Polymer最新文献_第10页

Fluorinated covalent organic framework modified separator with lithiophilic site for high-performance lithium metal batteries 高性能锂金属电池用亲水性氟化共价有机骨架改性隔膜

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-22 DOI: 10.1016/j.polymer.2025.129500

Zhaojia Zhang , Yongfen Tong , Juanqi Zhong , Aiqing Zhang , Dan Zhou , Yu Xie , Jinsheng Zhao

The widespread adoption of lithium metal batteries is critically impeded by the growth of lithium dendrites at the electrode-electrolyte interface, a phenomenon that compromises safety and curtails cycle life. A promising strategy to address this challenge is to engineer a synergistic mechanism that promotes uniform Li⁺ deposition while selectively repelling anions. Such a dual-function approach enhances ionic conductivity and raises the Li⁺ transference number, thereby alleviating local concentration polarization and suppressing dendrite initiation. However, conventional commercial separators lack the structural uniformity and ion-selective capability necessary to guide homogeneous ion flux or differentiate between cations and anions. This inherent limitation highlights the urgent demand for advanced separator design to achieve stable and dendrite-free lithium metal anodes. Herein, a highly ordered covalent organic framework (TA-COF), synthesized from a triazine-containing amino monomer and fluorine-rich aldehyde, was used to modify a polypropylene (PP) separator. The CN⋯Li interaction in the TA-COF promotes uniform lithium flux and deposition, while its electronegative fluorinated walls suppress anion migration and enhance lithium-ion transference. The high surface area of TA-COF also improves separator wettability, reducing the electrolyte contact angle from 45.8° to 13.5°. The modified separator (TA-COF@PP) achieves a lithium-ion transference number of 0.74 (vs. 0.34 for PP) and boosts capacity retention to 86.0 % after 140 cycles at 0.5 C, compared to 15.0 % for unmodified PP.

锂金属电池的广泛采用受到电极-电解质界面锂枝晶生长的严重阻碍，这种现象危及安全性并缩短循环寿命。解决这一挑战的一个有希望的策略是设计一种协同机制，在选择性排斥阴离子的同时促进均匀的Li+沉积。这种双功能方法增强了离子电导率，提高了Li+转移数，从而减轻了局部浓度极化，抑制了枝晶的萌生。然而，传统的商用分离器缺乏结构均匀性和离子选择能力，无法引导均匀的离子通量或区分阳离子和阴离子。这种固有的限制突出了对先进分离器设计的迫切需求，以实现稳定和无枝晶的锂金属阳极。本文用含三嗪的氨基单体和富氟醛合成了一种高有序共价有机骨架（TA-COF），并对聚丙烯（PP）分离器进行了改性。TA-COF中的CN⋯Li相互作用促进了均匀的锂通量和沉积，而其电负性氟化壁抑制阴离子迁移并增强锂离子转移。TA-COF的高表面积也提高了分离器的润湿性，将电解质接触角从45.8°降低到13.5°。改性后的隔膜（TA-COF@PP）的锂离子转移数为0.74 (PP为0.34)，在0.5 C下循环140次后，容量保持率提高到86.0%，而未改性的PP为15.0%。

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引用次数: 0

A synergistic phosphorus-nitrogen flame retardant containing both oxazine ring and biphenyl structures effectively addresses the flame retardancy and char formation issues in epoxy resins 一种同时含有恶嗪环和联苯结构的磷氮协同阻燃剂，有效地解决了环氧树脂的阻燃和成焦问题

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-22 DOI: 10.1016/j.polymer.2025.129512

Yang Fang , Yuhao Zhou , Zijian Yang , Chen Liu , Quanyi Liu , Xulin Yang , Penglun Zheng

