Pub Date : 2026-01-12DOI: 10.1016/j.reactfunctpolym.2026.106648
Alexandra Lupu , Luiza Madalina Gradinaru , Maria Bercea , Mihaela Avadanei , Vasile Robert Gradinaru , Irina Rosca , Daniela Rusu
Novel water-soluble thermoresponsive polyurethanes containing Pluronic F127 and lysine- or hexametylene-based diisocyanate are synthesized via a controlled polymerization approach. Subsequently, composite hydrogels of poly(vinyl alcohol) (PVA) and polyurethane (PU) are prepared and their morphological and rheological characteristics are systematically investigated. These physical networks are built through the combined action of two types of non-covalent interactions: hydrogen bonding (applying successive freezing/thawing cycles leads to the formation of a PVA network structure), and temperature-induced hydrophobic interactions (thermostating the samples at 37 °C changes the hydrophobic/hydrophilic balance and favors the gelation of PU micelles). This dual reinforcement strategy enhances the structural integrity and responsiveness of the composite matrix. The hydrogels are loaded with thiamine and neomycin sulfate to study their delivery in phosphate-buffered saline solution at pH = 7.4 and physiological temperature. In the presence of polyurethane, the release profile is dominated by both diffusional and relaxation contributions. The incorporation of different concentrations of a model active vitamin enhances the antibiotic delivery, but has no influence on the antimicrobial activity. Thus, this study opens a new window for the design of suitable eco-friendly biomaterials for wound dressing applications.
{"title":"Smart supramolecular hydrogels as a potential platform for wound dressings: Harnessing thiamine to boost neomycin efficacy","authors":"Alexandra Lupu , Luiza Madalina Gradinaru , Maria Bercea , Mihaela Avadanei , Vasile Robert Gradinaru , Irina Rosca , Daniela Rusu","doi":"10.1016/j.reactfunctpolym.2026.106648","DOIUrl":"10.1016/j.reactfunctpolym.2026.106648","url":null,"abstract":"<div><div>Novel water-soluble thermoresponsive polyurethanes containing Pluronic F127 and lysine- or hexametylene-based diisocyanate are synthesized via a controlled polymerization approach. Subsequently, composite hydrogels of poly(vinyl alcohol) (PVA) and polyurethane (PU) are prepared and their morphological and rheological characteristics are systematically investigated. These physical networks are built through the combined action of two types of non-covalent interactions: hydrogen bonding (applying successive freezing/thawing cycles leads to the formation of a PVA network structure), and temperature-induced hydrophobic interactions (thermostating the samples at 37 °C changes the hydrophobic/hydrophilic balance and favors the gelation of PU micelles). This dual reinforcement strategy enhances the structural integrity and responsiveness of the composite matrix. The hydrogels are loaded with thiamine and neomycin sulfate to study their delivery in phosphate-buffered saline solution at pH = 7.4 and physiological temperature. In the presence of polyurethane, the release profile is dominated by both diffusional and relaxation contributions. The incorporation of different concentrations of a model active vitamin enhances the antibiotic delivery, but has no influence on the antimicrobial activity. Thus, this study opens a new window for the design of suitable eco-friendly biomaterials for wound dressing applications.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106648"},"PeriodicalIF":5.1,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979968","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 : 2026-01-10DOI: 10.1016/j.reactfunctpolym.2026.106646
Elizangela Hafemann Fragal , Kamila Augusta Leão de Oliveira , Elisangela Pacheco da Silva , Karina Miyuki Retamiro , Celso Vataru Nakamura , Rafael Silva , Elias Basile Tambourgi , Adley Forti Rubira
A natural bioactive compound named berberine (Ber) has shown high therapeutic potential for chronic diseases, but suffers from extremely low gastrointestinal absorption, which limits its clinical application. In this work, we developed pH-responsive hybrid hydrogels based on sodium alginate (SA), cellulose nanocrystals (CNC), and 3-(trimethoxysilyl)propyl methacrylate (TMSPM) to enhance the intestinal bioavailability of Ber. The synthesis approach involved vinyl-functionalizing the SA and CNC to enable covalent crosslinking with the TMSPM via free-radical polymerization. Infrared spectroscopy confirmed the formation mechanism of the hybrid network, revealing covalent linkages (C-C, Si-O-C, and Si-O-Si) and non-covalent interactions (hydrogen bonding) among SA, CNC, and TMSPM. The hydrogel composed of SA containing 10% of CNC and 10% of TMPSM showed a Young's modulus 1.8-fold higher than that of the hydrogel containing 100% of SA. Swelling and release studies exhibited strong pH responsiveness, with sustained release at pH 7.4 (simulated intestinal fluid, SIF) and reduced diffusion at pH 1.2 (simulated gastric fluid, SGF). The optimized formulations sustained Ber release for up to 150 h, achieving 70–80% release at pH 7.4. The release of Ber was governed by super transport case II at pH 1.2 (faster release) and anomalous transport at pH 7.4 in a slower release, as confirmed by a reduced release rate constant. Cytotoxicity tests using the L929 fibroblast assay confirmed the biocompatibility of these hydrogels, supporting their potential as long-term, pH-responsive carriers for intestinal drug delivery and controlled therapeutic release.
