Pub Date : 2025-12-11DOI: 10.1016/j.polymer.2025.129466
Sumedha Amaraweera, Steven Pratt, Paul Lant, Bronwyn Laycock, Ian Levett
{"title":"Quantifying urea permeability through biodegradable PHBV/PBAT thin films","authors":"Sumedha Amaraweera, Steven Pratt, Paul Lant, Bronwyn Laycock, Ian Levett","doi":"10.1016/j.polymer.2025.129466","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.129466","url":null,"abstract":"","PeriodicalId":405,"journal":{"name":"Polymer","volume":"27 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732294","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 : 2025-12-10DOI: 10.1016/j.polymer.2025.129464
Menghao Lin , Meiling Du , Li Chen , Can Deng , Jiaxin Li , Ling Qin , Lichun Dong , Cailong Zhou
To address the key bottleneck in interlayered thin-film composite (TFCi) nanofiltration membranes, where enhanced water permeance is often accompanied by a decline in molecular selectivity (primarily attributed to the lack of functional groups within the interlayer), this study proposes an innovative strategy. The hydrophobic covalent organic frameworks (COFs) were graft-modified via thiol-yne click chemistry to successfully introduce hydrophilic functional groups, yielding superhydrophilic COF materials. The modified COFs were deposited as the interlayer and a polyamide (PA) selective layer was formed via interfacial polymerization, constructing a structurally robust TFCi membrane. This membrane demonstrates exceptional permeability, with TFCi(10) achieving a pure water permeance of 62.5 ± 0.2 L m−2 h−1 bar−1. It also exhibits precise size-selective separation performance for dyes and common pharmaceutical molecules, achieving over 95 % rejection for dyes and over 90 % rejection for pharmaceutical compounds.
为了解决层间薄膜复合材料（TFCi）纳滤膜的关键瓶颈，其中水渗透性增强通常伴随着分子选择性的下降（主要是由于层间缺乏官能团），本研究提出了一种创新策略。通过巯基键合化学对疏水共价有机骨架（COFs）进行接枝改性，成功引入亲水性官能团，制备了超亲水性COFs材料。通过界面聚合形成聚酰胺（PA）选择层，构建结构坚固的TFCi膜。该膜具有优异的渗透性，TFCi（10）的纯水渗透率为62.5±0.2 L m−2 h−1 bar−1。它还具有精确的染料和普通药物分子的大小选择性分离性能，对染料的回收率超过95%，对药物化合物的回收率超过90%。
{"title":"Superhydrophilic COFs synthetized through click chemistry and the application in interlayered thin-film composite membranes for nanofiltration","authors":"Menghao Lin , Meiling Du , Li Chen , Can Deng , Jiaxin Li , Ling Qin , Lichun Dong , Cailong Zhou","doi":"10.1016/j.polymer.2025.129464","DOIUrl":"10.1016/j.polymer.2025.129464","url":null,"abstract":"<div><div>To address the key bottleneck in interlayered thin-film composite (TFCi) nanofiltration membranes, where enhanced water permeance is often accompanied by a decline in molecular selectivity (primarily attributed to the lack of functional groups within the interlayer), this study proposes an innovative strategy. The hydrophobic covalent organic frameworks (COFs) were graft-modified via thiol-yne click chemistry to successfully introduce hydrophilic functional groups, yielding superhydrophilic COF materials. The modified COFs were deposited as the interlayer and a polyamide (PA) selective layer was formed via interfacial polymerization, constructing a structurally robust TFCi membrane. This membrane demonstrates exceptional permeability, with TFCi(10) achieving a pure water permeance of 62.5 ± 0.2 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup>. It also exhibits precise size-selective separation performance for dyes and common pharmaceutical molecules, achieving over 95 % rejection for dyes and over 90 % rejection for pharmaceutical compounds.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"343 ","pages":"Article 129464"},"PeriodicalIF":4.5,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731985","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 : 2025-12-10DOI: 10.1016/j.polymer.2025.129463
Keira E. Culley , Christopher W. Johnson , Andrew W. Fehr , Richard D. Noble , Douglas L. Gin
Molecular-size-selective heterogeneous catalysts are advantageous for chemical transformations because they allow for convenient catalyst separation/reuse and can exclude reactants or products of a certain molecular diameter. The ability to preferentially react with or more rapidly convert a functional reactant with a certain degree of substitution (i.e., class) over another is also important for selective transformations of mixtures containing the same functional group. However, there are very few heterogeneous catalysts known that perform molecular size-selective and functional group class-selective reactions. A bicontinuous cubic (Q), lyotropic liquid crystal (LLC) polymer resin with TEMPO-based alcohol oxidation catalysis capabilities is presented that exhibits both excellent molecular-size selectivity and good primary (1°) over secondary (2°) alcohol class selectivity. This nanoporous catalytic LLC resin shows a (30 ± 5) selectivity for the oxidation of benzyl alcohol (BA, 0.69 nm diameter) over a larger BA derivative (1.68 nm), as well as faster oxidation rates compared to a previously reported TEMPO-based hexagonal-phase resin. It also shows a ca. 7-fold preference for reacting 1° BAs over 2° BAs in a 1:1 M mixture of the two alcohols. This solid-state oxidation catalyst can be recycled and reused with negligible loss in catalyst mass, catalytic activity, or molecular-size or class selectivity.