To address the issue of limited flame retardancy in organophosphorus compounds, this study employed γ-aminopropyltriethoxysilane (KH550), 4,4′-dihydroxybiphenyl, polyformaldehyde, and DOPO to synthesize the phosphorus-nitrogen synergistic flame retardant LKD containing both oxazine ring and biphenyl structures via a one-pot method. The application of LKD to epoxy resin (EP) imparts excellent flame retardancy and char formation properties to EP. Research indicates that the thermal stability and impact strength of EP composites increase with the addition of LKD. Compared to EP, the C_y800 of EP/5-LKD shows a 44.2 % improvement in thermal stability and a 51.6 % increase in impact strength. Increasing the LKD content progressively enhances the flame retardancy of EP, with a 5 wt% LKD content yielding the optimal flame retardancy performance for EP. EP/5-LKD achieved a UL-94 rating of V-0 with a LOI of 31.4 %. In cone calorimeter testing (CCT), EP/5-LKD demonstrated reductions of 65.9 %, 52.3 %, 38.2 %, and 100.0 % in PHRR, THR, TSR, and SPR respectively compared to EP, effectively suppressing thermal and smoke release from the system. According to studies on its flame-retardant mechanism, LKD enhances the quality of the char layer while concurrently attaining dual flame-retardant effects in the condensed phase and gas phase of EP through radical quenching and combustible gas dilution. This improves the system's fire safety performance.

为解决有机磷类化合物阻燃性有限的问题，本研究以γ-氨基丙基三乙氧基硅烷（KH550）、4,4′-二羟基联苯、聚甲醛和DOPO为原料，采用一锅法合成了同时含有氧杂嗪环和联苯结构的磷氮协同阻燃剂LKD。LKD在环氧树脂（EP）中的应用使环氧树脂具有优异的阻燃性和成焦性。研究表明，加入LKD后，EP的热稳定性和冲击强度均有所提高。与EP相比，EP/5-LKD的Cy800热稳定性提高了44.2%，冲击强度提高了51.6%。随着LKD含量的增加，EP的阻燃性逐渐增强，当LKD含量为5 wt%时，EP的阻燃性能最佳。EP/5-LKD的UL-94等级为V-0， LOI为31.4。在锥热计测试（CCT）中，与EP相比，EP/5-LKD分别降低了65.9%、52.3%、38.2%和100.0%的PHRR、THR、TSR和SPR，有效地抑制了系统的热释放和烟雾释放。对其阻燃机理的研究表明，LKD通过自由基猝灭和可燃气体稀释，在提高EP凝聚相和气相质量的同时，实现了EP凝聚相和气相的双重阻燃效果。这提高了系统的消防安全性能。

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引用次数: 0

Dual-functional PVA based microtubes: Leveraging natural lubrication and surface modification for antibacterial interventions 双功能聚乙烯醇微管：利用天然润滑和表面改性抗菌干预

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-22 DOI: 10.1016/j.polymer.2025.129508

Zhaohui Chen, Xuan Wang, Li Li

Poor surface lubrication and bacterial infection have always been key challenges affecting the clinical safety and comfort of interventional medical catheters. In this study, a novel strategy combining melt extrusion and surface co-modification was proposed to fabricate a multifunctional poly(vinyl alcohol) (PVA) intercalated microtube with excellent lubricity, strong antibacterial activity, and favorable biocompatibility. By using water as a green plasticizer to disrupt the intrinsic hydrogen bonding of PVA, stable and continuous melt extrusion of PVA microtubes with the outer diameter of 3.5 mm were achieved. By in-situ co-depositing of polydopamine (PDA) and low-alcoholysis PVA (L-PVA) on the surface of microtube, excellent antibacterial performance and lubrication were imparted. Scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR) analyses confirmed the uniformity and aqueous stability of the composite coating, with a thickness of approximately 26 μm. Tribological tests revealed that PVA-PDA/L-PVA microtube exhibited a remarkably low friction coefficient in deionized water (∼0.0303), outperforming all other tested coating formulations. In vitro antibacterial tests showed that the inhibition rates of microtubes on Escherichia coli and Staphylococcus aureus were ∼100 % and ∼97 %, respectively. The cytotoxicity assays confirmed that the microtube had no significant toxicity toward L929 cells, indicating its excellent biocompatibility. Compared with most mainstream commercial catheters, this PVA microtube possesses superior overall performance. This work provides a simple, scalable, and environmentally friendly approach for constructing interventional PVA-based catheters with integrated lubrication and antibacterial functionalities, expanding the application of PVA in the field of biomedicine.

