Reactive & Functional Polymers最新文献

Balancing flame retardancy, mechanical properties, and transparency in epoxy resins with a phosphorus/sulfur-containing oligomer synthesized via thiol-ene click chemistry 通过巯基化学合成含磷/含硫低聚物，平衡环氧树脂的阻燃性、机械性能和透明度

IF 5.1 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers

Pub Date : 2025-12-06 DOI: 10.1016/j.reactfunctpolym.2025.106599

Fei Zhu , Xianwen Yan , Bohao Lv , Sai Zhang , Mengyan Zeng , Wenqiang Qiao

The development of high-performance epoxy resins (EPs) is crucial for advanced applications, but is often challenged by a need to balance flame retardancy, mechanical strength, and transparency. This study addresses this challenge by developing a novel oligomeric flame retardant (PB-TBPO), which was synthesized through a thiol-ene click chemistry between polybutadiene (PB) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The well-designed PB-TBPO exhibited remarkable flame-retardant efficiency, leveraging the synergistic effect of phosphorus and sulfur elements. Impressively, with a minimal loading of only 3 phr, the EP composite attained the highest vertical burning (UL-94) rating of V-0 and a limiting oxygen index (LOI) of 27.7 %. Cone calorimeter tests (CCT) further demonstrated significant reductions in peak heat release rate (PHRR, 32.1 %) and fire growth rate (FIGRA, 52.4 %) compared to neat EP. The mechanical properties were substantially enhanced; the composite with 5 phr PB-TBPO showed dramatic increases in flexural strength, flexural modulus, impact strength, tensile strength, elongation at break, and Young's modulus by 203 %, 51.4 %, 632 %, 192 %, 343 %, and 48.7 %, respectively. Moreover, dynamic mechanical analysis (DMA) and ultraviolet-visible (UV–vis) spectroscopy confirmed that the composites maintained a high glass transition temperature (T_g, 182 °C) and outstanding transparency (87.4 % transmittance at 780 nm). Consequently, this work presents a viable strategy for designing multifunctional oligomeric flame retardants to produce advanced EP composites with exceptional flame retardancy, mechanical robustness, and optical transparency for broad applications.

高性能环氧树脂（EPs）的开发对于先进应用至关重要，但经常受到需要平衡阻燃性，机械强度和透明度的挑战。本研究通过聚丁二烯（PB）和9,10-二氢-9-氧-10-磷菲-10-氧化物（DOPO）之间的巯基键合反应合成了一种新型低聚阻燃剂（PB- tbpo）。经过精心设计的PB-TBPO利用磷和硫元素的协同作用，表现出显著的阻燃效果。令人印象深刻的是，在最小负荷仅为3 phr的情况下，EP复合材料达到了最高的垂直燃烧（UL-94）等级V-0和极限氧指数（LOI） 27.7%。锥形量热计测试（CCT）进一步表明，与纯EP相比，峰值热释放率（PHRR, 32.1%）和火焰生长率（FIGRA, 52.4%）显著降低。力学性能显著提高；添加5phr PB-TBPO的复合材料的抗弯强度、抗弯模量、冲击强度、抗拉强度、断裂伸长率和杨氏模量分别提高了203%、51.4%、632%、192%、343%和48.7%。此外，动态力学分析（DMA）和紫外可见光谱（UV-vis）证实，复合材料保持了较高的玻璃化转变温度（Tg, 182°C）和出色的透明度（在780 nm处透过率为87.4%）。因此，这项工作为设计多功能低聚阻燃剂提供了一种可行的策略，以生产具有卓越阻燃性，机械稳健性和光学透明度的先进EP复合材料。

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引用次数: 0

Synthesis of polyalumino-titanocarbonsilane from a commercial polycarbosilane 以商品聚碳硅烷为原料合成聚铝钛碳硅烷