{"title":"Exploring the use of pH-responsive alginate, cellulose nanocrystal and organosilane hybrid hydrogels for controlled berberine release","authors":"Elizangela Hafemann Fragal , Kamila Augusta Leão de Oliveira , Elisangela Pacheco da Silva , Karina Miyuki Retamiro , Celso Vataru Nakamura , Rafael Silva , Elias Basile Tambourgi , Adley Forti Rubira","doi":"10.1016/j.reactfunctpolym.2026.106646","DOIUrl":"10.1016/j.reactfunctpolym.2026.106646","url":null,"abstract":"<div><div>A natural bioactive compound named berberine (Ber) has shown high therapeutic potential for chronic diseases, but suffers from extremely low gastrointestinal absorption, which limits its clinical application. In this work, we developed pH-responsive hybrid hydrogels based on sodium alginate (SA), cellulose nanocrystals (CNC), and 3-(trimethoxysilyl)propyl methacrylate (TMSPM) to enhance the intestinal bioavailability of Ber. The synthesis approach involved vinyl-functionalizing the SA and CNC to enable covalent crosslinking with the TMSPM via free-radical polymerization. Infrared spectroscopy confirmed the formation mechanism of the hybrid network, revealing covalent linkages (C-C, Si-O-C, and Si-O-Si) and non-covalent interactions (hydrogen bonding) among SA, CNC, and TMSPM. The hydrogel composed of SA containing 10% of CNC and 10% of TMPSM showed a Young's modulus 1.8-fold higher than that of the hydrogel containing 100% of SA. Swelling and release studies exhibited strong pH responsiveness, with sustained release at pH 7.4 (simulated intestinal fluid, SIF) and reduced diffusion at pH 1.2 (simulated gastric fluid, SGF). The optimized formulations sustained Ber release for up to 150 h, achieving 70–80% release at pH 7.4. The release of Ber was governed by super transport case II at pH 1.2 (faster release) and anomalous transport at pH 7.4 in a slower release, as confirmed by a reduced release rate constant. Cytotoxicity tests using the L929 fibroblast assay confirmed the biocompatibility of these hydrogels, supporting their potential as long-term, pH-responsive carriers for intestinal drug delivery and controlled therapeutic release.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106646"},"PeriodicalIF":5.1,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979970","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 : 2026-01-09DOI: 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":"2026-01-09","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 : 2026-01-07DOI: 10.1016/j.reactfunctpolym.2026.106643
Zhenpeng Wang , Yalu Liu , Yapeng Zhang , Jiutao Hu , Youjie Rong , Jing Lv , Xiaobo Huang
In recent years, with the rapid development of photopolymerization 3D printing technology, ion-conductive gels have been widely used in the field of wearable flexible sensors owing to their excellent flexibility and electrical conductivity. Gels prepared by the photocurable 3D printing are mainly formed through covalent cross-linking. However, due to the lack of sufficient energy dissipation mechanisms, such gels are susceptible to fatigue fracture under dynamic loading. Herein, we report an ionogel with outstanding tear resistance constructed through strong electrostatic interactions between [2-(acryloyloxy)ethyl]trimethylammonium chloride (AETC) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]). The molecular sieve SBA-15-4.2 is incorporated as a microscale physical crosslinker. The physical barrier formed by the molecular sieve under stress effectively disperses stress concentration at crack tips, thereby inhibiting gel fracture. Under external stress, molecular sieves permit polymer chains to migrate internally, thereby alleviating the restrictions imposed by covalent crosslinking on the fluidity of the polymer network. The elongation of this gel exceeds 1800%, and its fracture strength is 680 kPa. Even with notches, it retains 98% of the tensile strain of the unnotched sample. Its high sensitivity (GF = 6.01) facilitates rapid electrical signal transmission. This work provides new insights for developing advanced wearable devices and smart electronics.
