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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引用次数: 0

Renewable zein-induced physical networks in PVDF composites for hydrogen bond-mediated crystallization control and ultrahigh energy storage performance 可再生玉米蛋白诱导的PVDF复合材料物理网络用于氢键介导结晶控制和超高储能性能

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-18 DOI: 10.1016/j.polymer.2025.129499

Qianqian Yu, Haijun Wang, Yisha Ma

This study presents a sustainable bio-composite strategy enhancing the dielectric energy storage performance of poly (vinylidene fluoride) (PVDF) through acetate-modified zein proteins. The amphiphilic structure of denatured zein, featuring exposed –OH, –NH₂, CO, and –COOH groups, enables multipoint hydrogen bonding with PVDF chains. These interactions achieve dual key effects: promoting β-phase crystallization in PVDF to significantly increase the dielectric constant by 40 % without elevating dielectric loss, while simultaneously forming hydrogen bond-mediated physical crosslinking networks. This network not only homogenizes electric field distribution and suppresses space charge accumulation but, crucially, counteracts the potential increase in dipole relaxation losses associated with reduced crystallinity by effectively restricting polymer chain mobility. The optimized microstructure delivered exceptional electrical properties including high breakdown strength, an energy density of 11.31 J/cm³, and 83.44 % energy efficiency at the maximum field, surpassing most reported PVDF composites. Unlike traditional inorganic fillers, this bio-derived modifier addresses crystalline limitations and interfacial defects while avoiding the brittleness associated with chemical crosslinking. This work fundamentally elucidates protein-polymer interfacial synergy and establishes a scalable, eco-friendly paradigm for high-performance dielectric composites, offering significant energy storage potential.

本研究提出了一种可持续的生物复合材料策略，通过醋酸酯修饰玉米蛋白来提高聚偏氟乙烯（PVDF）的介电储能性能。变性玉米蛋白的两亲性结构，暴露了-OH、-NH2、C=O和-COOH基团，使其能够与PVDF链形成多点氢键。这些相互作用实现了双重关键效应：促进PVDF中β相结晶，在不增加介电损耗的情况下显著提高介电常数40%，同时形成氢键介导的物理交联网络。该网络不仅使电场分布均匀化，抑制空间电荷积累，而且至关重要的是，通过有效限制聚合物链的迁移率，抵消了与结晶度降低相关的偶极子弛豫损失的潜在增加。优化后的微结构具有优异的电学性能，包括高击穿强度、11.31 J/cm3的能量密度和83.44%的最大场能效，超过了大多数报道的PVDF复合材料。与传统的无机填料不同，这种生物衍生改性剂解决了晶体限制和界面缺陷，同时避免了化学交联带来的脆性。这项工作从根本上阐明了蛋白质-聚合物界面协同作用，并为高性能介电复合材料建立了可扩展的、环保的范例，提供了巨大的能量存储潜力。

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引用次数: 0

Nanocomposite materials based on mesoporous polymer matrices with palladium and platinum nanoparticles via rheological explosion 基于介孔聚合物基质的钯和铂纳米颗粒流变爆炸纳米复合材料

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-18 DOI: 10.1016/j.polymer.2025.129502

Olga V. Arzhakova , Artem S. Khramtsovskii , Ivan A. Tikhonov , Denis K. Chaplygin , Aleksandra A. Zvonova , Aleksandr Yu Kopnov , Anastasiya V. Bolshakova , Aleksei I. Aleksandrov

This work offers a new “green” approach for the bottom-up preparation of the polymer-based nanocomposite materials containing platinum and palladium nanoparticles via rheological explosion within the confined space of the polymer matrices. The mesoporous polymer matrices with a unique fibrillar-porous structure were prepared via environmental intercrystallite crazing and serve as nanocontainers for the incorporated palladium and platinum salts. This mechanochemical approach involves the stress-induced in situ reduction of platinum and palladium ions to a zero-valence state under a single the short-term pulsed action. Reduction of metal ions within the confined nanoscale porous space via rheological explosion is provided by the generation of alternative “green” redox agents and leads to the formation of spherical Pd and Pt nanoparticles with average dimensions of 3–5 nm due the governing role of the mesoporous polymer matrix. This short-term process with enhanced kinetics proceeds at room temperature, requires no use of toxic reagents, and the resultant materials contain numerous nanoparticles, which are uniformly distributed within the volume of the nanocomposite materials without any aggregation. These nanocomposite materials can be used for the heterogenous catalysis, as biomedical and electroconductive materials as well as the polymer-based sensors.