表面润滑不良和细菌感染一直是影响介入医疗导管临床安全性和舒适性的主要挑战。本研究提出了一种熔体挤出和表面共改性相结合的新策略，制备了具有良好润滑性、抗菌活性和良好生物相容性的多功能聚乙烯醇（PVA）插层微管。利用水作为绿色增塑剂破坏PVA的固有氢键，实现了外径为3.5 mm的PVA微管的稳定连续熔融挤出。将聚多巴胺（PDA）与低醇解PVA （L-PVA）原位共沉积在微管表面，获得了优异的抗菌性能和润滑性能。扫描电镜（SEM）和傅里叶变换红外光谱（FTIR）分析证实了复合涂层的均匀性和水稳定性，涂层厚度约为26 μm。摩擦学测试表明，PVA-PDA/L-PVA微管在去离子水中表现出非常低的摩擦系数（~ 0.0303），优于所有其他测试涂层配方。体外抑菌试验表明，微管对大肠杆菌和金黄色葡萄球菌的抑制率分别为~ 100%和~ 97%。细胞毒性实验证实该微管对L929细胞无明显毒性，表明其具有良好的生物相容性。与大多数主流商用导管相比，PVA微管具有优越的综合性能。本研究为构建集润滑和抗菌功能于一体的PVA介入导管提供了一种简单、可扩展、环保的方法，拓展了PVA在生物医学领域的应用。

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引用次数: 0

Functionalisation of polystyrene surface using atmospheric-pressure DCSBD plasma in pure O2 and N2: Enhanced wettability and surface properties 常压DCSBD等离子体在纯O2和N2中对聚苯乙烯表面的功能化：增强润湿性和表面性能

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-21 DOI: 10.1016/j.polymer.2025.129510

Leila Zahedi, Pedram Ghourchi Beigi, Monika Stupavská, František Zažímal, Petra Šrámková, Tomáš Homola, Dušan Kováčik

Polystyrene (PS) suffers from inherent surface limitations such as low surface energy and poor wettability, which hinder its performance in applications requiring strong adhesion, coating, or biocompatibility. These limitations restrict its broader utility in biomedical engineering, microfluidics, and flexible electronics. To address these challenges, we employed atmospheric pressure diffuse coplanar surface barrier discharge (DCSBD) plasma treatment using pure oxygen and nitrogen gases to enhance the surface properties of PS. Our study demonstrates that even a short exposure time of 0.5–2 s can significantly increase the hydrophilicity of the PS surface, with WCA decreasing from 94.2° to 27.2° and 30.5° using nitrogen and oxygen as working gases, respectively. The improvements were sustained, notably after 7 days of aging, confirming the semi-permanence of plasma effects. Additionally, surface morphology and chemistry analyses (AFM, SEM, XPS) revealed gas-dependent increases in roughness and the incorporation of functional groups, further supporting the improved wettability and potential for enhanced surface interactions. This work demonstrates a rapid, low-cost, and vacuum-free method to overcome the surface limitations of PS, expanding its functionality for advanced material applications.

PS具有固有的表面限制，如低表面能和较差的润湿性，这阻碍了其在需要强附着力、涂层或生物相容性的应用中的性能。这些限制限制了其在生物医学工程、微流体和柔性电子领域的广泛应用。为了解决这些问题，我们采用常压扩散共面表面阻挡放电（DCSBD）等离子体处理纯氧和纯氮气来提高PS的表面性能。我们的研究表明，即使是0.5-2秒的短曝光时间也可以显著提高PS表面的亲水性，在氮气和氧气作为工作气体时，WCA分别从94.2°降低到27.2°和30.5°。这种改善是持续的，特别是在7天的老化后，证实了等离子体效应的半永久性。此外，表面形貌和化学分析（AFM， SEM， XPS）显示，粗糙度和官能团的结合与气体有关，进一步支持了润湿性的改善和表面相互作用的增强。这项工作展示了一种快速、低成本和无真空的方法来克服PS的表面限制，扩大了其在先进材料应用中的功能。

