Polymer Degradation and Stability最新文献_第4页

Porous organic polymers containing Tröger's base for enhanced NOx adsorption 含有Tröger碱的多孔有机聚合物，用于增强氮氧化物吸附

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-13 DOI: 10.1016/j.polymdegradstab.2025.111548

Huimin Chen , Xin Li , Wenjiang Li , Aoao Lu , Chenguang Li , Qiang Li , Dabin Liu , Hongfei Ma , Binbin Wang

{"title":"Porous organic polymers containing Tröger's base for enhanced NOx adsorption","authors":"Huimin Chen , Xin Li , Wenjiang Li , Aoao Lu , Chenguang Li , Qiang Li , Dabin Liu , Hongfei Ma , Binbin Wang","doi":"10.1016/j.polymdegradstab.2025.111548","DOIUrl":"10.1016/j.polymdegradstab.2025.111548","url":null,"abstract":"<div><div>The safe long-term storage of nitrocellulose (NC) has become increasingly challenging under extreme environmental conditions due to accelerated NO<sub>x</sub> release, which promotes self-catalytic decomposition of NC. In this study, Tröger’s base (TB) was integrated into porous organic polymers (POPs) to achieve dual functionality: efficient physical adsorption and stable in-situ chemical fixation of NO<sub>x</sub> within confined pore spaces. Solid-state CP/MAS <sup>13</sup>C NMR spectroscopy and quantum chemical calculations were employed to confirm that NO<sub>x</sub> immobilization occurs preferentially at the ortho positions of tertiary amine moieties on aromatic rings. Among the synthesized materials, the polymer resulting from the Trögerization of the Tetrakis (4-aminophenyl) methane (TAPM-TB) was identified as the optimal adsorbent, characterized by accessible ortho-active sites, a microporous structure, and an exceptional NO<sub>x</sub> uptake capacity of 3.31 mmol/g under standard conditions. Furthermore, TAPM-TB was demonstrated to extend the stability time of NC by 3.23 times in methyl violet tests. These findings highlight a novel strategy for designing materials capable of simultaneous physical adsorption and stable chemical immobilization of NO<sub>x</sub> or other gases.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111548"},"PeriodicalIF":6.3,"publicationDate":"2025-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144654085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

TiO2-loaded halloysite nanocomposites: achieving the UV resistance and dielectric stability of polyurea 负载tio2的高岭土纳米复合材料：实现聚脲的抗紫外线和介电稳定性

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-13 DOI: 10.1016/j.polymdegradstab.2025.111549

Le Li , Yifan Liu , Haishun Zhang , Huajie Shen , Xiaoxuan Yin , Haoyi Li , Honggang Peng , Songsong Zhou , Yunpeng Liu

{"title":"TiO2-loaded halloysite nanocomposites: achieving the UV resistance and dielectric stability of polyurea","authors":"Le Li , Yifan Liu , Haishun Zhang , Huajie Shen , Xiaoxuan Yin , Haoyi Li , Honggang Peng , Songsong Zhou , Yunpeng Liu","doi":"10.1016/j.polymdegradstab.2025.111549","DOIUrl":"10.1016/j.polymdegradstab.2025.111549","url":null,"abstract":"<div><div>This study proposes a modification strategy for polyurea (PU) using halloysite nanotubes (HNTs) loaded with titanium dioxide (TiO<sub>2</sub>) to enhance the ultraviolet (UV) aging resistance of PU materials. TiO<sub>2</sub>–HNT nanocomposite fillers were prepared through the surface loading modification, and the effects of different TiO<sub>2</sub>–HNT concentrations (2–10 wt %) on the structural, hydrophobic, and dielectric properties of PU composites were systematically investigated. Through the analysis of the test results, we discovered an interesting phenomenon: the UV shielding performance of the nanocomposite enhances the UV resistance of PU at low content levels, whereas at high content levels, the photocatalytic effect of TiO<sub>2</sub> accelerates PU degradation. With 4 wt % TiO<sub>2</sub>–HNT loading, PU exhibited the best stability and achieved a 76.4 % enhancement in dielectric constant while maintaining hydrophobicity (contact angle >110°). After 300 h of accelerated UV aging, the optimized PU retained 83.9 % of its initial breakdown strength, outperforming pure PU (76.1 % retention), and its dielectric loss was 25.8 % lower than that of pure PU. The developed nanocomposite offers a green and efficient solution for enhancing the durability and stability of insulation materials in high-voltage transmission systems.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111549"},"PeriodicalIF":6.3,"publicationDate":"2025-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144663305","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Life cycle design of polylactic acid with superior flame retardancy, mechanical stability under UV, and cyclic utilization 具有优异阻燃性、紫外线下机械稳定性和循环利用的聚乳酸的生命周期设计

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-12 DOI: 10.1016/j.polymdegradstab.2025.111546

Xin Chen , Xinyu Cui , Yifang Hua , Jinlong Huang , Yanfeng Sui , Jun Sun , Hongfei Li , Xiaoyu Gu , Sheng Zhang

