrometric techniques. 1H and 13C NMR spectra were sequentially dried at 40 °C, 60 °C, and 80 °C over 4 days, then
recorded on a Bruker AVANCE III 300 MHz spectrometer tested under a constant external heat flux of 50 kW/m2 at
with CDCl3 as solvent, while 31P NMR spectra were obtained ambient temperature (26 °C) and relative humidity of 50%.
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Figure 1. Synthesis of core−shell structured phosphorus-containing emulsion system: (a) core composition, (b) interlayer composition, and (c)
shell composition. (d) Synthetic route of phosphorus-containing methacrylate monomers (DPMA and DPOMA) and (e) TEM image of core−
shell acrylic emulsion particles.

Finally, the microstructure of char residues obtained after displayed characteristic peaks corresponding to aromatic
CCT was examined by FE-SEM (JEOL JSM-7610F) to protons and the phosphorus environments (Figure S1). FAB-
observe surface morphology, and further analyzed by Raman MS further verified the molecular weights of the synthesized
spectroscopy (Horiba LabRAM HR800) with a 532 nm monomers. FT-IR spectra (Figure S2) showed absorption
excitation laser at room temperature. The degree of bands attributable to P�O and C�O functional groups,
graphitization in the residual char was determined from the confirming successful synthesis of the target molecules.
intensity ratio of the D band (∼1350 cm−1) to the G band 3.2. Structural Design and Polymerization Property
(∼1590 cm−1), expressed as ID/IG. Evaluation of Emulsion System
The gas-phase analysis was performed using a TG−GC/MS
As illustrated in Figure 1, the synthesized phosphorus-
system (NFEC-2021−04−270025), which combined a ther-
containing monomers were incorporated into the shell phase
mal analyzer (TG209F1, Netzsch) with a gas chromatograph−
of a core−shell structured emulsion system. The core layer
mass spectrometer (8890/5977B, Agilent). The measurements
consisted of ST and BA, chosen to provide a soft−hard
were conducted under an argon atmosphere at a heating rate of
copolymer base (Figure 1a). To enhance interfacial stability
10 °C/min over the temperature range of 30−700 °C.
between the core and shell, an interlayer was introduced
(Figure 1b). This layer, composed of AMA and EA, provided
3. RESULTS AND DISCUSSION cross-linkable sites and was subsequently coated with a shell
layer containing BA, MMA and one of the two phosphorus-
3.1. Synthesis and Structural Characterization of
containing monomers (DPMA or DPOMA) (Figure 1c). The
Phosphorus-Containing Monomers
key difference between DPMA and DPOMA lies in their
This study employed two phosphorus-containing methacrylate bonding environments: DPMA contains a P−Ph bond with an
monomers, DPMA and DPOMA, with distinct oxidation states oxidation state of +1, whereas DPOMA contains a P−O−C
to impart flame retardancy in the shell of a core−shell polymer. bond with an oxidation state of +5.
DPMA and DPOMA were synthesized by reacting 2-HEMA Table 1 summarizes the conversion yield, solid content, and
with diphenylphosphinic chloride and diphenyl phosphoryl average particle size of PA, PA-DPMA, and PA-DPOMA
chloride, respectively. The reactions were carried out under emulsions. The conversion yields ranged from 82% to 90%,
mild conditions using DCM as solvent and a TEA/DMAP showing that the incorporation of phosphorus-containing
catalyst system. Both monomers were successfully obtained in monomers had little effect on the overall polymerization
high yields of 92% and 97%, respectively, demonstrating efficiency. This indicates that the phosphorus-containing
excellent synthetic accessibility. monomers were successfully integrated into the emulsion
The chemical structures of DPMA and DPOMA were system without disrupting the shell formation process. In
confirmed by 1H, 13C, and 31P NMR spectroscopy, which addition, the solid content remained within a narrow range of
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Table 1. Conversion Yield, Solid Content, and Particle Size consistent with the DLS results, which showed narrow particle
Average of PA, PA-DPMA, and PA-DPOMA Emulsions size distributions with PDI values ranging from 0.01 to 0.05
(Figure S3), confirming the formation of uniform, mono-
Conversion Yield Solid Content Particle Size Avg
(%) (%) (nm) disperse latex particles.
PA 90 30 189.2
TEM analysis revealed that the particles with phosphorus-
PA-DPMA30 87 30 243.9
containing shell layers were larger in size than the core-only
PA-DPMA50 87 30 206.3
particles (Figure S5). The core and shell regions showed a
PA-DPMA70 82 28 167.7 gradual contrast transition from the darker center to the lighter
PA-DPMA100 84 29 244.8 periphery, confirming the formation of the shell layer, and
PA-DPOMA30 87 29 184.7 partial contact and fusion between adjacent particles were also
PA-DPOMA50 83 29 190.8 observed.37 These results demonstrate that the shell layer
PA-DPOMA70 88 30 173.6 progressively grew over the core surface during the seeded
PA- 88 30 196.4 emulsion polymerization process.
DPOMA100 In contrast, the PA-DPOMA series displayed distinct
morphological variations compared with the PA-DPMA
counterparts. At low DPOMA concentrations (30 and 50 wt
28−30%, which is close to the theoretical value of 31%, %), the particles maintained a smooth spherical morphology
confirming consistent formulation quality. (Figure 2e,f), whereas at higher concentrations (70 and 100 wt
The average particle size, determined by dynamic light %), partial particle fusion occurred and the boundaries became
scattering (DLS), is summarized in Table 1. The PA emulsion
indistinct (Figure 2g,h). This phenomenon is likely attributed
exhibited an average particle size of 189 nm. The PA-DPMA
to the structural characteristics of DPOMA, in which the P−
series showed particle sizes ranging from 168 to 245 nm,
O−C linkages impart additional flexibility to the polymer
whereas the PA-DPOMA series exhibited a narrower range of
matrix. The enhanced matrix flexibility could facilitate
174−196 nm, indicating that the particle size distribution was
affected by the type of phosphorus-containing monomer. particle−particle interactions or coalescence.42
Overall, both monomers were successfully incorporated into Furthermore, the particle size distributions of the PA-
the shell layer, confirming that the phosphorus-containing DPOMA series were slightly broader than those of the PA-
methacrylates did not interfere with polymerization and were DPMA series, with PDI values ranging from 0.03 to 0.06
compatibly integrated into the emulsion system. (Figure S3). This trend indicates a clear correlation between
the morphological changes observed by SEM and the intrinsic
3.3. Morphology of Core−Shell Particles
structural differences of the two phosphorus-containing
The morphology of the synthesized core−shell emulsions was polymer systems.
examined using SEM, and representative images are presented
3.4. Thermal Properties
in Figure 2. For all PA-DPMA samples (Figure 2a−d), the
particles exhibited a uniform spherical shape and densely The transition behavior and thermal stability of the PA, PA-
packed arrangement, independent of the phosphorus-contain- DPMA, and PA-DPOMA series were investigated using DSC,
ing monomer content. These morphological features were TGA, and derivative thermogravimetry (DTG), with results

