Polymer Degradation and Stability最新文献_第8页

Gravity-induced asymmetric gradient PVA-based films with superior radiative cooling and flame retardancy for energy-saving building 节能建筑用重力致不对称梯度聚乙烯醇基辐射冷却阻燃膜

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-28 DOI: 10.1016/j.polymdegradstab.2026.111964

Lian Yin , Yuanyuan Zhang , Yizhi Liu , Sheng Zhang , Keqing Zhou

Polymer-based radiative cooling materials show great promise for green building and carbon neutrality by offering passive cooling. However, their effectiveness is limited by absorption of ambient heat radiation, and inherent flammability, which poses a serious challenge to meeting building safety regulations. Hence, this study modified TiO₂ surfaces using KH-550 and phytic acid to prepare silicon/phosphorus co-modified TiO₂ nanohybrids (KH-TiO₂-PA), which were incorporated into a polyvinyl alcohol (PVA) matrix. Through gravity-induced self-assembly, an asymmetrically gradient multifunctional composite film was formed, exhibiting effective radiative cooling, flame retardancy, and enhanced mechanical strength. Owing to its unique gravity-induced asymmetric gradient structure and the vibrational characteristics of C-C, Ti-O-Ti, Si-O-Si, P-O, and P=O bonds, the PVA/37.5%KH-TiO₂-PA composite film achieved a solar reflectivity of 84.7% and an infrared emissivity of 91.1%. Furthermore, the film demonstrated remarkable cooling performance, reducing temperature by up to 10.4°C in outdoor tests, with daytime and nighttime cooling power values of 61.1 W·m⁻² and 98.1 W·m⁻², respectively. According to EnergyPlus simulations, deploying the film on buildings significantly reduced energy consumption (up to 88.24% savings) and cut CO₂ emissions (up to 2.69 tons and $ 486.97 per year). Meanwhile, the incorporation of KH-TiO₂-PA facilitated gas-phase radical quenching and condensed-phase barrier effects, leading to a 40.5% reduction in peak heat release rate and a 58.6% suppression of peak CO₂ production, which substantially enhanced fire safety. Notley, when reinforced with the nanoparticles, the PVA/12.5%KH-TiO₂-PA composite achieved a tensile strength of 113.28 MPa and a Young’s modulus of 4.82 GPa, demonstrating 39.9% and 56.5% enhancements, respectively. This study offers a viable strategy for addressing climate challenges and supporting safe green building development, thereby promoting the application of multifunctional materials in energy-efficient buildings.

聚合物基辐射冷却材料通过提供被动冷却，在绿色建筑和碳中和方面显示出巨大的前景。然而，它们的有效性受到环境热辐射的吸收和固有的可燃性的限制，这对满足建筑安全法规提出了严重的挑战。因此，本研究利用KH-550和植酸对TiO2表面进行改性，制备了硅/磷共改性TiO2纳米杂化物（KH-TiO2-PA），并将其掺入聚乙烯醇（PVA）基体中。通过重力诱导的自组装，形成了一种不对称梯度的多功能复合膜，具有有效的辐射冷却、阻燃和增强的机械强度。由于其独特的重力诱导不对称梯度结构和C-C、Ti-O-Ti、Si-O-Si、P-O和P=O键的振动特性，PVA/37.5%KH-TiO2-PA复合膜的太阳反射率为84.7%，红外发射率为91.1%。此外，该薄膜表现出显著的冷却性能，在室外测试中降低温度高达10.4°C，白天和夜间冷却功率分别为61.1 W·m−2和98.1 W·m−2。根据EnergyPlus的模拟，在建筑物上部署该薄膜可显着降低能耗（节省高达88.24%）并减少二氧化碳排放（每年高达2.69吨和486.97美元）。同时，h - tio2 - pa的掺入促进了气相自由基猝灭和凝聚相势垒效应，峰值放热率降低40.5%，峰值CO2产量降低58.6%，大大提高了防火安全性。结果表明，PVA/12.5%KH-TiO2-PA复合材料的抗拉强度为113.28 MPa，杨氏模量为4.82 GPa，分别提高了39.9%和56.5%。本研究为应对气候挑战和支持安全绿色建筑发展提供了可行的策略，从而促进多功能材料在节能建筑中的应用。

