Pub Date : 2025-12-29DOI: 10.1016/j.eurpolymj.2025.114477
Ming-Xuan Du, Chang-Hao Han, Hong-Jian Lv, Kai-Xuan Li, Yao-Nan Xiao, Shao-Hua Wu, Jia-Jian Liu, Chun-Cheng Li
Driven by growing environmental concerns, bio-based polymers have been extensively investigated in recent years. In this work, a series of poly(carbonate-ester)s were synthesized via a two-step polycondensation of bio-based monomer isosorbide (Is) with aliphatic diols (1,4-butanediol (BDO), 1,6-hexanediol (HDO), or 1,8-octanediol (ODO)), dimethyl carbonate (DMC), and dimethyl 2,6-naphthalenedicarboxylate (DMN). The synthesized poly(isosorbide carbonate-co- alkylene naphthalate) (PICANs) are intrinsically fluorescent in the bulk state and possess a tunable emission wavelength spanning from 387 nm to 455 nm. Besides, the PICANs copolymers also demonstrate robust thermal stability and substantial stretchability, positioning them as attractive materials for bio-based fluorescent flexible plastics.
{"title":"Isosorbide-based copolymers poly(isosorbide carbonate-co-alkylene naphthalate): Synthesis, properties and fluorescence Regulation","authors":"Ming-Xuan Du, Chang-Hao Han, Hong-Jian Lv, Kai-Xuan Li, Yao-Nan Xiao, Shao-Hua Wu, Jia-Jian Liu, Chun-Cheng Li","doi":"10.1016/j.eurpolymj.2025.114477","DOIUrl":"10.1016/j.eurpolymj.2025.114477","url":null,"abstract":"<div><div>Driven by growing environmental concerns, bio-based polymers have been extensively investigated in recent years. In this work, a series of poly(carbonate-ester)s were synthesized via a two-step polycondensation of bio-based monomer isosorbide (Is) with aliphatic diols (1,4-butanediol (BDO), 1,6-hexanediol (HDO), or 1,8-octanediol (ODO)), dimethyl carbonate (DMC), and dimethyl 2,6-naphthalenedicarboxylate (DMN). The synthesized poly(isosorbide carbonate-co- alkylene naphthalate) (PICANs) are intrinsically fluorescent in the bulk state and possess a tunable emission wavelength spanning from 387 nm to 455 nm. Besides, the PICANs copolymers also demonstrate robust thermal stability and substantial stretchability, positioning them as attractive materials for bio-based fluorescent flexible plastics.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114477"},"PeriodicalIF":6.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882471","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-29DOI: 10.1016/j.eurpolymj.2025.114476
Sheng-Li Han , Hui-Qin Zhang , Feng Yang , Yun Liu , Hong-Hui Shu , Lian-Bing Zhang , Cheng-Mei Liu
Value-added utilisation of industrial and agricultural residues is an attractive strategy to address resource shortages and promote greener chemical production. PH3, a hazardous by-product of hypophosphite preparation, requires careful handling due to its high toxicity and flammability. In this study, we developed a method to convert PH3 tail gas into hydrolytically stable single-ion conducting polymers (SICPs) with potential recyclability after service. Oligoether-containing styrenic monomers (VBP-nEO) were synthesised from 4-vinylbenzyl(bis(hydromethyl))phosphine oxide (VBzHPO) via Williamson etherification in water, and the resulting functional monomers underwent conventional free-radical polymerisation to produce both homo- and co-polymers. The water-soluble homopolymers exhibited high hydrolysis resistance under both acidic and basic conditions because the phosphorus atom was covalently bonded to three substituents through P–C bonds. The co-polymers containing dissociable lithium salt segments exhibited promising ionic conductivity at moderate temperatures (4.48 × 10−6 S/cm at 90 °C), which depended on the ethylene oxide (EO) content and EO/Li+ ratio within the co-polymers. All co-polymers showed high thermal stability, with initial decomposition temperatures exceeding 300 °C and calculated LOI values above 21 %.
