Pub Date : 2025-12-31DOI: 10.1016/j.polymdegradstab.2025.111914
Chao Deng , Feixiang Song , Zhirong Chen , Wanhui Wu , Xiangfei Zheng , Rongxian Ou , Lichao Sun , Xiaolong Hao , Tao Liu , Qingwen Wang
The inherent flammability of wood restricts its use as a fire-resistant construction material. To overcome this challenge, the development of environmentally friendly, bio-based flame-retardant wood coatings offers a promising solution. In this study, phytic acid was reacted with three kinds of amino acids to synthesize phytic acid-amino acid salt curing agents (APA, LPA, and HPA), which were subsequently incorporated into a melamine-urea-formaldehyde resin to produce transparent, intumescent flame-retardant wood coatings (designated AMP, LMP, and HMP). Experimental results indicate that the AMP coating exhibits superior water resistance and mechanical performance compared to HMP and LMP. Moreover, when the curing agents’ ratio exceeded 10%, the limiting oxygen index (LOI) surpassed 36%, and the UL-94 rating reached V-0. Cone calorimeter tests revealed that the time to ignition (TTI) for wood coated with AMP-4 was 189 s, a 63-fold increase relative to untreated wood. Furthermore, the total heat release (THR), peak smoke release rate (pSPR), and total smoke production (TSP) of AMP-4 coated wood were respectively reduced by 50.6%, 61.9%, and 38.3%, demonstrating exceptional flame-retardant performance. The proposed mechanism suggests that the flame-retardant coatings decomposes at elevated temperatures, releasing non-combustible gases and catalyzing the dehydration of carbohydrates, forming an expanded char layer that provides both thermal and oxygen barriers. The prepared wood coating effectively inhibits combustion in both condensed and gas phases. This study provides an environmentally friendly and viable approach for the practical application of bio-based flame-retardant wood coatings.
{"title":"Bio-based phytic acid-amino acid salt curing agents for high-performance, transparent, intumescent flame-retardant wood coatings","authors":"Chao Deng , Feixiang Song , Zhirong Chen , Wanhui Wu , Xiangfei Zheng , Rongxian Ou , Lichao Sun , Xiaolong Hao , Tao Liu , Qingwen Wang","doi":"10.1016/j.polymdegradstab.2025.111914","DOIUrl":"10.1016/j.polymdegradstab.2025.111914","url":null,"abstract":"<div><div>The inherent flammability of wood restricts its use as a fire-resistant construction material. To overcome this challenge, the development of environmentally friendly, bio-based flame-retardant wood coatings offers a promising solution. In this study, phytic acid was reacted with three kinds of amino acids to synthesize phytic acid-amino acid salt curing agents (APA, LPA, and HPA), which were subsequently incorporated into a melamine-urea-formaldehyde resin to produce transparent, intumescent flame-retardant wood coatings (designated AMP, LMP, and HMP). Experimental results indicate that the AMP coating exhibits superior water resistance and mechanical performance compared to HMP and LMP. Moreover, when the curing agents’ ratio exceeded 10%, the limiting oxygen index (LOI) surpassed 36%, and the UL-94 rating reached V-0. Cone calorimeter tests revealed that the time to ignition (TTI) for wood coated with AMP-4 was 189 s, a 63-fold increase relative to untreated wood. Furthermore, the total heat release (THR), peak smoke release rate (pSPR), and total smoke production (TSP) of AMP-4 coated wood were respectively reduced by 50.6%, 61.9%, and 38.3%, demonstrating exceptional flame-retardant performance. The proposed mechanism suggests that the flame-retardant coatings decomposes at elevated temperatures, releasing non-combustible gases and catalyzing the dehydration of carbohydrates, forming an expanded char layer that provides both thermal and oxygen barriers. The prepared wood coating effectively inhibits combustion in both condensed and gas phases. This study provides an environmentally friendly and viable approach for the practical application of bio-based flame-retardant wood coatings.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111914"},"PeriodicalIF":7.4,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922113","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.2025.111909
Yulu Zhu , Yujia Ding , Jianing Yang , Daoguang Han , Zheng Zhou , Meng Ma , Si Chen , Yanqin Shi , Huiwen He , Wei Wang , Xu Wang
The escalating production of plastic waste underscores an urgent need for sustainable polymer recycling. Polyurethane (PU) foam, representing over 50 % of PU output, is particularly challenging to recycle due to its crosslinked structure. While chemical degradation can recover polyols, the hard segment residues (PUSR) remain underutilized. This study presents an innovative strategy for upcycling waste PU foam into a value-added flame retardant. Through a tailored chemical alcoholysis and phosphorylation process, PUSR was converted into a novel "three-in-one" flame retardant (P1D1), integrating carbon, acid, and gas sources. When incorporated into soft polyvinyl chloride (PVC), P1D1 endowed the composite with a UL-94 V-0 rating and a limiting oxygen index of 24.2 %, significantly enhancing its flame retardancy. Remarkably, this improvement was achieved without compromising mechanical properties, as evidenced by a 42 % increase in elongation at break. This work not only establishes a promising path for PUSR valorization but also provides a sustainable solution for developing high-performance flame-retardant polymers.
