European Polymer Journal最新文献_第4页

Synergistic nitrate ester group bioconversion and thermal hazard mitigation through Rhodococcus-mediated nitrocellulose powder degradation 通过红球菌介导的硝化纤维素粉末降解协同硝酸盐酯基生物转化和热危害缓解

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2026-01-10 DOI: 10.1016/j.eurpolymj.2026.114505

Juan Huang , Alei Zhang , Qi Yang , Yajun Ding , Zhongliang Xiao

Nitrocellulose (NC), a persistent organic pollutant, is widely distributed across various habitats and poses significant threats to both ecological systems and human safety. The microbial degradation of NC is crucial for future environmental sustainability. This study systematically investigates the biodegradation potential of Rhodococcus pyridinivorans toward NC powder through multi-dimensional characterization. Morphological analysis revealed that microbes degraded NC by disrupting its powdery structure into shredded fragments, accompanied by the formation of gully-like features on the fiber matrices. Structural investigations confirmed the transformation of energetic groups (–ONO₂) to hydroxyl moieties (–OH), accompanied by 1.0–1.3% nitrogen removal, indicating degradation process coupled with hydrolysis reaction. Molecular weight analysis demonstrated substantial depolymerization, with maximum number-average (M_n) and weight-average (M_w) molecular weights decreasing by 27.3% and 15.4%, respectively, suggesting cleavage of β-1,4-glycosidic bonds. The thermal decomposition mechanism of biotreated NC was evaluated based on kinetic parameters. The biodegradation preserved primary thermal decomposition pathways of NC while modifying its energetic behavior: biotreated NC reduced heat release and increased activation energy, indicating enhanced thermal stability. These findings demonstrate that R. pyridinivorans mediates NC degradation through synergistic denitration-hydrolysis mechanisms. This work provides mechanistic insights into microbial NC transformation and proposes a bio-based strategy for NC-containing wastes, with dual benefits of environmental remediation and safety enhancement for energetic material handling.

硝基纤维素（nitroccellulose， NC）是一种持久性有机污染物，广泛分布于各种生境中，对生态系统和人类安全构成重大威胁。微生物降解对未来环境的可持续性至关重要。本研究通过多维表征系统探讨了吡啶红球菌对NC粉末的生物降解潜力。形态学分析表明，微生物通过破坏NC的粉状结构将其分解成碎片，并在纤维基质上形成沟壑状特征。结构研究证实了含能基团（-ONO2）向羟基（-OH）的转变，并伴有1.0-1.3%的氮去除，表明降解过程伴随着水解反应。分子量分析表明，β-1,4-糖苷键发生了明显的解聚，最大数平均分子量（Mn）和重量平均分子量（Mw）分别下降了27.3%和15.4%。基于动力学参数对生物处理NC的热分解机理进行了评价。生物降解保留了NC的主要热分解途径，同时改变了其能量行为：经过生物处理的NC减少了热释放，增加了活化能，表明热稳定性增强。这些结果表明，啶虫霉通过协同脱硝水解机制介导NC降解。这项工作提供了微生物NC转化的机理见解，并提出了一种基于生物的NC废物处理策略，具有环境修复和增强高能材料处理安全性的双重好处。

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引用次数: 0

Solvent-free mechanochemical polycondensation to generate tyrosine-based polyphosphoramidates 无溶剂机械化学缩聚生成酪氨酸基多磷酸酯

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2026-01-08 DOI: 10.1016/j.eurpolymj.2026.114506

Anastasia E. Gater , Mitchell A. Nascimento , Malachy M. Gilbert , Erin M. Leitao

Polyphosphoramidates are polymers featuring phosphorus-nitrogen bonds within their side or main chain, which impart unique characteristics such as acid-lability and flame retardancy. However, polyphosphoramidates generally require clever design of (P-N)-containing monomers which can then be linked together through conventional polymerisation strategies. Herein, we report the synthesis and characterisation of tyrosine-based polyphosphoramidates with up to ca. 30 repeat units via solvent-free mechanochemically-assisted polycondensation. This polymer synthesis takes advantage of the bifunctional amino and phenolic moieties of tyrosine to form a random copolymer of N-P-N, N-P-O, and O-P-O bonding motifs between tyrosine methyl ester and phenyldichlorophosphate. While polycondensation routes to polyphosphoramidates have been reported previously, this work also represents the first example of a mechanochemical synthesis of a polyphosphoramidate. The use of solid phase synthesis enables the formation of high molecular weight linear species unobtainable under traditional solution phase methods. The obtained polymer exhibits a T_g of ca. 81 ℃, resists degradation up to 250 ℃, and has a char yield of 45.0% remaining at 700 ℃ in N₂. These results demonstrate a solvent-free mechanochemical route to partially bio-based polyphosphoramidates.