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引用次数: 0

Achieving high crystallization performance of poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] with a designed melt-miscible nucleating agent 用设计的熔融混溶成核剂实现聚[(R)-3-羟基丁酸酯-co-(R)-3-羟基己酸酯]的高结晶性能

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-19 DOI: 10.1016/j.polymer.2025.129507

Jian Wang , Lina Chen , Xinyu Wu , Xue-Wei Wei , Tianyu Wu , Cheng Zhang , Hai-Mu Ye

Poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] (PHBH), a promising biodegradable polyester, still suffers from poor crystallization ability, which limits its practical applications. In this study, a novel nucleating agent, 1,4-bis(methyl succinate) dihydrazide (MSOD), was designed and synthesized to address this challenge. MSOD features a unique molecular structure capable of forming continuous hydrogen bonds, enhancing its self-assembly and interfacial interactions with the PHBH matrix. The incorporation of MSOD significantly improved the crystallization behavior of PHBH with HH copolymerization content of 6 mol%, as evidenced by a remarkable increase in crystallization temperature (up to 94.7 °C at only 0.5 wt% loading at a rate of 10 °C/min) and crystallinity (from 7.3 % of neat PHBH to 37.7 % at only 0.5 wt% loading), along with the elimination of cold crystallization. Through comprehensive analyses including DSC, POM, FTIR, and WAXD, we elucidated that MSOD dissolves in the PHBH melt and self-assembles into fibrous crystals upon cooling, which subsequently template the epitaxial crystallization of PHBH via abundant intermolecular interactions and lattice matching. This work not only presents an efficient nucleating agent for PHBH but also provides deep insights into the mechanism of melt-miscible nucleation, offering a viable strategy for enhancing the crystallization and performance of polyhydroxyalkanoates and relevant polyesters.

聚[(R)-3-羟基丁酸酯-co-(R)-3-羟基己酸酯]（PHBH）是一种很有前途的生物可降解聚酯，但其结晶能力较差，限制了其实际应用。本研究设计并合成了一种新型成核剂1,4-双（丁二酸甲酯）二肼（MSOD）来解决这一难题。MSOD具有独特的分子结构，能够形成连续的氢键，增强其自组装和与PHBH基质的界面相互作用。MSOD的掺入显著改善了HH共聚含量为6 mol%时PHBH的结晶行为，结晶温度（以10°C/min的速度在0.5 wt%的负载下高达94.7°C）和结晶度（在0.5 wt%的负载下从7.3%的纯PHBH提高到37.7%）显著提高，同时消除了冷结晶。通过DSC、POM、FTIR和WAXD等综合分析，我们发现MSOD可溶解于PHBH熔体中，并在冷却后自组装成纤维状晶体，随后通过丰富的分子间相互作用和晶格匹配模板PHBH的外延结晶。本研究不仅为PHBH提供了一种高效的成核剂，而且对熔融混相成核机制提供了深刻的见解，为提高聚羟基烷酸酯及相关聚酯的结晶和性能提供了可行的策略。

