Pub Date : 2026-04-01Epub Date: 2026-01-05DOI: 10.1016/j.reactfunctpolym.2026.106640
Baoyu Li , Jiaping Feng , Dan Huang , Huiping Shao , Rui Xu , Yufeng Zheng , Jiulong Li , Hongquan Fu , Juan Zhang , Hejun Gao
The accumulation of bilirubin in the body can severely damage the nervous system and cause diseases like nuclear jaundice. Thus, developing adsorbent materials with high bio-compatibility and low cost is crucial. This work innovatively employed a one-step in situ polymerization method to graft polypyrrole onto microcrystalline cellulose surfaces, successfully constructing a nitrogen-doped cellulose@polypyrrole composite for highly efficient bilirubin removal. Extensive structural analysis using FT-IR, XPS, BET and SEM showed the material has a porous structure, and the specific surface area of the optimum material is 17 times higher than that of microcrystalline cellulose, ideal for bilirubin adsorption. Adsorption tests revealed a capacity of 710.76 mg/g for unconjugated bilirubin and 264.34 mg/g for conjugated bilirubin. DFT clarified that the adsorption mechanism is dominated by hydrogen bonding with π-π interactions as a secondary factor, elucidating the reason for the performance enhancement at the structure level. This novel, high-performance, and low -cost adsorbent offers a new solution for efficient bilirubin removal.
{"title":"Efficient removal of bilirubin through the construction of nitrogen-rich biomass-based cellulose@polypyrrole","authors":"Baoyu Li , Jiaping Feng , Dan Huang , Huiping Shao , Rui Xu , Yufeng Zheng , Jiulong Li , Hongquan Fu , Juan Zhang , Hejun Gao","doi":"10.1016/j.reactfunctpolym.2026.106640","DOIUrl":"10.1016/j.reactfunctpolym.2026.106640","url":null,"abstract":"<div><div>The accumulation of bilirubin in the body can severely damage the nervous system and cause diseases like nuclear jaundice. Thus, developing adsorbent materials with high bio-compatibility and low cost is crucial. This work innovatively employed a one-step in situ polymerization method to graft polypyrrole onto microcrystalline cellulose surfaces, successfully constructing a nitrogen-doped cellulose@polypyrrole composite for highly efficient bilirubin removal. Extensive structural analysis using FT-IR, XPS, BET and SEM showed the material has a porous structure, and the specific surface area of the optimum material is 17 times higher than that of microcrystalline cellulose, ideal for bilirubin adsorption. Adsorption tests revealed a capacity of 710.76 mg/g for unconjugated bilirubin and 264.34 mg/g for conjugated bilirubin. DFT clarified that the adsorption mechanism is dominated by hydrogen bonding with π-π interactions as a secondary factor, elucidating the reason for the performance enhancement at the structure level. This novel, high-performance, and low -cost adsorbent offers a new solution for efficient bilirubin removal.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106640"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145928743","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 : 2026-04-01Epub Date: 2026-01-26DOI: 10.1016/j.reactfunctpolym.2026.106664
Maksims Jurinovs , Nikolass Rukavisnikovs , Sabine Greivule , Olesja Starkova , Andrejs Kovalovs , Jānis Brunāvs , Jan Macutkevič , Inna Juhnevica , Oskars Platnieks , Sergejs Gaidukovs
High-performance coatings require rapid and sustainable processing, robust mechanical properties, and long-term durability. However, conventional epoxy systems rely on slow and energy-intensive thermal curing. Here, we develop UV-curable epoxy-acrylate systems optimized through three sequential stages: neat UV-cured epoxy, interpenetrating epoxy-acrylate networks, and nanoclay-reinforced IPN composites. The formulations cure into ∼300 μm films under 2 min of UV exposure, removing the need for thermal treatment. The epoxy-acrylate networks exhibit a markedly increased hardness (up to 38% increase) and improved water-barrier performance compared to neat UV-cured epoxy. The incorporation of nanoclay platelets yields nanostructure-reinforced epoxy-acrylate composite coating and further enhances materials' thermal stability, reduces water uptake (by up to 46%), and improves stiffness (by up to 50%). Mechanical property predictions from finite-element analysis (FEA), derived from experimentally measured hardness and modulus values, confirmed the formation of efficiently reinforced and mechanically stable networks across the optimized compositions. Moisture transport was quantified using Fickian sorption models, establishing clear correlations between polymer network architecture, platelet alignment, and material stiffness with water barrier behavior. Together, these results demonstrate a predictable and tunable route to rapidly and sustainably produce high-performance UV-curable epoxy-acrylate coatings for marine environment applications, combining the speed of photopolymerization with the durability of nanoparticle-reinforced thermoset composites.