{"title":"Photocurable 3D-printed anti-tearing ionogels for flexible sensors","authors":"Zhenpeng Wang , Yalu Liu , Yapeng Zhang , Jiutao Hu , Youjie Rong , Jing Lv , Xiaobo Huang","doi":"10.1016/j.reactfunctpolym.2026.106643","DOIUrl":"10.1016/j.reactfunctpolym.2026.106643","url":null,"abstract":"<div><div>In recent years, with the rapid development of photopolymerization 3D printing technology, ion-conductive gels have been widely used in the field of wearable flexible sensors owing to their excellent flexibility and electrical conductivity. Gels prepared by the photocurable 3D printing are mainly formed through covalent cross-linking. However, due to the lack of sufficient energy dissipation mechanisms, such gels are susceptible to fatigue fracture under dynamic loading. Herein, we report an ionogel with outstanding tear resistance constructed through strong electrostatic interactions between [2-(acryloyloxy)ethyl]trimethylammonium chloride (AETC) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]). The molecular sieve SBA-15-4.2 is incorporated as a microscale physical crosslinker. The physical barrier formed by the molecular sieve under stress effectively disperses stress concentration at crack tips, thereby inhibiting gel fracture. Under external stress, molecular sieves permit polymer chains to migrate internally, thereby alleviating the restrictions imposed by covalent crosslinking on the fluidity of the polymer network. The elongation of this gel exceeds 1800%, and its fracture strength is 680 kPa. Even with notches, it retains 98% of the tensile strain of the unnotched sample. Its high sensitivity (GF = 6.01) facilitates rapid electrical signal transmission. This work provides new insights for developing advanced wearable devices and smart electronics.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106643"},"PeriodicalIF":5.1,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145928716","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 : 2026-01-07DOI: 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":"2026-01-07","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 : 2026-01-06DOI: 10.1016/j.reactfunctpolym.2026.106641
Xiaoyan Sun , Ziheng Zhao , Chunfan Xu , Min Hao , Madeleine Bussemaker , Lian X. Liu , Ru Zhou
Rigid polyurethane foam (RPUF) is extensively employed in construction and transportation for its superior insulation and structural integrity. However, its inherent high flammability restricts its utility across various applications. The excessive use of traditional flame retardants can lead to a reduction in the physical properties of materials and the generation of toxic by-products during combustion. To address this challenge, we developed an innovative flame-retardant system for RPUF, using nitrogen-containing polyols synthesized from formaldehyde and melamine, and replacing traditional polyols with 2-methyl-1,3-propanediol (MPD), alongside boron-containing polyols derived from glycerol and boric acid. The incorporation of nitrogen- and boron-containing polyols at a 1:1 ratio has markedly raised the limiting oxygen index of RPUF from 19.1 % (pure RPUF) to 26.8 % while maintaining its mechanical properties, with the compressive strength ranging from 0.48 MPa to 0.50 MPa. Compared to traditional polyether polyols, MPD offers an environmentally friendly alternative by reducing toxic byproduct emissions during combustion, providing a safer profile in fire scenarios. Additionally, compared to pure RPUF, the total heat release and total smoke production were significantly reduced by 68.8 % and 52.4 %, respectively. Thermogravimetric analysis demonstrated enhanced thermal stability and char-forming ability, further confirmed by scanning electron microscopy. These findings suggest that the newly developed system has great potential for enhancing RPUF's flame retardancy and smoke reduction while maintaining its mechanical properties at the same time.
