Polymer Degradation and Stability最新文献_第5页

Tuning sequence length to regulate both toughness and biodegradation behavior of poly (butylene succinate-co-butylene adipate) 调整序列长度调节聚丁二酸-己二酸共丁二烯的韧性和生物降解行为

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-16 DOI: 10.1016/j.polymdegradstab.2026.111948

Haoran Sun , Shufeng Li , Junyu Li , Yuchuan Tian , Yi Liu , Liuchun Zheng

The extensive use of conventional plastics has resulted in severe environmental pollution, driving increasing interest in biodegradable polyesters that combine excellent performance with complete degradability. Poly (butylene succinate-co-butylene adipate) (PBSA), derived from poly (butylene succinate) (PBS) by incorporating flexible butylene adipate (BA) units, exhibits broad potential in composting, packaging, and agricultural films. In this study, a series of PBSA polyester materials with systematically varied BA unit sequence lengths were prepared by fine-tuning the composition of adipic acid (AA) and succinic acid (SA), aiming to investigate the effect of BA sequence length on the properties of PBSA. The results indicate that as the BA sequence length decreases, the crystal growth orientation of PBSA shifts from (020), (021), and other planes to (111), accompanied by increased interlamellar spacing and reduced crystallinity, these changes significantly accelerate the enzymatic degradation rate. Meanwhile, the shortened BA sequence promotes spherulite growth, which restricts the mobility of molecular chains and consequently leads to decreases in elongation at break and impact strength. Specific data show that after the shortening of the BA sequence, the elongation at break of PBSA decreases from 810% to 350%, the impact strength drops from 307.2 J/m to 211.9 J/m, and the degradation mass loss rate increases from 71.2% to 99.5%. This study confirms that regulating the BA sequence length enables the synergistic control of both mechanical properties and degradation performance of PBSA polyester materials.

传统塑料的广泛使用造成了严重的环境污染，促使人们对具有优异性能和完全可降解性的可生物降解聚酯越来越感兴趣。聚丁二酸-己二酸共丁二酸酯（PBSA），由聚丁二酸酯（PBS）通过结合柔性己二酸丁二烯（BA）单元衍生而来，在堆肥、包装和农用薄膜方面表现出广泛的潜力。本研究通过对己二酸（AA）和琥珀酸（SA）的组成进行微调，制备了一系列BA单元序列长度系统变化的PBSA聚酯材料，旨在研究BA序列长度对PBSA性能的影响。结果表明，随着BA序列长度的减小，PBSA的晶体生长方向由（020）、（021）等平面向（111）平面转变，层间间距增大，结晶度降低，酶解速率明显加快。同时，缩短的BA序列促进了球晶的生长，限制了分子链的迁移，从而导致断裂伸长率和冲击强度下降。具体数据表明，缩短BA序列后，PBSA的断裂伸长率从810%下降到350%，冲击强度从307.2 J/m下降到211.9 J/m，降解质量损失率从71.2%上升到99.5%。本研究证实，调节BA序列长度可以协同控制PBSA聚酯材料的力学性能和降解性能。

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引用次数: 0

Improving flame retardancy, mechanical and water resistance properties of polypropylene using zinc oleate-modified intumescent flame retardant and coated red phosphorus 用油酸锌改性膨胀阻燃剂和包覆红磷改善聚丙烯的阻燃性能、力学性能和耐水性

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-15 DOI: 10.1016/j.polymdegradstab.2026.111947

Ziyi Zhang , Yangming Zou , Jun Sun , Hongfei Li , Qing Zhang , Xiaoyu Gu , Sheng Zhang

