Pub Date : 2026-03-18Epub Date: 2026-02-01DOI: 10.1016/j.eurpolymj.2026.114549
Jian-Peng Han , Wei Li , Tian-Tian Wang , Chao Wang , Zheng-Hong Luo , Yin-Ning Zhou
The accumulation of non-degradable chloroprene rubber (CR) causes detrimental environmental concerns. In this work, deconstruction of CR (i.e., CR240T) and upcycling of CR240T with norbornene (NBE) through olefin metathesis reaction using the second-generation Grubbs catalyst (G2) are investigated. Experimental results show that the number-averaged molar mass (Mn) of deconstruction product (DCR) decreases from 136 to 21 kDa with the increase of G2 concentration. Meanwhile, deconstruction mechanism becomes more complex from the cross-metathesis with G2 dominated to the cross-metathesis and ring-closing metathesis (RCM) reaction coexisted. Besides, concurrent ring-opening metathesis polymerization of norbornene (NBE) and macromolecular cross-metathesis between CR240T and PNBE enables the synthesis of CR and PNBE multiblock-like copolymer (CRNBE). The Mn of the resulting CRNBE increases as NBE concentration increases or G2 concentration decreases. The copolymers CRNBE0.5 and CRNBE1 own much higher Young’s modulus as 91.0 ± 3.9 MPa and 347.8 ± 16.7 MPa, respectively, compared to that of the pristine CR240T (28.1 ± 2.7 MPa). This study provides meaningful insights into the deconstruction mechanism of CR via metathesis reaction and a facile way for its upcycling.
{"title":"Olefin metathesis-driven deconstruction and upcycling of chloroprene rubber","authors":"Jian-Peng Han , Wei Li , Tian-Tian Wang , Chao Wang , Zheng-Hong Luo , Yin-Ning Zhou","doi":"10.1016/j.eurpolymj.2026.114549","DOIUrl":"10.1016/j.eurpolymj.2026.114549","url":null,"abstract":"<div><div>The accumulation of non-degradable chloroprene rubber (CR) causes detrimental environmental concerns. In this work, deconstruction of CR (i.e., CR240T) and upcycling of CR240T with norbornene (NBE) through olefin metathesis reaction using the second-generation Grubbs catalyst (<strong>G2</strong>) are investigated. Experimental results show that the number-averaged molar mass (<em>M</em><sub>n</sub>) of deconstruction product (DCR) decreases from 136 to 21 kDa with the increase of <strong>G2</strong> concentration. Meanwhile, deconstruction mechanism becomes more complex from the cross-metathesis with <strong>G2</strong> dominated to the cross-metathesis and ring-closing metathesis (RCM) reaction coexisted. Besides, concurrent ring-opening metathesis polymerization of norbornene (NBE) and macromolecular cross-metathesis between CR240T and PNBE enables the synthesis of CR and PNBE multiblock-like copolymer (CRNBE). The <em>M</em><sub>n</sub> of the resulting CRNBE increases as NBE concentration increases or <strong>G2</strong> concentration decreases. The copolymers CRNBE<sub>0.5</sub> and CRNBE<sub>1</sub> own much higher Young’s modulus as 91.0 ± 3.9 MPa and 347.8 ± 16.7 MPa, respectively, compared to that of the pristine CR240T (28.1 ± 2.7 MPa). This study provides meaningful insights into the deconstruction mechanism of CR <em>via</em> metathesis reaction and a facile way for its upcycling.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"246 ","pages":"Article 114549"},"PeriodicalIF":6.3,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122693","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 : 2026-03-18Epub Date: 2026-02-11DOI: 10.1016/j.eurpolymj.2026.114573
Jinglei Xing , Yujie Zhang , Lei Yang , Tianci Ma , Yanling Wang , Xingzhong Fang , Long Wang , Guofei Chen
With the rapid development of flexible optoelectronic devices, higher requirements are placed on the heat resistance and transparency of colorless polyimide (CPI). In this study, two imide-containing diacyl chlorides derived from 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), HC-HPMDA and MC-HPMDA, were successfully designed and synthesized, and two series of poly(amide-imide)s (PAIs) were obtained by polymerization with 2,2′-bis(trifluoromethyl)benzidine (TFDB), 9,9-bis(4-aminophenyl)fluorene (FDA) and m-phenylenediamine (m-PDA), respectively. The rigid amide bonds in the molecular chains could generate hydrogen bonds to enhance intermolecular forces. In addition, the introduction of the alicyclic structures disrupted the conjugation effect of the main chain to improve the transparency of the polymers. The obtained PAI films had high glass transition temperature (Tg > 389 ℃), low coefficient of thermal expansion (CTE < 49.8 ppm/K) and excellent optical transparency. Therefore, the incorporation of imide rings and amide bonds into the main chain through polymerization with HPMDA-derived diacyl chloride provided a simple method for the synthesis of heat-resistant transparent PAIs. In addition, the introduction of CH3 groups limited the movement of the chain segments, which improved the comprehensive properties of PAIs. In particular, PAI-TFDB-M exhibited high Tg of 426 ℃, low CTE of 36.1 ppm/K, high transmittance of 87% at 400 nm and good mechanical properties with tensile strength of 140 MPa and tensile modulus of 4.2 GPa, which is expected to be applied in the field of flexible optoelectronics.