聚磷酸酯是在其侧链或主链中具有磷-氮键的聚合物，具有独特的特性，如耐酸性和阻燃性。然而，聚磷酸酯通常需要巧妙地设计含有（P-N）的单体，这些单体可以通过传统的聚合策略连接在一起。在此，我们报告了酪氨酸基多磷酸酯的合成和表征，通过无溶剂机械化学辅助缩聚，具有多达30个重复单元。这种聚合物的合成利用了酪氨酸的双功能氨基和酚基，在酪氨酸甲酯和苯二氯磷酸之间形成N-P-N， N-P-O和O-P-O键基序的无规共聚物。虽然以前已经报道过缩聚途径合成聚磷酸酯，但这项工作也代表了机械化学合成聚磷酸酯的第一个例子。使用固相合成技术可以形成高分子量的线性物质，这在传统的固相合成方法下是无法实现的。所得聚合物的Tg约为81℃，在250℃下抗降解，在700℃的N2中炭收率为45.0%。这些结果证明了一个无溶剂的机械化学途径，部分生物基聚磷酸酯。

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引用次数: 0

Enzyme biocatalyst for removal of residual monomer fractions in waterborne polymers 用于去除水性聚合物中残留单体组分的酶生物催化剂

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2026-01-08 DOI: 10.1016/j.eurpolymj.2026.114507

Ana Trajcheva , Christina Gkountela , Justine Elgoyhen , Oihane Sanz , Stamatina Vouyiouka , Radmila Tomovska

This study explores a sustainable post-polymerization approach for waterborne methyl methacrylate/butyl acrylate (MMA/BA) polymer dispersions (latexes) using horseradish peroxidase (HRP) in the presence of hydrogen peroxide and acetylacetone to catalyze radical initiation at extremely low monomer concentrations (ppm level). In the heterogeneous latex system, where residual monomers are primarily confined within polymer particles, the initial monomer conversion was hindered by aqueous-phase radical generation via the enzymatic catalyst, limited monomer diffusion, and restricted penetration of growing oligomers into the particles. Extending the post-polymerization reaction time and supplying an additional fraction of initiator successfully overcame these constraints, enabling very high conversion at 22 °C (>95 % for MMA and ∼ 90 % for BA). As a result, the biocatalytic latex treatment at 22 °C reduced the residual monomer content in the latex from 2345 to 114 ppm. Polymer films prepared from the treated latexes contained MMA/BA oligomers formed during post-polymerization and traces of the enzyme, which reduced mechanical strength but did not affect water uptake. However, the films exhibited improved thermal stability, likely due to enhanced char formation from residual HRP that delayed thermal degradation. Overall, this work demonstrates that HRP-mediated post-polymerization provides a greener strategy for eliminating residual monomers in waterborne polymers, with minimal adverse impact on polymer performance. Traditional polymerization methods, especially chemical ones, often require relatively high monomer concentrations to drive chain propagation efficiently. Demonstrating enzymatic polymerization in very dilute systems reveals previously unexplored operational regimes, providing enhanced mechanistic understanding under these conditions.

本研究探索了一种可持续的水性甲基丙烯酸甲酯/丙烯酸丁酯（MMA/BA）聚合物分散体（乳胶）聚合方法，使用辣根过氧化物酶（HRP）在过氧化氢和乙酰丙酮的存在下催化极低单体浓度（ppm水平）的自由基起始。在非均相乳胶体系中，残余单体主要局限在聚合物颗粒中，初始单体转化受到酶催化水相自由基生成、单体扩散受限以及生长的低聚物渗透受限等因素的阻碍。延长聚合后反应时间和提供额外的引发剂成功地克服了这些限制，在22°C下实现了非常高的转化率（MMA为95%，BA为90%）。结果表明，生物催化乳胶在22℃下处理后，乳胶中残留单体含量从2345 ppm降至114 ppm。经处理的乳胶制备的聚合物薄膜含有聚合后形成的MMA/BA低聚物和微量的酶，这降低了机械强度，但不影响吸水。然而，薄膜表现出更好的热稳定性，可能是由于残余HRP增强了炭的形成，延迟了热降解。总的来说，这项工作表明，酶标介导的后聚合为消除水性聚合物中的残留单体提供了一种更环保的策略，对聚合物性能的不利影响最小。传统的聚合方法，特别是化学聚合方法，通常需要相对较高的单体浓度来驱动链的有效增殖。在非常稀的体系中展示酶促聚合揭示了以前未探索的操作机制，在这些条件下提供了增强的机制理解。