To address the issue of excessive addition amount when using the expansive intumescent flame retardant (IFR, PAPP:MPP = 7:3) alone, a combination of high flame retardant efficiency and low toxicity coated red phosphorus ((w)RP) and IFR was added to polypropylene (PP) to improve the flame retardant performance of the PP composite. When the total addition amount of flame retardant decreases to 13 wt.%, it still could reach the UL-94 V-0 rating, with a limit oxygen index (LOI) value of 27.2%. Subsequently, in order to synergistically enhance its flame retardant performance, mechanical properties, and water resistance, the IFR needed to be modified. Zinc oleate (ZnOA) has good compatibility with PP and hydrophobicity, so it was selected to modify IFR to synthesis ZnOPM. Compared to PP/10%IFR/3%(w)RP, the PP/10%ZnOPM/3%(w)RP composite showed increased LOI to 28.8% while maintaining UL-94 V-0 rating, with peak heat release rate (pHRR) and total smoke production (TSP) reduced by 23.1% and 71.5% respectively. Additionally, compared with PP/10%IFR/3%(w)RP, the tensile strength and elongation at break of PP/10%ZnOPM/3%(w)RP increased by 25.1% and 98.1%. After water immersion tests, water absorption and flame retardant leaching rate of PP/10%ZnOPM/3%(w)RP decreased to 0.6% and 0.38%, with the composite maintaining excellent flame retardancy and mechanical properties. This study proposes a highly promising strategy for manufacturing PP composites with excellent flame retardant, smoke suppression, water resistance, and mechanical properties.

为解决膨胀型膨胀型阻燃剂（IFR, ppp:MPP = 7:3）单独使用时添加量过大的问题，在聚丙烯（PP）中添加高难燃低毒包覆红磷（(w)RP）和IFR的组合，以提高PP复合材料的阻燃性能。当阻燃剂的总添加量减少到13 wt.%时，仍能达到UL-94的V-0额定值，极限氧指数（LOI）为27.2%。随后，为了协同提高其阻燃性能、机械性能和耐水性，需要对IFR进行改性。油酸锌（ZnOA）与PP具有良好的相容性和疏水性，因此选择它对IFR进行改性以合成ZnOPM。与PP/10%IFR/3%(w)RP相比，PP/10%ZnOPM/3%(w)RP复合材料在保持UL-94 V-0额定值的同时，LOI提高至28.8%，峰值放热率（pHRR）和总产烟率（TSP）分别降低23.1%和71.5%。与PP/10%IFR/3%(w)RP相比，PP/10%ZnOPM/3%(w)RP的拉伸强度和断裂伸长率分别提高了25.1%和98.1%。经浸水试验，PP/10%ZnOPM/3%(w)RP的吸水率和阻燃浸出率分别降至0.6%和0.38%，复合材料保持了优异的阻燃性能和力学性能。该研究为制造具有优异阻燃、抑烟、耐水和机械性能的PP复合材料提供了一种非常有前途的策略。

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引用次数: 0

Novel formulations for the protection of wooden artifacts 保护木制文物的新配方

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-10 DOI: 10.1016/j.polymdegradstab.2026.111934

Laura Vespignani , Giulia Villano , Micol Bucci , Alessandra Cecchetti , Mara Camaiti , Antonella Salvini

Wooden artifacts are highly susceptible to degradation from moisture, pollutants, and ultraviolet (UV) radiation, which presents significant challenges in Cultural Heritage conservation. This study investigates the performances of novel formulations containing short-chain fluorinated oligoamides or fluorinated amines as protective treatments for wood artifacts and the effect of specific additives to increase their stability against photodegradation. Derivatives with C4 and C6 perfluorinated chains were obtained through ring-opening reactions and their formulations optimized for use with environmentally friendly solvents. When applied to beech wood, the coated surfaces significantly improved water and oil repellency, with Water Contact Angles (WCA) exceeding 125° and Oil Contact Angles (OCA) over 100°, while causing minimal visual changes to the surface. The addition of light stabilizers, particularly selected UV Absorbers (UVA), enhanced the durability of the coatings and slightly reduced photo-induced color changes observed in virgin wood and even when the coating alone was used. Accelerated aging tests and spectroscopic analysis confirmed the maintenance of protective properties over time by the formulations, supporting their potential as sustainable and reversible treatments for the long-term protection of wooden Cultural Heritage materials.