{"title":"Nanoporous, lyotropic bicontinuous cubic polymer network for highly selective heterogeneous catalytic oxidation of alcohols","authors":"Keira E. Culley , Christopher W. Johnson , Andrew W. Fehr , Richard D. Noble , Douglas L. Gin","doi":"10.1016/j.polymer.2025.129463","DOIUrl":"10.1016/j.polymer.2025.129463","url":null,"abstract":"<div><div>Molecular-size-selective heterogeneous catalysts are advantageous for chemical transformations because they allow for convenient catalyst separation/reuse and can exclude reactants or products of a certain molecular diameter. The ability to preferentially react with or more rapidly convert a functional reactant with a certain degree of substitution (i.e., class) over another is also important for selective transformations of mixtures containing the same functional group. However, there are very few heterogeneous catalysts known that perform molecular size-selective and functional group class-selective reactions. A bicontinuous cubic (Q), lyotropic liquid crystal (LLC) polymer resin with TEMPO-based alcohol oxidation catalysis capabilities is presented that exhibits both excellent molecular-size selectivity and good primary (1°) over secondary (2°) alcohol class selectivity. This nanoporous catalytic LLC resin shows a (30 ± 5) selectivity for the oxidation of benzyl alcohol (BA, 0.69 nm diameter) over a larger BA derivative (1.68 nm), as well as faster oxidation rates compared to a previously reported TEMPO-based hexagonal-phase resin. It also shows a ca. 7-fold preference for reacting 1° BAs over 2° BAs in a 1:1 M mixture of the two alcohols. This solid-state oxidation catalyst can be recycled and reused with negligible loss in catalyst mass, catalytic activity, or molecular-size or class selectivity.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"343 ","pages":"Article 129463"},"PeriodicalIF":4.5,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731986","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 : 2025-12-09DOI: 10.1016/j.polymer.2025.129449
Hanxin Jian , Weijie Wang , Yuan Yao , Yunpeng Yang , Yisheng Huang , Hao Huang , Shuguang Yang
Heat, humidity, and light responsive polymeric materials are fabricated from poly(urethane urea) through photoisomerization and cold drawing induced orientation. The crystallizable polyether diol reacted with diisocyanate, followed by chain extension with azobenzene-containing diamine. The resulting PUU shows ductile behaviors and drawing-induced orientation when the soft segments possess high crystallinity. The oriented strips display bending under UV irradiation or heating, whereas pristine strips remain unchanged. In contrast, humidity induces bending in both pristine and oriented strips, but in opposite directions. The orientation not only amplifies the azobenzene photoisomerization into macroscopic motion, but also stores entropic elastic energy that is released upon heating or humidification to drive bending deformation. This work provides an effective strategy to construct multi-stimuli responsive polymeric materials by combining molecular design and post-processing, and illustrates the synergy of functional moieties and oriented structures, which is meaningful for advanced intelligent materials.