IF 5.1 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers

Pub Date : 2025-12-06 DOI: 10.1016/j.reactfunctpolym.2025.106600

Xiaohong Li , Cai Ye , Jianjun Chen , Zahoor Ahmad

In this work, a novel polyalumino-titanocarbonsilane (PATCS) was synthesized by the reaction of commercial spinning grade polycarbosilane (PCS) with aluminum acetylacetonate (Al(AcAc)₃) and titanocene dichloride (Ti(C₅H₅)₂Cl₂). A dense SiC ceramic fiber was obtained by melt-spinning, thermal oxidation curing in relatively short curing time (∼ 1 h) at 473 K, and pyrolysis of the PATCS. To reveal the thermal polymerization mechanisms of PATCS, the as-synthesized PATCS were investigated by FT-IR, XPS, GPC, ²⁹Si NMR, TG, rotary rheometer, metaloscope. The results showed that the PATCS was consisted of SiH bonds, Si-CH₃ groups, Si-CH₂-Si groups, and a small amount of SiO bonds and CC bonds. The polymerization mechanism of PATCS involves the reactions of SiH bonds in polycarbosilane (PCS) with TiCl, CC, and Al-O-R groups to form SiTi, Si-C-C, Si-C-Ti, and Si-O-Al bonds. The TGA results showed that mass residual rate under high temperature had an obviously increase with adding Al(AcAc)₃ and Ti(C₅H₅)₂Cl₂. The PCS, PACS and PATCS were pseudoplastic fluid and their viscosity decreased with rising temperature. Suitable melt-spinning temperature range of the PATCS-1 was 553–593 K. A continuous PATCS-1 fiber with a diameter of 29.33 ± 2.99 μm was obtained by the melt-spinning process at 553 K. The Ti element and CC bonds in PATCS might accelerate the curing of the PATCS fibers in air. The study provides a facile synthetic method for preparing a novel precursor polymer, which serves as a precursor for high-performance double-metal heterogeneous element-containing SiC ceramic fiber and can be efficiently cured in air.

本文以工业纺丝级聚碳硅烷（PCS）为原料，与乙酰丙酮铝（Al(AcAc)3）和二氯化茂钛（Ti(C5H5)2Cl2）反应合成了新型聚铝-钛碳硅烷（PATCS）。通过熔融纺丝、473 K下较短的固化时间（~ 1 h）的热氧化固化和PATCS的热解，得到了致密的SiC陶瓷纤维。为了揭示PATCS的热聚合机理，采用FT-IR、XPS、GPC、29Si NMR、TG、旋转流变仪、金相显微镜对合成的PATCS进行了表征。结果表明，PATCS由SiH键、Si-CH3基团、Si-CH2-Si基团以及少量的SiO键和CC键组成。聚碳硅烷（PCS）中的SiH键与TiCl、CC和Al-O-R基团反应形成SiTi、Si-C-C、Si-C-Ti和Si-O-Al键。TGA结果表明，加入Al(AcAc)3和Ti(C5H5)2Cl2后，高温下的质量残留率明显提高。PCS、PACS和PATCS均为假塑性流体，其粘度随温度升高而降低。PATCS-1的适宜熔融纺丝温度范围为553 ~ 593 K。在553 K温度下，采用熔融纺丝工艺获得了直径为29.33±2.99 μm的连续型PATCS-1纤维。PATCS中的Ti元素和CC键可以加速PATCS纤维在空气中的固化。本研究为制备新型前驱体聚合物提供了一种简便的合成方法，该前驱体聚合物可作为高性能双金属非均相元素SiC陶瓷纤维的前驱体，并可在空气中高效固化。

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引用次数: 0

Feasibility of an eco-friendly high-solids waterborne polyurethane ink for DIW 3D printing 用于DIW 3D打印的环保型高固体水性聚氨酯油墨的可行性

