European Polymer Journal最新文献_第6页

Scalable Polymerization-Induced Crystallization-Driven Self-Assembly toward 3D multilayer rhombic nanosheets 可伸缩聚合诱导结晶驱动的三维多层菱形纳米片自组装

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-12-13 DOI: 10.1016/j.eurpolymj.2025.114445

Tianwen Liu , Yiming Wang , Xuelei Dong , Yanwei Zhang , Min Wang , Xiongwei Qu , Shengli Chen

The construction of three-dimensional (3D) nanostructures via block copolymer self-assembly remains challenging due to insufficient thermodynamic driving forces and limitations in scalable fabrication. Herein, we report a robust polymerization-induced crystallization-driven self-assembly (PI-CDSA) strategy for the in situ synthesis and hierarchical self-assembly of poly(ethylene glycol monomethyl ether)-block-poly(L-lactide) (mPEG-b-PLLA) diblock copolymers in γ-butyrolactone at room temperature. By synergizing ring-opening polymerization with crystallization-driven assembly, we achieved the scalable fabricated well-defined 3D multilayer rhombic nanosheets with high morphological uniformity and macroscopic dispersibility. The geometry of the nanosheets, including edge length, surface area, and layer number, can be precisely controlled by tuning the degrees of polymerization of the PLLA block and mPEG macroinitiator. Systematic investigations using TEM, SEM, AFM, and OM revealed a clear morphological evolution from spherical micelles to 2D rhombic lamellae and ultimately to 3D multilayered stacked nanosheets. This work not only demonstrates the potential of PI-CDSA as a scalable and programmable platform for constructing complex 3D nanoparticles but also provides mechanistic insights into hierarchical self-assembly, with promising applications in nanomedicine and energy storage.

由于热力学驱动力不足和可扩展制造的限制，通过嵌段共聚物自组装构建三维（3D）纳米结构仍然具有挑战性。在此，我们报道了一个强大的聚合诱导结晶驱动自组装（PI-CDSA）策略，用于在室温下在γ-丁内酯中原位合成和分层自组装聚乙二醇单甲醚-嵌段聚l -丙交酯（mPEG-b-PLLA）二嵌段共聚物。通过开环聚合和结晶驱动组装的协同作用，我们获得了可扩展的、具有良好形态均匀性和宏观分散性的三维多层菱形纳米片。通过调整聚乳酸嵌段和mPEG宏观引发剂的聚合程度，可以精确控制纳米片的几何形状，包括边缘长度、表面积和层数。通过TEM， SEM， AFM和OM的系统研究揭示了从球形胶束到二维菱形片层，最终到三维多层堆叠纳米片的清晰形态演变。这项工作不仅证明了PI-CDSA作为构建复杂3D纳米粒子的可扩展和可编程平台的潜力，而且还提供了分层自组装的机理见解，在纳米医学和能量存储方面具有前景。

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引用次数: 0

Structure and gelation properties of thermoresponsive bottlebrush hydrogels 热敏瓶刷水凝胶的结构与凝胶性能

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-12-13 DOI: 10.1016/j.eurpolymj.2025.114446

Apollinariya Yu. Konyakhina , Akmal Z. Umarov , Jessica Garcia , Foad Vashahi , Evgeniy V. Dubrovin , Elena N. Subcheva , Aleksandr I. Buglakov , Sergei S. Sheiko , Dimitri A. Ivanov

Thermosensitive bottlebrush triblock copolymers combining poly(N-isopropylacrylamide) (PNIPAM) and poly(ethylene glycol) (PEG) represent a promising class of responsive soft materials. We investigate their molecular morphology and gelation behavior using direct-space imaging, synchrotron small-angle X-ray scattering (SAXS), and coarse-grained simulations. Atomic Force Microscopy (AFM) revealed wormlike bottlebrush backbones, while PNIPAM end blocks were detected under specific conditions using modified substrates. Transmission and scanning transmission electron microscopy (TEM/STEM) with negative staining corroborated AFM observations and provided consistent contour-length distributions. Variable-temperature SAXS revealed fully reversible structural reorganization upon heating above the PNIPAM LCST. This transition was marked by the emergence of an ordered gel network, evidenced by an interference peak corresponding to interdomain spacing and form-factor oscillations associated with PNIPAM micelles. Analysis indicated modest micelle growth while the interdomain spacing remained constant. Complementary dissipative particle dynamics simulations reproduced these features and revealed a crossover at ϕ_pol ≈ 0.04, where bridging subchains dominate network formation. Together, these results provide a multiscale understanding of bottlebrush copolymer gelation and identify key parameters controlling their responsive behavior.

