Polymer Degradation and Stability最新文献_第10页

Machine learning-guided optimization of flame retardancy in rigid polyurethane foams 基于机器学习的硬质聚氨酯泡沫阻燃性能优化研究

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2025-12-04 DOI: 10.1016/j.polymdegradstab.2025.111838

Xiaoyan Sun , Jiankun Fu , Min Hao , Madeleine Bussemaker , Juncheng Jiang , Ru Zhou , Lian X. Liu

Rigid polyurethane foam (RPUF) is extensively used in insulation and structural applications. However, its high flammability, with a limiting oxygen index (LOI) of 18 %, presents significant safety concerns. Traditional flame-retardant optimization methods largely depend on trial and error, making them time-consuming and costly. In this study, a machine learning approach was developed to optimize flame-retardant design for RPUF. A curated database of 435 RPUF formulations containing reactive flame retardants was constructed using data from 89 published sources. This database consists of 806 input features, including 800 molecular descriptors generated using alvaDesc 3.0.6, which encompass topological, physicochemical, and electronic features, as well as six formulation-related variables such as additive content and curing conditions. A three-step feature selection strategy reduced dimensionality by 75.2 %, retaining 200 key descriptors. An Extreme Gradient Boosting (XGBoost) model was trained to predict LOI, achieving strong performance with a mean squared error (MSE) of 1.79 and coefficient of determination (R²) of 0.84. Feature importance analysis identified key predictive descriptors, while boxplot-based thresholding defined optimal descriptor ranges. Based on these insights, a phosphorus–boron-based reactive flame retardant (THPO-B) was synthesized and combined with a nitrogen-containing polyol (FRP_N) at a 1:1 ratio (total loading: 26.0 wt.%). Experimental validation produced an LOI of 26.8 ± 0.3 %, closely matching the predicted value of 26.2 ± 1.34 %, with a relative error of 2.2 %, and representing a 43.2 % improvement over unmodified RPUF. This study demonstrates that machine learning can effectively guide the design of high-performance flame-retardant systems, offering a faster and more efficient alternative to conventional methods.

硬质聚氨酯泡沫（RPUF）广泛应用于绝缘和结构应用。然而，它的高可燃性，极限氧指数（LOI）为18%，带来了重大的安全问题。传统的阻燃剂优化方法在很大程度上依赖于试错，这使得它们既耗时又昂贵。在这项研究中，开发了一种机器学习方法来优化RPUF的阻燃设计。使用来自89个已发表来源的数据，构建了435个含有反应性阻燃剂的RPUF配方的策划数据库。该数据库由806个输入特征组成，包括使用alvaDesc 3.0.6生成的800个分子描述符，包括拓扑、物理化学和电子特征，以及6个配方相关变量，如添加剂含量和固化条件。三步特征选择策略降低了75.2%的维数，保留了200个关键描述符。利用极限梯度增强（XGBoost）模型预测LOI，均方误差（MSE）为1.79，决定系数（R²）为0.84。特征重要性分析确定了关键的预测描述符，而基于箱线图的阈值法定义了最佳描述符范围。基于这些见解，合成了一种磷硼基反应性阻燃剂（THPO-B），并以1:1的比例（总负载：26.0 wt.%）与含氮多元醇（FRPN）结合。实验验证的LOI为26.8±0.3%，与预测值26.2±1.34%非常接近，相对误差为2.2%，比未修改的RPUF提高了43.2%。这项研究表明，机器学习可以有效地指导高性能阻燃系统的设计，为传统方法提供了更快、更有效的替代方案。

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引用次数: 0

Degradable poly(di)olefins enabled by acid-labile acetal without compromising the performances 可降解聚（二）烯烃由酸不稳定缩醛启用而不影响性能

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2025-12-04 DOI: 10.1016/j.polymdegradstab.2025.111841

