Degradable poly(butylene succinate-co-butylene adipate-co-butylene 5-sodiosulfoisophthalate) (PBSAS) incorporating sodium dimethyl isophthalate-5-sulfonate (SIPM) units were synthesized via an optimized two-step melt transesterification polycondensation. The introduced ionic groups enhanced polarity for microwave heating, while simultaneously reducing crystallinity and broadening the melting range from 23 to 35 °C. They also acted as cross-links, improving melt strength and mechanical properties. Consequently, PBSAS5 foam achieved exceptional stability (25.3 times), a tunable bimodal cell structure, superior compression performance, and an ultralow thermal conductivity of 35.2 mW/m·K. Furthermore, SIPM imparted pronounced hydrophilicity and pH-responsive degradation, resulting in an accelerated degradation rate of PBSAS foams under acidic conditions. This integrated strategy of efficient polymerization and microwave-assisted foaming enables the fabrication of ultralight PBSAS foams, providing a universal method for the sustainable production of degradable materials.
{"title":"Green fabrication of degradable poly(butylene succinate-co-butylene adipate) foams: Effect of ionic monomers on in-situ polymerization and microwave-assisted foaming","authors":"Wentao Guo, Zhirui Wang, Xiulu Gao, Meixia Zhang, Yichong Chen, Ling Zhao, Dongdong Hu","doi":"10.1016/j.polymdegradstab.2025.111906","DOIUrl":"10.1016/j.polymdegradstab.2025.111906","url":null,"abstract":"<div><div>Degradable poly(butylene succinate-<em>co</em>-butylene adipate-<em>co</em>-butylene 5-sodiosulfoisophthalate) (PBSAS) incorporating sodium dimethyl isophthalate-5-sulfonate (SIPM) units were synthesized via an optimized two-step melt transesterification polycondensation. The introduced ionic groups enhanced polarity for microwave heating, while simultaneously reducing crystallinity and broadening the melting range from 23 to 35 °C. They also acted as cross-links, improving melt strength and mechanical properties. Consequently, PBSAS5 foam achieved exceptional stability (25.3 times), a tunable bimodal cell structure, superior compression performance, and an ultralow thermal conductivity of 35.2 mW/m·K. Furthermore, SIPM imparted pronounced hydrophilicity and pH-responsive degradation, resulting in an accelerated degradation rate of PBSAS foams under acidic conditions. This integrated strategy of efficient polymerization and microwave-assisted foaming enables the fabrication of ultralight PBSAS foams, providing a universal method for the sustainable production of degradable materials.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111906"},"PeriodicalIF":7.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881161","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}
Pub Date : 2026-03-01Epub Date: 2025-12-29DOI: 10.1016/j.polymdegradstab.2025.111908
Xinchao Li , Shansan Yuan , Ping Wang , Jianfeng Li , Jin Zhang , Fafu Zong , Zhaohui Zheng , Guoxing Sun , Mingjun Chen , Ting Wang , Zhicheng Fu , Wenli An , Jinni Deng
Flammability and droplet behavior are the key obstacle to the development of polypropylene (PP) materials. Traditional flame retardants (FRs) for this are inefficient and often lead to strong damage in mechanical performance, due to their whole-part distribution and incompatibility in PP blends. To address this, in this work, novel intumescent flame retardants with Si-P-N single-molecule synergy (SMIFRs) were prepared and introduced in PP by melt-blending process. Owing to the low-surface-energy properties of Si, it’s confirmed that SMIFRs could mostly aggregate on the surface, demonstrating high-efficient flame retardancy and obviously enhanced mechanical properties in PP blend. More specifically, with just 3.3 wt% phosphorus content, PP blend can achieve V-0 rating without any melt-droplet phenomenon, exhibiting increased limiting oxygen index (LOI) value by 58% and reduced peak heat release rate (pHRR) by 81%, compared with pure PP. Notably, just because of the surface aggregation that not only decreases the content of SMIFRs but also lowers its internal distribution in PP, the damage of mechanical properties of PP blend is greatly weakened (elongation is 57% higher than the blend prepared by mixed FRs at the same ratio), demonstrating optimal mechanical properties compared with flame-retardant PP blends reported before. This mechanism based on surface aggregation and single-molecule synergy would provide a novel strategy for PP to acquire both high-efficient flame retardancy and good mechanical performance.