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引用次数: 0

From waste to resource: valorizing hard segments from acidolyzed PU foam as additives in PVC 从废物到资源：酸化PU泡沫硬段作为PVC添加剂的增值

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2025-12-31 DOI: 10.1016/j.polymdegradstab.2025.111909

Yulu Zhu , Yujia Ding , Jianing Yang , Daoguang Han , Zheng Zhou , Meng Ma , Si Chen , Yanqin Shi , Huiwen He , Wei Wang , Xu Wang

The escalating production of plastic waste underscores an urgent need for sustainable polymer recycling. Polyurethane (PU) foam, representing over 50 % of PU output, is particularly challenging to recycle due to its crosslinked structure. While chemical degradation can recover polyols, the hard segment residues (PUSR) remain underutilized. This study presents an innovative strategy for upcycling waste PU foam into a value-added flame retardant. Through a tailored chemical alcoholysis and phosphorylation process, PUSR was converted into a novel "three-in-one" flame retardant (P₁D₁), integrating carbon, acid, and gas sources. When incorporated into soft polyvinyl chloride (PVC), P₁D₁ endowed the composite with a UL-94 V-0 rating and a limiting oxygen index of 24.2 %, significantly enhancing its flame retardancy. Remarkably, this improvement was achieved without compromising mechanical properties, as evidenced by a 42 % increase in elongation at break. This work not only establishes a promising path for PUSR valorization but also provides a sustainable solution for developing high-performance flame-retardant polymers.

塑料废物的不断增加凸显了可持续聚合物回收的迫切需要。聚氨酯（PU）泡沫占PU产量的50%以上，由于其交联结构，回收尤其具有挑战性。虽然化学降解可以回收多元醇，但硬段残基（PUSR）仍未得到充分利用。本研究提出了一种创新的策略，将废弃聚氨酯泡沫升级为增值阻燃剂。通过量身定制的化学醇解和磷酸化工艺，PUSR被转化为一种新型的“三合一”阻燃剂（P1D1），集碳、酸和气源于一体。与软质聚氯乙烯（PVC）混合后，P1D1具有UL-94的V-0额定值和24.2%的极限氧指数，显著提高了其阻燃性。值得注意的是，这种改进是在不影响机械性能的情况下实现的，断裂伸长率提高了42%。这项工作不仅为PUSR的增值开辟了一条有前途的道路，而且为开发高性能阻燃聚合物提供了一个可持续的解决方案。

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引用次数: 0

Novel biosurfactant assisted biodegradation of polystyrene by Actinomycetes and its chemical understanding 新型生物表面活性剂辅助放线菌生物降解聚苯乙烯及其化学性质的研究

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.2026.111946

Amrapali Sakpal , Nazrul Haq , Santanu Dasgupta , Fars Alanazi , Ibrahim A. Alsarra , Mahboob Alam , Syed G. Dastager

The current study highlights the effective biodegradation of polystyrene by two actinobacterial strains, Glutamicibacter sp. K-1 and Rhodococcus sp. BG-30. FT-IR, Raman spectroscopy, and GPC data showed the degradation pattern of polystyrene. Additionally, GC-MS analysis showed that strain K-1 produced a variety of degradation by-products, including alkanes, 2,4-Di-ter-butyl phenol, 2-propenoic acid, tridecyl ester, and dibutyl phthalate, while strain BG-30 produced a greater amount of alkenes, phthalic acid, and isobutyl octyl esters. GPC detected a drop in polystyrene's average molecular weight (Mn), which suggests chain scission of the polymer. Changes in polystyrene's roughness and other morphological properties were shown by AFM and FE-SEM. The effects of a conventional rhamnolipid and a novel thermostable biosurfactant fatty alkene (0.1 % each) on the breakdown of polystyrene were examined. Strain K-1 and BG-30 resulted in increasing the degradation of polystyrene to 12 % (w/w) and 16 % (w/w), respectively in the presence of fatty alkene biosurfactant, there was 10 % (w/w) and 8 % (w/w), degradation in presence of rhamnolipid. To the best of our knowledge, degradation of polystyrene by Glutamicibacter sp. has been reported as a newly identified strain and use of a novel biosurfactant together revealed their potential in biodegradation of plastic to mitigate the plastic pollution using microbial resources.