Figure 2. SEM images of PA, PA-DPMA, and PA-DPOMA series: (a−d) PA-DPMA series containing 30, 50, 70, and 100 wt % DPMA, and (e−
h) PA-DPOMA series containing 30, 50, 70, and 100 wt % DPOMA, respectively.

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Figure 3. DSC, TGA, DTG curves, and the trends of CY700 and phosphorus content with increasing phosphorus-containing monomer content: (a,
c, e, g) PA-DPMA series, and (b, d, f, h) PA-DPOMA series.

summarized in Figure 3. These analyses highlight the effect of With increasing DPMA content, the Tg gradually increased,
the chemical environment and phosphorus content on Tg and reaching ∼28.6 °C at high concentrations. This increase is
thermal stability of the core−shell particles. attributed to the rigid aromatic P−Ph structure, which reduces
The Tg values of the emulsions were evaluated by DSC chain mobility. In contrast, the PA-DPOMA series showed a
(Figure 3a−b). All samples exhibited a single Tg despite their decreasing Tg trend as phosphorus content increased, which is
multilayer structure, indicating high compatibility and associated with the flexible P−O−C bonds that enhance chain
miscibility between the core and shell components and thus mobility and rotational freedom, thereby reducing the effective
preventing phase separation.39 The similar chemical compo- cross-link density.40−42
sition of the core and shell likely contributed to this result. The TGA and DTG results are shown in Figure 3c−f. The
Structural differences between DPMA and DPOMA, however, PA sample began to decompose at a T5% of 321.7 °C and
led to distinct Tg trends. The Tg of the PA sample was 8.2 °C. showed a Tmax at 373.4 °C, with the lowest CY700 of 1.01%
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Figure 4. CCT results of PA, PA-DPMA, and PA-DPOMA series: (a) HRR, (b) THR, (c) COP, (d) SPR, (e) TSP, and (f) CO2P.

Table 2. Key Parameters Obtained from CCT

Pk-HRR (kW/m2) tHRR (s) FGI THR (MJ/m2) TSP (m2) av-COY (kg/kg) av-CO2Y (kg/kg) av-EHC (MJ/kg)
PA 870.8 50 17.42 39.1 5.5 0.0047 2.7630 38.5
PA/DPMA-30 619.3 55 11.26 31.2 9.1 0.1692 2.0398 29.5
PA/DPMA-70 483.5 55 8.79 23.4 12.2 0.2050 1.3104 20.4
PA/DPOMA-30 694.0 40 17.35 28.6 7.71 0.1303 2.3897 34.7
PA/DPOMA-70 704.0 30 23.46 26.4 7.51 0.1870 1.9772 29.2