结合聚n -异丙基丙烯酰胺（PNIPAM）和聚乙二醇（PEG）的热敏瓶刷三嵌段共聚物代表了一类有前途的响应性软材料。我们使用直接空间成像、同步加速器小角度x射线散射（SAXS）和粗粒度模拟来研究它们的分子形态和凝胶行为。原子力显微镜（AFM）显示蚓状瓶刷骨架，而PNIPAM端块在特定条件下使用改性底物检测。透射和扫描透射电子显微镜（TEM/STEM）阴性染色证实了AFM观察结果，并提供了一致的轮廓长度分布。变温SAXS在PNIPAM LCST上方加热后显示出完全可逆的结构重组。这种转变的标志是有序凝胶网络的出现，与PNIPAM胶束相关的域间间距和形状因子振荡相对应的干涉峰证明了这一点。分析表明胶束生长适度，而畴间间距保持不变。互补耗散粒子动力学模拟再现了这些特征，并揭示了在ϕpol≈0.04处的交叉，其中桥接子链主导网络形成。总之，这些结果提供了对瓶刷共聚物凝胶化的多尺度理解，并确定了控制其响应行为的关键参数。

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引用次数: 0

Self-healable and self-crosslinkable 1 K waterborne polyurethane loaded with curing agent 自愈合和自交联的1k水性聚氨酯负载固化剂

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-12-13 DOI: 10.1016/j.eurpolymj.2025.114448

Ismail Omrani, Mohammad Taghizadeh, Ali Salimi, Azizollah Nodehi

In this study, a waterborne polyurethane (WPU) adhesive with self-healing and self-crosslinking capabilities was developed via an encapsulation-based strategy, exhibiting exceptional chemical and physical properties. The encapsulation system employed in this study utilized a furan-functionalized crosslinker in combination with an unsaturated WPU, enabling uniform dispersion under aqueous conditions. A reversibly cross-linked WPU adhesive was achieved, exhibiting remarkable recyclability and outstanding self-healing performance via the Diels–Alder (DA) reaction. Using dynamic light scattering (DLS) and transmission electron microscopy (TEM), it was confirmed that the crosslinker-containing synthesized WPU particles have a particle size of 150 nm with a narrow size distribution. The thermal and mechanical properties of the resulting films were investigated using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile testing. The incorporation of the crosslinker led to a significant enhancement in mechanical performance. Notably, when the three-functionalized crosslinker (WPU3) was employed, the Young’s modulus increased markedly from 23 MPa to 81 MPa. Reversible cross-linked WPUs exhibit remarkable recyclability and a notable self-healing capability, achieving an initial tensile strength of up to 85 %. Due to its rich polar functionality, crosslinked WPU demonstrates robust bonding capabilities across a variety of substrates, including aluminum, steel, carbon steel, and epoxy composites. Thanks to specific structural design, the newly synthesized WPU showed reliable reusability, i.e., retaining 87 % of its original shear strength after multiple repair cycles. This study presents an effective method for self-curing WPU, enabling the development of high-performance, rapidly self-healing, and environmentally friendly adhesives.

在这项研究中，通过基于封装的策略开发了一种具有自修复和自交联能力的水性聚氨酯（WPU）粘合剂，具有优异的化学和物理性能。本研究中采用的包封体系利用呋喃功能化交联剂与不饱和WPU相结合，使其在水条件下均匀分散。通过Diels-Alder （DA）反应制备了一种可逆交联WPU胶粘剂，具有良好的可回收性和自愈性。通过动态光散射（DLS）和透射电镜（TEM）分析，证实了含交联剂的合成WPU颗粒粒径为150 nm，粒径分布较窄。利用差示扫描量热法（DSC）、热重分析（TGA）和拉伸测试研究了所得薄膜的热性能和力学性能。交联剂的掺入使机械性能显著提高。值得注意的是，当使用三功能化交联剂（WPU3）时，杨氏模量从23 MPa显著增加到81 MPa。可逆交联wpu具有显著的可回收性和显著的自愈能力，初始抗拉强度可达85%。由于其丰富的极性功能，交联WPU在各种基材上表现出强大的粘合能力，包括铝、钢、碳钢和环氧复合材料。由于特殊的结构设计，新合成的WPU具有可靠的可重复使用性，即在多次修复循环后，其原始抗剪强度仍保持87%。本研究提出了一种有效的WPU自固化方法，使高性能、快速自愈和环保胶粘剂的开发成为可能。