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引用次数: 0

Tailoring tensile properties of polymer nanocomposites with randomly dispersed multi-thread carbon nanothreads 随机分散多线程碳纳米线聚合物纳米复合材料的裁剪拉伸性能

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2026-01-08 DOI: 10.1016/j.eurpolymj.2026.114503

Chengkai Li , Bonan Li , Yilin Gui , Haifei Zhan

Understanding interfacial load transfer is the key challenge in developing high-performance polymer nanocomposites reinforced by one-dimensional nanothreads (NTHs). Here, large-scale molecular dynamics simulations are employed to elucidate how random dispersion of NTHs, the number of aggregated threads, functionalization, and cross-linking influence the tensile performance of poly (methyl methacrylate) (PMMA) nanocomposites. Without cross-linking, tightly aggregated NTHs enhance Young’s modulus and tensile strength by reducing void formation and promoting stronger filler-filler interactions. Quad-thread pristine NTHs yields ∼ 7 % enhancement in Young’s modulus compared with individually dispersed NTHs as reinforcements. Meanwhile, –COOH functionalization provides the highest reinforcement effect. Covalent cross-linking at the filler-matrix interface markedly improves load transfer efficiency. However, increasing the number of cross-linking filler-matrix bonds disrupts the multi-thread architecture, resulting in excessive voids and weakening the non-bonded filler-filler interactions, leading to a reduction in the reinforcement efficiency. In this regard, adding inter-filler bonds between adjacent NTHs can stabilize the multi-thread architecture and further improve the mechanical properties of polymer nanocomposites. Both internal and external cross-linked multi-thread samples show average ∼ 10 % enhancement of Young’s modulus and UTS than non-internally and externally cross-linked counterparts. These findings unveil the interplay between filler architectures, aggregation and interface modification in determining overall load transfer and reinforcement efficiency, which is beneficial for the development of high-performance polymer nanocomposites.

了解界面载荷传递是开发高性能一维纳米线增强聚合物纳米复合材料的关键挑战。本文采用大规模分子动力学模拟来阐明NTHs的随机分散、聚合线的数量、功能化和交联如何影响聚甲基丙烯酸甲酯（PMMA）纳米复合材料的拉伸性能。在没有交联的情况下，紧密聚集的NTHs通过减少空隙形成和促进更强的填料-填料相互作用来提高杨氏模量和抗拉强度。与单独分散的NTHs作为增强材料相比，四线程原始NTHs的杨氏模量提高了7%。同时-COOH功能化的强化效果最高。填料与基体界面的共价交联显著提高了载荷传递效率。然而，增加交联填料-基体键的数量会破坏多线程结构，导致空隙过多，削弱非键合填料-填料的相互作用，导致增强效率降低。因此，在相邻nth之间添加填充间键可以稳定多线程结构，进一步提高聚合物纳米复合材料的力学性能。内部和外部交联的多线程样品与非内部和外部交联的样品相比，杨氏模量和UTS平均提高了10%。这些发现揭示了填料结构、聚集和界面修饰之间的相互作用，决定了总体负载传递和增强效率，这有利于高性能聚合物纳米复合材料的发展。

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引用次数: 0

Functionalized crosslinked polyesters incorporating fatty, coumarin, and PEG units: An attractive approach to the fluorescent hydrogels preparation 含有脂肪、香豆素和PEG单元的功能化交联聚酯：一种有吸引力的荧光水凝胶制备方法

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2026-01-08 DOI: 10.1016/j.eurpolymj.2026.114508

Andrade-Acuña Daniela , Sanchez A. Susana , Aguilar Joao , Aguilar-Bolados Hector , Dahrouch Mohamed

Fluorescent crosslinking polyesters composed of a siloxane fatty ester, polyethylene glycols, and coumarin units were successfully synthesized via a polytransesterification reaction under melting and high vacuum conditions. Their respective structures were identified by spectroscopic analysis, showing that the different monomers, particularly the coumarin compound, were successfully covalently incorporated. The crosslinking polyesters displayed appropriate thermal properties and hydrogel-forming capabilities, and the incorporation of the fluorescent molecule showed improved swelling properties in water. The results determined by the rheological studies are promising thinking in potential different applications, and these fluorescent crosslinking polyesters showed to be biocompatible. Confocal microscopy revealed that the coumarin units are part of the polymer structure, conferring attractive fluorescent properties to these new crosslinking polyesters and their corresponding hydrogels.

