Pub Date : 2025-02-11DOI: 10.1016/j.eurpolymj.2025.113814
Jinxing Shi , Xuewei Li , Axiang Li , Haixia Wei , Enyang Zhang , Wangqing Zhang
With the features of easy-operation, fast-bonding and convenient recycling, thermoplastic polyurethane hot-melt adhesives are widely used in daily life and industry. However, thermoplastic polyurethane hot-melt adhesives face the deficiency of poor adhesion strength. Herein, we demonstrate a thermoplastic polyurethane hot-melt adhesive with high adhesion strength on a variety of substrates including metals and plastics under moderate operation conditions. Ascribed to the synergistic effect of the furan moieties in the backbone and the 2-ureido-4-pyrimidinone moieties in the side-chains, the synthesized polyurethane hot-melt adhesive realizes a high adhesion strength of 12.63 MPa. Meanwhile, this adhesive can maintain about 89% original adhesion strength after five recycling use. Besides, such adhesive has favorable tolerance to harsh conditions such as diverse liquids at extremely low temperature of −196 °C. It is expected that this polyurethane hot-melt adhesive has promising application.
{"title":"Polyurethane hot-melt adhesives for strong and tough adhesion","authors":"Jinxing Shi , Xuewei Li , Axiang Li , Haixia Wei , Enyang Zhang , Wangqing Zhang","doi":"10.1016/j.eurpolymj.2025.113814","DOIUrl":"10.1016/j.eurpolymj.2025.113814","url":null,"abstract":"<div><div>With the features of easy-operation, fast-bonding and convenient recycling, thermoplastic polyurethane hot-melt adhesives are widely used in daily life and industry. However, thermoplastic polyurethane hot-melt adhesives face the deficiency of poor adhesion strength. Herein, we demonstrate a thermoplastic polyurethane hot-melt adhesive with high adhesion strength on a variety of substrates including metals and plastics under moderate operation conditions. Ascribed to the synergistic effect of the furan moieties in the backbone and the 2-ureido-4-pyrimidinone moieties in the side-chains, the synthesized polyurethane hot-melt adhesive realizes a high adhesion strength of 12.63 MPa. Meanwhile, this adhesive can maintain about 89% original adhesion strength after five recycling use. Besides, such adhesive has favorable tolerance to harsh conditions such as diverse liquids at extremely low temperature of −196 °C. It is expected that this polyurethane hot-melt adhesive has promising application.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113814"},"PeriodicalIF":5.8,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The present paper describes the synthesis and characterization of aromatic polyketones (PKs) and polyetherketones (PEKs) derived from divanillic acid (DVA) via Friedel–Crafts acylation. Various alkyl side-chains with carbon numbers of 2–8 were introduced into the hydroxyl groups of DVA units. Polyketones (PKs) were synthesized from DVA monomers and 2,2′-dimethoxybiphenyl, and polyetherketones (PEKs and PEKOMes; PEKOMes = polyetherketones with methoxy groups) were synthesized from DVA monomers and diphenylether and 3,3′-oxybis(methoxybenzene), respectively. Unexpectedly, some alkyl side-chains were eliminated during polymerization under Friedel–Crafts conditions in a polar solvent, and elimination was suppressed in a non-polar solvent. Longer alkyl side-chains were eliminated more easily. The molecular weights of the PKs, PEKs, and PEKOMes were 12.5–32.7 × 103, 4.1–6.3 × 103, and 10.6–15.3 × 103 g/mol, respectively. DVA-based PKs and PEKs with relatively high molecular weights compared with those obtained by the previously reported method were obtained via Friedel–Crafts acylation. The aryl comonomers with methoxy moieties produced polymers with higher molecular weights, likely owing to their electron-donating properties. These polymers were all amorphous; their glass transition temperatures were 181–252 °C (PKs), 105–152 °C (PEKs), and 149–218 °C (PEKOMes).