{"title":"Cold drawing of azobenzene incorporated Poly(urethane urea)s for heat, humidity and light responsiveness","authors":"Hanxin Jian , Weijie Wang , Yuan Yao , Yunpeng Yang , Yisheng Huang , Hao Huang , Shuguang Yang","doi":"10.1016/j.polymer.2025.129449","DOIUrl":"10.1016/j.polymer.2025.129449","url":null,"abstract":"<div><div>Heat, humidity, and light responsive polymeric materials are fabricated from poly(urethane urea) through photoisomerization and cold drawing induced orientation. The crystallizable polyether diol reacted with diisocyanate, followed by chain extension with azobenzene-containing diamine. The resulting PUU shows ductile behaviors and drawing-induced orientation when the soft segments possess high crystallinity. The oriented strips display bending under UV irradiation or heating, whereas pristine strips remain unchanged. In contrast, humidity induces bending in both pristine and oriented strips, but in opposite directions. The orientation not only amplifies the azobenzene photoisomerization into macroscopic motion, but also stores entropic elastic energy that is released upon heating or humidification to drive bending deformation. This work provides an effective strategy to construct multi-stimuli responsive polymeric materials by combining molecular design and post-processing, and illustrates the synergy of functional moieties and oriented structures, which is meaningful for advanced intelligent materials.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"343 ","pages":"Article 129449"},"PeriodicalIF":4.5,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145710941","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 : 2025-12-09DOI: 10.1016/j.polymer.2025.129462
Nur Yusra Farzana Awang , Sarah Sapuan , Juzaili Azizi , Azman Seeni , Enis Nadia Md Yusof , Muhammad Idiris Saleh , Lee D. Wilson , Sumiyyah Sabar
This study reports the synthesis of a novel water-soluble chitosan derivative (8HQ-CS) via grafting of 8-hydroxyquinoline (8HQ) onto the chitosan (CS) backbone. Physicochemical analyses confirmed successful modification, as evidenced by enhanced water solubility, reduced crystallinity, altered surface morphology, and a lower thermal degradation onset due to structural changes introduced by the grafted 8HQ moieties. The antioxidant activity of 8HQ-CS was evaluated using 2,2-diphenyl-1-picrylhydrazyl free radical (DPPH), 2,2-azino-bis-(3-ethylbenzothiazoline-6-sulfonate cation radical (ABTS), ferric-reducing antioxidant power (FRAP), hydroxyl radical antioxidant capacity (HORAC), superoxide anion radical (O2•-) scavenging, and cupric ion (Cu2+) chelation assays. At 5 mg/mL, 8HQ-CS demonstrated markedly enhanced antioxidant performance, exhibiting approximately 1.7-fold and 1.6-fold increases in DPPH and FRAP activities, respectively, compared to CS. ABTS radical scavenging at 20 mg/mL increased about 3-fold (11.03 ± 2.02 μg TE/mg compared to 3.64 ± 0.71 μg TE/mg), while HORAC activity at 10 mg/mL enhanced over 4-fold (9.04 ± 0.89 μM GAE/mg). Moreover, 8HQ-CS demonstrated measurable O2•− scavenging (2.23 ± 0.20 μg GAE/mg) and Cu2+ chelation capacity (11.4 ± 0.52 μg EDTAE/mg), with no activity detected in CS. These improvements are attributed to the antioxidant-active phenolic hydroxyl and pyridine groups introduced by the 8HQ moiety. Cytotoxicity assays on human cervical cancer (HeLa) cells revealed a dose-dependent reduction in cell viability, with a 50 % decrease observed at 500 μg/mL. Apoptosis analysis further confirmed a significant increase in late apoptotic cells (24.53 % compared to 1.43 % in the control), without evidence of cell cycle arrest, indicating apoptosis-mediated anticancer activity. These findings indicate that the incorporation of 8HQ into the CS framework significantly enhances its antioxidant and anticancer properties, highlighting the potential of 8HQ-CS as a multifunctional biomaterial for biomedical applications targeting oxidative stress and cancer.
