Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes

Svetlana Tretsiakova-McNally; Aloshy Baby; Paul Joseph; Doris Pospiech; Eileen Schierz; Albena Lederer; Malavika Arun; Gaëlle Fontaine

doi:10.3390/molecules28010278

Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes

Svetlana Tretsiakova-McNally
, Aloshy Baby
, Paul Joseph
, Doris Pospiech
, Eileen Schierz
, Albena Lederer
, Malavika Arun
, Gaëlle Fontaine

Research output: Contribution to journal › Article › peer-review

7 Citations (Scopus)

109 Downloads (Pure)

Abstract

Polystyrene (PS) was modified by covalently binding P-, P-N- and/or N- containing fireretardant 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

Original language	English
Article number	278
Pages (from-to)	1-18
Number of pages	18
Journal	Molecules
Volume	28
Issue number	1
Early online date	29 Dec 2022
DOIs	https://doi.org/10.3390/molecules28010278
Publication status	Published (in print/issue) - 29 Dec 2022

Bibliographical note

Funding Information:
This research was funded by the Royal Society of Chemistry, grant number R19-3521.

Publisher Copyright:
© 2022 by the authors.

Funding

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 11 Sustainable Cities and Communities
SDG 12 Responsible Consumption and Production

Keywords

polystyrene
thermal decomposition
reactive modification
P- and N-containing fire retardants;
mode of action of fire retardance
gaseous-phase inhibition
char formation
P- and N-containing fire retardants

Access to Document

10.3390/molecules28010278

molecules-28-00278 published versionFinal published version, 12.8 MBLicence: CC BY

Cite this

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title = "Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes",

abstract = "Polystyrene (PS) was modified by covalently binding P-, P-N- and/or N- containing fireretardant 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",

keywords = "polystyrene, thermal decomposition, reactive modification, P- and N-containing fire retardants;, mode of action of fire retardance, gaseous-phase inhibition, char formation, P- and N-containing fire retardants",

author = "Svetlana Tretsiakova-McNally and Aloshy Baby and Paul Joseph and Doris Pospiech and Eileen Schierz and Albena Lederer and Malavika Arun and Ga{\"e}lle Fontaine",

note = "Funding Information: This research was funded by the Royal Society of Chemistry, grant number R19-3521. Publisher Copyright: {\textcopyright} 2022 by the authors.",

year = "2022",

month = dec,

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doi = "10.3390/molecules28010278",

language = "English",

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TY - JOUR

T1 - Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes

AU - Tretsiakova-McNally, Svetlana

AU - Baby, Aloshy

AU - Joseph, Paul

AU - Pospiech, Doris

AU - Schierz, Eileen

AU - Lederer, Albena

AU - Arun, Malavika

AU - Fontaine, Gaëlle

PY - 2022/12/29

Y1 - 2022/12/29

N2 - Polystyrene (PS) was modified by covalently binding P-, P-N- and/or N- containing fireretardant 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

AB - Polystyrene (PS) was modified by covalently binding P-, P-N- and/or N- containing fireretardant 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

KW - polystyrene

KW - thermal decomposition

KW - reactive modification

KW - P- and N-containing fire retardants;

KW - mode of action of fire retardance

KW - gaseous-phase inhibition

KW - char formation

KW - P- and N-containing fire retardants

UR - https://www.scopus.com/pages/publications/85145692186

U2 - 10.3390/molecules28010278

DO - 10.3390/molecules28010278

M3 - Article

C2 - 36615472

SN - 1420-3049

VL - 28

SP - 1

EP - 18

JO - Molecules

JF - Molecules

IS - 1

M1 - 278

ER -

Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes

Abstract

Bibliographical note

Funding

UN SDGs

Keywords

Access to Document

Other files and links

Fingerprint

Synergistic effect of phosphorus and nitrogen-containing groups in fire retardancy of polystyrene

Cite this

Gaseous- and Condensed-Phase Activities of Some Reactive P- and N-Containing Fire Retardants in Polystyrenes

Abstract

Bibliographical note

Funding

UN SDGs

Keywords

Access to Document

Other files and links

Fingerprint

Student theses

Synergistic effect of phosphorus and nitrogen-containing groups in fire retardancy of polystyrene

Cite this