{"title":"Nanostructure-reinforced epoxy-acrylate interpenetrated networks for UV-curable high-performance coatings","authors":"Maksims Jurinovs , Nikolass Rukavisnikovs , Sabine Greivule , Olesja Starkova , Andrejs Kovalovs , Jānis Brunāvs , Jan Macutkevič , Inna Juhnevica , Oskars Platnieks , Sergejs Gaidukovs","doi":"10.1016/j.reactfunctpolym.2026.106664","DOIUrl":"10.1016/j.reactfunctpolym.2026.106664","url":null,"abstract":"<div><div>High-performance coatings require rapid and sustainable processing, robust mechanical properties, and long-term durability. However, conventional epoxy systems rely on slow and energy-intensive thermal curing. Here, we develop UV-curable epoxy-acrylate systems optimized through three sequential stages: neat UV-cured epoxy, interpenetrating epoxy-acrylate networks, and nanoclay-reinforced IPN composites. The formulations cure into ∼300 μm films under 2 min of UV exposure, removing the need for thermal treatment. The epoxy-acrylate networks exhibit a markedly increased hardness (up to 38% increase) and improved water-barrier performance compared to neat UV-cured epoxy. The incorporation of nanoclay platelets yields nanostructure-reinforced epoxy-acrylate composite coating and further enhances materials' thermal stability, reduces water uptake (by up to 46%), and improves stiffness (by up to 50%). Mechanical property predictions from finite-element analysis (FEA), derived from experimentally measured hardness and modulus values, confirmed the formation of efficiently reinforced and mechanically stable networks across the optimized compositions. Moisture transport was quantified using Fickian sorption models, establishing clear correlations between polymer network architecture, platelet alignment, and material stiffness with water barrier behavior. Together, these results demonstrate a predictable and tunable route to rapidly and sustainably produce high-performance UV-curable epoxy-acrylate coatings for marine environment applications, combining the speed of photopolymerization with the durability of nanoparticle-reinforced thermoset composites.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106664"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079073","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 : 2026-04-01Epub Date: 2026-01-18DOI: 10.1016/j.reactfunctpolym.2026.106654
Zijian Feng , Runyang Xiang , Jie Huang , Ming Zeng
In pursuit of high-performance and environmentally friendly materials for superhigh-frequency communication applications, a novel biobased benzoxazine resin (poly(SF-f)) is firstly synthesized from fluorinated Schiff base based bisphenol (SF) and furfurylamine. The bulky fluorinated Schiff base structure in SF can impart low polarity, enhance flame retardancy, and reduce the density of polar group, while low polar and reactive furan ring in furfurylamine can increase the cross-linking density. Interestingly, the newly developed benzoxazine SF-f exhibits the lowest onset polymerization temperature, relatively high exothermic enthalpy, and relatively low activation energy compared to other similar structures, due to the presence of both Schiff base moiety and furan ring. Notably, the prepared benzoxazine resin displays good thermal and flame retardancy properties, including the glass transition temperature of 302 °C, the char yield at 800 °C of 56.5%, the limiting oxygen index of 40.10, the heat release capacity of 30.9 J/g K, the total heat release of 2.9 KJ/g, and UL-94 V-0 rating. Besides, the poly(SF-f) also shows low dielectric constants (2.73, 5 GHz; 2.68, 10 GHz) and low dielectric losses (0.0064, 5 GHz; 0.0062, 10 GHz), resulting from the increased cross-linking density, strengthened hydrogen-bonding, and decreased molecular polarity. Therefore, this study not only provides an effective method to design and prepare bio-benzoxazine resin containing Schiff base with good comprehensive properties of high thermally stable, intrinsic flame-retardant, and superhigh-frequency low dielectric properties, but also gives a new insight for the development of high-performance benzoxazine chemistry.
