Pub Date : 2026-03-19Epub Date: 2026-02-07DOI: 10.1016/j.polymer.2026.129719
Peng Yue , Dandan Li , Wei Wang , Youhai Yu , Guangtao Qian , Chunhai Chen
To achieve high-performance colorless polyimide (CPI) films, this study employed a molecular structure design strategy aimed at suppressing the charge transfer complex (CTC) effect between molecular chains by introducing twisted and non-coplanar structure into the polymer backbone. Drawing inspiration from previous research, three benzimidazole-based diamine monomers with twisted non-coplanar structures were designed and synthesized by modulating the relative positions of amino groups and the structures of substituents. These monomers were subsequently polymerized with two dianhydrides, namely 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), yielding two series of polybenzimidazole-imides (PBIIs): semi-aromatic and fully aromatic polymers, respectively. The resulting semi-aromatic polymer films demonstrated a combination of excellent thermal resistance, with glass transition temperature (Tg) exceeding 400 °C, and high optical transparency, exhibiting over 80% transmittance at 400 nm (T400). This work not only provides an effective molecular design strategy for developing high-performance CPI materials but also expands the application prospects of PBII materials in the field of high-temperature optical devices.
{"title":"Twisted non-coplanar benzimidazole diamines enabling colorless, high-Tg polyimide films for flexible displays","authors":"Peng Yue , Dandan Li , Wei Wang , Youhai Yu , Guangtao Qian , Chunhai Chen","doi":"10.1016/j.polymer.2026.129719","DOIUrl":"10.1016/j.polymer.2026.129719","url":null,"abstract":"<div><div>To achieve high-performance colorless polyimide (CPI) films, this study employed a molecular structure design strategy aimed at suppressing the charge transfer complex (CTC) effect between molecular chains by introducing twisted and non-coplanar structure into the polymer backbone. Drawing inspiration from previous research, three benzimidazole-based diamine monomers with twisted non-coplanar structures were designed and synthesized by modulating the relative positions of amino groups and the structures of substituents. These monomers were subsequently polymerized with two dianhydrides, namely 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), yielding two series of polybenzimidazole-imides (PBIIs): semi-aromatic and fully aromatic polymers, respectively. The resulting semi-aromatic polymer films demonstrated a combination of excellent thermal resistance, with glass transition temperature (T<sub>g</sub>) exceeding 400 °C, and high optical transparency, exhibiting over 80% transmittance at 400 nm (T<sub>400</sub>). This work not only provides an effective molecular design strategy for developing high-performance CPI materials but also expands the application prospects of PBII materials in the field of high-temperature optical devices.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"348 ","pages":"Article 129719"},"PeriodicalIF":4.5,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135321","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-19Epub Date: 2026-02-08DOI: 10.1016/j.polymer.2026.129703
Yanan Sun , Zhuoming Duan , Kexin Huan , Minhua Li , Yanli Shi , Weili Gao , Haifeng Jia , Yuetao Liu
UV-curable silicone rubber exhibits promising prospects in fields such as flexible electronics and advanced coatings due to its high processing efficiency and patternability. This study developed a synergistic crosslinking strategy that combines Michael addition and UV curing to prepare high-performance dual network silicone rubber and achieve curing within seconds. The system comprised key components: trifluoropropyl-grafted acrylic silicone resin (PAT-SR), pentaerythritol tetraacrylate (PET4A), and aminopropyl silicone oil (ASO). Initially, the primary amine groups of ASO underwent a catalyst-free Michael addition with the acrylate groups in PAT-SR and PET4A, forming a malleable, partially cross-linked prepolymer. Subsequently, the material was cured within seconds via free radical polymerization of the residual acrylate groups upon UV irradiation. The trifluoropropyl group imparted outstanding hydrophobicity and chemical resistance to the material. PET4A, acting as a rigid cross-linking center, significantly enhanced the mechanical strength; the sample ASO0.7/PA0.4-FSR achieved a tensile strength of 0.92 MPa and an elongation at break of 612%. Furthermore, the material demonstrated good interfacial compatibility with various functional fillers. This research provides a simple and efficient novel strategy for preparing high-performance dual-network silicone rubber materials that combine excellent comprehensive properties with high processability, holding broad application potential in areas such as anti-fouling, protective coatings, and flexible electronics.