{"title":"Synthesis and characterization of aromatic polyketones and polyetherketones derived from divanillic acid via Friedel–Crafts acylation","authors":"Takaaki Kamishima , Kouji Inagaki , Akira Nukazuka , Tadahisa Iwata , Yukiko Enomoto","doi":"10.1016/j.eurpolymj.2025.113823","DOIUrl":"10.1016/j.eurpolymj.2025.113823","url":null,"abstract":"<div><div>The present paper describes the synthesis and characterization of aromatic polyketones (PKs) and polyetherketones (PEKs) derived from divanillic acid (DVA) <em>via</em> Friedel–Crafts acylation. Various alkyl side-chains with carbon numbers of 2–8 were introduced into the hydroxyl groups of DVA units. Polyketones (PKs) were synthesized from DVA monomers and 2,2′-dimethoxybiphenyl, and polyetherketones (PEKs and PEKOMes; PEKOMes = polyetherketones with methoxy groups) were synthesized from DVA monomers and diphenylether and 3,3′-oxybis(methoxybenzene), respectively. Unexpectedly, some alkyl side-chains were eliminated during polymerization under Friedel–Crafts conditions in a polar solvent, and elimination was suppressed in a non-polar solvent. Longer alkyl side-chains were eliminated more easily. The molecular weights of the PKs, PEKs, and PEKOMes were 12.5–32.7 × 10<sup>3</sup>, 4.1–6.3 × 10<sup>3</sup>, and 10.6–15.3 × 10<sup>3</sup> g/mol, respectively. DVA-based PKs and PEKs with relatively high molecular weights compared with those obtained by the previously reported method were obtained via Friedel–Crafts acylation. The aryl comonomers with methoxy moieties produced polymers with higher molecular weights, likely owing to their electron-donating properties. These polymers were all amorphous; their glass transition temperatures were 181–252 °C (PKs), 105–152 °C (PEKs), and 149–218 °C (PEKOMes).</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113823"},"PeriodicalIF":5.8,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419122","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polymerization is considered one of the valorization techniques of lignin for various applications. Generally, polymerization techniques affect the molecular structure of polymers. In this work, we evaluated a hypothesis that the polymerization strategy and, thus, the molecular weight distribution of lignin-derived polymers would impact their effectiveness as a colloidal disability agent (i.e., flocculant) for a suspension system. To achieve our goal, different lignin-polymethacrylic acid (PMAA) polymers were synthesized via free radical polymerization (FRP) and atom transfer radical polymerization (ATRP) techniques. The experiments were designed such that two sets of polymers with different molecular polydispersities but similar average molecular weights, charge densities, radii of gyration, and hydrodynamic diameters were obtained. Both systems developed colloidal destabilization mainly via bridging phenomenon. The flocculation performance of the ATRP-synthesized samples with narrower molecular weight distribution was notably better than that of FRP-induced samples. The rheological and flocculation analyses under different shear rates confirmed that the ATRP-induced sample promoted the entanglement of particles and had a higher flocculation efficiency. The flocculant prepared using the ATRP technique demonstrated a significantly lower optimal dosage, requiring only 0.4 mg per gram, compared to 25.6 mg per gram for the samples produced using the FRP method. Also, this sample produced stronger flocs with more re-flocculation tendency under different shear rates, while it generated larger flocs under stirring conditions. Such ATRP-derived flocs had an average chord length of approximately 60 μm, and those of FRP-based ones had a 30 μm chord length, while both FRP and ATRP polymers had 500 Da molecular weight. The results of this work confirmed that, while lignin-derived polymers can be an effective flocculant, strategies must be taken into account for generating lignin-derived polymers with a controlled and preferably narrow molecular weight distribution.