{"title":"From waste to resource: valorizing hard segments from acidolyzed PU foam as additives in PVC","authors":"Yulu Zhu , Yujia Ding , Jianing Yang , Daoguang Han , Zheng Zhou , Meng Ma , Si Chen , Yanqin Shi , Huiwen He , Wei Wang , Xu Wang","doi":"10.1016/j.polymdegradstab.2025.111909","DOIUrl":"10.1016/j.polymdegradstab.2025.111909","url":null,"abstract":"<div><div>The escalating production of plastic waste underscores an urgent need for sustainable polymer recycling. Polyurethane (PU) foam, representing over 50 % of PU output, is particularly challenging to recycle due to its crosslinked structure. While chemical degradation can recover polyols, the hard segment residues (PUSR) remain underutilized. This study presents an innovative strategy for upcycling waste PU foam into a value-added flame retardant. Through a tailored chemical alcoholysis and phosphorylation process, PUSR was converted into a novel \"three-in-one\" flame retardant (P<sub>1</sub>D<sub>1</sub>), integrating carbon, acid, and gas sources. When incorporated into soft polyvinyl chloride (PVC), P<sub>1</sub>D<sub>1</sub> endowed the composite with a UL-94 V-0 rating and a limiting oxygen index of 24.2 %, significantly enhancing its flame retardancy. Remarkably, this improvement was achieved without compromising mechanical properties, as evidenced by a 42 % increase in elongation at break. This work not only establishes a promising path for PUSR valorization but also provides a sustainable solution for developing high-performance flame-retardant polymers.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"246 ","pages":"Article 111909"},"PeriodicalIF":7.4,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941223","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 : 2025-12-30DOI: 10.1016/j.polymdegradstab.2025.111905
Simon Kunz , Susanne Brunner , Janine Köppen , Erik Rettler , Eleonora Bresolin , Isabella del Gaudio , Bastiaan Staal , Till Gruendling , Elena Gómez-Sánchez
This study compares naturally aged (NA) closed-cell polyester urethane (PU-ES) foams with an artificially aged (AA) chemically crosslinked, comparable PU-ES. The foams are shoe soles part of a museum collection from a well-defined time, place, and use, and were thoroughly characterised visually, chemically, and, where possible, mechanically. Under museum conditions, naturally aged materials displayed hydrolysis related phenomena namely blooming, pox, and dried fluids, consisting either of adipic acid deposits, or resulting from reactions between polyester polyol oligomers and shoe metal components.
Shore hardness, only method applicable to both sets of samples, showed that 56 days at 70 °C and 98 %RH produced a loss of elasticity in AA material comparable to ∼25 years of natural ageing. Yet, artificial ageing was not able to replicate NA surface phenomena, signalling a fundamental difference between material undergoing both kinds of ageing.
Particular effort was devoted to the mechanical and chemical characterization, and to evaluating pyrolysis-GCMS for monitoring ageing in PU-ES. While detailed MS interpretation enabled proposal of several structures of pyrolysis products, certain key issues intrinsically affected the repeatability of py-GCMS analysis, making MDA, a proposed marker for PU-ES degradation, unsuitable for following ageing. Alternative methods for this purpose included the infrared band ratio 1727 cm⁻¹ / 1706 cm⁻¹, which increased consistently with accelerated ageing but was reliable only when adipic acid did not obscure the region. In contrast, GCMS of material extracts showed higher repeatability and promise for identifying molecular ageing markers.