{"title":"A novel bio-based polybenzoxazine prepared from fluorinated Schiff base and furfurylamine with superior thermal, flame-retardant and superhigh-frequency low dielectric properties","authors":"Zijian Feng , Runyang Xiang , Jie Huang , Ming Zeng","doi":"10.1016/j.reactfunctpolym.2026.106654","DOIUrl":"10.1016/j.reactfunctpolym.2026.106654","url":null,"abstract":"<div><div>In pursuit of high-performance and environmentally friendly materials for superhigh-frequency communication applications, a novel biobased benzoxazine resin (poly(SF-f)) is firstly synthesized from fluorinated Schiff base based bisphenol (SF) and furfurylamine. The bulky fluorinated Schiff base structure in SF can impart low polarity, enhance flame retardancy, and reduce the density of polar group, while low polar and reactive furan ring in furfurylamine can increase the cross-linking density. Interestingly, the newly developed benzoxazine SF-f exhibits the lowest onset polymerization temperature, relatively high exothermic enthalpy, and relatively low activation energy compared to other similar structures, due to the presence of both Schiff base moiety and furan ring. Notably, the prepared benzoxazine resin displays good thermal and flame retardancy properties, including the glass transition temperature of 302 °C, the char yield at 800 °C of 56.5%, the limiting oxygen index of 40.10, the heat release capacity of 30.9 J/g K, the total heat release of 2.9 KJ/g, and UL-94 <em>V</em>-0 rating. Besides, the poly(SF-f) also shows low dielectric constants (2.73, 5 GHz; 2.68, 10 GHz) and low dielectric losses (0.0064, 5 GHz; 0.0062, 10 GHz), resulting from the increased cross-linking density, strengthened hydrogen-bonding, and decreased molecular polarity. Therefore, this study not only provides an effective method to design and prepare bio-benzoxazine resin containing Schiff base with good comprehensive properties of high thermally stable, intrinsic flame-retardant, and superhigh-frequency low dielectric properties, but also gives a new insight for the development of high-performance benzoxazine chemistry.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106654"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038461","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 : 2026-04-01Epub Date: 2026-01-09DOI: 10.1016/j.reactfunctpolym.2026.106647
Abdulsalam Mahdy , Jalal A. Zahra , Violet Kasabri , Randa N. Haddadin , Osama Younis
A novel and versatile platform of quinoline-based benzoxazine (quinolinoxazine) monomers and their corresponding polybenzoxazines has been developed to reveal deep insights into the structure–property correlations governing thermal robustness, biological functionality, and photophysical response. The monomers were synthesized from 8-hydroxyquinoline and a series of aliphatic diamines, thoroughly characterized via FTIR and NMR spectroscopy, and subsequently polymerized. The evolution of structure, curing dynamics, and thermal characteristics of the resulting polymers was comprehensively investigated through FTIR, DSC, and TGA analyses, while morphological and crystallographic features were examined using SEM and XRD. The results identified the diamine spacer length as a decisive factor in modulating polymer performance. Among them, Poly(QZ-C3), featuring a symmetric C3 linker, exhibited the highest glass transition temperature (Tg = 247 °C) and remarkable char yield (43%), correlating to an exceptional Limiting Oxygen Index (LOI) of 34.7%. Biological assays revealed compelling multifunctionality: Mono(QZ-C2) demonstrated broad-spectrum antimicrobial activity and high antioxidative DPPH radical scavenging capacities compared to the respective reference agents. Mono(QZ-C3) outperformed the reference NSAID indomethacin, exerting exceptional anti-inflammatory potency at the nanomolar level. All tested compounds displayed both selective cytotoxicity and differential anti-inflammatory/immunomodulatory physiologically regulated activities, outperforming the antineoplastic proapoptotic cisplatin in the majority of malignancy cell lines. None of the tested synthetic compounds exerted toxicity toward normal noncancerous cells (PDL fibroblasts or RAW264.7 macrophages), unlike cisplatin. Photoluminescence investigations further revealed concentration-dependent emission behavior in the monomers, resulting in solid-state white-light emission. Upon polymerization, the chromophores became effectively confined within the network, enabling excitation-dependent color tuning and stable white-light coordinates. Altogether, this study positions quinolinoxazines as a powerful multifunctional materials framework, deliberately integrating superior thermal stability, broad-spectrum bioactivity, and tunable luminescence through a unified molecular design, offering a strategic blueprint for the rational design of next-generation multifunctional polymers.