{"title":"Correlation of molecular weight diversity and colloidal disability performance of anionic lignin derived polymer","authors":"Farzad Gholami , Weijue Gao , Ehsan Behzadfar , Pedram Fatehi","doi":"10.1016/j.eurpolymj.2025.113820","DOIUrl":"10.1016/j.eurpolymj.2025.113820","url":null,"abstract":"<div><div>Polymerization is considered one of the valorization techniques of lignin for various applications. Generally, polymerization techniques affect the molecular structure of polymers. In this work, we evaluated a hypothesis that the polymerization strategy and, thus, the molecular weight distribution of lignin-derived polymers would impact their effectiveness as a colloidal disability agent (i.e., flocculant) for a suspension system. To achieve our goal, different lignin-polymethacrylic acid (PMAA) polymers were synthesized via free radical polymerization (FRP) and atom transfer radical polymerization (ATRP) techniques. The experiments were designed such that two sets of polymers with different molecular polydispersities but similar average molecular weights, charge densities, radii of gyration, and hydrodynamic diameters were obtained. Both systems developed colloidal destabilization mainly via bridging phenomenon. The flocculation performance of the ATRP-synthesized samples with narrower molecular weight distribution was notably better than that of FRP-induced samples. The rheological and flocculation analyses under different shear rates confirmed that the ATRP-induced sample promoted the entanglement of particles and had a higher flocculation efficiency. The flocculant prepared using the ATRP technique demonstrated a significantly lower optimal dosage, requiring only 0.4 mg per gram, compared to 25.6 mg per gram for the samples produced using the FRP method. Also, this sample produced stronger flocs with more re-flocculation tendency under different shear rates, while it generated larger flocs under stirring conditions. Such ATRP-derived flocs had an average chord length of approximately 60 μm, and those of FRP-based ones had a 30 μm chord length, while both FRP and ATRP polymers had 500 Da molecular weight. The results of this work confirmed that, while lignin-derived polymers can be an effective flocculant, strategies must be taken into account for generating lignin-derived polymers with a controlled and preferably narrow molecular weight distribution.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113820"},"PeriodicalIF":5.8,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-10DOI: 10.1016/j.eurpolymj.2025.113817
Andrey S. Kozlov , Ping Song , Oleg I. Afanasyev , Klim O. Biriukov , Igor A. Nikovskii , Konstantin L. Boldyrev , Maria I. Godovikova , Saihu Liao , Denis Chusov
A superacid (H(OEt2)2)[Al(OtfBu)4] has been demonstrated as a highly active catalyst for the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL), which shows the highest catalytic activity among the known Brønsted acid catalysts in this process. With this superacid catalyst, the polymerization can be conducted in solvent and bulk conditions, either at elevated or at room temperature, and synthesis of high molecular weight polymers (> 100 kg/mol) is also successfully achieved.
{"title":"Krossing’s acid as efficient catalyst for ε-caprolactone polymerization","authors":"Andrey S. Kozlov , Ping Song , Oleg I. Afanasyev , Klim O. Biriukov , Igor A. Nikovskii , Konstantin L. Boldyrev , Maria I. Godovikova , Saihu Liao , Denis Chusov","doi":"10.1016/j.eurpolymj.2025.113817","DOIUrl":"10.1016/j.eurpolymj.2025.113817","url":null,"abstract":"<div><div>A superacid (H(OEt<sub>2</sub>)<sub>2</sub>)[Al(O<sup>t</sup><sub>f</sub>Bu)<sub>4</sub>] has been demonstrated as a highly active catalyst for the ring-opening polymerization (ROP) of <em>ε-</em>caprolactone (<em>ε-</em>CL), which shows the highest catalytic activity among the known Brønsted acid catalysts in this process. With this superacid catalyst, the polymerization can be conducted in solvent and bulk conditions, either at elevated or at room temperature, and synthesis of high molecular weight polymers (> 100 kg/mol) is also successfully achieved.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113817"},"PeriodicalIF":5.8,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-10DOI: 10.1016/j.eurpolymj.2025.113822
Luis Alfonso Valdez-Olea , María Alejandra González-Urías , Angel Licea-Claveríe , Mirian A. González-Ayón , Alejandro Ramírez-Jiménez
In this work, multicomponent responsive core–shell nanogels, based on crosslinked 2-(N,N-diethylamino) ethyl methacrylate (DEAEMA), homo- or copolymerized with N-vinylcaprolactam (NVCL), as the core, and poly(ethylene glycol) methyl ether methacrylate (PEGMA, Mn=950 g mol-1) as the shell, were synthesized by the Surfactant-Free Emulsion Polymerization (SFEP). Thermo- and pH responsive behavior was revealed by Dynamic Light Scattering (DLS) measurements showing nanogel expansion by decreasing pH and nanogel contraction by increasing temperature taking as reference normal physiological conditions. Nanogels composition was calculated by 1H NMR, Dh was measured by DLS, thermal transitions were determined by Differential Scanning Calorimetry (DSC). The systems with the best properties were selected for the loading and releasing of diorganotin(IV) complexes which have demonstrated cytotoxic activity against different cancer cells lines. Results showed that the systems have the potential to be used as nanocarriers of metallodrugs towards cancer tissues.