{"title":"Valorisation of phosphine tail gas into phosphorus-containing single-ion conducting polymers with high hydrolytic stability and potential recyclability","authors":"Sheng-Li Han , Hui-Qin Zhang , Feng Yang , Yun Liu , Hong-Hui Shu , Lian-Bing Zhang , Cheng-Mei Liu","doi":"10.1016/j.eurpolymj.2025.114476","DOIUrl":"10.1016/j.eurpolymj.2025.114476","url":null,"abstract":"<div><div>Value-added utilisation of industrial and agricultural residues is an attractive strategy to address resource shortages and promote greener chemical production. PH<sub>3</sub>, a hazardous by-product of hypophosphite preparation, requires careful handling due to its high toxicity and flammability. In this study, we developed a method to convert PH<sub>3</sub> tail gas into hydrolytically stable single-ion conducting polymers (SICPs) with potential recyclability after service. Oligoether-containing styrenic monomers (VBP-nEO) were synthesised from 4-vinylbenzyl(bis(hydromethyl))phosphine oxide (VBzHPO) via Williamson etherification in water, and the resulting functional monomers underwent conventional free-radical polymerisation to produce both homo- and co-polymers. The water-soluble homopolymers exhibited high hydrolysis resistance under both acidic and basic conditions because the phosphorus atom was covalently bonded to three substituents through P–C bonds. The co-polymers containing dissociable lithium salt segments exhibited promising ionic conductivity at moderate temperatures (4.48 × 10<sup>−6</sup> S/cm at 90 °C), which depended on the ethylene oxide (EO) content and EO/Li<sup>+</sup> ratio within the co-polymers. All co-polymers showed high thermal stability, with initial decomposition temperatures exceeding 300 °C and calculated LOI values above 21 %.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114476"},"PeriodicalIF":6.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882473","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-27DOI: 10.1016/j.eurpolymj.2025.114475
Sibel Küçükertuğrul Çelik , Sema Şentürk , Kevser Bal , Özlem Kaplan , Mehmet Koray Gök
The continuous advancement of therapeutic technologies has intensified the pursuit of drug delivery systems that respond intelligently to physiological and pathological stimuli, thereby enabling precise, localized, and sustained therapeutic outcomes. Among redox-based approaches, systems responsive to intracellular glutathione (GSH) have attracted particular attention due to their ability to trigger disulfide bond cleavage and controlled release within diseased tissues. Mucoadhesive systems, on the other hand, prolong residence time on mucosal surfaces through non-covalent interactions and covalent bond formation, thereby facilitating increased absorption and decreased clearance. Despite their individual successes, the integration of these two mechanisms remains underexplored. This review critically examines the coupling of redox sensitivity and mucoadhesion, highlighting how disulfide-based bonds can simultaneously function as both redox-cleavable and mucoadhesive moieties.
{"title":"Redox-Responsive and mucoadhesive nanoparticles: An overlooked synergy in modern drug delivery","authors":"Sibel Küçükertuğrul Çelik , Sema Şentürk , Kevser Bal , Özlem Kaplan , Mehmet Koray Gök","doi":"10.1016/j.eurpolymj.2025.114475","DOIUrl":"10.1016/j.eurpolymj.2025.114475","url":null,"abstract":"<div><div>The continuous advancement of therapeutic technologies has intensified the pursuit of drug delivery systems that respond intelligently to physiological and pathological stimuli, thereby enabling precise, localized, and sustained therapeutic outcomes. Among redox-based approaches, systems responsive to intracellular glutathione (GSH) have attracted particular attention due to their ability to trigger disulfide bond cleavage and controlled release within diseased tissues. Mucoadhesive systems, on the other hand, prolong residence time on mucosal surfaces through non-covalent interactions and covalent bond formation, thereby facilitating increased absorption and decreased clearance. Despite their individual successes, the integration of these two mechanisms remains underexplored. This review critically examines the coupling of redox sensitivity and mucoadhesion, highlighting how disulfide-based bonds can simultaneously function as both redox-cleavable and mucoadhesive moieties.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114475"},"PeriodicalIF":6.3,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882474","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 : 2025-12-25DOI: 10.1016/j.eurpolymj.2025.114474
Minji Choi , Nam-Ho You , Hee Jeung Oh , Youngjae Yoo
Silicon-based anodes are promising materials for next-generation lithium-ion batteries due to their high theoretical capacity. However, their practical application is hindered by drastic volume expansion during cycling, which leads to particle fracture, capacity fading, and instability of the electrode structure. In addition, most conventional binders require toxic organic solvents, raising environmental and safety concerns. To address these issues, a water-based polyimide binder with high mechanical robustness was synthesized through an aqueous process by combining 3,5-diaminobenzoic acid (DABA) and 4,7,10-trioxa-1,13-tridecanediamine (TTDDA) in different ratios. The –COOH groups in DABA enhanced adhesion and structural stability, while the –O– linkages in TTDDA improved flexibility and Li+ transport. Among the synthesized binders, D8T2-PI exhibited the best balance between mechanical strength and elasticity, achieving superior cycling performance and higher capacity compared with conventional PAA and CMC binders. The flexible polymer network improved electrode–electrolyte interfacial contact and facilitated Li+ diffusion, thereby enhancing electrochemical performance. These results demonstrate that a sustainable, water-processable polyimide binder can effectively enhance both the mechanical and electrochemical stability of silicon anodes, providing a practical and design strategy for high-performance lithium-ion batteries.