{"title":"Reactive nitrogen–boron polyols for flame-retardant and low-smoke rigid polyurethane foams","authors":"Xiaoyan Sun , Ziheng Zhao , Chunfan Xu , Min Hao , Madeleine Bussemaker , Lian X. Liu , Ru Zhou","doi":"10.1016/j.reactfunctpolym.2026.106641","DOIUrl":"10.1016/j.reactfunctpolym.2026.106641","url":null,"abstract":"<div><div>Rigid polyurethane foam (RPUF) is extensively employed in construction and transportation for its superior insulation and structural integrity. However, its inherent high flammability restricts its utility across various applications. The excessive use of traditional flame retardants can lead to a reduction in the physical properties of materials and the generation of toxic by-products during combustion. To address this challenge, we developed an innovative flame-retardant system for RPUF, using nitrogen-containing polyols synthesized from formaldehyde and melamine, and replacing traditional polyols with 2-methyl-1,3-propanediol (MPD), alongside boron-containing polyols derived from glycerol and boric acid. The incorporation of nitrogen- and boron-containing polyols at a 1:1 ratio has markedly raised the limiting oxygen index of RPUF from 19.1 % (pure RPUF) to 26.8 % while maintaining its mechanical properties, with the compressive strength ranging from 0.48 MPa to 0.50 MPa. Compared to traditional polyether polyols, MPD offers an environmentally friendly alternative by reducing toxic byproduct emissions during combustion, providing a safer profile in fire scenarios. Additionally, compared to pure RPUF, the total heat release and total smoke production were significantly reduced by 68.8 % and 52.4 %, respectively. Thermogravimetric analysis demonstrated enhanced thermal stability and char-forming ability, further confirmed by scanning electron microscopy. These findings suggest that the newly developed system has great potential for enhancing RPUF's flame retardancy and smoke reduction while maintaining its mechanical properties at the same time.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106641"},"PeriodicalIF":5.1,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145928744","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 : 2026-01-05DOI: 10.1016/j.reactfunctpolym.2026.106639
Qijun Li , Yudan Yi , Haoyue Li , Bi Shi , Ya-nan Wang
Amphoteric acrylic polymers offer a promising solution to the incompatibility between innovative chrome-free tanning methods and conventional anionic chemicals, making them ideal retanning agents for sustainable leather production. However, their practical application is severely limited by their propensity for aggregation around the isoelectric point (pI). In this study, a series of amphoteric acrylic polymers (PDAs) were synthesized by adjusting the molar ratio of dimethylaminopropyl methacrylamide (DMAPMA) to acrylic acid (AA) to achieve tailored pIs (4.11–5.29). The PDA solutions exhibited high stability and remained transparent near their pIs, with a turbidity below 3.0 NTU. Notably, PDA with lower pI exhibited higher uptake rate in retanning process. PDA0.5 (DMAPMA/AA molar ratio 0.5:1, pI 4.24) exhibited the most uniform penetration within chrome-free tanned leather among the synthetized PDAs, which can be attributed to its stable solution property and optimal charge regulation ability. Consequently, PDA0.5 retanned leather showed more uniform dispersion of post-tanning chemicals, enhanced fullness and higher porosity (54.24 %) compared to leather retanned with other PDAs or a commercial amphoteric retanning agent. The non-aggregating nature of the PDAs at their pI conferred superior retanning performance, thus enabling more efficient chrome-free leather processing.