这项工作提供了一种新的“绿色”方法，通过在聚合物基质的有限空间内流变爆炸，自下而上地制备含有铂和钯纳米颗粒的聚合物基纳米复合材料。采用环境晶间刻蚀法制备了具有独特纤维多孔结构的介孔聚合物基质，并将其作为掺杂钯和铂盐的纳米容器。这种机械化学方法涉及应力诱导的铂和钯离子在单一的短期脉冲作用下原位还原到零价态。在受限的纳米级多孔空间中，金属离子通过流变爆炸还原是由替代的“绿色”氧化还原剂的产生提供的，并且由于介孔聚合物基质的控制作用，导致平均尺寸为3-5 nm的球形Pd和Pt纳米颗粒的形成。这一短期过程在室温下进行，动力学增强，不需要使用有毒试剂，所得到的材料含有大量纳米颗粒，这些纳米颗粒均匀分布在纳米复合材料的体积内，没有任何聚集。这些纳米复合材料可用于多相催化、生物医学和导电材料以及聚合物基传感器。

{"title":"Nanocomposite materials based on mesoporous polymer matrices with palladium and platinum nanoparticles via rheological explosion","authors":"Olga V. Arzhakova , Artem S. Khramtsovskii , Ivan A. Tikhonov , Denis K. Chaplygin , Aleksandra A. Zvonova , Aleksandr Yu Kopnov , Anastasiya V. Bolshakova , Aleksei I. Aleksandrov","doi":"10.1016/j.polymer.2025.129502","DOIUrl":"10.1016/j.polymer.2025.129502","url":null,"abstract":"<div><div>This work offers a new “green” approach for the bottom-up preparation of the polymer-based nanocomposite materials containing platinum and palladium nanoparticles via rheological explosion within the confined space of the polymer matrices. The mesoporous polymer matrices with a unique fibrillar-porous structure were prepared via environmental intercrystallite crazing and serve as nanocontainers for the incorporated palladium and platinum salts. This mechanochemical approach involves the stress-induced <em>in situ</em> reduction of platinum and palladium ions to a zero-valence state under a single the short-term pulsed action. Reduction of metal ions within the confined nanoscale porous space via rheological explosion is provided by the generation of alternative “green” redox agents and leads to the formation of spherical Pd and Pt nanoparticles with average dimensions of 3–5 nm due the governing role of the mesoporous polymer matrix. This short-term process with enhanced kinetics proceeds at room temperature, requires no use of toxic reagents, and the resultant materials contain numerous nanoparticles, which are uniformly distributed within the volume of the nanocomposite materials without any aggregation. These nanocomposite materials can be used for the heterogenous catalysis, as biomedical and electroconductive materials as well as the polymer-based sensors.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"345 ","pages":"Article 129502"},"PeriodicalIF":4.5,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771221","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

Efficient CuAAC click polymerization of α, ω-bifunctional macromonomers with reaction enhanced reactivity of intermediates (RERI) mechanism 具有反应增强中间体反应活性（rei）机理的α， ω-双官能团大单体的高效CuAAC点击聚合

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-18 DOI: 10.1016/j.polymer.2025.129486

Zhuo Zhou , Xiuzhe Yin , Yundong Zhang , Yue Yang , Zeyuan Liu , Wangmeng Hou , Zhijia Liu , Yi Shi , Yongming Chen