{"title":"Development of a bioactive water-soluble 8-hydroxyquinoline-chitosan derivative with enhanced antioxidant and anticancer properties","authors":"Nur Yusra Farzana Awang , Sarah Sapuan , Juzaili Azizi , Azman Seeni , Enis Nadia Md Yusof , Muhammad Idiris Saleh , Lee D. Wilson , Sumiyyah Sabar","doi":"10.1016/j.polymer.2025.129462","DOIUrl":"10.1016/j.polymer.2025.129462","url":null,"abstract":"<div><div>This study reports the synthesis of a novel water-soluble chitosan derivative (8HQ-CS) via grafting of 8-hydroxyquinoline (8HQ) onto the chitosan (CS) backbone. Physicochemical analyses confirmed successful modification, as evidenced by enhanced water solubility, reduced crystallinity, altered surface morphology, and a lower thermal degradation onset due to structural changes introduced by the grafted 8HQ moieties. The antioxidant activity of 8HQ-CS was evaluated using 2,2-diphenyl-1-picrylhydrazyl free radical (DPPH), 2,2-azino-bis-(3-ethylbenzothiazoline-6-sulfonate cation radical (ABTS), ferric-reducing antioxidant power (FRAP), hydroxyl radical antioxidant capacity (HORAC), superoxide anion radical (O<sub>2</sub><sup>•-</sup>) scavenging, and cupric ion (Cu<sup>2+</sup>) chelation assays. At 5 mg/mL, 8HQ-CS demonstrated markedly enhanced antioxidant performance, exhibiting approximately 1.7-fold and 1.6-fold increases in DPPH and FRAP activities, respectively, compared to CS. ABTS radical scavenging at 20 mg/mL increased about 3-fold (11.03 ± 2.02 μg TE/mg compared to 3.64 ± 0.71 μg TE/mg), while HORAC activity at 10 mg/mL enhanced over 4-fold (9.04 ± 0.89 μM GAE/mg). Moreover, 8HQ-CS demonstrated measurable O<sub>2</sub><sup>•−</sup> scavenging (2.23 ± 0.20 μg GAE/mg) and Cu<sup>2+</sup> chelation capacity (11.4 ± 0.52 μg EDTAE/mg), with no activity detected in CS. These improvements are attributed to the antioxidant-active phenolic hydroxyl and pyridine groups introduced by the 8HQ moiety. Cytotoxicity assays on human cervical cancer (HeLa) cells revealed a dose-dependent reduction in cell viability, with a 50 % decrease observed at 500 μg/mL. Apoptosis analysis further confirmed a significant increase in late apoptotic cells (24.53 % compared to 1.43 % in the control), without evidence of cell cycle arrest, indicating apoptosis-mediated anticancer activity. These findings indicate that the incorporation of 8HQ into the CS framework significantly enhances its antioxidant and anticancer properties, highlighting the potential of 8HQ-CS as a multifunctional biomaterial for biomedical applications targeting oxidative stress and cancer.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"343 ","pages":"Article 129462"},"PeriodicalIF":4.5,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711041","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 shear elasticity Gʹ of entangled amorphous monodisperse poly (methyl methacrylate)s with three different molecular weights M = 6.56 × 104, 29.8 × 104, and 153.1 × 104 g/mol upon transition from the glassy to the quasi-plateau terminal is perfectly reproduced by the affine network theory using the regular hexagons-molecular model consisting six motion-constraining intermolecular interaction-network points and is proportional to the applied thermal energy RT. Structural movements of the hexagons, inducing segmental conformational motions, generate a reversible constraining-loosening interaction energy ΔE, which follows Boltzmann's energy-partition law and corresponds to the energy dissipated from the stored energy. The ΔE and the backward difference of network points ns per dT replicated T-dependent curves of the loss tangent and loss elasticity, respectively. The starting and ending temperatures (Tsg and Teg = plateau's starting Tsp) in the glass transition Tg region are relatively independent of M. Although the Ms between entanglements at Tsp is approximately 1 × 103 g/mol, Ms0 at the plateau's end temperature Ts0 is 1.00 × 104 g/mol as the reference entanglement molecular weight, appearing at different Ts0 values by M. The gradual increase in Ms from Tsp to Ts0 arises from the RT-dependent loosening of the entanglement. Exceeding the threshold Ts0 toward fluid deformation, the six-strand nanostructures with stored energy RTs0 of one strand sequentially collapse due to loosening of the constraint as the RT increases.