{"title":"Additive Manufacturing of UV Cured Dual-Network Silicone Elastomer with 3D Multifunctional Structure","authors":"Yanan Sun , Zhuoming Duan , Kexin Huan , Minhua Li , Yanli Shi , Weili Gao , Haifeng Jia , Yuetao Liu","doi":"10.1016/j.polymer.2026.129703","DOIUrl":"10.1016/j.polymer.2026.129703","url":null,"abstract":"<div><div>UV-curable silicone rubber exhibits promising prospects in fields such as flexible electronics and advanced coatings due to its high processing efficiency and patternability. This study developed a synergistic crosslinking strategy that combines Michael addition and UV curing to prepare high-performance dual network silicone rubber and achieve curing within seconds. The system comprised key components: trifluoropropyl-grafted acrylic silicone resin (PAT-SR), pentaerythritol tetraacrylate (PET4A), and aminopropyl silicone oil (ASO). Initially, the primary amine groups of ASO underwent a catalyst-free Michael addition with the acrylate groups in PAT-SR and PET4A, forming a malleable, partially cross-linked prepolymer. Subsequently, the material was cured within seconds via free radical polymerization of the residual acrylate groups upon UV irradiation. The trifluoropropyl group imparted outstanding hydrophobicity and chemical resistance to the material. PET4A, acting as a rigid cross-linking center, significantly enhanced the mechanical strength; the sample ASO<sub>0.7</sub>/PA<sub>0.4</sub>-FSR achieved a tensile strength of 0.92 MPa and an elongation at break of 612%. Furthermore, the material demonstrated good interfacial compatibility with various functional fillers. This research provides a simple and efficient novel strategy for preparing high-performance dual-network silicone rubber materials that combine excellent comprehensive properties with high processability, holding broad application potential in areas such as anti-fouling, protective coatings, and flexible electronics.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"348 ","pages":"Article 129703"},"PeriodicalIF":4.5,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138958","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-19Epub Date: 2026-02-04DOI: 10.1016/j.polymer.2026.129700
Jungju Ryu , Anna V. Sokolova , Minjeong Kang , Yoolee Lee , Ngoc Nguyen Quang , Daun Seol , Sanghoon Cho , Hoeil Chung , Daewon Sohn
The internal structure of tetra-arm poly(ethylene glycol) networks crosslinked via coordination bonds was investigated to understand the structural aspects of these networks, which are connected by finite polymer units. In tetra-arm poly(ethylene glycol) modified with catechol moieties (4-PCA), the networks were preserved by coordination bonds of catechol-Fe(III) ions using optimal quantitative ratios (RCA/Fe) that form bis and tris-complexes depending on pH values. The network is established with finite units associated with changes in geometrical connections. This research focuses on the structural aspects composed of controllable coordination bonding units. The samples were investigated using small-angle X-ray scattering (SAXS) and neutron scattering (SANS) measurements. The apparent correlation lengths of the gels were discussed as the presence of nano-defects. The contrast variation SANS results support the presence of nano-defects, Rg ∼3 nm. The defects are incorporated by partial irregularity of missing linkages and subsequent distortion of the topology. The rapid and sensitive controls using metal-mediated coordination bond may generate defects in the polymer network. It suggests that diverse strategies for metal-mediated hydrogels can be found by monitoring their nanostructures.
