{"title":"Hydrophosphonylation strategy to achieve oxazine ring-substituted bio-benzoxazines showing both roles of thermal latent catalyst and flame retardant","authors":"Jiaqi Wang, Yin Lu, Ruiyu Yuan, Kan Zhang","doi":"10.1016/j.polymdegradstab.2025.111615","DOIUrl":"10.1016/j.polymdegradstab.2025.111615","url":null,"abstract":"<div><div>The increasing frequent occurrence of fire accidents alone with the desirable sustainable development have accelerated searching for more resilient and safer flame-retardant polymers derived from natural renewable resources. Here we have successfully designed and synthesized bio-based benzoxazine monomers (<strong>pH-fa-[<em>2</em>-pH,<em>4</em>-DEP]</strong> and <strong>pH-fa-[<em>2</em>-<em>o</em>OHph,<em>4</em>-DEP]</strong>) with oxazine ring substituted by diethyl phosphite (DEP) via hydrophosphonylation for the first time, thereby achieving non-flammable green thermoset materials. Specifically, <strong>pH-fa-[<em>2</em>-<em>o</em>OHph,<em>4</em>-DEP]</strong> with phenolic -OH group also shows a latent catalytic feature through its in-built intramolecular hydrogen bonding. As a result, we chose this newly synthesized monomer as both latent catalyst and flame retardant for enhancing the comprehensive properties of the well-commercialized benzoxazine resin (BA-a). The peak curing temperature of BA-a thermosetting system was decreased 23.3 °C and the glass transition temperature of resulting thermoset increased by 61.7 % with only adding 3 mol% of <strong>pH-fa-[<em>2</em>-<em>o</em>OHph,<em>4</em>-DEP]</strong>. Finally, the mechanistic insights into both advantages including low curing temperature and excellent flame retardancy have been discussed. With this work we demonstrate the possibilities for achieving bio-based non-flammable thermosets using benzoxazine chemistry, and offer molecular level insights into the functions, paving the way for new applications of green thermosetting resins for high-performance non-flammable composite materials.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111615"},"PeriodicalIF":7.4,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144887122","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chuanshen Wang , Hongliang Ding , Lu Liu , Hongfei He , Bicheng Lin , Na Sun , Keqing Zhou , Wei Wang , Yuan Hu , Bin Yu
{"title":"Organophosphate-intercalated high-entropy LDHs for high-performance fire-safe thermoplastic polyurethane composites","authors":"Chuanshen Wang , Hongliang Ding , Lu Liu , Hongfei He , Bicheng Lin , Na Sun , Keqing Zhou , Wei Wang , Yuan Hu , Bin Yu","doi":"10.1016/j.polymdegradstab.2025.111613","DOIUrl":"10.1016/j.polymdegradstab.2025.111613","url":null,"abstract":"<div><div>Polymer materials pose significant fire hazards, including rapid heat release and the emission of toxic smoke. Herein, we report a flame-retardant thermoplastic polyurethane (TPU) composite engineered with organophosphonic acid-intercalated high-entropy layered double hydroxides (HE-LDHs), achieving synergistic flame retardancy, smoke suppression, and mechanical enhancement. Meanwhile, tensile strength was enhanced to 38 MPa. The NiCoFeAlZn/DPA/TPU system demonstrated 42.1 % reduction in peak heat release rate (pHRR), 48.5 % decrease in total smoke release (TSR), and 36.4 % decrease in CO production rate compared to pure TPU, attributed to a hierarchical flame-retardant mechanism involving gas-phase dilution, physical barrier formation, and catalytic charring. The synergistic effect of multi-metal components of HE-LDHs and the intercalation (diphenylphosphoric acid, phenylphosphinic acid) agents restructured the thermal decomposition pathway of the material. Early-stage fire warning through HE-LDHs decomposition of interlayer water and organic acid anions releases CO<sub>2</sub>/H<sub>2</sub>O to dilute flammable gases; Intermediate flame inhibition through HE-LDHs catalyze dehydrogenation crosslinking of TPU, capture by PO· radicals from phosphonates, effectively suppressing flame propagation; High-temperature protection through collapse of LDH layers generates metal oxides and phosphorus-carbon hybrid barriers, triggering endothermic phase transitions, with an increase in the amount of residual carbon. This work establishes a theoretical framework for regulating the structure-property relationship of HE-LDHs and pioneers an integrated, active-passive design for fire-safe, high-risk polymer applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111613"},"PeriodicalIF":7.4,"publicationDate":"2025-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144890654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ailin Peng , Zhenlei Wang , Ziqiu Zeng , Wendong Chen , Xiaobo Liu , Yumin Huang
