Pub Date : 2026-04-01Epub Date: 2026-01-06DOI: 10.1016/j.reactfunctpolym.2026.106638
Humaira Parveen , Nawaa Ali H. Alshammari , Nawaf Albeladi , Eman H. Tawfik , Hayat D. Zagloul , Hedia Ouni , M. Monier
In the current research, a novel cyanoethylated resorcinol–formaldehyde resin (RF-CN) was synthesized through phase-transfer catalysis (PTC) using acrylonitrile. The degree of cyanoethylation (DCE) was optimized through reaction condition manipulation and confirmed by gravimetry analysis, elemental analysis, and FTIR spectroscopy. Solid-state 13C NMR also confirmed structural modification through characteristic resonances of the introduced –CN groups. Morphological analysis via SEM displayed conspicuous changes in surface texture and porosity upon modification. Thermogravimetric analysis (TGA) demonstrated enhanced thermal stability of RF-CN through a two-stage degradation profile compared to the single-stage degradation of pure RF. Thermodynamic parameters (ΔG°, ΔH°, and ΔS°) and Van't Hoff analysis attested to the spontaneity and endothermicity of the functionalization under PTC. Kinetic studies via initial rate measurements allowed the estimation of activation energy, testifying to the catalytic efficiency of benzyltriphenyl phosphonium chloride (BTPP) in lowering the energy barrier of the reaction. Further, the versatility of RF-CN as a platform was testified by nucleophilic post-functionalization with hydroxylamine and salicylic acid hydrazide to give amidoxime (AOX-RF) and hydrazidine (SAH-RF) derivatives. The derivatives were characterized neatly by elemental analysis, FTIR, and 13C NMR, testifying to successful incorporation. Overall, this study describes a systematic approach to the design of functionalized RF-based sorbents with tunable properties for advanced applications.
{"title":"Phase-transfer catalyzed cyanoethylation of resorcinol–formaldehyde resin: Synthesis and characterization","authors":"Humaira Parveen , Nawaa Ali H. Alshammari , Nawaf Albeladi , Eman H. Tawfik , Hayat D. Zagloul , Hedia Ouni , M. Monier","doi":"10.1016/j.reactfunctpolym.2026.106638","DOIUrl":"10.1016/j.reactfunctpolym.2026.106638","url":null,"abstract":"<div><div>In the current research, a novel cyanoethylated resorcinol–formaldehyde resin (RF-CN) was synthesized through phase-transfer catalysis (PTC) using acrylonitrile. The degree of cyanoethylation (DCE) was optimized through reaction condition manipulation and confirmed by gravimetry analysis, elemental analysis, and FTIR spectroscopy. Solid-state <sup>13</sup>C NMR also confirmed structural modification through characteristic resonances of the introduced –CN groups. Morphological analysis via SEM displayed conspicuous changes in surface texture and porosity upon modification. Thermogravimetric analysis (TGA) demonstrated enhanced thermal stability of RF-CN through a two-stage degradation profile compared to the single-stage degradation of pure RF. Thermodynamic parameters (ΔG°, ΔH°, and ΔS°) and Van't Hoff analysis attested to the spontaneity and endothermicity of the functionalization under PTC. Kinetic studies via initial rate measurements allowed the estimation of activation energy, testifying to the catalytic efficiency of benzyltriphenyl phosphonium chloride (BTPP) in lowering the energy barrier of the reaction. Further, the versatility of RF-CN as a platform was testified by nucleophilic post-functionalization with hydroxylamine and salicylic acid hydrazide to give amidoxime (AOX-RF) and hydrazidine (SAH-RF) derivatives. The derivatives were characterized neatly by elemental analysis, FTIR, and <sup>13</sup>C NMR, testifying to successful incorporation. Overall, this study describes a systematic approach to the design of functionalized RF-based sorbents with tunable properties for advanced applications<strong>.</strong></div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106638"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038404","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: 2026-01-12DOI: 10.1016/j.reactfunctpolym.2026.106649
Huseyin Cem Kiliclar , Berkay Sütay , Palani Natajaran , Onder Metin , Yusuf Yagci , Kerem Kaya