{"title":"A versatile platform of Quinolinoxazine monomers and polymers: Unlocking structure-property relationships in thermal stability, biological activity, and white-light emission","authors":"Abdulsalam Mahdy , Jalal A. Zahra , Violet Kasabri , Randa N. Haddadin , Osama Younis","doi":"10.1016/j.reactfunctpolym.2026.106647","DOIUrl":"10.1016/j.reactfunctpolym.2026.106647","url":null,"abstract":"<div><div>A novel and versatile platform of quinoline-based benzoxazine (quinolinoxazine) monomers and their corresponding polybenzoxazines has been developed to reveal deep insights into the structure–property correlations governing thermal robustness, biological functionality, and photophysical response. The monomers were synthesized from 8-hydroxyquinoline and a series of aliphatic diamines, thoroughly characterized via FTIR and NMR spectroscopy, and subsequently polymerized. The evolution of structure, curing dynamics, and thermal characteristics of the resulting polymers was comprehensively investigated through FTIR, DSC, and TGA analyses, while morphological and crystallographic features were examined using SEM and XRD. The results identified the diamine spacer length as a decisive factor in modulating polymer performance. Among them, Poly(QZ-C3), featuring a symmetric C3 linker, exhibited the highest glass transition temperature (Tg = 247 °C) and remarkable char yield (43%), correlating to an exceptional Limiting Oxygen Index (LOI) of 34.7%. Biological assays revealed compelling multifunctionality: Mono(QZ-C2) demonstrated broad-spectrum antimicrobial activity and high antioxidative DPPH radical scavenging capacities compared to the respective reference agents. Mono(QZ-C3) outperformed the reference NSAID indomethacin, exerting exceptional anti-inflammatory potency at the nanomolar level. All tested compounds displayed both selective cytotoxicity and differential anti-inflammatory/immunomodulatory physiologically regulated activities, outperforming the antineoplastic proapoptotic cisplatin in the majority of malignancy cell lines. None of the tested synthetic compounds exerted toxicity toward normal noncancerous cells (PDL fibroblasts or RAW264.7 macrophages), unlike cisplatin. Photoluminescence investigations further revealed concentration-dependent emission behavior in the monomers, resulting in solid-state white-light emission. Upon polymerization, the chromophores became effectively confined within the network, enabling excitation-dependent color tuning and stable white-light coordinates. Altogether, this study positions quinolinoxazines as a powerful multifunctional materials framework, deliberately integrating superior thermal stability, broad-spectrum bioactivity, and tunable luminescence through a unified molecular design, offering a strategic blueprint for the rational design of next-generation multifunctional polymers.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106647"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979966","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 : 2026-04-01Epub Date: 2026-01-14DOI: 10.1016/j.reactfunctpolym.2026.106652
Jordi Guardià , Krzysztof Artur Bogdanowicz , José Antonio Reina , Marta Giamberini , Agnieszka Iwan , Xavier Montané
Designing biomimetic membranes with controlled and selective ion transport pathways is essential for next-generation electrochemical and energy-conversion systems. In this work, the cation transport properties of hybrid membranes composed of a side chain liquid crystalline poly(2-oxazoline), poly(2-(3,4,5-tris(4-dodecyloxybenzyloxy)phenyl)-2-oxazoline (PTOx40), supported on a polyester fabric were investigated. Polymer columns were homeotropically oriented by thermal treatment. X-ray diffraction revealed that hydrophobic substrates (fluorinated ethylene propylene resin and silanized glass) promoted better homeotropic orientation of the polymer columns than hydrophilic substrates (untreated glass). Wettability studies indicated comparable absorption behaviour for water and methanol in all membranes. Methanol uptake was consistently lower than that of water, highlighting their suitability for methanol-based hydrogen systems. Compared with Nafion® 117, these PTOx40-based membranes exhibited superior dimensional stability and a hydrophobic character. Cation transport was examined through electrochemical impedance spectroscopy (EIS), permeability tests, and linear sweep voltammetry (LSV). Although EIS confirmed the non-ionic nature of these membranes, LSV measurements demonstrated that oriented membranes exhibited lower resistance densities than unoriented ones. This strong dependence on column alignment underscores the role of columnar self-assembly in facilitating selective ion transport. The PTOx40-based membranes exhibited lower absolute conductivity than Nafion® 117. However, they showed remarkable proton selectivity, highlighting their potential for proton-transfer applications in artificial photosynthesis and sustainable energy technologies.
{"title":"Synthesis and characterization of biomimetic hybrid membranes based on a side chain liquid crystalline poly(2-oxazoline) for selective proton transport","authors":"Jordi Guardià , Krzysztof Artur Bogdanowicz , José Antonio Reina , Marta Giamberini , Agnieszka Iwan , Xavier Montané","doi":"10.1016/j.reactfunctpolym.2026.106652","DOIUrl":"10.1016/j.reactfunctpolym.2026.106652","url":null,"abstract":"<div><div>Designing biomimetic membranes with controlled and selective ion transport pathways is essential for next-generation electrochemical and energy-conversion systems. In this work, the cation transport properties of hybrid membranes composed of a side chain liquid crystalline poly(2-oxazoline), poly(2-(3,4,5-tris(4-dodecyloxybenzyloxy)phenyl)-2-oxazoline (PTOx40), supported on a polyester fabric were investigated. Polymer columns were homeotropically oriented by thermal treatment. X-ray diffraction revealed that hydrophobic substrates (fluorinated ethylene propylene resin and silanized glass) promoted better homeotropic orientation of the polymer columns than hydrophilic substrates (untreated glass). Wettability studies indicated comparable absorption behaviour for water and methanol in all membranes. Methanol uptake was consistently lower than that of water, highlighting their suitability for methanol-based hydrogen systems. Compared with Nafion® 117, these PTOx40-based membranes exhibited superior dimensional stability and a hydrophobic character. Cation transport was examined through electrochemical impedance spectroscopy (EIS), permeability tests, and linear sweep voltammetry (LSV). Although EIS confirmed the non-ionic nature of these membranes, LSV measurements demonstrated that oriented membranes exhibited lower resistance densities than unoriented ones. This strong dependence on column alignment underscores the role of columnar self-assembly in facilitating selective ion transport. The PTOx40-based membranes exhibited lower absolute conductivity than Nafion® 117. However, they showed remarkable proton selectivity, highlighting their potential for proton-transfer applications in artificial photosynthesis and sustainable energy technologies.