{"title":"Nanostructures of tetra-arm Poly(ethylene glycol) networks by Iron(III)-Catechol coordinative crosslinking units","authors":"Jungju Ryu , Anna V. Sokolova , Minjeong Kang , Yoolee Lee , Ngoc Nguyen Quang , Daun Seol , Sanghoon Cho , Hoeil Chung , Daewon Sohn","doi":"10.1016/j.polymer.2026.129700","DOIUrl":"10.1016/j.polymer.2026.129700","url":null,"abstract":"<div><div>The internal structure of tetra-arm poly(ethylene glycol) networks crosslinked via coordination bonds was investigated to understand the structural aspects of these networks, which are connected by finite polymer units. In tetra-arm poly(ethylene glycol) modified with catechol moieties (4-PCA), the networks were preserved by coordination bonds of catechol-Fe(III) ions using optimal quantitative ratios (R<sub>CA/Fe</sub>) that form bis and tris-complexes depending on pH values. The network is established with finite units associated with changes in geometrical connections. This research focuses on the structural aspects composed of controllable coordination bonding units. The samples were investigated using small-angle X-ray scattering (SAXS) and neutron scattering (SANS) measurements. The apparent correlation lengths of the gels were discussed as the presence of nano-defects. The contrast variation SANS results support the presence of nano-defects, R<sub>g</sub> ∼3 nm. The defects are incorporated by partial irregularity of missing linkages and subsequent distortion of the topology. The rapid and sensitive controls using metal-mediated coordination bond may generate defects in the polymer network. It suggests that diverse strategies for metal-mediated hydrogels can be found by monitoring their nanostructures.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"348 ","pages":"Article 129700"},"PeriodicalIF":4.5,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110985","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-19Epub Date: 2026-02-06DOI: 10.1016/j.polymer.2026.129678
Jun Zhao , Yangyang Yu , Kejing Wu , Yingying Liu , Yingming Zhu , Houfang Lu , Hairong Yue , Bin Liang
The presence of salt ions significantly enhances the stability of polymer/surfactant composite foam systems, offering great potential for optimizing CO2 foam flooding performance in high-salinity reservoirs. However, the molecular-level mechanism underlying this “salt ion-induced enhancement” effect remains unclear. This study systematically investigates the evolution of foam performance and the synergistic salt-tolerance mechanism of a polymer/surfactant system across a wide salinity range (0∼20 × 104 mg/L) through interface/bulk characterization combined with molecular dynamics simulations. Research demonstrates that salt ions weaken polymer/surfactant-H2O interactions through competitive hydration, while simultaneously promoting hydrogen bonds between the polymer/surfactant interface to form a highly elastic interfacial film. Additionally, the “salt thickening” effect of the foam base-fluid drives to form a supramolecular network, which is a key mechanism behind the enhanced viscoelasticity. Compared to a salt-free system, high salinity (20 × 104 mg/L) delays foam drainage (the drainage activation energy increases to 51.46 kJ/mol) and suppresses coarsening (Ostwald ripening rate decreases by 57.4%), thereby enhancing the foam comprehensive index by 1.78 times. This study elucidates the key pathways for salt ion-induced synergistic salt-tolerance in polymer/surfactant composite systems, providing theoretical support for constructing green, efficient CO2 foam systems adapted to high-salinity environments.