在熔融和高真空条件下，通过多酯交换反应成功合成了由硅氧烷脂肪酯、聚乙二醇和香豆素单元组成的荧光交联聚酯。通过光谱分析鉴定了它们各自的结构，表明不同的单体，特别是香豆素化合物，成功地共价结合。交联聚酯具有良好的热性能和水凝胶形成能力，荧光分子的掺入改善了其在水中的溶胀性能。流变学研究结果表明，这些荧光交联聚酯具有生物相容性，具有潜在的应用前景。共聚焦显微镜显示香豆素单元是聚合物结构的一部分，赋予这些新的交联聚酯及其相应的水凝胶吸引人的荧光特性。

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引用次数: 0

Advancing periodontitis treatment with hydrogels: Mechanisms and future trends in polymer design and material synergy 用水凝胶推进牙周炎治疗：聚合物设计和材料协同作用的机制和未来趋势

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2026-01-07 DOI: 10.1016/j.eurpolymj.2026.114502

Shuai Wang , Fazhan Ren , Lili Ren , Jiale Zhang , Wei Song , Qingzhu Zhang

Periodontitis, a disease triggered by bacterial infection, not only destroys periodontal tissues but may also lead to tooth loss, severely impacting patients’ quality of life and well-being. Traditional treatments such as pharmacological therapy and surgery face challenges due to their significant side effects, suboptimal efficacy, high costs, and the complexity of pathogenic mechanisms, making safe and effective management of periodontitis difficult. Hydrogels, as cross-linked polymeric networks, have emerged as a novel therapeutic option for periodontitis owing to their outstanding biocompatibility, biodegradability, tunable properties, and multifunctionality. This review summarizes recent advances in hydrogel-based strategies for periodontitis treatment, categorizing their applications based on raw materials for hydrogel fabrication. Furthermore, it delves into their roles in antibacterial action, tissue repair, and bone regeneration. The aim is to provide insights for optimizing hydrogel-based therapies and to promote their broader development in managing periodontitis and other oral diseases.

牙周炎是一种由细菌感染引发的疾病，不仅会破坏牙周组织，还可能导致牙齿脱落，严重影响患者的生活质量和健康。传统的治疗方法，如药物治疗和手术治疗，由于其明显的副作用、不理想的疗效、高昂的费用和致病机制的复杂性，使安全有效地管理牙周炎变得困难。水凝胶作为一种交联聚合物网络，由于其出色的生物相容性、生物可降解性、可调节特性和多功能性，已成为牙周炎的一种新的治疗选择。本文综述了基于水凝胶的牙周炎治疗策略的最新进展，并根据水凝胶制备的原材料对其应用进行了分类。此外，它还深入研究了它们在抗菌作用、组织修复和骨再生中的作用。目的是为优化基于水凝胶的治疗方法提供见解，并促进其在牙周炎和其他口腔疾病治疗中的更广泛发展。

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引用次数: 0

A redox switchable smart anti-cancer polymer coated nano-surface 一种氧化还原可切换智能抗癌聚合物包覆纳米表面

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2026-01-06 DOI: 10.1016/j.eurpolymj.2026.114501

Moumita Dhara , Vidya Chitta Voina , Somdatta Rudra , Anand K. Kondapi , Tushar Jana