{"title":"Molecular weight dependence of temperature-dependent elasticity based on the nanostructure modeling of entangled amorphous monodisperse poly(methyl methacrylate)","authors":"Takashi Sawaguchi , Daisuke Sasaki , Atsushi Takamura , Sumire Takahashi , Takeshi Koike , Hiroki Ikake","doi":"10.1016/j.polymer.2025.129456","DOIUrl":"10.1016/j.polymer.2025.129456","url":null,"abstract":"<div><div>The shear elasticity <em>G</em>ʹ of entangled amorphous monodisperse poly (methyl methacrylate)s with three different molecular weights <em>M</em> = 6.56 × 10<sup>4</sup>, 29.8 × 10<sup>4</sup>, and 153.1 × 10<sup>4</sup> g/mol upon transition from the glassy to the quasi-plateau terminal is perfectly reproduced by the affine network theory using the regular hexagons-molecular model consisting six motion-constraining intermolecular interaction-network points and is proportional to the applied thermal energy <em>RT</em>. Structural movements of the hexagons, inducing segmental conformational motions, generate a reversible constraining-loosening interaction energy Δ<em>E,</em> which follows Boltzmann's energy-partition law and corresponds to the energy dissipated from the stored energy. The Δ<em>E</em> and the backward difference of network points <em>n</em><sub>s</sub> per d<em>T</em> replicated <em>T</em>-dependent curves of the loss tangent and loss elasticity, respectively. The starting and ending temperatures (<em>T</em><sub>sg</sub> and <em>T</em><sub>eg</sub> = plateau's starting <em>T</em><sub>sp</sub>) in the glass transition <em>T</em><sub>g</sub> region are relatively independent of <em>M</em>. Although the <em>M</em><sub>s</sub> between entanglements at <em>T</em><sub>sp</sub> is approximately 1 × 10<sup>3</sup> g/mol, <em>M</em><sub>s0</sub> at the plateau's end temperature <em>T</em><sub>s0</sub> is 1.00 × 10<sup>4</sup> g/mol as the reference entanglement molecular weight, appearing at different <em>T</em><sub>s0</sub> values by <em>M</em>. The gradual increase in <em>M</em><sub>s</sub> from <em>T</em><sub>sp</sub> to <em>T</em><sub>s0</sub> arises from the <em>RT</em>-dependent loosening of the entanglement. Exceeding the threshold <em>T</em><sub>s0</sub> toward fluid deformation, the six-strand nanostructures with stored energy <em>RT</em><sub>s0</sub> of one strand sequentially collapse due to loosening of the constraint as the <em>RT</em> increases.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"343 ","pages":"Article 129456"},"PeriodicalIF":4.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145705070","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 : 2025-12-08DOI: 10.1016/j.polymer.2025.129455
Shuqing Sun , Rui Yuan , Li Gao , Chao Zhang , Bingxin Liu , Jing Yuan , Shiai Xu
Low-temperature environments have a significant impact on the performance of resin films. What changes occur within the resin under such conditions? To address this question, this study focuses on plasticizers/polyvinyl chloride (PVC) films, synthesizing six benzene dicarboxylate plasticizers with varying molecular structures. Experimental testing and molecular dynamics (MD) simulations were employed to investigate the effect of low temperatures on the mechanical properties of benzene dicarboxylate/PVC composites and the microscopic mechanisms of low-temperature failure. Experimental results show that the tensile strength of the composite material increases with decreasing temperature, while the elongation at break decreases with decreasing temperature. Raman in situ low-temperature experiments observed the migration of DOP toward the material surface at low temperatures, with crystallization forming at −60 °C. MD simulations confirmed these observations and further revealed that low-temperature failure is attributed to the differing rates of volume contraction between the plasticizer and PVC at low temperatures.