{"title":"Mechanisms of polymer-surfactant synergy for enhanced salt-tolerance in CO2 foams","authors":"Jun Zhao , Yangyang Yu , Kejing Wu , Yingying Liu , Yingming Zhu , Houfang Lu , Hairong Yue , Bin Liang","doi":"10.1016/j.polymer.2026.129678","DOIUrl":"10.1016/j.polymer.2026.129678","url":null,"abstract":"<div><div>The presence of salt ions significantly enhances the stability of polymer/surfactant composite foam systems, offering great potential for optimizing CO<sub>2</sub> foam flooding performance in high-salinity reservoirs. However, the molecular-level mechanism underlying this “salt ion-induced enhancement” effect remains unclear. This study systematically investigates the evolution of foam performance and the synergistic salt-tolerance mechanism of a polymer/surfactant system across a wide salinity range (0∼20 × 10<sup>4</sup> mg/L) through interface/bulk characterization combined with molecular dynamics simulations. Research demonstrates that salt ions weaken polymer/surfactant-H<sub>2</sub>O interactions through competitive hydration, while simultaneously promoting hydrogen bonds between the polymer/surfactant interface to form a highly elastic interfacial film. Additionally, the “salt thickening” effect of the foam base-fluid drives to form a supramolecular network, which is a key mechanism behind the enhanced viscoelasticity. Compared to a salt-free system, high salinity (20 × 10<sup>4</sup> mg/L) delays foam drainage (the drainage activation energy increases to 51.46 kJ/mol) and suppresses coarsening (<em>Ostwald</em> ripening rate decreases by 57.4%), thereby enhancing the foam comprehensive index by 1.78 times. This study elucidates the key pathways for salt ion-induced synergistic salt-tolerance in polymer/surfactant composite systems, providing theoretical support for constructing green, efficient CO<sub>2</sub> foam systems adapted to high-salinity environments.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"348 ","pages":"Article 129678"},"PeriodicalIF":4.5,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129701","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-19Epub Date: 2026-02-09DOI: 10.1016/j.polymer.2026.129707
Md. Homayun Kabir , Kavya Adot Veetil , Senthil Kannan , Ook Choi , Tae-Hyun Kim
A series of crosslinked rubbery polymer membranes based on poly(ethylene glycol)/poly(propylene glycol) (PEG/PPG) and doped with varying amounts of poly[2,3,5,6-tetra(carbazol-9-yl)terephthalonitrile] (p-4CzTPN)-derived porous carbon (c-4CzTPN) were fabricated via ring-opening metathesis polymerization (ROMP) to enhance their gas permeability and improve CO2 transport across the network of the PEG/PPG polymer matrix. The incorporation of c-4CzTPN significantly increased the gas diffusivity, facilitating the permeation of gas molecules, particularly CO2, across the polymer matrix. The membranes exhibit good CO2 separation performance, with CO2 permeabilities ranging from 442.92 to 558.35 Barrer and CO2/N2 and CO2/CH4 selectivities of 41.87–48.67 and 14.77–15.91, respectively. The PEG/PPG-c-4CzTPN-0.5 membrane demonstrates excellent performance, exceeding Robeson's 2008 upper bound for CO2/N2 separation. It also shows strong resistance to plasticization under a feed gas pressure up to 10 atm and maintains excellent anti-aging stability over 236 days.
{"title":"c-4CzTPN porous carbon-doped crosslinked rubbery PEG/PPG membranes synthesized via ROMP for enhanced CO2 separation","authors":"Md. Homayun Kabir , Kavya Adot Veetil , Senthil Kannan , Ook Choi , Tae-Hyun Kim","doi":"10.1016/j.polymer.2026.129707","DOIUrl":"10.1016/j.polymer.2026.129707","url":null,"abstract":"<div><div>A series of crosslinked rubbery polymer membranes based on poly(ethylene glycol)/poly(propylene glycol) (PEG/PPG) and doped with varying amounts of poly[2,3,5,6-tetra(carbazol-9-yl)terephthalonitrile] (p-4CzTPN)-derived porous carbon (c-4CzTPN) were fabricated via ring-opening metathesis polymerization (ROMP) to enhance their gas permeability and improve CO<sub>2</sub> transport across the network of the PEG/PPG polymer matrix. The incorporation of c-4CzTPN significantly increased the gas diffusivity, facilitating the permeation of gas molecules, particularly CO<sub>2</sub>, across the polymer matrix. The membranes exhibit good CO<sub>2</sub> separation performance, with CO<sub>2</sub> permeabilities ranging from 442.92 to 558.35 Barrer and CO<sub>2</sub>/N<sub>2</sub> and CO<sub>2</sub>/CH<sub>4</sub> selectivities of 41.87–48.67 and 14.77–15.91, respectively. The PEG/PPG-<em>c</em>-4CzTPN-0.5 membrane demonstrates excellent performance, exceeding Robeson's 2008 upper bound for CO<sub>2</sub>/N<sub>2</sub> separation. It also shows strong resistance to plasticization under a feed gas pressure up to 10 atm and maintains excellent anti-aging stability over 236 days.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"348 ","pages":"Article 129707"},"PeriodicalIF":4.5,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146437","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-19Epub Date: 2026-02-03DOI: 10.1016/j.polymer.2026.129654
Sreedevi T. , Franck Ducos , Jesiya Susan George , Jyotishkumar Parameswaranpillai , Asha Bhanu A.V. , Henri Vahabi , Poornima Vijayan P.