{"title":"High-efficient flame retardancy and low mechanical performance impact in polypropylene blend based on surface aggregation and Si-P-N single-molecule synergy","authors":"Xinchao Li , Shansan Yuan , Ping Wang , Jianfeng Li , Jin Zhang , Fafu Zong , Zhaohui Zheng , Guoxing Sun , Mingjun Chen , Ting Wang , Zhicheng Fu , Wenli An , Jinni Deng","doi":"10.1016/j.polymdegradstab.2025.111908","DOIUrl":"10.1016/j.polymdegradstab.2025.111908","url":null,"abstract":"<div><div>Flammability and droplet behavior are the key obstacle to the development of polypropylene (PP) materials. Traditional flame retardants (FRs) for this are inefficient and often lead to strong damage in mechanical performance, due to their whole-part distribution and incompatibility in PP blends. To address this, in this work, novel intumescent flame retardants with Si-P-N single-molecule synergy (SMIFRs) were prepared and introduced in PP by melt-blending process. Owing to the low-surface-energy properties of Si, it’s confirmed that SMIFRs could mostly aggregate on the surface, demonstrating high-efficient flame retardancy and obviously enhanced mechanical properties in PP blend. More specifically, with just 3.3 wt% phosphorus content, PP blend can achieve V-0 rating without any melt-droplet phenomenon, exhibiting increased limiting oxygen index (LOI) value by 58% and reduced peak heat release rate (pHRR) by 81%, compared with pure PP. Notably, just because of the surface aggregation that not only decreases the content of SMIFRs but also lowers its internal distribution in PP, the damage of mechanical properties of PP blend is greatly weakened (elongation is 57% higher than the blend prepared by mixed FRs at the same ratio), demonstrating optimal mechanical properties compared with flame-retardant PP blends reported before. This mechanism based on surface aggregation and single-molecule synergy would provide a novel strategy for PP to acquire both high-efficient flame retardancy and good mechanical performance.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111908"},"PeriodicalIF":7.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881165","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}
Pub Date : 2026-03-01Epub Date: 2025-12-19DOI: 10.1016/j.polymdegradstab.2025.111874
Carla I. La Fuente Arias, Chelo González-Martínez, Amparo Chiralt
Biodegradation of bioplastics in marine ecosystems is affected by biotic and abiotic factors related to the marine zone and the material composition. In this study, the biodegradation and disintegration behavior of PHBV films containing or not containing catechin and cellulose fibers was studied in a simulated Sublittoral zone at laboratory scale. The films were produced by melt blending and compression molding. Biodegradation rate was monitored through the respirometric method, according to the standard ISO 19,679:2020. Disintegration rate (mass loss) of the samples was also analyzed at different exposure times, while the changes in microstructure and thermal behavior of the residual film were characterized. Likewise, the influence of the antimicrobial (catechin) on the bacterial biofilm and taxonomic profiles after 200 exposure days was studied by DNA extraction and the analysis by Amplicon Sequencing. Cellulose fibers slightly accelerated the films' biodegradation by promoting bulk hydrolysis in the matrix due to their hydrophilic nature. In contrast, Catechin delayed the biodegradation and disintegration of PHBV films, which was attributed to its crosslinking effect in the polymer amorphous phase and its influence on the biofilm bacterial population, which could reduce the predominance of enzyme-producing bacteria responsible for film depolymerization.
{"title":"Biodegradation of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in simulated sublittoral marine environment, as affected by reinforcing and antimicrobial agents","authors":"Carla I. La Fuente Arias, Chelo González-Martínez, Amparo Chiralt","doi":"10.1016/j.polymdegradstab.2025.111874","DOIUrl":"10.1016/j.polymdegradstab.2025.111874","url":null,"abstract":"<div><div>Biodegradation of bioplastics in marine ecosystems is affected by biotic and abiotic factors related to the marine zone and the material composition. In this study, the biodegradation and disintegration behavior of PHBV films containing or not containing catechin and cellulose fibers was studied in a simulated Sublittoral zone at laboratory scale. The films were produced by melt blending and compression molding. Biodegradation rate was monitored through the respirometric method, according to the standard ISO 19,679:2020. Disintegration rate (mass loss) of the samples was also analyzed at different exposure times, while the changes in microstructure and thermal behavior of the residual film were characterized. Likewise, the influence of the antimicrobial (catechin) on the bacterial biofilm and taxonomic profiles after 200 exposure days was studied by DNA extraction and the analysis by Amplicon Sequencing. Cellulose fibers slightly accelerated the films' biodegradation by promoting bulk hydrolysis in the matrix due to their hydrophilic nature. In contrast, Catechin delayed the biodegradation and disintegration of PHBV films, which was attributed to its crosslinking effect in the polymer amorphous phase and its influence on the biofilm bacterial population, which could reduce the predominance of enzyme-producing bacteria responsible for film depolymerization.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111874"},"PeriodicalIF":7.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838548","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}