硅基阳极具有较高的理论容量，是下一代锂离子电池的理想材料。然而，它们的实际应用受到循环过程中剧烈的体积膨胀的阻碍，这会导致颗粒断裂、容量衰减和电极结构不稳定。此外，大多数传统粘合剂需要有毒的有机溶剂，这引起了环境和安全问题。为解决上述问题，以3,5-二氨基苯甲酸（DABA）和4,7,10-三氧基-1,13-三胺（TTDDA）为原料，采用水相法合成了一种机械强度高的水基聚酰亚胺粘合剂。DABA中的- cooh基团增强了黏附性和结构稳定性，而TTDDA中的- o -键提高了柔韧性和Li+的运输。在合成的粘结剂中，D8T2-PI在机械强度和弹性之间表现出最好的平衡，与常规PAA和CMC粘结剂相比，具有更好的循环性能和更高的容量。柔性聚合物网络改善了电极-电解质界面接触，促进了Li+扩散，从而提高了电化学性能。这些结果表明，一种可持续的、可水处理的聚酰亚胺粘合剂可以有效地提高硅阳极的机械和电化学稳定性，为高性能锂离子电池的设计提供了一种实用的策略。
{"title":"Water-based polyimide binders with dual functional groups for enhanced electrochemical performance of silicon anodes","authors":"Minji Choi , Nam-Ho You , Hee Jeung Oh , Youngjae Yoo","doi":"10.1016/j.eurpolymj.2025.114474","DOIUrl":"10.1016/j.eurpolymj.2025.114474","url":null,"abstract":"<div><div>Silicon-based anodes are promising materials for next-generation lithium-ion batteries due to their high theoretical capacity. However, their practical application is hindered by drastic volume expansion during cycling, which leads to particle fracture, capacity fading, and instability of the electrode structure. In addition, most conventional binders require toxic organic solvents, raising environmental and safety concerns. To address these issues, a water-based polyimide binder with high mechanical robustness was synthesized through an aqueous process by combining 3,5-diaminobenzoic acid (DABA) and 4,7,10-trioxa-1,13-tridecanediamine (TTDDA) in different ratios. The –COOH groups in DABA enhanced adhesion and structural stability, while the –O– linkages in TTDDA improved flexibility and Li<sup>+</sup> transport. Among the synthesized binders, D8T2-PI exhibited the best balance between mechanical strength and elasticity, achieving superior cycling performance and higher capacity compared with conventional PAA and CMC binders. The flexible polymer network improved electrode–electrolyte interfacial contact and facilitated Li<sup>+</sup> diffusion, thereby enhancing electrochemical performance. These results demonstrate that a sustainable, water-processable polyimide binder can effectively enhance both the mechanical and electrochemical stability of silicon anodes, providing a practical and design strategy for high-performance lithium-ion batteries.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114474"},"PeriodicalIF":6.3,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882469","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 : 2025-12-24DOI: 10.1016/j.eurpolymj.2025.114464
Juan Torres-Rodríguez , Charlotte Fornaciari , Ricardo A. Pérez-Camargo , Agurtzane Mugica , Manuela Zubitur , Giovanni Preda , Dario Pasini , Olivier Coulembier , Alejandro J. Müller
We report on the synthesis and crystallization behavior of poly(propylene oxide) (PPO) with tunable molar masses and defined stereoconfiguration (PPO-R and PPO-S), obtained through controlled oxyanionic ring-opening polymerization using hexaethylene glycol (EG6) as the initiator, with an equimolar mixture of potassium acetate (KOAc) and 18-crown-6 ether (18C6). This method provides access to well-defined enantiopure PPO samples across a broad range of number-average molecular weights (Mn), allowing for the independent evaluation of how molecular weight and stereoconfiguration influence crystallization. Morphology, thermal transitions, structural features, and crystallization kinetics were analyzed using Polarized Light Optical Microscopy (PLOM), Differential Scanning Calorimetry (DSC), in situ Wide- and Small-angle X-ray Scattering (WAXS/SAXS), and, for the first time in PPO, thermal fractionation via Successive Self-nucleation and Annealing (SSA). Both PPO-R and PPO-S display increasing thermal transitions with Mn, eventually reaching a plateau. Although they crystallize into identical orthorhombic unit cells, the two enantiomers show small yet consistent and reproducible kinetic differences across all techniques used: PPO-R crystallizes faster at low Mn, while PPO-S does so at high Mn. This crossover, related to a specific Mn value, though unexpected for two enantiomeric polymers forming identical lattices, was consistently observed by different experimental techniques across nucleation, spherulitic growth, overall crystallization rate, and SSA fractionation. This confirms the effect is real and experimentally reliable. We provide a mechanistic interpretation suggesting that stereoconfiguration could be influencing melt dynamics, likely through subtle differences in chain diffusion and entanglement onset. Racemic PPO-R:S blends were prepared at both low and high Mn. No stereocomplexation was observed; however, these blends exhibited lower melting transitions and slower crystallization kinetics than the enantiopure samples, possibly due to packing frustration between chains of opposite helicities. Overall, molecular weight and stereoconfiguration are effective parameters for tuning PPO crystallization kinetics, thereby enabling PPO-based blends and copolymers with controlled crystallization rates and expanded processability in biodegradable polymer systems.