IF 5.1 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers

Pub Date : 2025-12-04 DOI: 10.1016/j.reactfunctpolym.2025.106584

Jhu-Lin You , Kai-Yen Chin , Yan-Ting Lai , Kuei-Ting Hsu , Shu-Mei Chang

Waterborne polyurethane (WPU) has attracted attention as an environmentally sustainable material for various applications. In this study, a high-solid-content WPU emulsion was successfully developed as an ink for direct ink writing (DIW) three-dimensional (3D) printing. Its viscosity was controlled in the range of 10² to 10⁶ mPa·s through surfactants and crosslinkers. A polyethylene glycol (PEG) surfactant content of 4 wt% resulted in the most stable low-viscosity emulsion (10² mPa·s). Additionally, the viscosity of the WPU emulsion was adjusted by introducing the cross-linking agent 2,2-Bis[4-(glycidyloxy)phenyl]propane, 4,4′-isopropylidenediphenol diglycidyl ether (BADGE). At a crosslinker content of 7 wt%, the WPU dispersion became highly viscous (10⁶ mPa·s). Its rheological properties included shear thinning behavior, high yield stress (1.7 kPa), a rheological phase angle of 46.80°, and a storage modulus of 10⁴ Pa; these all meet the requirements for DIW 3D printing. Finally, DIW 3D printing was performed using various movement speeds and nozzle flow rates, to evaluate the printing performance and determine the optimal parameters for DIW 3D printing with WPU materials. The high-solid-content WPU system developed in this work can be effectively applied to create 3D structures without generating air pollution or toxic wastewater, ensuring ecological sustainability and environmental safety.

水性聚氨酯（WPU）作为一种环境可持续发展的材料，在各种领域得到了广泛的应用。在这项研究中，成功开发了一种高固含量的WPU乳液，作为直接墨水书写（DIW）三维（3D）打印的油墨。通过表面活性剂和交联剂将其粘度控制在102 ~ 106 mPa·s之间。当聚乙二醇（PEG）表面活性剂含量为4 wt%时，乳液的稳定性最高（102 mPa·s）。此外，通过引入交联剂2,2-双[4-（缩水甘油氧基）苯基]丙烷，4,4 ' -异丙二酚二缩水甘油醚（BADGE）来调节WPU乳液的粘度。交联剂含量为7 wt%时，WPU分散体具有高粘性（106 mPa·s）。其流变特性包括剪切变薄，高屈服应力（1.7 kPa），流变相角为46.80°，存储模量为104 Pa；这些都符合DIW 3D打印的要求。最后，采用不同的运动速度和喷嘴流量进行DIW 3D打印，以评估WPU材料DIW 3D打印的打印性能，并确定最佳参数。本工作开发的高固含量WPU系统可以有效地应用于创建3D结构，而不会产生空气污染或有毒废水，确保生态可持续性和环境安全。

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引用次数: 0

Multifunctional polyamides: Designing rigid and flexible architectures for flame retardant, dye adsorbent, single-material white-light emitting, and color-tunable photoluminescent systems 多功能聚酰胺：设计阻燃、染料吸附剂、单一材料白光发射和颜色可调光致发光系统的刚性和柔性结构

IF 5.1 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers

Pub Date : 2025-12-03 DOI: 10.1016/j.reactfunctpolym.2025.106597

Osama Younis , Aya Harby , Esam A. Orabi , Adel M. Kamal El-Dean , Marwa M. Sayed , Mahmoud S. Tolba

Two novel polyamides, Poly(Oxa) and Poly(Pip), were successfully synthesized through the polycondensation of 1,4-bis(2-chloroacetamido)benzene with either 5,5′-(1,4-phenylene)bis(1,3,4-oxadiazole-2-thiol) or piperazine, respectively. Comprehensive computational, structural, morphological, thermal, and photophysical analyses revealed distinct structure–property relationships governed by the nature of the polymer backbone. Poly(Oxa), containing a heteroaromatic framework, exhibited pronounced conjugation and semi-crystallinity, confirmed by FT-IR and XRD analyses. This architecture imparted exceptional thermal stability (char yield: 42.4 %), high flame retardancy (LOI = 34.5 %), and a heterogeneous morphology with strong π–π stacking interactions, which enhanced methylene blue adsorption. Remarkably, Poly(Oxa) displayed excitation-dependent photoluminescence, shifting from deep-blue to white-light emission, suggesting the contribution of both local excited and charge-transfer states. In contrast, Poly(Pip), comprising aliphatic piperazine units, exhibited a highly crystalline, densely packed morphology, superior initial thermal stability, and red-shifted excimeric emission. However, its lower char yield and reduced dye adsorption efficiency reflected the limited π-conjugation of its structure. Density functional theory calculations provided molecular-level validation, revealing significantly stronger intermolecular interactions in Poly(Oxa) compared to Poly(Pip) and larger affinity of Poly(Oxa) for the methylene blue dye. Overall, this study demonstrates that molecular rigidity and backbone design play pivotal roles in dictating the thermal, morphological, and optical properties of polyamides. The contrasting behaviors of Poly(Oxa) and Poly(Pip) establish a rational framework for tailoring advanced polymeric materials with tunable luminescence, enhanced stability, and multifunctional potential for optoelectronic and environmental applications.

