This study addresses the challenges of prolonged film-forming time and unclear film-forming mechanisms in traditional suppressants by developing a polyvinyl alcohol-graphene oxide (PVA-GO) composite. We propose a dual-path synergistic mechanism wherein GO enhances film formation by simultaneously increasing the water diffusion coefficient and extending the hydrogen bond lifetime. Through integrated experimental and molecular dynamics simulation approaches, we demonstrate that the PVA-GO composite exhibits a porous cross-linked structure with improved crystallinity and thermal stability, including a ∼70 °C increase in decomposition temperature compared to pure PVA. Notably, the film-forming time was reduced with the addition of GO, while maintaining complete peelability. Molecular dynamics simulations confirmed an 11 % increase in water diffusion coefficient (from 0.0056 to 0.0062 nm2/ps) and a 108 % extension in hydrogen bond lifetime (from 2.493 ps to 5.182 ps). This work provides fundamental insights and a material solution for efficient radioactive aerosol suppression, with potential applications in nuclear decommissioning and other high-risk environments, thereby contributing to public safety and environmental protection.
{"title":"Mechanism of graphene oxide in enhancing PVA film formation and thermal stability probed by experiments and molecular dynamics","authors":"Ruomeng Hou, Sufen Li, Xingfu Cai, Fei Wang, Jiqing Zhang, Keke Shen","doi":"10.1016/j.polymer.2025.129493","DOIUrl":"10.1016/j.polymer.2025.129493","url":null,"abstract":"<div><div>This study addresses the challenges of prolonged film-forming time and unclear film-forming mechanisms in traditional suppressants by developing a polyvinyl alcohol-graphene oxide (PVA-GO) composite. We propose a dual-path synergistic mechanism wherein GO enhances film formation by simultaneously increasing the water diffusion coefficient and extending the hydrogen bond lifetime. Through integrated experimental and molecular dynamics simulation approaches, we demonstrate that the PVA-GO composite exhibits a porous cross-linked structure with improved crystallinity and thermal stability, including a ∼70 °C increase in decomposition temperature compared to pure PVA. Notably, the film-forming time was reduced with the addition of GO, while maintaining complete peelability. Molecular dynamics simulations confirmed an 11 % increase in water diffusion coefficient (from 0.0056 to 0.0062 nm<sup>2</sup>/ps) and a 108 % extension in hydrogen bond lifetime (from 2.493 ps to 5.182 ps). This work provides fundamental insights and a material solution for efficient radioactive aerosol suppression, with potential applications in nuclear decommissioning and other high-risk environments, thereby contributing to public safety and environmental protection.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"344 ","pages":"Article 129493"},"PeriodicalIF":4.5,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785493","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 : 2025-12-16DOI: 10.1016/j.polymer.2025.129491
Bingbing Cao , Yuesheng Zhang , Yanxu Tian , Jinrong Liu , Jiangang Zhang , Wen Cao , Xiong Liu , Jianna Bao
Polylactic acid (PLA), a sustainable biodegradable polymer, possesses significant commercial potential. Nevertheless, its inherent flammability and low crystallinity substantially restrict its applications. In this study, flame retardants consisting of polyethyleneimine (PEI), phytic acid (PA), and melamine (MEL), PA@MEL, PEI@PA, and PEI@PA@MEL with different compositions were prepared using a self-assembly method in an aqueous solution, without the use of organic solvents the generation of by-products. The structures of the three flame retardants were characterized and their effects on the thermal stability, flame retardancy, and mechanical properties of the PLA were evaluated. Results demonstrated that the macromolecular P–N synergistic flame retardant PEI@PA@MEL could significantly enhance flame resistance while maintaining the mechanical performance of PLA. By combining with nitrogen-rich MEL to establish a P–N synergistic effect, the addition of 3.0 wt% PEI@PA@MEL improved the UL-94 rating of PLA composite to V-0 with 26.8 % limiting oxygen index. The incorporation of 7 wt% PEI@PA@MEL drastically reduced flammability: total heat release dropped from 93.1 to 84.7 MJ/m2, and effective combustion heat from 24.4 to 23.3 MJ/kg. The high flame retardant efficiency of PEI@PA@MEL was due to the release of non-flammable gases (e.g., NH3), highly active free radical capture by phosphorus-containing free radicals, and the formation of carbon layers that blocked material exchange. The amino-rich PEI@PA@MEL flame retardant significantly enhanced the crystallization properties of PLA. At 110 °C, with only 1 wt% addition, the half-crystallization time was reduced from 1784 to 492 s, achieving a 72 % improvement compared to pure PLA. The mechanical properties of the composites were preserved relative to those of neat PLA, as evidenced by a tensile strength of around 75 MPa. The multifunctional flame retardant synthesized in this study improved both the flame retardancy and crystallization behavior of PLA without compromising its mechanical performance, demonstrating potential value for expanding the application fields of PLA.