Smart nano-surfaces with switchable properties are emerging as promising candidates for next-generation biomedical applications. Here we report a simple fabrication strategy for a poly(ferrocenyl methacrylate)-functionalized nano-surface that is externally redox-switchable and exhibits strong cytotoxicity toward cancer cells. Strategic positioning of poly(ferrocenyl methacrylate) on the interface of a nano-surface rather than in solution or nanoparticle cores, we envision spatially localized and tunable biological responses. The surface design is based on well-defined poly(2-(methacryloyloxy)ethylferrocenecarboxylate) (pFcMA) brushes tethered to silica nanoparticles (SiNPs) via surface-initiated reversible addition–fragmentation chain transfer (SI-RAFT) polymerization. Transmission electron microscopy (TEM) revealed polymer grafted SiNP core size varies in the range of 46–70 nm, while the grafting density of pFcMA brushes could be systematically tuned between 0.103 and 0.045 chains nm⁻². Variation in monomer loading allowed systematic modulation of chain conformation from “mushroom” to “brush” regimes as confirmed by thermal and microscopic studies. The surface attached pFcMA shells displayed reversible redox behaviour, validated by cyclic voltammetry (CV), UV–visible spectroscopy, and dynamic light scattering (DLS) analysis. In human neuroblastoma and embryonic kidney cell lines, the redox-switchable poly(ferrocenyl methacrylate) coatings exhibited substantial cytotoxicity, presenting as redox-responsive nano-surface with potential applicability in stimuli-regulated guest loading and release under control. This innovative fusion of redox regulation, anticancer activity, and interfacial design reveals promising prospects in biosensing, on-demand therapeutic interfaces, and smart implant coatings.

具有可切换特性的智能纳米表面正在成为下一代生物医学应用的有前途的候选者。在这里，我们报告了一种简单的制造策略，聚（二茂铁甲基丙烯酸酯）功能化纳米表面是外部氧化还原可切换的，并对癌细胞表现出很强的细胞毒性。将聚二茂铁甲基丙烯酸酯战略性地定位在纳米表面的界面上，而不是在溶液或纳米颗粒核心中，我们设想空间定位和可调的生物反应。表面设计是基于定义良好的聚（2-（甲基丙烯氧基）乙基二茂铁羧酸酯）（pFcMA）刷，通过表面引发的可逆加成-破碎链转移（SI-RAFT）聚合，将其拴在二氧化硅纳米颗粒（SiNPs）上。透射电镜（TEM）显示，聚合物接枝的SiNP芯尺寸在46 ~ 70 nm之间，而pFcMA刷的接枝密度可以在0.103 ~ 0.045链nm−2之间系统调节。单体负载的变化允许从“蘑菇”到“刷状”的链构象的系统调节，这一点得到了热学和微观研究的证实。通过循环伏安法（CV）、紫外可见光谱和动态光散射（DLS）分析证实，表面附着的pFcMA壳具有可逆的氧化还原行为。在人类神经母细胞瘤和胚胎肾细胞系中，氧化还原可切换的聚二茂铁甲基丙烯酸酯涂层表现出实质性的细胞毒性，表现为氧化还原响应的纳米表面，在刺激调节的客体加载和释放控制下具有潜在的适用性。这种氧化还原调节、抗癌活性和界面设计的创新融合在生物传感、按需治疗界面和智能植入物涂层方面显示出广阔的前景。

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引用次数: 0

pH-responsive nanocarrier: Chitosan- polydeoxyribonucleotide (PDRN) nanoparticles for transdermal nucleic acid therapy ph响应纳米载体：壳聚糖-聚脱氧核糖核苷酸（PDRN）纳米颗粒用于透皮核酸治疗

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2026-01-05 DOI: 10.1016/j.eurpolymj.2026.114499

Yuxin Liu , Wenxin Hu , Caiyun Zhao , Chengke Zhao , Yan Liu , Xiaojing Pei , Jun Zhu , Yongbo Lyu , Zhaohui Qu

Polydeoxyribonucleotide (PDRN) has been demonstrated to possess pharmacological activities, including tissue repair and anti-inflammation, thus rendering it a promising ingredient in both regenerative medicine and cosmetics. However, its application is limited by issues including poor cell membrane permeability due to negative charge, susceptibility to nuclease degradation, and impaired transdermal delivery by the skin barrier. Herein, we constructed the pH-responsive PDRN nanocarrier (CP-NPs) using chitosan (CS) via electrostatic self-assembly. By regulating the molar ratio of CS amino groups to PDRN phosphate groups and optimizing the preparation process, uniform CP-NPs with an average particle size of 161.1 ± 6.2 nm were obtained. PDRN aggregation and protection against nuclease degradation was confirmed through a combination of characterization techniques, including dynamic light scattering, scanning electron microscopy, and infrared spectroscopy, in conjunction with agarose gel electrophoresis. The pH-responsive properties of the material were confirmed through zeta potential and UV analysis. Furthermore, experimental findings demonstrated that CP-NPs exhibit excellent stability and biocompatibility, significantly enhancing antioxidant performance and hydration capacity. Further results proved that CP-NPs promoted the proliferation and migration of human dermal fibroblasts (HDFs), with the migration rate increased by 174.16 %, enhancing in vitro transdermal delivery capacity by 55.3 %, and improving in vivo penetration ability by 167.6 %. Human trials confirmed that CP-NPs could improve skin moisture content, transepidermal water loss (TEWL), glossiness, and elasticity without adverse reactions. This study provides a viable PDRN transdermal delivery approach, advancing “non-invasive nucleic acid therapy” in regenerative medicine and cosmetics and laying a foundation for topical PDRN clinical translation.