{"title":"How chain stereoconfiguration and molecular weight influence Poly(propylene oxide) crystallization","authors":"Juan Torres-Rodríguez , Charlotte Fornaciari , Ricardo A. Pérez-Camargo , Agurtzane Mugica , Manuela Zubitur , Giovanni Preda , Dario Pasini , Olivier Coulembier , Alejandro J. Müller","doi":"10.1016/j.eurpolymj.2025.114464","DOIUrl":"10.1016/j.eurpolymj.2025.114464","url":null,"abstract":"<div><div>We report on the synthesis and crystallization behavior of poly(propylene oxide) (PPO) with tunable molar masses and defined stereoconfiguration (PPO-<em>R</em> and PPO-<em>S</em>), obtained through controlled oxyanionic ring-opening polymerization using hexaethylene glycol (EG6) as the initiator, with an equimolar mixture of potassium acetate (KOAc) and 18-crown-6 ether (18C6). This method provides access to well-defined enantiopure PPO samples across a broad range of number-average molecular weights (<em>M<sub>n</sub></em>), allowing for the independent evaluation of how molecular weight and stereoconfiguration influence crystallization. Morphology, thermal transitions, structural features, and crystallization kinetics were analyzed using Polarized Light Optical Microscopy (PLOM), Differential Scanning Calorimetry (DSC), in situ Wide- and Small-angle X-ray Scattering (WAXS/SAXS), and, for the first time in PPO, thermal fractionation via Successive Self-nucleation and Annealing (SSA). Both PPO-<em>R</em> and PPO-<em>S</em> display increasing thermal transitions with <em>M<sub>n</sub></em>, eventually reaching a plateau. Although they crystallize into identical orthorhombic unit cells, the two enantiomers show small yet consistent and reproducible kinetic differences across all techniques used: PPO-<em>R</em> crystallizes faster at low <em>M<sub>n</sub></em>, while PPO-<em>S</em> does so at high <em>M<sub>n</sub></em>. This crossover, related to a specific <em>M<sub>n</sub></em> value, though unexpected for two enantiomeric polymers forming identical lattices, was consistently observed by different experimental techniques across nucleation, spherulitic growth, overall crystallization rate, and SSA fractionation. This confirms the effect is real and experimentally reliable. We provide a mechanistic interpretation suggesting that stereoconfiguration could be influencing melt dynamics, likely through subtle differences in chain diffusion and entanglement onset. Racemic PPO-<em>R:S</em> blends were prepared at both low and high <em>M<sub>n</sub></em>. No stereocomplexation was observed; however, these blends exhibited lower melting transitions and slower crystallization kinetics than the enantiopure samples, possibly due to packing frustration between chains of opposite helicities. Overall, molecular weight and stereoconfiguration are effective parameters for tuning PPO crystallization kinetics, thereby enabling PPO-based blends and copolymers with controlled crystallization rates and expanded processability in biodegradable polymer systems.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114464"},"PeriodicalIF":6.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939768","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 : 2025-12-24DOI: 10.1016/j.eurpolymj.2025.114470
Jie Liu , Jun Yang , Zijia Zhang , Qian Jiang , Lele Sun , Chaoyi Peng , Jin Wang , Li Xiang , Anlian Pan
In order to prepare polyimide materials with excellent optical transparency and UV barrier, the effects of the number and substitution position of −CF3 groups on polyimide properties were investigated. Researchers synthesized four novel diamine monomers (BPA-O, BPA-NH2, BPAF-O, BPAF-NH2) and synthesized eight high-performance colorless polyimides (PI-1 ∼ PI-8). On the one hand, the strong electron-withdrawing effect of −CF3 restricts electron movement within the molecular chain, weakening the CTC effect of the molecular chain and thereby enhancing the transparency of the film. On the other hand, the ortho-substitution of −CF3 on the imide ring induces greater twisting of molecular chains, disrupts their close packing, and thereby exerts a positive effect on enhancing the optical transparency of the film. The high bond energy of the C-F bond and the introduction of the flexible group −O- act as an “energy buffer,” suppressing UV-induced main chain breakage and achieving high UV barrier. All CPI films exhibit excellent transparency and thermal stability, with a cut-off wavelength range of 325 nm-381 nm and a transmittance range of 78.7 %-88 % at 550 nm. They have good optical properties, with Td5% distributed in the range of 511.5 °C − 533.7 °C, and the glass transition temperature (Tg) distributed in the range of 197.3 °C-234.4 °C, demonstrating good thermal stability. Additionally, the cut-off wavelength is at a relatively high level, reaching up to 381 nm.