{"title":"Thermo- and pH responsive core–shell nanogels: Easy method of synthesis, properties and its use for the loading and releasing of organotin(IV) compounds","authors":"Luis Alfonso Valdez-Olea , María Alejandra González-Urías , Angel Licea-Claveríe , Mirian A. González-Ayón , Alejandro Ramírez-Jiménez","doi":"10.1016/j.eurpolymj.2025.113822","DOIUrl":"10.1016/j.eurpolymj.2025.113822","url":null,"abstract":"<div><div>In this work, multicomponent responsive core–shell nanogels, based on crosslinked 2-(<em>N,N-</em>diethylamino) ethyl methacrylate (DEAEMA), homo- or copolymerized with <em>N</em>-vinylcaprolactam (NVCL), as the core, and poly(ethylene glycol) methyl ether methacrylate (PEGMA, <em>Mn</em>=950 g mol<sup>-1</sup>) as the shell, were synthesized by the Surfactant-Free Emulsion Polymerization (SFEP). Thermo- and pH responsive behavior was revealed by Dynamic Light Scattering (DLS) measurements showing nanogel expansion by decreasing pH and nanogel contraction by increasing temperature taking as reference normal physiological conditions. Nanogels composition was calculated by <sup>1</sup>H NMR, <em>D<sub>h</sub></em> was measured by DLS, thermal transitions were determined by Differential Scanning Calorimetry (DSC). The systems with the best properties were selected for the loading and releasing of diorganotin(IV) complexes which have demonstrated cytotoxic activity against different cancer cells lines. Results showed that the systems have the potential to be used as nanocarriers of metallodrugs towards cancer tissues.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113822"},"PeriodicalIF":5.8,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143395335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-10DOI: 10.1016/j.eurpolymj.2025.113821
Ramisa Yahyapour , Yusuf Ziya Menceloglu
The rising demand for sustainable alternatives to conventional plastics highlights polyhydroxyalkanoates (PHAs), particularly polyhydroxybutyrate (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), as promising biodegradable thermoplastics. While PHAs offer advantages like non-toxicity and a reduced carbon footprint, their brittleness, narrow processing window, and high production costs limit their broader use, particularly in packaging, the largest source of municipal solid waste. This review provides an overview of PHAs, emphasizing the properties that make them suitable for packaging and the key factors influencing their market longevity. Blending PHAs with natural polymers, such as polylactic acid, cellulose derivatives, and chitin/chitosan improves mechanical, thermal, and barrier properties while enhancing biodegradability by reducing crystallinity or increasing hydrophilicity, thereby facilitating microbial degradation. Additives such as plasticizers, nucleating agents, and compatibilizers, alongside optimized processing conditions and advanced techniques, like reactive blending and the use of block and graft copolymers, improve interfacial adhesion and blend homogeneity, mitigating brittleness and enhancing flexibility and strength. The thermal instability of PHB, which poses challenges during melt processing, can be addressed by incorporating bioplasticizers to lower its glass transition temperature and melt viscosity, allowing processing at lower temperatures and minimizing thermal degradation. Furthermore, in-situ polymerization and bio-based coupling agents further enhance blend uniformity and overall performance. Special attention is given to the potential of PHB/chitosan blends for developing antibacterial, eco-friendly packaging solutions. By reviewing market trends and advances in PHA processing, this review underscores the potential of PHA-based blends to reduce plastic waste and facilitate their commercialization as sustainable, green packaging materials.