聚脱氧核糖核苷酸（PDRN）已被证明具有包括组织修复和抗炎症在内的药理活性，因此使其成为再生医学和化妆品中有前景的成分。然而，它的应用受到一些问题的限制，包括由于负电荷导致的细胞膜渗透性差，对核酸酶降解的易感性以及皮肤屏障的透皮递送受损。本研究以壳聚糖（CS）为原料，通过静电自组装构建ph响应型PDRN纳米载体（CP-NPs）。通过调节CS氨基与PDRN磷酸基的摩尔比，优化制备工艺，可制得均匀的CP-NPs，平均粒径为161.1±6.2 nm。通过动态光散射、扫描电子显微镜、红外光谱以及琼脂糖凝胶电泳等表征技术的结合，证实了PDRN的聚集和对核酸酶降解的保护作用。通过zeta电位和UV分析证实了材料的ph响应性能。此外，实验结果表明，CP-NPs具有良好的稳定性和生物相容性，显著提高了抗氧化性能和水合能力。进一步的结果证明，CP-NPs促进了人真皮成纤维细胞（HDFs）的增殖和迁移，其迁移率提高了174.16%，体外透皮递送能力提高了55.3%，体内渗透能力提高了167.6%。人体试验证实，CP-NPs可以改善皮肤含水量、经皮失水（TEWL）、光泽度和弹性，没有不良反应。本研究提供了一种可行的PDRN经皮给药途径，推进了再生医学和化妆品领域的“无创核酸治疗”，为局部PDRN临床转化奠定了基础。

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引用次数: 0

Self-initiated copolymer grafting on ground tire rubber for controlled interfacial properties 自引发共聚物接枝在地面轮胎橡胶的界面性能控制

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2026-01-05 DOI: 10.1016/j.eurpolymj.2026.114497

Reymark D. Maalihan, Eugene B. Caldona

Ground tire rubber (GTR) is a plentiful secondary polymer resource, but its aged, nonpolar surface limits compatibility with polar matrices. This study presents a scalable “graft-from” copolymerization of acrylic acid (AA) and methyl methacrylate (MMA) onto cryo-milled GTR, initiated by mechanoradicals generated during milling, eliminating the need for external initiators. By varying the AA:MMA ratio, copolymer grafts with tunable polarity were obtained and correlated with surface and dispersion properties. Spectroscopy confirmed successful co-grafting, with compositional trends identified by principal component analysis. Electron paramagnetic resonance indicated near-complete radical consumption. Thermogravimetric analysis confirmed surface-limited modification. Increasing AA content transformed fractured carbon-rich surfaces into continuous oxygen-rich films, with greater surface roughness. Contact angle tests showed rapid wetting on AA-rich surfaces versus poor wetting on neat or MMA-rich samples. Dielectric measurements showed that permittivity increased from 4.36 for the neat GTR to ∼11 for AA-rich grafts. The 50:50 AA:MMA composition achieved ∼8.0 at 100 Hz. Kelvin probe force microscopy confirmed increasing surface potential with AA content. Dispersion tests in mixed polar solvents showed that 50:50 and 60:40 grafted GTR remained suspended for over 8 h, while other formulations showed partial stabilization or faster settling, with significantly shorter suspension times for neat or homopolymer-grafted samples. These findings demonstrate a tunable, initiator-free method to enhance interfacial polarity, dielectric response, and colloidal stability of GTR, enabling its use in coatings, adhesives, and dielectric elastomers.