Step-growth polymerization of A₂+B₂ monomer pair provides valuable opportunities for synthesizing polymeric materials with diverse functions along the polymer backbones. Herein, a copper-catalyzed azide-alkyne cycloaddition (CuAAC) click polymerization of α, ω-bifunctional macromonomers (MMs) with reaction enhanced reactivity of intermediates (RERI) mechanism was reported to synthesize high-molecular-weight polymers with controlled insertion of multi-functionalities along the polymer backbones. In this CuAAC click polymerization, the polyethylene glycol (PEG), polystyrene (PS), poly(tert-butyl acrylate) (PtBA) homopolymers with molecular weight ranging from 1.0 to 4.0 kDa, were utilized for α, ω-bis-alkynyl-terminated MMs (A₂-MMs), and 2,2-bis(azidomethyl)propane-1,3-diol was used as the pair B₂ monomers. Given the RERI effect of B₂ monomer, these A₂-MMs can be quantitatively consumed with slightly excess of B₂ in the polymerization, producing high-molecular-weight poly(PEG), poly(PS) and poly(PtBA) with multiple functional groups along the backbones. In addition, by taking the CuAAC copolymerization of these A₂-MMs, a series of functional multiblock copolymers (MBCPs) with can be facile synthesized. Moreover, the ester groups from A₂-MM units endowed poly(A₂-MM) products with degradability under mild condition. The multiple hydroxyl groups from B₂ units could be further modified by efficient coupling reactions with anhydride, propargyl ester or isocyanide molecules, promoting the fabrication of polymer materials with desired functions.

A2+B2单体对的分步生长聚合为沿聚合物骨架合成具有多种功能的高分子材料提供了宝贵的机会。本文报道了一种铜催化叠氮化物-炔环加成（CuAAC）键合聚合α， ω-双官能团大单体（MMs）的反应增强中间体反应活性（rei）机制，合成了沿聚合物骨架可控制多官能团插入的高分子量聚合物。以分子量为1.0 ~ 4.0 kDa的聚乙二醇（PEG）、聚苯乙烯（PS）、聚丙烯酸叔丁酯（PtBA）均聚物（a2 - mm）和2,2-双（叠氮多甲基）丙烷-1,3-二醇为B2对单体进行了CuAAC点击聚合。考虑到B2单体的rei效应，这些a2 - mm可以在聚合过程中被少量过量的B2定量消耗，产生沿主干有多个官能团的高分子量聚（PEG）、聚（PS）和聚（PtBA）。此外，通过将这些a2 - mm进行CuAAC共聚，可以很容易地合成一系列功能化的多嵌段共聚物（MBCPs）。此外，A2-MM单元的酯基赋予了poly（A2-MM）产物在温和条件下的可降解性。通过与酸酐、丙炔酯或异氰酸酯分子的有效偶联反应，可以进一步修饰B2单元上的多个羟基，促进制备具有所需功能的高分子材料。

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引用次数: 0

Maleate-bonded acemannan (Aloe vera leaf mucilage): Synthesis, characterization, efficient removal of Pb(II) from groundwater, kinetics, mechanism, and regeneration studies 马来酸键合葡甘露聚糖（芦荟叶粘液）：合成、表征、地下水中铅（II）的有效去除、动力学、机制和再生研究

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-18 DOI: 10.1016/j.polymer.2025.129498

Arshad Ali , Muaz Ali , Sidra Qasim , Hassan Ali , Amina Mumtaz , Khaled Fahmy Fawy , Umar Nishan , Muhammad Ashraf Shaheen , Azhar Abbas

Because of the extensive pollution caused by industrialization and anthropogenic activities, life on the earth is in danger. Among a number of contaminants, the contamination due to the existence of toxic heavy metals in freshwater reservoirs is one of the main issues that need urgent attention. The mucilage/acemannan (AC) was extracted from the Aloe vera plant leaf. AC was then esterified with maleic anhydride through a base-catalysed esterification reaction and converted to maleated-acemannan (MAL-AC). The MAL-AC was neutralized to sodium salt of MAL-AC (Na-MAL-AC) by saponification with NaHCO₃, dried, and stored. The FTIR spectroscopic analysis of AC, MAL-AC, and Na-MAL-AC confirmed the formation of MAL-AC and Na-MAL-AC. The TGA analysis witnessed the greater stability of Na-MAL-AC than AC. SEM images revealed the rough and porous nature of AC, MAL-AC, Na-MAL-AC, and Pb-MAL-AC. The pH_ZPC of Na-MAL-AC was 4.90 which indicated the presence of negative charge on its surface. The highest adsorption capacity of Na-MAL-AC to remove Pb(II) was 625 mg/L from DW and 555.55 mg/L from HGW according to Langmuir isotherm. The pseudo-2nd order kinetic model best described the Pb(II) adsorption on Na-MAL-AC surface according to chemisorption mechanism. The EDX analysis and ideal fitting of Boyd's model to adsorption data indicated the involvement of ion-exchange mechanisms in Pb(II) adsorption. The thermodynamic study showed the spontaneity and exothermic nature of Pb(II) adsorption by Na-MAL-AC. The Na-MAL-AC was found regenerable and hence can be used several times prior to replace.