{"title":"High heat-resistant transparent poly(amide-imide)s based on diacyl chloride containing imide and cyclohexane structures by ortho-methyl side group effect","authors":"Jinglei Xing , Yujie Zhang , Lei Yang , Tianci Ma , Yanling Wang , Xingzhong Fang , Long Wang , Guofei Chen","doi":"10.1016/j.eurpolymj.2026.114573","DOIUrl":"10.1016/j.eurpolymj.2026.114573","url":null,"abstract":"<div><div>With the rapid development of flexible optoelectronic devices, higher requirements are placed on the heat resistance and transparency of colorless polyimide (CPI). In this study, two imide-containing diacyl chlorides derived from 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), HC-HPMDA and MC-HPMDA, were successfully designed and synthesized, and two series of poly(amide-imide)s (PAIs) were obtained by polymerization with 2,2′-bis(trifluoromethyl)benzidine (TFDB), 9,9-bis(4-aminophenyl)fluorene (FDA) and <em>m</em>-phenylenediamine (<em>m</em>-PDA), respectively. The rigid amide bonds in the molecular chains could generate hydrogen bonds to enhance intermolecular forces. In addition, the introduction of the alicyclic structures disrupted the conjugation effect of the main chain to improve the transparency of the polymers. The obtained PAI films had high glass transition temperature (<em>T</em><sub>g</sub> > 389 ℃), low coefficient of thermal expansion (CTE < 49.8 ppm/K) and excellent optical transparency. Therefore, the incorporation of imide rings and amide bonds into the main chain through polymerization with HPMDA-derived diacyl chloride provided a simple method for the synthesis of heat-resistant transparent PAIs. In addition, the introduction of CH<sub>3</sub> groups limited the movement of the chain segments, which improved the comprehensive properties of PAIs. In particular, PAI-TFDB-M exhibited high <em>T</em><sub>g</sub> of 426 ℃, low CTE of 36.1 ppm/K, high transmittance of 87% at 400 nm and good mechanical properties with tensile strength of 140 MPa and tensile modulus of 4.2 GPa, which is expected to be applied in the field of flexible optoelectronics.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"246 ","pages":"Article 114573"},"PeriodicalIF":6.3,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186817","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 : 2026-03-18Epub Date: 2026-01-13DOI: 10.1016/j.eurpolymj.2026.114514
Samah Saied-Ahmad, Ofir Binenthal, Keshet Yelin, Michael S. Silverstein
PolyMIPEs are macroporous polymers templated within medium internal phase emulsions (MIPEs), 30 to 74 vol % internal phase. Emulsion-templated biocompatible and biodegradable polycaprolactone (PCL) polyMIPEs, attractive for biomedical applications such as tissue engineering, have been generated using oligomeric polyols. Macroporous, high molecular weight PCLs, advantageous for many applications, can be accessed through the ring-opening polymerization (ROP) of ε-caprolactone (CL) within oil-in-oil (O/O) emulsions. Here, a novel toolset for synthesizing macroporous biodegradable, and even printable polyesters was generated by combining ROP, emulsion templating, and foaming in a versatile design platform to provide enhanced control over the macromolecular architecture, porous structure, properties, and degradation.
Highly interconnected, macroporous PCLs, with densities and moduli suitable for soft tissue scaffolds, were synthesized under various conditions. The relatively low-temperature, metal-free organo-catalysts are of interest for biomedical applications and the room temperature UV catalysis can enable access to additive manufacturing. The introduction of hierarchical porosity through foaming reduced the density and modulus, while enhancing the degradation rate. Poly(l-lactide) polyMIPEs, with densities and moduli similar to those of the PCL polyMIPEs, exhibited significantly higher degradation rates.
