Pub Date : 2025-12-13DOI: 10.1016/j.reactfunctpolym.2025.106605
Farzaneh Qodrati-nasrabadi , Issa Sardivand-chegini , Saeed Zakavi
<div><div>In order to overcome the problem of leaching of porphyrins from solid supports as well as the extensive degradation of porphyrin sensitizers, the tetra sodium salts of <em>meso</em>-tetrakis(4-carboxyphenyl)porphyrin (Na<sub>4</sub>H<sub>2</sub>TCPP) and the corresponding Zn(II) complex (Na<sub>4</sub>ZnTCPP), immobilized into the pores of nanostructured mesoporous Amberlite IRA-900, nanoAmbN(Me)<sub>3</sub>Cl, were synthesized and used as sensitizers in aerobic photooxidation of sulfides in acetonitrile and water. Also, the molecular complex of nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP with 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and its dication with H<sub>2</sub>SO<sub>4</sub> were prepared and used in photooxidation of sulfides. FESEM, BET, TGA, FT-IR and UV–vis diffuse reflectance spectroscopy (DRS) were used to characterize the nanocomposites. Interestingly, nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP was highly stable against leaching of the porphyrin under long-term exposure to acidic conditions at a pH value as low as zero (1.0 M HCl). This finding was attributed to the very low solubility of the peripherally tetra-protonated porphyrins (H<sub>6</sub>TCPP and H<sub>4</sub>ZnTCPP) in water as well as the strong electrostatic interactions between the –COOH groups of the porphyrin and –<sup>+</sup>N(CH<sub>3</sub>)<sub>3</sub> residues of the polymer. The singlet oxygen quantum yield (ϕ<sub>Δ</sub>) of the sensitizers decreased as nanoAmbN(Me)<sub>3</sub>@ZnTCPP (0.73) > > nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP (0.22) ≥ nanoAmbN(Me)<sub>3</sub>@H<sub>4</sub>TCPP(HSO<sub>4</sub>)<sub>2</sub> (0.18) ∼ nanoAmbN(Me)<span><span><sub>3</sub>@H<sub>2</sub>TCPP(DDQ)<sub>2</sub> (0.17</span><svg><path></path></svg></span>). Although a similar photocatalytic activity was observed for nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP and nanoAmbN(Me)<sub>3</sub>@ZnTCPP in the oxidation of more reactive sulfides, the former was significantly more efficient in the oxidation of sulfides with electron-withdrawing and/or sterically demanding substituents at the sulfur atom. This observation was attributed to the higher degree of oxidative degradation of nanoAmbN(Me)<sub>3</sub>@ZnTCPP. The oxidative stability of nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP was significantly increased due to the formation of the H<sub>2</sub>SO<sub>4</sub> diacid and DDQ molecular complex of H<sub>2</sub>TCPP. However, a two- to three-fold increase in the time required for the completion of the reaction was observed in the presence of the latter sensitizers. The increased steric hindrance around the singlet oxygen generating sites of the sensitizers caused by the presence of HSO<sub>4</sub><sup>−</sup> anions and the DDQ molecules was suggested to explain this observation. Furthermore, a significant decrease in the reactivity of sulfides towards singlet oxygen by increasing steric hindrance around the sulfur atom was observed. The presence CH<sub>3</sub>C
{"title":"Meso-tetrakis(4-carboxyphenyl)porphyrin derivatives anchored to nanostructured amberlite: New porphyrin photosensitizers with unusually high long-term leaching stability, photocatalytic activity and oxidative stability","authors":"Farzaneh Qodrati-nasrabadi , Issa Sardivand-chegini , Saeed Zakavi","doi":"10.1016/j.reactfunctpolym.2025.106605","DOIUrl":"10.1016/j.reactfunctpolym.2025.106605","url":null,"abstract":"<div><div>In order to overcome the problem of leaching of porphyrins from solid supports as well as the extensive degradation of porphyrin sensitizers, the tetra sodium salts of <em>meso</em>-tetrakis(4-carboxyphenyl)porphyrin (Na<sub>4</sub>H<sub>2</sub>TCPP) and the corresponding Zn(II) complex (Na<sub>4</sub>ZnTCPP), immobilized into the pores of nanostructured mesoporous Amberlite IRA-900, nanoAmbN(Me)<sub>3</sub>Cl, were synthesized and used as sensitizers in aerobic photooxidation of sulfides in acetonitrile and water. Also, the molecular complex of nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP with 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and its dication with H<sub>2</sub>SO<sub>4</sub> were prepared and used in photooxidation of sulfides. FESEM, BET, TGA, FT-IR and UV–vis diffuse reflectance spectroscopy (DRS) were used to characterize the nanocomposites. Interestingly, nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP was highly stable against leaching of the porphyrin under long-term exposure to acidic conditions at a pH value as low as zero (1.0 M HCl). This finding was attributed to the very low solubility of the peripherally tetra-protonated porphyrins (H<sub>6</sub>TCPP and H<sub>4</sub>ZnTCPP) in water as well as the strong electrostatic interactions between the –COOH groups of the porphyrin and –<sup>+</sup>N(CH<sub>3</sub>)<sub>3</sub> residues of the polymer. The singlet oxygen quantum yield (ϕ<sub>Δ</sub>) of the sensitizers decreased as nanoAmbN(Me)<sub>3</sub>@ZnTCPP (0.73) > > nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP (0.22) ≥ nanoAmbN(Me)<sub>3</sub>@H<sub>4</sub>TCPP(HSO<sub>4</sub>)<sub>2</sub> (0.18) ∼ nanoAmbN(Me)<span><span><sub>3</sub>@H<sub>2</sub>TCPP(DDQ)<sub>2</sub> (0.17</span><svg><path></path></svg></span>). Although a similar photocatalytic activity was observed for nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP and nanoAmbN(Me)<sub>3</sub>@ZnTCPP in the oxidation of more reactive sulfides, the former was significantly more efficient in the oxidation of sulfides with electron-withdrawing