{"title":"Study on the preparation of novel transparent UV- barrier polyimide films via regulating molecular chain Configuration and electronic orbital Arrangement by –CF3 and their application properties","authors":"Jie Liu , Jun Yang , Zijia Zhang , Qian Jiang , Lele Sun , Chaoyi Peng , Jin Wang , Li Xiang , Anlian Pan","doi":"10.1016/j.eurpolymj.2025.114470","DOIUrl":"10.1016/j.eurpolymj.2025.114470","url":null,"abstract":"<div><div>In order to prepare polyimide materials with excellent optical transparency and UV barrier, the effects of the number and substitution position of −CF<sub>3</sub> groups on polyimide properties were investigated. Researchers synthesized four novel diamine monomers (BPA-O, BPA-NH<sub>2</sub>, BPAF-O, BPAF-NH<sub>2</sub>) and synthesized eight high-performance colorless polyimides (PI-1 ∼ PI-8). On the one hand, the strong electron-withdrawing effect of −CF<sub>3</sub> restricts electron movement within the molecular chain, weakening the CTC effect of the molecular chain and thereby enhancing the transparency of the film. On the other hand, the <em>ortho</em>-substitution of −CF<sub>3</sub> on the imide ring induces greater twisting of molecular chains, disrupts their close packing, and thereby exerts a positive effect on enhancing the optical transparency of the film. The high bond energy of the C-F bond and the introduction of the flexible group −O- act as an “energy buffer,” suppressing UV-induced main chain breakage and achieving high UV barrier. All CPI films exhibit excellent transparency and thermal stability, with a cut-off wavelength range of 325 nm-381 nm and a transmittance range of 78.7 %-88 % at 550 nm. They have good optical properties, with T<sub>d5%</sub> distributed in the range of 511.5 °C − 533.7 °C, and the glass transition temperature (<em>T<sub>g</sub></em>) distributed in the range of 197.3 °C-234.4 °C, demonstrating good thermal stability. Additionally, the cut-off wavelength is at a relatively high level, reaching up to 381 nm.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"242 ","pages":"Article 114470"},"PeriodicalIF":6.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836866","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 article considers current trends in the development of relatively new types of thermoplastic elastomers (TPE) with a unique combination of structure and properties. The fundamental principles of selecting compatibilizers that improve the compatibility of thermoplastics with an elastomer component are shown. Using polyolefins and polar synthetic elastomers as an example, the possibilities of obtaining TPE with an improved set of physical, mechanical-physical and chemical properties are considered. The use of such modern physical methods for analyzing TPE and its modifications as SEM and X-ray phase analysis, derivatography, step dilatometry made it possible to obtain information on the structure–property relationship in the polymer–polymer and polymer-filler systems. Much attention is paid to studying the influence of various types of dispersed and fibrous fillers, as well as nanoparticles, on the main physical, mechanical and thermal characteristics of filled TPE. The use of the integral thermo-deformation method of analysis (Kanavets), as well as the stress–strain dependence made it possible to determine the content of the elastomer component, at which phase inversion occurs and a region of highly elastic deformation characteristic of rubbers is formed. For the first time, the influence of a cross-linking agent (sulfur and dicumyl peroxide (DCP)) on the pattern of changes in the physical and mechanical properties of filled and cross-linked TPE composites is considered. Attention is paid to problems associated with the technology of obtaining dynamically vulcanized TPE, studying the influence of the temperature regime and pressure of reaction extrusion and injection molding on the quality of the composite.
