Pub Date : 2026-01-05DOI: 10.1016/j.polymdegradstab.2026.111926
Hongshan Li , Xu Zhang , Kelu Ni , Tongda Liu , Tenghua Huang , Hongxing Yang , Xin Ran , Guanben Du , Long Yang
The widespread use of petroleum-based plastics depletes finite fossil resources, exacerbates ecological degradation, and poses persistent environmental threats. Furthermore, these materials are flammable and emit toxic gases upon combustion, creating significant safety risks. Thus, developing recyclable, flame-retardant polymers is a pressing research challenge. Herein, a tough film was prepared from a binary aqueous solution of the natural polymer sodium alginate and tetrahydroxydiborane. The C–O–B dynamic bonds in the polymer film contribute significantly to the enhanced mechanical properties of the material, while boron simultaneously acts as a flame retardant, improving the overall flame retardancy. The optimized film demonstrated outstanding mechanical performance and flame retardancy, exhibiting a tensile strength of 88.38 MPa, a Young’s modulus of 3.2 GPa, a toughness of 3.17 MJ·m-3, a limiting oxygen index of 42%, and a V-0 flame retardancy rating. Moreover, the material maintained its excellent mechanical and flame-retardant properties after simple recycling and reprocessing, enabling the reuse of waste films. Its biodegradability further enhances the overall sustainability. This study provides a viable strategy for developing sustainable natural polymers as environmentally friendly alternatives to conventional petroleum-based polymers.
{"title":"A dynamically crosslinked biomass film featuring high flame retardancy, excellent thermal stability, closed-loop recyclability, and biodegradability","authors":"Hongshan Li , Xu Zhang , Kelu Ni , Tongda Liu , Tenghua Huang , Hongxing Yang , Xin Ran , Guanben Du , Long Yang","doi":"10.1016/j.polymdegradstab.2026.111926","DOIUrl":"10.1016/j.polymdegradstab.2026.111926","url":null,"abstract":"<div><div>The widespread use of petroleum-based plastics depletes finite fossil resources, exacerbates ecological degradation, and poses persistent environmental threats. Furthermore, these materials are flammable and emit toxic gases upon combustion, creating significant safety risks. Thus, developing recyclable, flame-retardant polymers is a pressing research challenge. Herein, a tough film was prepared from a binary aqueous solution of the natural polymer sodium alginate and tetrahydroxydiborane. The C–O–B dynamic bonds in the polymer film contribute significantly to the enhanced mechanical properties of the material, while boron simultaneously acts as a flame retardant, improving the overall flame retardancy. The optimized film demonstrated outstanding mechanical performance and flame retardancy, exhibiting a tensile strength of 88.38 MPa, a Young’s modulus of 3.2 GPa, a toughness of 3.17 MJ·m<sup>-3</sup>, a limiting oxygen index of 42%, and a V-0 flame retardancy rating. Moreover, the material maintained its excellent mechanical and flame-retardant properties after simple recycling and reprocessing, enabling the reuse of waste films. Its biodegradability further enhances the overall sustainability. This study provides a viable strategy for developing sustainable natural polymers as environmentally friendly alternatives to conventional petroleum-based polymers.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"246 ","pages":"Article 111926"},"PeriodicalIF":7.4,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908895","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 : 2026-01-02DOI: 10.1016/j.polymdegradstab.2026.111920
Dong Shi , Yanbei Hou , Shuming Liu , Xu Chang , Yuan Hu
To address the escalating safety concerns of conventional silicone encapsulants and improve the thermal conductivity and flame retardancy of silicones for high-power LED packaging, this research introduces hexagonal boron nitride (h-BN) as a functional filler. Through ball milling–ultrasonic dispersion, h-BN was integrated into a two-component silicone system at mass fractions ranging from 0.25 to 0.75 wt% and subsequently cured into composite materials. The synergistic influence of BN on the mechanical, thermal, and combustion properties of the composites was systematically examined. Results show that at 0.25–0.5 wt%, BN disperses uniformly, increasing thermal conductivity from 0.182 to 0.2565 W·m⁻¹·K⁻¹ (an improvement of approximately 40.9%), while tensile strength rises by about 27.6% compared to pure silicone, with elongation at break largely preserved. Cone calorimetry tests reveal a significant reduction in peak heat release rate (pHRR) from 749.56 to 256.58 kW·m⁻² (around 65.8%), along with a 21.5% decrease in total heat release (THR), accompanied by suppressed smoke and CO emissions, and no observable dripping in vertical burning tests. Mechanistic analysis suggests that h-BN forms a dense protective barrier during combustion, facilitates heat dissipation, and captures free radicals, thereby inhibiting chain combustion reactions and achieving a synergistic enhancement of thermal conductivity and flame retardancy at very low filler loadings. This work provides a feasible strategy for the development of high-performance electronic encapsulation materials with improved thermal management and fire safety.