and/or sterically demanding substituents at the sulfur atom. This observation was attributed to the higher degree of oxidative degradation of nanoAmbN(Me)<sub>3</sub>@ZnTCPP. The oxidative stability of nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP was significantly increased due to the formation of the H<sub>2</sub>SO<sub>4</sub> diacid and DDQ molecular complex of H<sub>2</sub>TCPP. However, a two- to three-fold increase in the time required for the completion of the reaction was observed in the presence of the latter sensitizers. The increased steric hindrance around the singlet oxygen generating sites of the sensitizers caused by the presence of HSO<sub>4</sub><sup>−</sup> anions and the DDQ molecules was suggested to explain this observation. Furthermore, a significant decrease in the reactivity of sulfides towards singlet oxygen by increasing steric hindrance around the sulfur atom was observed. The presence CH<sub>3</sub>C","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106605"},"PeriodicalIF":5.1,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799425","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-13DOI: 10.1016/j.reactfunctpolym.2025.106608
Ecaterina Stela Dragan, Maria Valentina Dinu
Nitrogen based synthetic polycations (NBSPC) imposed themselves in the daily life by their tremendous applications. This review systematically presents the main categories of NBSPC following a structural criterion, with a focus on the synthesis strategies, namely: homo- and copolymerization of the monomers containing preformed amino or quaternary ammonium salt groups, ring-opening polymerization, condensation polymerization, cyclopolymerization and chemical reactions on nonionic polymers. Composites based on NBSPCs with polysaccharides, other organic polymers, inorganic particles such as silica, clays, metal oxides have emerged as versatile materials with even more expanded applications. The key studies on the environmental applications of the NBSPCs-based composites, highlighted in this review, support the broad potential of these very attractive materials in the carbon capture, removal of dyes, heavy metal ions, oxyanions, pesticides. Identification of the most suitable NBSPCs and their composites for biomedical applications such as drug delivery systems, gene transfection, wound management is also extensively followed in the review. The wide opportunities in designing novel NBSPCs-based composites have been assessed.
{"title":"Nitrogen based synthetic polycations as ubiquitous items of composites with environmental and biomedical applications","authors":"Ecaterina Stela Dragan, Maria Valentina Dinu","doi":"10.1016/j.reactfunctpolym.2025.106608","DOIUrl":"10.1016/j.reactfunctpolym.2025.106608","url":null,"abstract":"<div><div>Nitrogen based synthetic polycations (NBSPC) imposed themselves in the daily life by their tremendous applications. This review systematically presents the main categories of NBSPC following a structural criterion, with a focus on the synthesis strategies, namely: homo- and copolymerization of the monomers containing preformed amino or quaternary ammonium salt groups, ring-opening polymerization, condensation polymerization, cyclopolymerization and chemical reactions on nonionic polymers. Composites based on NBSPCs with polysaccharides, other organic polymers, inorganic particles such as silica, clays, metal oxides have emerged as versatile materials with even more expanded applications. The key studies on the environmental applications of the NBSPCs-based composites, highlighted in this review, support the broad potential of these very attractive materials in the carbon capture, removal of dyes, heavy metal ions, oxyanions, pesticides. Identification of the most suitable NBSPCs and their composites for biomedical applications such as drug delivery systems, gene transfection, wound management is also extensively followed in the review. The wide opportunities in designing novel NBSPCs-based composites have been assessed.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106608"},"PeriodicalIF":5.1,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799427","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.reactfunctpolym.2025.106606
Tihe Zheng, Wenxing Yuan, Rende Qin, Qin Gui, Hailiang Zhang
Polyamide 6 (PA6) is widely used in the automotive, electrical, and textile industries due to its high strength, excellent wear resistance, and processability. However, its high moisture absorption, poor dimensional stability, and low heat distortion temperature (HDT) greatly limit its applications under humid or high-temperature environments. To overcome these inherent drawbacks, we propose an in situ polymerization and blending modification strategy to construct PSU/PA6 composites with simultaneously enhanced mechanical, thermal, and moisture-resistant properties. In this strategy, polysulfone (PSU) and carboxyl-functionalized polysulfone (CPSU) are synthesized and incorporated into the hydrolytic ring-opening polymerization of ε-caprolactam to prepare PSU/PA6 composite and CPSU-g-PA6/PA6 grafted composite. Compared with pure PA6, both PSU/PA6 and CPSU-g-PA6/PA6 exhibit significantly reduced water absorption and markedly improved HDT and mechanical properties. Moreover, CPSU-g-PA6/PA6 outperforms PSU/PA6 blends in moisture resistance and mechanical properties, and does not exhibit the pronounced phase separation commonly observed in the latter. Specifically, the 96 h water absorption decreases from 3.01 % for PA6 to 2.40 % for G-8. The HDT increased from 56.3 °C to 75.2 °C. The tensile strength and flexural strength increased from 64.5 MPa and 83.6 MPa to 79.7 MPa and 106.4 MPa, respectively.