木制文物极易受到湿气、污染物和紫外线（UV）辐射的影响，这对文化遗产保护提出了重大挑战。本研究探讨了含有短链氟化低聚酰胺或氟化胺的新型配方作为木制品保护处理的性能，以及特定添加剂对提高其抗光降解稳定性的影响。通过开环反应获得了具有C4和C6全氟链的衍生物，并优化了其配方，以便与环保溶剂一起使用。当应用于山毛榉木材时，涂层表面显着提高了水和油的拒水性，水接触角（WCA）超过125°，油接触角（OCA）超过100°，同时对表面造成最小的视觉变化。添加光稳定剂，特别是精选的紫外线吸收剂（UVA），增强了涂层的耐久性，并略微减少了在原始木材中观察到的光致颜色变化，甚至当单独使用涂层时也是如此。加速老化测试和光谱分析证实，随着时间的推移，配方保持了保护性能，支持它们作为可持续和可逆的处理方法，长期保护木制文化遗产材料的潜力。

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引用次数: 0

Thermo-aging induces adhesion between silicone foam and metal-mechanism behind 热老化引起泡沫硅酮与金属之间的黏附，其背后的机理

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-11 DOI: 10.1016/j.polymdegradstab.2026.111941

Yunpeng Xie , Zhaohui Xu , Lei Yu , Dayang Wang , Xiaolin Lu

Silicone foam, as a damping material, is widely used between metal components in integrative device systems. After long-term service, silicone foam tends to adhere to metal substrates, thus leading to the disassembly difficulty and compromising the system reliability. Owing to the interfacial complexity when the silicone foam and the metal component stick to each other, the underlying adhesion mechanisms still remain unclear. This study aims to elucidate the adhesion mechanism between the silicone foam and the metal substrate using a stainless steel/silicone foam/stainless steel sandwiched structure through accelerated aging and under compressive stress. Multiscale techniques from morphology, spectroscopy and depth profile were applied to study the joint interfacial structures and elucidate the adhesion mechanism between the silicone foam and stainless steel. It was demonstrated that the silicone foam-stainless steel adhesion behavior arose from the synergistic effects of thermo-oxidative aging and compressive stress, which had induced physical and chemical changes of the silicone foam at the interface. Specifically, the interfacial interactions were comprised of covalent bonding (Si−O−Metal), micro-mechanical interlocking, hydrogen bonding, and van der Waals force. Such findings shall provide new insights into the adhesion mechanisms of polymer-metal interfaces and offer practical guidance for the design and reliability assessment of damping materials in engineering applications.

有机硅泡沫作为一种阻尼材料，在集成器件系统中广泛应用于金属部件之间。长期使用后，硅酮泡沫易于粘附在金属基板上，从而导致拆卸困难，影响系统的可靠性。由于有机硅泡沫材料与金属材料相互粘附时界面的复杂性，其粘附机理尚不清楚。本研究采用不锈钢/泡沫硅酮/不锈钢夹层结构，通过加速时效和压应力作用，研究泡沫硅酮与金属基体的粘附机理。采用形貌、光谱和深度剖面等多尺度技术研究了有机硅泡沫与不锈钢的结合界面结构，阐明了有机硅泡沫与不锈钢的粘附机理。结果表明，热氧化老化和压应力的共同作用导致泡沫硅树脂与不锈钢的黏附行为发生了物理和化学变化。具体来说，界面相互作用由共价键（Si−O−Metal）、微机械联锁、氢键和范德华力组成。这些发现将为聚合物-金属界面的粘附机制提供新的见解，并为工程应用中阻尼材料的设计和可靠性评估提供实用指导。

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引用次数: 0

Correlations among polylactic acid biodegradation, bacterial communities, and predicted functional genes under mesophilic and thermophilic composts 中温和亲热堆肥下聚乳酸生物降解、细菌群落和预测功能基因的相关性