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106652"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038403","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 : 2026-04-01Epub Date: 2026-01-07DOI: 10.1016/j.reactfunctpolym.2026.106642
Yanfei Zhang , Xiaoting Li , Jinxin Liu , Ning Ma , Minli Tao , Wenqin Zhang
This work introduces a novel class of recyclable guanidine-modified polyacrylonitrile fiber catalysts (PANGF-1* to PANGF-5*) specifically designed for the hydroxymethylation reaction, a key transformation in organic synthesis for introducing hydroxymethyl groups. The catalysts were thoroughly characterized using Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TG), scanning electron microscopy (SEM), elemental analysis (EA), and mechanical performance testing, confirming the successful incorporation of guanidine groups onto polyacrylonitrile fiber. By fine-tuning the catalyst's hydrophilicity, we optimized the catalytic microenvironment, facilitating the nucleophilic attack on the benzamide carbonyl group, accelerating the reaction kinetics, and ultimately improving yields. Under optimized conditions (100 °C, water as solvent for 12 h), PANGF-2* achieved a high yield of 94.9%. The catalyst demonstrated excellent substrate versatility, achieving yields exceeding 90.0% for most benzamide derivatives, underscoring its broad applicability. Importantly, PANGF-2* maintained a yield of 90.6% after six cycles, highlighting its exceptional stability and recyclability. Furthermore, gram-scale experiments confirmed the catalyst's practical applicability, with a high separation efficiency of 87.6%, further demonstrating its potential for sustainable and scalable organic synthesis.
{"title":"Guanidine-functionalized polyacrylonitrile fiber as efficient heterogeneous catalyst: Tuning hydrophilicity for optimized catalytic microenvironment","authors":"Yanfei Zhang , Xiaoting Li , Jinxin Liu , Ning Ma , Minli Tao , Wenqin Zhang","doi":"10.1016/j.reactfunctpolym.2026.106642","DOIUrl":"10.1016/j.reactfunctpolym.2026.106642","url":null,"abstract":"<div><div>This work introduces a novel class of recyclable guanidine-modified polyacrylonitrile fiber catalysts (PAN<sub>G</sub>F-1* to PAN<sub>G</sub>F-5*) specifically designed for the hydroxymethylation reaction, a key transformation in organic synthesis for introducing hydroxymethyl groups. The catalysts were thoroughly characterized using Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TG), scanning electron microscopy (SEM), elemental analysis (EA), and mechanical performance testing, confirming the successful incorporation of guanidine groups onto polyacrylonitrile fiber. By fine-tuning the catalyst's hydrophilicity, we optimized the catalytic microenvironment, facilitating the nucleophilic attack on the benzamide carbonyl group, accelerating the reaction kinetics, and ultimately improving yields. Under optimized conditions (100 °C, water as solvent for 12 h), PAN<sub>G</sub>F-2* achieved a high yield of 94.9%. The catalyst demonstrated excellent substrate versatility, achieving yields exceeding 90.0% for most benzamide derivatives, underscoring its broad applicability. Importantly, PAN<sub>G</sub>F-2* maintained a yield of 90.6% after six cycles, highlighting its exceptional stability and recyclability. Furthermore, gram-scale experiments confirmed the catalyst's practical applicability, with a high separation efficiency of 87.6%, further demonstrating its potential for sustainable and scalable organic synthesis.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106642"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979965","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 : 2026-04-01Epub Date: 2026-01-13DOI: 10.1016/j.reactfunctpolym.2026.106650
Beibei Ji , Qiyong Xu , Yue Pan, Ke Duan, Wei Liao, Changping Yin, Suli Xing, Nan Wu
The pursuit of higher performance in the aerospace industry is pushing the limits of resin-based wave-transparent composites, demanding superior thermal resistance and lower dielectric constants. However, simultaneously optimizing thermal and dielectric performance in polymer matrices remains challenging due to their inherent trade-off. In this study, a novel polyhedral oligomeric silsesquioxane (POSS) monomer end-capped with phthalonitrile groups, TtSPPN, was synthesized and employed as an organic-inorganic copolymerization modifier to a baseline phthalonitrile resin (BPh). Results indicate that TtSPPN exhibited superior thermal stability, with a 5% thermal decomposition temperature (Td5%) exceeding 500 °C. Owing to its terminal phthalonitrile groups, the modifier enables molecular-level dispersion and participates in copolymerization cross-linking. The copolymers demonstrated exceptional thermal properties, with a Td5% reaching 584 °C and a glass transition temperature above 500 °C. Additionally, the incorporation of 5 wt% TtSPPN significantly reduced the dielectric constant and dielectric loss of the composite to 3.28 and 0.007 at 12 GHz, respectively, compared to 3.54 and 0.013 for pure BPh resin. Notably, the addition of TtSPPN into the cured samples significantly decreased water absorption. This study presents a novel design strategy for PN resins specifically engineered for extreme environments, demonstrating transformative potential for applications in high-performance composite materials.