Pub Date : 2026-03-01Epub Date: 2025-12-08DOI: 10.1016/j.polymdegradstab.2025.111855
Tian Y. Liu , Wei J. Zhang , Tian C. Shi , Ze Y. Zhang , Zhi C. Zhen , Ping L. Wang , Xiu B. Yang , Dan Huang , Jun H. Ji , Ge X. Wang
Existing biodegradable plastics encounter performance limitations and degrade slowly in natural environments, especially seawater. Incorporating degradation-promoting monomers can accelerate breakdown but often weakens polymer backbone bonds and reduces crystallinity, sacrificing strength. Consequently, materials with both high strength and rapid degradability are currently missing. This study addresses this issue by enhancing intermolecular interactions in polymers to compensate for reduced mechanical strength. First, adipic acid, a long-chain aliphatic monomer, is introduced into non-degradable PET as a molecular chain flexibility regulator. Using fluorescence screening, polyethylene adipate-co-terephthalate (PEAT) with an optimal A/T ratio of 30/70, demonstrating the strongest intermolecular interactions, is selected as the base material. Glycolic (GA) and lactic (LA) acid are then incorporated as easily hydrolysable sites to synthesis PEATG and PEATL copolyesters. Despite being amorphous, these copolyesters maintain high mechanical strength (up to 70 MPa). Hydroxy acid incorporation accelerates hydrolysis, enabling rapid degradation in seawater and compost environments, especially in PEATG copolyesters. For example, after 238 days in seawater, the molecular weight of PEATG120 (69.9 MPa) drops below 103 g mol−1. After 122 days of composting, PEATG80 (58.5 MPa) and PEATL80 (61.3 MPa) achieve mineralization rates of 43.6 % and 19.1 %, respectively. This approach enables high-strength, fast-degrading materials for natural environments.
现有的可生物降解塑料在自然环境特别是海水中存在性能限制和降解缓慢的问题。加入促进降解的单体可以加速分解，但往往会削弱聚合物的主键，降低结晶度，从而牺牲强度。因此，目前缺乏具有高强度和快速降解性的材料。本研究通过增强聚合物中的分子间相互作用来弥补机械强度的降低，从而解决了这一问题。首先，将长链脂肪族单体己二酸作为分子链柔韧性调节剂引入不可降解PET中。通过荧光筛选，选择具有最强分子间相互作用的最佳A/T比为30/70的聚己二甲酸乙二醇酯（PEAT）作为基础材料。然后将乙醇酸（GA）和乳酸（LA）作为易水解位点掺入合成PEATG和PEATL共聚酯。尽管是无定形的，这些共聚酯保持高机械强度（高达70兆帕）。羟基酸的掺入加速了水解，使其能够在海水和堆肥环境中快速降解，特别是在PEATG共聚酯中。例如，在海水中浸泡238天后，PEATG120的分子量（69.9 MPa）降至103 g mol−1以下。经过122 d的堆肥处理，PEATG80 （58.5 MPa）和peat80 （61.3 MPa）的矿化率分别达到43.6%和19.1%。这种方法使高强度、快速降解的材料适用于自然环境。
{"title":"Breaking the strength-degradability trade-off in PET-based copolyesters via enhanced intermolecular interactions and embedding easily hydrolysable sites","authors":"Tian Y. Liu , Wei J. Zhang , Tian C. Shi , Ze Y. Zhang , Zhi C. Zhen , Ping L. Wang , Xiu B. Yang , Dan Huang , Jun H. Ji , Ge X. Wang","doi":"10.1016/j.polymdegradstab.2025.111855","DOIUrl":"10.1016/j.polymdegradstab.2025.111855","url":null,"abstract":"<div><div>Existing biodegradable plastics encounter performance limitations and degrade slowly in natural environments, especially seawater. Incorporating degradation-promoting monomers can accelerate breakdown but often weakens polymer backbone bonds and reduces crystallinity, sacrificing strength. Consequently, materials with both high strength and rapid degradability are currently missing. This study addresses this issue by enhancing intermolecular interactions in polymers to compensate for reduced mechanical strength. First, adipic acid, a long-chain aliphatic monomer, is introduced into non-degradable PET as a molecular chain flexibility regulator. Using fluorescence screening, polyethylene adipate-co-terephthalate (PEAT) with an optimal A/T ratio of 30/70, demonstrating the strongest intermolecular interactions, is selected as the base material. Glycolic (GA) and lactic (LA) acid are then incorporated as easily hydrolysable sites to synthesis PEATG and PEATL copolyesters. Despite being amorphous, these copolyesters maintain high mechanical strength (up to 70 MPa). Hydroxy acid incorporation accelerates hydrolysis, enabling rapid degradation in seawater and compost environments, especially in PEATG copolyesters. For example, after 238 days in seawater, the molecular weight of PEATG120 (69.9 MPa) drops below 10<sup>3</sup> g mol<sup>−1</sup>. After 122 days of composting, PEATG80 (58.5 MPa) and PEATL80 (61.3 MPa) achieve mineralization rates of 43.6 % and 19.1 %, respectively. This approach enables high-strength, fast-degrading materials for natural environments.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111855"},"PeriodicalIF":7.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145789188","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}