{"title":"Life cycle design of polylactic acid with superior flame retardancy, mechanical stability under UV, and cyclic utilization","authors":"Xin Chen , Xinyu Cui , Yifang Hua , Jinlong Huang , Yanfeng Sui , Jun Sun , Hongfei Li , Xiaoyu Gu , Sheng Zhang","doi":"10.1016/j.polymdegradstab.2025.111546","DOIUrl":"10.1016/j.polymdegradstab.2025.111546","url":null,"abstract":"<div><div>Polylactic acid (PLA) is a promising recyclable polymer, however, it suffers form high flammability, significant mechanical deterioration under ultraviolet (UV) irradiation, and slow degradation after its service life. In this work, a multifunctional additive is synthesized by chitosan (CS), 2,3,4-trihydroxybenzaldehyde (THBA), and sodium tripolyphosphate (TPP). The resulting product, TPP-TCS, simultaneously improves the fire safety and UV resistance of PLA while alos accelerating its degradation in an alkaline solution. At a loading of 10 wt. % TPP-TCS, the PLA composite achieves a V-0 rating in the UL-94 test. In addition, TPP-TCS improves the ductility of PLA and remains the enhancement after 100 h UV irradiation. Specifically, the tensile strength and elongation at break of the control PLA decrease by 50.0 % and 44.1 %, respectively, whereas the losses are reduced to only 19.4 % and 1.0 %, respectively, with 10 wt. % TPP-TCS. Futhermore, the hydrolytic degradation rate of PLA is accelerated by a factor of 50. Finally, the degradation products were successfully repolymerized, demonstrating the potential for a degradation-based recycling route for PLA. This work presents a practical approach to fabricating PLA materials with enhanced overall performance and true recyclability.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111546"},"PeriodicalIF":6.3,"publicationDate":"2025-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144654086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Molecularly designed piperazine-derived advanced styrene thermoplastic elastomers with high modulus, fire safety and compatibility properties 分子设计的哌嗪衍生的高级苯乙烯热塑性弹性体具有高模量，防火安全和相容性

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-11 DOI: 10.1016/j.polymdegradstab.2025.111545

Ao Qin , Chentao Yan , Tao Wu , Kai Xu , Xueqian Fan , Peirui Song , Yongqi Chen , Yangtian Shi , Yue Xu , Lubin Liu

{"title":"Molecularly designed piperazine-derived advanced styrene thermoplastic elastomers with high modulus, fire safety and compatibility properties","authors":"Ao Qin , Chentao Yan , Tao Wu , Kai Xu , Xueqian Fan , Peirui Song , Yongqi Chen , Yangtian Shi , Yue Xu , Lubin Liu","doi":"10.1016/j.polymdegradstab.2025.111545","DOIUrl":"10.1016/j.polymdegradstab.2025.111545","url":null,"abstract":"<div><div>The rapid development of new energy sources, rail transport and other emerging fields poses great challenges to the fire safety, compatibility and durability of TPS composites. Although the commonly used phosphorus-nitrogen flame retardants can decrease the flammability of TPS, their flame retardant efficiency and compatibility in TPS need to be further improved. Hereon, a piperazine-derived diethylphosphonic acid-phosphoric acid piperazine (PDHP) flame retardant containing P-C and P-O structures was successfully synthesized. The construction of various phosphorous-containing groups for PDHP not only realized efficient flame retardancy of TPS by the effect of gas and condensed phase, but also possessed good compatibility with TPS matrix by its terminal ethyl structure. With the incorporation of 25 wt % PDHP, TPS/PDHP25 composites passed a UL-94 V-0 rating. Compared to pure TPS, the PHRR and THR of TPS/PDHP25 composites were decreased by 77.6 % and 18.3 %. Condensed and gas phase analysis indicated that the flame retardant mechanism of PDHP was mainly characterized by catalytic charring and inhibition effects. The elastic modulus of TPS/PDHP25 composites was about twice as high as that of pure TPS and their mechanical performance was significantly retained. Meanwhile, the compatibility performance of TPS/PDHP system at the molecular level was elucidated by molecular dynamics simulations. Compared to reported flame retardant TPS composites, TPS/PDHP composite realizes an optimal balance between efficient flame retardancy and mechanical performance. This study provides valuable insights into the design and manufacture of flame retardant TPS composites with excellent mechanical properties, flame retardancy, and compatibility.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111545"},"PeriodicalIF":6.3,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144654088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Degradation of polypropylene random copolymer in aqueous solution of chlorine dioxide: Effect of crystalline structure and morphology 聚丙烯无规共聚物在二氧化氯水溶液中的降解：结晶结构和形态的影响

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-11 DOI: 10.1016/j.polymdegradstab.2025.111540