Shurui Sun, Lai Wei, Tingting Ren, Dirong Gong

The all-chain carbon-carbon bond renders the synthetic polyolefins exceptional stable yet environmentally persistent, with end-of-life incineration or landfilling posing significant ecological threats. This work, for the first time, has demonstrated the balance between in-service mechanical stability and triggered degradation at their end-of-life. Acid-degradable acetal units have been incorporated into poly(di)olefin backbone via ring-opening metathesis copolymerization (ROMP) of 2-aryl-4,7-dihydro-2H-1,3-dioxepins (aryl: modified with M2, H; M3, o-F; M4, o-OMe; M5, p-NMe₂ and M6, p-Cl) with 1,5-cyclooctadiene (COD) and cyclooctene (COE). This strategy allows for engineering of a novel type of TPE-like materials with excellent and tailored mechanical properties. Critically, the acid-triggered programmed degradation at their end-life generates novel α,ω-telechelic, hydroxyl-terminated, low molecular weight polymers within hours. The sequence of acetal incorporated along the main chain fundamentally affects the degradation performances. The decomposition follows a nearly first-order for PCODM3, PCODM5 and PCODM6, and second-order for PCODM1, PCODM2 and PCODM5 with respect to the acetal, and the functionality-dependent rate varies from 0.01010 mmol·L⁻¹·h⁻¹ to 0.04642 mmol·L⁻¹·h⁻¹. The produced novel degraded oligomer could serve as a versatile intermediate for solid rocket propellants, adhesives, sealants, lubricants, insulating materials, or high-value polymer building blocks. This work establishes a promising circular approach for recycling used poly(di)olefins into an important feedstock by infusing acid-triggered acetal degradation.

全链碳-碳键使合成聚烯烃异常稳定，但具有环境持久性，报废焚烧或填埋造成重大的生态威胁。这项工作首次证明了在使用期间机械稳定性与寿命结束时触发退化之间的平衡。通过与1,5-环二烯（COD）和环烯（COE）的开环复分解共聚（ROMP），将2-芳基-4,7-二氢- 2h -1,3-二甲氧基（芳基：由M2， H; M3, o-F; M4, o-OMe; M5， p-NMe2和M6， p-Cl修饰）的酸降解缩醛单元纳入聚（二）烯烃骨架中。这种策略允许一种新型的tpe类材料的工程，具有优异的和定制的机械性能。关键的是，酸触发的程序降解在它们的末端寿命产生新的α，ω-远螺旋，羟基端，低分子量聚合物在数小时内。缩醛沿主链结合的顺序从根本上影响降解性能。对于缩醛来说，PCODM3、PCODM5和PCODM6的分解几乎是一级的，而PCODM1、PCODM2和PCODM5的分解是二级的，其功能依赖率从0.01010 mmol·L⁻¹·h⁻¹到0.04642 mmol·L⁻·h⁻¹不等。所生产的新型降解低聚物可作为固体火箭推进剂、粘合剂、密封剂、润滑剂、绝缘材料或高价值聚合物构建块的多功能中间体。这项工作建立了一个很有前途的循环方法，通过注入酸触发缩醛降解，将使用过的聚（二）烯烃回收为重要的原料。

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引用次数: 0

Synergistic effect of modified carbon nanotubes and magnesium hydroxide on flame retardancy and smoke suppression of silicone rubber foam 改性碳纳米管与氢氧化镁对硅橡胶泡沫阻燃抑烟的协同作用

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2025-12-03 DOI: 10.1016/j.polymdegradstab.2025.111835

Furu Kang , Jingxiao Pan , Lanlan Guo , Jun Deng , Dengke Wang , Zujin Bai , Shuaijing Ren , Chang Su , Chao Pan , Zibo Tian