Pub Date : 2026-03-01Epub Date: 2025-12-15DOI: 10.1016/j.polymdegradstab.2025.111857
Ákos Pomázi , Gergely Magyar , Andrea Toldy
Destructive tests are typically used to evaluate the fire performance of polymers and their composites, implying high material costs and long testing times. Developing numerical models to predict flammability requires advanced mathematical expertise, IT resources, and realistic input parameters. In this study, we aimed to predict the key flammability parameters based on the chemical structure of the resin matrices and fibre content of composites, providing a potential alternative to costly experimental methods. We employed Random Forest Classifier (RFC), XGBoost algorithms, and an artificial neural network (ANN) model to predict key combustion parameters: peak heat release rate (pHRR), time to ignition (TTI), total heat release (THR) and the char residue (CR) solely based on chemical structure of the epoxy matrix and fibre content of the composite. After making the predictions, we assessed the performance of the models using consistent statistical indicators (mean absolute error (MAE), mean square error (MSE), and the determination parameter (R2)).
{"title":"Methods for predicting the fire behaviour of fibre reinforced thermoset composites","authors":"Ákos Pomázi , Gergely Magyar , Andrea Toldy","doi":"10.1016/j.polymdegradstab.2025.111857","DOIUrl":"10.1016/j.polymdegradstab.2025.111857","url":null,"abstract":"<div><div>Destructive tests are typically used to evaluate the fire performance of polymers and their composites, implying high material costs and long testing times. Developing numerical models to predict flammability requires advanced mathematical expertise, IT resources, and realistic input parameters. In this study, we aimed to predict the key flammability parameters based on the chemical structure of the resin matrices and fibre content of composites, providing a potential alternative to costly experimental methods. We employed Random Forest Classifier (RFC), XGBoost algorithms, and an artificial neural network (ANN) model to predict key combustion parameters: peak heat release rate (pHRR), time to ignition (TTI), total heat release (THR) and the char residue (CR) solely based on chemical structure of the epoxy matrix and fibre content of the composite. After making the predictions, we assessed the performance of the models using consistent statistical indicators (mean absolute error (MAE), mean square error (MSE), and the determination parameter (R<sup>2</sup>)).</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111857"},"PeriodicalIF":7.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145789249","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}
Pub Date : 2026-03-01Epub Date: 2025-12-23DOI: 10.1016/j.polymdegradstab.2025.111878
Ruiqi Shao , Youxiang Qiu , Gaohui Wang , Tianshuai Ma , Nishonov Akbarjon , Tianyu Li , Amna Siddique , Shouguo Liu , Xiaoyuan Pei , Zhiwei Xu
Polyacrylonitrile (PAN)-based carbon fibers exhibit mechanical properties affected by structural evolution of microfibrils during pre-oxidation. Irradiation can effectively regulate microstructure and enhance the pre-oxidation effect of fibers. To precisely evaluate the effect of irradiation dose on microfibrils, synchrotron-based ultra-small-angle X-ray scattering (USAXS), in combination with small angle X-ray scattering and wide angle X-ray scattering, was employed. Results reveal that γ-irradiation induces dose-dependent structural modifications in the microfibril network, which is governed by the evolution of microporous structures and crystalline order in PAN fibers. At low-dose irradiation (≤100 kGy), cross-linking dominates, resulting in pore compression, improved orientation angle of microfibrils (from 7.26 to 6.21°).
In contrast, high doses (≥200 kGy) lead to chain scission, pore coarsening, and loss of microfibrils orientation. During irradiation fiber heat treatment, microfibrils evolution occurs in three stages and is regulated by irradiation dose. Initially (180–220 °C), ordering of segments in the amorphous region causes an increase in microfibrils dimensions while maintaining high orientation. Low-dose irradiation provides support through crosslinking, whereas high doses weaken stability due to chain breakage. Intermediately (220–250 °C), cyclization reactions disrupt crystalline regions, causing microfibrils breakage and orientation disorder. The crosslinked network from low-dose irradiation suppresses chain slip and mitigates damage. In contrast, high doses amplify defects and exacerbate disruption. Finally (250–280 °C), trapezoidal structures are formed, driving lateral compression and axial rearrangement of microfibrils. Low-dose irradiation promotes ordered densification; high doses cause disorder and loosening. An optimal dose of 100 kGy concurrently optimizes microfibrillar and microporous morphology, enhancing thermal stability and carbon yield.