{"title":"Blending strategies for green packaging: Enhancing polyhydroxybutyrate performance for sustainable solutions","authors":"Ramisa Yahyapour , Yusuf Ziya Menceloglu","doi":"10.1016/j.eurpolymj.2025.113821","DOIUrl":"10.1016/j.eurpolymj.2025.113821","url":null,"abstract":"<div><div>The rising demand for sustainable alternatives to conventional plastics highlights polyhydroxyalkanoates (PHAs), particularly polyhydroxybutyrate (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), as promising biodegradable thermoplastics. While PHAs offer advantages like non-toxicity and a reduced carbon footprint, their brittleness, narrow processing window, and high production costs limit their broader use, particularly in packaging, the largest source of municipal solid waste. This review provides an overview of PHAs, emphasizing the properties that make them suitable for packaging and the key factors influencing their market longevity. Blending PHAs with natural polymers, such as polylactic acid, cellulose derivatives, and chitin/chitosan improves mechanical, thermal, and barrier properties while enhancing biodegradability by reducing crystallinity or increasing hydrophilicity, thereby facilitating microbial degradation. Additives such as plasticizers, nucleating agents, and compatibilizers, alongside optimized processing conditions and advanced techniques, like reactive blending and the use of block and graft copolymers, improve interfacial adhesion and blend homogeneity, mitigating brittleness and enhancing flexibility and strength. The thermal instability of PHB, which poses challenges during melt processing, can be addressed by incorporating bioplasticizers to lower its glass transition temperature and melt viscosity, allowing processing at lower temperatures and minimizing thermal degradation. Furthermore, in-situ polymerization and bio-based coupling agents further enhance blend uniformity and overall performance. Special attention is given to the potential of PHB/chitosan blends for developing antibacterial, eco-friendly packaging solutions. By reviewing market trends and advances in PHA processing, this review underscores the potential of PHA-based blends to reduce plastic waste and facilitate their commercialization as sustainable, green packaging materials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113821"},"PeriodicalIF":5.8,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143395898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-09DOI: 10.1016/j.eurpolymj.2025.113816
Lezhi Wang, Theoni K. Georgiou
This study investigated the thermoresponsive properties of a novel series of ABC triblock terpolymers synthesized from ethylene glycol (EG)-based comonomers with varying lengths of PEG pendant chains. The terpolymers, with a targeted molar mass of 8100 g/mol, were synthesized using sequential Group Transfer Polymerization (GTP) and featured a range of compositions. Specifically, the hydrophobic content of methoxy ethylene glycol methacrylate (MEGMA, block B) was varied between 25 % and 55 % w/w, with corresponding adjustments to the thermoresponsive oligo(ethylene glycol) methyl ether methacrylate (OEGMA with an average molar mass of 300 g/mol, block A) and di(ethylene glycol) methyl ether methacrylate (DEGMA, block C), resulting in 16 distinct compositions. The cloud point temperatures were determined via turbidimetry, while dynamic light scattering (DLS) was employed to assess micellar self-assembly behavior. Of the 16 terpolymers, three demonstrated the ability to form thermogels. Blending these terpolymers with a high-performing diblock copolymer enabled tunable sol-to-gel transitions and identified a specific concentration that facilitated thermogel formation at physiological temperatures. Notably, the M1 polymer solution—a mixture of a triblock terpolymer and its diblock counterpart, both with 50 % w/w MEGMA content—exhibited superior sustained release of the sodium fluorescein model drug, outperforming the industry-standard Pluronic F127. This study underscores the importance of balancing hydrophilicity and hydrophobicity for effective sol–gel transitions in these novel triblock terpolymers and presents a straightforward yet effective strategy for diversifying polymer mixtures to fine-tune the gelation range and enhance versatility.