目前的研究重点是两种放线菌菌株谷氨酰胺杆菌sp. K-1和红球菌sp. BG-30对聚苯乙烯的有效生物降解。FT-IR，拉曼光谱和GPC数据显示了聚苯乙烯的降解模式。此外，GC-MS分析表明，菌株K-1产生了多种降解副产物，包括烷烃、2,4-二叔丁基苯酚、2-丙烯酸、三烷基酯和邻苯二甲酸二丁酯，而菌株BG-30产生了更多的烯烃、邻苯二甲酸和异丁基辛酯。GPC检测到聚苯乙烯的平均分子量（Mn）下降，这表明聚合物发生了链断裂。AFM和FE-SEM分析了聚苯乙烯的粗糙度和其他形态性能的变化。研究了传统鼠李糖脂和新型耐热生物表面活性剂脂肪烯烃（各0.1%）对聚苯乙烯裂解的影响。菌株K-1和BG-30在脂肪烯烃生物表面活性剂存在下对聚苯乙烯的降解率分别提高到12% （w/w）和16% (w/w)，在鼠李糖脂存在下的降解率分别提高到10% （w/w）和8% （w/w）。据我们所知，谷氨酰胺杆菌是一种新发现的降解聚苯乙烯的菌株，而新型生物表面活性剂的使用显示了它们在塑料生物降解方面的潜力，可以利用微生物资源减轻塑料污染。

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引用次数: 0

Surface-modified piperazine pyrophosphate: Migration resistance and high-efficiency flame retardancy in polypropylene 表面改性焦磷酸哌嗪：在聚丙烯中耐迁移和高效阻燃

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.2026.111936

Mingliang Wang , Jiaqi Gao , Xintai Chen , Junzhao Su , Xuhuang Chen

Piperazine pyrophosphate (PAPP), a prominent representative of intumescent flame retardants (IFR), has garnered significant attention due to its high efficiency, halogen-free, and environmentally friendly properties. Nevertheless, PAPP is highly hydrophilic, which predisposes it to powder agglomeration, exudation, and migration within the polymer matrix. This study proposes an innovative surface treatment strategy to enhance the dispersibility and anti-exudation property of PAPP in polypropylene (PP) by forming a hydrophobic cross-linked layer of hydrogen-containing silicone oil (PMHS) and vinyl silicone oil (VSO) on the surface of PAPP. The experimental results showed that the water contact angle of PAPP modified with a hydrophobic cross-linked surface layer (i.e., PHV@PAPP) increased from 0° to 147° The results of migration test under boiling conditions of PP/PHV@PAPP showed that the introduction of PHV@PAPP reduced the precipitation rate of PP/PAPP from 2.29% to 0.17%, and the water absorption rate decreased from 5.75% to 1.41%. The flame-retardant performance of PP/PHV@PAPP showed significant enhancement compared to PP/PAPP, achieving UL-94 V-0 classification with merely 21 wt% flame retardant loading. Additionally, the peak heat release rate (PHRR) decreased from 66 kW·m⁻² to 39 kW·m⁻², and the time to peak heat release rate (T_PHRR) increased from 240 s to 550 s. Moreover, the total smoke production (TSP) and peak smoke production rate (PSPR) were decreased. The analysis of the carbon layer after combustion shows that the density of the PP/PHV@PAPP carbon layer is greater than that of the PP/PAPP carbon layer, indicating that the modified PAPP can effectively inhibit the heat and mass transfer during combustion.