{"title":"Porous Degradable Polyesters from Ring-Opening Polymerization within Oil-in-Oil Emulsions: Initiation, Catalysis, and Foaming","authors":"Samah Saied-Ahmad, Ofir Binenthal, Keshet Yelin, Michael S. Silverstein","doi":"10.1016/j.eurpolymj.2026.114514","DOIUrl":"10.1016/j.eurpolymj.2026.114514","url":null,"abstract":"<div><div>PolyMIPEs are macroporous polymers templated within medium internal phase emulsions (MIPEs), 30 to 74 vol % internal phase. Emulsion-templated biocompatible and biodegradable polycaprolactone (PCL) polyMIPEs, attractive for biomedical applications such as tissue engineering, have been generated using oligomeric polyols. Macroporous, high molecular weight PCLs, advantageous for many applications, can be accessed through the ring-opening polymerization (ROP) of ε-caprolactone (CL) within oil-in-oil (O/O) emulsions. Here, a novel toolset for synthesizing macroporous biodegradable, and even printable polyesters was generated by combining ROP, emulsion templating, and foaming in a versatile design platform to provide enhanced control over the macromolecular architecture, porous structure, properties, and degradation.</div><div>Highly interconnected, macroporous PCLs, with densities and moduli suitable for soft tissue scaffolds, were synthesized under various conditions. The relatively low-temperature, metal-free organo-catalysts are of interest for biomedical applications and the room temperature UV catalysis can enable access to additive manufacturing. The introduction of hierarchical porosity through foaming reduced the density and modulus, while enhancing the degradation rate. Poly(<span>l</span>-lactide) polyMIPEs, with densities and moduli similar to those of the PCL polyMIPEs, exhibited significantly higher degradation rates.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"246 ","pages":"Article 114514"},"PeriodicalIF":6.3,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122696","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 : 2026-03-18Epub Date: 2026-02-08DOI: 10.1016/j.eurpolymj.2026.114566
Jinhui Liu , Zipeng Zhang , Yueqin Yu , Yuetao Liu , Jianzhi Liu
Injectable photo-crosslinkable adhesive hydrogels represent an effective strategy for achieving in vivo wound hemostasis and promoting healing. However, developing adhesive gel dressings that simultaneously possess strong tissue adhesion, injectability, photo-curability, inherent antimicrobial properties, and excellent biocompatibility remains a significant challenge. Herein, by employing photo-controlled reversible addition–fragmentation chain transfer (RAFT) polymerization, in which the polymerization process can be “turned on” and “suspend” by regulating the light source, a spatiotemporally controllable hydrogel was prepared using the photo-RAFT agent (InZ), acrylic acid (AA), and acryloyl chitosan (AeCS).Benefiting from the properties of photoinitiator InZ, the photopolymerization process can be precisely regulated under ambient conditions, allowing for in situ gel formation directly at wound sites. The obtained hydrogel exhibited excellent mechanical properties, swelling behavior, and biocompatibility (>80%). It showed strong adhesion (>11.8kpa) and repeatable adhesiveness to skin tissue and also adhered well to various substrates. Moreover, it displayed good inherent antimicrobial capability against Escherichia coli (73.4%∼89.96%) and Staphylococcus aureus (72.7%∼87.04%). By introducing a natural macromolecular crosslinker, the hydrogel was endowed with degradability. Notably, based on the characteristics of photo-controlled RAFT polymerization, a prepolymer solution with tunable viscosity was obtained, endowing the hydrogel with injectability. Taken together, these results indicate that the constructed hydrogel holds great potential as a biomedical material.