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引用次数: 0

Disproportionation termination mechanism in the radical polymerization of methacrylonitrile 甲基丙烯腈自由基聚合的歧化终止机理

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-12-11 DOI: 10.1016/j.eurpolymj.2025.114444

Liang Keyuan , Jiang Qimin , Huang Wenyan , Jiang Bibiao

The disproportionation termination mechanism in 1,1-disubstituted monomers, while critical for controlling polymer architecture, still lack comprehensive experimental validation. This study systematically investigates the disproportionation termination mechanism in the radical polymerization of methacrylonitrile (MAN), a prototypical 1,1-disubstituted monomer, employing an integrated analytical approach combining advanced NMR techniques (¹H NMR, ¹³C NMR, DEPT135-NMR, HSQC-NMR, and HMBC-NMR) with size exclusion chromatography (SEC). Our findings demonstrate that disproportionation in MAN polymerization occurs via hydrogen radical transfer from the β-methyl group of the chain radical. Significantly, this mechanistic framework extends to other methacrylate monomers: NMR analyses of poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA) prepared through radical polymerization reveal identical β-methyl-derived hydrogen transfer patterns. Furthermore, radical copolymerization of poly(methacrylonitrile) (PMAN) with styrene (initiated by AIBN) provides compelling supplementary evidence, confirming the specific β-methyl origin of the transferred hydrogen. These results resolve longstanding ambiguities surrounding disproportionation termination and establish a unified mechanistic paradigm for 1,1-disubstituted monomers.

1,1-二取代单体歧化终止机理虽然对控制聚合物结构至关重要，但仍缺乏全面的实验验证。本研究采用先进的核磁共振技术（1H NMR、13C NMR、DEPT135-NMR、HSQC-NMR和HMBC-NMR）和粒径不相容色谱（SEC）相结合的综合分析方法，系统地研究了甲基丙烯腈（MAN）自由基聚合过程中的歧化终止机理。我们的研究结果表明，歧化在MAN聚合中通过氢自由基从链自由基的β-甲基转移发生。值得注意的是，这种机制框架扩展到其他甲基丙烯酸酯单体：通过自由基聚合制备的聚甲基丙烯酸甲酯（PMMA）和聚甲基丙烯酸乙酯（PEMA）的核磁共振分析显示相同的β-甲基衍生的氢转移模式。此外，聚甲基丙烯腈（PMAN）与苯乙烯（由AIBN引发）的自由基共聚提供了令人信服的补充证据，证实了转移氢的特定β-甲基来源。这些结果解决了围绕歧化终止的长期歧义，并为1,1-二取代单体建立了统一的机制范式。

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引用次数: 0

Enzyme- and protein-modulated cascade mesophase transitions of polymeric formulations 酶和蛋白质调节的聚合物配方的级联中间相转变

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-12-08 DOI: 10.1016/j.eurpolymj.2025.114442

Keerthana Mulamukkil , Orr Sarid , Shahar Tevet , Roey J. Amir

Polymeric systems capable of undergoing multiple mesophase transitions are highly intriguing and hold great promise as next-generation materials for applications such as advanced drug delivery systems. While most reported examples rely on polymers functionalized with multiple types of stimuli-responsive groups, micellar formulations composed of diblock (DBA) and triblock amphiphiles (TBA) with similar hydrophilic to hydrophobic ratios offer a simpler alternative. Due to the distinct enzymatic degradability of these two polymeric architectures, mixed micelles can undergo sequential mesophase transitions in response to enzymatic activation: from co-assembled micelles to a TBA-based hydrogel/microgels, followed by further degradation into hydrophilic polymer fragments.