焦磷酸哌嗪（PAPP）是膨胀型阻燃剂（IFR）的杰出代表，因其高效、无卤、环保等特性而备受关注。然而，PAPP是高度亲水的，这使它易于在聚合物基质内形成粉末结块、渗出和迁移。本研究提出了一种创新的表面处理策略，通过在PAPP表面形成含氢硅油（PMHS）和乙烯基硅油（VSO）的疏水交联层，提高PAPP在聚丙烯（PP）中的分散性和抗渗出性能。实验结果表明，疏水交联表面层（即PHV@PAPP）改性后的PAPP的水接触角从0°增加到147°。PP/PHV@PAPP沸水条件下迁移试验结果表明，PHV@PAPP的引入使PP/PAPP的沉淀率从2.29%降低到0.17%，吸水率从5.75%降低到1.41%。与PP/ ppp相比，PP/PHV@PAPP的阻燃性能得到了显著提高，仅在21 wt%的阻燃负荷下就达到了UL-94 V-0级。此外，峰值热量释放速率（PHRR）从66 kW·m⁻²下降到39 kW·m⁻²，峰值热量释放速率（TPHRR）的时间从240 s增加到550 s。总产烟量（TSP）和峰值产烟率（PSPR）均有所降低。对燃烧后碳层的分析表明，PP/PHV@PAPP碳层的密度大于PP/PAPP碳层的密度，说明改性后的PAPP能有效抑制燃烧过程中的传热传质。

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引用次数: 0

A dynamically crosslinked biomass film featuring high flame retardancy, excellent thermal stability, closed-loop recyclability, and biodegradability 一种动态交联生物质薄膜，具有高阻燃性、优异的热稳定性、闭环可回收性和生物降解性

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.2026.111926

Hongshan Li , Xu Zhang , Kelu Ni , Tongda Liu , Tenghua Huang , Hongxing Yang , Xin Ran , Guanben Du , Long Yang

The widespread use of petroleum-based plastics depletes finite fossil resources, exacerbates ecological degradation, and poses persistent environmental threats. Furthermore, these materials are flammable and emit toxic gases upon combustion, creating significant safety risks. Thus, developing recyclable, flame-retardant polymers is a pressing research challenge. Herein, a tough film was prepared from a binary aqueous solution of the natural polymer sodium alginate and tetrahydroxydiborane. The C–O–B dynamic bonds in the polymer film contribute significantly to the enhanced mechanical properties of the material, while boron simultaneously acts as a flame retardant, improving the overall flame retardancy. The optimized film demonstrated outstanding mechanical performance and flame retardancy, exhibiting a tensile strength of 88.38 MPa, a Young’s modulus of 3.2 GPa, a toughness of 3.17 MJ·m^-3, a limiting oxygen index of 42%, and a V-0 flame retardancy rating. Moreover, the material maintained its excellent mechanical and flame-retardant properties after simple recycling and reprocessing, enabling the reuse of waste films. Its biodegradability further enhances the overall sustainability. This study provides a viable strategy for developing sustainable natural polymers as environmentally friendly alternatives to conventional petroleum-based polymers.

石油基塑料的广泛使用耗尽了有限的化石资源，加剧了生态退化，并构成了持续的环境威胁。此外，这些材料是易燃的，燃烧时会释放有毒气体，造成重大的安全风险。因此，开发可回收的阻燃聚合物是一项紧迫的研究挑战。本文以天然聚合物海藻酸钠和四羟基二硼烷二元水溶液为原料制备了一种坚韧膜。聚合物膜中的C-O-B动态键显著提高了材料的机械性能，而硼同时起到阻燃剂的作用，提高了材料的整体阻燃性。优化后的膜具有良好的力学性能和阻燃性能，拉伸强度为88.38 MPa，杨氏模量为3.2 GPa，韧性为3.17 MJ·m-3，极限氧指数为42%，阻燃等级为V-0。此外，该材料经过简单的回收和再加工后，仍保持了优异的机械性能和阻燃性能，实现了废膜的再利用。其生物降解性进一步提高了整体可持续性。这项研究为开发可持续的天然聚合物作为传统石油基聚合物的环保替代品提供了可行的策略。

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引用次数: 0

Synergistic thermal shielding and corrosion protection via Al2O3@HAP-reinforced polypropylene 通过Al2O3@HAP-reinforced聚丙烯协同热屏蔽和防腐

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.2026.111958

Salman Khalid , Mohammad Tabish , Yifang Hua , Muhammad Mubeen , Xinyu Chen , Libo Li , H.M. Ahsen Ilyas , Jun Sun , Xiaoyu Gu , Ghulam Yasin , Sheng Zhang