among all samples at 700 °C. Incorporation of phosphorus- 3.5. Flame Retardancy Performance
containing monomers decreased the thermal stability of all CCT is widely recognized as a reliable and standardized
samples, with the effect being most pronounced in the PA- method for simulating real fire scenarios and for systematically
DPOMA series. This reduction is attributed to the presence of assessing the flame-retardant performance of polymeric
easily cleavable P−O−C bonds, resulting in a marked decrease materials under controlled conditions.47 Figure 4 presents
in T5% to 250−290 °C.43−46
the heat release rate (HRR), total heat release (THR), smoke
DTG curves (Figure 3d,f) further confirmed these trends.
release rate (SPR), total smoke production (TSP), CO
The PA-DPOMA series exhibited a two-step decomposition
production (COP), and CO2 production (CO2P) for all
process corresponding to sequential cleavage of P−O−C and
samples. Detailed key parameters, including peak heat release
P−Ph bonds, whereas the PA-DPMA series displayed a single-
step degradation profile at 360−390 °C. Conversely, the CY700 rate (pk-HRR), time to pk-HRR (tHRR), fire growth index
increased with higher phosphorus content, and the effect was (FGI), defined as FGI = pk-HRR/tHRR, THR, TSP, average
most significant for the PA-DPOMA series, which achieved a CO yield (av-COY), average CO2 yield (av-CO2Y), and
maximum char yield of 13.3%. This enhanced char formation is average effective heat of combustion (av-EHC), are
attributed to the less stable P−O−C bonds that facilitate early summarized in Table 2.
decomposition, generating phosphorus-containing acids that In addition, UL-94 were performed to provide further
catalyze dehydration reactions and promote the formation of insight into the burning behavior. This combined analysis
dense char layers.31,32,35,36 highlights how the chemical structure and oxidation state of
These results are consistent with earlier studies reporting phosphorus govern the combustion characteristics of the
that P−O−C bonds promote early decomposition and polymers. For this evaluation, representative samples contain-
enhance char formation.31,32 In our case, DPOMA with ing 30 and 70 wt % phosphorus-containing monomers in the
flexible P−O−C bonds lowered the decomposition temper- shell (PA-DPMA30, PA-DPMA70, PA-DPOMA30, and PA-
ature and increased the char yield, while DPMA with rigid P− DPOMA70) were selected.
Ph bonds reduced segmental mobility, leading to a higher Tg CCT clearly demonstrated that the incorporation of
and delayed degradation. Therefore, the bonding environment phosphorus-containing monomers markedly altered the
of the phosphorus unit flexible P−O−C versus rigid P−Ph combustion profiles compared with the PA sample. The neat
critically influences both the thermal decomposition pathway PA sample exhibited the most intense combustion, with a pk-
and the segmental dynamics of the polymers. HRR of 870.8 kW/m2 and a THR of 39.1 MJ/m,2 confirming
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its high flammability and the absence of intrinsic flame- guidance for the molecular design of next-generation
retardant functionality. halogen-free polymers and their potential extension to practical
The addition of DPMA significantly suppressed heat release. coating and adhesive systems.
In particular, PA-DPMA70 exhibited the lowest pk-HRR 3.6. Analysis of Residual Char Layer Obtained after CCT
(483.5 kW/m2) and a drastically reduced THR (23.4 MJ/m2).
Figure 5 presents digital images of the residual char layers
This strong suppression was accompanied by the lowest FGI obtained after CCT. The PA sample produced almost no char,
(8.79), clearly reflecting its effectiveness in delaying flame
propagation.48 Furthermore, the av-EHC decreased to 20.4
MJ/kg, suggesting reduced combustion efficiency of volatile
components.49 However, this improvement came at the
expense of higher TSP (12.2 m2) compared with PA (5.5
m2). The increase in av-COY and decrease in av-CO2Y further
support the conclusion that DPMA promotes incomplete
combustion.50−52 These results indicate that the PA-DPMA
series primarily follows a gas-phase flame-retardant mechanism,
in which phosphorus radicals suppress flame propagation by
quenching active species, thereby reducing heat release but
simultaneously leading to enhanced smoke generation.53,54
In contrast, the PA-DPOMA series exhibited more
moderate improvements. For PA-DPOMA70, pk-HRR and
THR decreased to 704.0 kW/m2 and 26.4 MJ/m2, respectively, Figure 5. Digital photograph of residual char layer from CCT for (a)
indicating partial flame suppression. However, these values PA, (b) PA-DPMA30, (c) PA-DPMA70, (d) PA-DPOMA30, and