Overall, the results indicate that while artificial ageing can reproduce certain mechanical changes, it cannot fully replicate the chemical and morphological complexity of long-term natural ageing, highlighting the importance of complementary analytical strategies and the potential of the study of naturally aged materials from industrial heritage collections. By leveraging their repetitive nature and well-established, industrially manufactured formulations from collections, this study demonstrates how such materials can uniquely bridge natural and artificial ageing research— not only refining conservation strategies to ensure their safeguarding for future generations, but also allowing the study of long-term polymer degradation processes otherwise difficult to access within current material science strategies.
{"title":"Comparative study of the artificial and natural, indoor ageing of crosslinked, polyurethane ester closed-cell foams","authors":"Simon Kunz , Susanne Brunner , Janine Köppen , Erik Rettler , Eleonora Bresolin , Isabella del Gaudio , Bastiaan Staal , Till Gruendling , Elena Gómez-Sánchez","doi":"10.1016/j.polymdegradstab.2025.111905","DOIUrl":"10.1016/j.polymdegradstab.2025.111905","url":null,"abstract":"<div><div>This study compares naturally aged (NA) closed-cell polyester urethane (PU-ES) foams with an artificially aged (AA) chemically crosslinked, comparable PU-ES. The foams are shoe soles part of a museum collection from a well-defined time, place, and use, and were thoroughly characterised visually, chemically, and, where possible, mechanically. Under museum conditions, naturally aged materials displayed hydrolysis related phenomena namely blooming, pox, and dried fluids, consisting either of adipic acid deposits, or resulting from reactions between polyester polyol oligomers and shoe metal components.</div><div>Shore hardness, only method applicable to both sets of samples, showed that 56 days at 70 °C and 98 %RH produced a loss of elasticity in AA material comparable to ∼25 years of natural ageing. Yet, artificial ageing was not able to replicate NA surface phenomena, signalling a fundamental difference between material undergoing both kinds of ageing.</div><div>Particular effort was devoted to the mechanical and chemical characterization, and to evaluating pyrolysis-GCMS for monitoring ageing in PU-ES. While detailed MS interpretation enabled proposal of several structures of pyrolysis products, certain key issues intrinsically affected the repeatability of py-GCMS analysis, making MDA, a proposed marker for PU-ES degradation, unsuitable for following ageing. Alternative methods for this purpose included the infrared band ratio 1727 cm⁻¹ / 1706 cm⁻¹, which increased consistently with accelerated ageing but was reliable only when adipic acid did not obscure the region. In contrast, GCMS of material extracts showed higher repeatability and promise for identifying molecular ageing markers.</div><div>Overall, the results indicate that while artificial ageing can reproduce certain mechanical changes, it cannot fully replicate the chemical and morphological complexity of long-term natural ageing, highlighting the importance of complementary analytical strategies and the potential of the study of naturally aged materials from industrial heritage collections. By leveraging their repetitive nature and well-established, industrially manufactured formulations from collections, this study demonstrates how such materials can uniquely bridge natural and artificial ageing research— not only refining conservation strategies to ensure their safeguarding for future generations, but also allowing the study of long-term polymer degradation processes otherwise difficult to access within current material science strategies.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111905"},"PeriodicalIF":7.4,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922158","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 : 2025-12-29DOI: 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":"2025-12-29","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 : 2025-12-29DOI: 10.1016/j.polymdegradstab.2025.111903
Soohyung Park , Junkyeong Jeong , Jisu Yoo , Donghee Kang , Kitae Kim , Keun Yong Lim , Do Kyung Hwang , Hyunbok Lee , Yeonjin Yi
The “burn-in” degradation of organic solar cells (OSCs) is a critical obstacle to their commercialization. Although environmental factors (e.g., O2) are known contributors, the interplay between these extrinsic stressors and the inherent susceptibility of active materials to photodegradation remains poorly understood. We systematically decouple these effects in a model polythieno[3,4-b]-thiophene-co-benzodithiophene (PTB7):[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) blend system by correlating the device performance with direct electronic structure measurements via ultraviolet photoelectron spectroscopy. We identify two distinct and competing degradation pathways dependent on the fabrication environment. Under inert conditions, we uncover a fundamental intrinsic degradation pathway in which visible light alone triggers the degradation of PTB7 within the blend, which is characterized by the formation of performance-limiting midgap states. In the presence of ambient air, a far more aggressive extrinsic photo-oxidation pathway dominates, causing catastrophic and indiscriminate degradation. This dual-pathway model provides a robust explanation for a key observation: midgap states, which are signatures of the intrinsic pathway, are not observed under ambient conditions because extrinsic photo-oxidation is so rapid and destructive that it bypasses this intermediate degradation stage. Our findings underscore that the future design of long-lasting OSCs should focus on the development of materials with enhanced inherent resistance to photodegradation.