{"title":"Preparation of adhesive and degradable hydrogels with adjustable viscosity by photo controlled RAFT polymerization","authors":"Jinhui Liu , Zipeng Zhang , Yueqin Yu , Yuetao Liu , Jianzhi Liu","doi":"10.1016/j.eurpolymj.2026.114566","DOIUrl":"10.1016/j.eurpolymj.2026.114566","url":null,"abstract":"<div><div>Injectable photo-crosslinkable adhesive hydrogels represent an effective strategy for achieving in vivo wound hemostasis and promoting healing. However, developing adhesive gel dressings that simultaneously possess strong tissue adhesion, injectability, photo-curability, inherent antimicrobial properties, and excellent biocompatibility remains a significant challenge. Herein, by employing photo-controlled reversible addition–fragmentation chain transfer (RAFT) polymerization, in which the polymerization process can be “turned on” and “suspend” by regulating the light source, a spatiotemporally controllable hydrogel was prepared using the photo-RAFT agent (InZ), acrylic acid (AA), and acryloyl chitosan (AeCS).Benefiting from the properties of photoinitiator InZ, the photopolymerization process can be precisely regulated under ambient conditions, allowing for in situ gel formation directly at wound sites. The obtained hydrogel exhibited excellent mechanical properties, swelling behavior, and biocompatibility (>80%). It showed strong adhesion (>11.8kpa) and repeatable adhesiveness to skin tissue and also adhered well to various substrates. Moreover, it displayed good inherent antimicrobial capability against <em>Escherichia coli</em> (73.4%∼89.96%) and <em>Staphylococcus aureus</em> (72.7%∼87.04%). By introducing a natural macromolecular crosslinker, the hydrogel was endowed with degradability. Notably, based on the characteristics of photo-controlled RAFT polymerization, a prepolymer solution with tunable viscosity was obtained, endowing the hydrogel with injectability. Taken together, these results indicate that the constructed hydrogel holds great potential as a biomedical material.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"246 ","pages":"Article 114566"},"PeriodicalIF":6.3,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186820","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 : 2026-03-18Epub Date: 2026-02-10DOI: 10.1016/j.eurpolymj.2026.114565
Panpan Gu , Dongshu Chen , Rui Zhang , Xiaoxu Xu , Dehong Cheng , Bai Wang , Jianshe Hu
Conductive elastomers have attracted extensive research interest due to their great potential in flexible electronics and health-monitoring applications. In this study, a novel green conductive elastomer (APC-PDES) based on aliphatic polycarbonate (APC) and polymeric deep eutectic solvent (PDES) was successfully prepared. The obtained elastomer APC-PDES displayed mechanical properties necessary for meeting the application, and exhibited a breaking stress of 89.8 kPa and an elongation at break of 219.1%. It also showed a low glass transition temperature of −6.70°C and good thermal stability with decomposition temperature of 247.39°C. Moreover, the elastomer exhibited exceptional self-healing capabilities, achieving self-healing efficiencies of 85.9% for strain and 82.4% for stress, high sensitivity with a gauge factor with increasing from 1.75 to 5.68 within the range of 0–200% of the strain, and stable response characteristics during the simultaneous real-time monitoring of human joint movements and microexpressions, when incorporated into flexible sensors. Additionally, this elastomer allowed for the acquisition of clear and stable electrocardiogram signals as a bio-electrode. This research provides a new idea for detecting human movement and health in the future.
{"title":"New conductive elastomers based on aliphatic polycarbonate and polymeric deep eutectic solvent for flexible wearable sensors","authors":"Panpan Gu , Dongshu Chen , Rui Zhang , Xiaoxu Xu , Dehong Cheng , Bai Wang , Jianshe Hu","doi":"10.1016/j.eurpolymj.2026.114565","DOIUrl":"10.1016/j.eurpolymj.2026.114565","url":null,"abstract":"<div><div>Conductive elastomers have attracted extensive research interest due to their great potential in flexible electronics and health-monitoring applications. In this study, a novel green conductive elastomer (APC-PDES) based on aliphatic polycarbonate (APC) and polymeric deep eutectic solvent (PDES) was successfully prepared. The obtained elastomer APC-PDES displayed mechanical properties necessary for meeting the application, and exhibited a breaking stress of 89.8 kPa and an elongation at break of 219.1%. It also showed a low glass transition temperature of −6.70°C and good thermal stability with decomposition temperature of 247.39°C. Moreover, the elastomer exhibited exceptional self-healing capabilities, achieving self-healing efficiencies of 85.9% for strain and 82.4% for stress, high sensitivity with a gauge factor with increasing from 1.75 to 5.68 within the range of 0–200% of the strain, and stable response characteristics during the simultaneous real-time monitoring of human joint movements and microexpressions, when incorporated into flexible sensors. Additionally, this elastomer allowed for the acquisition of clear and stable electrocardiogram signals as a bio-electrode. This research provides a new idea for detecting human movement and health in the future.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"246 ","pages":"Article 114565"},"PeriodicalIF":6.3,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186818","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 : 2026-03-18Epub Date: 2026-02-06DOI: 10.1016/j.eurpolymj.2026.114563
Giacomo Damonte, Louise Dullaert, Alessandro Pellis, Leonardo Giribaldi, Orietta Monticelli
Despite its many advantages over other bioplastics, poly(ε-caprolactone) (PCL) still faces limited applications and a lack of sustainable chemical recycling routes that could extend its life cycle, reduce its carbon footprint, and enhance its applicability. In this work, to address this gap, a novel bulk alcoholysis process was developed for upcycling PCL into functional hydroxyl-terminated oligomers using two bio-based fatty alcohols, 1-dodecanol and 1,12-dodecandiol, in the presence of zinc stearate as a catalyst. This approach enables precise control over the final properties of the resulting oligomers by varying the type and the concentration of the alcohol, yielding mono- and difunctional telechelic structures suitable for further synthesis. The prepared PCL-based oligomers were used directly, without purification, as macroinitiators for the ring-opening polymerization (ROP) of L-lactide to synthesize well-defined diblock (PCL-PLA) and triblock (PLA-PCL-PLA) copolymers with a PCL/PLA ratio of 1 and tailored chain lengths. These copolymers were then applied in two different scenarios. The diblock copolymers were tested as compatibilizers for PLA/PCL blends, where they enhanced the elongation at break by improving interfacial adhesion between the two polymer phases. Moreover, two telechelic systems, namely a PCL oligomer and a PLA-PCL-PLA copolymer, were used in the preparation of thermoplastic polyurethanes (TPUs) via chain-extension reactions with methylene diphenyl diisocyanate (MDI), leveraging the residual catalyst and demonstrating efficient polymerization. Overall, the developed approach provides a robust, solvent-free, scalable, and effective strategy for valorizing PCL waste, establishing a platform for producing sustainable, functional polyester-based building blocks.