{"title":"Flame retardancy of boron nitride-reinforced silicone encapsulants: From material design to performance reinforcement","authors":"Dong Shi , Yanbei Hou , Shuming Liu , Xu Chang , Yuan Hu","doi":"10.1016/j.polymdegradstab.2026.111920","DOIUrl":"10.1016/j.polymdegradstab.2026.111920","url":null,"abstract":"<div><div>To address the escalating safety concerns of conventional silicone encapsulants and improve the thermal conductivity and flame retardancy of silicones for high-power LED packaging, this research introduces hexagonal boron nitride (h-BN) as a functional filler. Through ball milling–ultrasonic dispersion, h-BN was integrated into a two-component silicone system at mass fractions ranging from 0.25 to 0.75 wt% and subsequently cured into composite materials. The synergistic influence of BN on the mechanical, thermal, and combustion properties of the composites was systematically examined. Results show that at 0.25–0.5 wt%, BN disperses uniformly, increasing thermal conductivity from 0.182 to 0.2565 W·m⁻¹·K⁻¹ (an improvement of approximately 40.9%), while tensile strength rises by about 27.6% compared to pure silicone, with elongation at break largely preserved. Cone calorimetry tests reveal a significant reduction in peak heat release rate (pHRR) from 749.56 to 256.58 kW·m⁻² (around 65.8%), along with a 21.5% decrease in total heat release (THR), accompanied by suppressed smoke and CO emissions, and no observable dripping in vertical burning tests. Mechanistic analysis suggests that h-BN forms a dense protective barrier during combustion, facilitates heat dissipation, and captures free radicals, thereby inhibiting chain combustion reactions and achieving a synergistic enhancement of thermal conductivity and flame retardancy at very low filler loadings. This work provides a feasible strategy for the development of high-performance electronic encapsulation materials with improved thermal management and fire safety.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111920"},"PeriodicalIF":7.4,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922116","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 : 2026-01-01DOI: 10.1016/j.polymdegradstab.2025.111918
Yu-Chiung Li , Po-Yi Lu , Yan-Cheng Lin , Wen-Chang Chen
Poly(butylene terephthalate) (PBT) is a widely used polymer in the plastics industry. However, its waste is resistant to natural degradation, posing environmental concerns. Conventional physical recycling can extend service life but often compromises material properties, making it difficult to achieve a sustainable solution. In contrast, glycolysis offers a high-value and environmentally friendly route for recycling waste polyesters. Among various catalysts, deep eutectic solvents (DESs) have gained increasing attention in glycolysis research due to their high efficiency, sustainability, and ease of preparation. Most reported studies focus on DESs composed of metal catalysts and third-party hydrogen bond donors (e.g., choline salts, amines, or urea derivatives) for polyester depolymerization. To date, no literature has reported the direct application of DESs from metal catalysts and reactant glycols in the glycolysis depolymerization. In this study, a DES was directly prepared by combining zinc chloride with reactant glycols (e.g., ethylene glycol and butane diol), serving simultaneously as solvent and catalyst without any additional components, and applied in the glycolysis of PBT. Both systems effectively promoted PBT glycolysis, with the ZnCl2/ethylene glycol system achieving the highest performance at 200 °C and a molar ratio beyond 1:8, yielding 88–100% conversion and up to 57% bis(2-hydroxyethyl) terephthalate. Kinetic analysis revealed that PBT depolymerization followed a first-order reaction model with an activation energy of 213 kJ mol–1. These findings confirm the feasibility of directly forming catalytic DESs and demonstrate their dual functionality in polyester depolymerization. Furthermore, the recovered bis(2-hydroxyethyl) terephthalate from ethylene glycol and bis(2-hydroxybutyl) terephthalate from butane diol were successfully repolymerized into polyesters, reducing dependence on virgin raw materials and enabling closed-loop recycling. From an economic perspective, this process offers sustainable viability by lowering both raw material procurement and waste management costs.