{"title":"One-pot and green synthesis of macromolecular P–N synergistic flame retardant and its polylactic acid composites: Composition, mechanical, flame retardancy, and crystallization performance","authors":"Bingbing Cao , Yuesheng Zhang , Yanxu Tian , Jinrong Liu , Jiangang Zhang , Wen Cao , Xiong Liu , Jianna Bao","doi":"10.1016/j.polymer.2025.129491","DOIUrl":"10.1016/j.polymer.2025.129491","url":null,"abstract":"<div><div>Polylactic acid (PLA), a sustainable biodegradable polymer, possesses significant commercial potential. Nevertheless, its inherent flammability and low crystallinity substantially restrict its applications. In this study, flame retardants consisting of polyethyleneimine (PEI), phytic acid (PA), and melamine (MEL), PA@MEL, PEI@PA, and PEI@PA@MEL with different compositions were prepared using a self-assembly method in an aqueous solution, without the use of organic solvents the generation of by-products. The structures of the three flame retardants were characterized and their effects on the thermal stability, flame retardancy, and mechanical properties of the PLA were evaluated. Results demonstrated that the macromolecular P–N synergistic flame retardant PEI@PA@MEL could significantly enhance flame resistance while maintaining the mechanical performance of PLA. By combining with nitrogen-rich MEL to establish a P–N synergistic effect, the addition of 3.0 wt% PEI@PA@MEL improved the UL-94 rating of PLA composite to V-0 with 26.8 % limiting oxygen index. The incorporation of 7 wt% PEI@PA@MEL drastically reduced flammability: total heat release dropped from 93.1 to 84.7 MJ/m<sup>2</sup>, and effective combustion heat from 24.4 to 23.3 MJ/kg. The high flame retardant efficiency of PEI@PA@MEL was due to the release of non-flammable gases (e.g., NH<sub>3</sub>), highly active free radical capture by phosphorus-containing free radicals, and the formation of carbon layers that blocked material exchange. The amino-rich PEI@PA@MEL flame retardant significantly enhanced the crystallization properties of PLA. At 110 °C, with only 1 wt% addition, the half-crystallization time was reduced from 1784 to 492 s, achieving a 72 % improvement compared to pure PLA. The mechanical properties of the composites were preserved relative to those of neat PLA, as evidenced by a tensile strength of around 75 MPa. The multifunctional flame retardant synthesized in this study improved both the flame retardancy and crystallization behavior of PLA without compromising its mechanical performance, demonstrating potential value for expanding the application fields of PLA.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"344 ","pages":"Article 129491"},"PeriodicalIF":4.5,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785492","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 : 2025-12-16DOI: 10.1016/j.polymer.2025.129479
Yunlan Liu , Xinming Ye , Fan Yang , Yongchang Mu , Yiwei Dong , Xinyi Jing , Jiankun Bai , Zhiqing Han , Wensheng Wang , Jie Li , Yingchun Li
In recent years, with the continuous development of high-frequency communication technology, it has become a challenge to develop new high-performance materials with thermal stability and low dielectric constant. Therefore, it is urgent to prepare a polymer material that satisfies both low dielectric constant and high thermal stability. In this paper, polymethacrylimide (PMI) foam with low dielectric constant and dielectric loss was prepared by free radical polymerization and heat treatment. The real part of the permittivity (ε՛) of pure PMI foam decreased to 1.884 at 12.4 GHz, and gradually decreased with the increase of electromagnetic wave frequency. The value of imaginary part of dielectric constant (ε״) at 12 GHz was close to 0, indicating that the PMI foam had little or no absorption of electromagnetic waves and the loss of electromagnetic waves was extremely small. Furthermore, polyhedral oligomeric phenyl silsesquioxane containing lithium (Li-Ph-POSS) and trisilanol hepta-phenyl polyhedral oligomeric silsesquioxane (Ph-T7-OH) were prepared and added to PMI as modifiers, respectively. The results showed that the initial decomposition temperature of PMI-17 (PMI foam with 17 g foaming agent) was increased to 269 °C when Ph-T7-OH was used as an additive, and the residual char was 24.52 wt% at 800 °C. At the same time, the HRR (heat release rate) and smoke release rate were significantly reduced. The peak of the PMI/Ph-T7-OH-17 composites’ (the amount of foaming agent was 17 g, and 10 wt% Ph-T7-OH were added in PMI) HRR decreased from 703.3 kW/m2 to 458.6 kW/m2, which was 34.5 % lower than the HRR of PMI-17. It also reduced the smoke release rate of PMI and greatly reduced the release of toxic gases. This halogen-free low-dielectric PMI composites combined silicon-based green flame retardant technology. This work presented an innovative material that combined low dielectric properties, high thermal stability and flame retardancy. It was a new generation of preferred materials in the field of high-frequency communication because it solved the challenges of signal loss and thermal management in high frequency.