Charge-transfer (CT) cocrystals of the strong π-acceptor 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) with a series of aromatic electron donor molecules, namely, N-ethylcarbazole (NEC), p-dimethoxybenzene (DMB) and diphenylacetylene (DPA), were prepared for the first time by solvent evaporation method and characterized by single-crystal X-ray diffraction, UV–Vis, NMR spectroscopy and theoretical studies. According to conducted measurements, all complexes crystallize in 1:1 donor–acceptor stoichiometry, with nearly planar π-systems that stack in alternating columns. While NEC-DDQ and DMB-DDQ pairs form strong face-to-face π–π stacks with centroid–centroid distances of 3.28 Å and 3.39 Å, respectively, DPA–DDQ complex shows a slipped geometry with partial overlap (larger shift distance) and weaker π–π interaction with centroid-centroid distance of 3.84 Å. NEC and DMB donors exhibited photoinitiation in the cationic polymerizations of cyclohexene oxide (CHO) and isobutyl vinyl ether (IBVE), under visible, white and near-infrared irradiation, attributed to their high electron-donating ability and favorable co-facial stacking with DDQ. In contrast, DPA-DDQ complex failed to initiate photocationic polymerization due to weak donor strength and poor π–π stacking. No complexes initiated ε-caprolactone (ECL) polymerization, indicating a need for stronger Lewis acid for the initiation. This study provides design principles for engineering solid-state CT photoinitiators via donor choice and crystal packing.
{"title":"Structure–reactivity relationships in DDQ-based charge-transfer complexes: Single-crystal XRD, spectroscopic, DFT studies and photoinitiation efficiency in cationic polymerization","authors":"Huseyin Cem Kiliclar , Berkay Sütay , Palani Natajaran , Onder Metin , Yusuf Yagci , Kerem Kaya","doi":"10.1016/j.reactfunctpolym.2026.106649","DOIUrl":"10.1016/j.reactfunctpolym.2026.106649","url":null,"abstract":"<div><div>Charge-transfer (CT) cocrystals of the strong <em>π</em>-acceptor 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) with a series of aromatic electron donor molecules, namely, <em>N</em>-ethylcarbazole (NEC), <em>p</em>-dimethoxybenzene (DMB) and diphenylacetylene (DPA), were prepared for the first time by solvent evaporation method and characterized by single-crystal X-ray diffraction, UV–Vis, NMR spectroscopy and theoretical studies. According to conducted measurements, all complexes crystallize in 1:1 donor–acceptor stoichiometry, with nearly planar <em>π</em>-systems that stack in alternating columns. While NEC-DDQ and DMB-DDQ pairs form strong face-to-face <em>π–π</em> stacks with centroid–centroid distances of 3.28 Å and 3.39 Å, respectively, DPA–DDQ complex shows a slipped geometry with partial overlap (larger shift distance) and weaker <em>π–π</em> interaction with centroid-centroid distance of 3.84 Å. NEC and DMB donors exhibited photoinitiation in the cationic polymerizations of cyclohexene oxide (CHO) and isobutyl vinyl ether (IBVE), under visible, white and near-infrared irradiation, attributed to their high electron-donating ability and favorable co-facial stacking with DDQ. In contrast, DPA-DDQ complex failed to initiate photocationic polymerization due to weak donor strength and poor <em>π–π</em> stacking. No complexes initiated ε-caprolactone (ECL) polymerization, indicating a need for stronger Lewis acid for the initiation. This study provides design principles for engineering solid-state CT photoinitiators via donor choice and crystal packing.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106649"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038405","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: 2026-01-19DOI: 10.1016/j.reactfunctpolym.2026.106656
Lifang Lin , Wei Cao , Hongbo Liu , Zhaoxi Zhou , Haopeng Wang , Qiming Chen , Xiaowen Pu , Dhandapani Kuzhandaivel , Zixiang Weng , Lixin Wu
The widespread adoption of vat photopolymerization (VPP) 3D printing for creating functional load-bearing components is often constrained by the inherent brittleness of photocurable stereolithography resins (SLRs), which typically exhibit high rigidity but low fracture toughness. To overcome this limitation, we designed and synthesized a novel low-molecular-weight aromatic copolyester, poly(adipic acid-co-phthalic acid)-co-(1,4-butanediol-co-neopentyl glycol) (PABN), which serves as a multifunctional toughening modifier. The PABN architecture was strategically engineered to incorporate rigid aromatic segments for enhanced thermal and mechanical properties, methyl-functionalized side chains to inhibit crystallization and promote chain mobility, and terminal carboxyl groups to form covalent bonds with the epoxy matrix, ensuring robust interfacial adhesion. This polyester was synthesized via melt polycondensation and incorporated into a commercial SLR formulation to create a series of SLR/PABN hybrid systems with varying polyester contents. Remarkably, the hybrid system containing 10 wt% PABN achieved a superior balance of properties, exhibiting simultaneous and significant enhancements in toughness, stiffness, and strength. Specifically, it increased the fracture toughness (KIC), elongation at break, elastic modulus, and hardness by approximately 18.2%, 70.0%, 65.2%, and 80.6%, respectively, compared to the unmodified resin. Furthermore, the hybrid resin maintained a suitable viscosity for processing and exhibited good stability. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) analyses revealed a phase-separated morphology that facilitated effective energy dissipation in the device. This study validates a sophisticated molecular-level design strategy for aromatic polyesters, providing a viable pathway for developing high-performance, toughened, photocurable resins for demanding industrial applications in additive manufacturing.
{"title":"Synthesis of an aromatic polyester for enhanced mechanical properties of stereolithography resins","authors":"Lifang Lin , Wei Cao , Hongbo Liu , Zhaoxi Zhou , Haopeng Wang , Qiming Chen , Xiaowen Pu , Dhandapani Kuzhandaivel , Zixiang Weng , Lixin Wu","doi":"10.1016/j.reactfunctpolym.2026.106656","DOIUrl":"10.1016/j.reactfunctpolym.2026.106656","url":null,"abstract":"<div><div>The widespread adoption of vat photopolymerization (VPP) 3D printing for creating functional load-bearing components is often constrained by the inherent brittleness of photocurable stereolithography resins (SLRs), which typically exhibit high rigidity but low fracture toughness. To overcome this limitation, we designed and synthesized a novel low-molecular-weight aromatic copolyester, poly(adipic acid-<em>co</em>-phthalic acid)-<em>co</em>-(1,4-butanediol-<em>co</em>-neopentyl glycol) (PABN), which serves as a multifunctional toughening modifier. The PABN architecture was strategically engineered to incorporate rigid aromatic segments for enhanced thermal and mechanical properties, methyl-functionalized side chains to inhibit crystallization and promote chain mobility, and terminal carboxyl groups to form covalent bonds with the epoxy matrix, ensuring robust interfacial adhesion. This polyester was synthesized via melt polycondensation and incorporated into a commercial SLR formulation to create a series of SLR/PABN hybrid systems with varying polyester contents. Remarkably, the hybrid system containing 10 wt% PABN achieved a superior balance of properties, exhibiting simultaneous and significant enhancements in toughness, stiffness, and strength. Specifically, it increased the fracture toughness (K<sub>IC</sub>), elongation at break, elastic modulus, and hardness by approximately 18.2%, 70.0%, 65.2%, and 80.6%, respectively, compared to the unmodified resin. Furthermore, the hybrid resin maintained a suitable viscosity for processing and exhibited good stability. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) analyses revealed a phase-separated morphology that facilitated effective energy dissipation in the device. This study validates a sophisticated molecular-level design strategy for aromatic polyesters, providing a viable pathway for developing high-performance, toughened, photocurable resins for demanding industrial applications in additive manufacturing.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106656"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038462","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: 2026-01-15DOI: 10.1016/j.reactfunctpolym.2026.106653
Jingjing An , Rui Wang , Jianfeng Wang , Yanyu Yang , Wanjie Wang , Yanxia Cao
In this study, recycled poly(vinyl butyral) (r-PVB) and maleic anhydride grafted poly(ethylene-octene) (POE-g-MA) were employed to synergistically toughen polypropylene (PP) via one-step reactive melt blending. Results revealed that hydroxyl groups of r-PVB reacted with anhydride groups of POE-g-MA at the interface, generating in situ compatibilizers and significantly improving interfacial adhesion. Although thermodynamic predictions suggested that POE-g-MA should encapsulate r-PVB, the actual morphology was dominated by viscosity-driven kinetics, leading to the formation of a unique core-shell structure with r-PVB as the shell and POE-g-MA as the core. This morphology effectively promoted energy dissipation, enabling the PP/r-PVB/POE-g-MA (70/10/20) blend to achieve a notched impact strength of 78.0 kJ/m2, which is 16.6 times higher than that of neat PP, thus realizing super-toughening. This work not only provides a new pathway for value-added recycling of r-PVB but also reveals a kinetic-dominated mechanism of phase morphology in reactive multicomponent blends.