{"title":"Self-catalytic bio-based benzoxazine-phthalonitrile thermosets with high heat resistance and flame retardancy","authors":"Ailin Peng , Zhenlei Wang , Ziqiu Zeng , Wendong Chen , Xiaobo Liu , Yumin Huang","doi":"10.1016/j.polymdegradstab.2025.111612","DOIUrl":"10.1016/j.polymdegradstab.2025.111612","url":null,"abstract":"<div><div>Developing sustainable bio-based thermoset resins with exceptional heat resistance and flame retardancy remains a critical challenge. This study synthesized a novel guaiacol-derived benzoxazine-containing phthalonitrile resin (GB-PN) and prepared its polymer Poly(GB-PN). The curing behavior, polymerization mechanism, and flame-retardant mechanism were systematically investigated. The optimal curing temperature was determined via curing kinetic parameters. Poly(GB-PN)-360 °C exhibited outstanding thermal stability, with T<sub>d5</sub> and T<sub>d10</sub> values of 461 °C and 507 °C, respectively, and a high char residue yield (Y<sub>c</sub>) of 66.2 %. Moreover, Poly(GB-PN)-360 °C exhibited significantly superior flame retardancy compared to analogous thermosetting resins, evidenced by a limiting oxygen index (LOI) of 43.98 %, a heat release capacity (HRC) of 15.5 J/(g·K), and a total heat release (THR) of 1.4 kJ/g. Characterization by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Raman spectroscopy, and Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS) confirmed the residual char mechanism of Poly(GB-PN)-360 °C and elucidated its pyrolysis pathways and char layer composition. This work provides an effective strategy and theoretical insights into char formation for developing thermosetting resins that integrate superior thermal resistance and flame-retardant properties.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111612"},"PeriodicalIF":7.4,"publicationDate":"2025-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144864353","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kai Wang, Jiaming Yang, Xindong Zhao, Xu Yang, Chengcheng Zhang, Xuan Wang, Hong Zhao
{"title":"Synergistic enhancement of thermal-oxidative stability and DC electrical properties in impact polypropylene copolymer via maleimide-functionalized antioxidant grafting","authors":"Kai Wang, Jiaming Yang, Xindong Zhao, Xu Yang, Chengcheng Zhang, Xuan Wang, Hong Zhao","doi":"10.1016/j.polymdegradstab.2025.111610","DOIUrl":"10.1016/j.polymdegradstab.2025.111610","url":null,"abstract":"<div><div>Grafting modification represents a critical method for augmenting the electrical properties of polypropylene (PP), as an insulating material in high-voltage direct current (HVDC) cables. Additionally, the aging performance requires further enhancement since cables are the power equipment that operates over the long term. Grafting antioxidants that contain charge trapping functional groups has the potential to enhance both the electrical and aging properties simultaneously. Nevertheless, direct grafting remains a formidable challenge due to the low grafting reactivity of antioxidants and the high susceptibility to degradation of PP. Drawing inspiration from click chemistry, this paper selects PP grafted with maleic anhydride (PP-g-MAH) as the reaction platform. N-phenyl-p-phenylenediamine (AD) is covalently attached to the MAH side groups through the maleimide-functionalized reaction. This results in forming a functionalized material, PP-g-(MAH-co-AD). Compared with PP and PP-g-MAH blended with traditional antioxidants, PP-g-(MAH-co-AD)s demonstrate enhanced thermo-oxidative aging resistance and more remarkable improvement in DC electrical properties. Before and after aging, it sustains a robust suppression of space charge and conduction current. Moreover, it displays a lower decline rate in DC breakdown strength and reveals a substantial reduction in the sensitivity of conductivity to temperature. The observed improvement can be ascribed to the (MAH-co-AD) groups. These groups introduce not only electron deep traps but also hole deep traps and maintain localized deep traps even after aging. In summary, compared with cross-linked polyethylene (XLPE) and PP modified by molecular grafting with single functional properties, the functionalized PP demonstrates superior aging resistance and more pronounced enhancement of electrical properties.