{"title":"Polyhedral oligomeric silsesquioxane nano-engineering: dual-functional enhancement of flame retardancy and low dielectric properties in PMI foam","authors":"Yunlan Liu , Xinming Ye , Fan Yang , Yongchang Mu , Yiwei Dong , Xinyi Jing , Jiankun Bai , Zhiqing Han , Wensheng Wang , Jie Li , Yingchun Li","doi":"10.1016/j.polymer.2025.129479","DOIUrl":"10.1016/j.polymer.2025.129479","url":null,"abstract":"<div><div>In recent years, with the continuous development of high-frequency communication technology, it has become a challenge to develop new high-performance materials with thermal stability and low dielectric constant. Therefore, it is urgent to prepare a polymer material that satisfies both low dielectric constant and high thermal stability. In this paper, polymethacrylimide (PMI) foam with low dielectric constant and dielectric loss was prepared by free radical polymerization and heat treatment. The real part of the permittivity (ε<sup>՛</sup>) of pure PMI foam decreased to 1.884 at 12.4 GHz, and gradually decreased with the increase of electromagnetic wave frequency. The value of imaginary part of dielectric constant (ε<sup>״</sup>) at 12 GHz was close to 0, indicating that the PMI foam had little or no absorption of electromagnetic waves and the loss of electromagnetic waves was extremely small. Furthermore, polyhedral oligomeric phenyl silsesquioxane containing lithium (Li-Ph-POSS) and trisilanol hepta-phenyl polyhedral oligomeric silsesquioxane (Ph-T<sub>7</sub>-OH) were prepared and added to PMI as modifiers, respectively. The results showed that the initial decomposition temperature of PMI-17 (PMI foam with 17 g foaming agent) was increased to 269 °C when Ph-T<sub>7</sub>-OH was used as an additive, and the residual char was 24.52 wt% at 800 °C. At the same time, the HRR (heat release rate) and smoke release rate were significantly reduced. The peak of the PMI/Ph-T<sub>7</sub>-OH-17 composites’ (the amount of foaming agent was 17 g, and 10 wt% Ph-T<sub>7</sub>-OH were added in PMI) HRR decreased from 703.3 kW/m<sup>2</sup> to 458.6 kW/m<sup>2</sup>, which was 34.5 % lower than the HRR of PMI-17. It also reduced the smoke release rate of PMI and greatly reduced the release of toxic gases. This halogen-free low-dielectric PMI composites combined silicon-based green flame retardant technology. This work presented an innovative material that combined low dielectric properties, high thermal stability and flame retardancy. It was a new generation of preferred materials in the field of high-frequency communication because it solved the challenges of signal loss and thermal management in high frequency.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"344 ","pages":"Article 129479"},"PeriodicalIF":4.5,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145777714","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 : 2025-12-16DOI: 10.1016/j.polymer.2025.129497
Gang Tang , Yani Zhang , Feilong Wang , Zhenfeng Cheng , Haojie Shi , Tiwen Xu , Xiuyu Liu , Xin Wang
The flammability of bismaleimide (BMI) resins limits the application in cutting-edge fields. However, the addition of phosphorus-containing flame retardants results in deteriorated thermal stability of BMI resins. A phosphorus-free flame retardant strategy has been adopted to modify BMI resins while preserving high heat resistance. 3, 3′-Bisallyl-4,4′-bishydroxydeoxybenzoin (BA-BHDB) was synthesized from desoxyanisoin and used as a modifier for BMI resins by replacing conventional 2, 2′-diallylbisphenol A (DBA). The thermal, mechanical and flammability properties of BA-BHDB-cured BMI resins were investigated and compared with those of DBA-cured BMI resins. The cured BA-BHDB-BMI resins exhibit an LOI value for combustion of 35.0 % and a UL-94 V-0 rating, whereas the cured DBA-BMI resins display a lower LOI value of 30.0 % and a UL-94 V-1 rating. In the cone calorimeter measurements, the PHRR and THR values for combustion of BA-BHDB-BMI were 381.1 kW/m2 and 92.5 MJ/m2, which were 53.2 % and 25.2 % lower than those of DBA-BMI, respectively. Additionally, the heat resistance of the cured BA-BHDB-BMI resins was greater than that of the DBA-BMI resins, with an initial thermal decomposition temperature of 428 °C and a glass transition temperature of 285 °C. The excellent anti-flammability of BA-BHDB-BMI may be attributed to the superior charring capacity of BA-BHDB, which contributes to the formation of a dense and protective char layer during thermal decomposition.