{"title":"Synergistic toughening of polypropylene using recycled PVB and POE-g-MA via one-step reactive blending","authors":"Jingjing An , Rui Wang , Jianfeng Wang , Yanyu Yang , Wanjie Wang , Yanxia Cao","doi":"10.1016/j.reactfunctpolym.2026.106653","DOIUrl":"10.1016/j.reactfunctpolym.2026.106653","url":null,"abstract":"<div><div>In this study, recycled poly(vinyl butyral) (r-PVB) and maleic anhydride grafted poly(ethylene-octene) (POE-g-MA) were employed to synergistically toughen polypropylene (PP) via one-step reactive melt blending. Results revealed that hydroxyl groups of r-PVB reacted with anhydride groups of POE-g-MA at the interface, generating in situ compatibilizers and significantly improving interfacial adhesion. Although thermodynamic predictions suggested that POE-g-MA should encapsulate r-PVB, the actual morphology was dominated by viscosity-driven kinetics, leading to the formation of a unique core-shell structure with r-PVB as the shell and POE-g-MA as the core. This morphology effectively promoted energy dissipation, enabling the PP/r-PVB/POE-g-MA (70/10/20) blend to achieve a notched impact strength of 78.0 kJ/m<sup>2</sup>, which is 16.6 times higher than that of neat PP, thus realizing super-toughening. This work not only provides a new pathway for value-added recycling of r-PVB but also reveals a kinetic-dominated mechanism of phase morphology in reactive multicomponent blends.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106653"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038460","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: 2026-01-21DOI: 10.1016/j.reactfunctpolym.2026.106658
Junyi Lin , Chuanzhuang Zhao , Li Zhang
Mechanical fragility under liquid-saturated conditions remains a critical limitation of conventional porous oil sorbents, including many polyvinyl formal (PVF) sponges that primarily rely on surface wettability optimization. In this work, a mechanically reinforced and highly hydrophobic PVF sponge is developed through a chemically integrated two-step modification strategy. First, a secondary glutaraldehyde-induced acetal crosslinking process is employed to densify the PVF network and substantially enhance structural rigidity. Subsequently, covalent grafting of dodecyltrimethoxysilane introduces low-surface-energy alkyl chains and hierarchical micro/nanoscale surface roughness, yielding stable hydrophobicity with a water contact angle of 131°, maintained under acidic, alkaline, and saline environments. The resulting sponge exhibits selective adsorption toward a broad range of organic solvents both on and beneath the water surface, with an adsorption capacity of up to 9.1 g g−1. Notably, the material retains a high compressive strength of 3.38 MPa even in the saturated state, effectively preventing structural collapse and secondary leakage during oil recovery. In emulsion separation, the sponge achieves an ultrahigh oil flux of 2.9 × 104 L m−2 h−1 bar−1 for water-in-oil emulsions and maintains over 94% removal efficiency for oil-in-water emulsions across 10 consecutive cycles. By directly addressing the mechanical instability of conventional PVF sorbents through covalent network reinforcement, this study offers a robust design strategy for developing durable functional polymer sponges for oil–water separation applications.