Poly(vinyl alcohol) (PVA) as a superior biodegradable polymer, it requires structural modifications using crosslinking agents and nanofillers to assure thermal integrity. PVA-cellulose nanofiber (CNF) composite films were fabricated by solvent casting with boric acid as crosslinking agent (named PVA-BA-CNF composite). Chemical interactions established between components of the composite film was characterised by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Newly formed B–O–C linkages were evident from chemical structure evaluation. Surface morphology of the film was evaluated using atomic force microscopy (AFM) and optical microscopy (OM). Morphological studies revealed a uniform dispersion of CNF in a PVA-BA crosslinked matrix especially at low boric acid content. Changes in crystallinity and crystalline size with extent of crosslinking in the composites has been evaluated using X-Ray diffraction (XRD) studies. Those parameters were correlated with melting temperature (Tm) of the composites obtained from differential scanning calorimetry (DSC). The higher glass transition temperature (Tg) recorded for PVA-BA-CNF composite films were correlated with increased crosslinking. The effect of boric acid content on thermal stability, degradation kinetics and the processing window for PVA-BA-CNF composites have been evaluated using thermogravimetric analysis (TGA). The apparent activation energy for thermal degradation was calculated using the Coats-Redfern method. Vertical flammability test was conducted to study flammability of composite films. The PVA-BA-CNF composites exhibit enhanced thermal properties making them as a potential candidate for applications where higher thermal resistance and processability are required.
{"title":"Chemical and microstructure correlation towards optimisation of thermal behaviour of boric acid crosslinked PVA-cellulose nanofiber composite","authors":"Sreedevi T. , Franck Ducos , Jesiya Susan George , Jyotishkumar Parameswaranpillai , Asha Bhanu A.V. , Henri Vahabi , Poornima Vijayan P.","doi":"10.1016/j.polymer.2026.129654","DOIUrl":"10.1016/j.polymer.2026.129654","url":null,"abstract":"<div><div>Poly(vinyl alcohol) (PVA) as a superior biodegradable polymer, it requires structural modifications using crosslinking agents and nanofillers to assure thermal integrity. PVA-cellulose nanofiber (CNF) composite films were fabricated by solvent casting with boric acid as crosslinking agent (named PVA-BA-CNF composite). Chemical interactions established between components of the composite film was characterised by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Newly formed B–O–C linkages were evident from chemical structure evaluation. Surface morphology of the film was evaluated using atomic force microscopy (AFM) and optical microscopy (OM). Morphological studies revealed a uniform dispersion of CNF in a PVA-BA crosslinked matrix especially at low boric acid content. Changes in crystallinity and crystalline size with extent of crosslinking in the composites has been evaluated using X-Ray diffraction (XRD) studies. Those parameters were correlated with melting temperature (<em>T</em><sub><em>m</em></sub>) of the composites obtained from differential scanning calorimetry (DSC). The higher glass transition temperature (<em>T</em><sub><em>g</em></sub>) recorded for PVA-BA-CNF composite films were correlated with increased crosslinking. The effect of boric acid content on thermal stability, degradation kinetics and the processing window for PVA-BA-CNF composites have been evaluated using thermogravimetric analysis (TGA). The apparent activation energy for thermal degradation was calculated using the Coats-Redfern method. Vertical flammability test was conducted to study flammability of composite films. The PVA-BA-CNF composites exhibit enhanced thermal properties making them as a potential candidate for applications where higher thermal resistance and processability are required.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"348 ","pages":"Article 129654"},"PeriodicalIF":4.5,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110986","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}