Achieving simultaneous flame retardancy and anti-corrosion properties in advanced polypropylene (PP) composites and coatings presents a significant challenge. In this work, porous alumina microspheres (Al₂O₃) were prepared via a hydrothermal method and subsequently calcined at 600°C for 3 hours (h). Al₂O₃ was then hybridized with hydroxyapatite (HAP) nanosheets through sonication followed by simple stirring at ambient temperature for 24 h to obtain the Al₂O₃@HAP nanohybrid. The synthesized Al₂O₃ and Al₂O₃@HAP, together with melamine polyphosphate (MPP) and piperazine pyrophosphate (PAPP), were incorporated into PP as fillers to enhance flame-retardant properties. An MPP/PAPP intumescent flame-retardant (IFR) system was employed due to its high char-forming efficiency and environmentally friendly characteristics, offering a promising alternative to halogenated flame-retardants. The PP/12%IFR/3%Al₂O₃@HAP composite exhibited excellent flame retardancy, as demonstrated by a high limiting oxygen index (LOI) of 28.2%, a V-0 rating in the vertical burning test (UL-94), and substantial reductions in peak heat release rate (pHRR, 86%), total heat release (THR, 43%), and total smoke production (TSP, 44%) compared with the control PP. Furthermore, the Al₂O₃@HAP nanohybrid effectively protected Zn-Al-Mg (ZAM) coated-steel against corrosion. The PP/PP-g-MAH/Al₂O₃@HAP nanocomposite coating maintained a high impedance (|Z|_{0.01 Hz}) of 5.46 × 10⁸ Ω cm² after 60 days of immersion in 3.5 wt% NaCl solution, indicating excellent long-term stability. Pull-off adhesion tests demonstrated that the incorporation of the fillers significantly enhanced the adhesion strength compared with the pristine PP/PP-g-MAH coating. Overall, this research presents an efficient strategy for fabricating advanced PP-based materials with simultaneously improved flame retardancy and corrosion resistance, offering substantial potential for diverse industrial applications.

在高级聚丙烯（PP）复合材料和涂层中实现同时阻燃和防腐性能是一个重大挑战。在这项工作中，通过水热法制备多孔氧化铝微球（Al2O3），随后在600°C下煅烧3小时(h)。通过超声将Al2O3与羟基磷灰石（HAP）纳米片杂交，然后在室温下简单搅拌24 h，得到Al2O3@HAP纳米杂化物。将合成的Al2O3和Al2O3@HAP与三聚氰胺聚磷酸（MPP）和焦磷酸哌嗪（PAPP）作为填料掺入PP中，以提高阻燃性能。采用MPP/PAPP膨胀型阻燃剂（IFR）体系，由于其高成炭效率和环保特性，为卤化阻燃剂提供了一个有前途的替代品。PP/12%IFR/3%Al2O3@HAP复合材料表现出优异的阻燃性能，其极限氧指数（LOI）高达28.2%，垂直燃烧试验（UL-94）的V-0等级较高，峰值放热率（pHRR, 86%）、总放热率（THR, 43%）和总产烟率（TSP, 44%）均显著降低。此外，Al2O3@HAP纳米杂化材料还能有效地保护Zn-Al-Mg （ZAM）涂层钢免受腐蚀。在3.5 wt% NaCl溶液中浸泡60天后，PP/PP-g- mah /Al2O3@HAP纳米复合涂层保持5.46 × 108 Ω cm2的高阻抗（|Z|0.01 Hz），具有良好的长期稳定性。拉拔附着力测试表明，与原始PP/PP-g- mah涂层相比，填料的掺入显著提高了附着力。总的来说，这项研究提出了一种制造先进pp基材料的有效策略，同时提高了阻燃性和耐腐蚀性，为各种工业应用提供了巨大的潜力。

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引用次数: 0

Stability of recycled plastics in an aqueous alkaline cementitious matrix 再生塑料在水性碱性胶凝基质中的稳定性

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-07 DOI: 10.1016/j.polymdegradstab.2025.111915

Hasanthi H. Kosgahakumbura , Ivan Kourtchev , Susanne Charlesworth , Damien L. Callahan , Will P. Gates