were still higher than those of PA-DPMA70, confirming that (e) PA-DPOMA70.
DPOMA was less effective in suppressing combustion
intensity. The TSP values for PA-DPOMA samples (7.5−7.7 whereas the phosphorus-containing samples generated increas-
m2) were higher than those of PA but lower than those of the ing amounts of char as the phosphorus content increased.
PA-DPMA series, suggesting milder incomplete combustion. Notably, PA-DPOMA70 formed a substantial char that was
Interestingly, the FGI increased to 23.46 for PA-DPOMA70, clearly visible to the naked eye. These results are consistent
implying that flame spread was not effectively suppressed at with the trend of CY 700 observed in TGA, further
higher DPOMA loadings. This behavior can be attributed to demonstrating the superior catalytic carbonization activity of
the structural characteristics of DPOMA, where flexible P−O− DPOMA.
C bonds enhance char formation but provide limited radical- SEM analysis (Figure 6) revealed distinct morphological
scavenging capacity compared to the P−Ph bonds of DPMA. differences. The residual char of PA showed numerous pores
The UL-94 results (Figure S4) further supported these and cracks, which provide pathways for heat and volatile
findings. All samples received a No Rating, but distinct products to escape during combustion, thereby failing to
differences were evident. The PA control separated from the protect the underlying polymer. In contrast, phosphorus-
substrate within 60 s after ignition, precluding further containing samples exhibited denser and more uniform
evaluation. In contrast, PA-DPMA70 self-extinguished within surfaces, with PA-DPOMA70 in particular forming the most
60 s without dripping, demonstrating improved flame compact and rigid residual char layer. This indicates that the
inhibition and self-extinguishing properties at high phosphorus incorporation of phosphorus-containing monomers, especially
content. On the other hand, PA-DPOMA70 continued DPOMA, significantly improves the barrier properties of the
burning beyond 180 s and exhibited dripping, consistent residual char.
with the limited flame-retardant efficiency observed in CCT. Raman spectroscopy was further employed to characterize
Overall, CCT and UL-94 results provide strong evidence the graphitization degree of the residual char layer.55 Two
that DPMA introduces an efficient gas-phase flame-retardant characteristic peaks were observed at ∼1350 cm−1 (D band)
mechanism, characterized by significant suppression of heat and ∼1580 cm−1 (G band).56 The intensity ratio (ID/IG) was
release, delayed flame propagation, and improved self- used as an indicator of graphitization, with lower values
extinguishing performance, albeit accompanied by increased corresponding to more ordered and higher-quality carbon
smoke generation. In contrast, DPOMA contributed to structures.57,58 A high-quality residual char layer functions as
condensed-phase activity, yielding moderate reductions in an effective physical barrier that delays the release of flammable
heat release and some improvement in char stability, but volatiles and reduces oxygen and heat transfer.59,60 Compared
without achieving effective suppression of flame spread. This with PA, all phosphorus-containing samples exhibited lower
clear difference demonstrates that the bonding environment of ID/IG values. Among them, PA-DPOMA70 displayed the
phosphorus P−Ph versus P−O−C determines whether flame lowest ratio of 1.56, confirming the formation of the most
retardancy proceeds predominantly through gas-phase radical graphitized residual char layer.
quenching (DPMA) or condensed-phase char promotion Overall, these results collectively demonstrate that the
(DPOMA). incorporation of DPOMA not only increases the amount of
Although none of the samples achieved the UL-94 V-0 residual char layer but also enhances its quality by producing a
rating, this small-scale test may not fully represent real-fire denser and more graphitized structure. This evidence suggests
conditions. Nevertheless, the cone-calorimetry results clearly that DPOMA-based flame-retardant systems rely predom-
demonstrate that the incorporation of phosphorus markedly inantly on condensed-phase mechanisms, where char for-
improves flame retardancy and elucidates the oxidation-state- mation and structural reinforcement play a key role in
dependent mechanisms. These findings provide valuable improving flame retardancy.
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Figure 6. SEM image and Raman spectra of residual char layer from CCT for (a) PA, (b) PA-DPMA30, (c) PA-DPMA70, (d) PA-DPOMA30,
and (e) PA-DPOMA70.