To enhance the flame retardancy and smoke suppression of silicone rubber foam (SRF), a composite material of hydroxylated carbon nanotubes (CNTs–OH)/ Mg(OH)₂/ SRF was synthesized. The flame retardancy, smoke suppression performance of the SRF composites were evaluated using limiting oxygen index (LOI), horizontal-vertical burning tests (UL-94), cone calorimetry, and smoke density testing. Furthermore, the composition and toxicity of the combustion-generated smoke were investigated through a smoke density chamber coupled with Fourier-transform infrared spectroscopy and animal toxicity experiments. The results indicate that the SRF composites with 1.5 wt% CNTs–OH and 7 wt% Mg(OH)₂ displayed optimal flame retardancy and smoke suppression, as evidenced by an LOI value of 30.5 % and a UL-94 V-0 classification. The peak heat release rate and total heat release are diminished by 35.5 % and 51.9 %, while the maximum smoke density and total smoke production are lowered by 69.6 % and 70.45 %, respectively. SO₂ was identified as the most critical gas causing casualties during the combustion of SRF composites, followed by CO₂ and CO. The SRF composite with 1.5 wt% CNTs–OH and 7 wt% Mg(OH)₂ was assigned a toxicity rating of ZA1. Moreover, studies reveal that the Mg(OH)₂/CNTs–OH/SRF composite achieves flame retardancy via condensed-phase mechanisms, including Mg(OH)₂-catalyzed dehydration of CNTs–OH to form a dense char, char stabilization by MgO, and the dilution of combustibles by H₂O. Synergistic effects establish dual SiO₂/carbon barriers that block heat and oxygen transfer, enhancing fire resistance and smoke suppression.

为了提高硅橡胶泡沫（SRF）的阻燃性和抑烟性，合成了羟基化碳纳米管(CNTs-OH)/ Mg(OH)2/ SRF复合材料。采用极限氧指数（LOI）、水平-垂直燃烧测试（UL-94）、锥量热法和烟雾密度测试对SRF复合材料的阻燃、抑烟性能进行了评价。此外，通过烟密度室结合傅里叶变换红外光谱和动物毒性实验，研究了燃烧产生的烟雾的组成和毒性。结果表明，添加1.5 wt% CNTs-OH和7 wt% Mg(OH)2的SRF复合材料具有最佳的阻燃和抑烟性能，LOI值为30.5%，UL-94 V-0等级。峰值放热率和总放热率分别降低了35.5%和51.9%，最大烟密度和总产烟量分别降低了69.6%和70.45%。SO2被认为是SRF复合材料燃烧过程中造成人员伤亡的最关键气体，其次是CO2和CO。含有1.5 wt% CNTs-OH和7 wt% Mg(OH)2的SRF复合材料的毒性等级为ZA1。此外，研究表明，Mg(OH)2/ CNTs-OH /SRF复合材料通过缩合相机制实现阻燃，包括Mg(OH)2催化CNTs-OH脱水形成致密炭、MgO稳定炭和H2O稀释可燃物。协同效应建立了双SiO2/碳屏障，阻止了热量和氧气的传递，增强了耐火性和抑烟性。

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引用次数: 0

Synergistic flame-retardant action of Fe/Co/Cu-diphenylphosphonic acid coordination compounds in flexible polyurethane foam: A mechanistic study Fe/Co/ cu -二苯基膦酸配位化合物在柔性聚氨酯泡沫中的协同阻燃作用：机理研究

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2025-12-03 DOI: 10.1016/j.polymdegradstab.2025.111834

Yongjiang Li , Ailing Zhang , Yanhui Wang , Donglei Fan , Yichao Lin , Jie Liu , Tao Tang

Phosphorus containing flame retardants with lower oxidation states (such as +1 or +3 valence) are often used to improve fire safety of polymers due to their excellent gas-phase flame retardancy. Unfortunately, these quenching radical-chain reactions also lead to incomplete combustion and, consequently, dense smoke. Transition metal ions can offset this drawback by catalyzing char formation, thereby reducing both heat and smoke release. Whether monovalent-phosphorus ligands combined with different metal centers can deliver balanced flame retardancy in flexible polyurethane foam (FPUF) has, however, remained an open question.