{"title":"Modern theoretical and practical approaches to development, research and processing of thermoplastic elastomers and their filled composites. review","authors":"Kh.V. Allahverdiyeva , N.T. Kakhramanov , F.A. Mustafayeva , A.A. Hasanova , L.M. Afandiyeva , R.V. Gurbanova , H.B. Bafadarova , E.I. Suleymanova , A.G. Habibova , T.M. Babayeva , O.M. Guliyeva","doi":"10.1016/j.eurpolymj.2025.114463","DOIUrl":"10.1016/j.eurpolymj.2025.114463","url":null,"abstract":"<div><div>The article considers current trends in the development of relatively new types of thermoplastic elastomers (TPE) with a unique combination of structure and properties. The fundamental principles of selecting compatibilizers that improve the compatibility of thermoplastics with an elastomer component are shown. Using polyolefins and polar synthetic elastomers as an example, the possibilities of obtaining TPE with an improved set of physical, mechanical-physical and chemical properties are considered. The use of such modern physical methods for analyzing TPE and its modifications as SEM and X-ray phase analysis, derivatography, step dilatometry made it possible to obtain information on the structure–property relationship in the polymer–polymer and polymer-filler systems. Much attention is paid to studying the influence of various types of dispersed and fibrous fillers, as well as nanoparticles, on the main physical, mechanical and thermal characteristics of filled TPE. The use of the integral thermo-deformation method of analysis (Kanavets), as well as the stress–strain dependence made it possible to determine the content of the elastomer component, at which phase inversion occurs and a region of highly elastic deformation characteristic of rubbers is formed. For the first time, the influence of a cross-linking agent (sulfur and dicumyl peroxide (DCP)) on the pattern of changes in the physical and mechanical properties of filled and cross-linked TPE composites is considered. Attention is paid to problems associated with the technology of obtaining dynamically vulcanized TPE, studying the influence of the temperature regime and pressure of reaction extrusion and injection molding on the quality of the composite.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114463"},"PeriodicalIF":6.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882475","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 : 2025-12-24DOI: 10.1016/j.eurpolymj.2025.114471
Osama Younis , Faten M. Taher , Marwa M. Sayed, Mostafa Sayed, Mostafa Ahmed
This study presents the design, synthesis, and characterization of two novel carbazole-based oxazine monomers, Mono-BenzOx and Mono-NaphthOx, and their corresponding polymers. The monomers, featuring an N-ethyl carbazole moiety, were synthesized through a sequential process of condensation, reduction, and Mannich cyclization, with structures confirmed by FTIR and NMR spectroscopy. Photoluminescence analysis revealed that both monomers exhibit concentration-independent blue emission in solution due to steric hindrance preventing excimer formation. In the solid state, however, a stark difference emerged upon polymerization. While Poly-BenzOx showed residual excimer emission, Poly-NaphthOx displayed intense, high-purity blue photoluminescence (CIE: 0.16, 0.05) due to the effective isolation of chromophores within its rigid cross-linked network. Thermogravimetric analysis further established the superiority of the naphthalene-based system compared to the benzoxazine analogue, with Poly-NaphthOx exhibiting a higher decomposition temperature (Td5 = 275 °C) and a significantly greater char yield (27 %) than Poly-BenzOx (Td5 = 233 °C, char yield: 4 %). The unique combination of efficient solid-state blue emission, exceptional thermal stability, and high char yield puts Poly-NaphthOx as a premier multifunctional material for advanced optoelectronic and high-performance applications.