Figure 7. (a) Comparison of flame-retardant mechanisms for PA-DPMA70 and PA-DPOMA70 based on CCT data and postcombustion analysis.
The radar chart summarizes key fire performance parameters. (b) Proposed flame-retardant mechanism.

3.7. Flame-Retardant Mechanism Analysis corresponding ion fragments with their m/z values are
To further verify the gas-phase flame-retardant behavior, TG− summarized in Table S1.
GC/MS analysis was conducted to identify the volatile For the phosphorus-free PA, the detected fragments
degradation products of the PA, PA-DPMA, and PA- indicated simple depolymerization of the acrylic backbone. In
DPOMA series. The TG−DTG curves are shown in Figure the PA-DPOMA series, a small amount of POx· species was
S6, while representative GC/MS spectra obtained at 350 and detected, while methyl methacrylate (MMA) appeared as the
400 °C (near Tmax) are presented in Figure S7. The dominant volatile product. In contrast, the PA-DPMA series
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exhibited strong peaks at m/z = 51.1, 77.1, and 231.1, strong suppression of combustion, with PA-DPMA70 reducing
corresponding to methyl diphenylphosphinate species derived pk-HRR by 44% (from 870.8 to 483.5 kW/m2) and THR by
from the DPMA structure. Additionally, signals at m/z = 63, 40% (to 23.4 MJ/m2). In contrast, the DPOMA-based
65, and 79 were observed, which correspond to PO2·, H2PO2·, polymers underwent two-step decomposition with reduced
and PO3· radicals, respectively, confirming that the decom- Tg but produced a dense residual char (13.3%) and highly
position products of the P−Ph structure are mainly distributed graphitized carbon structure (ID/IG = 1.56), indicative of a
in the gas phase. Therefore, compared with DPOMA (+5 condensed-phase barrier effect. These results clearly demon-
oxidation state), DPMA (+1 oxidation state) exhibits a more strate that the oxidation state and bonding characteristics of
pronounced gas-phase flame-retardant mechanism. phosphorus play a pivotal role in determining the dominant
Figure 7 summarizes the numerical results and the proposed flame-retardant mechanism, whether through gas-phase radical
flame-retardant mechanisms of the PA-DPMA and PA- inhibition (DPMA) or condensed-phase carbonization
DPOMA series. Incorporating phosphorus-containing mono- (DPOMA).
mers with different oxidation states (DPMA and DPOMA) Therefore, the present work establishes shell-specific
into the shell of a core−shell structure led to fundamentally functionalization as an effective strategy for tailoring flame-
distinct flame-retardant behaviors, depending on the chemical retardant behavior and provides useful guidance for the design
bonding and oxidation environment of the phosphorus. of next-generation halogen-free flame-retardant polymers with
For the PA-DPMA series (P−Ph, +1 oxidation state), a tunable performance for advanced applications.
dominant gas-phase flame-retardant mechanism was observed.
This was supported by significant reductions in pk-HRR, av-
EHC, and FGI (Figure 4, Table 2), along with rapid self-
■ ASSOCIATED CONTENT
* Supporting Information
sı
extinguishing behavior in the UL-94 vertical burning test The Supporting Information is available free of charge at
(Figure S4). The enhanced performance can be attributed to [Link]
the generation of phosphorus-containing radicals during 1
combustion. These radicals effectively quench highly reactive H, 13C, and 31P NMR spectra and FT-IR analysis of the
flame-propagating species such as H· and OH· in the gas phase, phosphorus-containing acrylate monomers; particle size
thereby suppressing combustion and improving flame inhib- distribution and PDI of the core−shell polymers; UL-94