{"title":"Dual triumph over thermal and dielectric constraints: Nitrile-functionalized POSS revolutionizes phthalonitrile for extreme environments","authors":"Beibei Ji , Qiyong Xu , Yue Pan, Ke Duan, Wei Liao, Changping Yin, Suli Xing, Nan Wu","doi":"10.1016/j.reactfunctpolym.2026.106650","DOIUrl":"10.1016/j.reactfunctpolym.2026.106650","url":null,"abstract":"<div><div>The pursuit of higher performance in the aerospace industry is pushing the limits of resin-based wave-transparent composites, demanding superior thermal resistance and lower dielectric constants. However, simultaneously optimizing thermal and dielectric performance in polymer matrices remains challenging due to their inherent trade-off. In this study, a novel polyhedral oligomeric silsesquioxane (POSS) monomer end-capped with phthalonitrile groups, TtSPPN, was synthesized and employed as an organic-inorganic copolymerization modifier to a baseline phthalonitrile resin (BPh). Results indicate that TtSPPN exhibited superior thermal stability, with a 5% thermal decomposition temperature (<em>T</em><sub>d5%</sub>) exceeding 500 °C. Owing to its terminal phthalonitrile groups, the modifier enables molecular-level dispersion and participates in copolymerization cross-linking. The copolymers demonstrated exceptional thermal properties, with a <em>T</em><sub>d5%</sub> reaching 584 °C and a glass transition temperature above 500 °C. Additionally, the incorporation of 5 wt% TtSPPN significantly reduced the dielectric constant and dielectric loss of the composite to 3.28 and 0.007 at 12 GHz, respectively, compared to 3.54 and 0.013 for pure BPh resin. Notably, the addition of TtSPPN into the cured samples significantly decreased water absorption. This study presents a novel design strategy for PN resins specifically engineered for extreme environments, demonstrating transformative potential for applications in high-performance composite materials.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106650"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038402","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}
This work presents the first photo-photo dual-curable vitrimer resin, representing a difference from previously reported dual-curable vitrimer resins that relied on photo-thermal curing of acrylate-epoxy formulations. The design, synthesis and characterization of a vitrimer based on cardanol and glycerol derivatives were performed. A life cycle assessment has shown that the fossil carbon footprint of epoxy cardanol resin NC-514S is 1.6 times lower than that of bisphenol A-based epoxy resins, confirming its suitability as a bio-based alternative to petroleum-based epoxy resin. Dual-curable resin compositions containing epoxidized cardanol resin NC-514S, different glycerol-based acrylates, and thiol pentaerythritol tetrakis(3-mercaptopropionate) were formulated to ensure both simultaneous cationic and radical photopolymerization. Photocuring kinetics studies revealed an optimal resin with viscosity and rheological characteristics close to those of common commercial 3D printing resins. The optimized resin containing 20 wt% of epoxidized cardanol resin NC-514S, 20 wt% of glycerol 1,3-diglycerolate diacrylate, 40 wt% of 2-hydroxy-3-phenoxypropyl acrylate, and 20 wt% of pentaerythritol tetrakis(3-mercaptopropionate demonstrated vitrimeric properties, including shape-memory recovery within 120 s above the topology freezing temperature and glass transition temperature, self-welding with a 76% increase in tensile strength and a 125% increase in Young's modulus after self-welding, and reprocessability with mechanical properties retained after 3 reprocessing cycles. These results demonstrate that synthesized vitrimer is a promising material for reconfigurable or reusable packaging and packaging component applications, as well as various other adaptive structures and devices, while supporting sustainable use in reprocessable materials and circular economy applications.