{"title":"Intrinsically anti-flammable and highly heat-resistant deoxybenzoin-derived bismaleimide resins containing no conventional flame-retardant elements","authors":"Gang Tang , Yani Zhang , Feilong Wang , Zhenfeng Cheng , Haojie Shi , Tiwen Xu , Xiuyu Liu , Xin Wang","doi":"10.1016/j.polymer.2025.129497","DOIUrl":"10.1016/j.polymer.2025.129497","url":null,"abstract":"<div><div>The flammability of bismaleimide (BMI) resins limits the application in cutting-edge fields. However, the addition of phosphorus-containing flame retardants results in deteriorated thermal stability of BMI resins. A phosphorus-free flame retardant strategy has been adopted to modify BMI resins while preserving high heat resistance. 3, 3′-Bisallyl-4,4′-bishydroxydeoxybenzoin (BA-BHDB) was synthesized from desoxyanisoin and used as a modifier for BMI resins by replacing conventional 2, 2′-diallylbisphenol A (DBA). The thermal, mechanical and flammability properties of BA-BHDB-cured BMI resins were investigated and compared with those of DBA-cured BMI resins. The cured BA-BHDB-BMI resins exhibit an LOI value for combustion of 35.0 % and a UL-94 V-0 rating, whereas the cured DBA-BMI resins display a lower LOI value of 30.0 % and a UL-94 V-1 rating. In the cone calorimeter measurements, the PHRR and THR values for combustion of BA-BHDB-BMI were 381.1 kW/m<sup>2</sup> and 92.5 MJ/m<sup>2</sup>, which were 53.2 % and 25.2 % lower than those of DBA-BMI, respectively. Additionally, the heat resistance of the cured BA-BHDB-BMI resins was greater than that of the DBA-BMI resins, with an initial thermal decomposition temperature of 428 °C and a glass transition temperature of 285 °C. The excellent anti-flammability of BA-BHDB-BMI may be attributed to the superior charring capacity of BA-BHDB, which contributes to the formation of a dense and protective char layer during thermal decomposition.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"344 ","pages":"Article 129497"},"PeriodicalIF":4.5,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145777715","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 : 2025-12-15DOI: 10.1016/j.polymer.2025.129480
Zheng Liu , Donghui Li , Yan Chen , Xiaohua Ma , Xiangyang Liu , Xu Wang
Conventional Polyimide (PI) typically exhibits insolubility and infusibility, resulting in limited processability that severely restricts its applicability. Although introducing side-chain functional groups or twisted structures can impart solubility, such modifications often degrade heat resistance, mechanical properties, and gas barrier performance. To address these limitations, this study employs a solution-processable PI system containing imidazole rings (6FDA-PABZ PI) as the model polymer. Metal ion coordination with PI molecular chains was leveraged to drive microstructural reconstruction of the films, thereby regulating their mechanical properties and gas barrier performance. Distinct coordination patterns between different metal ions and PI were identified: Cu2+ preferentially forms η6-type coordination (point-to-face interaction) with the benzimidazole electron-rich system, while Co2+, Ni2+, and Zn2+ predominantly establish σ-type coordination (point-to-point interaction) with the imidazole ring's CN group. Notably, Ni2+ and Cu2+ exhibit stronger coordination interactions, with Ni2+ forming kinetically inert crosslinks characterized by the slowest dissociation. The metal coordination induces more compact chain packing within the polymer matrix, concurrently enhancing the film's gas barrier properties and mechanical strength. Thanks to its unique ‘point-to-face’ coordination form, the gas barrier performance of the Cu2+ coordinated polymer film is enhanced the most. Even for small-sized gases, it still exhibits excellent barrier properties. These findings provide a theoretical foundation and design principles for developing high-performance PI protective coatings with superior processability.