In biological environments, such systems encounter various proteins that can alter their behavior, and hence we investigated in this study how non-specific protein-polymer interactions influence their enzymatic degradation and subsequent mesophase transition. Specifically, we examined the effects of varying concentrations of the activating enzyme, porcine liver esterase, and bovine serum albumin (BSA), as a model protein known to form non-specific interactions with hydrophobic domains. Our findings revealed that higher enzyme concentrations accelerated DBA degradation, resulting in faster transition to the hydrogel mesophase. Increasing BSA concentration also accelerated DBA degradation and significantly shifted the mesophase transition to occur at a DBA to TBA ratio that was approximately 30% higher than in the absence of BSA. These results underscore the crucial role of both specific and non-specific protein-polymer interactions in dictating mesophase transitions, providing fundamental insights into the mechanisms governing the structural transformations of such mesophase-shifting polymeric formulations under biologically relevant conditions.

能够经历多个中间相转变的聚合物系统是非常有趣的，并且作为下一代材料具有很大的前景，例如先进的药物输送系统。虽然大多数报道的例子依赖于具有多种刺激反应基团的聚合物功能化，但由亲疏水比相似的双嵌段（DBA）和三嵌段两亲体（TBA）组成的胶束配方提供了一种更简单的替代方案。由于这两种聚合物结构具有不同的酶降解性，混合胶束可以在酶激活下经历连续的中间相转变：从共组装胶束到基于tba的水凝胶/微凝胶，然后进一步降解成亲水聚合物片段。在生物环境中，这样的系统会遇到各种可以改变其行为的蛋白质，因此我们在本研究中研究了非特异性蛋白质-聚合物相互作用如何影响它们的酶降解和随后的中间阶段转变。具体来说，我们研究了不同浓度的激活酶、猪肝酯酶和牛血清白蛋白（BSA）的影响，作为一种已知与疏水结构域形成非特异性相互作用的模型蛋白。我们的研究结果表明，较高的酶浓度加速了DBA的降解，导致更快地过渡到水凝胶中间期。BSA浓度的增加也加速了DBA的降解，并显著地改变了中间阶段的转变，使DBA与TBA的比例比没有BSA时高出约30%。这些结果强调了特异性和非特异性蛋白质-聚合物相互作用在决定中间相转变中的关键作用，为在生物学相关条件下控制这种中间相转移聚合物配方结构转变的机制提供了基本见解。

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引用次数: 0

Green preparation of ultra-high molecular weight narrow-distribution polystyrene by enzymatic synthesis 酶法合成超高分子量窄分布聚苯乙烯的绿色制备

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-12-07 DOI: 10.1016/j.eurpolymj.2025.114441

Xuanyu Zhang , Zongjiang Yu , Jihua Ma , Yu Liu , Huibin Zou , Chao Xu , Mo Xian

Enzymatic polymerization has been applied and demonstrated advantages in the preparation of polystyrene (PS). However, the weight-average molecular weight (M_w) of PS which is synthesized by enzymatic methods is usually below 1 × 10⁶ g/mol, and the current enzymatic methods cannot be applied in the production of ultra-high molecular weight (UHMW) polystyrene. In this study, we present an innovative enzymatic strategy employing horseradish peroxidase (HRP) in synergy with 5,5-dimethyl-1,3-cyclohexanedione (DM) to achieve precise synthesis of UHMW-PS. Through systematic optimization of the enzyme-initiator system, this study successfully fabricated PS with a record-breaking M_w of 3.4 × 10⁶ g/mol with narrow molecular weight distribution (PDI = 1.3), which surpassed prior enzymatic methods. Structural characterization by FTIR and ¹H NMR confirmed the integrity of the PS architecture, while SEM analysis revealed the formation of uniform nanospheres. This work not only elucidates the mechanistic role of enzyme-initiator synergy in regulating polymerization kinetics, but also breaks through the molecular weight limitations of traditional enzymatic systems, establishing a sustainable paradigm for green polymer synthesis.