{"title":"On the upcycling of PCL to produce building blocks for the development of PCL-PLA copolymers","authors":"Giacomo Damonte, Louise Dullaert, Alessandro Pellis, Leonardo Giribaldi, Orietta Monticelli","doi":"10.1016/j.eurpolymj.2026.114563","DOIUrl":"10.1016/j.eurpolymj.2026.114563","url":null,"abstract":"<div><div>Despite its many advantages over other bioplastics, poly(ε-caprolactone) (PCL) still faces limited applications and a lack of sustainable chemical recycling routes that could extend its life cycle, reduce its carbon footprint, and enhance its applicability. In this work, to address this gap, a novel bulk alcoholysis process was developed for upcycling PCL into functional hydroxyl-terminated oligomers using two bio-based fatty alcohols, 1-dodecanol and 1,12-dodecandiol, in the presence of zinc stearate as a catalyst. This approach enables precise control over the final properties of the resulting oligomers by varying the type and the concentration of the alcohol, yielding mono- and difunctional telechelic structures suitable for further synthesis. The prepared PCL-based oligomers were used directly, without purification, as macroinitiators for the ring-opening polymerization (ROP) of <em>L</em>-lactide to synthesize well-defined diblock (PCL-PLA) and triblock (PLA-PCL-PLA) copolymers with a PCL/PLA ratio of 1 and tailored chain lengths. These copolymers were then applied in two different scenarios. The diblock copolymers were tested as compatibilizers for PLA/PCL blends, where they enhanced the elongation at break by improving interfacial adhesion between the two polymer phases. Moreover, two telechelic systems, namely a PCL oligomer and a PLA-PCL-PLA copolymer, were used in the preparation of thermoplastic polyurethanes (TPUs) via chain-extension reactions with methylene diphenyl diisocyanate (MDI), leveraging the residual catalyst and demonstrating efficient polymerization. Overall, the developed approach provides a robust, solvent-free, scalable, and effective strategy for valorizing PCL waste, establishing a platform for producing sustainable, functional polyester-based building blocks.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"246 ","pages":"Article 114563"},"PeriodicalIF":6.3,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186816","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}
Thermoset polymers are employed as matrices for fiber-reinforced composite materials due to their outstanding thermo-mechanical and chemical properties. However, the irreversible nature of their covalently crosslinked network makes conventional recycling methods unsuitable for their efficient and economically competitive reprocessing. Moreover, the most common thermoset systems typically rely on depletable and often hazardous fossil-based sources. Vitrimers have been introduced in recent years to offer potential advantages over traditional thermosets, as they can mitigate some of these issues thanks to their three-dimensional covalent network, able to undergo temperature-activated dynamic bond-exchange reactions leading to topological rearrangement. As the environmental concerns about the end-of-life of materials are paired with the need to replace fossil-based resources, research is moving towards the formulation of vitrimeric composites obtained from biobased constituents. This work employed an algae-derived epoxy resin (phloroglucinol triglycidyl ether) with glutaric anhydride to develop an easy-reprocessable, catalyst-free vitrimer for the production of glass fiber-reinforced composites. The vitrimeric behavior of these systems was assessed via rheological stress relaxation, which was found to be fast at moderately high temperatures (3 min at 200 °C, 100 min at 120 °C) and could be repeated multiple times due to the high chemical reversibility of the network. The resin was then employed as matrix for a thermoformable and weldable glass fiber-reinforced laminate with excellent adhesion strength (54 MPa) and easy chemical recyclability in mild conditions (150 °C, ambient pressure). Finally, the enhanced circularity of the produced composite was compared to a standard thermoset counterpart employing the Material Circularity Indicator.