{"title":"The coordination behavior of metal ions with polyimides containing benzimidazole units and its influence on the mechanical properties and gas barrier performance of the films","authors":"Zheng Liu , Donghui Li , Yan Chen , Xiaohua Ma , Xiangyang Liu , Xu Wang","doi":"10.1016/j.polymer.2025.129480","DOIUrl":"10.1016/j.polymer.2025.129480","url":null,"abstract":"<div><div>Conventional Polyimide (PI) typically exhibits insolubility and infusibility, resulting in limited processability that severely restricts its applicability. Although introducing side-chain functional groups or twisted structures can impart solubility, such modifications often degrade heat resistance, mechanical properties, and gas barrier performance. To address these limitations, this study employs a solution-processable PI system containing imidazole rings (6FDA-PABZ PI) as the model polymer. Metal ion coordination with PI molecular chains was leveraged to drive microstructural reconstruction of the films, thereby regulating their mechanical properties and gas barrier performance. Distinct coordination patterns between different metal ions and PI were identified: Cu<sup>2+</sup> preferentially forms η<sup>6</sup>-type coordination (point-to-face interaction) with the benzimidazole electron-rich system, while Co<sup>2+</sup>, Ni<sup>2+</sup>, and Zn<sup>2+</sup> predominantly establish σ-type coordination (point-to-point interaction) with the imidazole ring's C<img>N group. Notably, Ni<sup>2+</sup> and Cu<sup>2+</sup> exhibit stronger coordination interactions, with Ni<sup>2+</sup> forming kinetically inert crosslinks characterized by the slowest dissociation. The metal coordination induces more compact chain packing within the polymer matrix, concurrently enhancing the film's gas barrier properties and mechanical strength. Thanks to its unique ‘point-to-face’ coordination form, the gas barrier performance of the Cu<sup>2+</sup> coordinated polymer film is enhanced the most. Even for small-sized gases, it still exhibits excellent barrier properties. These findings provide a theoretical foundation and design principles for developing high-performance PI protective coatings with superior processability.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"344 ","pages":"Article 129480"},"PeriodicalIF":4.5,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753388","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 bio-based polycarbonate synthesized through the polymerization of isosorbide and dimethyl carbonate exhibits remarkable environmental sustainability, excellent optical clarity, and robust thermal stability. However, the material currently grapples with significant challenges, including inherent rigidity-induced brittleness, inadequate toughness, and suboptimal mechanical performance. Therefore, it is necessary to improve the flexibility and mechanical properties of co-polymerized biobased polycarbonate (PICs) by compounding with other flexible monomers while ensuring their thermal performance. This research systematically explored an array of diversified diols (including both aliphatic and aromatic variants) as potential third monomers for enhancing the properties of polycarbonate with basic ionic liquid ([TEDA-(tetra)2] [IM]2). By preserving the molecular weight of polycarbonate, the enhanced material demonstrates remarkably low water absorption, a compelling indicator of its superior corrosion resistance. By meticulously optimizing the proportion of the 1,6-hexanediol third monomer, high molecular weight copolymer PICs were successfully synthesized. Comprehensive evaluations of their hardness, thermal stability, and mechanical performance were conducted. The incorporation of 1,6-hexanediol flexible chains not only significantly enhances the material flexibility and processability but also ensures its exceptional mechanical strength.
{"title":"Tough, strong, corrosion and heat-resistant biobased isosorbide polycarbonate with diols copolymerization modification","authors":"Lili Deng, Xiang Li, Haiyue Wang, Yafei Shi, Liying Guo","doi":"10.1016/j.polymer.2025.129484","DOIUrl":"10.1016/j.polymer.2025.129484","url":null,"abstract":"<div><div>The bio-based polycarbonate synthesized through the polymerization of isosorbide and dimethyl carbonate exhibits remarkable environmental sustainability, excellent optical clarity, and robust thermal stability. However, the material currently grapples with significant challenges, including inherent rigidity-induced brittleness, inadequate toughness, and suboptimal mechanical performance. Therefore, it is necessary to improve the flexibility and mechanical properties of co-polymerized biobased polycarbonate (PICs) by compounding with other flexible monomers while ensuring their thermal performance. This research systematically explored an array of diversified diols (including both aliphatic and aromatic variants) as potential third monomers for enhancing the properties of polycarbonate with basic ionic liquid ([TEDA-(tetra)<sub>2</sub>] [IM]<sub>2</sub>). By preserving the molecular weight of polycarbonate, the enhanced material demonstrates remarkably low water absorption, a compelling indicator of its superior corrosion resistance. By meticulously optimizing the proportion of the 1,6-hexanediol third monomer, high molecular weight copolymer PICs were successfully synthesized. Comprehensive evaluations of their hardness, thermal stability, and mechanical performance were conducted. The incorporation of 1,6-hexanediol flexible chains not only significantly enhances the material flexibility and processability but also ensures its exceptional mechanical strength.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"343 ","pages":"Article 129484"},"PeriodicalIF":4.5,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753337","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 : 2025-12-15DOI: 10.1016/j.polymer.2025.129485
Manisha Handa, Parbati Biswas
Ring polymers have structurally simple polymer architecture with distinct properties from linear polymers. These unique properties result from the circular symmetry due to the absence of free chain ends. The advancement in understanding these properties for model ring polymers may facilitate better understanding of the biomacromolecules, which exist in the circular form. The solution properties of polymers are influenced by the presence of hydrodynamic and excluded volume interactions. This review revisits and compiles significant earlier theories, experiments, and simulation studies, where the relevant structural and dynamic properties of ring polymers are explored. It discusses the recent theoretical methods to model the distance dependent excluded volume interactions of ring polymers in dilute solutions including the hydrodynamic interactions, which are generally addressed through the Zimm model. It also accounts for the conformational and dynamic properties obtained from the same model in good, theta, and poor solvent conditions.