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-05 DOI: 10.1016/j.polymdegradstab.2026.111921

Ian Cho, Kyung-Suk Cho

As a sustainable alternative to petroleum-based plastics, biodegradable plastics such as polylactic acid (PLA) have garnered increasing attention. However, despite being the most widely used biodegradable plastic, studies investigating the post-use degradation of PLA remain limited. This study compared the degradation behavior of PLA samples under mesophilic (35 °C) and thermophilic (58 °C) compost conditions and analyzed associated changes in microbial communities and predicted functional genes throughout the degradation process. The PLA film was completely degraded within 15 days under thermophilic conditions, whereas only a 13.7 % weight loss was observed after 40 days under mesophilic conditions. For PLA granules, weight loss after 65 days reached 24.8 % and 6.1 % under thermophilic and mesophilic conditions, respectively. SEM and FTIR analyses confirmed evidence of microbial degradation, such as surface erosion and ester bond cleavage. Spearman’s correlation analysis revealed that Bacillaceae-dominated microbial communities play an active role in PLA biodegradation in thermophilic environments, while Georgenia and Cupriavidus may function as potential PLA degraders in mesophilic environments. Functional gene prediction revealed that K01126 (glycerophosphodiester phosphodiesterase) and K01048 (lysophospholipase), both associated with PLA degradation, exhibited strong positive correlations with degradation rate, suggesting their key enzymatic roles in PLA hydrolysis. Furthermore, a promising PLA-degrading bacterium, Ralstonia sp. AF1, was isolated from compost following the degradation process. Overall, this study demonstrates the biodegradability of PLA under compost conditions through comprehensive analysis of degradation characteristics and bacterial community dynamics, and provides fundamental insights to enhance the degradation efficiency of PLA in compost environments.

聚乳酸（PLA）等可生物降解塑料作为石油基塑料的可持续替代品，越来越受到人们的关注。然而，尽管聚乳酸是应用最广泛的可生物降解塑料，但对其使用后降解的研究仍然有限。本研究比较了PLA样品在中温（35°C）和亲热（58°C）堆肥条件下的降解行为，分析了降解过程中微生物群落的相关变化，并预测了功能基因。PLA薄膜在亲热条件下在15天内完全降解，而在中温条件下40天后仅观察到13.7%的重量损失。PLA颗粒在亲热和中温条件下，65天后的失重率分别达到24.8%和6.1%。SEM和FTIR分析证实了微生物降解的证据，如表面侵蚀和酯键裂解。Spearman的相关分析表明，在嗜热环境下，杆菌科为主的微生物群落在降解聚乳酸中发挥积极作用，而在中温环境下，Georgenia和Cupriavidus可能是潜在的聚乳酸降解菌。功能基因预测显示，K01126（甘油磷酸二酯磷酸二酯酶）和K01048（溶血磷脂酶）都与PLA降解有关，与降解率呈强正相关，表明它们在PLA水解中起关键作用。此外，在降解过程中从堆肥中分离到一种有前途的pla降解细菌Ralstonia sp. AF1。总体而言，本研究通过对降解特性和细菌群落动态的综合分析，论证了聚乳酸在堆肥条件下的生物降解性，为提高聚乳酸在堆肥环境中的降解效率提供了基础性的见解。

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引用次数: 0

Synthesis and degradation mechanisms of Schiff-base-containing phthalonitrile resins: Thermal stability and bond reconfiguration 含席夫碱邻苯二腈树脂的合成及降解机理：热稳定性和键重构型

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-15 DOI: 10.1016/j.polymdegradstab.2026.111945

Xiaolu Sun , Shilin Wang , Siyuan Dong , Xi Chen , Xinbo Dong , Yang Wang , Xigao Jian , Cheng Liu