{"title":"Catalyst-free epoxy vitrimers from phloroglucinol and glutaric anhydride for reusable-by-design biobased glass-fiber-reinforced composites","authors":"Giulia Altamura, Stefano Turri, Gianmarco Griffini","doi":"10.1016/j.eurpolymj.2026.114559","DOIUrl":"10.1016/j.eurpolymj.2026.114559","url":null,"abstract":"<div><div>Thermoset polymers are employed as matrices for fiber-reinforced composite materials due to their outstanding thermo-mechanical and chemical properties. However, the irreversible nature of their covalently crosslinked network makes conventional recycling methods unsuitable for their efficient and economically competitive reprocessing. Moreover, the most common thermoset systems typically rely on depletable and often hazardous fossil-based sources. Vitrimers have been introduced in recent years to offer potential advantages over traditional thermosets, as they can mitigate some of these issues thanks to their three-dimensional covalent network, able to undergo temperature-activated dynamic bond-exchange reactions leading to topological rearrangement. As the environmental concerns about the end-of-life of materials are paired with the need to replace fossil-based resources, research is moving towards the formulation of vitrimeric composites obtained from biobased constituents. This work employed an algae-derived epoxy resin (phloroglucinol triglycidyl ether) with glutaric anhydride to develop an easy-reprocessable, catalyst-free vitrimer for the production of glass fiber-reinforced composites. The vitrimeric behavior of these systems was assessed <em>via</em> rheological stress relaxation, which was found to be fast at moderately high temperatures (3 min at 200 °C, 100 min at 120 °C) and could be repeated multiple times due to the high chemical reversibility of the network. The resin was then employed as matrix for a thermoformable and weldable glass fiber-reinforced laminate with excellent adhesion strength (54 MPa) and easy chemical recyclability in mild conditions (150 °C, ambient pressure). Finally, the enhanced circularity of the produced composite was compared to a standard thermoset counterpart employing the Material Circularity Indicator.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"246 ","pages":"Article 114559"},"PeriodicalIF":6.3,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122695","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 : 2026-03-18Epub Date: 2026-02-05DOI: 10.1016/j.eurpolymj.2026.114568
Guolong Zhang , Wenjing Feng , Chenying Liu , Linhua Wang , Cui Cheng , Xiao Han , Wenjuan Chen
This study develops a multifunctional hydrogel that achieves highly effective treatment of hepatocellular carcinoma (HCC) by combining phototherapy with immunotherapy and remodeling tumor microenvironment (TME). The hydrogel is prepared via dynamic Schiff base crosslinking between carboxymethyl chitosan and four-arm PEG benzaldehyde, incorporating polyvinylpyrrolidone-modified Bi2WO6-x (BWO-PVP) nanoparticles and fucoidan (Fu). In vitro studies demonstrate that the hydrogel exhibites good self-healing properties, injectability, and TME-responsive degradation behavior. Under 808 nm laser irradiation, it generates substantial hyperthermia and reactive oxygen species, leading to significant inhibition of HepG2 cell proliferation. Moreover, the hydrogel can release Fu to suppresse the activation of cancer-associated fibroblasts (CAFs), which contributing to TME remodeling. In H22 hepatoma-bearing mice, the hydrogel can also load the STING agonist (cyclic dinucleotide, CDN), thereby suppressing tumor growth and reversing immunosuppressive TME conditions. Hence, this combinatory strategy provides a promising platform for enhancing HCC treatment through integrated phototherapy, TME regulation and immunotherapy.