In this work, three coordination compounds of diphenylphosphinic acid (DPPA) with Cu²⁺, Co²⁺, and Fe³⁺ (DPPA-Cu, DPPA-Co and DPPA-Fe) were compared. At 5 wt% (with respect to polyol 330), DPPA-Cu raised the limiting oxygen index (LOI) of FPUF to 21.3 %, confirming pronounced gas-phase flame retardancy. The same loading of DPPA-Co or DPPA-Fe almost completely inhibited the gas-phase interaction of DPPA. The foam containing DPPA-Fe (5DPPA-Fe foam) did not produce molten droplets during vertical combustion. We analyzed the flame-retardant mechanism of different samples and the resulting droplets and residual char after combustion, revealing the decomposition mechanism of FPUF by different metal ions. This study provides ideas for the design of FPUF flame retardants.

含磷阻燃剂具有较低的氧化态（如+1价或+3价），由于其优异的气相阻燃性，常用于提高聚合物的防火安全性。不幸的是，这些猝灭的自由基链反应也会导致不完全燃烧，从而产生浓烟。过渡金属离子可以通过催化炭的形成来抵消这个缺点，从而减少热量和烟雾的释放。然而，与不同金属中心结合的一价磷配体是否能在柔性聚氨酯泡沫（FPUF）中提供平衡的阻燃性仍然是一个悬而未决的问题。本文比较了二苯基膦酸（DPPA）与Cu2+、Co2+和Fe3+的三种配位化合物（DPPA- cu、DPPA- co和DPPA- fe）。在5 wt%（相对于多元醇330）时，DPPA-Cu将FPUF的极限氧指数（LOI）提高到21.3%，证实了明显的气相阻燃性。相同负载的DPPA- co或DPPA- fe几乎完全抑制了DPPA的气相相互作用。含DPPA-Fe的泡沫（5DPPA-Fe泡沫）在垂直燃烧时不产生熔滴。分析了不同样品的阻燃机理以及燃烧后产生的液滴和残炭，揭示了不同金属离子对FPUF的分解机理。本研究为FPUF阻燃剂的设计提供了思路。

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引用次数: 0

Sustainable toughening of recycled polypropylene using pinecone powder as a bio-based nucleating agent 松果粉作为生物基成核剂对再生聚丙烯的可持续增韧

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2025-12-03 DOI: 10.1016/j.polymdegradstab.2025.111809

Phuong Do van , Prabhakar M․N․ , Dong-Woo Lee , Maksym Li , Jung-il Song

Mechanical recycling of polypropylene (PP) is limited by thermal and mechanical degradation during repeated processing, which causes chain scission that reduces molecular weight and decreases structural performance. Therefore, this study restored and enhanced the mechanical properties of recycled PP (rPP) by blending it with native PP (nPP) and a pinecone powder (PCP) bio-based nucleating agent. After six extrusion cycles, rPP exhibited a 10–15% increase in crystallinity and a decline in tensile strength from 26.57 MPa to 24.6 MPa owing to chain scission-induced embrittlement. Differential scanning calorimetry and X-ray diffraction analyses confirmed that rPP exhibited enhanced molecular ordering, an increased crystallization temperature from 98 °C to 103 °C, and intensified crystalline peaks compared with nPP. Blending 30 wt% rPP with 70 wt% nPP improved the tensile strength of the polymer to 28 MPa and increased its flexural modulus by 20%, mitigating the effects of degradation. Addition of 15 wt% PCP promoted β-phase crystallization and improved toughness, impact strength, and ductility to achieve a tensile strength of 31.95 MPa and a 25% increase in flexural modulus (to 1.78 GPa) compared with that of rPP. Finally, scanning electron microscope observations revealed strong interfacial bonding and mechanical interlocking between PP and PCP that improved load transfer. Therefore, this study demonstrated a scalable approach for effectively enhancing the structural integrity of rPP that counters the effects of recycling-induced degradation while increasing crystallinity to improve mechanical performance. The proposed method provides a promising route for applying recycled polymers in high-value sustainable engineering components.