以1,4-双（2-氯乙酰氨基）苯为原料，分别与5,5′-（1,4-苯基）双（1,3,4-恶二唑-2-硫醇）或哌嗪缩聚合成了聚（Oxa）和聚（Pip）两种新型聚酰胺。综合计算、结构、形态、热和光物理分析揭示了聚合物主链性质所支配的独特结构-性能关系。FT-IR和XRD分析证实，含有杂芳骨架的聚氧杂氧杂醚具有明显的共轭性和半结晶性。这种结构赋予了优异的热稳定性（炭产率：42.4%），高阻燃性（LOI = 34.5%），以及具有强π -π堆叠相互作用的非均相形态，从而增强了亚甲基蓝的吸附。值得注意的是，Poly（Oxa）表现出激发依赖的光致发光，从深蓝色光发射到白光发射，表明局部激发态和电荷转移态都有贡献。相比之下，含有脂肪族哌嗪单元的聚（Pip）表现出高度结晶，密集堆积的形态，优越的初始热稳定性和红移的准分子发射。然而，其较低的炭产率和较低的染料吸附效率反映了其结构的有限π共轭。密度泛函理论计算提供了分子水平的验证，揭示了与聚（Pip）相比，聚（Oxa）的分子间相互作用明显更强，聚（Oxa）对亚甲基蓝染料的亲和力更大。总的来说，本研究表明分子刚度和主链设计在决定聚酰胺的热、形态和光学性能方面起着关键作用。Poly（Oxa）和Poly（Pip）的对比行为为定制具有可调谐发光，增强稳定性和光电和环境应用多功能潜力的先进聚合物材料建立了合理的框架。

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引用次数: 0

Building a potentially active NiFe2O4 embedded lignin framework for adsorption coupled photocatalytic degradation and fluorescence detection of doxorubicin and safranin-O 构建具有潜在活性的NiFe2O4包埋木质素框架用于吸附耦合光催化降解和荧光检测阿霉素和红花素o

IF 5.1 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers

Pub Date : 2025-11-30 DOI: 10.1016/j.reactfunctpolym.2025.106589

Nidhi , Deepika Sharma , Minakshi , Simranjit Kaur , Sandeep Bansal , Paramdeep Kaur , Sonal Singhal

Population expansion and industrial expansion have intensified water consumption, which consequently contributes to water contamination. To tackle this challenge, binary sustainable materials, namely lignin‑nickel ferrite (LNF) composites, were fabricated via a simple hydrothermal route and innovatively explored for their dual role in photodegradation and fluorescence sensing applications. Integrating lignin with photocatalytic ferrite particles not only improves the catalytic efficiency of nickel ferrite, but also extends its applicability towards fluorescence-based pollutant detection. Detailed characterizations, including XRD, FT-IR, FE-SEM, HR-TEM, XPS, BET, VSM, UV-DRS analyses, were carried out to investigate the structural, morphological and optical properties of the devised composites. Compared with pristine nickel ferrite, LNF composites revealed markedly improved catalytic removal efficiency, attributable to synergistic adsorption ensued from the lignin counterpart. Among them, the LNF2 composite, with the highest lignin loading, displayed best efficacy, achieving removal of 94 % (180 min) for doxorubicin (DOX) and 98 % (90 min) for safranin-O (SO). Moreover, LNF2 was successfully deployed as fluorescent sensor, enabling sensitive detection of DOX and SO in aqueous samples with detection limits of 1.422 μM and 1.273 μM, respectively. Real sample analysis further substantiated the feasibility of LNF composites for diverse environmental samples. Overall, the present study elicits fresh insights into the formulation of efficient and sustainable bifunctional materials for simultaneous removal and detection of pollutants.