由于工业化和人为活动造成的广泛污染，地球上的生命正处于危险之中。在众多污染物中，淡水水库中有毒重金属的存在所造成的污染是亟待关注的主要问题之一。从芦荟植物叶片中提取粘液/乙酰甘露聚糖（AC）。AC与马来酸酐通过碱催化酯化反应生成马来甘露聚糖（MAL-AC）。用NaHCO3皂化法将MAL-AC中和为MAL-AC （Na-MAL-AC）钠盐，干燥后贮存。对AC、MAL-AC和Na-MAL-AC的FTIR光谱分析证实了MAL-AC和Na-MAL-AC的形成。热重分析表明Na-MAL-AC比AC更稳定。扫描电镜图像显示了AC、MAL-AC、Na-MAL-AC和Pb-MAL-AC的粗糙和多孔性。Na-MAL-AC的pHZPC为4.90，表明其表面存在负电荷。根据Langmuir等温线，Na-MAL-AC对DW和HGW的最高吸附量分别为625 mg/L和555.55 mg/L。拟二级动力学模型从化学吸附机理上较好地描述了Pb（II）在Na-MAL-AC表面的吸附。EDX分析和Boyd模型对吸附数据的理想拟合表明离子交换机制参与了Pb（II）的吸附。热力学研究表明了Na-MAL-AC吸附Pb（II）的自发性和放热性质。发现Na-MAL-AC可再生，因此在更换之前可以多次使用。

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引用次数: 0

Multi-stimuli responsive shape memory properties of 3D-printed PLA/TPU/CNT composites 3d打印PLA/TPU/CNT复合材料的多刺激响应形状记忆性能

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-16 DOI: 10.1016/j.polymer.2025.129496

Yuqin Zhou , Jiaxin Shi , Haibo Wang , Tianyun Shao , Ke Su , Yumei Gong , Xiaohang Tuo , Dongzhe Li

In the field of smart responsive materials, traditional shape memory polymer composites suffer from the problems of single response mode and insufficient environmental adaptability. In this study, polylactic acid (PLA)/thermoplastic polyurethane (TPU)/carbon nanotubes (CNT) multi-stimuli responsive shape memory composites were prepared by fused deposition modeling (FDM) 3D-printing technology. The effects of CNT content (0–20 wt%) on the microscopic observation, thermal properties, mechanical analysis, and shape memory behavior of the composites were thoroughly investigated. These results indicated that the addition of CNT disrupts the original sea-island structure of the PLA/TPU matrix and promotes the interface blending of the two phases. Meanwhile, CNT constructed a thermal/electrical conductive network, significantly enhancing the response behavior of 3D-printed composites to heat, near-infrared light, and electric fields. A CNT content of 20 % was the threshold for balancing the formability, mechanical stability, and functional efficiency of composite materials. Based on this the shape recovery time of the composite under 80 °C oven heating, 0.67 W/cm² infrared light irradiation, and 85 V electric field was shortened to 77 s, 20 s, and 80 s, respectively, demonstrating the multi-stimulus-responsive characteristics. In addition, the 3D-printing technology enabled programmable deformation of complex structures, verifying the application potential of the material in the field of smart devices and providing a new direction for the development of multi-functional shape memory polymer composites.