The rising problem of plastic waste, coupled with a shortage of construction materials, has prompted research into the replacement of traditional aggregates with recycled plastic aggregates (rPA) in cementitious structures. However, the impact of the highly alkaline pore solution present in cement on the long-term stability and performance of rPA is still not fully understood. This research examined the alkaline stability of two types of commonly recycled plastics that increasingly serve as aggregate substitutes in concrete: polyethylene terephthalate (rPET) and high-density polyethylene (rHDPE) in two size ranges, when exposed to extremely alkaline conditions. The effects of exposure to simulated alkaline cement pore solutions on rPA stability were analysed by assessing alterations to polymer mass, surface features, functional groups, and crystallinity. Prolonged exposure (up to 75 days) to simulated cement pore solution significantly decreased the stability of rPA, while fine particle sizes underwent faster degradation, losing up to 40 % of weight. Recycled HDPE demonstrated greater alkali resistance than rPET, suggesting better suitability as an alternative aggregate in concrete, although factors like surface hydrophobicity should be considered. The amorphous regions of rPET surfaces proved more susceptible to hydroxyl reactions compared to crystalline regions, resulting in inferior stability of rPET compared to rHDPE, and therefore raises questions about the use of rPET as an alternative aggregate. Overall, this study elucidated the physical and chemical stability of recycled plastics in alkaline cementitious matrices, revealing how plastic type, intrinsic properties, particle size, and exposure duration govern their suitability as aggregate replacements.

塑料垃圾问题的日益严重，再加上建筑材料的短缺，促使人们研究用再生塑料骨料（rPA）代替传统骨料用于胶凝结构。然而，水泥中存在的高碱性孔隙溶液对rPA长期稳定性和性能的影响尚不完全清楚。本研究检测了两种常用的再生塑料在暴露于极端碱性条件下的碱性稳定性，这两种塑料越来越多地用作混凝土中的骨料替代品：聚对苯二甲酸乙二醇酯（rPET）和高密度聚乙烯（rHDPE），其尺寸范围为两种。通过评估聚合物质量、表面特征、官能团和结晶度的变化，分析了暴露于模拟碱性水泥孔隙溶液对rPA稳定性的影响。长时间暴露于模拟水泥孔隙溶液中（长达75天）会显著降低rPA的稳定性，而细颗粒尺寸的降解速度更快，重量损失高达40%。再生HDPE表现出比rPET更强的耐碱性，这表明它更适合作为混凝土的替代骨料，尽管需要考虑表面疏水性等因素。与结晶区域相比，rPET表面的无定形区域更容易发生羟基反应，导致rPET与rHDPE相比稳定性较差，因此提出了关于使用rPET作为替代聚集体的问题。总体而言，本研究阐明了再生塑料在碱性胶凝基质中的物理和化学稳定性，揭示了塑料类型、内在性质、粒径和暴露时间如何决定它们作为骨料替代品的适用性。

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引用次数: 0

Continuous glycolysis of waste PET via reactive extrusion and copolymerization with PTMG for enhanced toughness 用反应挤出法对废PET进行连续糖酵解，并与PTMG共聚以增强韧性

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-04-01 Epub Date: 2026-01-01 DOI: 10.1016/j.polymdegradstab.2025.111916

Huihui Liu , Yu Zhang , Xinyi Xie , Xuzhen Zhang

In this paper, an efficient continuous glycolysis strategy for waste polyethylene terephthalate (PET) depolymerization was presented using a twin-screw extruder system with ethylene glycol (EG) and zinc acetate (Zn(OAc)₂) catalyst. Under optimized conditions (150 rpm, controlled EG/PET ratio, and reaction parameters), PET was rapidly converted into well-defined oligomers (M_n = 1265-6588 Da) within minutes. Structural characterization (FT-IR, NMR, MALDI-TOF MS) confirmed hydroxyl-terminated bis(2-hydroxyethyl terephthalate) oligomer (BHET oligomer) as the dominant product. Selected oligomers (M_n = 1265 Da) were copolymerized with poly(tetramethylene ether) glycol (PTMG) to synthesize poly(ethylene terephthalate)- ε-poly(tetramethylene ether) glycol copolyetherester (PETMG). By tuning the oligomer/PTMG ratio, the resulting PETMG₃₀ exhibited outstanding toughness (elongation at break: 1102%, impact strength: 105.6 kJ/m²). The developed “polymer-oligomer-polymer” approach significantly enhances processing efficiency and reduces reaction time compared to conventional methods, offering a sustainable pathway for high-value PET upcycling. This work advances circular economy practices by establishing a rapid, controllable recycling paradigm for plastic waste valorization.