聚丙烯（PP）的机械回收受到重复加工过程中的热降解和机械降解的限制，这会导致链断裂，从而降低分子量和降低结构性能。因此，本研究通过将再生PP （rPP）与天然PP （nPP）和松果粉（PCP）生物基成核剂共混，恢复并增强了再生PP （rPP）的力学性能。经过6次挤压循环后，rPP的结晶度提高了10 ~ 15%，抗拉强度由26.57 MPa下降到24.6 MPa。差示扫描量热法和x射线衍射分析证实，与nPP相比，rPP的分子有序性增强，结晶温度从98°C提高到103°C，结晶峰增强。将30 wt% rPP与70 wt% nPP混合后，聚合物的拉伸强度提高到28 MPa，弯曲模量提高了20%，减轻了降解的影响。添加15wt %的PCP促进了β相结晶，提高了韧性、冲击强度和延展性，与rPP相比，拉伸强度达到31.95 MPa，弯曲模量提高25%（达到1.78 GPa）。最后，扫描电镜观察显示PP和PCP之间的强界面键合和机械联锁改善了负载传递。因此，本研究展示了一种可扩展的方法，可有效增强rPP的结构完整性，以对抗回收引起的降解影响，同时增加结晶度以改善机械性能。该方法为将再生聚合物应用于高价值可持续工程部件提供了一条有前途的途径。

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引用次数: 0

Contribution of silane coupling agent modified tungsten tailings in polypropylene composites to strengthen fire-resistant performance 硅烷偶联剂改性钨尾矿对聚丙烯复合材料耐火性能的贡献

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2025-12-02 DOI: 10.1016/j.polymdegradstab.2025.111833

Hui Liu, Weixuan Li, Long Yan, Feiyue Wang

The tungsten tailings are stockpiled in large quantities, and are difficult to be properly handled, which is an economic and security issue. Utilizing of tungsten tailings as high-demand polymer filler represents an effective way for high-value and large-scale applications of tailings, which is in line with the requirements of sustainable development. Modifying tungsten tailings with silane coupling agents (K-TTF) resolved the poor compatibility between organic and inorganic interfaces, enabling their incorporation into polypropylene composites. The influences of modified tungsten tailings fillers on the fire resistance of flame-retardant polypropylene composites were analyzed by cone calorimeter, thermogravimetric analyzer and limiting oxygen index. The obtained results show that the introduction of K-TTF filler effectively improves the fire-resistant performance of polypropylene composites. The overall performance of the polypropylene composite (PP-3) reaches the optimization point when the amount of K-TTF filler reaches 3.0 wt%. Compared with the flame-retardant polypropylene composites without K-TTF filler, the PP-3 sample shows an increase of 7.2 % in limiting oxygen index, a reduction of 36.1 % in total heat release, a reduction of 16.1 % in total smoke production, and an increase of 153.8 % in char residue at 800°C. The flame-retardant mechanism indicates that tungsten tailings are a multi-component flame-retardant synergist, and different components play different synergistic effects, among which the silicon dioxide component shows the highest synergistic efficiency. The study designs an economical and efficient flame-retardant polypropylene composite, and provides a high-value application pathway of solid waste.

钨尾矿堆存量大，处理困难，是一个经济和安全问题。利用钨尾矿作为高需求聚合物填料，是实现尾矿高价值、规模化应用的有效途径，符合可持续发展的要求。用硅烷偶联剂（K-TTF）改性钨尾矿，解决了有机界面和无机界面相容性差的问题，使其能够掺入聚丙烯复合材料中。采用锥形量热仪、热重仪和极限氧指数分析了改性钨尾砂填料对阻燃聚丙烯复合材料耐火性能的影响。结果表明，K-TTF填料的加入有效地提高了聚丙烯复合材料的耐火性能。当K-TTF填充量达到3.0 wt%时，聚丙烯复合材料（PP-3）的综合性能达到最佳。与未添加K-TTF的阻燃聚丙烯复合材料相比，在800℃下，PP-3样品的极限氧指数提高了7.2%，总放热量降低了36.1%，总产烟量降低了16.1%，炭渣增加了153.8%。阻燃机理表明，钨尾矿是一种多组分阻燃增效剂，不同组分的协同增效效果不同，其中二氧化硅组分的协同增效效果最高。本研究设计了一种经济高效的阻燃聚丙烯复合材料，为固体废物的高价值应用提供了一条途径。

