European Polymer Journal最新文献

{"title":"Overcoming synthetic challenges in developing High-Performance polybenzoxazine from Diamine-Functionalized Double-Decker silsesquioxane (DDSQ) cage","authors":"Hui-Wen Chen,&nbsp;Mohamed Gamal Mohamed,&nbsp;Yang-Chin Kao,&nbsp;Wei-Cheng Chen,&nbsp;Kevin Chiou,&nbsp;Shiao-Wei Kuo","doi":"10.1016/j.eurpolymj.2025.113929","DOIUrl":"10.1016/j.eurpolymj.2025.113929","url":null,"abstract":"<div><div>A new diamine-functionalized double-decker silsesquioxane (DDSQ-NH₂) derivative was first synthesized from the phenyltrimethoxysilane as the starting material by following sol–gel reaction in NaOH to form DDNa, corner capping with methylvinyldichlorosilane to form the DDSQ-CH=CH₂ derivative and finally reacted with 4-bromoaniline by using Heck reaction to obtain the target compound. Various synthetic approaches, including one-pot Mannich condensation and three-step synthesis based on this new diamine-functionalized DDSQ (DDSQ-NH₂) compound, were explored but proved unsuccessful due to low selectivity and DDSQ structural degradation. The novel DDSQ-based benzoxazine monomer (DDSQ-BZ (III) in this study) was successfully synthesized through a Schiff-base reaction between DDSQ-NH₂ and 3-phenyl-3,4-dihydro-2H-benzo[e][<span><span>1</span></span>,<span><span>3</span></span>]oxazine-6-carbaldehyde (CHO-BZ) monomer, maintaining the fully closed-cage DDSQ structure, which is thoroughly characterized using FTIR, NMR, DSC, and TGA analyses, confirming the retention of the DDSQ cage and the formation of the benzoxazine ring. Thermal polymerization behavior was analyzed, revealing record-high stability (<em>T</em>_d10 = 644 °C, char yield = 82.8 wt%). TEM, SEM, and EDX analyses demonstrated homogeneous dispersion of the DDSQ cage structure within the polybenzoxazine matrix, ensuring enhanced thermal stability.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"232 ","pages":"Article 113929"},"PeriodicalIF":5.8,"publicationDate":"2025-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143807390","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}

{"title":"Effect of pendant group functionality on the biological activity of quaternized Poly(4-vinylpyridine) copolymers","authors":"Eda Nur Yetiskin Morkan ,&nbsp;Ilknur Yilmaz ,&nbsp;Busra Akgul ,&nbsp;Emrah Sefik Abamor ,&nbsp;Tulin Ozbek ,&nbsp;Murat Topuzogullari","doi":"10.1016/j.eurpolymj.2025.113930","DOIUrl":"10.1016/j.eurpolymj.2025.113930","url":null,"abstract":"<div><div>Cationic polymers are remarkable materials effectively used in a wide range of biomedical applications such as drug delivery, tissue engineering and gene delivery. It is well established that the functional groups within polymer structures exert a profound influence on their biological activities. Elucidating the specific effects of these functional groups on the biological properties of polymers is paramount, as it will facilitate the development and application of novel polymeric materials across a diverse range of biomedical fields. Here, the antibacterial activity, cytotoxicity and gene transfection efficiency of the cationic copolymer of quaternized 4-vinylpyridine (Q4VP) and oligo(ethylene glycol) methyl ether methacrylate (OEGMA₅₀₀) which has distinct functionalities (hydrophobic, hydrophilic, zwitterionic) as pendant groups were investigated in vitro. The functional groups of alkyl, alkenyl, quaternary ammonium, hydroxyl, carboxylic acid, phenyl and ester were included into the structure of the copolymer as the pendant groups by quaternization. The degrees of quaternization ranged from 35-43 %, and zeta potentials of the copolymers were measured between +19.2 and +28.2 mV. In antibacterial activity test evaluated by broth microdilution method, MIC values were found to be between 4–16 μg/mL against <em>Escherichia coli</em> (<em>E. coli</em>) and 2–32 μg/mL against <em>Staphylococcus aureus</em> (<em>S. aureus</em>). In vitro cytotoxicity test on the L929 cell line, using the MTT method, revealed inhibition concentration values (IC₅₀) ranging from 192.3 to 972.6 μg/mL for the quaternized copolymers. Moreover, the transfection efficiency of polyelectrolyte complexes formed by the quaternized copolymer with plasmid DNA encoding green fluorescent protein (GFP) were systematically examined in HEK293T cells. The study revealed that, contingent upon the functionality of the pendant groups, a peak transfection efficiency exceeding 90 % was attained. The results clearly demonstrate the direct impact of the pendant group functionality on the biological activity of the cationic copolymer.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"232 ","pages":"Article 113930"},"PeriodicalIF":5.8,"publicationDate":"2025-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143817340","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}

