Flame Retardant Polylimonen Carbonate: Material Innovation as a Game Changer

  • Main message: This research seeks to understand and identify the most promising approaches to enhance the flame resistance of poly(limonene carbonate) (PLimC). Furthermore, the goal is to develop a PLimC-based material that incorporates halogen-free flame retardants (FRs) that are not only highly effective but also environmentally sustainable, contributing to the advancement of greener materials for safer use. Introduction The plastic industry depends on fossil-based materials, causing environmental concerns. PLimC, a sustainable polymer derived from limonene and CO₂ [1], offers a promising alternative. Its use in fire safe applications underscores the need to optimize its performance. This study evaluates halogen free FRs to identify and understand the most promising approaches to enhance PLimC’s flame resistance, aiming to improve fire safety and support eco-friendly material development. Experimental: This study has as its main task to conduct experimental evaluations to analyze theMain message: This research seeks to understand and identify the most promising approaches to enhance the flame resistance of poly(limonene carbonate) (PLimC). Furthermore, the goal is to develop a PLimC-based material that incorporates halogen-free flame retardants (FRs) that are not only highly effective but also environmentally sustainable, contributing to the advancement of greener materials for safer use. Introduction The plastic industry depends on fossil-based materials, causing environmental concerns. PLimC, a sustainable polymer derived from limonene and CO₂ [1], offers a promising alternative. Its use in fire safe applications underscores the need to optimize its performance. This study evaluates halogen free FRs to identify and understand the most promising approaches to enhance PLimC’s flame resistance, aiming to improve fire safety and support eco-friendly material development. Experimental: This study has as its main task to conduct experimental evaluations to analyze the thermal properties, flammability, and fire behavior of each system. Pyrolysis, together with the evolved gases of the samples, were analyzed by thermogravimetric analysis coupled with a FTIR spectrometer. The energy content was determined by using a bomb calorimeter. The flammability of the samples was assessed by the reaction to small flame tests such as the UL 94 burning chamber and limiting oxygen index (LOI). The burning behavior in forced flamed conditions was evaluated using the cone calorimeter. Results and Discussion: Thermal properties were first evaluated to gain a deeper understanding of the pure PLimC thermal stability and fire behavior. This analysis builds on PLimC's structural similarity to polycarbonate (PC), due to its carbonate group, and to polyolefins (PO), due to its aliphatic limonene-derived segment, providing insights into optimizing PLimC for sustainable, fire-safe applications. The initial results, which defined our starting point, showed that the LOI of PLimC was 17.2%, very close to that of PO such as polyethylene (PE) and polypropylene (PP) (~18%). In contrast, PC has a higher LOI of ~24%. Additionally, PLimC did not produce any char (0 wt.-%), similar to PO, whereas PC forms char due to its phenolic structures. The effective heat of combustion of PLimC, measured using bomb calorimetry, was determined to be 31.1 MJ/kg. This value is comparable to that of PC (~30 MJ/kg) but significantly lower than PO (~44 MJ/kg). These findings, which demonstrated similarities to both PO and PC, prompted the evaluation of various commercially available FRs at standard market concentrations. Four halogen-free FR systems were chosen for evaluation: 1. mixture of APP (20 wt.-%) + pentaerythritol (10 wt.-%) as an intumescent system [PLimC / APP / Penta], 2. mixture of the phosphorus compound PX200® (16 wt.-%) + PTFE (0.4 wt.-%) as antidripping [PLimC / PhosC / PTFE], 3. metal hydroxide ATH (50 wt.-%) [PLimC / ATH], and the potassium sulfonate salt Bayowet® (0.4 wt.-%) [PLimC / SulfS]. The concentrations were decided according to the standards used in the industry for polyolefins (system 1 and 3), the mixture polycarbonate / ABS (system 2) and polycarbonates (system 4). PLimC has the usual behavior of a non-charring specimen (fast burning and high peak of heat release). ATH proved to be the most effective flame retardant, achieving the biggest reductions in the effective heat of combustion (EHC) and total heat evolved (THE), as demonstrated by cone calorimeter measurements. Additionally, ATH achieved the highest increase in the LOI (17.1% —> 26.0%). With these results, we understood that the FRs commonly used with polyolefins (at concentrations standard in the industry) exhibit similar behavior in terms of flammability and flame retardancy when applied to PLimC. Although ATH has proven to be an effective flame retardant for PLimC, offering a sustainable solution due to its abundance, non-toxicity, and low environmental impact, we aim to explore bio-based flame retardants to further enhance the material’s sustainability. Since phytic acid salts [2] and lignin [3] have demonstrated flame retardant efficacy in polyolefins, we believe these compounds could also perform well in our system. Phytic acid salts are particularly promising due to their high phosphorus content—and in some cases, nitrogen—which promotes char formation and enhances flame retardancy. Lignin’s unique ability to promote charring could significantly improve flame retardancy, due to the fact that PLimC like polyolefins, lacks inherent char formation. By integrating these bio-based flame retardants, we move closer to developing a fully sustainable material that aligns with the Sustainable Development Goals of the United Nations, contributing to a greener and more resilient future.zeige mehrzeige weniger

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Metadaten
Autor*innen:Jose P. Chacon Castro
Koautor*innen:Bernhard SchartelORCiD
Dokumenttyp:Vortrag
Veröffentlichungsform:Präsentation
Sprache:Englisch
Jahr der Erstveröffentlichung:2025
Organisationseinheit der BAM:7 Bauwerkssicherheit
7 Bauwerkssicherheit / 7.5 Technische Eigenschaften von Polymerwerkstoffen
DDC-Klassifikation:Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Ingenieurbau
Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Sanitär- und Kommunaltechnik; Umwelttechnik
Freie Schlagwörter:Halogen free flame retardants; Poly(limonene carbonate); Sustainability
Themenfelder/Aktivitätsfelder der BAM:Infrastruktur
Infrastruktur / Fire Science
Umwelt
Umwelt / Circular Economy
Veranstaltung:20th European Meeting on Fire Retardant Polymeric Materials (FRPM2025)
Veranstaltungsort:Madrid, Spain
Beginndatum der Veranstaltung:03.06.2025
Enddatum der Veranstaltung:06.06.2025
Verfügbarkeit des Dokuments:Datei im Netzwerk der BAM verfügbar ("Closed Access")
Datum der Freischaltung:17.06.2025
Referierte Publikation:Nein
Eingeladener Vortrag (wissenschaftliche Konferenzen):Nein
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