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引用次数: 0

Cold plasma-assisted degradation of melamine-resin microplastics: A multiscale analysis of fragmentation and morphological evolution 冷等离子体辅助降解三聚氰胺树脂微塑料：碎片和形态演变的多尺度分析

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2025-12-01 DOI: 10.1016/j.polymdegradstab.2025.111825

K. Bexeitova , U. Zhantikeyev , Y. Yeszhan , A. Baimenov , K. Toshtay , S. Mikhalovsky , M. Illsley , Jechan Lee , S. Azat

Microplastics, particularly melamine-resin polymers, are emerging environmental contaminants with high persistence and potential toxicity. Conventional degradation methods are often inefficient in fully breaking down stable carbon backbones of such polymers. Cold plasma technology has recently attracted attention as a non-thermal advanced oxidation process capable of generating highly reactive species under ambient conditions. This study aims to investigate the degradation behavior of melamine-resin microplastics under cold plasma treatment and to characterize the structural transformations, fragmentation dynamics, and degradation efficiency over time. A custom-built cold plasma reactor operating at 10 kV and 3 A was used to treat aqueous suspensions of melamine resin microparticles (2 µm). The plasma reactor enabled gas-liquid phase interactions, enhancing the generation of oxidative species. The degradation process was assessed at different exposure times (5, 20 and 30 min). Structural and morphological changes were analyzed using Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS), zeta potential measurements, turbidity analysis, and gravimetric mass loss.

Cold plasma treatment induced a progressive reduction in particle size from 2004 ± 93 nm to 119 ± 47 nm after 30 min, accompanied by a 43 % weight loss and increased turbidity (from 2.06 NTU to 7.22 NTU), indicating significant fragmentation. TEM images confirmed morphological transformation from smooth spherical particles to irregular, porous, nano-sized fragments (68–119 nm). Oxidative degradation pathways are attributed to interactions with reactive oxygen species such as •OH, O₃, and H₂O₂ generated within the plasma zone. Cold plasma demonstrates high efficiency in degrading melamine-resin microplastics through advanced oxidative mechanisms, leading to significant fragmentation and nanostructural disruption. The findings support the use of cold plasma as a sustainable and effective method for the remediation of microplastic-contaminated water and offer insights into degradation kinetics and mechanisms of polymer breakdown under plasma exposure.

微塑料，特别是三聚氰胺树脂聚合物，是新兴的具有高持久性和潜在毒性的环境污染物。传统的降解方法在完全分解这种聚合物的稳定碳骨架方面往往效率低下。冷等离子体技术作为一种能够在环境条件下产生高活性物质的非热高级氧化工艺，近年来引起了人们的关注。本研究旨在研究三聚氰胺树脂微塑料在冷等离子体处理下的降解行为，并表征其随时间的结构转变、破碎动力学和降解效率。采用特制的冷等离子体反应器，工作电压为10 kV，电流为3 A，处理2µm的三聚氰胺树脂微颗粒水悬浮液。等离子体反应器使气液相相互作用，增强氧化物质的产生。在不同的暴露时间（5、20和30分钟）下评估降解过程。通过透射电子显微镜（TEM）、动态光散射（DLS）、zeta电位测量、浊度分析和重量质量损失分析结构和形态变化。冷等离子体处理导致30分钟后颗粒尺寸从2004±93 nm逐渐减小到119±47 nm，伴随着43%的重量减轻和浊度增加（从2.06 NTU到7.22 NTU），表明明显的碎片化。TEM图像证实了从光滑的球形颗粒到不规则的多孔纳米碎片（68-119 nm）的形态转变。氧化降解途径归因于与等离子区产生的•OH、O₃和H₂O₂等活性氧物质的相互作用。冷等离子体通过先进的氧化机制高效降解三聚氰胺树脂微塑料，导致显著的碎片化和纳米结构破坏。研究结果支持冷等离子体作为一种可持续和有效的修复微塑料污染水的方法，并提供了等离子体暴露下聚合物降解动力学和降解机制的见解。