{"title":"Achieving high crystallization performance of poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] with a designed melt-miscible nucleating agent","authors":"Jian Wang , Lina Chen , Xinyu Wu , Xue-Wei Wei , Tianyu Wu , Cheng Zhang , Hai-Mu Ye","doi":"10.1016/j.polymer.2025.129507","DOIUrl":"10.1016/j.polymer.2025.129507","url":null,"abstract":"<div><div>Poly[(<em>R</em>)-3-hydroxybutyrate-<em>co</em>-(<em>R</em>)-3-hydroxyhexanoate] (PHBH), a promising biodegradable polyester, still suffers from poor crystallization ability, which limits its practical applications. In this study, a novel nucleating agent, 1,4-bis(methyl succinate) dihydrazide (MSOD), was designed and synthesized to address this challenge. MSOD features a unique molecular structure capable of forming continuous hydrogen bonds, enhancing its self-assembly and interfacial interactions with the PHBH matrix. The incorporation of MSOD significantly improved the crystallization behavior of PHBH with HH copolymerization content of 6 mol%, as evidenced by a remarkable increase in crystallization temperature (up to 94.7 °C at only 0.5 wt% loading at a rate of 10 °C/min) and crystallinity (from 7.3 % of neat PHBH to 37.7 % at only 0.5 wt% loading), along with the elimination of cold crystallization. Through comprehensive analyses including DSC, POM, FTIR, and WAXD, we elucidated that MSOD dissolves in the PHBH melt and self-assembles into fibrous crystals upon cooling, which subsequently template the epitaxial crystallization of PHBH via abundant intermolecular interactions and lattice matching. This work not only presents an efficient nucleating agent for PHBH but also provides deep insights into the mechanism of melt-miscible nucleation, offering a viable strategy for enhancing the crystallization and performance of polyhydroxyalkanoates and relevant polyesters.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"344 ","pages":"Article 129507"},"PeriodicalIF":4.5,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145777711","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}

引用次数: 0

Impact of adsorption performance and neutron irradiation on structural stability of solidified resin for low-level organic liquid waste treatment 吸附性能和中子辐照对固化树脂处理低浓度有机废液结构稳定性的影响

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-19 DOI: 10.1016/j.polymer.2025.129503

Yong-ju Sun , Jian-song Zhang , Xing-yu Jiang , Zhao-rui Chen , Hua-ping Mei , Chen Chao , Jie Yu

A highly crosslinked radiation-resistant resin based on ∗p∗-tert-butylstyrene-divinylbenzene copolymer was developed. Hierarchical macroporous structures were constructed using dual-mode porogens (toluene/∗n∗-dodecanol), integrating triple radiation resistance mechanisms: tert-butyl steric shielding, cyano electron capture, and epoxy radical quenching. The resin efficiently adsorbed 10 × 30 % TBP-OK organic waste, achieving >99 % volume reduction via calcination at 600 °C for 4 h, with an aqueous equilibrium leaching rate of ≈11 %. Neutron irradiation tests established a tolerance threshold of 10¹³ n/cm². Medium-low dose irradiation induced crosslinking densification and fused-ring conjugation, causing UV absorption attenuation and peak narrowing; high doses triggered irreversible degradation. XRD/SEM confirmed irradiation-driven molecular rearrangement forming nano-lamellar ordered structures. This study provides a theoretical foundation for designing solidified materials for radioactive organic liquid treatment.

研制了一种以*p*-叔丁基苯乙烯-二乙烯基苯为共聚物的高交联耐辐射树脂。采用双模多孔剂（甲苯/*n*-十二醇）构建了分层大孔结构，整合了叔丁基位阻屏蔽、氰基电子捕获和环氧自由基猝灭三重抗辐射机制。该树脂有效吸附10×30% TBP-OK有机废物，在600°C下煅烧4 h，体积减少99%，水平衡浸出率≈11%。中子辐照试验确定的容许阈值为1013 n/cm2。中低剂量辐照引起交联致密化和熔环共轭，引起紫外吸收衰减和峰变窄；高剂量会引发不可逆转的退化。XRD/SEM证实辐照驱动分子重排形成纳米层状有序结构。该研究为放射性有机液体处理固化材料的设计提供了理论依据。

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引用次数: 0

Esterification-based post-modification for high-frequency low-Dk polyimides 高频低dk聚酰亚胺的酯化后改性

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-19 DOI: 10.1016/j.polymer.2025.129506