Biodegradable shape memory scaffolds have the unique potential to heal irregularly shaped craniomaxillofacial (CMF) defects through conformal ‘self-fitting’. These have been previously prepared from poly(ε-caprolactone) diacrylate (PCL-DA), but the slow biodegradation rate of PCL is expected to limit neotissue formation. Subsequently, telechelic siloxane macromers polydimethylsiloxane-dimethacrylate (PDMS-DMA) and polymethylhydrosiloxane-DMA (PMHS-DMA) were combined with PCL-DA at varying weight (wt)% ratios, resulting in PCL/PDMS and PCL/PMHS co-network scaffolds with accelerated degradation rates owing to phase separation that increased water uptake. Still, these siloxane macromers lack a hydrolytically unstable backbone thus limiting degradation. Herein, poly(silyl fumarate) (PSF) was synthesized as a hybrid siloxane macromer with a hydrolytically unstable backbone as well as interchain crosslinkability. PCL/PSF scaffolds were prepared at 90:10, 75:25, 60:40, and 50:50 wt% of PCL-DA to PSF via solvent-casting particulate leaching (SCPL) with a fused salt template. Despite a reduction in PCL crystallinity (i.e., switching segments) with 40 and 50 wt% PSF, all scaffolds maintained excellent shape memory behavior. PCL/PSF scaffolds with 10 and 25 wt% PSF also maintained the modulus of the PCL-only scaffold as well as the corresponding PCL/PDMS and PCL/PMHS scaffolds. In vitro degradation under basic conditions revealed that PCL/PSF scaffolds with just 10 wt% PSF degraded faster than the PCL-only scaffold and further increased with 25 wt% PSF to surpass that of the corresponding PCL/PDMS scaffold. A lack of phases separation was observed, and thus indicated that faster degradation was achieved by the hydrolytic instability of the PSF.
{"title":"Biodegradable poly(ε-caprolactone)/poly(silyl fumarate) shape memory scaffolds","authors":"Jenlyan Negrón Hernández , Kaley Beach , Paola Chavarria , Melissa A. Grunlan","doi":"10.1016/j.polymer.2026.129694","DOIUrl":"10.1016/j.polymer.2026.129694","url":null,"abstract":"<div><div>Biodegradable shape memory scaffolds have the unique potential to heal irregularly shaped craniomaxillofacial (CMF) defects through conformal ‘self-fitting’. These have been previously prepared from poly(ε-caprolactone) diacrylate (PCL-DA), but the slow biodegradation rate of PCL is expected to limit neotissue formation. Subsequently, telechelic siloxane macromers polydimethylsiloxane-dimethacrylate (PDMS-DMA) and polymethylhydrosiloxane-DMA (PMHS-DMA) were combined with PCL-DA at varying weight (wt)% ratios, resulting in PCL/PDMS and PCL/PMHS co-network scaffolds with accelerated degradation rates owing to phase separation that increased water uptake. Still, these siloxane macromers lack a hydrolytically unstable backbone thus limiting degradation. Herein, poly(silyl fumarate) (PSF) was synthesized as a hybrid siloxane macromer with a hydrolytically unstable backbone as well as interchain crosslinkability. PCL/PSF scaffolds were prepared at 90:10, 75:25, 60:40, and 50:50 wt% of PCL-DA to PSF via solvent-casting particulate leaching (SCPL) with a fused salt template. Despite a reduction in PCL crystallinity (i.e., switching segments) with 40 and 50 wt% PSF, all scaffolds maintained excellent shape memory behavior. PCL/PSF scaffolds with 10 and 25 wt% PSF also maintained the modulus of the PCL-only scaffold as well as the corresponding PCL/PDMS and PCL/PMHS scaffolds. <em>In vitro</em> degradation under basic conditions revealed that PCL/PSF scaffolds with just 10 wt% PSF degraded faster than the PCL-only scaffold and further increased with 25 wt% PSF to surpass that of the corresponding PCL/PDMS scaffold. A lack of phases separation was observed, and thus indicated that faster degradation was achieved by the hydrolytic instability of the PSF.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"348 ","pages":"Article 129694"},"PeriodicalIF":4.5,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135322","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-19Epub Date: 2026-02-10DOI: 10.1016/j.polymer.2026.129721
Matheus H. Nachbar, Marion Colella, Sébastien Livi, Jannick D. Rumeau