With the rapid development of the aerospace field, higher requirements have been put forward for the heat resistance of thermosetting resins. In this study, an asymmetrical phthalonitrile monomer containing Schiff base moiety (SchB-PN) was synthesized by a two-step method with N-4′-hydroxybenzylidene-4-hydroxyaniline (N-hy) and 4-nitro-o-phthalonitrile. The structure and properties of SchB-PN were characterized by ¹H NMR, ¹³C NMR, ¹H–¹H gCOSY, HRMS, FTIR, XRD, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and rheology. SchB-PN had a relatively low viscosity of 0.179 Pa·s when molten, and due to the presence of imine and cyano groups, SchB-PN resin exhibited self-curing characteristics. Furthermore, SchB-PN resins were cured with different curing agents and curing processes. It was found that SchB-PN-APn-400 resin cured by SchB-PN and p-aminobenzonitrile (APn) at 400 °C demonstrated excellent thermal stability and thermal oxidative stability, with the temperature of 5 % weight loss (T_{5 %}) of 530 °C in nitrogen and 534 °C in air, and the residual carbon rate was 74.9 % at 800 °C in nitrogen atmosphere. The curing mechanism of SchB-PN-APn resin and the cooperative curing mechanism of imine bonds and cyano groups were studied and clarified through FTIR, in-situ infrared technology, SEM and EDS. In addition, the thermal stability and pyrolysis mechanism of SchB-PN were systematically investigated by TGA and TG-FTIR techniques, as well as the compensatory effect of the Schiff base bond breaking and reconnection during the degradation process. The relevant data and analysis results highlight the potential application prospects of SchB-PN-APn resin in aerospace and high-performance engineering fields.

随着航空航天领域的飞速发展，对热固性树脂的耐热性提出了更高的要求。本研究以N-4′-羟基苄基-4-羟基苯胺（N-hy）和4-硝基-邻苯二腈为原料，采用两步法合成了含席夫碱部分的不对称邻苯二腈单体（SchB-PN）。采用¹H NMR、13C NMR、1h gCOSY、HRMS、FTIR、XRD、差示扫描量热法（DSC）、热重分析（TGA）和流变学表征了SchB-PN的结构和性能。熔融时，SchB-PN树脂的粘度较低，为0.179 Pa·s，由于亚胺和氰基的存在，SchB-PN树脂具有自固化特性。此外，采用不同的固化剂和固化工艺对SchB-PN树脂进行了固化。结果表明，SchB-PN-APn-400树脂经SchB-PN和对氨基苯腈（APn）在400℃固化后，表现出优异的热稳定性和热氧化稳定性，在530℃的氮气和534℃的空气中，其失重率（T5 %）为5%，在800℃的氮气气氛中，残碳率为74.9%。通过FTIR、原位红外技术、SEM和EDS等研究并阐明了SchB-PN-APn树脂的固化机理以及亚胺键与氰基的协同固化机理。此外，通过TGA和TG-FTIR技术系统地研究了SchB-PN的热稳定性和热解机理，以及降解过程中席夫碱键断裂和重连的补偿作用。相关数据和分析结果突出了SchB-PN-APn树脂在航空航天和高性能工程领域的潜在应用前景。

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引用次数: 0

Biomimetic soil-root-mineral system toward VER composites with enhanced mechanical property, good recyclability and excellent flame retardancy 仿生土壤-根-矿物体系研究VER复合材料力学性能增强、可回收性好、阻燃性优异

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-15 DOI: 10.1016/j.polymdegradstab.2026.111943