人口扩张和工业扩张加剧了水的消耗，从而导致水污染。为了解决这一挑战，通过简单的水热方法制备了二元可持续材料，即木质素-镍铁氧体（LNF）复合材料，并创新地探索了其在光降解和荧光传感应用中的双重作用。将木质素与光催化铁氧体颗粒结合，不仅提高了镍铁氧体的催化效率，而且扩大了其在基于荧光的污染物检测中的适用性。采用XRD、FT-IR、FE-SEM、HR-TEM、XPS、BET、VSM、UV-DRS等方法对复合材料的结构、形貌和光学性能进行了表征。与原始铁氧体镍相比，LNF复合材料的催化去除效率明显提高，这是由于木质素对其的协同吸附。其中，木质素负荷最高的LNF2复合材料效果最佳，对阿霉素（DOX）的去除率为94% (180 min)，对红花素- o （SO）的去除率为98% （90 min）。此外，LNF2作为荧光传感器成功部署，在水溶液中实现了DOX和SO的灵敏检测，检测限分别为1.422 μM和1.273 μM。实际样品分析进一步证实了LNF复合材料在不同环境样品中的可行性。总的来说，本研究为同时去除和检测污染物的高效和可持续双功能材料的配方提供了新的见解。

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引用次数: 0

Thiourea-based hybrid sPEEK membranes using a Sol-Gel approach: Elaboration of stabilized hybrid sPEEK membranes 采用溶胶-凝胶方法的硫脲基混合sPEEK膜：稳定混合sPEEK膜的细化

IF 5.1 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers

Pub Date : 2025-11-30 DOI: 10.1016/j.reactfunctpolym.2025.106588

E. Ferri , C. Tougne , M. Daoudi , F. Gouanvé , O. Gain , L. Gonon , V.H. Mareau , H. Mendil-Jakani , A. El Kaddouri , J.C. Perrin , J. Dillet , O. Lottin , C.C. Santini , E. Espuche , V. Dufaud

Chemically stabilized hybrid membranes derived from sulfonated Poly (Ether Ether Ketone) membrane (sPEEK) have been developed for fuel cell applications. The synthesis is based on Sol Gel (SG) chemistry involving the in situ growth of a reactive SG phase containing antioxidant thiourea functions, namely N,N′-bis[3-(triethoxysilyl)propyl]thiourea (HTU) and N-phenyl,N′[3-(triethoxysilyl)propyl] thiourea (TTU) for SG uptake up to 20 wt%. Well-nanostructured sPEEK membranes with intact thiourea functional groups and a SG phase highly condensed (up to 85 %) and homogeneously dispersed are obtained. Despite the incorporation of the reactive silicate phase, the functional properties of the membrane electrolyte - namely thermal stability, water uptake, gas permeability, and ionic conductivity - are retained. Accelerated ageing tests in H₂O₂ solution demonstrate the ability of the sol-gel (SG) phase to mitigate oxidative degradation, thereby significantly enhancing membrane durability.

由磺化聚醚醚酮膜（sPEEK）衍生的化学稳定杂化膜已被开发用于燃料电池。该合成基于溶胶-凝胶（SG）化学，涉及含有抗氧化硫脲功能的反应性SG相的原位生长，即N，N ' -双[3-（三乙基氧基硅基）丙基]硫脲（HTU）和N-苯基，N '[3-（三乙基氧基）丙基]硫脲（TTU）， SG吸收率高达20%。获得了具有完整硫脲官能团和SG相高度凝聚（高达85%）和均匀分散的纳米结构良好的sPEEK膜。尽管加入了活性硅酸盐相，膜电解质的功能特性——即热稳定性、吸水性、气体渗透性和离子电导率——仍被保留。在h2o2溶液中的加速老化试验证明了溶胶-凝胶（SG）相减轻氧化降解的能力，从而显着提高了膜的耐久性。

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引用次数: 0

Biogenic carrageenan-silver nanocomposite based on Argemone maxicana for efficient photocatalytic degradation of ciprofloxacin in contaminated water 生物源卡拉胶-银纳米复合材料对污染水中环丙沙星的高效光催化降解研究