{"title":"Naphthoxazine outperforms benzoxazine: carbazole-based polymers with enhanced blue luminescence and high thermal stability","authors":"Osama Younis , Faten M. Taher , Marwa M. Sayed, Mostafa Sayed, Mostafa Ahmed","doi":"10.1016/j.eurpolymj.2025.114471","DOIUrl":"10.1016/j.eurpolymj.2025.114471","url":null,"abstract":"<div><div>This study presents the design, synthesis, and characterization of two novel carbazole-based oxazine monomers, <strong>Mono-BenzOx</strong> and <strong>Mono-NaphthOx</strong>, and their corresponding polymers. The monomers, featuring an N-ethyl carbazole moiety, were synthesized through a sequential process of condensation, reduction, and Mannich cyclization, with structures confirmed by FTIR and NMR spectroscopy. Photoluminescence analysis revealed that both monomers exhibit concentration-independent blue emission in solution due to steric hindrance preventing excimer formation. In the solid state, however, a stark difference emerged upon polymerization. While <strong>Poly-BenzOx</strong> showed residual excimer emission, <strong>Poly-NaphthOx</strong> displayed intense, high-purity blue photoluminescence (CIE: 0.16, 0.05) due to the effective isolation of chromophores within its rigid cross-linked network. Thermogravimetric analysis further established the superiority of the naphthalene-based system compared to the benzoxazine analogue, with <strong>Poly-NaphthOx</strong> exhibiting a higher decomposition temperature (T<sub>d5</sub> = 275 °C) and a significantly greater char yield (27 %) than <strong>Poly-BenzOx</strong> (T<sub>d5</sub> = 233 °C, char yield: 4 %). The unique combination of efficient solid-state blue emission, exceptional thermal stability, and high char yield puts <strong>Poly-NaphthOx</strong> as a premier multifunctional material for advanced optoelectronic and high-performance applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114471"},"PeriodicalIF":6.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839548","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 : 2025-12-24DOI: 10.1016/j.eurpolymj.2025.114472
Ruizhen Zhang , Chengwen Jin , Pengjie Xie , Tao Chen
The coordinated release of multiple substances presents a significant technical challenge, primarily due to their distinct release kinetics and potential intermolecular interactions. To address this, we developed a composite nanoreactor and strategically selected two hydrophobic fluorescent dyes, Coumarin 102 and Nile Red, as model payloads. Firstly, a photoresponsive block copolymer, P(DMA50-b-SPMA60) (P1), containing carbamate spiropyran methacrylate units, and a thermoresponsive block copolymer with an Upper Critical Solution Temperature (UCST), P(DMA50-b-SBMA48) (P2), were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. These copolymers self-assembled into micelles, which encapsulated Coumarin 102 and Nile Red within the hydrophobic cores of P1 and P2, respectively. The individual stimulus-responsive release profiles were monitored via fluorescence spectroscopy. Composite nanoreactors were then prepared by physical blending the two loaded micelle types. The stability of the composite system was verified by fluorescence spectroscopy, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). Upon exposure to specific stimuli (light or temperature), selective release of the respective hydrophobic molecules was achieved: UV irradiation triggered a 80% release of Coumarin 102 from M3 micelles, while heating above the UCST induced a 75% release of Nile Red from M4 micelles. The composite micelles thus integrate multiple orthogonal stimulation responses with precise selective release control, offering a promising platform for advanced controlled-release applications in nanotechnology and biotechnology.