{"title":"Radiation-thermal coupling-driven dynamic restructuring of PAN microfibril: dose-response mechanism of γ-irradiation pre-oxidation revealed by synchrotron radiation USAXS","authors":"Ruiqi Shao , Youxiang Qiu , Gaohui Wang , Tianshuai Ma , Nishonov Akbarjon , Tianyu Li , Amna Siddique , Shouguo Liu , Xiaoyuan Pei , Zhiwei Xu","doi":"10.1016/j.polymdegradstab.2025.111878","DOIUrl":"10.1016/j.polymdegradstab.2025.111878","url":null,"abstract":"<div><div>Polyacrylonitrile (PAN)-based carbon fibers exhibit mechanical properties affected by structural evolution of microfibrils during pre-oxidation. Irradiation can effectively regulate microstructure and enhance the pre-oxidation effect of fibers. To precisely evaluate the effect of irradiation dose on microfibrils, synchrotron-based ultra-small-angle X-ray scattering (USAXS), in combination with small angle X-ray scattering and wide angle X-ray scattering, was employed. Results reveal that γ-irradiation induces dose-dependent structural modifications in the microfibril network, which is governed by the evolution of microporous structures and crystalline order in PAN fibers. At low-dose irradiation (≤100 kGy), cross-linking dominates, resulting in pore compression, improved orientation angle of microfibrils (from 7.26 to 6.21°).</div><div>In contrast, high doses (≥200 kGy) lead to chain scission, pore coarsening, and loss of microfibrils orientation. During irradiation fiber heat treatment, microfibrils evolution occurs in three stages and is regulated by irradiation dose. Initially (180–220 °C), ordering of segments in the amorphous region causes an increase in microfibrils dimensions while maintaining high orientation. Low-dose irradiation provides support through crosslinking, whereas high doses weaken stability due to chain breakage. Intermediately (220–250 °C), cyclization reactions disrupt crystalline regions, causing microfibrils breakage and orientation disorder. The crosslinked network from low-dose irradiation suppresses chain slip and mitigates damage. In contrast, high doses amplify defects and exacerbate disruption. Finally (250–280 °C), trapezoidal structures are formed, driving lateral compression and axial rearrangement of microfibrils. Low-dose irradiation promotes ordered densification; high doses cause disorder and loosening. An optimal dose of 100 kGy concurrently optimizes microfibrillar and microporous morphology, enhancing thermal stability and carbon yield.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111878"},"PeriodicalIF":7.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881198","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}
Pub Date : 2026-03-01Epub Date: 2025-12-27DOI: 10.1016/j.polymdegradstab.2025.111898
Hongbo Zhao , Rongjia Li , Hongkang Wang , Ziyao Wang , Qianyun Zhong , Shaofeng Wang , Hui Li , Chuanmei Jiao , Xilei Chen , Shouke Yan
Utilizing the adsorptivity of porous materials or the barrier effect of physical structures to prevent the spread of leaked substances is currently a crucial method for addressing hazardous chemical leaks. In this study, a superhydrophobic and flame-retardant polyurethane sponge (designated as Si@PBA@MBN@PU) was fabricated via a layer-by-layer self-assembly approach. During the preparation process, hexagon boron nitride (BN) modified with bio-based tannic acid (TA) and phytic acid (PA) was first loaded onto the sponge skeleton, followed by the firm anchoring of Prussian blue analog (CoFe-PBA) on the surface of the skeleton. This sponge exhibits excellent flame-retardant performance: cone calorimetry test (CCT) demonstrated with the mass proportion of combustion residues increased by 19.1% and the heat release rate (HHR), smoke production rate (SPR), and total smoke production (TSP) decreased by 41.6%, 41.3%, and 50.1% respectively, while the production rates of carbon monoxide (COP) and carbon dioxide (CO2P) decreased by 21.6% and 23.7% respectively. Additionally, the sponge possesses outstanding durability, demulsification capability, and superhydrophobicity. Specifically, it exhibits superhydrophobicity with a water contact angle (WCA) of 153° and an oil adsorption capacity ranging from 38.3 to 76.3 g/g. Overall, the sponge not only enhances flame retardancy but also reduces environmental pollution, providing a novel, safe, and environmentally friendly solution for handling hazardous chemical leakage incidents.