{"title":"In situ polymerization with Carboxylated Polysulfone for enhanced mechanical, thermal, and dimensional stability of PA6","authors":"Tihe Zheng, Wenxing Yuan, Rende Qin, Qin Gui, Hailiang Zhang","doi":"10.1016/j.reactfunctpolym.2025.106606","DOIUrl":"10.1016/j.reactfunctpolym.2025.106606","url":null,"abstract":"<div><div>Polyamide 6 (PA6) is widely used in the automotive, electrical, and textile industries due to its high strength, excellent wear resistance, and processability. However, its high moisture absorption, poor dimensional stability, and low heat distortion temperature (HDT) greatly limit its applications under humid or high-temperature environments. To overcome these inherent drawbacks, we propose an in situ polymerization and blending modification strategy to construct PSU/PA6 composites with simultaneously enhanced mechanical, thermal, and moisture-resistant properties. In this strategy, polysulfone (PSU) and carboxyl-functionalized polysulfone (CPSU) are synthesized and incorporated into the hydrolytic ring-opening polymerization of ε-caprolactam to prepare PSU/PA6 composite and CPSU-g-PA6/PA6 grafted composite. Compared with pure PA6, both PSU/PA6 and CPSU-g-PA6/PA6 exhibit significantly reduced water absorption and markedly improved HDT and mechanical properties. Moreover, CPSU-g-PA6/PA6 outperforms PSU/PA6 blends in moisture resistance and mechanical properties, and does not exhibit the pronounced phase separation commonly observed in the latter. Specifically, the 96 h water absorption decreases from 3.01 % for PA6 to 2.40 % for G-8. The HDT increased from 56.3 °C to 75.2 °C. The tensile strength and flexural strength increased from 64.5 MPa and 83.6 MPa to 79.7 MPa and 106.4 MPa, respectively.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"219 ","pages":"Article 106606"},"PeriodicalIF":5.1,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786936","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.reactfunctpolym.2025.106602
Xiangru Li , Ximing Zhang , Wenyu Wu , Penglin Kang , Yuan Lai , Leixin Hou , Xiaodong Li , Wenjie Liu , Xiaojuan Fu
High-energy insensitive composite explosives have become a key research direction in energetic materials due to their balanced energy output and safety. However, composite particles prepared by traditional methods often have limitations such as low sphericity and poor uniformity. In this paper, the coaxial flow-focusing microdroplet method was used to prepare RDX/F, RDX/F/E, and RDX/E composite particles, with RDX/F/E-P prepared by physical kneading method used as the process control samples to demonstrate the superiority of the process and investigate the effect of the binder formulation on the properties of the samples. Results showed that RDX/F/E has the best sphericity and particle size uniformity, indicating that adjusting the binder system can significantly improve the morphology and particle size distribution of the particles. In addition, the chemical and crystal structures of all samples remained unchanged. Thermal analysis and mechanical sensitivity tests revealed that compared to raw RDX, the apparent activation energy of RDX/F/E increased by 24.75 kJ∙mol−1, and the impact energy threshold and critical friction force were enhanced by 42.5 J and 120 N, respectively, demonstrating excellent thermal and mechanical safety. In ignition tests, the RDX/F/E microspheres produced the clearest and brightest flames, with a significantly shorter burning duration than raw RDX and all other samples, demonstrating that the F2604 and EVA binder system ensures stable combustion while promoting concentrated energy release. This study demonstrates the superiority of the coaxial flow-focusing microdroplet technique, and the proposed F2604-EVA composite binder system provides practical guidance for formulation optimization and performance regulation.