{"title":"Multifunctional hydrogel integrating phototherapy and tumor microenvironment remodeling combined with immunotherapy for synergistic treatment of HCC","authors":"Guolong Zhang , Wenjing Feng , Chenying Liu , Linhua Wang , Cui Cheng , Xiao Han , Wenjuan Chen","doi":"10.1016/j.eurpolymj.2026.114568","DOIUrl":"10.1016/j.eurpolymj.2026.114568","url":null,"abstract":"<div><div>This study develops a multifunctional hydrogel that achieves highly effective treatment of hepatocellular carcinoma (HCC) by combining phototherapy with immunotherapy and remodeling tumor microenvironment (TME). The hydrogel is prepared via dynamic Schiff base crosslinking between carboxymethyl chitosan and four-arm PEG benzaldehyde, incorporating polyvinylpyrrolidone-modified Bi<sub>2</sub>WO<sub>6-x</sub> (BWO-PVP) nanoparticles and fucoidan (Fu). <em>In vitro</em> studies demonstrate that the hydrogel exhibites good self-healing properties, injectability, and TME-responsive degradation behavior. Under 808 nm laser irradiation, it generates substantial hyperthermia and reactive oxygen species, leading to significant inhibition of HepG2 cell proliferation. Moreover, the hydrogel can release Fu to suppresse the activation of cancer-associated fibroblasts (CAFs), which contributing to TME remodeling. In H22 hepatoma-bearing mice, the hydrogel can also load the STING agonist (cyclic dinucleotide, CDN), thereby suppressing tumor growth and reversing immunosuppressive TME conditions. Hence, this combinatory strategy provides a promising platform for enhancing HCC treatment through integrated phototherapy, TME regulation and immunotherapy.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"246 ","pages":"Article 114568"},"PeriodicalIF":6.3,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186815","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 : 2026-03-18Epub Date: 2026-02-10DOI: 10.1016/j.eurpolymj.2026.114571
Mahmoud S. Tolba , Aya Harby , Adel M. Kamal El-Dean , Marwa M. Sayed , Osama Younis
This work explores a family of four newly designed polyhydrazides obtained through polycondensation, in which two subtle yet decisive structural variables were deliberately tuned: the geometry of the phenylene linkage (ortho versus para) and the length of the aliphatic spacer (C1 versus C2). A broad suite of analytical techniques, including FT-IR, XRD, SEM, TGA, DSC, dye adsorption experiments, and photoluminescence spectroscopy, reveals that these minor architectural adjustments translate into remarkably divergent macroscopic properties. The rigid and linear Poly(C1-para) stands out for its higher thermal resistance (Td10 = 256 °C), elevated char yield (33.3%), and highest methylene blue adsorption capacity (Qt = 22.7 mg/g), a performance linked to its amorphous yet densely packed framework. In contrast, the more compliant Poly(C2-ortho) forms a semi-crystalline, plate-like morphology and exhibits rapid initial dye uptake, albeit with limited retention. All polymers exhibit pronounced flame-retardant character, with Limited Oxygen Index values ranging from 27 to 31%. In addition, each material exhibits intrinsic, excitation-dependent photoluminescence, allowing for emission tuning from deep blue to near-white light. Colorimetric analysis confirms a consistent decrease in correlated color temperature with longer excitation wavelengths, an effect amplified by the flexible C2 spacer, which allows finer modulation of white-light tone. Collectively, these results demonstrate that backbone linearity and rigidity favor thermal robustness and adsorption efficiency, whereas spacer flexibility governs morphology and photophysical behavior, offering a clear design strategy for multifunctional polymeric aterials.
{"title":"Molecular engineering of polyhydrazides: a unified framework for tunable white-light emission, thermal robustness, and high-performance dye adsorption","authors":"Mahmoud S. Tolba , Aya Harby , Adel M. Kamal El-Dean , Marwa M. Sayed , Osama Younis","doi":"10.1016/j.eurpolymj.2026.114571","DOIUrl":"10.1016/j.eurpolymj.2026.114571","url":null,"abstract":"<div><div>This work explores a family of four newly designed polyhydrazides obtained through polycondensation, in which two subtle yet decisive structural variables were deliberately tuned: the geometry of the phenylene linkage (<em>ortho</em> versus <em>para</em>) and the length of the aliphatic spacer (C1 versus C2). A broad suite of analytical techniques, including FT-IR, XRD, SEM, TGA, DSC, dye adsorption experiments, and photoluminescence spectroscopy, reveals that these minor architectural adjustments translate into remarkably divergent macroscopic properties. The rigid and linear <strong>Poly(C1-para)</strong> stands out for its higher thermal resistance (T<sub>d10</sub> = 256 °C), elevated char yield (33.3%), and highest methylene blue adsorption capacity (Q<sub>t</sub> = 22.7 mg/g), a performance linked to its amorphous yet densely packed framework. In contrast, the more compliant <strong>Poly(C2-ortho)</strong> forms a semi-crystalline, plate-like morphology and exhibits rapid initial dye uptake, albeit with limited retention. All