{"title":"Novel strategy for flame-retardant superhydrophobic polyurethane sponge preparation via layer-by-layer self-assembly and its practical application","authors":"Hongbo Zhao , Rongjia Li , Hongkang Wang , Ziyao Wang , Qianyun Zhong , Shaofeng Wang , Hui Li , Chuanmei Jiao , Xilei Chen , Shouke Yan","doi":"10.1016/j.polymdegradstab.2025.111898","DOIUrl":"10.1016/j.polymdegradstab.2025.111898","url":null,"abstract":"<div><div>Utilizing the adsorptivity of porous materials or the barrier effect of physical structures to prevent the spread of leaked substances is currently a crucial method for addressing hazardous chemical leaks. In this study, a superhydrophobic and flame-retardant polyurethane sponge (designated as Si@PBA@MBN@PU) was fabricated via a layer-by-layer self-assembly approach. During the preparation process, hexagon boron nitride (BN) modified with bio-based tannic acid (TA) and phytic acid (PA) was first loaded onto the sponge skeleton, followed by the firm anchoring of Prussian blue analog (CoFe-PBA) on the surface of the skeleton. This sponge exhibits excellent flame-retardant performance: cone calorimetry test (CCT) demonstrated with the mass proportion of combustion residues increased by 19.1% and the heat release rate (HHR), smoke production rate (SPR), and total smoke production (TSP) decreased by 41.6%, 41.3%, and 50.1% respectively, while the production rates of carbon monoxide (COP) and carbon dioxide (CO<sub>2</sub>P) decreased by 21.6% and 23.7% respectively. Additionally, the sponge possesses outstanding durability, demulsification capability, and superhydrophobicity. Specifically, it exhibits superhydrophobicity with a water contact angle (WCA) of 153° and an oil adsorption capacity ranging from 38.3 to 76.3 g/g. Overall, the sponge not only enhances flame retardancy but also reduces environmental pollution, providing a novel, safe, and environmentally friendly solution for handling hazardous chemical leakage incidents.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111898"},"PeriodicalIF":7.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881164","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}
Pub Date : 2026-03-01Epub Date: 2025-12-27DOI: 10.1016/j.polymdegradstab.2025.111897
Ziying Zheng , Keqing Zhou , Changhao Wang , Yulun Zhang , Bin Yu , Sheng Zhang
Epoxy resin (EP) is extensively employed in construction on account of its exceptional comprehensive performance. However, its inherent fire hazards and insufficient mechanical properties pose significant safety issues. In this study, a CPM (CeHPP@PDA@MoS₂) hybrid material with hierarchical architectures was constructed using electrostatically driven self-assembly technology. Following the introduction of 2D rare-earth metal phenylphosphate (CeHPP) into the graphene analogue MoS₂ via PDA surface functionalization, the PDA-induced hierarchical structure effectively mitigated the stacking and re-agglomeration of MoS₂. Moreover, it significantly enhanced the interfacial adhesion between MoS₂ and EP, thus leading to notable improvements in the thermal stability, flame retardancy, and mechanical performance of EP composites. Relative to pure EP, the peak heat release rate (PHRR), total heat release (THR), peak smoke production rate (PSPR), and total smoke production (TSP) of the EP/CPM 2.0 composite showed marked decreases, by 46.6 %, 21.1 %, 39.8 %, and 45.4 %, respectively. Furthermore, the char yield of the EP composites demonstrated a growth to 25 %, up from an initial 7 %. The flexural and tensile strengths of the EP/CPM 2.0 composites were reinforced by 40.8 % and 31.6 %, respectively. The flame retardant and mechanical reinforcement mechanisms were explored. This research identifies a novel methodological avenue for engineering high-performance epoxy composites.