{"title":"Photo-photo dual-cured vitrimer based on cardanol and glycerol derivatives","authors":"Austeja Leimontaite , Aysu Nasiribouyony , Sigita Grauzeliene , Kastytis Pamakstys , Visvaldas Varzinskas , Jolita Ostrauskaite","doi":"10.1016/j.reactfunctpolym.2026.106655","DOIUrl":"10.1016/j.reactfunctpolym.2026.106655","url":null,"abstract":"<div><div>This work presents the first photo-photo dual-curable vitrimer resin, representing a difference from previously reported dual-curable vitrimer resins that relied on photo-thermal curing of acrylate-epoxy formulations. The design, synthesis and characterization of a vitrimer based on cardanol and glycerol derivatives were performed. A life cycle assessment has shown that the fossil carbon footprint of epoxy cardanol resin NC-514S is 1.6 times lower than that of bisphenol A-based epoxy resins, confirming its suitability as a bio-based alternative to petroleum-based epoxy resin. Dual-curable resin compositions containing epoxidized cardanol resin NC-514S, different glycerol-based acrylates, and thiol pentaerythritol tetrakis(3-mercaptopropionate) were formulated to ensure both simultaneous cationic and radical photopolymerization. Photocuring kinetics studies revealed an optimal resin with viscosity and rheological characteristics close to those of common commercial 3D printing resins. The optimized resin containing 20 wt% of epoxidized cardanol resin NC-514S, 20 wt% of glycerol 1,3-diglycerolate diacrylate, 40 wt% of 2-hydroxy-3-phenoxypropyl acrylate, and 20 wt% of pentaerythritol tetrakis(3-mercaptopropionate demonstrated vitrimeric properties, including shape-memory recovery within 120 s above the topology freezing temperature and glass transition temperature, self-welding with a 76% increase in tensile strength and a 125% increase in Young's modulus after self-welding, and reprocessability with mechanical properties retained after 3 reprocessing cycles. These results demonstrate that synthesized vitrimer is a promising material for reconfigurable or reusable packaging and packaging component applications, as well as various other adaptive structures and devices, while supporting sustainable use in reprocessable materials and circular economy applications.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106655"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038459","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 : 2026-04-01Epub Date: 2026-01-14DOI: 10.1016/j.reactfunctpolym.2026.106651
Zhaoqun Pan, Zhiliang Shen, Ming Zhong
To satisfy the synergistic protection requirements of oxidation resistance and electrical insulation for copper substrates in high-temperature environments, this study developed a polysilazane-based composite coating with high-temperature resistance and electrical insulation properties. The composite protective coating was formulated with polysilazane serving as the matrix resin and silicon carbide (SiC) as the functional filler. Meanwhile, an oligomer modifier (DMS-560) was synthesized via the hydrolysis-condensation of dimethyldiethoxysilane (KH−212) and γ-glycidoxypropyltrimethoxysilane (KH-560) for SiC surface modification, which effectively improved the interfacial compatibility between SiC filler and the polysilazane matrix. Furthermore, SiC underwent hydroxylation treatment using hydrogen peroxide to increase the number of surface-active sites, thereby enhancing the grafting efficiency of the oligomer modifier. The chemical structural alterations of SiC powder before and after modification were analyzed using Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The microstructural morphology of the resultant coatings was characterized by scanning electron microscopy (SEM), and their key properties—including high-temperature resistance, hydrophobicity, hardness, and electrical insulation—were systematically evaluated. The findings indicate that the modified SiC demonstrates significantly enhanced dispersibility within the coating, with a notable reduction in agglomeration. The coating maintains its structural integrity after exposure to high-temperature conditions at 750 °C for 30 min, exhibiting excellent hydrophobicity and high hardness (maintaining a hardness of 7H after baking at 750 °C), as well as superior electrical insulation. This study concludes that surface modification using the silane oligomer modifier effectively optimizes SiC filler dispersion and interfacial bonding, thus realizing the synergistic enhancement of thermal resistance and electrical-mechanical protective properties of the polysilazane/SiC composite coating.