{"title":"Decoupling intrinsic and extrinsic photodegradation pathways in organic solar cells","authors":"Soohyung Park , Junkyeong Jeong , Jisu Yoo , Donghee Kang , Kitae Kim , Keun Yong Lim , Do Kyung Hwang , Hyunbok Lee , Yeonjin Yi","doi":"10.1016/j.polymdegradstab.2025.111903","DOIUrl":"10.1016/j.polymdegradstab.2025.111903","url":null,"abstract":"<div><div>The “burn-in” degradation of organic solar cells (OSCs) is a critical obstacle to their commercialization. Although environmental factors (e.g., O<sub>2</sub>) are known contributors, the interplay between these extrinsic stressors and the inherent susceptibility of active materials to photodegradation remains poorly understood. We systematically decouple these effects in a model polythieno[3,4-b]-thiophene-co-benzodithiophene (PTB7):[6,6]-phenyl-C<sub>71</sub>-butyric acid methyl ester (PC<sub>71</sub>BM) blend system by correlating the device performance with direct electronic structure measurements via ultraviolet photoelectron spectroscopy. We identify two distinct and competing degradation pathways dependent on the fabrication environment. Under inert conditions, we uncover a fundamental intrinsic degradation pathway in which visible light alone triggers the degradation of PTB7 within the blend, which is characterized by the formation of performance-limiting midgap states. In the presence of ambient air, a far more aggressive extrinsic photo-oxidation pathway dominates, causing catastrophic and indiscriminate degradation. This dual-pathway model provides a robust explanation for a key observation: midgap states, which are signatures of the intrinsic pathway, are not observed under ambient conditions because extrinsic photo-oxidation is so rapid and destructive that it bypasses this intermediate degradation stage. Our findings underscore that the future design of long-lasting OSCs should focus on the development of materials with enhanced inherent resistance to photodegradation.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111903"},"PeriodicalIF":7.4,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881166","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 : 2025-12-28DOI: 10.1016/j.polymdegradstab.2025.111904
Reetik Singh, Sanat Kumar Mukherjee
This study presents a novel nanocomposite coating based on SiO2-decorated graphene nanosheets, developed to enhance the mechanical and anticorrosion durability of aerospace-grade aluminium alloy AA7075. This research investigates the synergistic effects of incorporating 1 wt% each of graphene, zinc, and silica nanoparticles into an epoxy matrix using high-shear dispersion. The resulting nanocomposites were applied as protective coatings on aluminium alloy and evaluated under aggressive environmental conditions. Corrosion resistance was assessed through electrochemical impedance spectroscopy (EIS), and salt spray exposure. Mechanical properties, including adhesion, scratch resistance, and penetration depth, along with surface wettability via contact angle measurements, were also examined. EIS confirmed enhanced barrier performance, showing ⃒Z⃒0.01 Hz and charge transfer resistance (Rct) above 108 Ω.cm2 even after 72 h in 3.5 % NaCl solution. The graphene-zinc-SiO2 coating also achieved a scratch hardness of 1.65 GPa, markedly higher than the 0.21 GPa of the pure epoxy.
