Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes
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-<i>p</i>-vinylbenzyl phosphonate (DEpVBP), acrylic acid-2-[(diethox...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/1/278 |
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| author | Svetlana Tretsiakova-McNally Aloshy Baby Paul Joseph Doris Pospiech Eileen Schierz Albena Lederer Malavika Arun Gaëlle Fontaine |
| author_facet | Svetlana Tretsiakova-McNally Aloshy Baby Paul Joseph Doris Pospiech Eileen Schierz Albena Lederer Malavika Arun Gaëlle Fontaine |
| author_sort | Svetlana Tretsiakova-McNally |
| collection | DOAJ |
| description | 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-<i>p</i>-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 <sup>31</sup>P 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. |
| first_indexed | 2024-03-09T03:29:12Z |
| format | Article |
| id | doaj.art-23f2af377b784556b79ce15d211ca88d |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T03:29:12Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-23f2af377b784556b79ce15d211ca88d2023-12-03T14:57:26ZengMDPI AGMolecules1420-30492022-12-0128127810.3390/molecules28010278Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in PolystyrenesSvetlana Tretsiakova-McNally0Aloshy Baby1Paul Joseph2Doris Pospiech3Eileen Schierz4Albena Lederer5Malavika Arun6Gaëlle Fontaine7Belfast School of Architecture and the Built Environment, Ulster University, 2-24 York Street, Belfast BT15 1AP, Northern Ireland, UKBelfast School of Architecture and the Built Environment, Ulster University, 2-24 York Street, Belfast BT15 1AP, Northern Ireland, UKInstitute for Sustainable Industries and Liveable Cities, College of Engineering and Science, Werribee West Campus, Victoria University, P.O. Box 14428, Melbourne, VIC 8001, AustraliaLeibniz-Institut für Polymerforschung Dresden, Hohe Straβe 6, 01069 Dresden, GermanyLeibniz-Institut für Polymerforschung Dresden, Hohe Straβe 6, 01069 Dresden, GermanyLeibniz-Institut für Polymerforschung Dresden, Hohe Straβe 6, 01069 Dresden, GermanyInstitute for Sustainable Industries and Liveable Cities, College of Engineering and Science, Werribee West Campus, Victoria University, P.O. Box 14428, Melbourne, VIC 8001, AustraliaCNRS, INRAE, Centrale Lille, UMR 8207-UMET-Unité Matériaux et Transformations, University of Lille, F-59000 Lille, FrancePolystyrene (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-<i>p</i>-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 <sup>31</sup>P 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.https://www.mdpi.com/1420-3049/28/1/278polystyrenethermal decompositionreactive modificationP- and N-containing fire retardantsmode of action of fire retardancegaseous-phase inhibition |
| spellingShingle | Svetlana Tretsiakova-McNally Aloshy Baby Paul Joseph Doris Pospiech Eileen Schierz Albena Lederer Malavika Arun Gaëlle Fontaine Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes Molecules polystyrene thermal decomposition reactive modification P- and N-containing fire retardants mode of action of fire retardance gaseous-phase inhibition |
| title | Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes |
| title_full | Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes |
| title_fullStr | Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes |
| title_full_unstemmed | Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes |
| title_short | Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes |
| title_sort | gaseous and condensed phase activities of some reactive p and n containing fire retardants in polystyrenes |
| topic | polystyrene thermal decomposition reactive modification P- and N-containing fire retardants mode of action of fire retardance gaseous-phase inhibition |
| url | https://www.mdpi.com/1420-3049/28/1/278 |
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