在智能响应材料领域，传统的形状记忆聚合物复合材料存在响应模式单一、环境适应性不足的问题。本研究采用熔融沉积建模（FDM） 3d打印技术制备了聚乳酸(PLA)/热塑性聚氨酯(TPU)/碳纳米管（CNT）多刺激响应形状记忆复合材料。研究了碳纳米管含量（0-20 wt%）对复合材料显微观察、热性能、力学分析和形状记忆行为的影响。这些结果表明，碳纳米管的加入破坏了PLA/TPU基体原有的海岛结构，促进了两相的界面共混。同时，碳纳米管构建了导热/导电网络，显著增强了3d打印复合材料对热、近红外光和电场的响应行为。碳纳米管含量为20%是平衡复合材料成形性、机械稳定性和功能效率的阈值。在此基础上，复合材料在80℃烘箱加热、0.67 W/cm2红外光照射和85 V电场下的形状恢复时间分别缩短至77 s、20 s和80 s，表现出多刺激响应特性。此外，3d打印技术实现了复杂结构的可编程变形，验证了材料在智能设备领域的应用潜力，为多功能形状记忆聚合物复合材料的发展提供了新的方向。

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引用次数: 0

Core-shell structures enable simultaneous improvements of toughness and near-native hydrogen barrier properties in PA6/POE-g-MAH blends with addition of a low-amount of EVOH component 核壳结构可以同时改善PA6/POE-g-MAH共混物的韧性和近天然氢屏障性能，并添加少量的EVOH成分

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-16 DOI: 10.1016/j.polymer.2025.129494

Zhimin Li , Bo Zhu , Chengrui Di , Jigang Hao , Yuqi Zhao , Anping Zhu , Yishi Wang , Wei Wang , Mingzhe Zhou , Kun Qiao

Type IV hydrogen storage vessels represent the inevitable trend in current hydrogen storage technology development. Integration of structural functionality into hydrogen storage vessel liner materials has attracted considerable research interest. However, achieving synergistic optimization of toughness and hydrogen barrier properties in nylon 6 (PA6) liner material is challenging. In the study, we fabricated PA6/POE-g-MAH binary and PA6/POE-g-MAH/EVOH ternary composites, by incorporating toughening agent, maleic anhydride-grafted polyolefin elastomer (POE-g-MAH), along with the barrier agent, ethylene vinyl alcohol copolymer (EVOH, a high-barrier polymer) into PA6 matrix via melt blending. While the binary composites exhibited improved toughness, this was accompanied by a reduction in modulus and an increase in hydrogen permeability. Remarkably, a core-shell structure emerged in the ternary composites, enabling simultaneous super-toughness and a low permeability coefficient. The ternary composite S80E20V8, incorporating merely 8 wt% EVOH, exhibited maximum toughness relative to the binary composite S80E20, demonstrating an impact strength of 104.89 kJ/m² (a 27.89 % increase) at 23 °C and 27.01 kJ/m² (a 5.34 % increase) at −30 °C, an elongation at break of 287.38 %, and a simultaneous 14.93 % reduction in the hydrogen permeability coefficient to 3.76 × 10⁻¹⁴ cm³ cm/(cm²·s·Pa). Most notably, compared to neat PA6, S80E20V8 achieved extraordinary toughness improvement, with impact strength enhancements of 820 % at 23 °C and 626 % at −30 °C. Moreover, the composites exhibited excellent thermal properties and low hygroscopicity. Although the barrier property did not surpass that of neat PA6, our strategy of integrating barrier-toughness-hygrothermal performance with low additive loading offers a promising route for next-generation liners in hydrogen storage vessels.