Sanchuan Qiao , Xinhao Nie , Zhuo Wang , Haoyuan Li , Jianhua Zhang , Daliao Tao

To address the pressing need for low dielectric constant (D_k) materials in high-frequency communications, the development of advanced polyimides (PIs) with low-D_k has become imperative. This work utilizes a diamine monomer (PBABOH) that features a novel molecular design incorporating both a triphenylpyridine unit and pendant hydroxy groups. This monomer was then copolymerized with 4,4'-[1,4-phenylenebis(oxy)]bis[3-(trifluoromethyl)aniline] (6FAPB) and bisphenol A dianhydride (BPADA) to yield a hydroxy-functionalized PI(PI-OH), achieving a preliminarily low D_k (D_k = 3.02). Moreover, the active –OH groups endowed PI-OH with efficient and straightforward post-modification capability, allowing for the regulation of PI properties by grafting functional groups. Building on this versatile platform, various fluorinated benzoyl chlorides were selected to modify PI-OH, successfully producing a series of PIs with different fluorine contents (PI–1F, PI-3F, and PI-5F). Fluorination further reduced the D_k and enhanced the hydrophobicity. Among them, PI-5F, with the highest fluorine content, significantly decreased molecular polarization, achieving a D_k as low as 2.35 at 10 GHz and water absorption merely 0.42 %. Meanwhile, the 5 % weight loss temperature (T_d5 _%) of PI-5F reached 419 °C, exhibiting excellent thermal stability and well-balanced mechanical properties. This study provides new insights into the molecular design of high-performance dielectric materials for high-frequency communication and demonstrates the flexibility and potential of post-modification strategies in the functionalization of polyimides.

为了解决高频通信中对低介电常数（Dk）材料的迫切需求，开发具有低介电常数的高级聚酰亚胺（pi）势在必行。这项工作利用二胺单体（PBABOH），其特点是一种新颖的分子设计，结合了三苯基吡啶单元和垂坠羟基。该单体与4,4′-[1,4-苯基双（氧）]双[3-（三氟甲基）苯胺]（6FAPB）和双酚A二酐（BPADA）共聚，得到羟基功能化PI(PI- oh)，初步得到较低的Dk （Dk = 3.02）。此外，活性的-OH基团赋予了PI-OH高效和直接的后修饰能力，允许通过接枝官能团来调节PI的性质。在此多功能平台上，选择多种含氟苯甲酰氯对PI-OH进行改性，成功制备了一系列不同氟含量的PI-1F、PI-3F和PI-5F。氟化进一步降低了Dk，增强了疏水性。其中，氟含量最高的PI-5F显著降低了分子极化，在10 GHz时Dk低至2.35，吸水率仅为0.42%。同时，PI-5F的5%失重温度（Td5 %）达到419℃，具有良好的热稳定性和平衡的力学性能。该研究为高性能高频通信介质材料的分子设计提供了新的见解，并展示了聚酰亚胺功能化后修饰策略的灵活性和潜力。

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引用次数: 0

Chemically recyclable films from thermoplastic ABA-triblock copolymers containing polylactide A-blocks and easily degradable polydioxolane B-block - towards the novel type of sustainable plastics 化学上可回收的薄膜由热塑性ba -三嵌段共聚物组成，含有聚丙交酯a -嵌段和易于降解的聚二氧索烷b -嵌段，朝向新型可持续塑料

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-19 DOI: 10.1016/j.polymer.2025.129501

Karolina Cichoń , Bartłomiej Kost , Marta Safandowska , Artur Rozanski , Malgorzata Basko

Research on the degradability of polymeric materials and their facilitated decomposition after use may significantly contribute to addressing the problem of increasing environmental pollution. In this work, recyclable films based on ABA triblock copolymers containing polylactide A-blocks and easily degradable polydioxolane B-blocks were prepared and investigated. To obtain copolymers suitable for commercial applications, a large-scale synthesis procedure was developed, and the process capacity was scaled up to hundreds of grams per batch. The results show that, under the conditions used, the molar mass and composition of the copolymers can be readily controlled by adjusting the ratio of cyclic ester to the α,ω-hydroxy-terminated polyacetal macroinitiator in the ring-opening polymerisation (ROP) catalyzed by tin(II) octoate (Sn(Oct)₂). To create copolymers with high potential for recovering recyclable compounds, a polyacetal block (7,000 g/mol) was combined with polyester blocks of varying lengths, whose molecular weights did not exceed 20,000 g/mol. Films formed from the studied copolymers were produced by compression moulding in a hot press and subsequently evaluated in detail for their thermal, barrier, and mechanical properties. Chemical recycling of the polymeric materials via depolymerization was examined using an acid catalyst at temperatures between 150 °C and 200 °C. We hypothesise that these novel films have strong potential to serve as next-generation recyclable materials, enabling the recovery of both the cyclic monomer and polylactide.