{"title":"Construction of hierarchical architectures with 2D rare earth metal phenylphosphate and graphene analogues for high-performance flame-retardant epoxy composites","authors":"Ziying Zheng , Keqing Zhou , Changhao Wang , Yulun Zhang , Bin Yu , Sheng Zhang","doi":"10.1016/j.polymdegradstab.2025.111897","DOIUrl":"10.1016/j.polymdegradstab.2025.111897","url":null,"abstract":"<div><div>Epoxy resin (EP) is extensively employed in construction on account of its exceptional comprehensive performance. However, its inherent fire hazards and insufficient mechanical properties pose significant safety issues. In this study, a CPM (CeHPP@PDA@MoS₂) hybrid material with hierarchical architectures was constructed using electrostatically driven self-assembly technology. Following the introduction of 2D rare-earth metal phenylphosphate (CeHPP) into the graphene analogue MoS₂ via PDA surface functionalization, the PDA-induced hierarchical structure effectively mitigated the stacking and re-agglomeration of MoS₂. Moreover, it significantly enhanced the interfacial adhesion between MoS₂ and EP, thus leading to notable improvements in the thermal stability, flame retardancy, and mechanical performance of EP composites. Relative to pure EP, the peak heat release rate (PHRR), total heat release (THR), peak smoke production rate (PSPR), and total smoke production (TSP) of the EP/CPM 2.0 composite showed marked decreases, by 46.6 %, 21.1 %, 39.8 %, and 45.4 %, respectively. Furthermore, the char yield of the EP composites demonstrated a growth to 25 %, up from an initial 7 %. The flexural and tensile strengths of the EP/CPM 2.0 composites were reinforced by 40.8 % and 31.6 %, respectively. The flame retardant and mechanical reinforcement mechanisms were explored. This research identifies a novel methodological avenue for engineering high-performance epoxy composites.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111897"},"PeriodicalIF":7.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881249","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}
Pub Date : 2026-03-01Epub Date: 2025-12-27DOI: 10.1016/j.polymdegradstab.2025.111881
Shuangjiang He , Zhong Zeng , Hui Liu , Shaowei Chen , Lin Gan , Youquan Ling , Shuai Li , Long Ni , Xiaowen Zhao , Mei Liang , Yang Chen , Huawei Zou
To overcome the inherent limitations of conventional low-molecular-weight antioxidants for rubber, such as pronounced migration propensity, inadequate long-term antioxidative efficiency, and potential toxicological or environmental hazards, this work, for the first time, reports the synthesis of a biomass-derived poly(tannic acid)-based antioxidant (PTRB) featuring hierarchical antioxidative moieties (aniline groups from N-phenyl-p-phenylenediamine, phenolic hydroxyls from tannic acid, and thioether-based secondary antioxidative moieties from 2-mercaptobenzimidazole). Comprehensive characterizations, which combining experimental methodologies, molecular dynamics (MD) simulations, and quantum mechanics (QM) simulations, elucidated the regulatory roles of PTRB on the thermo-oxidative aging resistance, solubility, dispersibility, diffusivity, and protective mechanisms of nitrile butadiene rubber (NBR). In comparison with commercial antioxidants, PTRB significantly enhances the aging resistance of NBR composites, with the aging performance exhibiting improvements ranging from 24% to 267% (quantified by the aging coefficient K following accelerated aging at 121°C for 120 h). QM simulations demonstrated that the aniline moiety significantly enhances the radical-scavenging capacity of the PTRB. Meanwhile, the thioether moiety offers additional synergistic protection through the degradation of peroxyl radicals (ROO·) into stable alcohols. MD simulations further confirmed that the PTRB/NBR composites display superior interfacial interactions, resulting in higher binding energy. This, in turn, this improves the solubility and dispersibility of PTRB within the NBR matrix and reduces its diffusion coefficient. Furthermore, PTRB effectively promotes the vulcanization of NBR by regulating the sulfide cross-linking structure and further enhances the interfacial compatibility between the filler and the rubber. Consequently, this study introduces a sustainable, biomass-derived, multi-mechanistic antioxidant. This antioxidant possesses considerable significance for the fabrication of NBR composites with long-term and high aging resistance, thereby addressing the crucial challenges encountered by conventional low-molecular-weight antioxidants in practical applications.
{"title":"Multi-mechanism biomass-derived poly(tannic acid)-based antioxidant (PTRB) for enhanced the thermo-oxidative resistance of NBR: Insights from experiments and molecular simulations","authors":"Shuangjiang He , Zhong Zeng , Hui Liu , Shaowei Chen , Lin Gan , Youquan Ling , Shuai Li , Long Ni , Xiaowen Zhao , Mei Liang , Yang Chen , Huawei Zou","doi":"10.1016/j.polymdegradstab.2025.111881","DOIUrl":"10.1016/j.polymdegradstab.2025.111881","url":null,"abstract":"<div><div>To overcome the inherent limitations of conventional low-molecular-weight antioxidants for rubber, such as pronounced migration propensity, inadequate long-term antioxidative efficiency, and potential toxicological or environmental hazards, this work, for the first time, reports the synthesis of a biomass-derived poly(tannic acid)-based antioxidant (PTRB) featuring hierarchical antioxidative moieties (aniline groups from N-phenyl-p-phenylenediamine, phenolic hydroxyls from tannic acid, and thioether-based secondary antioxidative moieties from 2-mercaptobenzimidazole). Comprehensive characterizations, which