{"title":"Influence of pendant pyridyl regioisomers on the pH-responsive behaviour of polymer-homopeptide copolymers and micelles","authors":"Cintya Dharmayanti ,&nbsp;Andrew J. Clulow ,&nbsp;Md.Saddam Hussain ,&nbsp;Todd A. Gillam ,&nbsp;Manuela Klingler-Hoffmann ,&nbsp;Hugo Albrecht ,&nbsp;Anton Blencowe","doi":"10.1016/j.eurpolymj.2025.113931","DOIUrl":"10.1016/j.eurpolymj.2025.113931","url":null,"abstract":"<div><div>Polymeric micelles that can respond to changes in pH have emerged as appealing systems to achieve localised drug release. These micelles can be prepared from homopeptide block copolymers, which are attractive alternatives to traditional synthetic polymers due to their unique ability to form secondary structures. However, naturally occurring amino acids have a limited variety of side chain functional groups, requiring additional modifications to tune pH-responsivity. In addition, further work is required to better understand how these structural changes to the peptide side chains can influence their pH-responsive behaviour and self-assembly. Herein, we investigate the pH responsive behaviour of a series of poly[(ethylene glycol)-<em>b</em>-(pyridinylmethyl glutamate)] (PEG-<em>b</em>-P#PG) copolymers modified with different pyridine regioisomers (<em>para</em> (# = 4)<em>, meta</em> (# = 3)<em>,</em> or <em>ortho</em> (# = 2) relative to the polymer chain). Potentiometric and nuclear magnetic resonance (NMR) spectroscopic titrations, coupled with zeta (ζ)-potential measurements, provided information on the ionisation behaviour of the copolymers and their acid dissociation constant (pK_a) values. At neutral pH, the copolymers assembled into micelles with unique structures and exhibited characteristic pK_a values resulting from the different pyridine regioisomers, which influenced the pH-responsive behaviour of the micelles. Changes in the morphology and secondary structure of the micelles as a function of pH were interrogated using dynamic light scattering (DLS), synchrotron small-angle X-ray scattering (SAXS) and circular dichroism (CD) spectroscopy. Disassembly of the PEG-<em>b</em>-P#PG micelles was observed when the solution pH was below the pK_a, indicating that a high degree of ionisation (&gt; 85 %) is necessary to disrupt the secondary structures of the peptide blocks. These results provide important insights into the design of pH-responsive polymer-homopeptide block copolymers and the influence of side chain regioisomers on their ionisation and assembly behaviour.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"234 ","pages":"Article 113931"},"PeriodicalIF":5.8,"publicationDate":"2025-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144190313","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}

{"title":"Copolymerization of styrene oxide with CO2 via modular optimization of bifunctional organoborane catalysts","authors":"Shuo Zhao,&nbsp;Cheng-Kai Xu,&nbsp;Yue Gong,&nbsp;Guan-Wen Yang,&nbsp;Guang-Peng Wu","doi":"10.1016/j.eurpolymj.2025.113912","DOIUrl":"10.1016/j.eurpolymj.2025.113912","url":null,"abstract":"<div><div>The ring-opening copolymerization (ROCOP) of CO₂ and epoxides presents significant challenges, primarily due to the tendency to form cyclic carbonates, especially when the epoxide contains electron-withdrawing groups, such as styrene oxide (SO). Building upon our previous research on organoborane and cationic components, we designed a series of novel tetranuclear, trinuclear, and dinuclear bifunctional organoborane catalysts. These catalysts facilitated SO/CO₂ copolymerization with remarkable polymer selectivity exceeding 99 % under mild conditions. ³¹P NMR spectroscopy revealed that the discrepancies in catalytic performance between trinuclear and dinuclear organoborane catalysts stem from variations in their overall Lewis acidity. These insights into the optimization of organoborane catalysts are expected to drive the development of more advanced catalysts in the future.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"232 ","pages":"Article 113912"},"PeriodicalIF":5.8,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143807389","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}