地面轮胎橡胶是一种丰富的二次聚合物资源，但其老化的非极性表面限制了其与极性基质的相容性。该研究提出了一种可扩展的丙烯酸（AA）和甲基丙烯酸甲酯（MMA）在低温铣削GTR上的接枝共聚，由铣削过程中产生的机械自由基引发，无需外部引发剂。通过改变AA:MMA的比例，得到极性可调的接枝共聚物，并与表面和分散性能相关。光谱分析证实共接枝成功，主成分分析确定了成分趋势。电子顺磁共振显示自由基消耗接近完全。热重分析证实了表面限制改性。增加AA含量可使断裂的富碳表面转变为连续的富氧膜，表面粗糙度增大。接触角测试表明，在富含aa的表面快速润湿，而在整洁或富含mma的样品上润湿较差。介电测量表明，纯GTR的介电常数从4.36增加到富aa接枝的介电常数为~ 11。50:50 AA:MMA组合在100 Hz下达到了~ 8.0。开尔文探针力显微镜证实，表面电位随AA含量的增加而增加。在混合极性溶剂中的分散测试表明，50:50和60:40接枝的GTR悬浮时间超过8小时，而其他配方的GTR表现出部分稳定或更快的沉降，纯聚合物或均聚接枝的GTR悬浮时间明显缩短。这些发现证明了一种可调的、无引发剂的方法可以增强GTR的界面极性、介电响应和胶体稳定性，使其能够用于涂料、粘合剂和介电弹性体。

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引用次数: 0

Molecular engineering of fluorene–thiophene architectures toward enhanced conjugation-dependent electrochromic energy storage 面向增强偶联依赖性电致变色储能的芴-噻吩结构的分子工程

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2026-01-05 DOI: 10.1016/j.eurpolymj.2026.114498

Jianhua Lv , Yuting Song , Yunjiao Jiang , Zibo Wei , Cheng Liu , Wang Zhang , Jian Liu , Beili Lu , Biao Huang , Jiayu Tao

Electrochromic polymers capable of simultaneously delivering optical modulation and energy storage functions are of great interest for next-generation smart energy devices. In particular, precise molecular engineering of conjugated backbones offers an effective strategy to regulate electronic structure, ion transport, and charge storage behavior. A series of fluorene–thiophene conjugated polymers (P3TF, P2TF, and P2TTF) were designed and electrochemically synthesized to investigate the impact of molecular conjugation length and substitution position on electrochromic and energy storage performance. The UV–Vis absorption spectra of three monomers and their corresponding polymer films in the neutral state exhibited a consistent trend of gradual red-shift in the maximum absorption (P2TTF > P2TF > P3TF). This evolution reflects the intrinsic structural effect of increasing thiophene content and optimized substitution position, which collectively enhance the π-conjugation and reduce the electronic bandgap. Electrochromic studies showed that P3TF achieved a high optical contrast of 72 % at 1100 nm. Galvanostatic charge–discharge testing revealed significantly highiest areal capacitances for P2TTF (9.29 mF/cm² at 0.8 mA/cm²) compared with P3TF and P2TF. Meanwhile, P2TTF shows superior stability in terms of both electrochromic and energy storage performance. The P2TTF-based electrochromic energy storage device, could power a LED light for over 15 s, maintaining over 86 % of its capacitance after 1500 cycles. These results highlight the critical role of molecular engineering in regulating conjugation and morphology to achieve synergistic electrochromic–energy storage performance.

能够同时提供光调制和能量存储功能的电致变色聚合物是下一代智能能源设备的重要研究方向。特别是，共轭骨架的精确分子工程提供了一种有效的策略来调节电子结构、离子传输和电荷存储行为。设计并合成了一系列芴-噻吩共轭聚合物（P3TF、P2TF和P2TTF），研究了分子共轭长度和取代位置对电致变色性能和储能性能的影响。三种单体及其相应的中性态聚合物膜的紫外-可见吸收光谱在最大吸收（P2TTF > P2TF > P3TF）处表现出一致的逐渐红移趋势。这种演变反映了增加噻吩含量和优化取代位置的内在结构效应，共同增强了π共轭性，减小了电子带隙。电致变色研究表明，P3TF在1100nm处实现了72%的高光学对比度。恒流充放电测试显示，与P3TF和P2TF相比，P2TTF在0.8 mA/cm2时的面电容显著高于P2TF （9.29 mF/cm2）。同时，P2TTF在电致变色性能和储能性能方面均表现出优异的稳定性。基于p2ttf的电致变色储能装置可以为LED灯供电超过15秒，在1500次循环后保持超过86%的电容。这些结果强调了分子工程在调节共轭和形态以实现协同电致变色储能性能方面的关键作用。

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