以乙二醇（EG）和醋酸锌（Zn(OAc)2）为催化剂，采用双螺杆挤出系统对废聚乙二醇（PET）进行了连续糖酵解。在优化的条件下（150 rpm，控制EG/PET比和反应参数），PET在几分钟内迅速转化为定义明确的低聚物（Mn = 1265-6588 Da）。结构表征（FT-IR， NMR, MALDI-TOF MS）证实端羟基双（对苯二甲酸2-羟乙酯）低聚物（BHET低聚物）为主导产物。将选定的低聚物（Mn = 1265 Da）与聚四亚甲基醚乙二醇（PTMG）共聚，合成聚对苯二甲酸乙酯- ε-聚四亚甲基醚乙二醇共聚醚酯（PETMG）。通过调整低聚物/PTMG的比例，得到的PETMG30具有优异的韧性（断裂伸长率为1102%，冲击强度为105.6 kJ/m²）。与传统方法相比，所开发的“聚合物-低聚物-聚合物”方法显著提高了加工效率，缩短了反应时间，为高价值PET升级回收提供了一条可持续的途径。这项工作通过建立一个快速、可控的塑料废物增值回收范例来推进循环经济实践。

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引用次数: 0

Multi-mechanistic bio-based antioxidants constructed by polyphenol-thiourea-rare earth synergy on enhancing thermo-oxidative aging resistance of NBR 多酚-硫脲-稀土协同构建的多机制生物基抗氧化剂增强丁腈橡胶抗热氧化老化性能

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-03-01 Epub Date: 2025-12-18 DOI: 10.1016/j.polymdegradstab.2025.111872

Shuangjiang He , Zhong Zeng , Wenbin Chen , Xiao Xiao , Ning An , Youquan Ling , Shuai Li , Long Ni , Xiaowen Zhao , Mei Liang , Yang Chen , Huawei Zou

To address the challenges encountered by conventional antioxidants, such as migration, toxicity, and single aging resistance mechanisms, which fail to meet the demands for high performance and sustainability. In this study, a series of multi-mechanistic bio-based antioxidants (PDTA-RE) featuring polyphenol-thiourea-rare earth synergy were designed through a sequential “polymerization-grafting-complexation” strategy. Then, the thermo-oxidative aging resistance of composites was evaluated via 121 °C accelerated aging tests, thermal analysis, and kinetic analysis of thermal-oxidative decomposition. Following 120 h of aging, the PDTASc/NBR composites exhibited a tensile strength retention rate of 93.63% and an aging coefficient (K) of 0.61, which were 79.85% and 258.82% higher than those of Neat/NBR, respectively, while superior to commercial antioxidants. Moreover, polyphenolic groups scavenge free radicals, thiourea mercapto decompose hydroperoxides, and rare earth ions trap residual radicals. Additionally, the polymerized framework and double bond anchoring endowed PDTA-RE with excellent anti-migration ability, avoiding high-temperature efficacy loss.

解决传统抗氧化剂在迁移、毒性、单一抗老化机制等方面无法满足高性能和可持续性要求的难题。本研究通过“聚合-接枝-络合”的顺序策略，设计了一系列具有多酚-硫脲-稀土协同作用的多机制生物基抗氧化剂（PDTA-RE）。然后，通过121℃加速老化试验、热分析和热氧化分解动力学分析来评价复合材料的耐热氧化老化性能。老化120 h后，PDTASc/NBR复合材料的抗拉强度保持率为93.63%，老化系数(K)为0.61，分别比Neat/NBR高79.85%和258.82%，优于工业抗氧化剂。此外，多酚基团清除自由基，硫脲硫醇分解氢过氧化物，稀土离子捕获残留自由基。此外，聚合框架和双键锚定使PDTA-RE具有优异的抗迁移能力，避免了高温效能损失。

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引用次数: 0

When PET meets phosphorus flame retardants: A ReaxFF molecular dynamics study 当PET遇到磷阻燃剂：ReaxFF分子动力学研究