ition.50,51 digital images; TEM images of the synthesized particles;
In contrast, the PA-DPOMA series (P−O−C, +5 oxidation TG−GC/MS thermolysis profiles; GC/MS spectra and
state) exhibited different characteristics. Sustained combustion analysis of core−shell polymers (PDF)
was observed in UL-94, and performance in the CCT was
lower compared with DPMA. However, the early decom-
position of the P−O−C bonds promoted the formation of a
■ AUTHOR INFORMATION
Corresponding Authors
dense residual char layer, as indicated by the lower ID/IG values Ka Yeon Ryu − Department of Chemistry and Research
in SEM and Raman analysis (Figures 5−6). This char acted as Institute of Nature Science, Gyeongsang National University,
a more effective physical barrier, reducing heat and oxygen Jinju 52828, Republic of Korea; Research Institute of
transfer and thereby protecting the polymer matrix.52−54 Molecular Alchemy, Gyeongsang National University, Jinju
In summary, DPMA primarily exerts its flame-retardant 52828, Republic of Korea; Email: ryuky@[Link]
effect through a gas-phase radical quenching mechanism, Sang-Hyun Pyo − Division of Biotechnology & Applied
whereas DPOMA acts predominantly via a condensed-phase Microbiology, Department of Process & Life Science
barrier mechanism by promoting char formation and structural Engineering, Faculty of Engineering, Lund University, Lund
reinforcement. This comparison underscores the importance of 22100, Sweden; [Link]/0000-0002-5037-2748;
the phosphorus bonding environment rigid P−Ph versus Email: [Link]@[Link]
flexible P−O−C in determining whether flame retardancy is Hoyoul Kong − Department of Chemistry and Research
governed mainly by gas-phase or condensed-phase pathways. Institute of Nature Science, Gyeongsang National University,
Such mechanistic insights highlight the advantage of Jinju 52828, Republic of Korea; Research Institute of
strategically selecting and incorporating phosphorus structures Molecular Alchemy, Gyeongsang National University, Jinju
tailored to the desired flame-retardant criteria. 52828, Republic of Korea; [Link]/0009-0006-4057-
5273; Email: hoyoulkong@[Link]
4. CONCLUSION
Two phosphorus-containing methacrylate monomers with Authors
different oxidation states, DPMA (+1, P−Ph) and DPOMA Youngeun Park − Department of Chemistry and Research
(+5, P−O−C), were synthesized and selectively incorporated Institute of Nature Science, Gyeongsang National University,
into the shell of core−shell polymers through seeded emulsion Jinju 52828, Republic of Korea
polymerization. In addition to previous studies that incorpo- Suhyeon Jo − Department of Chemistry and Research Institute
rated phosphorus acrylates into bulk polymers or introduced of Nature Science, Gyeongsang National University, Jinju
single flame-retardant monomers into core−shell systems, this 52828, Republic of Korea
study demonstrates for the first time the shell-specific Xuancheng Tie − Division of Biotechnology & Applied
incorporation of two acrylate monomers with distinct Microbiology, Department of Process & Life Science
oxidation states, allowing direct comparison of their flame- Engineering, Faculty of Engineering, Lund University, Lund
retardant mechanisms. 22100, Sweden
Comprehensive analyses confirmed both structural integra- Woo Geun Kim − Basic Materials Laboratory, Miwon
tion and mechanistic divergence. The DPMA-based polymers Specialty Chemicals Co. Ltd, Yongin-Si, Gyeonggi-Do 16864,
showed a single-step decomposition with an increased Tg and Republic of Korea
J [Link]
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ACS Omega [Link] Article