{"title":"Closed-loop recycling of polyesters through glycolysis using catalytic deep eutectic solvents and the influence of glycol types on reaction kinetics","authors":"Yu-Chiung Li , Po-Yi Lu , Yan-Cheng Lin , Wen-Chang Chen","doi":"10.1016/j.polymdegradstab.2025.111918","DOIUrl":"10.1016/j.polymdegradstab.2025.111918","url":null,"abstract":"<div><div>Poly(butylene terephthalate) (PBT) is a widely used polymer in the plastics industry. However, its waste is resistant to natural degradation, posing environmental concerns. Conventional physical recycling can extend service life but often compromises material properties, making it difficult to achieve a sustainable solution. In contrast, glycolysis offers a high-value and environmentally friendly route for recycling waste polyesters. Among various catalysts, deep eutectic solvents (DESs) have gained increasing attention in glycolysis research due to their high efficiency, sustainability, and ease of preparation. Most reported studies focus on DESs composed of metal catalysts and third-party hydrogen bond donors (e.g., choline salts, amines, or urea derivatives) for polyester depolymerization. To date, no literature has reported the direct application of DESs from metal catalysts and reactant glycols in the glycolysis depolymerization. In this study, a DES was directly prepared by combining zinc chloride with reactant glycols (e.g., ethylene glycol and butane diol), serving simultaneously as solvent and catalyst without any additional components, and applied in the glycolysis of PBT. Both systems effectively promoted PBT glycolysis, with the ZnCl<sub>2</sub>/ethylene glycol system achieving the highest performance at 200 °C and a molar ratio beyond 1:8, yielding 88–100% conversion and up to 57% bis(2-hydroxyethyl) terephthalate. Kinetic analysis revealed that PBT depolymerization followed a first-order reaction model with an activation energy of 213 kJ mol<sup>–1</sup>. These findings confirm the feasibility of directly forming catalytic DESs and demonstrate their dual functionality in polyester depolymerization. Furthermore, the recovered bis(2-hydroxyethyl) terephthalate from ethylene glycol and bis(2-hydroxybutyl) terephthalate from butane diol were successfully repolymerized into polyesters, reducing dependence on virgin raw materials and enabling closed-loop recycling. From an economic perspective, this process offers sustainable viability by lowering both raw material procurement and waste management costs.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111918"},"PeriodicalIF":7.4,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922159","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 : 2026-01-01DOI: 10.1016/j.polymdegradstab.2025.111916
Huihui Liu , Yu Zhang , Xinyi Xie , Xuzhen Zhang
In this paper, an efficient continuous glycolysis strategy for waste polyethylene terephthalate (PET) depolymerization was presented using a twin-screw extruder system with ethylene glycol (EG) and zinc acetate (Zn(OAc)2) catalyst. Under optimized conditions (150 rpm, controlled EG/PET ratio, and reaction parameters), PET was rapidly converted into well-defined oligomers (Mn = 1265-6588 Da) within minutes. Structural characterization (FT-IR, NMR, MALDI-TOF MS) confirmed hydroxyl-terminated bis(2-hydroxyethyl terephthalate) oligomer (BHET oligomer) as the dominant product. Selected oligomers (Mn = 1265 Da) were copolymerized with poly(tetramethylene ether) glycol (PTMG) to synthesize poly(ethylene terephthalate)- ε-poly(tetramethylene ether) glycol copolyetherester (PETMG). By tuning the oligomer/PTMG ratio, the resulting PETMG30 exhibited outstanding toughness (elongation at break: 1102%, impact strength: 105.6 kJ/m²). The developed “polymer-oligomer-polymer” approach significantly enhances processing efficiency and reduces reaction time compared to conventional methods, offering a sustainable pathway for high-value PET upcycling. This work advances circular economy practices by establishing a rapid, controllable recycling paradigm for plastic waste valorization.
{"title":"Continuous glycolysis of waste PET via reactive extrusion and copolymerization with PTMG for enhanced toughness","authors":"Huihui Liu , Yu Zhang , Xinyi Xie , Xuzhen Zhang","doi":"10.1016/j.polymdegradstab.2025.111916","DOIUrl":"10.1016/j.polymdegradstab.2025.111916","url":null,"abstract":"<div><div>In this paper, an efficient continuous glycolysis strategy for waste polyethylene terephthalate (PET) depolymerization was presented using a twin-screw extruder system with ethylene glycol (EG) and zinc acetate (Zn(OAc)<sub>2</sub>) catalyst. Under optimized conditions (150 rpm, controlled EG/PET ratio, and reaction parameters), PET was rapidly converted into well-defined oligomers (<em>M</em><sub>n</sub> = 1265-6588 Da) within minutes. Structural characterization (FT-IR, NMR, MALDI-TOF MS) confirmed hydroxyl-terminated bis(2-hydroxyethyl terephthalate) oligomer (BHET oligomer) as the dominant product. Selected oligomers (<em>M</em><sub>n</sub> = 1265 Da) were copolymerized with poly(tetramethylene ether) glycol (PTMG) to synthesize poly(ethylene terephthalate)- ε-poly(tetramethylene ether) glycol copolyetherester (PETMG). By tuning the oligomer/PTMG ratio, the resulting PETMG<sub>30</sub> exhibited outstanding toughness (elongation at break: 1102%, impact strength: 105.6 kJ/m²). The developed “polymer-oligomer-polymer” approach significantly enhances processing efficiency and reduces reaction time compared to conventional methods, offering a sustainable pathway for high-value PET upcycling. This work advances circular economy practices by establishing a rapid, controllable recycling paradigm for plastic waste valorization.