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111610"},"PeriodicalIF":7.4,"publicationDate":"2025-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144864354","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Upcycling PET waste into Al-MOFs with one-step hydrothermal method and its application in flame retardant of PA66","authors":"Botong Liu , Yichen Huang , Zhenfeng Dong , Yuhang Wu , Hanjiang Huang , Linhan Bing , Zhiguo Zhu , Jianfei Wei , Rui Wang","doi":"10.1016/j.polymdegradstab.2025.111611","DOIUrl":"10.1016/j.polymdegradstab.2025.111611","url":null,"abstract":"<div><div>We developed a sustainable closed-loop strategy to convert post-consumer PET waste into functional aluminum-based metal-organic frameworks (Al-MOFs) via a one-step hydrothermal method. This process uses PET-derived terephthalic acid as the organic linker. The resulting rod-like Al-MOFs (5–10 μm, MIL-53 structure) exhibit high thermal stability and were incorporated into polyamide 66 (PA66) as flame-retardant additives. At an optimal 4 wt% loading, the PA66/Al composite achieves a 40 % increase in limiting oxygen index (from 25 % to 35 %) and reduces peak heat release rate by 33.04 % (from 727.61 kW·m⁻² to 487.24 kW·m⁻²), while enhancing tensile strength by 19.74 % (from 57.42 MPa to 68.76 MPa). Mechanistic studies confirm that Al-MOFs function through a condensed-phase flame-retardant mechanism: catalytic carbonization promotes continuous char formation, evidenced by a 47.71 % increase in experimental char residue (4.895 %) over the theoretical value (3.314 %) under N₂. Concurrently, in situ-generated Al₂O₃ (XPS Al 2p at 74.6 eV) reinforces the char barrier, suppressing heat/oxygen transfer and volatile release. This effect further reduces peak smoke production rate by 56.38 % (0.1442 to 0.0629 m²·s⁻¹) and decreases CO/CO₂ evolution. The combined flame suppression and mechanical enhancement stem from interfacial interactions between Al-MOFs carboxyl groups and PA66 amide bonds. This work provides a scalable approach to transform plastic waste into high-performance polymer additives that simultaneously impart flame retardancy and reinforcement without compromising material properties.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111611"},"PeriodicalIF":7.4,"publicationDate":"2025-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144887123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dan Xie , Alex Momoh Lansana , Xiayida Nuermaimaiti , Qiao Kang , Fengqing Chen , Baiyu Jiang , Jia Gao , Pingan Song , Jinfeng Dai
{"title":"Making polycarbonate flame retardant and transparent: Current advances and future challenges in flame retardant selection and mechanisms","authors":"Dan Xie , Alex Momoh Lansana , Xiayida Nuermaimaiti , Qiao Kang , Fengqing Chen , Baiyu Jiang , Jia Gao , Pingan Song , Jinfeng Dai","doi":"10.1016/j.polymdegradstab.2025.111607","DOIUrl":"10.1016/j.polymdegradstab.2025.111607","url":null,"abstract":"<div><div>Polycarbonate (PC) is the only thermoplastic engineering plastic among general engineering plastics that possesses excellent transparency (> 90 %) and inherent flame retardancy (UL-94 V-2 rating). However, in the field of photoelectric safety engineering applications, achieving a UL-94 V-0 rating without compromising transparency remains a critical challenge. Conventional flame-retardant additives often suffer from inefficiency, high loading requirements, and poor compatibility, leading to significant deterioration of optical properties. Addressing these limitations necessitates the strategic design of additives to enhance flame-retardant efficiency while ensuring compatibility with the PC matrix. This review comprehensively summarizes recent advances in environmentally benign flame-retardant systems for transparent PC, including organic phosphorus, sulfonate, organosilicon, and nanomaterials flame retardants. By elucidating the structure-performance relationships and mechanistic pathways of these additives, this work highlights innovative strategies to optimize flame-retardant performance while preserving optical