研究高分子材料的可降解性及其在使用后的易分解性对解决日益严重的环境污染问题具有重要意义。本文制备并研究了含聚丙交酯a嵌段和易降解聚二氧索烷b嵌段的ABA三嵌段共聚物的可回收膜。为了获得适合商业应用的共聚物，开发了大规模合成工艺，并将工艺容量扩大到每批数百克。结果表明，在上述条件下，通过调节环酯与α，ω-羟基端聚缩醛引发剂的比例，可以很容易地控制共聚物的摩尔质量和组成。为了创造具有高回收潜力的可回收化合物的共聚物，将聚缩醛嵌段（7,000 g/mol）与不同长度的聚酯嵌段结合，其分子量不超过20,000 g/mol。由所研究的共聚物形成的薄膜是在热压机中通过压缩成型生产的，随后详细评估了它们的热学、阻隔性和机械性能。采用酸性催化剂，在150 ~ 200℃的温度下，研究了聚合物材料解聚的化学再循环。我们假设这些新型薄膜具有强大的潜力，可以作为下一代可回收材料，使环状单体和聚丙交酯都能回收。

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引用次数: 0

Investigating HDPE composites with phosphorus- and nitrogen-modified lignins 磷、氮改性木质素HDPE复合材料的研究

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-19 DOI: 10.1016/j.polymer.2025.129495

Alexander F. Tiniakos , Christina Samiotaki , Alexandra Zamboulis , Alexios Grigoropoulos , Stefania Koutsourea , Evangelia Tarani , Aikaterini Teknetzi , George Vourlias , Alexandros Zoikis Karathanasis , Dimitrios N. Bikiaris , Ioanna Deligkiozi

The present research work focuses on the modification of Kraft lignin with phosphorus and nitrogen functionalities, and their subsequent evaluation as flame retardant additives in HDPE composites. Lignin is an inexpensive bio-based compound; this study focuses on modified lignins as environmentally friendly alternatives to the current state of art flame retardant additives, that include highly halogenated and mostly toxic compounds. Modified lignins were incorporated to HDPE in loadings ranging from 1 % wt. to 30 % wt. and the resulting composites were further studied. The produced HDPE/modified lignin composites were found to have a higher char residue and a higher temperature of maximum weight loss compared to HDPE/pristine Kraft lignin composites. Furthermore, up to 5 % modified lignin loading, the composites maintained or slightly improved the mechanical properties. Antioxidant properties were enhanced proportionally to the additive loading, with Kraft and P additives displaying the strongest antioxidant activity. Contact angle measurements of the composites on the other hand revealed a hydrophobic surface in most cases. Finally, UL-94 flame retardancy test showed lower dripping and longer burning times for all composites in comparison to neat HDPE. All these confirm the potential of lignin and modified lignins as sustainable additives for polymeric matrices.