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引用次数: 0

Stimulus-responsive multifunctional coating with active protection and antibacterial properties 具有活性保护和抗菌性能的刺激反应多功能涂层

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2025-11-29 DOI: 10.1016/j.polymdegradstab.2025.111823

Chengbin Guo , Tian Zhang , Zhenyu Chen

To retard the epoxy coating degradation and microbial adhesion in marine environments, a dual-responsive nanocontainer system, PNIPAM@BTA@MPN, was developed for pH/temperature-triggered self-healing when incorporated into an epoxy matrix. This system consists of thermosensitive poly(N-isopropylacrylamide) (PNIPAM) nanoparticles loaded with the corrosion inhibitor benzotriazole (BTA). These PNIPAM@BTA nanoparticles are then encapsulated within a pH-responsive metal-polyphenol network (MPN). Moreover, an alkaline phosphatase (ALP)-responsive bactericidal hydrogel layer was generated through surface polymerization of methacrylate monomers, utilizing phosphate crosslinkers.

After 50 days of immersion under temperature-alternating conditions, the resistance of the composite coating sample at 0.01 Hz (1.01×10⁹ Ω·cm²) was nearly two orders of magnitude higher than that of the pristine epoxy coating. Density functional theory (DFT) and molecular dynamics (MD) simulations revealed enhanced mechanical integrity and barrier properties. Furthermore, EIS, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM/EDS), and wire beam electrode (WBE) analyses collectively confirmed the active protection mechanism of the scratched composite coating under conditions of lower pH and higher temperature. In addition to its protective qualities, the ALP-responsive gel layer exhibited notable antibacterial activity, demonstrating an antibacterial efficiency exceeding 80 % against both S. aureus and P. aeruginosa.

This self-adaptive coating offers durable corrosion protection and antimicrobial properties, making it suitable for extended use in marine environments.

为了延缓环氧涂层在海洋环境中的降解和微生物粘附，研究人员开发了一种双响应纳米容器系统PNIPAM@BTA@MPN，该系统可在pH/温度触发的情况下与环氧树脂基体结合进行自修复。该系统由热敏型聚n -异丙基丙烯酰胺（PNIPAM）纳米颗粒组成，负载缓蚀剂苯并三唑（BTA）。然后将这些PNIPAM@BTA纳米颗粒封装在ph响应金属-多酚网络（MPN）中。此外，利用磷酸盐交联剂，通过甲基丙烯酸酯单体的表面聚合，生成了碱性磷酸酶（ALP）响应的杀菌水凝胶层。在温度交替条件下浸泡50 d后，复合涂层样品在0.01 Hz （1.01×109 Ω·cm2）下的电阻比原始环氧涂层高出近两个数量级。密度泛函理论（DFT）和分子动力学（MD）模拟显示了增强的机械完整性和屏障性能。此外，EIS、扫描电镜（SEM/EDS）和线束电极（WBE）分析共同证实了复合涂层在低pH和高温条件下的主动保护机制。除了具有保护作用外，alp反应凝胶层还表现出显著的抗菌活性，对金黄色葡萄球菌和铜绿假单胞菌的抗菌效率均超过80%。这种自适应涂层提供持久的防腐和抗菌性能，使其适合在海洋环境中广泛使用。

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引用次数: 0

Formaldehyde‑free phosphamide flame retardant with high atom economy for cotton based on p-π conjugation 基于p-π共轭的高原子经济性棉花无甲醛磷酰胺阻燃剂

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2025-11-29 DOI: 10.1016/j.polymdegradstab.2025.111803

Fayu Sun , Jiayang Li , Hui Xu , Tian Li , Hejun Li , Jieyu Wei , Guangming Sun , Shuai He , Guangxian Zhang