液体饱和条件下的机械脆弱性仍然是传统多孔吸油剂的一个关键限制,包括许多主要依赖于表面润湿性优化的聚乙烯醇(PVF)海绵。在这项工作中,通过化学集成的两步改性策略,开发了一种机械增强和高度疏水性的PVF海绵。首先,采用二次戊二醛诱导缩醛交联工艺使PVF网络致密化,并大大提高结构刚度。随后,十二烷基三甲氧基硅烷的共价接枝引入了低表面能烷基链和分层微/纳米级表面粗糙度,产生了稳定的疏水性,水接触角为131°,在酸性、碱性和盐水环境下都能保持。所得海绵对各种有机溶剂均有选择性吸附,吸附量高达9.1 g g−1。值得注意的是,即使在饱和状态下,该材料也保持了3.38 MPa的高抗压强度,有效地防止了采油过程中的结构坍塌和二次泄漏。在乳状液分离中,海绵对油包水乳状液的油通量达到2.9 × 104 L m−2 h−1 bar−1,在连续10个循环中对油包水乳状液的去除率保持在94%以上。通过共价网络增强直接解决传统PVF吸附剂的机械不稳定性问题,该研究为开发用于油水分离的耐用功能聚合物海绵提供了强大的设计策略。
{"title":"Rigid highly hydrophobic polyvinyl formal sponges via dual glutaraldehyde crosslinking and silane grafting for high-performance oil sorption","authors":"Junyi Lin , Chuanzhuang Zhao , Li Zhang","doi":"10.1016/j.reactfunctpolym.2026.106658","DOIUrl":"10.1016/j.reactfunctpolym.2026.106658","url":null,"abstract":"<div><div>Mechanical fragility under liquid-saturated conditions remains a critical limitation of conventional porous oil sorbents, including many polyvinyl formal (PVF) sponges that primarily rely on surface wettability optimization. In this work, a mechanically reinforced and highly hydrophobic PVF sponge is developed through a chemically integrated two-step modification strategy. First, a secondary glutaraldehyde-induced acetal crosslinking process is employed to densify the PVF network and substantially enhance structural rigidity. Subsequently, covalent grafting of dodecyltrimethoxysilane introduces low-surface-energy alkyl chains and hierarchical micro/nanoscale surface roughness, yielding stable hydrophobicity with a water contact angle of 131°, maintained under acidic, alkaline, and saline environments. The resulting sponge exhibits selective adsorption toward a broad range of organic solvents both on and beneath the water surface, with an adsorption capacity of up to 9.1 g g<sup>−1</sup>. Notably, the material retains a high compressive strength of 3.38 MPa even in the saturated state, effectively preventing structural collapse and secondary leakage during oil recovery. In emulsion separation, the sponge achieves an ultrahigh oil flux of 2.9 × 10<sup>4</sup> L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup> for water-in-oil emulsions and maintains over 94% removal efficiency for oil-in-water emulsions across 10 consecutive cycles. By directly addressing the mechanical instability of conventional PVF sorbents through covalent network reinforcement, this study offers a robust design strategy for developing durable functional polymer sponges for oil–water separation applications.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106658"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079071","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: 2026-01-12DOI: 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":"2026-04-01","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 : 2026-04-01Epub 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":"2026-04-01","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 : 2026-04-01Epub 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":"2026-04-01","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}
Pub Date : 2026-04-01Epub Date: 2026-01-22DOI: 10.1016/j.reactfunctpolym.2026.106663
Haitao Liu , Hengde Li , Saman Hamidi , Xi Chen , Mohsen Adeli , Angelo H. All
Targeted therapy for the central nervous system (CNS) has traditionally relied on intravenous injections or direct intracerebroventricular delivery. Recently, neuronal transport-mediated delivery from the periphery to the CNS, such as intranasal, has emerged as a promising alternative. The rabies virus is capable of efficiently entering the CNS via the neuromuscular junction, intra-axonal retrograde transport and synaptic cleft crossing, thus bypassing the restrictive blood-brain barrier (BBB). RVG29, a peptide derived from the rabies virus glycoprotein, exhibits excellent neurotropic properties. Inspired by this concept, we designed