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"246 ","pages":"Article 111916"},"PeriodicalIF":7.4,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974646","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 : 2025-12-31DOI: 10.1016/j.polymdegradstab.2025.111913
Lei Yu , Guochao Yang , Xuanye Wang , Zhengqiang Fan , Jian Fang , Jing He , Qiuhui Zhang
The intrinsic flammability and dense smoke emission of rigid polyurethane foam (RPUF) critically limit its applications. Herein, a multifunctional hybrid coating was constructed via an in-situ strategy, wherein phytic acid (PA) chelates with Fe/Ni-loaded ZSM-5 zeolite (Fe-Ni-Z). The resulting composite, RPUF@PA/Fe-Ni-Z, achieved a UL-94 V-0 rating and a limiting oxygen index of 35.1%, with its char residual yield at 800 °C increasing by a remarkable 1434.47%. Cone calorimetry revealed a 45.06% reduction in peak heat release rate and a 58.33% decrease in peak smoke production rate. This performance is attributed to a synergistic integration of condensed- and gas-phase mechanisms: PA promotes the formation of a phosphorus-rich char layer, which is structurally enhanced by Fe-Ni-Z, while the bimetallic sites catalytically oxidize CO and other toxic volatiles via the Mars-van Krevelen mechanism. The formation of a highly graphitized, Fe-Ni-Z-reinforced char layer was confirmed by Raman spectroscopy. This facile approach demonstrates a new paradigm for designing advanced fire safety materials that combines physical barrier protection with active catalytic detoxification, offering significant potential for improving fire safety in applications such as construction, packaging, and furniture.
硬质聚氨酯泡沫塑料（RPUF）固有的可燃性和浓烟排放严重限制了其应用。本文通过原位策略构建了一种多功能杂化涂层，其中植酸（PA）与负载Fe/ ni的ZSM-5沸石（Fe- ni - z）螯合。得到的复合材料RPUF@PA/Fe-Ni-Z达到UL-94的V-0等级，极限氧指数为35.1%，800℃时残余炭收率显著提高1434.47%。锥形量热法显示，峰值放热率降低了45.06%，峰值产烟率降低了58.33%。这种性能归因于凝聚和气相机制的协同整合：PA促进富磷炭层的形成，这是由Fe-Ni-Z结构增强的，而双金属位点通过Mars-van Krevelen机制催化氧化CO和其他有毒挥发性物质。拉曼光谱证实了铁-镍- z增强炭层的形成。这种简单的方法展示了一种设计先进消防安全材料的新范例，该材料将物理屏障保护与活性催化解毒相结合，为改善建筑、包装和家具等应用的消防安全提供了巨大的潜力。
{"title":"Phytic acid-chelated Fe/Ni bimetallic zeolite framework for catalytic detoxification and flame retardancy","authors":"Lei Yu , Guochao Yang , Xuanye Wang , Zhengqiang Fan , Jian Fang , Jing He , Qiuhui Zhang","doi":"10.1016/j.polymdegradstab.2025.111913","DOIUrl":"10.1016/j.polymdegradstab.2025.111913","url":null,"abstract":"<div><div>The intrinsic flammability and dense smoke emission of rigid polyurethane foam (RPUF) critically limit its applications. Herein, a multifunctional hybrid coating was constructed via an in-situ strategy, wherein phytic acid (PA) chelates with Fe/Ni-loaded ZSM-5 zeolite (Fe-Ni-Z). The resulting composite, RPUF@PA/Fe-Ni-Z, achieved a UL-94 V-0 rating and a limiting oxygen index of 35.1%, with its char residual yield at 800 °C increasing by a remarkable 1434.47%. Cone calorimetry revealed a 45.06% reduction in peak heat release rate and a 58.33% decrease in peak smoke production rate. This performance is attributed to a synergistic integration of condensed- and gas-phase mechanisms: PA promotes the formation of a phosphorus-rich char layer, which is structurally enhanced by Fe-Ni-Z, while the bimetallic sites catalytically oxidize CO and other toxic volatiles via the Mars-van Krevelen mechanism. The formation of a highly graphitized, Fe-Ni-Z-reinforced char layer was confirmed by Raman spectroscopy. This facile approach demonstrates a new paradigm for designing advanced fire safety materials that combines physical barrier protection with active catalytic detoxification, offering significant potential for improving fire safety in applications such as construction, packaging, and furniture.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111913"},"PeriodicalIF":7.4,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922081","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 : 2025-12-31DOI: 10.1016/j.polymdegradstab.2025.111919
Shuheng Wang , Congling Shi , Yanan Hou , Xiaodong Qian , Kaihao Wang , Jun Sun , Xiaoyu Gu , Sheng Zhang