{"title":"Mitigating aggregation near isoelectric point in amphoteric acrylic polymers for high-performance chrome-free leather retanning","authors":"Qijun Li , Yudan Yi , Haoyue Li , Bi Shi , Ya-nan Wang","doi":"10.1016/j.reactfunctpolym.2026.106639","DOIUrl":"10.1016/j.reactfunctpolym.2026.106639","url":null,"abstract":"<div><div>Amphoteric acrylic polymers offer a promising solution to the incompatibility between innovative chrome-free tanning methods and conventional anionic chemicals, making them ideal retanning agents for sustainable leather production. However, their practical application is severely limited by their propensity for aggregation around the isoelectric point (pI). In this study, a series of amphoteric acrylic polymers (PDAs) were synthesized by adjusting the molar ratio of dimethylaminopropyl methacrylamide (DMAPMA) to acrylic acid (AA) to achieve tailored pIs (4.11–5.29). The PDA solutions exhibited high stability and remained transparent near their pIs, with a turbidity below 3.0 NTU. Notably, PDA with lower pI exhibited higher uptake rate in retanning process. PDA<sub>0.5</sub> (DMAPMA/AA molar ratio 0.5:1, pI 4.24) exhibited the most uniform penetration within chrome-free tanned leather among the synthetized PDAs, which can be attributed to its stable solution property and optimal charge regulation ability. Consequently, PDA<sub>0.5</sub> retanned leather showed more uniform dispersion of post-tanning chemicals, enhanced fullness and higher porosity (54.24 %) compared to leather retanned with other PDAs or a commercial amphoteric retanning agent. The non-aggregating nature of the PDAs at their pI conferred superior retanning performance, thus enabling more efficient chrome-free leather processing.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106639"},"PeriodicalIF":5.1,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903954","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 : 2026-01-05DOI: 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":"2026-01-05","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 : 2026-01-02DOI: 10.1016/j.reactfunctpolym.2025.106637
Qianzhao Wang , Zijian Wu , Yue Zhao , Zhaojun Wang , Hang Li , Wenhua Yang , Ning Guo , Ling Weng , Wei Zhao , Guoxing Yang , Juanna Ren , Hassan Algadi , Junguo Gao
This study successfully developed a high-performance thermal management composite material through innovative material design to address the heat dissipation demands of high-power electronic devices. Employing a hydrothermal synthesis method, the research achieved in-situ growth of one-dimensional zinc oxide (ZnO) nanorods on the surface of two-dimensional hexagonal boron nitride (h-BN) with excellent insulation properties, thereby constructing a unique “sea urchin-like” h-BN@ZnO hybrid filler. The filler was a composite with a thermoplastic polyurethane (TPU) matrix via a scrape coating process. Leveraging the bridging effect of one-dimensional nanorods, this structure interconnects isolated three-dimensional thermal conduction pathways into a continuous network, thereby effectively mitigating the limitation of inferior out-of-plane thermal conductivity induced by the in-plane orientation of two-dimensional hexagonal boron nitride (h-BN).Processing shear forces induced orientated alignment of the filler particles, while the bridging effect of ZnO nanorods formed an efficient three-dimensional thermal conduction network within the polymer matrix. At a 60 wt% filler loading, the composite exhibits outstanding comprehensive properties: an out-of-plane thermal conductivity as high as 2.13 W/(m·K), representing a 61-fold improvement over pure TPU. It simultaneously maintains excellent electrical insulation and thermal stability, with minimal performance degradation after 120 thermal cycles. This composite material, combining high thermal conductivity, high insulation, and tunable flexibility, offers advanced thermal solutions for flexible electronics, aerospace, and other fields, presenting broad application prospects.
{"title":"“Urchin-like” h-BN@ZnO hybrids inspire highly thermally conductive polyurethane composites via 3D phonon pathways","authors":"Qianzhao Wang , Zijian Wu , Yue Zhao , Zhaojun Wang , Hang Li , Wenhua Yang , Ning Guo , Ling Weng , Wei Zhao , Guoxing Yang , Juanna Ren , Hassan Algadi , Junguo Gao","doi":"10.1016/j.reactfunctpolym.2025.106637","DOIUrl":"10.1016/j.reactfunctpolym.2025.106637","url":null,"abstract":"<div><div>This study successfully developed a high-performance thermal management composite material through innovative material design to address the heat dissipation demands of high-power electronic devices. Employing a hydrothermal synthesis method, the research achieved in-situ growth of one-dimensional zinc oxide (ZnO) nanorods on the surface of two-dimensional hexagonal boron nitride (h-BN) with excellent insulation properties, thereby constructing a unique “sea urchin-like” h-BN@ZnO hybrid filler. The filler was a composite with a thermoplastic polyurethane (TPU) matrix via a scrape coating process. Leveraging the bridging effect of one-dimensional nanorods, this structure interconnects isolated three-dimensional thermal conduction pathways into a continuous network, thereby effectively mitigating the limitation of inferior out-of-plane thermal