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In the present study, polystyrene (PS) is chemically modified with diethyl(acryloyloxymethyl)phosphonate (DEAMP) and an N‐containing monomer, selected from different classes of compounds, via a ter‐polymerization route; thus, exploring possible P–N synergistic effects on fire retardance of the base polymer. The successful incorporation of P and N monomeric units is confirmed by Fourier Transform Infrared (FT‐IR), 1H and 31P Nuclear Magnetic Resonance (NMR) spectroscopies. The thermal degradation and combustion attributes of modified polymeric materials are measured using standard techniques, including Thermo‐Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), "bomb" calorimetry, and Pyrolysis Combustion Flow Calorimetry (PCFC). The thermal and combustion studies demonstrate that the thermal stability and combustion characteristics of styrenic polymers are significantly altered by the presence of even nominal amounts of P‐ and N‐containing groups, and in certain cases, synergistic interactions of these groups are also evident. For instance, as revealed by TGA, the extent of char formation, under the oxidative atmosphere, in the prepared ter‐polymers, is enhanced by 16–44%, when compared to the unmodified PS. The heat release rates and heat release capacities of ter‐polymers, measured using the PCFC technique, are reduced by 18–50%, in comparison to the same parameters obtained for the unmodified counterpart. [ABSTRACT FROM AUTHOR]

Polystyrene (PS) was modified by covalently binding P-, P-N- and/or N- containing fire-retardant moieties through co- or ter-polymerization reactions of styrene with diethyl(acryloyloxymethyl)phosphonate (DEAMP), diethyl-p-vinylbenzyl phosphonate (DEpVBP), acrylic acid-2-[(diethoxyphosphoryl)methylamino]ethyl ester (ADEPMAE) and maleimide (MI). In the present study, the condensed-phase and the gaseous-phase activities of the abovementioned fire retardants within the prepared co- and ter-polymers were evaluated for the first time. Pyrolysis–Gas Chromatography/Mass Spectrometry was employed to identify the volatile products formed during the thermal decomposition of the modified polymers. Benzaldehyde, α-methylstyrene, acetophenone, triethyl phosphate and styrene (monomer, dimer and trimer) were detected in the gaseous phase following the thermal cracking of fire-retardant groups and through main chain scissions. In the case of PS modified with ADEPMAE, the evolution of pyrolysis gases was suppressed by possible inhibitory actions of triethyl phosphate in the gaseous phase. The reactive modification of PS by simultaneously incorporating P- (DEAMP or DEpVBP) and N- (MI) monomeric units, in the chains of ter-polymers, resulted in a predominantly condensed-phase mode of action owing to synergistic P and N interactions. The solid-state 31P NMR spectroscopy, Scanning Electron Microscopy/Energy Dispersive Spectroscopy, Inductively-Coupled Plasma/Optical Emission Spectroscopy and X-ray Photoelectron Spectroscopy of char residues, obtained from ter-polymers, confirmed the retention of the phosphorus species in their structures. [ABSTRACT FROM AUTHOR]

The aspects of fire retardation in some phosphorus-modified polymethyl methacrylate (PMMA) and polystyrene (PSt) polymers are reported in the present paper. Both additive and reactive strategies were employed to obtain the desired level of loading of the phosphorus-bearing compound/moiety (2 wt.% of P in each case). Test samples were obtained using bulk polymerization. The modifying compounds contained the P-atom in various chemical environments, as well as in an oxidation state of either III or V. With a view to gain an understanding of the chemical constitution of the gaseous products formed from the thermal decomposition of liquid additives/reactives, these materials were subjected to GC/MS analysis, whereas the decomposition of solid additives was detailed using the pyrolysis-GC/MS technique. Other investigations included the use of: Inductively-coupled Plasma/Optical Emission Spectroscopy (ICP/OES), solid-state NMR and FT-IR spectroscopy. In the case of PMMA-based systems, it was found that the modifying phosphonate ester function, upon thermal cracking, produced 'phosphorus' acid species which initiated the charring process. In the case of solid additives, it is more likely that the resultant phosphorus- and/or oxygenated phosphorus-containing volatiles acted as flame inhibitors in the gaseous phase. With the PSt-based systems, a probable process involving the phosphorylation of the phenyl groups leading to crosslinking and char formation is feasible. [ABSTRACT FROM AUTHOR]