High loading of flame retardants typically impairs the mechanical and thermal insulation properties of polypropylene foam (PPF). Herein, a silicone resin-based (poly-DDPM) coating containing expandable graphite (EG) and montmorillonite (MMT) was applied to PPF via brush painting, aiming to enhance flame retardancy while preserving intrinsic performance. At an ultra-low coating loading of ∼5 mg/cm², flammability evaluations revealed significant improvements. The limiting oxygen index (LOI) increased to 31% from 21% for pure PPF, UL 94 rating reached V-0, and peak heat release rate and peak smoke production rate decreased by 35.8% and 31.3%, respectively. Additionally, the compressive strength was improved by 14.3% with retained thermal insulation property, resolving the traditional fire safety-performance trade-off. When PP matrix suffered burning, poly-DDPM formed a continuous "Si-O"/"Si-C" network that suppressed melt dripping, creating a stable base for EG to expand into a "worm-like" char layer. This porous structure was further reinforced by MMT, which intercalated into the char to increase pore density, reduce pore size, and enhance phonon scattering during heat penetration. Collectively, these components built a robust barrier that blocked heat, oxygen, and fuel transfer. This coated PPF composite shows strong commercial potential in structural insulation and aerospace applications.
{"title":"Flame resistant polypropylene foam enabled by a silicone/expandable graphite/montmorillonite coating","authors":"Shuheng Wang , Congling Shi , Yanan Hou , Xiaodong Qian , Kaihao Wang , Jun Sun , Xiaoyu Gu , Sheng Zhang","doi":"10.1016/j.polymdegradstab.2025.111919","DOIUrl":"10.1016/j.polymdegradstab.2025.111919","url":null,"abstract":"<div><div>High loading of flame retardants typically impairs the mechanical and thermal insulation properties of polypropylene foam (PPF). Herein, a silicone resin-based (poly-DDPM) coating containing expandable graphite (EG) and montmorillonite (MMT) was applied to PPF via brush painting, aiming to enhance flame retardancy while preserving intrinsic performance. At an ultra-low coating loading of ∼5 mg/cm², flammability evaluations revealed significant improvements. The limiting oxygen index (LOI) increased to 31% from 21% for pure PPF, UL 94 rating reached V-0, and peak heat release rate and peak smoke production rate decreased by 35.8% and 31.3%, respectively. Additionally, the compressive strength was improved by 14.3% with retained thermal insulation property, resolving the traditional fire safety-performance trade-off. When PP matrix suffered burning, poly-DDPM formed a continuous \"Si-O\"/\"Si-C\" network that suppressed melt dripping, creating a stable base for EG to expand into a \"worm-like\" char layer. This porous structure was further reinforced by MMT, which intercalated into the char to increase pore density, reduce pore size, and enhance phonon scattering during heat penetration. Collectively, these components built a robust barrier that blocked heat, oxygen, and fuel transfer. This coated PPF composite shows strong commercial potential in structural insulation and aerospace applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"246 ","pages":"Article 111919"},"PeriodicalIF":7.4,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941233","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 : 2025-12-31DOI: 10.1016/j.polymdegradstab.2025.111912
Weichen Sheng , Min Zhong , Yi Liu , Junhong Zhang , Tiancheng Zhao , Fuping Xie , Kan Zhang
Conventional benzoxazines are largely limited by the dependence on non-renewable resources, insufficient thermal stability, and poor flame retardance properties. This study presents two high-performance monofuran-diamine-type difunctional bio-benzoxazine monomers (MDOPH-fda and DMOPH-fda), whiche were synthesized by reacting 2,5-bis(aminomethyl)furan and paraformaldehyde with either sesamol or 3,4-dimethoxyphenol. The benzoxazine structure was validated using FT-IR, 1H NMR, 13C NMR, HMQC NMR, and HR-MS. The polymerization behavior of the monomers was monitored by DSC and in situ FT-IR. The results demonstrated that the polymerization temperatures of the two benzoxazine monomers were close. The thermal stability and thermomechanical properties of polymers derived from the two benzoxazines were evaluated by TGA and DMA). Due to the monofuran-diamine linking structure that leads to the formation of two oxazine rings, both poly(MDOPH-fda) and poly(DMOPH-fda) exhibit good thermal stability. Their respective Td₁₀ values are 374.8 °C and 330.4 °C, and their char yields at 800 °C are 63.5% and 52.8%, respectively. Due to the benzodioxole structure, poly(MDOPH-fda) exhibit superior thermal stability. Regarding thermomechanical properties, the storage modulus of poly(MDOPH-fda) is 3364.8 MPa, while that of poly(DMOPH-fda) is 3856.1 MPa. Their glass transition temperatures (Tg) are 260 °C and 272 °C, respectively. While these values are close, both are higher than those of commercial benzoxazine resins. Experiments using a Microscale Combustion Calorimeter (MCC) and a vertical combustion test (UL-94) confirmed that the sesamol-based benzoxazine resin, poly(MDOPH-fda), exhibits excellent flame retardance. Its heat release capacity (HRC) is 38.7 J·g-1·K-1, and its total heat release (THR) is as low as 0.7 kJ·g-1, reaching the UL-94 V0 level in the vertical combustion test. Analyses of the surface morphology and chemical composition of the residues after combustion using Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS) and Raman Spectroscopy (LRS) show that poly(MDOPH-fda) is conducive to the formation of a dense graphitized carbon layer at high temperatures. This makies it a strong competitor in the field of high-performance flame-retardant resins.