{"title":"The future of polymer brushes","authors":"Alessio Lo Bocchiaro,&nbsp;Elena Avanzini,&nbsp;Francesca Lorandi,&nbsp;Edmondo M. Benetti","doi":"10.1016/j.eurpolymj.2025.113927","DOIUrl":"10.1016/j.eurpolymj.2025.113927","url":null,"abstract":"<div><div>More than 35 years after the seminal inception of the concept of assemblies of surface-tethered polymer chains, or “polymer brushes”, a new subfield of polymer science has been progressively emerging, encompassing various interdisciplinary aspects of polymer chemistry, surface science, and materials science. The application of polymer brushes is now widespread across a broad range of formulations, and advancements in controlled chain-growth polymerizations have been accompanied by simultaneous refinements in corresponding surface-initiated processes. Thanks to these progresses, generating a brush on a solid substrate is now accessible enough to serve as an undergraduate-level lab exercise. However, while polymer brushes are finding fascinating new applications in biotechnology, energy materials, and catalysis, their translation into technology remains an ongoing challenge. In this short perspective article, we summarize the latest developments in the synthesis and application of polymer brushes, particularly highlighting the potential future directions of this exciting field of research.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"232 ","pages":"Article 113927"},"PeriodicalIF":5.8,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143821132","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}

{"title":"Development of new bio-based shape memory hybrid polybenzoxazines through green strategy","authors":"Arunkumar Krishnan ,&nbsp;Hariharan Arumugam ,&nbsp;Panuwat Luengrojanakul ,&nbsp;Nuttinan Boonnao ,&nbsp;Alagar Muthukaruppan ,&nbsp;Cheol-Hee Ahn ,&nbsp;Sarawut Rimdusit","doi":"10.1016/j.eurpolymj.2025.113926","DOIUrl":"10.1016/j.eurpolymj.2025.113926","url":null,"abstract":"<div><div>In the present work, hybridized bio-based benzoxazines were developed with a green strategy for shape memory applications. Herein, two bio-based materials of cardanol and guaiacol were utilized to synthesize bio-based benzoxazine monomers of cardanol-Jeffamine D230 (CJ) and bis-guaiacol-furfurylamine (BGF) by using a solvent-free method. Different weight percentage ratios (wt %) of BGF and CJ benzoxazines were hybridized (BGF-CJ – 100–0, 80–20, 60–40, 40–60 and 0–100) and studied their thermal stimulus responsive properties. The structure of synthesized benzoxazine was analyzed using ¹H nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infra-red (FTIR) spectroscopy. The thermal properties of polybenzoxazines were analyzed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Among the co-polymers, P(BGF20-CJ80) shows the lower value of glass transition temperature with the highest degradation temperature. Similarly, the co-polymer of P(BGF60-CJ40) possess excellent shape memory properties and for consecutive analysis, the shape fixity ratio is 95 − 96 % for BGF60-CJ40, and its shape recovery ratio is 98–100 %. The principle behind this excellent performance results were related to the synergistic effects of rigid cross-linked oxazine rings and long aliphatic chain present in cardanol-Jeffamine D230 benzoxazine. The present research work is mainly focused on the utilization of bio-based raw materials, and the replacement of fossil-based bisphenol-A, with an objective of alleviation of environmental problems.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"231 ","pages":"Article 113926"},"PeriodicalIF":5.8,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143792693","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}

{"title":"Synergistic effects of methoxy and Benzhydryl substituents in α-Diimine nickel catalysts for Homo- and copolymerization of 1-Hexene and norbornene","authors":"Chantsalnyam Bariashir ,&nbsp;Yujin Seong ,&nbsp;Seul Lee ,&nbsp;BongSoo Kim ,&nbsp;Sungwoo Cho ,&nbsp;Qiuyue Zhang ,&nbsp;Chiyoung Park","doi":"10.1016/j.eurpolymj.2025.113908","DOIUrl":"10.1016/j.eurpolymj.2025.113908","url":null,"abstract":"<div><div>A series of unsymmetrical α-diimine nickel(II) catalysts bearing <em>ortho</em>-bulky dibenzhydryl and electron-donating <em>N</em>-aryl substituents were synthesized, fully characterized, and applied in the homo- and copolymerization of 1-hexene and norbornene. These catalysts exhibited high catalytic activity and remarkable polymerization efficiency upon activation with MAO and B(C₆F₅)₃. In the homopolymerization of 1-hexene, the catalysts demonstrated turnover frequencies up to 78 h⁻¹, yielding highly branched, high-molecular-weight poly(1-hexene) (M_n: 182 kg mol⁻¹). For norbornene polymerization, the highest catalytic activity of 2.61 × 10⁴ g mol⁻¹h⁻¹ and molecular weight of 274 kg mol⁻¹ were achieved. The copolymerization of norbornene and 1-hexene yielded copolymers with tunable 1-hexene incorporation (27.8–33.4 mol%) and high molecular weights (up to 106 kg mol⁻¹), displaying excellent thermal stability (&gt;400 °C). These findings highlight the synergistic effects of steric bulk and electronic modifications in enhancing catalytic performance and polymer properties.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"231 ","pages":"Article 113908"},"PeriodicalIF":5.8,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783847","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}