polymers exhibit pronounced flame-retardant character, with Limited Oxygen Index values ranging from 27 to 31%. In addition, each material exhibits intrinsic, excitation-dependent photoluminescence, allowing for emission tuning from deep blue to near-white light. Colorimetric analysis confirms a consistent decrease in correlated color temperature with longer excitation wavelengths, an effect amplified by the flexible C2 spacer, which allows finer modulation of white-light tone. Collectively, these results demonstrate that backbone linearity and rigidity favor thermal robustness and adsorption efficiency, whereas spacer flexibility governs morphology and photophysical behavior, offering a clear design strategy for multifunctional polymeric aterials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"246 ","pages":"Article 114571"},"PeriodicalIF":6.3,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146187104","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 : 2026-03-11Epub Date: 2026-02-03DOI: 10.1016/j.eurpolymj.2026.114521
Ahmad Shaaban, Mohamed Keshawy
Oil spills and organic pollutants from accidents and industrial effluents threaten aquatic ecosystems through toxicity and bioaccumulation, requiring efficient cleanup technologies. Here, we report three hyperbranched organogel sorbents (OG1-OG3) synthesized by one-pot self-condensing vinyl polymerization (SCVP) via atom transfer radical polymerization (ATRP) of chloromethyl styrene (CMS) inimer. Copolymerization of CMS with p-methylstyrene (MS), poly(ethylene glycol) methacrylate (PEGMA), and sulfobetaine methacrylate (SBMA) created hydrophobic, three-dimensional porous scaffolds with high crosslink density, tunable flexibility (PEGMA), and zwitterionic antifouling functionality (SBMA). FTIR, SEM, AFM, TGA, and water contact-angle measurements confirmed the intended chemical structure, porous morphology, and surface hydrophobicity. In static oil-swelling tests with five model pollutants (xylene, chloroform, crude oil, waste motor oil, and used cooking oil), OG3 showed an exceptional capacity ( in xylene), exceeding conventional sorbents. Uptake followed a pseudo-second-order kinetic model, reaching of equilibrium uptake within 30 min and maintaining of their capacity over many sorption–desorption cycles. Batch sorption isotherms fit the Langmuir model well, while Freundlich analysis indicated some site heterogeneity. Overall, these organogels outperform previously reported polymer sorbents and commercial resins of similar composition, combining a facile synthesis, ultra-high capacity, fast kinetics, chemical stability, and robustness, promising features for oil spill and wastewater remediation.
{"title":"Multifunctional superabsorbent organogel hyperbranched copolymers via SCVP–ATRP for oil spill/wastewater remediation","authors":"Ahmad Shaaban, Mohamed Keshawy","doi":"10.1016/j.eurpolymj.2026.114521","DOIUrl":"10.1016/j.eurpolymj.2026.114521","url":null,"abstract":"<div><div>Oil spills and organic pollutants from accidents and industrial effluents threaten aquatic ecosystems through toxicity and bioaccumulation, requiring efficient cleanup technologies. Here, we report three <em>hyperbranched</em> organogel sorbents (OG1-OG3) synthesized by <em>one-pot</em> self-condensing vinyl polymerization (SCVP) via atom transfer radical polymerization (ATRP) of chloromethyl styrene (CMS) inimer. Copolymerization of CMS with <em>p</em>-methylstyrene (MS), poly(ethylene glycol) methacrylate (PEGMA), and sulfobetaine methacrylate (SBMA) created hydrophobic, three-dimensional porous scaffolds with high crosslink density, tunable flexibility (PEGMA), and zwitterionic antifouling functionality (SBMA). FTIR, SEM, AFM, TGA, and water contact-angle measurements confirmed the intended chemical structure, porous morphology, and surface hydrophobicity. In static oil-swelling tests with five model pollutants (xylene, chloroform, crude oil, waste motor oil, and used cooking oil), OG3 showed an exceptional capacity (<span><math><mrow><mspace></mspace><mn>90</mn><mi>g</mi><mo>/</mo><mi>g</mi></mrow></math></span> in xylene), exceeding conventional sorbents. Uptake followed a pseudo-second-order kinetic model, reaching <span><math><mrow><mspace></mspace><mn>81</mn><mo>%</mo></mrow></math></span> of equilibrium uptake within 30 min and maintaining <span><math><mrow><mspace></mspace><mn>80</mn><mo>%</mo></mrow></math></span> of their capacity over many sorption–desorption cycles. Batch sorption isotherms fit the Langmuir model well, while Freundlich analysis indicated some site heterogeneity. Overall, these organogels outperform previously reported polymer sorbents and commercial resins of similar composition, combining a facile synthesis, ultra-high capacity, fast kinetics, chemical stability, and robustness, promising features for oil spill and wastewater remediation.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"245 ","pages":"Article 114521"},"PeriodicalIF":6.3,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185365","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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