IF 5.1 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers

Pub Date : 2025-11-30 DOI: 10.1016/j.reactfunctpolym.2025.106587

Shilpa Kumari , Seema Kumari , Asha Kumari , Neha Kondal , Rahul Sharma

Herein, we demonstrate an eco-friendly sustainable synthesis of silver nanoparticles (AgNPs) and silver-carrageenan nanocomposites (Ag-Carr NCs) by a green approach, using leaf extract of Argemone mexicana. The ubiquitous presence of pharmaceutical pollutants, especially antibiotic e.g. Ciprofloxacin (CIP), in water environment is now a serious environmental issue, because the ability of long persistence and the detrimental effects on the living organism and human health in the aquatic system. In this study, we report a green photocatalyst for efficient CIP decomposing in the contaminated water. Carrageenan, biodegradable and biocompatible biomaterial, has been employed as a capping layer for silver nanoparticles to improve their stability, dispersibility, and photocatalytic activity. The prepared NPs and NPs-C composites were analysed systematically with UV–Visible, XRD, FTIR, HRTEM, EDS, and XPS. Photocatalytic tests revealed that the as-prepared carrageenan-contained Ag nanocomposite presented excellent photocatalytic performance and removed 86.26 % CIP within 60 min under optimal conditions. Kinetic study suggested the effectiveness of the photocatalytic process; LC-MS was used to analyse the degradation intermediates before and after the reaction, which revealed the potential degradation pathway. This green nanocomposite not only provides an efficient support for removal of antibiotics, but also promotes the development of sustainable materials used for environmental remediation.

在此，我们展示了一种生态友好的可持续合成银纳米颗粒（AgNPs）和银-卡拉胶纳米复合材料（Ag-Carr NCs）的绿色方法，使用银银酮墨西哥叶提取物。水环境中普遍存在的药物污染物，特别是环丙沙星（CIP）等抗生素污染物，由于其长期存在的能力和对水生系统生物和人体健康的不利影响，已成为一个严重的环境问题。在本研究中，我们报道了一种绿色光催化剂，用于在污染水中高效分解CIP。卡拉胶是一种可生物降解和生物相容性的生物材料，被用作银纳米颗粒的封盖层，以提高其稳定性、分散性和光催化活性。采用uv -可见、XRD、FTIR、HRTEM、EDS、XPS对制备的NPs和NPs- c复合材料进行了系统分析。光催化实验表明，在最佳条件下，制备的含卡拉胶银纳米复合材料具有良好的光催化性能，在60 min内脱除了86.26%的CIP。动力学研究表明光催化过程是有效的；采用LC-MS对反应前后的降解中间体进行分析，揭示了潜在的降解途径。这种绿色纳米复合材料不仅为抗生素的去除提供了有效的支持，而且还促进了可持续环境修复材料的发展。

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引用次数: 0

Branched Fluoro-polyether copolymer for constructing polyvinyl chloride composites with reinforced antibiofouling performance 支链氟聚醚共聚物用于构建增强抗污性能的聚氯乙烯复合材料

IF 5.1 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers

Pub Date : 2025-11-30 DOI: 10.1016/j.reactfunctpolym.2025.106586

Liang Yan , Bin Wang , Rongxu Zhao , Ze Yang , Xiaolu Wu , Lin Shi

Polyvinyl chloride (PVC) is a widely used medical plastic, yet surface biofouling remains a critical limiting factor that affecting its application performance. Currently, immobilizing copolymers containing hydrophilic and fluorinated segments onto material surfaces via grafting or coating techniques has proven effective for constructing high-performance antifouling interfaces. However, the antifouling behavior of such copolymers in polymer blend, especially in PVC plastics, remains insufficiently elucidated. Herein, we designed and synthesized a series of novel branched copolymers with well-defined architectures comprising fluorinated cores and poly(ethylene glycol) peripheral segments, along with control polymers including poly(ethylene glycol) and poly(hexafluorobutyl acrylate). These polymers were blended with PVC to prepare composite films. UV–vis, DSC, TGA, SEM, tensile testing revealed that although the fluorinated core exhibits poor compatibility with PVC, the polyether segments can enhance the copolymer's compatibility with PVC. The composite films exhibited decent transparency, low T_g, good thermal stability, and superior mechanical properties. Antifouling characterization revealed that the synergistic effect between the fouling-resistant property of polyether segments and the fouling-release capability of fluorinated segments in the composite films lead to significantly enhanced antifouling performance. The optimal film exhibited 98 % inhibition of E. coli adhesion and platelet attachment, and minimal BSA adsorption.