Geon Hui Lee − Basic Materials Laboratory, Miwon Specialty (13) Sain, M.; Park, S. H.; Suhara, F.; Law, S. Flame retardant and
Chemicals Co. Ltd, Yongin-Si, Gyeonggi-Do 16864, Republic mechanical properties of natural fibre−PP composites containing
of Korea magnesium hydroxide. Polym. Degrad. Stab. 2004, 83 (2), 363−367.
(14) Chen, Q.; Xu, S.; Li, R.; Sun, B.; Fang, H.; Zhang, Q. Synthesis
Complete contact information is available at: of highly dispersed magnesium hydroxide and its application in flame-
[Link] retardant EVA composites. RSC Adv. 2025, 15 (16), 12854−12865.
(15) Doanh, T. C.; Thi, N. H.; Nguyen, H. T.; Oanh, H. T.; Doan,
Notes T. D.; Tuyen, N. D.; Vu, M.-T.; Hoang, M. H. Preparation and
synergistic effect of aluminum hydroxide nanoplates on the fire
The authors declare no competing financial interest. resistance and thermal stability of the intumescent flame retardant

■ ACKNOWLEDGMENTS
This work was supported by the Technology Innovation
epoxy composite. RSC Adv. 2025, 15 (21), 16814−16825.
(16) Zhang, H.; Wang, H.; Wang, H. Flame retardant mechanism
and surface modification of magnesium hydroxide flame retardant.
IOP Conf. Ser.: Earth Environ. Sci. 2018, 170, 032028.
Program (or Industrial Strategic Technology Development (17) Ai, L.; Chen, S.; Zeng, J.; Yang, L.; Liu, P. Synergistic Flame
Program) (Project No. 20021909), funded by the Ministry of Retardant Effect of an Intumescent Flame Retardant Containing
Trade, Industry & Energy (MOTIE, Korea). This research was Boron and Magnesium Hydroxide. ACS Omega 2019, 4 (2), 3314−
also supported by the National Research Foundation of Korea 3321.
(NRF) grant funded by the Ministry of Education (Project No. (18) Maroufi, P.; Najafi Moghadam, P.; Vahabi, H. New nitrogen-
RS-2023-00301974). This work was supported by the rich flame retardant based on conductive poly(aniline-co-melamine).
React. Funct. Polym. 2020, 150, 104548.
Research Resurgence under the Glocal University 30 Project (19) Chu, Y.; Chen, Z.; Yu, Y.; Chen, T.; Chen, Z.; Zhang, Q.; Li,
at Gyeongsang National University in 2025. C.; Yang, H.; Jiang, J. Synthesis of a novel phosphorus-containing

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L [Link]
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ACS Omega [Link] Article

Retardant Silicone−Acrylic Emulsion Adhesive for Electrostatic

Flocking. J. Inorg. Organomet. Polym. Mater. 2020, 30 (11), 4342−
4349.

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