{"title":"Multifunctional epoxy-based composites: Integrating graphene, zinc, and silicon dioxide for superior mechanical and corrosion performance","authors":"Reetik Singh, Sanat Kumar Mukherjee","doi":"10.1016/j.polymdegradstab.2025.111904","DOIUrl":"10.1016/j.polymdegradstab.2025.111904","url":null,"abstract":"<div><div>This study presents a novel nanocomposite coating based on SiO<sub>2</sub>-decorated graphene nanosheets, developed to enhance the mechanical and anticorrosion durability of aerospace-grade aluminium alloy AA7075. This research investigates the synergistic effects of incorporating 1 wt% each of graphene, zinc, and silica nanoparticles into an epoxy matrix using high-shear dispersion. The resulting nanocomposites were applied as protective coatings on aluminium alloy and evaluated under aggressive environmental conditions. Corrosion resistance was assessed through electrochemical impedance spectroscopy (EIS), and salt spray exposure. Mechanical properties, including adhesion, scratch resistance, and penetration depth, along with surface wettability via contact angle measurements, were also examined. EIS confirmed enhanced barrier performance, showing ⃒Z⃒<sub>0.01</sub> Hz and charge transfer resistance (R<sub>ct</sub>) above 10<sup>8</sup> Ω.cm<sup>2</sup> even after 72 h in 3.5 % NaCl solution. The graphene-zinc-SiO<sub>2</sub> coating also achieved a scratch hardness of 1.65 GPa, markedly higher than the 0.21 GPa of the pure epoxy.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111904"},"PeriodicalIF":7.4,"publicationDate":"2025-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922160","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}
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":"2025-12-28","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}
Achieving simultaneous exceptional adhesion and recyclability remains a formidable challenge due to the inherent strength-toughness trade-off and stability-switchability conflict in adhesive systems. Inspired by the hierarchical architecture of cartilage, we report a bioinspired cross-linked network integrating B-N coordination bonds and dynamic boronic ester linkages for high-performance recyclable adhesives. The biomimetic design replicates the structural organization of cartilage's collagen-proteoglycan matrix, where dynamic B-N coordination bonds between network junctions facilitate energy dissipation through bond dissociation-induced network elongation. The network is constructed via 3-amino-1,2-propanediol-mediated epoxy ring-opening and subsequent cross-linking with 1,4-phenylenediboronic acid, forming a dynamic covalent polymer network, denoted as BEAD (boronic ester adhesive), with high cross-linking density. BEAD exhibits exceptional mechanical properties (46.42 ± 5.32 MPa tensile strength, 2.60 ± 0.31 MJ/m³ toughness) and robust adhesion (26.69 ± 0.74 MPa lap shear strength on steel). The synergy of B-N coordination (enhancing cohesion) and boronic ester exchange (enabling reprocessability) yields an optimal balance of strength and recyclability, retaining 80.7% adhesion performance after five reprocessing cycles. The study presents a biomimetic dynamic bonding strategy to overcome the strength-recyclability trade-off in adhesives, establishing a sustainable paradigm for structural materials.
{"title":"Cartilage-inspired boronic ester dynamic cross-linking networks for high-strength and reversible adhesives","authors":"Xuebin Lian, Yuanjian Li, Minghui Li, Yongxin Bai, Xinyu Zhao, Jiangwen Li, Shujun Zhao","doi":"10.1016/j.polymdegradstab.2025.111907","DOIUrl":"10.1016/j.polymdegradstab.2025.111907","url":null,"abstract":"<div><div>Achieving simultaneous exceptional adhesion and recyclability remains a formidable challenge due to the inherent strength-toughness trade-off and stability-switchability conflict in adhesive systems. Inspired by the hierarchical architecture of cartilage, we report a bioinspired cross-linked network integrating B-N coordination bonds and dynamic boronic ester linkages for high-performance recyclable adhesives. The biomimetic design replicates the structural organization of cartilage's collagen-proteoglycan matrix, where dynamic B-N coordination bonds between network junctions facilitate energy dissipation through bond dissociation-induced network elongation. The network is constructed via 3-amino-1,2-propanediol-mediated epoxy ring-opening and subsequent cross-linking with 1,4-phenylenediboronic acid, forming a dynamic covalent polymer network, denoted as BEAD (boronic ester adhesive), with high cross-linking density. BEAD exhibits exceptional mechanical properties (46.42 ± 5.32 MPa tensile strength, 2.60 ± 0.31 MJ/m³ toughness) and robust adhesion (26.69 ± 0.74 MPa lap shear strength on steel). The synergy of B-N coordination (enhancing cohesion) and boronic ester exchange (enabling reprocessability) yields an optimal balance of strength and recyclability, retaining 80.7% adhesion performance after five reprocessing cycles. The study presents a biomimetic dynamic bonding strategy to overcome the strength-recyclability trade-off in adhesives, establishing a sustainable paradigm for structural materials.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111907"},"PeriodicalIF":7.4,"publicationDate":"2025-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881162","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 : 2025-12-27DOI: 10.1016/j.polymdegradstab.2025.111882