{"title":"Thermogelling Formulations based on In-House synthesized ethylene Glycol-Containing ABC triblock copolymers and their mixtures with diblocks","authors":"Lezhi Wang, Theoni K. Georgiou","doi":"10.1016/j.eurpolymj.2025.113816","DOIUrl":"10.1016/j.eurpolymj.2025.113816","url":null,"abstract":"<div><div>This study investigated the thermoresponsive properties of a novel series of ABC triblock terpolymers synthesized from ethylene glycol (EG)-based comonomers with varying lengths of PEG pendant chains. The terpolymers, with a targeted molar mass of 8100 g/mol, were synthesized using sequential Group Transfer Polymerization (GTP) and featured a range of compositions. Specifically, the hydrophobic content of methoxy ethylene glycol methacrylate (MEGMA, block B) was varied between 25 % and 55 % w/w, with corresponding adjustments to the thermoresponsive oligo(ethylene glycol) methyl ether methacrylate (OEGMA with an average molar mass of 300 g/mol, block A) and di(ethylene glycol) methyl ether methacrylate (DEGMA, block C), resulting in 16 distinct compositions. The cloud point temperatures were determined via turbidimetry, while dynamic light scattering (DLS) was employed to assess micellar self-assembly behavior. Of the 16 terpolymers, three demonstrated the ability to form thermogels. Blending these terpolymers with a high-performing diblock copolymer enabled tunable sol-to-gel transitions and identified a specific concentration that facilitated thermogel formation at physiological temperatures. Notably, the M1 polymer solution—a mixture of a triblock terpolymer and its diblock counterpart, both with 50 % w/w MEGMA content—exhibited superior sustained release of the sodium fluorescein model drug, outperforming the industry-standard Pluronic F127. This study underscores the importance of balancing hydrophilicity and hydrophobicity for effective sol–gel transitions in these novel triblock terpolymers and presents a straightforward yet effective strategy for diversifying polymer mixtures to fine-tune the gelation range and enhance versatility.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113816"},"PeriodicalIF":5.8,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-09DOI: 10.1016/j.eurpolymj.2025.113818
Aqila Che Ab Rahman , Siyoung Yang , Sooman Lim
The advancement of microneedle technology offers a promising alternative to conventional drug delivery methods by enhancing drug loading efficiency, controlled release, and patient comfort. In this study, we developed a high-resolution microneedle array fabricated via vat photopolymerization using a biocompatible UV-curable polymer. Engineered indentations were introduced to increase the surface area, enhancing drug loading capacity and improving drug uptake. Additionally, the microneedles were mounted on a mechanically adaptive substrate designed to accommodate dynamic movements and conform to curved or flexible surfaces. Mechanical characterization demonstrated that the microneedle patch withstood up to 46.8 ± 2 % strain without failure while maintaining penetration efficiency in rat skin. Drug release analysis showed an initial burst phase within the first 60 h, followed by a sustained release profile. The optimized microneedle design with a 0.25 mm indentation achieved a drug loading efficiency of 27.5 ± 0.6 % and a cumulative release of 37.6 ± 0.7 % after 25 h. These findings highlight the potential of biomimetic structural modifications and vat photopolymerization in advancing microneedle-based transdermal drug delivery, offering a minimally invasive, efficient, and patient-friendly alternative to conventional drug administration.