{"title":"Investigation on the mechanism of low temperature failure of benzene dicarboxylate plasticizers/polyvinyl chloride","authors":"Shuqing Sun , Rui Yuan , Li Gao , Chao Zhang , Bingxin Liu , Jing Yuan , Shiai Xu","doi":"10.1016/j.polymer.2025.129455","DOIUrl":"10.1016/j.polymer.2025.129455","url":null,"abstract":"<div><div>Low-temperature environments have a significant impact on the performance of resin films. What changes occur within the resin under such conditions? To address this question, this study focuses on plasticizers/polyvinyl chloride (PVC) films, synthesizing six benzene dicarboxylate plasticizers with varying molecular structures. Experimental testing and molecular dynamics (MD) simulations were employed to investigate the effect of low temperatures on the mechanical properties of benzene dicarboxylate/PVC composites and the microscopic mechanisms of low-temperature failure. Experimental results show that the tensile strength of the composite material increases with decreasing temperature, while the elongation at break decreases with decreasing temperature. Raman in situ low-temperature experiments observed the migration of DOP toward the material surface at low temperatures, with crystallization forming at −60 °C. MD simulations confirmed these observations and further revealed that low-temperature failure is attributed to the differing rates of volume contraction between the plasticizer and PVC at low temperatures.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"343 ","pages":"Article 129455"},"PeriodicalIF":4.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145710966","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 : 2025-12-08DOI: 10.1016/j.polymer.2025.129459
Dandan Li , Chenyang Zhao , Shuo Wang , Guangtao Qian , Chunhai Chen
High-temperature-resistant colorless polyimide films are gaining significant attention as alternatives to glass substrates in next-generation flexible display technologies. A well-established design strategy involves incorporating bulky pendant groups to increase free volume, thereby enhancing optical transparency while maintaining thermal stability. Leveraging the inherently superior thermal resistance of poly(benzimidazole imide)s (PBIIs), we reported the synthesis of novel PBII materials featuring tailored phenyl and biphenyl pendant groups. These advanced PBIIs exhibited exceptional thermal resistance with glass transition temperatures (Tg) ranging from 338 to 374 °C and improved optical transmittance exceeding 80 % at 450 nm (T450). More importantly, the structure-property relationships elucidating how pendant group architecture influences both optical and thermal properties have been established through systematic theoretical calculations and comprehensive property analysis. The optimized pendant structure proved critical for suppressing coloration while preserving the intrinsic thermal resistance of benzimidazole-based polyimides. This rational design approach holds significant potential for developing high-performance engineering polymers with tailored properties for advanced optoelectronic applications.
{"title":"Achieving synergy in thermal, mechanical, and optical properties in polyimide films by modulating N-substituents on benzimidazole units","authors":"Dandan Li , Chenyang Zhao , Shuo Wang , Guangtao Qian , Chunhai Chen","doi":"10.1016/j.polymer.2025.129459","DOIUrl":"10.1016/j.polymer.2025.129459","url":null,"abstract":"<div><div>High-temperature-resistant colorless polyimide films are gaining significant attention as alternatives to glass substrates in next-generation flexible display technologies. A well-established design strategy involves incorporating bulky pendant groups to increase free volume, thereby enhancing optical transparency while maintaining thermal stability. Leveraging the inherently superior thermal resistance of poly(benzimidazole imide)s (PBIIs), we reported the synthesis of novel PBII materials featuring tailored phenyl and biphenyl pendant groups. These advanced PBIIs exhibited exceptional thermal resistance with glass transition temperatures (T<sub>g</sub>) ranging from 338 to 374 °C and improved optical transmittance exceeding 80 % at 450 nm (T<sub>450</sub>). More importantly, the structure-property relationships elucidating how pendant group architecture influences both optical and thermal properties have been established through systematic theoretical calculations and comprehensive property analysis. The optimized pendant structure proved critical for suppressing coloration while preserving the intrinsic thermal resistance of benzimidazole-based polyimides. This rational design approach holds significant potential for developing high-performance engineering polymers with tailored properties for advanced optoelectronic applications.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"343 ","pages":"Article 129459"},"PeriodicalIF":4.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732289","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 : 2025-12-08DOI: 10.1016/j.polymer.2025.129461
Weiwang Wang , Changshen Li , Wentao Huang , Leiyu Hu , George Chen , Yu Feng , Shengtao Li
Space charge accumulation at the electrode/insulation interface indicates a significant challenge to composite insulation in high-power electric and electronic devices. The present study implements an external magnetic field to fabricate the non-uniform distribution of γ-Fe2O3@BNNS (boron nitride nanosheets) nanoparticles at the electrode/epoxy nanocomposite interface. The pulsed electro-acoustic method (PEA) technique was utilized to evaluate the space charge accumulation under DC and square-wave voltages. Furthermore, the dielectric and trap parameters of the nanocomposites were explored by wide-band dielectric spectrum and thermally stimulated current (TSC) technique, respectively. The findings indicate that the incorporation of γ-Fe2O3@BNNS markedly diminished both the average charge density and the maximum electric field. The modified γ-Fe2O3@BNNS effectively mitigated space charge accumulation at the electrode/sample interface under square-wave voltages. Specifically, the 0.5 wt% modified γ-Fe2O3@BNNS yields a 53 % decrease in charge accumulation at a frequency of 500 Hz. While, the 0.1 wt% sample demonstrates a 30 % reduction in electric field distortion compared to the neat epoxy at 500 Hz. Hetero-charge accumulation is detected in epoxy nanocomposites. The modified γ-Fe2O3@BNNS fillers at interface introduced additional deep traps, contributing to reduction in charge injection and increase in charge recombination. Consequently, it improves the space charge characteristics of epoxy resin composites for high-power electrical and electronic applications.