{"title":"Silane oligomer modified SiC and its application in polysilazane-based high-temperature resistant electrical insulation coatings","authors":"Zhaoqun Pan, Zhiliang Shen, Ming Zhong","doi":"10.1016/j.reactfunctpolym.2026.106651","DOIUrl":"10.1016/j.reactfunctpolym.2026.106651","url":null,"abstract":"<div><div>To satisfy the synergistic protection requirements of oxidation resistance and electrical insulation for copper substrates in high-temperature environments, this study developed a polysilazane-based composite coating with high-temperature resistance and electrical insulation properties. The composite protective coating was formulated with polysilazane serving as the matrix resin and silicon carbide (SiC) as the functional filler. Meanwhile, an oligomer modifier (DMS-560) was synthesized via the hydrolysis-condensation of dimethyldiethoxysilane (KH−212) and γ-glycidoxypropyltrimethoxysilane (KH-560) for SiC surface modification, which effectively improved the interfacial compatibility between SiC filler and the polysilazane matrix. Furthermore, SiC underwent hydroxylation treatment using hydrogen peroxide to increase the number of surface-active sites, thereby enhancing the grafting efficiency of the oligomer modifier. The chemical structural alterations of SiC powder before and after modification were analyzed using Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The microstructural morphology of the resultant coatings was characterized by scanning electron microscopy (SEM), and their key properties—including high-temperature resistance, hydrophobicity, hardness, and electrical insulation—were systematically evaluated. The findings indicate that the modified SiC demonstrates significantly enhanced dispersibility within the coating, with a notable reduction in agglomeration. The coating maintains its structural integrity after exposure to high-temperature conditions at 750 °C for 30 min, exhibiting excellent hydrophobicity and high hardness (maintaining a hardness of 7H after baking at 750 °C), as well as superior electrical insulation. This study concludes that surface modification using the silane oligomer modifier effectively optimizes SiC filler dispersion and interfacial bonding, thus realizing the synergistic enhancement of thermal resistance and electrical-mechanical protective properties of the polysilazane/SiC composite coating.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106651"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079084","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 : 2026-04-01Epub Date: 2026-01-27DOI: 10.1016/j.reactfunctpolym.2026.106666
Shuai Yang , Guxia Wang , Tingxuan Dong , Dan Li , Ning Wu , Zhiyi Wu , Liyang Ding , Shengwei Guo , Yen Wei
To address the issues of flammability and inadequate UV resistance of low-density polyethylene (LDPE) in outdoor cable applications, we encapsulated ammonium polyphosphate (APP) surface with polysiloxane to mitigate its antagonistic impact (Si-APP), and grafted 4-amino-2,2,6,6-tetramethylpiperidine (TEMP) onto Si-APP by reacting with melamine (ME) and benzylamine (Bn), resulting in the formation of TEMP-ME@Si-APP and TEMP-Bn@Si-APP, which were then combined with tris(2-hydroxyethyl) isocyanurate (THEIC) and incorporated into LDPE. The resulting LDPE/TEMP-ME@Si-APP/THEIC composites demonstrated a carbonyl index of 10.45, reflecting substantial UV resistance. Compared with pure LDPE, the composites exhibited a limiting oxygen index (LOI) of 31.0%, along with a reduction of 75.8% in peak heat release rate (pHRR), a 59.9% decrease in smoke release rate (pSPR), and a 49.7% reduction in peak carbon monoxide production (pCOP). After 100 h of UV aging, the samples retained an LOI of 30.3% and achieved UL-94 V-0 rating. The tensile strength and elongation at break decreased by only 2.06% and 2.29%, respectively, which was significantly lower than that observed in control samples. This study confirms that the combination of polysiloxane encapsulation and amine salt grafting effectively enhances the UV stability, flame retardancy, and mechanical properties of LDPE.
{"title":"A robust strategy for enhanced UV stability and flame retardancy of LDPE via synergistic polysiloxane encapsulation and amine grafting","authors":"Shuai Yang , Guxia Wang , Tingxuan Dong , Dan Li , Ning Wu , Zhiyi Wu , Liyang Ding , Shengwei Guo , Yen Wei","doi":"10.1016/j.reactfunctpolym.2026.106666","DOIUrl":"10.1016/j.reactfunctpolym.2026.106666","url":null,"abstract":"<div><div>To address the issues of flammability and inadequate UV resistance of low-density polyethylene (LDPE) in outdoor cable applications, we encapsulated ammonium polyphosphate (APP) surface with polysiloxane to mitigate its antagonistic impact (Si-APP), and grafted 4-amino-2,2,6,6-tetramethylpiperidine (TEMP) onto Si-APP by reacting with melamine (ME) and benzylamine (Bn), resulting in the formation of TEMP-ME@Si-APP and TEMP-Bn@Si-APP, which were then combined with tris(2-hydroxyethyl) isocyanurate (THEIC) and incorporated into LDPE. The resulting LDPE/TEMP-ME@Si-APP/THEIC composites demonstrated a carbonyl index of 10.45, reflecting substantial UV resistance. Compared with pure LDPE, the composites exhibited a limiting oxygen index (LOI) of 31.0%, along with a reduction of 75.8% in peak heat release rate (pHRR), a 59.9% decrease in smoke release rate (pSPR), and a 49.7% reduction in peak carbon monoxide production (pCOP). After 100 h of UV aging, the samples retained an LOI of 30.3% and achieved UL-94 V-0 rating. The tensile strength and elongation at break decreased by only 2.06% and 2.29%, respectively, which was significantly lower than that observed in control samples. This study confirms that the combination of polysiloxane encapsulation and amine salt grafting effectively enhances the UV stability, flame retardancy, and mechanical properties of LDPE.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106666"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079072","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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