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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]

In this paper, we report on the thermal degradation behaviours and combustion attributes of some polymers based on polystyrene (PSt). Here, both additive and reactive strategies were employed, through the bulk polymerization route, where the modifying groups incorporated P-atom in various chemical environments. These included oxidation states of III or V, and the loading of phosphorus was kept at ca. 2 wt.% in all cases. The characterization techniques that were employed for the recovered products included spectroscopic, thermal, and calorimetric. It was found that the presence of different modifying groups influenced the degradation characteristics of the base polymer, and also exerted varying degrees of combustion inhibition. In all cases, the modification of the base matrix resulted in a noticeable degree of fire retardance as compared to that of the virgin material. Therefore, some of the modifications presented have the potential to be explored on a commercial scale. [ABSTRACT FROM AUTHOR]

Polystyrene, despite its high flammability, is widely used as a thermal insulation material for buildings, for food packaging, in electrical and automotive industries, etc. A number of modification routes have been explored to improve the fire retardance and boost the thermal stability of commercially important styrene-based polymeric products. The earlier strategies mostly involved the use of halogenated fire retardants. Nowadays, these compounds are considered to be persistent pollutants that are hazardous to public and environmental health. Many well-known halogen-based fire retardants, regardless of their chemical structures and modes of action, have been withdrawn from built environments in the European Union, USA, and Canada. This had triggered a growing research interest in, and an industrial demand for, halogen-free alternatives, which not only will reduce the flammability but also address toxicity and bioaccumulation issues. Among the possible options, phosphorus-containing compounds have received greater attention due to their excellent fire-retarding efficiencies and environmentally friendly attributes. Numerous reports were also published on reactive and additive modifications of polystyrene in different forms, particularly in the last decade; hence, the current article aims to provide a critical review of these publications. The authors mainly intend to focus on the chemistries of phosphorous compounds, with the P atom being in different chemical environments, used either as reactive, or additive, fire retardants in styrene-based materials. The chemical pathways and possible mechanisms behind the fire retardance are discussed in this review. [ABSTRACT FROM AUTHOR]