The Influence of Phosphorus- and Nitrogen- Containing Groups on the Thermal Stability and Combustion Characteristics of Styrenic Polymers

Aloshy Baby, Svetlana Tretsiakova-McNally, Paul Joseph, Malavika Arun, Jianping Zhang, Doris Pospiech

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The effects of covalently bound phosphorus (P-) and nitrogen (N-) bearing groups on the thermal and combustion attributes of polystyrene have been investigated. The necessary chemical modifications were achieved through co- and ter-polymerisation reactions, in a suitable solvent, under radical initiation conditions. The influence of P-N cooperative interactions on the combustion properties of styrenic polymers was studied. The co-monomers of interest included: diethyl(acryloyloxymethyl)phosphonate (DEAMP), diethyl-p-vinylbenzylphosphonate (DEpVBP), acrylic acid-2-[(diethoxyphosphoryl)methyl amino]ethyl ester (ADEPMAE) and maleimide (MI). For the first time, the ter-polymers of styrene containing both P- groups, DEAMP or DEpVBP, and N- groups, MI, were prepared via solution polymerisation. It was found that the thermal stability and combustion characteristics of polystyrene were significantly altered by the presence of nominal amounts of P- and N- containing groups, and, in certain cases, cooperative interactions of these groups were also evident. For instance, the extents of char formation post-degradation of the prepared ter-polymers, as revealed by thermogravimetric investigations in an inert atmosphere (nitrogen), were found to be enhanced by more than 20%, as compared to the unmodified polystyrene. The heat release rates and heat release capacities of the ter-polymers, as measured using the pyrolysis combustion flow calorimetric (PCFC) technique, were reduced by almost 50% in comparison to the same parameters obtained for the unmodified counterpart.
Original languageEnglish
Pages (from-to)229-241
Number of pages13
JournalJournal of Thermal Analysis and Calorimetry
Early online date20 Jun 2022
Publication statusPublished online - 20 Jun 2022

Bibliographical note

Funding Information:
This research was supported by the Royal Society of Chemistry (ID R19-3521).

Publisher Copyright:
© 2022, The Author(s).


  • styrenic polymer
  • chemical modification
  • thermal stability
  • combustion characteristics
  • phosphorus-nitrogen cooperative effect
  • polystyrene
  • Chemical modification
  • Combustion characteristics
  • Phosphorus-nitrogen cooperative effect
  • Styrenic polymer
  • Polystyrene
  • Thermal stability


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