{"title":"Biocompatible microneedles with engineered indentation design fabricated via vat photopolymerization for enhanced transdermal drug delivery","authors":"Aqila Che Ab Rahman , Siyoung Yang , Sooman Lim","doi":"10.1016/j.eurpolymj.2025.113818","DOIUrl":"10.1016/j.eurpolymj.2025.113818","url":null,"abstract":"<div><div>The advancement of microneedle technology offers a promising alternative to conventional drug delivery methods by enhancing drug loading efficiency, controlled release, and patient comfort. In this study, we developed a high-resolution microneedle array fabricated via vat photopolymerization using a biocompatible UV-curable polymer. Engineered indentations were introduced to increase the surface area, enhancing drug loading capacity and improving drug uptake. Additionally, the microneedles were mounted on a mechanically adaptive substrate designed to accommodate dynamic movements and conform to curved or flexible surfaces. Mechanical characterization demonstrated that the microneedle patch withstood up to 46.8 ± 2 % strain without failure while maintaining penetration efficiency in rat skin. Drug release analysis showed an initial burst phase within the first 60 h, followed by a sustained release profile. The optimized microneedle design with a 0.25 mm indentation achieved a drug loading efficiency of 27.5 ± 0.6 % and a cumulative release of 37.6 ± 0.7 % after 25 h. These findings highlight the potential of biomimetic structural modifications and vat photopolymerization in advancing microneedle-based transdermal drug delivery, offering a minimally invasive, efficient, and patient-friendly alternative to conventional drug administration.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113818"},"PeriodicalIF":5.8,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419144","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Unsaturated polyesters (UPs) are a family of thermoset polymers largely used for glass fiber reinforced composite (GFRC) manufacturing, but their recycling is very challenging due to their crosslinked structure. Here, novel recyclable-by-design model unsaturated polymer resins were redesigned, positioning the C=C acrylic unsaturations as end groups and replacing styrene with alternative reactive diluents bearing –OH groups. The crosslinked polymers showed thermomechanical properties in line with conventional UPs, and the corresponding GFRCs containing 30 %vol of GFs were successfully prepared. Both the crosslinked unsaturated polymers and their composites were effectively solvolyzed in mild conditions (T = 200 °C, atmospheric pressure, t = 1–3 h) using different alcohols and glycols as solvent media, and 1,5,7-trazabicyclo[4.4.0]dec-5-ene as transesterification catalyst. Liberated GFs were found to be clean (as assessed by thermogravimetric analysis) and retained nearly 100 % of their original modulus and strength. The recovered organic recyclate showed a high –OH functional group reactivity and could be reused as hydroxylated binder in the formulation of bicomponent polyurethane coatings. These materials were found to exhibit excellent optical clarity, high Tg (> 100 °C), good substrate adhesion (3.45 MPa on glass), and moderate hydrophilicity (water contact angle of 65°). Finally, the same unsaturated polymer resins were prepared with the addition of the transesterification catalyst directly in the liquid prepolymer formulation. While the base physical properties of the crosslinked material remained unchanged, the resulting network showed a dynamic behavior, with thermally-induced stress-relaxation response clearly dependent on both hydroxyl group content and catalyst concentration, and easy post-cure thermoformability.
{"title":"Revisiting Unsaturated Polyesters: Recyclable-by-Design Vinylester Resins for the Circular Economy","authors":"Giulia Altamura, Eleonora Manarin, Gianmarco Griffini, Stefano Turri","doi":"10.1016/j.eurpolymj.2025.113819","DOIUrl":"10.1016/j.eurpolymj.2025.113819","url":null,"abstract":"<div><div>Unsaturated polyesters (UPs) are a family of thermoset polymers largely used for glass fiber reinforced composite (GFRC) manufacturing, but their recycling is very challenging due to their crosslinked structure. Here, novel recyclable-by-design model unsaturated polymer resins were redesigned, positioning the C=C acrylic unsaturations as end groups and replacing styrene with alternative reactive diluents bearing –OH groups. The crosslinked polymers showed thermomechanical properties in line with conventional UPs, and the corresponding GFRCs containing 30 %vol of GFs were successfully prepared. Both the crosslinked unsaturated polymers and their composites were effectively solvolyzed in mild conditions (T = 200 °C, atmospheric pressure, t = 1–3 h) using different alcohols and glycols as solvent media, and 1,5,7-trazabicyclo[4.4.0]dec-5-ene as