a novel brain-targeted system, PAA-PEG-RVG29, consisting of poly(amido amine)s (PAAs) functionalized with poly(ethylene glycol) (PEG) to reduce cytotoxicity and aggregation, and conjugated with RVG29 to enhance neuronal transport capability. Moreover, Rhodamine B (RhB) was loaded into this system as a model cargo by intermolecular hydrogen bonding, and its efficiency for intra- and inter-neuronal distribution was evaluated. PAA-PEG-RVG29 (RhB) exhibited a hydrodynamic radius of 29.9 nm, a zeta potential of +25 mV, and a RhB loading capacity of 36.4 μg/mg. Cytotoxicity and cellular uptake studies demonstrated promising biocompatibility and efficient internalization in Neuro2a, NSC34, and primary neurons. Furthermore, patch-clamp electrophysiology confirmed that there was no significant alteration effect on primary spinal neuronal action potential generation and propagation. In a two-compartment microfluidic chamber, PAA-PEG-RVG29 (RhB) exhibited effective retrograde axonal transport. A three-compartment chamber further showed progressive trans-synaptic delivery to neighboring neuronal somas. These results highlight the potential of PAA-PEG-RVG29 (RhB) for neuronal transport and synaptic cleft crossing, offering a promising strategy for neuronal delivery, bioimaging, and tracking.
{"title":"RVG29-modified PAA-PEG nanocarriers enable synaptic cleft crossing and neuronal delivery","authors":"Haitao Liu , Hengde Li , Saman Hamidi , Xi Chen , Mohsen Adeli , Angelo H. All","doi":"10.1016/j.reactfunctpolym.2026.106663","DOIUrl":"10.1016/j.reactfunctpolym.2026.106663","url":null,"abstract":"<div><div>Targeted therapy for the central nervous system (CNS) has traditionally relied on intravenous injections or direct intracerebroventricular delivery. Recently, neuronal transport-mediated delivery from the periphery to the CNS, such as intranasal, has emerged as a promising alternative. The rabies virus is capable of efficiently entering the CNS <em>via</em> the neuromuscular junction, intra-axonal retrograde transport and synaptic cleft crossing, thus bypassing the restrictive blood-brain barrier (BBB). RVG29, a peptide derived from the rabies virus glycoprotein, exhibits excellent neurotropic properties. Inspired by this concept, we designed a novel brain-targeted system, PAA-PEG-RVG29, consisting of poly(amido amine)s (PAAs) functionalized with poly(ethylene glycol) (PEG) to reduce cytotoxicity and aggregation, and conjugated with RVG29 to enhance neuronal transport capability. Moreover, Rhodamine B (RhB) was loaded into this system as a model cargo by intermolecular hydrogen bonding, and its efficiency for intra- and inter-neuronal distribution was evaluated. PAA-PEG-RVG29 (RhB) exhibited a hydrodynamic radius of 29.9 nm, a zeta potential of +25 mV, and a RhB loading capacity of 36.4 μg/mg. Cytotoxicity and cellular uptake studies demonstrated promising biocompatibility and efficient internalization in Neuro2a, NSC34, and primary neurons. Furthermore, patch-clamp electrophysiology confirmed that there was no significant alteration effect on primary spinal neuronal action potential generation and propagation. In a two-compartment microfluidic chamber, PAA-PEG-RVG29 (RhB) exhibited effective retrograde axonal transport. A three-compartment chamber further showed progressive trans-synaptic delivery to neighboring neuronal somas. These results highlight the potential of PAA-PEG-RVG29 (RhB) for neuronal transport and synaptic cleft crossing, offering a promising strategy for neuronal delivery, bioimaging, and tracking.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106663"},"PeriodicalIF":5.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079083","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: 2026-01-06DOI: 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":"2026-04-01","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}