The textile industry has recently been identified as a major contributor to plastic production and environmental pollution. The rising consumption of clothing with shorter lifespans, driven by fast fashion, has led to a significant increase in the production of synthetic fibers. Among these, poly(ethylene terephthalate) (PET) is the most widely used on the market. In this study, we propose a promising upcycling strategy for textile-grade PET via reactive extrusion to obtain covalent adaptable networks (CANs). A comparative study was performed using a conventional catalyst, Zn(acac)2 and a metallic ionic liquid (MIL). The use of ionic liquids as transesterification catalysts demonstrated promising results and represents a compelling alternative to traditional metal-organic catalysts, owing to their lower toxicity and superior thermal stability. The resulting CAN systems exhibited high gel fractions and fast relaxation, regardless of the catalyst employed. Notably, faster relaxation times were achieved with the MIL catalyst, attributed to increased PET chain scission during the extrusion process. This work highlights the potential of ionic liquids as catalysts in PET-based CANs and emphasizes the importance of balancing catalyst loading to optimize final material properties while minimizing chain degradation during processing.
{"title":"Metal-based ionic liquids as new catalyst of covalent adaptable networks based on poly(ethylene terephthalate) from textile grade","authors":"Matheus H. Nachbar, Marion Colella, Sébastien Livi, Jannick D. Rumeau","doi":"10.1016/j.polymer.2026.129721","DOIUrl":"10.1016/j.polymer.2026.129721","url":null,"abstract":"<div><div>The textile industry has recently been identified as a major contributor to plastic production and environmental pollution. The rising consumption of clothing with shorter lifespans, driven by fast fashion, has led to a significant increase in the production of synthetic fibers. Among these, poly(ethylene terephthalate) (PET) is the most widely used on the market. In this study, we propose a promising upcycling strategy for textile-grade PET via reactive extrusion to obtain covalent adaptable networks (CANs). A comparative study was performed using a conventional catalyst, Zn(acac)<sub>2</sub> and a metallic ionic liquid (MIL). The use of ionic liquids as transesterification catalysts demonstrated promising results and represents a compelling alternative to traditional metal-organic catalysts, owing to their lower toxicity and superior thermal stability. The resulting CAN systems exhibited high gel fractions and fast relaxation, regardless of the catalyst employed. Notably, faster relaxation times were achieved with the MIL catalyst, attributed to increased PET chain scission during the extrusion process. This work highlights the potential of ionic liquids as catalysts in PET-based CANs and emphasizes the importance of balancing catalyst loading to optimize final material properties while minimizing chain degradation during processing.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"348 ","pages":"Article 129721"},"PeriodicalIF":4.5,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146153081","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}
To address the urgent need for low-dielectric-loss (Df) materials in high-frequency communication, developing novel polymers that suppress dipole and interfacial polarization is crucial. Incorporating rigid planar conjugated units into the backbone to enhance π–π stacking provides a viable route for reducing Df. This work introduces an innovative “bifunctional monomer synergy” strategy to regulate such stacking. A novel quinoxaline monomer, M1, featuring a rigid planar conjugated skeleton and trifluoromethyl groups, was designed and synthesized. To balance processability, a rotatable quinoxaline monomer, M2, was simultaneously introduced. Ternary copolymerization of M1, M2 with three bisphenols (BHF, 6F-BPA, DHPZ) yielded three poly(arylene ether)s (PAEs): PBEQ-FEI, P6FEQ-FEI, and PDEQ-FEI.In stark contrast to commercial PEEK (Df typically 0.01–0.02 in the GHz range), PBEQ-FEI performs best, achieving a low dielectric constant (Dk) of 2.687 and an ultra-low Df of 0.00368 at 15 GHz. It also possesses a high glass-transition temperature (Tg) (320°C), a tensile strength of 127.7 MPa, low water absorption (0.41%), and a low coefficient of thermal expansion (CTE) (37.89 ppm/K).The M1 unit is the core driver for constructing an effective intermolecular π–π stacking network, which restricts chain-segment motion and reduces loss. The trifluoromethyl group and M2 synergistically lower polarity and improve processability. Comparative studies reveal that BHF, owing to its rigid planar structure, shows optimal spatial and electronic synergy with M1, leading to a moderately ordered interchain stacking pattern. This work provides a useful reference and solid experimental foundation for regulating polymer aggregation structures via molecular co-design, enabling the synergistic optimization of high-frequency dielectric and thermomechanical properties.