{"title":"Continuous preparation and performance investigation of RDX-based composite microspheres via a coaxial flow-focusing microdroplet method","authors":"Xiangru Li , Ximing Zhang , Wenyu Wu , Penglin Kang , Yuan Lai , Leixin Hou , Xiaodong Li , Wenjie Liu , Xiaojuan Fu","doi":"10.1016/j.reactfunctpolym.2025.106602","DOIUrl":"10.1016/j.reactfunctpolym.2025.106602","url":null,"abstract":"<div><div>High-energy insensitive composite explosives have become a key research direction in energetic materials due to their balanced energy output and safety. However, composite particles prepared by traditional methods often have limitations such as low sphericity and poor uniformity. In this paper, the coaxial flow-focusing microdroplet method was used to prepare RDX/F, RDX/F/E, and RDX/E composite particles, with RDX/F/E-P prepared by physical kneading method used as the process control samples to demonstrate the superiority of the process and investigate the effect of the binder formulation on the properties of the samples. Results showed that RDX/F/E has the best sphericity and particle size uniformity, indicating that adjusting the binder system can significantly improve the morphology and particle size distribution of the particles. In addition, the chemical and crystal structures of all samples remained unchanged. Thermal analysis and mechanical sensitivity tests revealed that compared to raw RDX, the apparent activation energy of RDX/F/E increased by 24.75 kJ∙mol<sup>−1</sup>, and the impact energy threshold and critical friction force were enhanced by 42.5 J and 120 N, respectively, demonstrating excellent thermal and mechanical safety. In ignition tests, the RDX/F/E microspheres produced the clearest and brightest flames, with a significantly shorter burning duration than raw RDX and all other samples, demonstrating that the F2604 and EVA binder system ensures stable combustion while promoting concentrated energy release. This study demonstrates the superiority of the coaxial flow-focusing microdroplet technique, and the proposed F2604-EVA composite binder system provides practical guidance for formulation optimization and performance regulation.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106602"},"PeriodicalIF":5.1,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799370","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.reactfunctpolym.2025.106601
Fenglan Liang , Jie Li , Yingzi Feng , Yanlong Zhou , Liang Cao , Daniel Omoding , Madhav Raj Jayswal , Abhinav Kumar , Zhenjun Song , Jun Wang , Ying Pan
Alzheimer's disease (AD) is a common central nervous system neurodegenerative disorder, with its diagnosis and treatment posing significant challenges in the field of neurodegenerative diseases. With the rising global incidence of AD, there is growing interest in nanomaterials that enable precise and efficient diagnosis and treatment of the disease. In particular, the early diagnosis and targeted therapy of AD have long been hindered by issues such as low sensitivity in biomarker detection, poor blood-brain barrier (BBB) penetration, and the complexity of pathological mechanisms, making effective diagnosis and treatment difficult. Consequently, novel approaches are needed to address these challenges. Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), owing to their high surface area, customizable structures, and excellent biocompatibility, demonstrate outstanding potential in ultra-sensitive biomarker detection, targeted drug delivery and controlled release, and AI-enhanced synergistic diagnosis and treatment for AD. This review focuses on the urgent needs in AD diagnosis and therapy, summarizing its pathogenesis, current diagnostic methods, and treatment status. It highlights the innovative roles of two porous nanomaterials, MOFs and COFs, across the entire process of “early diagnosis-targeted therapy-intelligent optimization” and elucidates their practical efficacy in AD management. Additionally, it explores the integration strategies of these materials with artificial intelligence (AI) and machine learning (ML) technologies. Finally, the review concludes by discussing the challenges and future prospects of MOFs and COFs as potential diagnostic and therapeutic systems for AD.
{"title":"Advances and prospects in Alzheimer's disease diagnosis and treatment using MOFs and COFs: Mechanism and AI-assisted strategies","authors":"Fenglan Liang , Jie Li , Yingzi Feng , Yanlong Zhou , Liang Cao , Daniel Omoding , Madhav Raj Jayswal , Abhinav Kumar , Zhenjun Song , Jun Wang , Ying Pan","doi":"10.1016/j.reactfunctpolym.2025.106601","DOIUrl":"10.1016/j.reactfunctpolym.2025.106601","url":null,"abstract":"<div><div>Alzheimer's disease (AD) is a common central nervous system neurodegenerative disorder, with its diagnosis and treatment posing significant challenges in the field of neurodegenerative diseases. With the rising global incidence of AD, there is growing interest in nanomaterials that enable precise and efficient diagnosis and treatment of the disease. In particular, the early diagnosis and targeted therapy of AD have long been hindered by issues such as low sensitivity in biomarker detection, poor blood-brain barrier (BBB) penetration, and the complexity of pathological mechanisms, making effective diagnosis and treatment difficult. Consequently, novel approaches are needed to address these challenges. Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), owing to their high surface area, customizable structures, and excellent biocompatibility, demonstrate outstanding potential in ultra-sensitive biomarker detection, targeted drug delivery and controlled release, and AI-enhanced synergistic diagnosis and treatment for AD. This review focuses on the urgent needs in AD diagnosis and therapy, summarizing its pathogenesis, current diagnostic methods, and treatment status. It highlights the innovative roles of two porous nanomaterials, MOFs and COFs, across the entire process of “early diagnosis-targeted therapy-intelligent optimization” and elucidates their practical efficacy in AD management. Additionally, it explores the integration strategies of these materials with artificial intelligence (AI) and machine learning (ML) technologies. Finally, the review concludes by discussing the challenges and future prospects of MOFs and COFs as potential diagnostic and therapeutic systems for AD.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"219 ","pages":"Article 106601"},"PeriodicalIF":5.1,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786937","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.reactfunctpolym.2025.106604