transesterification catalyst. Liberated GFs were found to be clean (as assessed by thermogravimetric analysis) and retained nearly 100 % of their original modulus and strength. The recovered organic recyclate showed a high –OH functional group reactivity and could be reused as hydroxylated binder in the formulation of bicomponent polyurethane coatings. These materials were found to exhibit excellent optical clarity, high T<sub>g</sub> (> 100 °C), good substrate adhesion (3.45 MPa on glass), and moderate hydrophilicity (water contact angle of 65°). Finally, the same unsaturated polymer resins were prepared with the addition of the transesterification catalyst directly in the liquid prepolymer formulation. While the base physical properties of the crosslinked material remained unchanged, the resulting network showed a dynamic behavior, with thermally-induced stress-relaxation response clearly dependent on both hydroxyl group content and catalyst concentration, and easy post-cure thermoformability.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113819"},"PeriodicalIF":5.8,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143387749","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-07DOI: 10.1016/j.eurpolymj.2025.113797
Jingwen Lan , Zihan Wei , Rukuan Liu , Airong Xu
Although hydrogel sensors have broad application prospects in wearable devices, biomedical electronic skin, human–computer interaction and other fields, the hydrogel sensor with the synergy of robust mechanical behaviors, super freeze-resistant ability and signal output stability still remain challenged. To overcome the challenge, here, a novel hydrogel sensor AICG were developed using polyvinyl alcohol (PVA), glycidyl trimethyl ammonium chloride (EPTAC), polyethyleneimine (PEI) and ethylene glycol (EG). The effects of PVA, PEI, EPTAC and EG contents in AICG hydrogel on mechanical properties were systematically investigated. The notably boosted mechanical properties (antibreakage performance, fatigue-resistant ability) and super freeze-resistant performance are primarily ascribed to the superhydrogen-bond networks of PVA with PEI, EPTAC and EG. The hydrogel is so strong that it can load a 60 Kg boy and endure super low temperature (−120 ℃). Besides rendering AICG hydrogel good conductivity (5.56 mS·cm−1), EPTAC was used to graft it on the PVA/PEI macromolecular chains of AICG hydrogel via ring-opening reaction of EPTAC, thus impeding the leakage of EPTAC from the hydrogel as much as possible and improving conductive stability. On being used a sensor, it can accurately detect human joint movements and simulate electronic skin due to high sensitivity and stable signal output ability. It is expected that this study can provide valuable information for the design and fabrication of the hydrogel sensor with desired high performances.
{"title":"Ultra-anti-freezing robust hydrogel snesor","authors":"Jingwen Lan , Zihan Wei , Rukuan Liu , Airong Xu","doi":"10.1016/j.eurpolymj.2025.113797","DOIUrl":"10.1016/j.eurpolymj.2025.113797","url":null,"abstract":"<div><div>Although hydrogel sensors have broad application prospects in wearable devices, biomedical electronic skin, human–computer interaction and other fields, the hydrogel sensor with the synergy of robust mechanical behaviors, super freeze-resistant ability and signal output stability still remain challenged. To overcome the challenge, here, a novel hydrogel sensor AICG were developed using polyvinyl alcohol (PVA), glycidyl trimethyl ammonium chloride (EPTAC), polyethyleneimine (PEI) and ethylene glycol (EG). The effects of PVA, PEI, EPTAC and EG contents in AICG hydrogel on mechanical properties were systematically investigated. The notably boosted mechanical properties (antibreakage performance, fatigue-resistant ability) and super freeze-resistant performance are primarily ascribed to the superhydrogen-bond networks of PVA with PEI, EPTAC and EG. The hydrogel is so strong that it can load a 60 Kg boy and endure super low temperature (−120 ℃). Besides rendering AICG hydrogel good conductivity (5.56 mS·cm<sup>−1</sup>), EPTAC was used to graft it on the PVA/PEI macromolecular chains of AICG hydrogel via ring-opening reaction of EPTAC, thus impeding the leakage of EPTAC from the hydrogel as much as possible and improving conductive stability. On being used a sensor, it can accurately detect human joint movements and simulate electronic skin due to high sensitivity and stable signal output ability. It is expected that this study can provide valuable information for the design and fabrication of the hydrogel sensor with desired high performances.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113797"},"PeriodicalIF":5.8,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143395336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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