{"title":"Improvements of dielectric and space charge accumulation in epoxy resin nanocomposites by magnetic field directional distribution of boron nitride nanosheets using γ-Fe2O3 surface modification","authors":"Weiwang Wang , Changshen Li , Wentao Huang , Leiyu Hu , George Chen , Yu Feng , Shengtao Li","doi":"10.1016/j.polymer.2025.129461","DOIUrl":"10.1016/j.polymer.2025.129461","url":null,"abstract":"<div><div>Space charge accumulation at the electrode/insulation interface indicates a significant challenge to composite insulation in high-power electric and electronic devices. The present study implements an external magnetic field to fabricate the non-uniform distribution of <em>γ</em>-Fe<sub>2</sub>O<sub>3</sub>@BNNS (boron nitride nanosheets) nanoparticles at the electrode/epoxy nanocomposite interface. The pulsed electro-acoustic method (PEA) technique was utilized to evaluate the space charge accumulation under DC and square-wave voltages. Furthermore, the dielectric and trap parameters of the nanocomposites were explored by wide-band dielectric spectrum and thermally stimulated current (TSC) technique, respectively. The findings indicate that the incorporation of <em>γ</em>-Fe<sub>2</sub>O<sub>3</sub>@BNNS markedly diminished both the average charge density and the maximum electric field. The modified <em>γ</em>-Fe<sub>2</sub>O<sub>3</sub>@BNNS effectively mitigated space charge accumulation at the electrode/sample interface under square-wave voltages. Specifically, the 0.5 wt% modified <em>γ</em>-Fe<sub>2</sub>O<sub>3</sub>@BNNS yields a 53 % decrease in charge accumulation at a frequency of 500 Hz. While, the 0.1 wt% sample demonstrates a 30 % reduction in electric field distortion compared to the neat epoxy at 500 Hz. Hetero-charge accumulation is detected in epoxy nanocomposites. The modified <em>γ</em>-Fe<sub>2</sub>O<sub>3</sub>@BNNS fillers at interface introduced additional deep traps, contributing to reduction in charge injection and increase in charge recombination. Consequently, it improves the space charge characteristics of epoxy resin composites for high-power electrical and electronic applications.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"344 ","pages":"Article 129461"},"PeriodicalIF":4.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732296","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 : 2025-12-08DOI: 10.1016/j.polymer.2025.129458
Yanan Qin , Shiyan Li , Zhaojie Meng , Ruxin Zang , Nian Wang , Victor Litvinov , Yongfeng Men
The relationship between the physical structures and mechanical properties of isotactic polybutene-1 (iPB-1) with a crystal-fixed form I was investigated using a combination of uniaxial tensile testing, dynamic mechanical analysis (DMA), and time-domain 1H NMR T2 relaxometry. Two samples with different crystallinity, the long-range periodicity of the lamellar structure and the density of physical network junctions in the amorphous phase were prepared by slow isothermal melt-crystallisation and by quenching of the polymer melt in ice water. The relative difference in the density of physical network junctions, which are caused by chain anchoring to crystallites and form tie molecules in amorphous domains between crystalline lamellae, was determined from the T2 relaxation time of the amorphous phase. Despite low crystallinity, the number of tie molecules was larger for the quenched sample than for the slowly-crystallised one due to two times smaller long-range period of the lamellar structure, as determined by SAXS. The population-weight-average T2 relaxation rate (1/T2PWAR) was introduced for estimating the contribution of crystalline (rigid) and amorphous (soft) domains to the volume-average macroscopic storage (G′) and shear (G) moduli. PWAR values for the entire sample (1/T2PWAR/all), for rigid (1/T2PWAR/rigid) and soft (1/T2PWAR/soft) domains were determined in a wide temperature range and compared with G′ and G values. A linear relationship was observed between 1/T2PWAR/all and G for both samples. The quenched sample displays a lower G value due to more disordered rigid domains and lower crystallinity. The effect of temperature on G′ and 1/T2PWAR values for rigid and soft domains is very similar. This study suggests that the temperature dependence of G′ and G depends on four physical structure characteristics: (1) crystallinity, (2) molecular mobility in rigid domains composed of crystal lamellae with the interfacial layer on their surface, (3) molecular mobility in soft domains, and (4) the density of network chains in the amorphous domains – tie molecules. The results of the present study are of interest for a better understanding of the role of different phases in the deformation properties of semicrystalline polymers.