Xuan Wang , Miaomiao Tian , Xiaoyu Gu , Yunxian Yang , Jun Sun , Sheng Zhang
The incorporation of flame retardants and pigments into polypropylene (PP) is essential for meeting fire safety and aesthetic requirements in commercial applications. However, their incompatibility often results in color deviations in the final PP products. In this study, the effect of two representative flame retardants, decabromodiphenyl ethane (DBDPE) and ammonium polyphosphate (APP), on the coloration performance of phthalocyanine blue (PiB) and the thermal degradation behavior of PP were systematically investigated. Color performance was evaluated using reflectance spectra and colorimetric parameters (L*, a*, b*), while thermal stability was assessed by thermogravimetric analysis. The results show that PiB enhance the thermal stability of PP by promoting char formation through a catalytic pathway. In contrast to PP, DBDPE-based BrFP flame retardant exhibits a pronounced antagonistic interaction with PiB, resulting in a significant reduction in the initial decomposition temperature (T5% decreased by approximately 60 oC). APP shows a clear synergistic effect with PiB, leading to an increase in the maximum decomposition temperature. In addition, the intrinsic reflectivity and whiteness of flame retardants, as well as their effect on the crystalline form of PP are not the primary factors governing the color performance of PiB-colored samples. Instead, reflectance variations mainly originate from differences in the microscopic dispersion state of flame retardants, which significantly affect the overall light scattering (S) and absorption (K) behavior in accordance with the Kubelka–Munk theory. while additional effects on pigment dispersion and conjugation length resulted in changes in color saturation and hue. The findings provide valuable insights into the industrial application of pigments and flame retardants in polymers.
{"title":"Impact of decabromodiphenyl ethane and ammonium polyphosphate on the coloration and thermal stability of polypropylene","authors":"Xuan Wang , Miaomiao Tian , Xiaoyu Gu , Yunxian Yang , Jun Sun , Sheng Zhang","doi":"10.1016/j.polymdegradstab.2025.111882","DOIUrl":"10.1016/j.polymdegradstab.2025.111882","url":null,"abstract":"<div><div>The incorporation of flame retardants and pigments into polypropylene (PP) is essential for meeting fire safety and aesthetic requirements in commercial applications. However, their incompatibility often results in color deviations in the final PP products. In this study, the effect of two representative flame retardants, decabromodiphenyl ethane (DBDPE) and ammonium polyphosphate (APP), on the coloration performance of phthalocyanine blue (PiB) and the thermal degradation behavior of PP were systematically investigated. Color performance was evaluated using reflectance spectra and colorimetric parameters (L*, a*, b*), while thermal stability was assessed by thermogravimetric analysis. The results show that PiB enhance the thermal stability of PP by promoting char formation through a catalytic pathway. In contrast to PP, DBDPE-based BrFP flame retardant exhibits a pronounced antagonistic interaction with PiB, resulting in a significant reduction in the initial decomposition temperature (T<sub>5%</sub> decreased by approximately 60 <sup>o</sup>C). APP shows a clear synergistic effect with PiB, leading to an increase in the maximum decomposition temperature. In addition, the intrinsic reflectivity and whiteness of flame retardants, as well as their effect on the crystalline form of PP are not the primary factors governing the color performance of PiB-colored samples. Instead, reflectance variations mainly originate from differences in the microscopic dispersion state of flame retardants, which significantly affect the overall light scattering (S) and absorption (K) behavior in accordance with the Kubelka–Munk theory. while additional effects on pigment dispersion and conjugation length resulted in changes in color saturation and hue. The findings provide valuable insights into the industrial application of pigments and flame retardants in polymers.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"246 ","pages":"Article 111882"},"PeriodicalIF":7.4,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975024","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 : 2025-12-27DOI: 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":"2025-12-27","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}
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