combining experimental methodologies, molecular dynamics (MD) simulations, and quantum mechanics (QM) simulations, elucidated the regulatory roles of PTRB on the thermo-oxidative aging resistance, solubility, dispersibility, diffusivity, and protective mechanisms of nitrile butadiene rubber (NBR). In comparison with commercial antioxidants, PTRB significantly enhances the aging resistance of NBR composites, with the aging performance exhibiting improvements ranging from 24% to 267% (quantified by the aging coefficient <em>K</em> following accelerated aging at 121°C for 120 h). QM simulations demonstrated that the aniline moiety significantly enhances the radical-scavenging capacity of the PTRB. Meanwhile, the thioether moiety offers additional synergistic protection through the degradation of peroxyl radicals (ROO·) into stable alcohols. MD simulations further confirmed that the PTRB/NBR composites display superior interfacial interactions, resulting in higher binding energy. This, in turn, this improves the solubility and dispersibility of PTRB within the NBR matrix and reduces its diffusion coefficient. Furthermore, PTRB effectively promotes the vulcanization of NBR by regulating the sulfide cross-linking structure and further enhances the interfacial compatibility between the filler and the rubber. Consequently, this study introduces a sustainable, biomass-derived, multi-mechanistic antioxidant. This antioxidant possesses considerable significance for the fabrication of NBR composites with long-term and high aging resistance, thereby addressing the crucial challenges encountered by conventional low-molecular-weight antioxidants in practical applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111881"},"PeriodicalIF":7.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922155","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}
Pub Date : 2026-03-01Epub Date: 2025-12-27DOI: 10.1016/j.polymdegradstab.2025.111899
Nannan Xu , Jizhe Xiao , Zheng Kuang , Tian Niu , Na Zhang , Yuetao Liu , Chuanhui Gao
Poly(vinyl chloride) (PVC) is inherently rigid due to strong interchain dipole–dipole interactions, and therefore requires plasticizers to improve its flexibility and processability. Conventional small-molecule plasticizers such as dioctyl phthalate (DOP) and tributyl citrate (TBC) offer high plasticizing efficiency but suffer from severe migration and poor flame retardancy. In this study, phosphate groups were introduced via a phosphorus oxychloride–hydroxyl substitution strategy, and the plasticizing behavior was further tuned by tailoring the ester-bond density to achieve a synergy between flexibility and flame retardancy. Results reveal that a balanced distribution of polar groups is crucial for effective plasticization: overly dense polar sites restrict chain mobility, whereas overly sparse sites weaken interfacial interactions. Polyester plasticizer poly(butylene adipate) (PBA), featuring an optimal balance of polarity and chain flexibility, increased the plasticizing efficiency to 156.8% and enabled simultaneous enhancement of tensile strength and elongation. After incorporating phosphate units, the efficiency further rose to 172.7%, while the limiting oxygen index improved from 28% to 32%. The synergistic interactions between ester and P=O groups effectively attenuate PVC dipole–dipole forces, promote chain unlocking, and thus realize cooperative improvements in flexibility and flame retardancy. This work provides new insight for developing high-efficiency flame-retardant PVC plasticizers.
{"title":"Performance-synergistic polyester plasticizers for achieving a flexibility–flame-retardancy balance in PVC","authors":"Nannan Xu , Jizhe Xiao , Zheng Kuang , Tian Niu , Na Zhang , Yuetao Liu , Chuanhui Gao","doi":"10.1016/j.polymdegradstab.2025.111899","DOIUrl":"10.1016/j.polymdegradstab.2025.111899","url":null,"abstract":"<div><div>Poly(vinyl chloride) (PVC) is inherently rigid due to strong interchain dipole–dipole interactions, and therefore requires plasticizers to improve its flexibility and processability. Conventional small-molecule plasticizers such as dioctyl phthalate (DOP) and tributyl citrate (TBC) offer high plasticizing efficiency but suffer from severe migration and poor flame retardancy. In this study, phosphate groups were introduced via a phosphorus oxychloride–hydroxyl substitution strategy, and the plasticizing behavior was further tuned by tailoring the ester-bond density to achieve a synergy between flexibility and flame retardancy. Results reveal that a balanced distribution of polar groups is crucial for effective plasticization: overly dense polar sites restrict chain mobility, whereas overly sparse sites weaken interfacial interactions. Polyester plasticizer poly(butylene adipate) (PBA), featuring an optimal balance of polarity and chain flexibility, increased the plasticizing efficiency to 156.8% and enabled simultaneous enhancement of tensile strength and elongation. After incorporating phosphate units, the efficiency further rose to 172.7%, while the limiting oxygen index improved from 28% to 32%. The synergistic interactions between ester and <em>P</em>=<em>O</em> groups effectively attenuate PVC dipole–dipole forces, promote chain unlocking, and thus realize cooperative improvements in flexibility and flame retardancy. This work provides new insight for developing high-efficiency flame-retardant PVC plasticizers.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111899"},"PeriodicalIF":7.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922156","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}
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