Ying-Ming Li , Hang-Ping Fang , Shuang-Lin Hu , Yao Deng , De-Yi Wang

The inherent flammability, poor mechanical property and non-recyclability of vinyl resins (VER) has hindered their widely use in aerospace and construction applications. In this work, inspired by the soil-root-mineral synergy in natural ecosystems, a novel P-N flame retardant (AT) was covalently immobilized within the polymer matrix, mimicking root anchoring in soil. Concurrently, functionalized glass fibers (FGF) were incorporated, analogous to mineral particles, to synergistically enhance the flame retardancy and mechanical reinforcement for VER. When incorporating 14 wt% AT and 1 wt% FGF, the composite achieved a UL-94 V-0 rating with a limiting oxygen index (LOI) of 31.3%. Cone calorimetry test (CCT) revealed that the VERAT/FGF₁ composite exhibited significant reductions in heat release rate (HRR), total heat release (THR), and smoke production rate (SPR) of 54.4%, 39.3%, and 20.1%, respectively, compared to pure VER. Comprehensive analyses demonstrated that the flame-retardant mechanism involved synergistic effects in both condensed and gas phases. Simultaneously, the VERAT/FGF₁ composite demonstrated 41.9% and 10.7% enhancements in tensile strength and impact resistance, respectively, compared to neat VER. Chemical degradation of VERAT/FGF₁ by solvent method for efficient recycling of glass fibers, providing a new strategy for reuse of vinyl polyester composites.

乙烯基树脂（VER）固有的易燃性、较差的力学性能和不可回收性阻碍了其在航空航天和建筑领域的广泛应用。在这项工作中，受自然生态系统中土壤-根-矿物协同作用的启发，一种新型的P-N阻燃剂（AT）被共价固定在聚合物基质中，模仿土壤中的根锚定。同时，加入功能化玻璃纤维（FGF），类似于矿物颗粒，以协同增强VER的阻燃性和机械增强。当掺入14 wt%的AT和1 wt%的FGF时，该复合材料达到了UL-94 V-0等级，极限氧指数（LOI）为31.3%。锥量热测试（CCT）显示，与纯VER相比，VERAT/FGF1复合材料的放热率（HRR）、总放热率（THR）和产烟率（SPR）分别显著降低54.4%、39.3%和20.1%。综合分析表明，其阻燃机理涉及凝聚态和气相的协同作用。同时，与纯VER相比，VERAT/FGF1复合材料的拉伸强度和抗冲击性分别提高了41.9%和10.7%。溶剂法化学降解VERAT/FGF1可有效回收玻璃纤维，为乙烯基聚酯复合材料的再利用提供了新的策略。

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引用次数: 0

Phosphate ester-based polyols as flame retardants for flexible polyurethane foam: fire behavior and mechanism 磷酸酯基多元醇作为柔性聚氨酯泡沫的阻燃剂：燃烧性能和机理

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-09 DOI: 10.1016/j.polymdegradstab.2026.111932

Zhuo-Lin Li , Wen Ye , Xiang Ao , Ping-Yang Li , Xiong Xiao , Xiao-Lei Li , Zhao-Cong Shang , De-Yi Wang

To address the high flammability, rapid flame spread, and non-self-extinguishing behavior of flexible polyurethane foams (FPUFs), a series of novel liquid reactive phosphate ester polyols, denoted as BOPF, CPF, and EPF, were synthesized by reacting propylene oxide with structurally distinct phosphorus compounds. When incorporated into FPUFs at 3 wt%, CPF demonstrated exceptional performance, achieving an LOI of 20.5% and a 16.4% reduction in peak heat release rate, which decreased to 740 kW/m². A key innovation was that FPUF-3CPF achieved rapid self-extinguishing within 5 s in the vertical burning test, while simultaneously exhibiting an 8.9% increase in tensile strength, effectively overcoming the common drawback of mechanical property deterioration associated with traditional flame retardants. Further investigation into the volatiles released during thermal degradation and the residues after cone calorimetry tests provided insight into the possible flame-retardant mechanisms. In the gaseous phase, the decomposition of phosphorus-based flame retardants generated phosphorus-containing free radicals, which inhibited the combustion chain reaction. In the condensed phase, these flame retardants promoted the formation of a dense and stable char layer on the foam surface. This work provided a feasible strategy for designing high-performance, halogen-free FPUFs that combine rapid self-extinction, enhanced mechanical properties, and significantly reduced fire hazard.