{"title":"Conformations and dynamics of ring polymers in dilute solutions","authors":"Manisha Handa, Parbati Biswas","doi":"10.1016/j.polymer.2025.129485","DOIUrl":"10.1016/j.polymer.2025.129485","url":null,"abstract":"<div><div>Ring polymers have structurally simple polymer architecture with distinct properties from linear polymers. These unique properties result from the circular symmetry due to the absence of free chain ends. The advancement in understanding these properties for model ring polymers may facilitate better understanding of the biomacromolecules, which exist in the circular form. The solution properties of polymers are influenced by the presence of hydrodynamic and excluded volume interactions. This review revisits and compiles significant earlier theories, experiments, and simulation studies, where the relevant structural and dynamic properties of ring polymers are explored. It discusses the recent theoretical methods to model the distance dependent excluded volume interactions of ring polymers in dilute solutions including the hydrodynamic interactions, which are generally addressed through the Zimm model. It also accounts for the conformational and dynamic properties obtained from the same model in good, theta, and poor solvent conditions.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"344 ","pages":"Article 129485"},"PeriodicalIF":4.5,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753336","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 : 2025-12-15DOI: 10.1016/j.polymer.2025.129490
Yongjie Dan, Jinqi Chen, Pengjian Gong, Yanhua Niu, Guangxian Li
In this study, a series of dicationic ionic liquids ([EOn(mim)2][TFSI]2) with two charged imidazolium rings bridged by varying oligo(ethylene oxide) (EO) linker lengths and bis(trifluoromethylsulfonyl)imide as anions were successfully synthesized. The aggregation of [EOn(mim)2][TFSI]2 and their influence on the dynamic behavior of poly(ethylene oxide) (PEO) chain were systematically investigated by combining simulation and experimental methods. For [EOn(mim)2][TFSI]2, there is a transition from unfolded to majority folded state depending on linker length, which could further affect the hydrogen-bonding (H-bonding) types between [EOn(mim)2][TFSI]2 and PEO. In the PEO/[EOn(mim)2][TFSI]2 mixtures, the introduction of [EO1(mim)2][TFSI]2 results in unexpectedly higher glass transition temperature (Tg) and flow activation energy (Ea) compared to neat PEO. As the linker length increases, both Tg and Ea exhibit an interesting decreasing trend followed by an increase, which is governed by the co-effects of [EOn(mim)2][TFSI]2 aggregation, H-bonding, and plasticization. [EOn(mim)2][TFSI]2 with shorter linker at unfolded state tend to form physical crosslinks among PEO chains through inter-chain H-bonding, causing higher Tg and Ea, while those with longer EO linker at folded state could more likely form intra-chain H-bonding. Besides, the PEO/[EOn(mim)2][TFSI]2 with longer EO linker (n > 3) exhibit higher heterogeneity order parameter (HOP) values, which implies larger [EOn(mim)2][TFSI]2 cluster and greater heterogeneity contributing to their higher crystallinity.
{"title":"Dynamic behavior of poly(ethylene oxide) in dicationic ionic liquids with varying oligo(ethylene oxide) linker lengths","authors":"Yongjie Dan, Jinqi Chen, Pengjian Gong, Yanhua Niu, Guangxian Li","doi":"10.1016/j.polymer.2025.129490","DOIUrl":"10.1016/j.polymer.2025.129490","url":null,"abstract":"<div><div>In this study, a series of dicationic ionic liquids ([EO<sub>n</sub>(mim)<sub>2</sub>][TFSI]<sub>2</sub>) with two charged imidazolium rings bridged by varying oligo(ethylene oxide) (EO) linker lengths and bis(trifluoromethylsulfonyl)imide as anions were successfully synthesized. The aggregation of [EO<sub>n</sub>(mim)<sub>2</sub>][TFSI]<sub>2</sub> and their influence on the dynamic behavior of poly(ethylene oxide) (PEO) chain were systematically investigated by combining simulation and experimental methods. For [EO<sub>n</sub>(mim)<sub>2</sub>][TFSI]<sub>2</sub>, there is a transition from unfolded to majority folded state depending on linker length, which could further affect the hydrogen-bonding (H-bonding) types between [EO<sub>n</sub>(mim)<sub>2</sub>][TFSI]<sub>2</sub> and PEO. In the PEO/[EO<sub>n</sub>(mim)<sub>2</sub>][TFSI]<sub>2</sub> mixtures, the introduction of [EO<sub>1</sub>(mim)<sub>2</sub>][TFSI]<sub>2</sub> results in unexpectedly higher glass transition temperature (<em>T</em><sub>g</sub>) and flow activation energy (<em>E</em><sub>a</sub>) compared to neat PEO. As the linker length increases, both <em>T</em><sub>g</sub> and <em>E</em><sub>a</sub> exhibit an interesting decreasing trend followed by an increase, which is governed by the co-effects of [EO<sub>n</sub>(mim)<sub>2</sub>][TFSI]<sub>2</sub> aggregation, H-bonding, and plasticization. [EO<sub>n</sub>(mim)<sub>2</sub>][TFSI]<sub>2</sub> with shorter linker at unfolded state tend to form physical crosslinks among PEO chains through <em>inter</em>-chain H-bonding, causing higher <em>T</em><sub>g</sub> and <em>E</em><sub>a</sub>, while those with longer EO linker at folded state could more likely form <em>intra</em>-chain H-bonding. Besides, the PEO/[EO<sub>n</sub>(mim)<sub>2</sub>][TFSI]<sub>2</sub> with longer EO linker (<em>n</em> > 3) exhibit higher heterogeneity order parameter (HOP) values, which implies larger [EO<sub>n</sub>(mim)<sub>2</sub>][TFSI]<sub>2</sub> cluster and greater heterogeneity contributing to their higher crystallinity.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"344 ","pages":"Article 129490"},"PeriodicalIF":4.5,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771224","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 : 2025-12-15DOI: 10.1016/j.polymer.2025.129488