酶促聚合在聚苯乙烯（PS）的制备中得到了广泛的应用，并显示出其优越性。然而，酶法合成的PS的均分子量（Mw）通常低于1 × 106 g/mol，目前的酶法还不能用于超高分子量聚苯乙烯的生产。在这项研究中，我们提出了一种创新的酶促策略，利用辣根过氧化物酶（HRP）与5,5-二甲基-1,3-环己二酮（DM）协同作用来实现UHMW-PS的精确合成。通过对酶-引发剂体系的系统优化，本研究成功制备了分子量为3.4 × 106 g/mol、分子量分布窄（PDI = 1.3）的破纪录的PS，超越了现有的酶促方法。FTIR和1H NMR的结构表征证实了PS结构的完整性，SEM分析显示形成了均匀的纳米球。这项工作不仅阐明了酶-引发剂协同作用在调节聚合动力学中的机理作用，而且突破了传统酶系统的分子量限制，为绿色聚合物合成建立了可持续的范例。

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引用次数: 0

Structural transformation and charge regulation of natural rubber-derived polymeric anticoagulants 天然橡胶聚合物抗凝剂的结构转化和电荷调节

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-12-05 DOI: 10.1016/j.eurpolymj.2025.114440

Katarzyna Byś , Pablo M. Blanco , Krzysztof Fink , Mateusz Psurski , Honorata Zachary , Miroslav Štěpánek , Peter Košovan , Mariusz Uchman

Heparin-mimicking polyelectrolytes act as anticoagulants in vivo due to their highly negative charge and high charge density. Unlike heparin, these polymers can be structurally tailored to tune chain length, sulfation degree and binding affinity, thereby modulating their therapeutic action. Here, we present two such heparin-mimicking polyelectrolytes, derived from natural rubber as an inexpensive and readily available raw material. These polymers, sodium poly((sulfamate-carboxylate) isoprene) (PISC) and poly((amino-carboxylate) isoprene (PACIS), contain sulfonate groups, as well as weakly acidic and basic groups on adjacent carbons, which enable us to tune their net charge in the biological pH range, while maintaining solubility and anticoagulation activity. Moreover, their activity may be further optimized by adjusting chain length. To test this tunability, we prepared a set of PISC- and PACIS-based copolymers varying in chain length and dispersity by post-polymerization modification of cis-1,4-polyisoprene. We characterized their structure and functionalization degree using various methods, further analyzing with potentiometric titration and computer simulations how their net charge varies with pH and affects aggregation. Despite aggregation, all PISC- and PACIS-based copolymers displayed heparin-mimicking activity, measured as activated partial thromboplastin time, while remaining biocompatible. In this context, the longest-chain copolymers performed best, extending aPTT by more than threefold in comparison with the control at 3.8 μg/mL, while maintaining biocompatibility up to 100 μg/mL across various cell lines. These findings demonstrate that natural rubber-derived polyelectrolytes provide a promising alternative to heparin for antithrombotic therapy.

模拟肝素的聚电解质由于其高负电荷和高电荷密度而在体内起抗凝血作用。与肝素不同，这些聚合物可以在结构上进行调整，以调整链长、磺化程度和结合亲和力，从而调节其治疗作用。在这里，我们提出了两种这样的模拟肝素的聚电解质，从天然橡胶中提取，作为一种廉价和容易获得的原料。这些聚合物，聚（（氨基-羧酸）异戊二烯钠）（PISC）和聚（氨基-羧酸）异戊二烯（PACIS），含有磺酸基团，以及相邻碳上的弱酸性和碱性基团，这使我们能够在生物pH范围内调节它们的净电荷，同时保持溶解性和抗凝活性。此外，通过调节链长可以进一步优化其活性。为了测试这种可调节性，我们制备了一组基于PISC和pacis的共聚物，这些共聚物通过顺式-1,4-聚异戊二烯的聚合后改性而改变了链长和分散性。我们用不同的方法表征了它们的结构和功能化程度，并进一步用电位滴定法和计算机模拟分析了它们的净电荷随pH值的变化和对聚集的影响。尽管聚合，所有的pisci -和PACIS-based共聚物显示肝素模拟活性，以活化的部分凝血活素时间来测量，同时保持生物相容性。在这种情况下，长链共聚物表现最好，与3.8 μg/mL的对照相比，aPTT延长了三倍以上，同时在各种细胞系之间保持高达100 μg/mL的生物相容性。这些发现表明，天然橡胶衍生的聚电解质为抗血栓治疗提供了一个有希望的肝素替代品。