conductivity induced by the in-plane orientation of two-dimensional hexagonal boron nitride (h-BN).Processing shear forces induced orientated alignment of the filler particles, while the bridging effect of ZnO nanorods formed an efficient three-dimensional thermal conduction network within the polymer matrix. At a 60 wt% filler loading, the composite exhibits outstanding comprehensive properties: an out-of-plane thermal conductivity as high as 2.13 W/(m·K), representing a 61-fold improvement over pure TPU. It simultaneously maintains excellent electrical insulation and thermal stability, with minimal performance degradation after 120 thermal cycles. This composite material, combining high thermal conductivity, high insulation, and tunable flexibility, offers advanced thermal solutions for flexible electronics, aerospace, and other fields, presenting broad application prospects.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106637"},"PeriodicalIF":5.1,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939719","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 : 2025-12-28DOI: 10.1016/j.reactfunctpolym.2025.106622
Praveen Balaji T , Andreas Seifert , Arnab Sarkar , Susanta Banerjee , Soumyadip Choudhury
Epoxidized natural rubber possesses dual functionality due to the presence of double bonds and epoxide groups. The double bonds can undergo traditional vulcanization, while the epoxide groups allow for an alternative pathway for crosslinking. This study investigates the crosslinking behavior of epoxidized natural rubber (ENR) when treated with hydroquinone (HQ) as a curing additive. The findings indicate that HQ can significantly initiate and cure ENR, a conclusion supported by FTIR analysis. The electrostatic interaction between the hydroxyl group of HQ and the less sterically hindered C-O-C carbon of the epoxide group effectively initiates the curing process. As the dosage of HQ and the epoxy content in ENR (specifically ENR-25 and ENR-50) increase, there is a noticeable rise in crosslinking density and rheometric torque in the rubber composites. This enhancement results in greater hardness, tensile strength, and both static and dynamic moduli. Additionally, the introduction of HQ into the ENR compounds contributes to the development of a crosslinked network, which increases the glass transition temperature (Tg) of the ENR materials. The composites produced from this innovative network can be utilized in various applications, including stretchable electronics and flexible robotics. Furthermore, these composites demonstrate significant optical transparency, making them suitable for transparent coatings and optical-grade elastomeric applications. This transparency, combined with mechanical durability and thermal stability, expands their potential uses in high-performance coatings and protective layers for electronic devices, as well as in stretchable electronic applications.
{"title":"Exploring hydroquinone as a non‑sulfur curing agent on epoxidized natural rubber towards the development of highly stretchable and transparent elastomeric composites","authors":"Praveen Balaji T , Andreas Seifert , Arnab Sarkar , Susanta Banerjee , Soumyadip Choudhury","doi":"10.1016/j.reactfunctpolym.2025.106622","DOIUrl":"10.1016/j.reactfunctpolym.2025.106622","url":null,"abstract":"<div><div>Epoxidized natural rubber possesses dual functionality due to the presence of double bonds and epoxide groups. The double bonds can undergo traditional vulcanization, while the epoxide groups allow for an alternative pathway for crosslinking. This study investigates the crosslinking behavior of epoxidized natural rubber (ENR) when treated with hydroquinone (HQ) as a curing additive. The findings indicate that HQ can significantly initiate and cure ENR, a conclusion supported by FTIR analysis. The electrostatic interaction between the hydroxyl group of HQ and the less sterically hindered C-O-C carbon of the epoxide group effectively initiates the curing process. As the dosage of HQ and the epoxy content in ENR (specifically ENR-25 and ENR-50) increase, there is a noticeable rise in crosslinking density and rheometric torque in the rubber composites. This enhancement results in greater hardness, tensile strength, and both static and dynamic moduli. Additionally, the introduction of HQ into the ENR compounds contributes to the development of a crosslinked network, which increases the glass transition temperature (T<sub><em>g</em></sub>) of the ENR materials. The composites produced from this innovative network can be utilized in various applications, including stretchable electronics and flexible robotics. Furthermore, these composites demonstrate significant optical transparency, making them suitable for transparent coatings and optical-grade elastomeric applications. This transparency, combined with mechanical durability and thermal stability, expands their potential uses in high-performance coatings and protective layers for electronic devices, as well as in stretchable electronic applications.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106622"},"PeriodicalIF":5.1,"publicationDate":"2025-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979967","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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