{"title":"Effect of crystallisation conditions on physical structures and mechanical properties of isotactic polybutene-1","authors":"Yanan Qin , Shiyan Li , Zhaojie Meng , Ruxin Zang , Nian Wang , Victor Litvinov , Yongfeng Men","doi":"10.1016/j.polymer.2025.129458","DOIUrl":"10.1016/j.polymer.2025.129458","url":null,"abstract":"<div><div>The relationship between the physical structures and mechanical properties of isotactic polybutene-1 (iPB-1) with a crystal-fixed form I was investigated using a combination of uniaxial tensile testing, dynamic mechanical analysis (DMA), and time-domain <sup>1</sup>H NMR <em>T</em><sub>2</sub> relaxometry. Two samples with different crystallinity, the long-range periodicity of the lamellar structure and the density of physical network junctions in the amorphous phase were prepared by slow isothermal melt-crystallisation and by quenching of the polymer melt in ice water. The relative difference in the density of physical network junctions, which are caused by chain anchoring to crystallites and form tie molecules in amorphous domains between crystalline lamellae, was determined from the <em>T</em><sub>2</sub> relaxation time of the amorphous phase. Despite low crystallinity, the number of tie molecules was larger for the quenched sample than for the slowly-crystallised one due to two times smaller long-range period of the lamellar structure, as determined by SAXS. The population-weight-average <em>T</em><sub>2</sub> relaxation rate (1/<em>T</em><sub>2</sub><sup>PWAR</sup>) was introduced for estimating the contribution of crystalline (rigid) and amorphous (soft) domains to the volume-average macroscopic storage (<em>G</em>′) and shear (<em>G</em>) moduli. PWAR values for the entire sample (1/<em>T</em><sub>2</sub><sup>PWAR/all</sup>), for rigid (1/<em>T</em><sub>2</sub><sup>PWAR/rigid</sup>) and soft (1/<em>T</em><sub>2</sub><sup>PWAR/soft</sup>) domains were determined in a wide temperature range and compared with <em>G</em>′ and <em>G</em> values. A linear relationship was observed between 1/<em>T</em><sub>2</sub><sup>PWAR/all</sup> and <em>G</em> for both samples. The quenched sample displays a lower <em>G</em> value due to more disordered rigid domains and lower crystallinity. The effect of temperature on <em>G</em>′ and 1/<em>T</em><sub>2</sub><sup>PWAR</sup> values for rigid and soft domains is very similar. This study suggests that the temperature dependence of <em>G</em>′ and <em>G</em> depends on four physical structure characteristics: (1) crystallinity, (2) molecular mobility in rigid domains composed of crystal lamellae with the interfacial layer on their surface, (3) molecular mobility in soft domains, and (4) the density of network chains in the amorphous domains – tie molecules. The results of the present study are of interest for a better understanding of the role of different phases in the deformation properties of semicrystalline polymers.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"343 ","pages":"Article 129458"},"PeriodicalIF":4.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732295","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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