为了解决柔性聚氨酯泡沫（fpuf）的高可燃性、快速火焰蔓延和非自熄行为，通过环氧丙烷与结构不同的磷化合物反应，合成了一系列新型液体反应性磷酸酯多元醇，分别为BOPF、CPF和EPF。当CPF以3 wt%的重量加入fpuf时，CPF表现出优异的性能，LOI达到20.5%，峰值热释放率降低16.4%，降至740 kW/m²。FPUF-3CPF的关键创新之处在于，在垂直燃烧测试中，FPUF-3CPF在5秒内实现了快速自熄，同时抗拉强度提高了8.9%，有效克服了传统阻燃剂机械性能下降的共同缺点。进一步研究热降解过程中释放的挥发物和锥量热法测试后的残留物，有助于深入了解可能的阻燃机制。在气相中，磷系阻燃剂的分解产生含磷自由基，抑制了燃烧链式反应。在凝聚相中，这些阻燃剂促进泡沫表面形成致密而稳定的炭层。这项工作为设计高性能、无卤素fpuf提供了一种可行的策略，该策略结合了快速自灭、增强机械性能和显著降低火灾危险。

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引用次数: 0

In-situ monitoring temporal evolution of functional groups for decoupling multi-stage depolymerization kinetics of polyurethane foam 聚氨酯泡沫解聚多阶段解聚动力学中官能团的实时监测

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-25 DOI: 10.1016/j.polymdegradstab.2026.111959

Xi Liu, Mengman Weng, Yongkui Ren, Fengliang Ji, Haowei Jiang, Zhao-Xia Huang, Jin-ping Qu

It is challenging to precisely control the depolymerization of chemically cross-linked polymers in heterogeneous solid-liquid systems, which requires more effort to illustrate the depolymerization kinetics, especially by utilizing in-situ characterization techniques to monitor the temporal evolution of chemical structures in heterogeneous solid-liquid systems. In this work, we employ the in-situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy to monitor the temporal evolution of functional groups during the depolymerization of waste polyurethane foams. A kinetic model based on two Boltzmann sigmoidal functions was developed to decouple the multi-stage depolymerization behavior. This model resolves the process into four mechanistic stages: induction and interfacial activation, rapid primary depolymerization and limited swelling, synergistic swelling and progressive depolymerization, and final network collapse leading to complete decrosslinking. It further identifies the time-dependent evolution of an inert aromatic C-H out-of-plane bending vibration, enabling the identification of characteristic transition times and a criterion for complete depolymerization. Temperature, catalyst loading, and solvent content significantly influence the kinetic parameters, with solvent content showing an apparent non-monotonic effect. Peak deconvolution of the carbonyl region further reveals distinct degradation behaviors for ester, urethane, and urea linkages. Overall, this study establishes an in-situ spectroscopic framework for elucidating multi-stage depolymerization kinetics in cross-linked polymer networks and provides mechanistic insight into polyurethane degradation processes.

精确控制化学交联聚合物在非均相固液体系中的解聚是一个挑战，这需要更多的努力来阐明解聚动力学，特别是利用原位表征技术来监测非均相固液体系中化学结构的时间演变。在这项工作中，我们采用原位衰减全反射傅立叶变换红外光谱（ATR-FTIR）来监测废聚氨酯泡沫解聚过程中官能团的时间演变。建立了基于两个玻尔兹曼s型函数的动力学模型来解聚。该模型将这一过程分为四个机制阶段：诱导和界面活化，快速初级解聚和有限溶胀，协同溶胀和渐进解聚，最终网络崩溃导致完全解交联。它进一步确定了惰性芳香族C-H面外弯曲振动的时间依赖演化，从而确定了特征过渡时间和完全解聚的标准。温度、催化剂负载和溶剂含量对反应动力学参数有显著影响，溶剂含量表现出明显的非单调效应。羰基区域的反卷积峰进一步揭示了酯、聚氨酯和尿素键的不同降解行为。总的来说，本研究建立了一个原位光谱框架，用于阐明交联聚合物网络中的多阶段解聚动力学，并为聚氨酯降解过程提供了机理见解。