{"title":"Photoresponsive and UCST-Type thermoresponsive block Copolymer-Based composite micelles for Dual-Stimuli-Triggered selective and programmable release","authors":"Ruizhen Zhang , Chengwen Jin , Pengjie Xie , Tao Chen","doi":"10.1016/j.eurpolymj.2025.114472","DOIUrl":"10.1016/j.eurpolymj.2025.114472","url":null,"abstract":"<div><div>The coordinated release of multiple substances presents a significant technical challenge, primarily due to their distinct release kinetics and potential intermolecular interactions. To address this, we developed a composite nanoreactor and strategically selected two hydrophobic fluorescent dyes, Coumarin 102 and Nile Red, as model payloads. Firstly, a photoresponsive block copolymer, P(DMA<sub>50</sub>-<em>b</em>-SPMA<sub>60</sub>) (<strong>P1</strong>), containing carbamate spiropyran methacrylate units, and a thermoresponsive block copolymer with an Upper Critical Solution Temperature (UCST), P(DMA<sub>50</sub>-<em>b</em>-SBMA<sub>48</sub>) (<strong>P2</strong>), were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. These copolymers self-assembled into micelles, which encapsulated Coumarin 102 and Nile Red within the hydrophobic cores of <strong>P1</strong> and <strong>P2</strong>, respectively. The individual stimulus-responsive release profiles were monitored via fluorescence spectroscopy. Composite nanoreactors were then prepared by physical blending the two loaded micelle types. The stability of the composite system was verified by fluorescence spectroscopy, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). Upon exposure to specific stimuli (light or temperature), selective release of the respective hydrophobic molecules was achieved: UV irradiation triggered a 80% release of Coumarin 102 from <strong>M3</strong> micelles, while heating above the UCST induced a 75% release of Nile Red from <strong>M4</strong> micelles. The composite micelles thus integrate multiple orthogonal stimulation responses with precise selective release control, offering a promising platform for advanced controlled-release applications in nanotechnology and biotechnology.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114472"},"PeriodicalIF":6.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839547","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 : 2025-12-24DOI: 10.1016/j.eurpolymj.2025.114473
Yulu Wang , Fengxiang Cao , Gang Liu , Zhen Fang , Zhuhui Qiao
The development of biobased thermosetting materials has garnered considerable interest as a promising alternative to conventional thermosets, which are often constrained by permanent cross-linking and dependence on petroleum-derived feedstocks. Nevertheless, both traditional and bio-based thermosets frequently exhibit limitations in reprocessability and recyclability. In this study, a novel epoxy covalent adaptable network (CAN) incorporating dynamic dual-crosslinking bonds (D-DCB) was synthesized from lignin-derived vanillin (VA) and glycerol propoxylate triglycidyl ether (GPTE). Specifically, a trialdehyde monomer (TAM) was first prepared from VA and GPTE, which subsequently reacted with disulfide-containing compounds (4,4′-diaminodiphenyl disulfide and cystamine) to form bio-based CANs (namely, TAM-APDS and TAM-Cys, respectively). This network synergistically combines imine and disulfide bonds as dynamic covalent units. The imine bonds not only provide fundamental mechanical strength and structural stability but also contribute UV-shielding properties due to their conjugated structure. The disulfide bonds impart reprocessability, self-healing capability, and degradability-enabling rapid disulfide exchange reactions within 1 h using a thiol/ethanol solution at 60 °C. Lap-shear adhesion tests on various substrates demonstrated that the resulting CANs exhibit a high strength of approximately 7 MPa on iron substrates, highlighting their potential as high-performance sustainable adhesives.
{"title":"Orthogonal imine and disulfide exchange in a biobased covalent adaptable network: toward healable and recyclable thermosets","authors":"Yulu Wang , Fengxiang Cao , Gang Liu , Zhen Fang , Zhuhui Qiao","doi":"10.1016/j.eurpolymj.2025.114473","DOIUrl":"10.1016/j.eurpolymj.2025.114473","url":null,"abstract":"<div><div>The development of biobased thermosetting materials has garnered considerable interest as a promising alternative to conventional thermosets, which are often constrained by permanent cross-linking and dependence on petroleum-derived feedstocks. Nevertheless, both traditional and bio-based thermosets frequently exhibit limitations in reprocessability and recyclability. In this study, a novel epoxy covalent adaptable network (CAN) incorporating dynamic dual-crosslinking bonds (D-DCB) was synthesized from lignin-derived vanillin (VA) and glycerol propoxylate triglycidyl ether (GPTE). Specifically, a trialdehyde monomer (TAM) was first prepared from VA and GPTE, which subsequently reacted with disulfide-containing compounds (4,4′-diaminodiphenyl disulfide and cystamine) to form bio-based CANs (namely, TAM-APDS and TAM-Cys, respectively). This network synergistically combines imine and disulfide bonds as dynamic covalent units. The imine bonds not only provide fundamental mechanical strength and structural stability but also contribute UV-shielding properties due to their conjugated structure. The disulfide bonds impart reprocessability, self-healing capability, and degradability-enabling rapid disulfide exchange reactions within 1 h using a thiol/ethanol solution at 60 °C. Lap-shear adhesion tests on various substrates demonstrated that the resulting CANs exhibit a high strength of approximately 7 MPa on iron substrates, highlighting their potential as high-performance sustainable adhesives.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114473"},"PeriodicalIF":6.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839544","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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