聚氯乙烯（PVC）是一种应用广泛的医用塑料，但表面生物污染是影响其应用性能的关键限制因素。目前，通过接枝或涂层技术将含有亲水性和氟化段的共聚物固定在材料表面已被证明是构建高性能防污界面的有效方法。然而，这种共聚物在聚合物共混物中的防污行为，特别是在PVC塑料中的防污行为，仍然没有得到充分的阐明。在此，我们设计并合成了一系列具有明确结构的新型支链共聚物，包括氟化核心和聚（乙二醇）外围段，以及包括聚（乙二醇）和聚（六氟丙烯酸丁酯）在内的控制聚合物。这些聚合物与PVC混合制成复合薄膜。UV-vis， DSC， TGA， SEM，拉伸测试结果表明，氟化芯与PVC的相容性较差，聚醚段可以增强共聚物与PVC的相容性。复合膜具有良好的透明性、低Tg、良好的热稳定性和优异的力学性能。防污性能表征表明，复合膜中聚醚段的耐污性能与氟化段的脱污能力之间的协同作用显著提高了复合膜的防污性能。最佳膜对大肠杆菌粘附和血小板粘附的抑制率为98%，对牛血清白蛋白的吸附最小。

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引用次数: 0

Molecular-scale investigation of anisotropic actuation and hysteretic behavior in oriented PNIPAM hydrogels 定向PNIPAM水凝胶各向异性驱动和滞后行为的分子尺度研究

IF 5.1 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers

Pub Date : 2025-11-30 DOI: 10.1016/j.reactfunctpolym.2025.106585

Yuri Jeon, Joonmyung Choi

Poly(N-isopropylacrylamide) (PNIPAM) is a thermoresponsive hydrogel suitable for biomedical actuators because of its reversible behavior near body temperature. Fibrillation of PNIPAM hydrogels enhances design flexibility by enabling programmable deformation. In this study, we employ molecular dynamics simulations to investigate the mechanism by which the initial molecular orientation and water-induced microstructural evolution govern the macroscopic deformation behavior of PNIPAM hydrogels. The results reveal that the degree of the initial chain alignment plays a critical role in determining both the magnitude and direction of water-induced swelling. Water molecules preferentially diffuse between the aligned, pre-extended chains, causing amplified expansion perpendicular to the alignment. Interestingly, oriented PNIPAM exhibits sustained shrinkage along the alignment direction during initial hydration–dehydration cycles, leading to irreversible deformation hysteresis. According to dynamic structural analysis, this result can be attributed to the spatial constraints of the densely aligned polymer chains that restrict the free conformational transition of the chains. Repeated water absorption–release cycles promote microstructural reorganization, causing the deformation response to gradually converge from a hysteretic to a reversible form. These findings offer molecular insights into the shape-memory behavior of fibrillated PNIPAM hydrogels and establish a theoretical framework for designing actuators with tunable and reliable actuation performance.

聚n -异丙基丙烯酰胺（PNIPAM）是一种热响应性水凝胶，由于其在体温附近具有可逆性，适合用于生物医学驱动器。PNIPAM水凝胶的纤颤通过实现可编程变形来增强设计灵活性。在这项研究中，我们采用分子动力学模拟来研究PNIPAM水凝胶的初始分子取向和水诱导的微观结构演变控制宏观变形行为的机制。结果表明，初始链的排列程度对水致膨胀的大小和方向起着关键作用。水分子优先在排列的预延伸链之间扩散，导致垂直于排列的放大膨胀。有趣的是，在初始水化-脱水循环过程中，取向PNIPAM沿着取向方向持续收缩，导致不可逆的变形滞后。根据动态结构分析，这一结果可归因于密集排列的聚合物链的空间约束，限制了链的自由构象转变。反复的吸水-释放循环促进了微观结构的重组，使变形响应从滞后形式逐渐收敛到可逆形式。这些发现为纤维化PNIPAM水凝胶的形状记忆行为提供了分子视角，并为设计具有可调和可靠驱动性能的致动器建立了理论框架。

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引用次数: 0

Synthesis and characterization of effective ABS-PMDA-ES composites for the removal of malachite green from aqueous media ABS-PMDA-ES去除孔雀石绿复合材料的合成与表征