{"title":"Synthesis and properties of high heat-resistant transparent polyimides containing terphenyl skeleton","authors":"Jinglei Xing ,&nbsp;Lei Yang ,&nbsp;Tianci Ma ,&nbsp;Xingzhong Fang ,&nbsp;Guofei Chen","doi":"10.1016/j.eurpolymj.2025.113924","DOIUrl":"10.1016/j.eurpolymj.2025.113924","url":null,"abstract":"<div><div>Colorless polyimide (CPI) films have good application prospects in flexible optoelectronic devices due to their excellent heat resistance and transparency. In this study, a diamine monomer containing a terphenyl skeleton and CF₃ group substituted at <em>ortho</em>-position of amino group, 1,4-bis(3-(trifluoromethyl)-4-aminophenyl)benzene (6FTD), was successfully designed and synthesized, and a series of corresponding polyimides (PIs) were obtained by copolymerization of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 6FTD and 2,2′-bis(trifluoromethyl)benzidine (TFDB). The introduction of rigid and linear terphenyl structure in 6FTD was beneficial to improve the heat resistance and mechanical properties of PI films. In addition, the CF₃ group derived from 6FTD effectively inhibited the rotation between the imide ring and the benzene, so that the 6FTD-containing PI film had a high glass transition temperature (<em>T</em>_g). At the same time, the CF₃ groups caused a large free volume between molecular chains, which ensured the excellent optical transparency and solubility. In particular, PI-50 exhibited high <em>T</em>_g of 399 °C, transmittance of 82% at 450 nm, tensile strength of 146 MPa and tensile modulus of 3.9 GPa. These results indicate that the design of rigid skeleton and side group provides an effective method for developing heat-resistant transparent PI.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"231 ","pages":"Article 113924"},"PeriodicalIF":5.8,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143777403","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}

{"title":"Ultra-heat resistance and low CTE polyimides with spirobis(indene)bis(benzoxazole)-benzimidazole unite for flexible substrate applications","authors":"Peng Xiao ,&nbsp;Xiaojie He ,&nbsp;Qinghua Lu","doi":"10.1016/j.eurpolymj.2025.113923","DOIUrl":"10.1016/j.eurpolymj.2025.113923","url":null,"abstract":"<div><div>The advancement of new technologies has driven the demand for the development of higher-performance polyimides (PI), especially in terms of heat resistance, dimensional stability, and mechanical properties. In this study, four highly rigid, twisted diamine isomers featuring a spirobis(indene)bis(benzoxazole) structure were synthesized. By their co-polycondensation with 5-amino-2-(4-aminobenzene)-benzimidazole (PABZ) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) followed by thermal imidization, a series of PIs with benzoxazole and benzimidazole structures were prepared. Owing to the rigid and linear structure and the formation of intermolecular hydrogen bonding, the PI films showed ultrahigh heat resistance (<em>T</em>_g: 417–510 °C; <em>T</em>_d^5% = 514–562 °C) and excellent dimensional stability (CTE: 2.1–23.5 ppm/K). Meanwhile, they also demonstrate excellent mechanical properties, with a tensile strength of up to 238.5 MPa and an initial modulus of up to 6.8 GPa. These polyimide films have great application potential in flexible display substrates.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"231 ","pages":"Article 113923"},"PeriodicalIF":5.8,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143777404","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}

{"title":"Recent advances in polycarbosilanes synthesis","authors":"Chunyu Chen,&nbsp;Ziwei Luo,&nbsp;Hao Zeng,&nbsp;Xin Yi,&nbsp;Junyang Cen,&nbsp;Ningyu Li,&nbsp;Yuening Pan,&nbsp;Ze Li,&nbsp;Pinglu Zhang","doi":"10.1016/j.eurpolymj.2025.113910","DOIUrl":"10.1016/j.eurpolymj.2025.113910","url":null,"abstract":"<div><div>Silicon incorporation polymers feature materials with many attractive properties, such as flexibility, nontoxicity, oxygen/thermal resistance. As one of the important and high-value added type of organosilicon polymers, polycarbosilane was widely used as the precursor of silicon carbide materials. In this comprehesive review, we would like to provide a summary of recent advancements in synthesizing polycarbosilanes from the view point of synthetic strategy and methodology. Significant focus is paid to the monomer scope, polymerization control, regioselectivity and stereoselectivity in the related polymerization process. We would like to provide inspiration in further synthesis and application in this field.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"231 ","pages":"Article 113910"},"PeriodicalIF":5.8,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783743","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}