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-03-01 Epub Date: 2025-12-23 DOI: 10.1016/j.polymdegradstab.2025.111876

Jiuke Chen , Sabyasachi Gaan , Manfred Heuberger , Ali Gooneie

Phosphorus-based flame retardants (P-FRs) are widely recognized as effective halogen-free additives for flammable thermoplastics, such as polyethylene terephthalate (PET), offering both strong flame resistance and relatively low toxicity. Due to its broad applications, it is crucial to pin down the degradation behavior of PET in the presence of P-FRs to enhance fire safety and polymer circularity. During conventional mechanical recycling, the underlying chemistry in the PET/P-FR materials may cause adverse reactions, leading to deteriorated mechanical properties of recycled products. This study employed reactive molecular dynamics (ReaxFF-MD) simulations based on reactive force field (ReaxFF) to explore the degradation of the PET containing two model P-FRs, specifically DOPO-PEPA (DP) and Aflammit PCO 900 (AF), at elevated temperatures. The predicted thermal behavior of PET was validated against experimental data, and the degradation mechanisms of PET were scrutinized through the analysis of degradation products, bonding evolution, and extensive trajectory analysis. The theoretically predicted thermal decomposition mechanisms of P-FRs were successfully verified by experiment, which is also consistent with existing research. Compared with DP, the molecule AF shows a retarded decomposition during the heat-up before a rapid fragmentation occurs, which can be attributed to its low-energy chair conformation; DP decomposes earlier due to the weaker CO bond linkage and availability of protons via hydrogen abstraction. Our ReaxFF-MD simulations are based on quantum mechanical calculations and allow for an explicit investigation of the interactions between PET and P-FRs by including polymeric chains and additives in the same simulation. The reactions involving phosphorus species in the PET/P-FR were identified; notably DP fragment that can combine with the polymeric chain-end, as well as gasification effects from AF, which together aids in the comprehensive understanding of their different modes of action. In addition to the temperature effects, the oxidative conditions were included in this study to determine the thermo-oxidative degradation behavior. In this study, ReaxFF-MD simulations provide valuable insights into how thermal and thermo-oxidative degradation pathways evolve and control the fragmentation of PET and PET/P-FR systems. This methodology is proposed as a foundation for future research aimed at understanding complex reaction networks and improving the recycling quality of PET/P-FR materials.

磷系阻燃剂（P-FRs）被广泛认为是可燃性热塑性塑料（如聚对苯二甲酸乙二醇酯（PET））的有效无卤添加剂，具有很强的阻燃性和相对较低的毒性。由于其广泛的应用，确定p - fr存在下PET的降解行为对于提高防火安全性和聚合物循环性至关重要。在常规的机械回收过程中，PET/P-FR材料中潜在的化学物质可能会引起不良反应，导致回收产品的机械性能恶化。本研究采用基于反应力场（ReaxFF）的反应分子动力学（ReaxFF- md）模拟研究了含DOPO-PEPA （DP）和Aflammit PCO 900 （AF）两种模型P-FRs的PET在高温下的降解。根据实验数据验证了预测的PET热行为，并通过降解产物分析、键合演化和广泛的轨迹分析来仔细研究PET的降解机制。实验成功验证了理论预测的P-FRs热分解机理，与已有研究结果一致。与DP分子相比，AF分子在加热过程中分解缓慢，然后发生快速破碎，这可归因于其低能椅形构象；由于较弱的CO键连接和质子通过抽氢的可用性，DP分解较早。我们的ReaxFF-MD模拟是基于量子力学计算的，通过在相同的模拟中包括聚合物链和添加剂，可以明确地研究PET和p - fr之间的相互作用。鉴定了PET/P-FR中涉及磷类的反应；值得注意的是，DP片段可以与聚合物链端结合，以及AF的气化效应，这有助于全面了解它们的不同作用模式。除温度影响外，本研究还考虑了氧化条件，以确定热氧化降解行为。在这项研究中，ReaxFF-MD模拟为热降解和热氧化降解途径如何演变和控制PET和PET/P-FR系统的破碎提供了有价值的见解。该方法是未来研究的基础，旨在了解复杂的反应网络和提高PET/P-FR材料的回收质量。

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引用次数: 0