clarity, further focusing on synergistic approaches, and interfacial compatibility enhancement. Finally, key challenges with current flame retardant system are discussed and some molecular design principles are proposed to guide the development of next-generation transparent PC materials that meet stringent safety and performance standards in optoelectronic and engineering applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111607"},"PeriodicalIF":7.4,"publicationDate":"2025-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144887124","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Vanillin-derived multifunctional reinforcing agent enabling recyclable epoxy vitrimer composites via hydrogen/dynamic covalent collaborative networks","authors":"Kai Dong, Di Zhao, Yang Pang, Chengji Zhao","doi":"10.1016/j.polymdegradstab.2025.111608","DOIUrl":"10.1016/j.polymdegradstab.2025.111608","url":null,"abstract":"<div><div>Epoxy vitrimers impart dynamic functionality to thermoset polymers and carbon fiber-reinforced composites (CFRC) through reversible crosslinking networks. However, this often results in reduced stability and a trade-off between dynamic performance and mechanical strength. Herein, a novel reinforcing agent (Bio-based Vanillin-Tyramine, BVT) containing Schiff base and tetraphenol hydroxyl groups was synthesized to address this challenge. The incorporation of BVT constructs the hierarchical crosslinking networks that simultaneously enhance the strength and toughness of bio-based vitrimers (Tensile strength and impact strength were increased by 44 % and 225 %, respectively.). The synergistic effect of dual dynamic imine and siloxane bonds further optimizes dynamic behaviors, resulting in a 51 s stress relaxation time and a 14 % decrease in activation energy for the dynamic bond exchange reaction. In addition, CFRC containing dynamic crosslinked networks demonstrate closed-loop recyclability under mild conditions, preserving the surface morphology and chemical structure of recovered carbon fibers, while maintaining the crosslinking architecture of the recycled vitrimer for reshaping. This work presents a simple and efficient strategy for constructing hybrid hydrogen-bonding/covalent adaptable networks, providing valuable insights into the development of high-performance, multifunctional, and recyclable bio-based epoxy vitrimers and CFRC.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111608"},"PeriodicalIF":7.4,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144864352","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiao-ting Qing , Wen-jing Wang , Yuan Dong , Zhi-mei Wei , Sheng-ru Long , Jie Yang , Jia-cao Yang , Xiao-jun Wang
{"title":"Hygrothermal aging behavior of short glass fiber reinforced polyphenylene sulfide composites under different liquid media","authors":"Xiao-ting Qing , Wen-jing Wang , Yuan Dong , Zhi-mei Wei , Sheng-ru Long , Jie Yang , Jia-cao Yang , Xiao-jun Wang","doi":"10.1016/j.polymdegradstab.2025.111602","DOIUrl":"10.1016/j.polymdegradstab.2025.111602","url":null,"abstract":"<div><div>This study aims to explore the hygrothermal aging behavior and damage mechanism of short glass fiber-reinforced Polyphenylene Sulfide (PPS/GF) composites under three complex environments: seawater, coolant, and alkali solution. The evolution of mechanical properties during hygrothermal aging was investigated through tensile, bending, and impact tests. Through Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), and Fourier Transform Infrared Spectroscopy (FTIR) revealed that the chemical structure of the resin did not change before and after hygrothermal aging. Analysis of the fiber-resin interface through Scanning Electron Microscopy (SEM) and microbond test showed that interfacial damage was the primary reason for the decrease in mechanical properties of PPS/GF composites. Furthermore, single-fiber tensile tests and FTIR study on fibers in an alkali solution environment revealed additional damage inflicted by the alkali solution on glass fibers.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111602"},"PeriodicalIF":7.4,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144887125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shi-Neng Li , Yu-Qin Yang , Yu-Tong Xu , Qing-Yue Ni , Baiyu Jiang , Ben Wang , Wei Wang , Long-Cheng Tang