IF 5.1 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers

Pub Date : 2025-11-29 DOI: 10.1016/j.reactfunctpolym.2025.106583

Arya S. Raj, M. Loganathan, A. Murugesan

Post-consumed Acrylonitrile Butadiene Styrene (ABS) is a challenge tasks in the waste management system and discharge of synthetic dyes into water contributes severely to environment degradation. The motive of this research is to develop a sustainable and low-cost adsorbent by chemical functionalization of Recycled Acrylonitrile Butadiene Styrene (RABS) with pyromellitic dianhydride (PMDA) and eggshell (ES) yielding ABS-PMDA-ES composite for effective removal of Malachite green (MG) dye from aqueous solution. The incorporation of PMDA (-COOH and -C=O) and ES (-OH, -NH₂, -CaO, -CO-NH-, -NO₂, -COOH and -C=O) significantly enhanced porosity and adsorption capacity of MG molecules. The surface and structural and thermal properties of the ABS-PMDA-ES were characterized by FTIR, XRD, SEM, BET, HRTEM-SEM and DSC analytic techniques. The adsorption parameters such as initial dye concentration (100 ppm), adsorbent dosage (60 mg), pH (6), contact time (120 min) and temperature (315 K) via batch adsorption process. The adsorption kinetics followed pseudo-second-order model with an R² value of 0.993, suggesting chemisorption mechanism. The adsorption isotherm was best fitted Freundlich model (R² = 0.997) confirming multilayer adsorption of MG onto ABS-PMDA-ES. Thermodynamic evaluations demonstrated that the adsorption process was both endothermic and spontaneous. The maximum adsorption capacity (q_e = 80.15 mg/g) for the adsorption of MG onto ABS-PMDA-ES was high compared to carbon nanotube/polyaniline composite (q_e = 13.95 mg/g), ferromagnetic gum grafted poly (n-isopropylacrylamide-co-acrylamide/magnetic nanocomposite (q_e = 19.77 mg/g), and polysaccharide based magnetic gel (q_e = 17.46 mg/g). Overall, the research demonstrated ABS-PMDA-ES composite not only provides a sustainable solution for plastic waste valorization but also serves as an efficient, reusable and eco-friendly adsorbent for the removal of MG dye from wastewater.

丙烯腈-丁二烯-苯乙烯（ABS）耗用后是废物处理系统中的一个难题，合成染料向水中排放会严重破坏环境。本研究的目的是通过将回收的丙烯腈-丁二烯-苯乙烯（RABS）与邻苯二甲酸二酐（PMDA）和蛋壳（ES）进行化学功能化，制备ABS-PMDA-ES复合材料，开发一种可持续的低成本吸附剂，以有效去除水中的孔雀石绿（MG）染料。PMDA （- cooh和- c =O）和ES （- oh, - nh2, - cao, - co - nh -, - no2， - cooh和- c =O）的掺入显著增强了MG分子的孔隙度和吸附能力。采用FTIR、XRD、SEM、BET、HRTEM-SEM和DSC等分析技术表征了ABS-PMDA-ES的表面、结构和热性能。对初始染料浓度（100 ppm）、吸附剂用量（60 mg）、pH(6)、接触时间（120 min）、温度（315 K）等吸附参数进行了间歇吸附。吸附动力学符合拟二级模型，R2值为0.993，表明吸附机理为化学吸附。吸附等温线最符合Freundlich模型（R2 = 0.997），证实MG在ABS-PMDA-ES上有多层吸附。热力学评价表明，吸附过程既吸热又自发。ABS-PMDA-ES对mg的最大吸附量（qe = 80.15 mg/g）高于碳纳米管/聚苯胺复合材料（qe = 13.95 mg/g）、铁磁胶接枝聚n-异丙基丙烯酰胺-共丙烯酰胺/磁性纳米复合材料（qe = 19.77 mg/g）和多糖基磁性凝胶（qe = 17.46 mg/g）。总体而言，研究表明ABS-PMDA-ES复合材料不仅为塑料废物的再生提供了可持续的解决方案，而且是一种高效、可重复使用和环保的吸附剂，可用于去除废水中的MG染料。

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