{"title":"Low-Dielectric-Loss Poly(arylene ether) Enabled by a Rigid Planar Quinoxaline Scaffold","authors":"Zhichao Yang, Lishuai Zong, Linyan Zhu, Wenguang Zhang, Jinyan Wang, Xigao Jian","doi":"10.1016/j.polymer.2026.129875","DOIUrl":"https://doi.org/10.1016/j.polymer.2026.129875","url":null,"abstract":"To address the urgent need for low-dielectric-loss (D<sub>f</sub>) materials in high-frequency communication, developing novel polymers that suppress dipole and interfacial polarization is crucial. Incorporating rigid planar conjugated units into the backbone to enhance π–π stacking provides a viable route for reducing D<sub>f</sub>. This work introduces an innovative “bifunctional monomer synergy” strategy to regulate such stacking. A novel quinoxaline monomer, M1, featuring a rigid planar conjugated skeleton and trifluoromethyl groups, was designed and synthesized. To balance processability, a rotatable quinoxaline monomer, M2, was simultaneously introduced. Ternary copolymerization of M1, M2 with three bisphenols (BHF, 6F-BPA, DHPZ) yielded three poly(arylene ether)s (PAEs): PBEQ-FEI, P6FEQ-FEI, and PDEQ-FEI.In stark contrast to commercial PEEK (D<sub>f</sub> typically 0.01–0.02 in the GHz range), PBEQ-FEI performs best, achieving a low dielectric constant (D<sub>k</sub>) of 2.687 and an ultra-low D<sub>f</sub> of 0.00368 at 15 GHz. It also possesses a high glass-transition temperature (T<sub>g</sub>) (320°C), a tensile strength of 127.7 MPa, low water absorption (0.41%), and a low coefficient of thermal expansion (CTE) (37.89 ppm/K).The M1 unit is the core driver for constructing an effective intermolecular π–π stacking network, which restricts chain-segment motion and reduces loss. The trifluoromethyl group and M2 synergistically lower polarity and improve processability. Comparative studies reveal that BHF, owing to its rigid planar structure, shows optimal spatial and electronic synergy with M1, leading to a moderately ordered interchain stacking pattern. This work provides a useful reference and solid experimental foundation for regulating polymer aggregation structures via molecular co-design, enabling the synergistic optimization of high-frequency dielectric and thermomechanical properties.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-18DOI: 10.1016/j.polymer.2026.129868
Nguyen Tan Tan, Cao Dang Hoang An, Ngoc Yen Nguyen, Thai Hai Nhan Nguyen, Ming-Hua Ho, Viet Nhan Hoa Nguyen, Doan Van Hong Thien
{"title":"Enhanced water permeability and salt rejection in FO membranes via hydrophilic hydroxyapatite-modified PVA/chitosan nanofiber supports","authors":"Nguyen Tan Tan, Cao Dang Hoang An, Ngoc Yen Nguyen, Thai Hai Nhan Nguyen, Ming-Hua Ho, Viet Nhan Hoa Nguyen, Doan Van Hong Thien","doi":"10.1016/j.polymer.2026.129868","DOIUrl":"https://doi.org/10.1016/j.polymer.2026.129868","url":null,"abstract":"","PeriodicalId":405,"journal":{"name":"Polymer","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496521","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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