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引用次数: 0

Main-chain azopoly(ether imide)s with low and high molecular mass targeted for versatile light-controlled applications 具有低分子质量和高分子质量的主链偶氮垄断（醚亚胺），用于多种光控应用

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-12-03 DOI: 10.1016/j.eurpolymj.2025.114434

Jolanta Konieczkowska , Anna Kozanecka-Szmigiel , Rafał Węgłowski , Mariola Siwy

This study focuses on linear azopoly(ether imide)s, a class of materials that has received comparatively limited attention in investigations of polarized-light-induced phenomena. We demonstrate that these polymers can be effectively employed to generate a wide range of photoresponsive effects, with their efficiency primarily governed by molar mass. The synthesized low-molar-mass azopolyimide exhibited highly efficient surface relief grating formation, producing sinusoidal modulations up to 700 nm in depth and achieving an efficiency approaching the theoretical maximum of 30 %. In contrast, the high-molar-mass azopolyimide showed substantial light-induced molecular ordering, resulting in pronounced and stable optical birefringence. This molecular ordering translated into effective mechanical bending in elastic foils and unidirectional alignment of liquid crystal molecules in LC cells. The bidirectional deformation of the azopolyimide further enabled the construction of a photo-controlled ON/OFF electrical circuit. Additionally, our findings reveal a significant influence of the excitation wavelength on the bending mechanism of the polymer foil. In particular, a high concentration of Z-isomers generated by light at wavelengths corresponding to the π–π* absorption band of the E-isomer facilitates effective bending even in materials with high Young’s modulus.

本研究的重点是线性偶氮聚合物（醚酰亚胺），一类在偏振光诱导现象的研究中受到相对有限关注的材料。我们证明这些聚合物可以有效地用于产生广泛的光响应效应，其效率主要由摩尔质量决定。合成的低摩尔质量偶氮聚酰亚胺表现出高效率的表面缓移光栅形成，产生深度达700 nm的正弦调制，效率接近理论最大值30%。相比之下，高摩尔质量的偶氮聚酰亚胺表现出明显的光诱导分子有序，导致明显而稳定的光学双折射。这种分子排序转化为弹性箔的有效机械弯曲和LC电池中液晶分子的单向排列。偶氮聚酰亚胺的双向变形进一步使光控开/关电路的构建成为可能。此外，我们的研究结果揭示了激发波长对聚合物箔弯曲机制的显著影响。特别是，在与e -异构体的π -π *吸收带对应的波长的光产生高浓度的z -异构体，即使在具有高杨氏模量的材料中，也有利于有效弯曲。

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引用次数: 0

A phosphorus-containing multielement flame retardant with schiff base structure imparting excellent flame retardancy, mechanical performance, and transparency to anhydride-cured epoxy resins 一种含磷多元素阻燃剂，希夫碱结构，对酸酐固化环氧树脂具有优异的阻燃性、机械性能和透明度

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-12-02 DOI: 10.1016/j.eurpolymj.2025.114439

Ming Huang, Yidi Liu, Xin Qu, Jingcheng Liu, Xiaojie Li, Wei Wei

Enhancing the flame retardancy of anhydride-cured epoxy resins (EP) while retaining favorable processability and mechanical properties remains a considerable challenge in the field of electronic packaging materials. In this work, a novel phosphorus/nitrogen/silicon-containing flame retardant, TMSi-VP, was synthesized via the reaction of diphenylphosphinyl chloride, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and subsequently incorporated into an anhydride-cured EP system. Owing to the synergistic flame-retardant contributions of phosphorus, nitrogen, and silicon, TMSi-VP significantly improved the fire safety of epoxy resins. At a phosphorus content of 1.5 wt%, the modified epoxy resin (EP-1.5) achieved a limiting oxygen index of 35.2 % and successfully passed the UL-94 V-0 test. Moreover, the peak heat release rate and total heat release of EP-1.5 were reduced to 601.2 kW/m² and 94.5MJ/m², corresponding to decreases of 30.1 % and 36.8 %, respectively, compared with that of neat EP. In terms of mechanical performance, TMSi-VP also effectively enhanced the strength and toughness of EP. At 1.0 wt% phosphorus content (EP-1.0), the flexural strength, tensile strength, and impact strength increased by 24.8 %, 16.6 %, and 54.2 %, respectively. Benefiting from the low intrinsic viscosity of TMSi-VP and its excellent compatibility with the epoxy matrix, the modified system maintained outstanding processability and transparency. This study provides a practical strategy for simultaneously improving the flame retardancy and mechanical performance of anhydride-cured epoxy resins, while preserving their ease of processing and high transparency.