{"title":"High performance intrinsically flame-retardant bio-benzoxazine resin derived from 2,5-furandimethylene amine and sesamol: Synthesis and investigations of structure-property relationship","authors":"Weichen Sheng , Min Zhong , Yi Liu , Junhong Zhang , Tiancheng Zhao , Fuping Xie , Kan Zhang","doi":"10.1016/j.polymdegradstab.2025.111912","DOIUrl":"10.1016/j.polymdegradstab.2025.111912","url":null,"abstract":"<div><div>Conventional benzoxazines are largely limited by the dependence on non-renewable resources, insufficient thermal stability, and poor flame retardance properties. This study presents two high-performance monofuran-diamine-type difunctional bio-benzoxazine monomers (MDOPH-fda and DMOPH-fda), whiche were synthesized by reacting 2,5-bis(aminomethyl)furan and paraformaldehyde with either sesamol or 3,4-dimethoxyphenol. The benzoxazine structure was validated using FT-IR, <sup>1</sup>H NMR, <sup>13</sup>C NMR, HMQC NMR, and HR-MS. The polymerization behavior of the monomers was monitored by DSC and in situ FT-IR. The results demonstrated that the polymerization temperatures of the two benzoxazine monomers were close. The thermal stability and thermomechanical properties of polymers derived from the two benzoxazines were evaluated by TGA and DMA). Due to the monofuran-diamine linking structure that leads to the formation of two oxazine rings, both poly(MDOPH-fda) and poly(DMOPH-fda) exhibit good thermal stability. Their respective Td₁₀ values are 374.8 °C and 330.4 °C, and their char yields at 800 °C are 63.5% and 52.8%, respectively. Due to the benzodioxole structure, poly(MDOPH-fda) exhibit superior thermal stability. Regarding thermomechanical properties, the storage modulus of poly(MDOPH-fda) is 3364.8 MPa, while that of poly(DMOPH-fda) is 3856.1 MPa. Their glass transition temperatures (Tg) are 260 °C and 272 °C, respectively. While these values are close, both are higher than those of commercial benzoxazine resins. Experiments using a Microscale Combustion Calorimeter (MCC) and a vertical combustion test (UL-94) confirmed that the sesamol-based benzoxazine resin, poly(MDOPH-fda), exhibits excellent flame retardance. Its heat release capacity (HRC) is 38.7 J·g<sup>-1</sup>·K<sup>-1</sup>, and its total heat release (THR) is as low as 0.7 kJ·g<sup>-1</sup>, reaching the UL-94 V0 level in the vertical combustion test. Analyses of the surface morphology and chemical composition of the residues after combustion using Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS) and Raman Spectroscopy (LRS) show that poly(MDOPH-fda) is conducive to the formation of a dense graphitized carbon layer at high temperatures. This makies it a strong competitor in the field of high-performance flame-retardant resins.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111912"},"PeriodicalIF":7.4,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922083","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 : 2025-12-31DOI: 10.1016/j.polymdegradstab.2025.111917
Bato Ch. Kholkhoev , Zakhar A. Matveev , Kseniia N. Bardakova , Nikolay A. Verlov , Anastasiya A. Akovantseva , Peter S. Timashev , Vitaliy F. Burdukovskii
Recently, high-temperature shape memory polymers containing benzimidazole units have attracted significant attention due to their potential applications in the aerospace industry. The space environment is highly complex, characterized by a range of extreme factors (temperature fluctuations, vacuum, and radiation exposure). This highlights the importance of investigating the durability of shape memory polybenzimidazoles under these demanding conditions. This study focuses on an accelerated examination of the effects of γ-radiation on shape memory polybenzimidazole derived from 3,3’-diaminobenzidine and sebacic acid (C8-PBI). The effects of γ-radiation on the chemical structure, thermal, mechanical, and thermomechanical properties, as well as the shape memory performance of C8-PBI, were investigated. It was found that γ-irradiation does not induce significant changes in the mechanical strength or glass transition temperature of C8-PBI compared to non-irradiated sample. Furthermore, C8-PBI maintains good shape memory performance, with both the shape fixity ratio and shape recovery ratio exceeding 89 %.