Ahmed Abdelhamid Maamoun , Mashael Daghash Alqahtani , Khalid Z. Elwakeel , Ahmed M. Elgarahy
Rising global water scarcity and worsening human-driven climate change urgently demand advanced wastewater treatment technologies that can produce environmentally safe and high-purity effluents. This study presents a high-performance flexible polyurethane foam (FPUF) composite enhanced with 2–10 wt% lignocellulosic wood waste (WW) bio-filler to improve wastewater treatment and energy recovery. The FPUF-WW composite aimed for efficient organic dyes removal and reuse as a solid fuel, addressing both environmental pollution and WW management. Physicochemical analyses (e.g., FTIR, TGA, SEM, gel fraction, rheology, compression performance, and porosity) confirmed successful WW integration and enhanced properties. Rheology showed increased viscosity with shear-thickening behavior from polymer–filler interactions. Cavity size reduced from 0.996 mm (neat FPUF) to 0.653 mm (FPUF-WW8), while porosity decreased from 78.64 % to 71.15 %. Foam density increased by 19.76 %, with a gel fraction peak at 95.2 % for 8 wt% WW. Thermal stability improved, increasing the T5% from 248.0 °C for blank FPUF to 260.0 °C for the FPUF/WW8. Compression strength rose by 22.96 % at 8 wt% WW compared to blank FPUF. The mechanical durability of the FPUF/WW8 improved by 10.88 % in density compared to the FPUF sample. The stable porous structure of FPUF-WW8 after dyes adsorption, supporting its reusability. Adsorption experiments for MB and CR dyes were systematically conducted by varying several operational parameters. Optimal removal efficiencies were 96.8 % (MB, pH 10.6) and 93.9 % (CR, pH 3.5). Adsorption kinetics followed a PSORE model; the Langmuir isotherm best described the process, with maximum capacities of 357.14 mg g−1, and 250 mg g−1, for MB and CR dyes, respectively. The adsorption retained >86 % efficiency after six reuse cycles. Real wastewater treatment showed >80 % dyes removal. Energy recovery from spent FPUF-WW8 composite revealed high calorific values: 23,410 kJ/kg (native), 23,128 kJ/kg (MB-laden), and 22,631 kJ/kg (CR-laden). With a production cost around €5.54/kg, the FPUF-WW material promises dual-function wastewater remediation and sustainable fuel generation, endorsing circular economy principles.
{"title":"Bifunctional flexible polyurethane foam-lignocellulosic wood waste composite for cationic/anionic dyes remediation and sustainable solid fuel recovery","authors":"Ahmed Abdelhamid Maamoun , Mashael Daghash Alqahtani , Khalid Z. Elwakeel , Ahmed M. Elgarahy","doi":"10.1016/j.reactfunctpolym.2025.106604","DOIUrl":"10.1016/j.reactfunctpolym.2025.106604","url":null,"abstract":"<div><div>Rising global water scarcity and worsening human-driven climate change urgently demand advanced wastewater treatment technologies that can produce environmentally safe and high-purity effluents. This study presents a high-performance flexible polyurethane foam (FPUF) composite enhanced with 2–10 wt% lignocellulosic wood waste (WW) bio-filler to improve wastewater treatment and energy recovery. The FPUF-WW composite aimed for efficient organic dyes removal and reuse as a solid fuel, addressing both environmental pollution and WW management. Physicochemical analyses (e.g., FTIR, TGA, SEM, gel fraction, rheology, compression performance, and porosity) confirmed successful WW integration and enhanced properties. Rheology showed increased viscosity with shear-thickening behavior from polymer–filler interactions. Cavity size reduced from 0.996 mm (neat FPUF) to 0.653 mm (FPUF-WW8), while porosity decreased from 78.64 % to 71.15 %. Foam density increased by 19.76 %, with a gel fraction peak at 95.2 % for 8 wt% WW. Thermal stability improved, increasing the T5% from 248.0 °C for blank FPUF to 260.0 °C for the FPUF/WW8. Compression strength rose by 22.96 % at 8 wt% WW compared to blank FPUF. The mechanical durability of the FPUF/WW8 improved by 10.88 % in density compared to the FPUF sample. The stable porous structure of FPUF-WW8 after dyes adsorption, supporting its reusability. Adsorption experiments for MB and CR dyes were systematically conducted by varying several operational parameters. Optimal removal efficiencies were 96.8 % (MB, pH 10.6) and 93.9 % (CR, pH 3.5). Adsorption kinetics followed a PSORE model; the Langmuir isotherm best described the process, with maximum capacities of 357.14 mg g<sup>−1</sup>, and 250 mg g<sup>−1</sup>, for MB and CR dyes, respectively. The adsorption retained >86 % efficiency after six reuse cycles. Real wastewater treatment showed >80 % dyes removal. Energy recovery from spent FPUF-WW8 composite revealed high calorific values: 23,410 kJ/kg (native), 23,128 kJ/kg (MB-laden), and 22,631 kJ/kg (CR-laden). With a production cost around €5.54/kg, the FPUF-WW material promises dual-function wastewater remediation and sustainable fuel generation, endorsing circular economy principles.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106604"},"PeriodicalIF":5.1,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145884796","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.reactfunctpolym.2025.106598