IV型储氢容器代表了当前储氢技术发展的必然趋势。将结构功能集成到储氢容器内衬材料中已经引起了相当大的研究兴趣。然而，实现尼龙6 （PA6）内衬材料的韧性和隔氢性能的协同优化是具有挑战性的。通过熔融共混，在PA6基体中加入增韧剂马来酸酐接枝聚烯烃弹性体（POE-g-MAH）和阻隔剂乙烯醇共聚物（EVOH），制备了PA6/POE-g-MAH二元复合材料和PA6/POE-g-MAH/EVOH三元复合材料。当二元复合材料表现出增强的韧性时，这伴随着模量的降低和氢渗透性的增加。值得注意的是，在三元复合材料中出现了核壳结构，同时实现了超韧性和低渗透系数。与二元复合材料S80E20相比，仅含8 wt% EVOH的三元复合材料S80E20V8表现出最大的韧性，在23°C和- 30°C时的冲击强度分别为104.89 kJ/m2和27.01 kJ/m2，分别提高27.89%和5.34%，断裂伸长率为287.38%，同时氢渗透系数降低14.93%，降至3.76 × 10−14 cm3 cm/（cm2·s·Pa）。最值得注意的是，与纯PA6相比，S80E20V8取得了非凡的韧性改善，在23°C和- 30°C的冲击强度分别提高了820%和626%。此外，复合材料具有优异的热性能和低吸湿性。虽然阻隔性能没有超过纯PA6，但我们将阻隔韧性、湿热性能与低添加剂负载相结合的策略为下一代储氢容器衬管提供了一条有前途的途径。

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引用次数: 0

Boric acid crosslinked network-like polysaccharides for adsorption of cationic dyes 硼酸交联网状多糖对阳离子染料的吸附

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-12-16 DOI: 10.1016/j.polymer.2025.129492

Zhaona Liu , Make Li , Yangyang Zheng , Huacheng Zhang

Network-like crosslinked polysaccharides including BA-S and BA-C have been thoroughly produced via the one-pot hydrothermal reaction of boric acid (BA) and starch (S)/cellulose (C), respectively. Characterization of those polymeric materials by FT-IR, XRD, SEM, BET, EDS, TGA and DTG indicates that their thermostable, amorphous and hierarchical porous architectures at microscopic scale (<300 nm) with reasonable surface area caused by the formation of ester bonds, leading to successful applications to adsorption of cationic dyes such as MB, MG and RB. Particularly, BA-S exhibits higher adsorption efficiency than BA-C on adsorbing MG with removal rate as 96.67 % at 60 min at 30 °C, and the maximum adsorption capacity of 742.5 mg g⁻¹ at 50 °C. Additionally, both polymeric materials maintained good removal rate, i.e. > 98 %, towards MG after four adsorption-desorption cycles under the same experimental conditions, i.e. pH = 7, 30 °C and initial concentration of dye at 50 mg L⁻¹. Adsorption models by kinetic and thermodynamic studies, as well as mechanism investigations by EDS, FT-IR, zeta potential and XPS further reveal that, firstly, chemical adsorption is still dominant driven by electrostatic and hydrogen bonding interactions between electron-rich network-like polymeric architecture and cationic dyes; secondly, monomolecular layer adsorption and multiple-molecular layer adsorption can be switched by those polymers according to variable temperatures and different cationic dyes; thirdly, the adsorption process at the solid-liquid interface is a spontaneous one.

通过硼酸（BA）和淀粉(S)/纤维素(C)的一锅水热反应，分别制备了BA-S和BA-C两种网状交联多糖。通过FT-IR、XRD、SEM、BET、EDS、TGA和DTG对这些高分子材料的表征表明，它们在微观尺度（< 300 nm）上具有热稳定性、无定形和分层多孔结构，并且由于酯键的形成而具有合理的表面积，从而成功地应用于吸附MB、MG和RB等阳离子染料。其中，BA-S对MG的吸附效率高于BA-C，在30˚C条件下，60 min的去除率为96.67%，在50˚C条件下的最大吸附量为742.5 MG g-1。此外，在相同的实验条件下，即pH = 7, 30°C，染料初始浓度为50 MG L-1，经过4次吸附-解吸循环后，两种高分子材料对MG的去除率均保持在98%以上。动力学和热力学吸附模型的研究以及EDS、FT-IR、zeta电位和XPS的机理研究进一步表明：第一，化学吸附仍然主要由静电和富电子网状聚合物结构与阳离子染料之间的氢键相互作用驱动；其次，这些聚合物可以根据不同的温度和不同的阳离子染料切换单分子层吸附和多分子层吸附；第三，固液界面处的吸附过程是自发的。

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