提高酸酐固化环氧树脂（EP）的阻燃性，同时保持良好的加工性能和力学性能，是电子封装材料领域的一个相当大的挑战。本文以二苯基膦酰氯、香兰素和1,3-双（3-氨基丙基）-1,1,3,3-四甲基二硅氧烷为原料，合成了一种新型的含磷/氮/硅阻燃剂TMSi-VP，并将其加入到酸酐固化的EP体系中。由于磷、氮和硅的协同阻燃作用，TMSi-VP显著提高了环氧树脂的防火安全性。在磷含量为1.5 wt%时，改性环氧树脂（EP-1.5）的极限氧指数为35.2%，并成功通过UL-94 V-0测试。EP-1.5的峰值放热率和总放热率分别为601.2 kW/m2和94.5MJ/m2，分别比纯EP降低30.1%和36.8%。在力学性能方面，TMSi-VP还能有效提高EP的强度和韧性。当磷含量为1.0 wt% （EP-1.0）时，抗弯强度、抗拉强度和冲击强度分别提高了24.8%、16.6%和54.2%。由于TMSi-VP具有较低的特性粘度和与环氧基体的良好相容性，改性后的体系保持了良好的可加工性和透明度。本研究为同时提高酸酐固化环氧树脂的阻燃性和力学性能，同时保持其易加工性和高透明度提供了一种实用的策略。

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引用次数: 0

Dual delivery of mulberry leaf extract and ciprofloxacin via mannitol/xylitol-coated zein nanoparticles for overcoming antibiotic resistance 甘露醇/木糖醇包膜玉米蛋白纳米颗粒双重递送桑叶提取物和环丙沙星以克服抗生素耐药性

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-12-02 DOI: 10.1016/j.eurpolymj.2025.114437

Han-Sol You , Young-Guk Na , Hong-Ki Lee , Cheong-Weon Cho , Jong-Suep Baek

The increasing prevalence of multidrug-resistant A. baumannii poses a major challenge in antibiotic therapy, highlighting the need for advanced delivery strategies. This study investigates the co-encapsulation of ciprofloxacin (CFX) and mulberry leaf (ML) within zein nanoparticles (NPs) coated with mannitol and xylitol. The optimized formulation (F7) exhibited sustained-release profile, ensuring sustained antibacterial efficacy. Minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) assays confirmed that F7 displayed stronger antibacterial activity and suppressed bacterial proliferation more effectively against A. baumannii than CFX alone. SEM and CLSM confirmed membrane disruption and biofilm inhibition, supported by nucleic acid and protein leakage assays. Cytotoxicity and hemocompatibility studies indicated reduced toxicity and excellent blood compatibility compared to free CFX. The contribution of ML provided additional antioxidant and antibacterial activity, whereas mannitol and xylitol improved stability and antibiotic penetration. Collectively, these findings suggest that zein-based nanocarriers represent a promising platform to enhance antibiotic efficacy and combat resistance.

多药耐药鲍曼不动杆菌的日益流行对抗生素治疗提出了重大挑战，强调需要先进的给药策略。本研究研究了环丙沙星（CFX）和桑叶（ML）在玉米蛋白纳米颗粒（NPs）中包被甘露醇和木糖醇的情况。优化后的配方（F7）具有缓释特性，具有持续的抗菌效果。最低抑菌浓度（MIC）和最低杀菌浓度（MBC）试验证实，F7对鲍曼不动杆菌的抑菌活性和抑菌效果优于CFX。SEM和CLSM证实了膜破坏和生物膜抑制，核酸和蛋白质泄漏实验也证实了这一点。细胞毒性和血液相容性研究表明，与游离CFX相比，毒性降低，血液相容性良好。ML的贡献提供了额外的抗氧化和抗菌活性，而甘露醇和木糖醇则提高了稳定性和抗生素渗透。总的来说，这些发现表明，基于玉米蛋白的纳米载体代表了一个有希望的平台，以提高抗生素的功效和对抗耐药性。

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