Chin-Lung Chiang , Yi-Jen Huang , Ming-Liao Tsai , Zi-Hao Wu , Yu-Cheng Kuo , Ting-Wei Wu , Ioannis Zuburtikudis
Chemical recycling has emerged as a promising approach in polymer recycling strategies due to its capacity for depolymerization, structural selectivity, and its pivotal role in advancing the development of sustainable recycled materials. However, recycled resins often exhibit inferior mechanical properties compared to their pristine counterparts. This study investigates the incorporation of a linear toughening agent, neopentyl glycol diglycidyl ether (LTA), in conjunction with ferric chloride (FeCl₃), a Lewis acid catalyst, to enhance the performance and reusability of recycled epoxy resins. Recycled resins obtained via catalytic degradation were compounded with pristine resin, LTA, and FeCl₃. The incorporation of LTA facilitated the formation of linear bridges between polymer chains, promoting effective crosslinking. The combined structural and mechanical results, including reduced swelling ratios, diminished -OH intensity in FTIR, and the incorporation of LTA, as confirmed by 13C NMR, suggest a more efficiently crosslinked network structure within the recycled resin matrix. Concurrently, FeCl₃ catalyzed esterification and crosslinking reactions between epoxy groups and anhydride curing agents, further contributing to network formation. Experimental findings revealed that the combined use of LTA and FeCl₃ significantly improved the tensile strength, thereby restoring the mechanical integrity of recycled epoxy resins and demonstrating their potential for reuse following mechanical recovery.
{"title":"Catalyst-assisted reconstruction of recycled epoxy resins with restored mechanical performance","authors":"Chin-Lung Chiang , Yi-Jen Huang , Ming-Liao Tsai , Zi-Hao Wu , Yu-Cheng Kuo , Ting-Wei Wu , Ioannis Zuburtikudis","doi":"10.1016/j.reactfunctpolym.2025.106598","DOIUrl":"10.1016/j.reactfunctpolym.2025.106598","url":null,"abstract":"<div><div>Chemical recycling has emerged as a promising approach in polymer recycling strategies due to its capacity for depolymerization, structural selectivity, and its pivotal role in advancing the development of sustainable recycled materials. However, recycled resins often exhibit inferior mechanical properties compared to their pristine counterparts. This study investigates the incorporation of a linear toughening agent, neopentyl glycol diglycidyl ether (LTA), in conjunction with ferric chloride (FeCl₃), a Lewis acid catalyst, to enhance the performance and reusability of recycled epoxy resins. Recycled resins obtained via catalytic degradation were compounded with pristine resin, LTA, and FeCl₃. The incorporation of LTA facilitated the formation of linear bridges between polymer chains, promoting effective crosslinking. The combined structural and mechanical results, including reduced swelling ratios, diminished -OH intensity in FTIR, and the incorporation of LTA, as confirmed by <sup>13</sup>C NMR, suggest a more efficiently crosslinked network structure within the recycled resin matrix. Concurrently, FeCl₃ catalyzed esterification and crosslinking reactions between epoxy groups and anhydride curing agents, further contributing to network formation. Experimental findings revealed that the combined use of LTA and FeCl₃ significantly improved the tensile strength, thereby restoring the mechanical integrity of recycled epoxy resins and demonstrating their potential for reuse following mechanical recovery.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106598"},"PeriodicalIF":5.1,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145760812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-06DOI: 10.1016/j.reactfunctpolym.2025.106599
Fei Zhu , Xianwen Yan , Bohao Lv , Sai Zhang , Mengyan Zeng , Wenqiang Qiao
The development of high-performance epoxy resins (EPs) is crucial for advanced applications, but is often challenged by a need to balance flame retardancy, mechanical strength, and transparency. This study addresses this challenge by developing a novel oligomeric flame retardant (PB-TBPO), which was synthesized through a thiol-ene click chemistry between polybutadiene (PB) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The well-designed PB-TBPO exhibited remarkable flame-retardant efficiency, leveraging the synergistic effect of phosphorus and sulfur elements. Impressively, with a minimal loading of only 3 phr, the EP composite attained the highest vertical burning (UL-94) rating of V-0 and a limiting oxygen index (LOI) of 27.7 %. Cone calorimeter tests (CCT) further demonstrated significant reductions in peak heat release rate (PHRR, 32.1 %) and fire growth rate (FIGRA, 52.4 %) compared to neat EP. The mechanical properties were substantially enhanced; the composite with 5 phr PB-TBPO showed dramatic increases in flexural strength, flexural modulus, impact strength, tensile strength, elongation at break, and Young's modulus by 203 %, 51.4 %, 632 %, 192 %, 343 %, and 48.7 %, respectively. Moreover, dynamic mechanical analysis (DMA) and ultraviolet-visible (UV–vis) spectroscopy confirmed that the composites maintained a high glass transition temperature (Tg, 182 °C) and outstanding transparency (87.4 % transmittance at 780 nm). Consequently, this work presents a viable strategy for designing multifunctional oligomeric flame retardants to produce advanced EP composites with exceptional flame retardancy, mechanical robustness, and optical transparency for broad applications.