{"title":"The impact of γ-radiation on the properties of high-temperature shape memory polybenzimidazole","authors":"Bato Ch. Kholkhoev , Zakhar A. Matveev , Kseniia N. Bardakova , Nikolay A. Verlov , Anastasiya A. Akovantseva , Peter S. Timashev , Vitaliy F. Burdukovskii","doi":"10.1016/j.polymdegradstab.2025.111917","DOIUrl":"10.1016/j.polymdegradstab.2025.111917","url":null,"abstract":"<div><div>Recently, high-temperature shape memory polymers containing benzimidazole units have attracted significant attention due to their potential applications in the aerospace industry. The space environment is highly complex, characterized by a range of extreme factors (temperature fluctuations, vacuum, and radiation exposure). This highlights the importance of investigating the durability of shape memory polybenzimidazoles under these demanding conditions. This study focuses on an accelerated examination of the effects of γ-radiation on shape memory polybenzimidazole derived from 3,3’-diaminobenzidine and sebacic acid (C8-PBI). The effects of γ-radiation on the chemical structure, thermal, mechanical, and thermomechanical properties, as well as the shape memory performance of C8-PBI, were investigated. It was found that γ-irradiation does not induce significant changes in the mechanical strength or glass transition temperature of C8-PBI compared to non-irradiated sample. Furthermore, C8-PBI maintains good shape memory performance, with both the shape fixity ratio and shape recovery ratio exceeding 89 %.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111917"},"PeriodicalIF":7.4,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922115","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}
Poly[(d-lactate)-co-(R)-3-hydroxybutyrate] (LAHB) is a microbial copolyester that exhibits excellent environmental biodegradability. LAHB also functions as a multifunctional modifier that markedly improves both the mechanical properties and biodegradability of non-biodegradable poly(l-lactide) (PLLA). The lactate (LA) fraction is a key determinant governing the material properties of LAHB as well as its d-LA-l-LA-mediated interactions with PLLA. Then, in this study, we attempted to reinforce the gene expression of lactate-polymerizing enzyme (LPE) in the recombinant strain of Cupriavidus necator that was plausibly to be a rate-limiting factor for LA-unit incorporation. Expectedly, with the improved LA fraction, high-cell-density cultivation of the engineered strain GSXd147 synergistically achieved 97 g L⁻¹ dry cell weight and 70 wt% LAHB within 48 h from glucose—the highest LAHB titer and productivity reported to date. It should be noted that the resulting LA-enriched LAHB retained a high-molecular weight (15 mol% LA, Mw 30 × 104) and consequently exhibited a well-balanced combination of strength and elongation, yielding overall toughness comparable to the petroleum-based polyethylene.
聚[（d-乳酸）-co-(R)-3-羟基丁酸酯]（LAHB）是一种微生物共聚聚酯，具有良好的环境生物降解性。LAHB还可以作为多功能改性剂，显著改善非生物降解聚l-丙交酯（PLLA）的力学性能和生物降解性。乳酸（LA）部分是控制LAHB材料性能以及其与PLLA介导的相互作用的关键决定因素。然后，在本研究中，我们试图加强乳酸聚合酶（LPE）基因在重组菌株Cupriavidus necator中的表达，这可能是LA-unit掺入的限速因素。预料中，随着LA分数的提高，高密度培养的工程菌株GSXd147在48小时内协同达到97 g L - 1干细胞重和70 wt%的LAHB，这是迄今为止报道的最高的LAHB滴度和生产力。值得注意的是，最终得到的富含LA的LAHB保持了高分子量（15 mol% LA, Mw 30 × 104），因此表现出良好的强度和伸长率组合，其整体韧性可与石油基聚乙烯相媲美。
{"title":"Tough and biodegradable lactate (LA)-based polyester (LAHB) hyperproduced by reinforcing LA-polymerizing enzyme gene expression","authors":"Sangho Koh , Furutate Sho , Yusuke Imai , Shunsuke Sato , Seiichi Taguchi","doi":"10.1016/j.polymdegradstab.2025.111910","DOIUrl":"10.1016/j.polymdegradstab.2025.111910","url":null,"abstract":"<div><div>Poly[(<span>d</span>-lactate)-<em>co</em>-(<em>R</em>)-3-hydroxybutyrate] (LAHB) is a microbial copolyester that exhibits excellent environmental biodegradability. LAHB also functions as a multifunctional modifier that markedly improves both the mechanical properties and biodegradability of non-biodegradable poly(<span>l</span>-lactide) (PLLA). The lactate (LA) fraction is a key determinant governing the material properties of LAHB as well as its <span>d</span>-LA-<span>l</span>-LA-mediated interactions with PLLA. Then, in this study, we attempted to reinforce the gene expression of lactate-polymerizing enzyme (LPE) in the recombinant strain of <em>Cupriavidus necator</em> that was plausibly to be a rate-limiting factor for LA-unit incorporation. Expectedly, with the improved LA fraction, high-cell-density cultivation of the engineered strain GSXd147 synergistically achieved 97 g L⁻¹ dry cell weight and 70 wt% LAHB within 48 h from glucose—the highest LAHB titer and productivity reported to date. It should be noted that the resulting LA-enriched LAHB retained a high-molecular weight (15 mol% LA, <em>M</em><sub>w</sub> 30 × 10<sup>4</sup>) and consequently exhibited a well-balanced combination of strength and elongation, yielding overall toughness comparable to the petroleum-based polyethylene.