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引用次数: 0

Enhancing flame retardancy, smoke suppression, and hydrothermal aging resistance of polypropylene composites via metal-oxide loaded acid-modified kaolin as a synergist 金属氧化物负载酸改性高岭土作为增效剂增强聚丙烯复合材料的阻燃、抑烟和水热老化性能

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-05 DOI: 10.1016/j.polymdegradstab.2026.111923

Mengyuan Zheng , Jingjing Yang , Gehao Guo , Yifang Hua , Si Guo , Lingyao Zeng , Yuhang Wang , Xiaoyu Gu , Wufei Tang , Sheng Zhang

A co-precipitation route is employed to load Mg²⁺, Cu²⁺, and Zn²⁺ onto acid-treated kaolin (AK), and then calcined at 450°C to obtain the corresponding metal oxides (MO) within the AK (MOAK). These MOAK are then used as synergists for the intumescent flame retardant (IFR) composed of PAPP (polyphosphoric acid piperazine salt)/MPP (melamine polyphosphate) at a mass ratio of 7:3, in the preparation of polypropylene (PP) composites. Partial replacement of IFR with 2 wt.% MOAK, exemplified by PP/14%IFR/2%ZnAK, markedly enhances flame retardancy. This composite achieves UL-94 V-0, while simultaneously reduces the peak heat release rate (pHRR) from 171 kW/m² to 95 kW/m², and the total smoke production (TSP) from 1.36 m² to 0.91 m². These values correspond to reductions of 44% and 33%, respectively, relative to PP/16%IFR composite. Furthermore, the three MOAK synergists demonstrate unique properties: the MgAK-containing composite achieves the most significant smoke suppression, reducing TSP by 97%; the CuAK-modified system meets flame-retardant requirements but compromises mechanical properties; whereas the ZnAK-containing composite achieves an optimal balance between flame retardancy and mechanical performance, alongside remarkable hydrothermal aging resistance. After immersion in 70°C water for 7 days, the PP/14%IFR/2%ZnAK retains 99.9% of its original limiting oxygen index (LOI) and 96.0% impact strength. Collectively, these findings indicate that co-precipitation and calcination of MO on AK enables efficient IFR systems, endowing PP with durable flame-retardant performance.

采用共沉淀法将Mg2+、Cu2+和Zn2+加载到酸处理的高岭土（AK）上，然后在450℃下煅烧得到AK内相应的金属氧化物（MO）（MOAK）。然后，这些MOAK作为增效剂用于由聚磷酸哌嗪盐(PAPP)/聚磷酸三聚氰胺（MPP）以7:3的质量比组成的膨胀阻燃剂（IFR），用于制备聚丙烯（PP）复合材料。用2% MOAK代替部分IFR，如PP/14%IFR/2%ZnAK，可显著提高阻燃性。该复合材料达到UL-94 V-0，同时将峰值热释放率（pHRR）从171 kW/m2降低到95 kW/m2，总产烟量（TSP）从1.36 m2降低到0.91 m2。这些数值对应于PP/16%IFR复合材料分别减少44%和33%。此外，三种MOAK增效剂表现出独特的性能：含mak的复合材料具有最显著的抑烟效果，可将TSP降低97%；经cuak改性的系统满足阻燃要求，但损害了机械性能；而含znak的复合材料在阻燃性和机械性能之间达到了最佳平衡，同时具有显著的水热老化性能。PP/14%IFR/2%ZnAK在70℃水中浸泡7天后，其极限氧指数（LOI）保持99.9%，冲击强度保持96.0%。总的来说，这些发现表明，MO在AK上的共沉淀和煅烧可以实现高效的IFR体系，赋予PP持久的阻燃性能。

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引用次数: 0