A novel green cotton phosphoramide flame retardant (ACPPFR) was synthesized from phosphorus pentoxide and ammonium carbonate. Phosphorus atoms were introduced into the cotton fabric via the generation of H₂N-P(=O)-O-C bonds with cellulose. The p-π conjugated structure formed by the nitrogen atom and P=O groups reduced the polarity of the phosphate bond and improved its stability. SEM and XRD results suggested that ACPPFR molecules entered the interior of cotton fibers. Energy-dispersive spectroscopy (EDS) elemental analysis showed that ACPPFR was applied to the cotton fibers, and FTIR spectroscopy suggested that it was grafted onto the fabrics via P(=O)-O-C covalent bonds. Thermogravimetric (TG), thermogravimetric infrared (TG-IR), and cone calorimetry data suggested that ACPPFR altered the thermal degradation process of cotton fibers, representing a condensed-phase flame retardant mechanism. Physical property tests suggested that ACPPFR made fabrics softer. According to AATCC 61–2013 3A standard, the LOI value of ACPPFR-20 % was 42.5 %, and the vertical burning damage length was 86 mm after 50 LCs. This indicated that ACPPFR-20 % had high durability and efficient flame retardancy. In this study, amidation reaction was carried out by introducing ammonium ions in inorganic ammonium carbonate, which had high atom economy and was a green reaction.

以五氧化二磷和碳酸铵为原料合成了一种新型绿棉磷酰胺阻燃剂（ACPPFR）。磷原子通过与纤维素生成H2N-P(=O)-O-C键进入棉织物。氮原子与p =O基团形成的p-π共轭结构降低了磷酸键的极性，提高了其稳定性。SEM和XRD结果表明，ACPPFR分子进入棉纤维内部。能谱（EDS）元素分析表明，ACPPFR通过P(=O)-O-C共价键接枝到织物上。热重（TG）、热重红外（TG- ir）和锥量热数据表明，ACPPFR改变了棉纤维的热降解过程，表现为凝聚相阻燃机理。物理性能测试表明，ACPPFR使织物更柔软。根据AATCC 61-2013 3A标准，acppfr - 20%的LOI值为42.5%，50 lc后垂直燃烧损伤长度为86 mm。这表明acppfr - 20%具有高耐久性和高效阻燃性。在无机碳酸铵中引入铵离子进行酰胺化反应，具有较高的原子经济性，是一种绿色反应。

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引用次数: 0

Facile and efficient chemical degradation of end-of-life tires into value-added liquid rubber 将废旧轮胎快速、高效地化学降解为增值液体橡胶

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2025-11-28 DOI: 10.1016/j.polymdegradstab.2025.111821

Hua Zhang , Yu Sun , Qi Yang , Xiaojian Liu , Lishuang Ma , Xuequan Zhang , Moris S. Eisen , Heng Liu

The ever-growing accumulation of polydiene sulphur vulcanizates, represented mainly by end-of-life tires (ELTs), causes substantial environmental pollutions, underscoring the urgency for effective and sustainable recycling strategies. In this report, a simple yet efficient synergistic system of Cp₂ZrCl₂/LiAlH₄ has been designed for the chemical degradation of polydiene sulphur vulcanizates, including end-of-life tires. By fine-tuning the reaction conditions, low-molecular-weight liquid polydiene rubbers (LPRs) with tunable chain structures and molecular weights are produced as the final products. The key factors influencing the degradation efficiency were systematically evaluated. Importantly, the resultant LPR can be directly reused as processing aids in new rubber compounds without compromising their mechanical performance, thus enabling a quasi-closed-loop recycling pathway. Overall, this study offers a sustainable solution to the growing challenge of managing tire waste.

以报废轮胎为代表的聚二烯硫硫化橡胶的不断积累造成了严重的环境污染，强调了制定有效和可持续的回收战略的紧迫性。在本报告中，设计了一种简单而高效的Cp2ZrCl2/LiAlH4协同体系，用于化学降解聚二烯硫硫化橡胶，包括报废轮胎。通过对反应条件的微调，可制得链结构和分子量可调的低分子量液态聚二烯橡胶（LPRs）。系统评价了影响降解效率的关键因素。重要的是，合成的LPR可以直接用作新橡胶化合物的加工助剂，而不会影响其机械性能，从而实现准闭环回收途径。总的来说，这项研究提供了一个可持续的解决方案，以管理轮胎废物日益增长的挑战。

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引用次数: 0