目前的研究工作主要集中在用磷和氮官能团对硫酸盐木质素进行改性，并对其作为HDPE复合材料阻燃添加剂进行评价。木质素是一种廉价的生物基化合物；本研究的重点是改性木质素作为环境友好的替代品，以取代目前最先进的阻燃添加剂，包括高卤化和大多数有毒的化合物。将改性木质素以1% ~ 30%的重量加入到HDPE中，并对所得复合材料进行了进一步研究。与HDPE/原始木质素复合材料相比，HDPE/改性木质素复合材料具有更高的炭渣和更高的最大失重温度。此外，当木质素含量达到5%时，复合材料的力学性能保持不变或略有改善。抗氧化性能随添加剂添加量的增加而增强，其中Kraft和P添加剂的抗氧化活性最强。另一方面，复合材料的接触角测量在大多数情况下显示出疏水表面。最后，UL-94阻燃测试表明，与纯HDPE相比，所有复合材料的滴落率更低，燃烧时间更长。所有这些都证实了木质素和改性木质素作为聚合物基质可持续添加剂的潜力。

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引用次数: 0

Low-temperature plasma-functionalised PHB/halloysite electrospun nanofibers: Enhanced interfacial and mechanical properties 低温等离子体功能化PHB/高岭土静电纺纳米纤维：增强界面和机械性能

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-19 DOI: 10.1016/j.polymer.2025.129505

Leila Zahedi , Pedram Ghourchi Beigi , Mária Kováčová , Pavel Souček , Mirko Černák , Dušan Kováčik

This study introduces a novel strategy to overcome the limitations of electrospun Polyhydroxybutyrate (PHB) nanofiber mats, particularly their suboptimal mechanical properties. Plasma-powder functionalisation using Diffuse Coplanar Surface Barrier Discharge (DCSBD) for different treatment times (up to 8 min) and subsequently reinforcing it with Halloysite Nanotubes (HNTs) developed an electrospun nanofiber mat with enhanced structural and mechanical properties, demonstrating a potential candidate for advanced applications. Although reinforcing the PHB electrospun nanofibers with HNTs increased the average diameter to 1.89 μm, 2-min plasma functionalisation of PHB powder (2min-pPHB-HNTs) developed a significantly thinner nanofiber mat, resulting in a 48 % decline in the average nanofiber diameter. Scanning Transmission Electron Microscopy (STEM) analysis revealed a well-dispersed HNTs network within the PHB matrix, resulting in a fibrous structure with enhanced tensile strength (4.59 MPa). In comparison, 2min-pPHB-HNTs represented 6.17 MPa in tensile strength. Toughness of the HNTs-reinforced, 2-min plasma-treated mat is 1.23 MJ/m³ compared to 0.65 MJ/m³ for HNTs-reinforced, untreated PHB mat. Also, the samples were characterised with other analytical methods, e.g., SEM, porosity, ATR-FTIR, WCA/SFE, and XRD, to evaluate the efficiency of plasma-powder functionalisation and HNTs reinforcement on the structural and chemical properties of the electrospun PHB-HNTs nanofiber mat.

本研究提出了一种新的策略来克服静电纺聚羟基丁酸酯（PHB）纳米纤维垫的局限性，特别是其不理想的力学性能。利用弥漫性共面表面阻挡放电（DCSBD）进行不同处理时间（长达8分钟）的等离子体粉末功能化，随后用高岭土纳米管（HNTs）增强，开发出具有增强结构和机械性能的电纺纳米纤维垫，展示了一种潜在的高级应用候选材料。虽然用HNTs增强PHB静电纺丝纳米纤维的平均直径增加到1.89 μm，但2分钟等离子体功能化PHB粉末（2min-pPHB-HNTs）形成了一个明显更薄的纳米纤维毡，导致纳米纤维平均直径下降48%。扫描透射电子显微镜（STEM）分析显示，PHB基体中存在分散良好的HNTs网络，从而形成具有增强抗拉强度（4.59 MPa）的纤维结构。相比之下，2min-pPHB-HNTs的拉伸强度为6.17 MPa。HNTs增强的2分钟等离子体处理垫的韧性为1.23 MJ/m3，而HNTs增强的未经处理的PHB垫的韧性为0.65 MJ/m3。此外，用其他分析方法（如SEM，孔隙率，ATR-FTIR， WCA/SFE和XRD）对样品进行了表征，以评估等离子体粉末功能化和HNTs增强对电纺PHB-HNTs纳米纤维垫的结构和化学性能的影响。

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