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"246 ","pages":"Article 111910"},"PeriodicalIF":7.4,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974651","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}
The development of sustainable, durable and multifunctional silk textiles has attracted great attention. In this study, a novel reactive vitamin derivative, namely ammonium riboflavin phosphate salt (ARPS), was synthesized by using biomass-derived riboflavin sodium phosphate and urea. ARPS reacted with the hydroxyl and amino groups of silk through phosphate ester bonding and ionic bonding, while citric acid served as a secondary cross-linker for the carboxylic ester bond, forming a robust dual-network structure that covalently grafted ARPS onto silk fibers. This one-step dipping process enabled the construction of durable, photochromic, antibacterial and flame-retardant silk fabrics. The isoalloxazine ring in ARPS imparted reversible photochromic behavior and enhanced antibacterial efficacy, achieving a 98.2% inhibition rate against Escherichia coli. The combined phosphorus-nitrogen system conferred excellent flame retardancy, with a limiting oxygen index of 28.9% and a damaged length of only 4.9 cm in vertical burning tests. The fabrics maintained stable flame-retardant performance after 45 laundering cycles, confirming the high durability of the dual-crosslinked network. Char residue analyses indicated a condensed-phase flame-retardant mechanism for the modified silk. Overall, the multifunctional silk fabrics exhibit significant potential for sustainable, high-value textile applications, particularly in flame-retardant interior textiles, protective apparel, decorative fabrics, and smart textiles requiring integrated antibacterial and photochromic functionalities.
{"title":"Reactive vitamin derivative as multifunctional and durable strategy for silk fabric: Photochromic, antimicrobial and flame retardancy","authors":"Wei-Lin He, Wen-Jie Jin, Yu Xin, Xian-Wei Cheng, Jin-Ping Guan","doi":"10.1016/j.polymdegradstab.2025.111911","DOIUrl":"10.1016/j.polymdegradstab.2025.111911","url":null,"abstract":"<div><div>The development of sustainable, durable and multifunctional silk textiles has attracted great attention. In this study, a novel reactive vitamin derivative, namely ammonium riboflavin phosphate salt (ARPS), was synthesized by using biomass-derived riboflavin sodium phosphate and urea. ARPS reacted with the hydroxyl and amino groups of silk through phosphate ester bonding and ionic bonding, while citric acid served as a secondary cross-linker for the carboxylic ester bond, forming a robust dual-network structure that covalently grafted ARPS onto silk fibers. This one-step dipping process enabled the construction of durable, photochromic, antibacterial and flame-retardant silk fabrics. The isoalloxazine ring in ARPS imparted reversible photochromic behavior and enhanced antibacterial efficacy, achieving a 98.2% inhibition rate against Escherichia coli. The combined phosphorus-nitrogen system conferred excellent flame retardancy, with a limiting oxygen index of 28.9% and a damaged length of only 4.9 cm in vertical burning tests. The fabrics maintained stable flame-retardant performance after 45 laundering cycles, confirming the high durability of the dual-crosslinked network. Char residue analyses indicated a condensed-phase flame-retardant mechanism for the modified silk. Overall, the multifunctional silk fabrics exhibit significant potential for sustainable, high-value textile applications, particularly in flame-retardant interior textiles, protective apparel, decorative fabrics, and smart textiles requiring integrated antibacterial and photochromic functionalities.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111911"},"PeriodicalIF":7.4,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881199","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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