Donglei Fan , Shenduo Sun , Minggang Li , Zhiwei Jiang , Tao Tang
For the first time, an innovative method for in-situ precisely forming cellular structure with reentrant and honeycomb shape in polymer foams simultaneously was established via supercritical CO2 (sc-CO2) foaming combining water as a co-blowing agent. This method was successfully applied to fabricate polyether block amide/polypropylene (PEBAX/PP) composite foams with zero Poisson's ratio (ZPR). More importantly, the Poisson's ratio of PEBAX/PP composite foam can be regulated continuously across positive through zero to negative value, through synergistically combining reentrant structure (island phase-induced) and honeycomb cell structure (sea phase-induced) by precisely controlled mass ratio and foaming parameters. After the introduction of compatibilizer (PP-g-MAH), the ZPR PEBAX/PP/PP-g-MAH composite foam with Reentrant-Honeycomb symbiotic structure can still maintain a Poisson's ratio close to zero under a wide range of strains, presenting near-strain-invariant zero Poisson's ratio characteristic. This is attributed to the deformation mechanism of the Reentrant-Honeycomb symbiotic structure, which is confirmed by finite element (FE) analysis. In addition, ZPR PEBAX/PP/PP-g-MAH composite foam has the most uniform stress distribution than PEBAX/PP composite foam and conventional positive Poisson's ratio (PPR) PP foam, and its shear performance and cycle compression performance are also superior. The above unique properties make ZPR PEBAX/PP/PP-g-MAH composite foam an ideal candidate for flexible skin in morphing wing.
{"title":"In-situ engineered reentrant-honeycomb symbiosis structure for preparing zero Poisson's ratio composite foam","authors":"Donglei Fan , Shenduo Sun , Minggang Li , Zhiwei Jiang , Tao Tang","doi":"10.1016/j.polymer.2025.129488","DOIUrl":"10.1016/j.polymer.2025.129488","url":null,"abstract":"<div><div>For the first time, an innovative method for in-situ precisely forming cellular structure with reentrant and honeycomb shape in polymer foams simultaneously was established via supercritical CO<sub>2</sub> (sc-CO<sub>2</sub>) foaming combining water as a co-blowing agent. This method was successfully applied to fabricate polyether block amide/polypropylene (PEBAX/PP) composite foams with zero Poisson's ratio (ZPR). More importantly, the Poisson's ratio of PEBAX/PP composite foam can be regulated continuously across positive through zero to negative value, through synergistically combining reentrant structure (island phase-induced) and honeycomb cell structure (sea phase-induced) by precisely controlled mass ratio and foaming parameters. After the introduction of compatibilizer (PP-g-MAH), the ZPR PEBAX/PP/PP-g-MAH composite foam with Reentrant-Honeycomb symbiotic structure can still maintain a Poisson's ratio close to zero under a wide range of strains, presenting near-strain-invariant zero Poisson's ratio characteristic. This is attributed to the deformation mechanism of the Reentrant-Honeycomb symbiotic structure, which is confirmed by finite element (FE) analysis. In addition, ZPR PEBAX/PP/PP-g-MAH composite foam has the most uniform stress distribution than PEBAX/PP composite foam and conventional positive Poisson's ratio (PPR) PP foam, and its shear performance and cycle compression performance are also superior. The above unique properties make ZPR PEBAX/PP/PP-g-MAH composite foam an ideal candidate for flexible skin in morphing wing.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"343 ","pages":"Article 129488"},"PeriodicalIF":4.5,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785488","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 : 2025-12-15DOI: 10.1016/j.polymer.2025.129487
Gang Zhu, Hao Chen, Shiwei Li, Xuezhi Zhao, Hongyao Yin, Yan Zhang, Yujun Feng
Water-in-oil (W/O) emulsions that remain stable under high-temperature and high-pressure (HTHP) conditions pose significant separation challenges. While superhydrophobic materials exhibit excellent performance at ambient conditions, many fail under HTHP due to insufficient thermal or interfacial stability. In this work, a series of poly(arylene ether sulfone) copolymers (N-g-FX) were synthesized by grafting 4-(trifluoromethyl)benzoyl chloride onto amino-functionalized polymer backbones. Increasing the grafting ratio caused only a slight decrease in thermal properties, while markedly enhancing hydrophobicity under HTHP conditions. The optimal variant, N-g-F87, demonstrated a water contact angle of 152.4° and maintained superhydrophobicity even after immersion in water at 120 °C for 7 days, attributed to its rigid aromatic structure and high fluorine content. Leveraging these properties, N-g-F87 powders were employed as a porous filtration layer to destabilize surfactant-stabilized W/O emulsions under harsh conditions (120 °C, 2 MPa, continuous flow). The system achieved consistent separation with a flux of 830 L m−2 h−1 and demulsification efficiency 99.70 % over 24 h. Mechanistic studies revealed that demulsification was driven by synergistic pore-size exclusion and surface wettability effects. Biphasic oil–water tests showed preferential oil permeation through the N-g-F87 layer before water breakthrough, confirming that wettability selectivity remains decisive under HTHP and pressure-driven flow, underscoring the potential of N-g-F87 for stable W/O emulsion separation in extreme environments.