{"title":"Balancing flame retardancy, mechanical properties, and transparency in epoxy resins with a phosphorus/sulfur-containing oligomer synthesized via thiol-ene click chemistry","authors":"Fei Zhu , Xianwen Yan , Bohao Lv , Sai Zhang , Mengyan Zeng , Wenqiang Qiao","doi":"10.1016/j.reactfunctpolym.2025.106599","DOIUrl":"10.1016/j.reactfunctpolym.2025.106599","url":null,"abstract":"<div><div>The development of high-performance epoxy resins (EPs) is crucial for advanced applications, but is often challenged by a need to balance flame retardancy, mechanical strength, and transparency. This study addresses this challenge by developing a novel oligomeric flame retardant (PB-TBPO), which was synthesized through a thiol-ene click chemistry between polybutadiene (PB) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The well-designed PB-TBPO exhibited remarkable flame-retardant efficiency, leveraging the synergistic effect of phosphorus and sulfur elements. Impressively, with a minimal loading of only 3 phr, the EP composite attained the highest vertical burning (UL-94) rating of V-0 and a limiting oxygen index (LOI) of 27.7 %. Cone calorimeter tests (CCT) further demonstrated significant reductions in peak heat release rate (PHRR, 32.1 %) and fire growth rate (FIGRA, 52.4 %) compared to neat EP. The mechanical properties were substantially enhanced; the composite with 5 phr PB-TBPO showed dramatic increases in flexural strength, flexural modulus, impact strength, tensile strength, elongation at break, and Young's modulus by 203 %, 51.4 %, 632 %, 192 %, 343 %, and 48.7 %, respectively. Moreover, dynamic mechanical analysis (DMA) and ultraviolet-visible (UV–vis) spectroscopy confirmed that the composites maintained a high glass transition temperature (<em>T</em><sub>g</sub>, 182 °C) and outstanding transparency (87.4 % transmittance at 780 nm). Consequently, this work presents a viable strategy for designing multifunctional oligomeric flame retardants to produce advanced EP composites with exceptional flame retardancy, mechanical robustness, and optical transparency for broad applications.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"219 ","pages":"Article 106599"},"PeriodicalIF":5.1,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145737418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-06DOI: 10.1016/j.reactfunctpolym.2025.106600
Xiaohong Li , Cai Ye , Jianjun Chen , Zahoor Ahmad
In this work, a novel polyalumino-titanocarbonsilane (PATCS) was synthesized by the reaction of commercial spinning grade polycarbosilane (PCS) with aluminum acetylacetonate (Al(AcAc)3) and titanocene dichloride (Ti(C5H5)2Cl2). A dense SiC ceramic fiber was obtained by melt-spinning, thermal oxidation curing in relatively short curing time (∼ 1 h) at 473 K, and pyrolysis of the PATCS. To reveal the thermal polymerization mechanisms of PATCS, the as-synthesized PATCS were investigated by FT-IR, XPS, GPC, 29Si NMR, TG, rotary rheometer, metaloscope. The results showed that the PATCS was consisted of SiH bonds, Si-CH3 groups, Si-CH2-Si groups, and a small amount of SiO bonds and CC bonds. The polymerization mechanism of PATCS involves the reactions of SiH bonds in polycarbosilane (PCS) with TiCl, CC, and Al-O-R groups to form SiTi, Si-C-C, Si-C-Ti, and Si-O-Al bonds. The TGA results showed that mass residual rate under high temperature had an obviously increase with adding Al(AcAc)3 and Ti(C5H5)2Cl2. The PCS, PACS and PATCS were pseudoplastic fluid and their viscosity decreased with rising temperature. Suitable melt-spinning temperature range of the PATCS-1 was 553–593 K. A continuous PATCS-1 fiber with a diameter of 29.33 ± 2.99 μm was obtained by the melt-spinning process at 553 K. The Ti element and CC bonds in PATCS might accelerate the curing of the PATCS fibers in air. The study provides a facile synthetic method for preparing a novel precursor polymer, which serves as a precursor for high-performance double-metal heterogeneous element-containing SiC ceramic fiber and can be efficiently cured in air.