{"title":"Facile synthesis of phosphorylated lignocellulosic nanofibril/graphene oxide composite film via co-milling method towards enhancing mechanical and flame-retardant performance","authors":"Shi-Neng Li , Yu-Qin Yang , Yu-Tong Xu , Qing-Yue Ni , Baiyu Jiang , Ben Wang , Wei Wang , Long-Cheng Tang","doi":"10.1016/j.polymdegradstab.2025.111604","DOIUrl":"10.1016/j.polymdegradstab.2025.111604","url":null,"abstract":"<div><div>Achieving both excellent flame retardancy and high mechanical performance is essential for the potential application of composite films in industrial application. However, designing and fabricating film materials that produce a feasible balance between the aforementioned features presents a daunting challenge. Herein, as a proof-of-concept, phosphorylated lignocellulosic nanofibrils (P<sub>L</sub>CNF) and ammonium polyphosphate (APP) were well integrated into a densified large/small graphene oxide-based network using a simple evaporation-induced self-assembly method. Benefiting from the incorporation of hydrogen bonding (P<sub>L</sub>CNF and APP) and nano-reinforcement (P<sub>L</sub>CNF), the mechanical and structural reliability of the interconnected networks gain a discernible improvement. Correspondingly, the optimized films exhibits markedly improved mechanical performance (i.e., tensile strength of 269.4 MPa, elongation at break of 7.92%, and toughness of 11.17 MJ⸱m<sup>-3</sup>, ∼2.0, 1.8 and 7.3 times surpass those of the virgin one) and good structural stability in aqueous solutions with different pH value and different reagents. Additionally, the resultant films demonstrated exceptional flame resistance attributed to the synergistic effect of P<sub>L</sub>CNF (phosphorous-containing group and lignin molecules) and APP (phosphorous- and nitrogen-containing group), as evidenced by their structural integrity after repeated exposure to a high-temperature flame. The key parameters for micro-scale combustion calorimetry testing, i.e., peak heat release rate and total heat release, dramatically decreased, and the corresponding value was lowered to 12.8 W⸱g⁻¹ and 0.40 kJ⸱g⁻¹, respectively. The reinforcing and flame-retardant mechanisms were elucidated through an analysis of structural evolution and performance variation. The strategy developed in this study offers a novel approach for the design and development of advanced film materials for fireproof coatings.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111604"},"PeriodicalIF":7.4,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144864351","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dan Wang , Yajing Wang , Wenyan Zhao , Yunhong Jiao , Jianzhong Xu , Haiyun Ma
{"title":"Zn2+ induced hierarchical all bio-based supramolecular folate/alginate dual network leading to ultra-light and fire-safety aerogels","authors":"Dan Wang , Yajing Wang , Wenyan Zhao , Yunhong Jiao , Jianzhong Xu , Haiyun Ma","doi":"10.1016/j.polymdegradstab.2025.111606","DOIUrl":"10.1016/j.polymdegradstab.2025.111606","url":null,"abstract":"<div><div>Aerogels based on supramolecular self-assembly have become one of the hotspots in aerogel research. Herein, we reported a full biobased hierarchical supramolecular aerogel with low density, excellent flame retardant and fire<em>-</em>warning response which was obtained via a simple supramolecular self-assembly of folic acid tetramer (FA-tetramer) and sodium alginate. The density of the resultant FSNZ aerogels was ultralow at 14.4∼17.8 mg/cm<sup>3</sup>, and the thermal conductivity reaches as low as 33.6 mW/(m∙K). Moreover, the resultant aerogel showed an excellent flame-retardancy and early fire warning capability (responses within 3 s), The heat and smoke release value were reduced by 53.6 % and 82.3 %, respectively. The flame-retardant mechanism of FSNZ aerogels is attributed to the zinc-catalyzed carbonization of FA-tetramer and alginate, while the fire early-warning mechanism is based on the temperature-responsive semiconducting properties resulting from the synergistic effect of zinc oxide and graphitic residue char. As a result, the supramolecular FSNZ aerogels in this work provide a novel strategy for the preparation of flame-retardant aerogels.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111606"},"PeriodicalIF":7.4,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144864342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}