油包水（W/O）乳液在高温高压（HTHP）条件下保持稳定，这给分离带来了重大挑战。虽然超疏水材料在环境条件下表现出优异的性能，但由于热稳定性或界面稳定性不足，许多超疏水材料在高温高压下失效。本文通过在氨基功能化聚合物骨架上接枝4-（三氟甲基）苯甲酰氯，合成了一系列聚芳醚砜共聚物（N-g-FX）。在高温高压条件下，接枝率的增加只会导致热性能的轻微下降，而疏水性明显增强。最优的N-g-F87由于其刚性芳香结构和高氟含量，即使在120°C的水中浸泡7天后，其水接触角仍保持152.4°的超疏水性。利用这些特性，N-g-F87粉末作为多孔过滤层，在恶劣条件下（120°C, 2 MPa，连续流动）破坏表面活性剂稳定的W/O乳状液的稳定性。该体系以830 L m−2 h−1的通量和99.70%的破乳效率在24 h内实现了一致的分离。机理研究表明，破乳是由协同的孔径排除效应和表面润湿性效应驱动的。油水双相测试结果表明，在水突破之前，N-g-F87层优先渗透油液，证实了在高温高压和压力驱动下，N-g-F87的润湿性选择性仍然具有决定性，强调了N-g-F87在极端环境下稳定分离水乳状液的潜力。
{"title":"Superhydrophobic poly(arylene ether sulfone) for water-in-oil emulsion separation under high temperature and high pressure","authors":"Gang Zhu, Hao Chen, Shiwei Li, Xuezhi Zhao, Hongyao Yin, Yan Zhang, Yujun Feng","doi":"10.1016/j.polymer.2025.129487","DOIUrl":"10.1016/j.polymer.2025.129487","url":null,"abstract":"<div><div>Water-in-oil (W/O) emulsions that remain stable under high-temperature and high-pressure (HTHP) conditions pose significant separation challenges. While superhydrophobic materials exhibit excellent performance at ambient conditions, many fail under HTHP due to insufficient thermal or interfacial stability. In this work, a series of poly(arylene ether sulfone) copolymers (N-<em>g</em>-FX) were synthesized by grafting 4-(trifluoromethyl)benzoyl chloride onto amino-functionalized polymer backbones. Increasing the grafting ratio caused only a slight decrease in thermal properties, while markedly enhancing hydrophobicity under HTHP conditions. The optimal variant, N-<em>g</em>-F87, demonstrated a water contact angle of 152.4° and maintained superhydrophobicity even after immersion in water at 120 °C for 7 days, attributed to its rigid aromatic structure and high fluorine content. Leveraging these properties, N-<em>g</em>-F87 powders were employed as a porous filtration layer to destabilize surfactant-stabilized W/O emulsions under harsh conditions (120 °C, 2 MPa, continuous flow). The system achieved consistent separation with a flux of 830 L m<sup>−2</sup> h<sup>−1</sup> and demulsification efficiency 99.70 % over 24 h. Mechanistic studies revealed that demulsification was driven by synergistic pore-size exclusion and surface wettability effects. Biphasic oil–water tests showed preferential oil permeation through the N-<em>g</em>-F87 layer before water breakthrough, confirming that wettability selectivity remains decisive under HTHP and pressure-driven flow, underscoring the potential of N-<em>g</em>-F87 for stable W/O emulsion separation in extreme environments.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"344 ","pages":"Article 129487"},"PeriodicalIF":4.5,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771225","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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