{"title":"Synthesis of polyalumino-titanocarbonsilane from a commercial polycarbosilane","authors":"Xiaohong Li , Cai Ye , Jianjun Chen , Zahoor Ahmad","doi":"10.1016/j.reactfunctpolym.2025.106600","DOIUrl":"10.1016/j.reactfunctpolym.2025.106600","url":null,"abstract":"<div><div>In this work, a novel polyalumino-titanocarbonsilane (PATCS) was synthesized by the reaction of commercial spinning grade polycarbosilane (PCS) with aluminum acetylacetonate (Al(AcAc)<sub>3</sub>) and titanocene dichloride (Ti(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Cl<sub>2</sub>). A dense SiC ceramic fiber was obtained by melt-spinning, thermal oxidation curing in relatively short curing time (∼ 1 h) at 473 K, and pyrolysis of the PATCS. To reveal the thermal polymerization mechanisms of PATCS, the as-synthesized PATCS were investigated by FT-IR, XPS, GPC, <sup>29</sup>Si NMR, TG, rotary rheometer, metaloscope. The results showed that the PATCS was consisted of Si<img>H bonds, Si-CH<sub>3</sub> groups, Si-CH<sub>2</sub>-Si groups, and a small amount of Si<img>O bonds and C<img>C bonds. The polymerization mechanism of PATCS involves the reactions of Si<img>H bonds in polycarbosilane (PCS) with Ti<img>Cl, C<img>C, and Al-O-R groups to form Si<img>Ti, Si-C-C, Si-C-Ti, and Si-O-Al bonds. The TGA results showed that mass residual rate under high temperature had an obviously increase with adding Al(AcAc)<sub>3</sub> and Ti(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Cl<sub>2</sub>. The PCS, PACS and PATCS were pseudoplastic fluid and their viscosity decreased with rising temperature. Suitable melt-spinning temperature range of the PATCS-1 was 553–593 K. A continuous PATCS-1 fiber with a diameter of 29.33 ± 2.99 μm was obtained by the melt-spinning process at 553 K. The Ti element and C<img>C bonds in PATCS might accelerate the curing of the PATCS fibers in air. The study provides a facile synthetic method for preparing a novel precursor polymer, which serves as a precursor for high-performance double-metal heterogeneous element-containing SiC ceramic fiber and can be efficiently cured in air.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"219 ","pages":"Article 106600"},"PeriodicalIF":5.1,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145737468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-04DOI: 10.1016/j.reactfunctpolym.2025.106584
Jhu-Lin You , Kai-Yen Chin , Yan-Ting Lai , Kuei-Ting Hsu , Shu-Mei Chang
Waterborne polyurethane (WPU) has attracted attention as an environmentally sustainable material for various applications. In this study, a high-solid-content WPU emulsion was successfully developed as an ink for direct ink writing (DIW) three-dimensional (3D) printing. Its viscosity was controlled in the range of 102 to 106 mPa·s through surfactants and crosslinkers. A polyethylene glycol (PEG) surfactant content of 4 wt% resulted in the most stable low-viscosity emulsion (102 mPa·s). Additionally, the viscosity of the WPU emulsion was adjusted by introducing the cross-linking agent 2,2-Bis[4-(glycidyloxy)phenyl]propane, 4,4′-isopropylidenediphenol diglycidyl ether (BADGE). At a crosslinker content of 7 wt%, the WPU dispersion became highly viscous (106 mPa·s). Its rheological properties included shear thinning behavior, high yield stress (1.7 kPa), a rheological phase angle of 46.80°, and a storage modulus of 104 Pa; these all meet the requirements for DIW 3D printing. Finally, DIW 3D printing was performed using various movement speeds and nozzle flow rates, to evaluate the printing performance and determine the optimal parameters for DIW 3D printing with WPU materials. The high-solid-content WPU system developed in this work can be effectively applied to create 3D structures without generating air pollution or toxic wastewater, ensuring ecological sustainability and environmental safety.
{"title":"Feasibility of an eco-friendly high-solids waterborne polyurethane ink for DIW 3D printing","authors":"Jhu-Lin You , Kai-Yen Chin , Yan-Ting Lai , Kuei-Ting Hsu , Shu-Mei Chang","doi":"10.1016/j.reactfunctpolym.2025.106584","DOIUrl":"10.1016/j.reactfunctpolym.2025.106584","url":null,"abstract":"<div><div>Waterborne polyurethane (WPU) has attracted attention as an environmentally sustainable material for various applications. In this study, a high-solid-content WPU emulsion was successfully developed as an ink for direct ink writing (DIW) three-dimensional (3D) printing. Its viscosity was controlled in the range of 10<sup>2</sup> to 10<sup>6</sup> mPa·s through surfactants and crosslinkers. A polyethylene glycol (PEG) surfactant content of 4 wt% resulted in the most stable low-viscosity emulsion (10<sup>2</sup> mPa·s). Additionally, the viscosity of the WPU emulsion was adjusted by introducing the cross-linking agent 2,2-Bis[4-(glycidyloxy)phenyl]propane, 4,4′-isopropylidenediphenol diglycidyl ether (BADGE). At a crosslinker content of 7 wt%, the WPU dispersion became highly viscous (10<sup>6</sup> mPa·s). Its rheological properties included shear thinning behavior, high yield stress (1.7 kPa), a rheological phase angle of 46.80°, and a storage modulus of 10<sup>4</sup> Pa; these all meet the requirements for DIW 3D printing. Finally, DIW 3D printing was performed using various movement speeds and nozzle flow rates, to evaluate the printing performance and determine the optimal parameters for DIW 3D printing with WPU materials. The high-solid-content WPU system developed in this work can be effectively applied to create 3D structures without generating air pollution or toxic wastewater, ensuring ecological sustainability and environmental safety.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"219 ","pages":"Article 106584"},"PeriodicalIF":5.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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