Rohollah Shamizade, Gholamreza Pircheraghi

{"title":"Degradation of polypropylene random copolymer in aqueous solution of chlorine dioxide: Effect of crystalline structure and morphology","authors":"Rohollah Shamizade, Gholamreza Pircheraghi","doi":"10.1016/j.polymdegradstab.2025.111540","DOIUrl":"10.1016/j.polymdegradstab.2025.111540","url":null,"abstract":"<div><div>The influence of crystal polymorphism (α, β, γ phases) and spherulite diameter (D<sub>s</sub>) on the degradation of polypropylene random copolymer (PP-R) in chlorine dioxide (ClO<sub>2</sub>) was investigated. Three PP-R samples—one neat (P) and two with α (A) or β (B) nucleating agents, resulting in initial spherulite diameters of <em>P</em> > <em>B</em> > <em>A</em>—were aged in 20 ppm ClO<sub>2</sub> solution at 60 °C. Chemical degradation, monitored by Carbonyl Index (FTIR) and elongation at break (tensile tests), was most pronounced in sample A (smallest spherulites) and least in sample P (largest spherulites). After 1440 h, sample A exhibited the highest carbonyl content, and its elongation at break reached 50 % of its initial value earlier than sample B, while sample P showed minimal degradation. Rheological and DSC analyses further characterized the degradation. The findings conclude that spherulite size, rather than crystalline phase, predominantly controls PP-R's chemical stability in ClO<sub>2</sub>, with smaller spherulites rendering the material more susceptible to degradation.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111540"},"PeriodicalIF":6.3,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144654083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Novel reactive flame-retardant coating prepared from waste polyethylene terephthalate, phenylphosphonic acid, and novolac glycidyl ether 以废聚对苯二甲酸乙二醇酯、苯基膦酸和新型缩水甘油酯为原料制备新型反应性阻燃涂料

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-11 DOI: 10.1016/j.polymdegradstab.2025.111544

Ngan T Nguyen , Lam H. Pham , Hai T Vo , DongQuy Hoang , Cuong N Hoang

{"title":"Novel reactive flame-retardant coating prepared from waste polyethylene terephthalate, phenylphosphonic acid, and novolac glycidyl ether","authors":"Ngan T Nguyen , Lam H. Pham , Hai T Vo , DongQuy Hoang , Cuong N Hoang","doi":"10.1016/j.polymdegradstab.2025.111544","DOIUrl":"10.1016/j.polymdegradstab.2025.111544","url":null,"abstract":"<div><div>As global production and consumption of poly(ethylene terephthalate) (PET) becomes higher, so does the amount of waste PET. Several methods of waste PET reduction like mechanical and chemical recycling have been investigated. In this report, we selected the new chemical recycling of PET by transesterification reaction with adipic acid to regain terephthalic acid and oligo(ethylene-adipate-co-terephthalate) (OEAT). Terephthalic acid can also be recovered from PET by hydrolysis in the presence of acid or base catalysts at high temperature and pressure, then sophisticated equipment is required. The advantage of the transesterification over hydrolysis process is performing at atmospheric pressure. OEAT contains both aliphatic and aromatic units and reactive carboxylic acid end groups contributing to the flexibility and thermal stability of the prepared polymer. By <sup>1</sup>H NMR characterization, the molar percentages of adipate and terephthalate units in OEAT were 59.4 % and 40.6 %, respectively. The reactions of OEAT and phenyl phosphonic acid with novolac glycidyl ether have been carefully investigated separately or as mixture. The combination of OEAT and phenyl phosphonic acid enhanced the flame retardancy of the obtained coating. Structures of the prepared polymers were confirmed by FTIR and their thermal properties were investigated by DSC-TGA. A simple dicarboxylic acid (adipic acid) was used in place of OEAT for comparison. The cured coating showed higher gel content, higher flexural ultimate stress, strain at break and modulus. However, the flame test of this sample failed. Consequently, both aromatic terephthalate units of OEAT and phosphonate group of PPA contribute to the flame retardancy of the coating.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111544"},"PeriodicalIF":6.3,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144654084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Impact of mechanical reprocessing on degradation and performance of PA 11 and PA 11–LDPE blends 机械再加工对pa11和pa11 - ldpe共混物降解及性能的影响

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-10 DOI: 10.1016/j.polymdegradstab.2025.111541

Johanna Morales , Rose Mary Michell , Denis Rodrigue

{"title":"Impact of mechanical reprocessing on degradation and performance of PA 11 and PA 11–LDPE blends","authors":"Johanna Morales , Rose Mary Michell , Denis Rodrigue","doi":"10.1016/j.polymdegradstab.2025.111541","DOIUrl":"10.1016/j.polymdegradstab.2025.111541","url":null,"abstract":"<div><div>This study examines the mechanical recycling of a virgin PA 11 and a post-consumer PA 11–low density polyethylene (LDPE) (90/10) blend over ten reprocessing cycles. Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (¹H NMR) analyses revealed changes in the intensity and position of specific absorption bands and proton signals, indicating progressive chain scission and molecular rearrangements. A carbonyl band was identified in the virgin PA 11 after reprocessing, a confirmation of thermo-oxidative degradation. Mechanical testing showed gradual reductions in elastic modulus, stress at break, and impact strength, with significant deterioration from the third cycle onward. Rheological analysis revealed consistent decreases in storage modulus (<em>G′</em>), loss modulus (<em>G″</em>), complex viscosity (<em>η*</em>), and changes in damping factor (tan <em>δ</em>), reflecting lower molecular weight and altered viscoelastic behavior. This was further confirmed via Cole–Cole and van Gurp–Palmen plots. In the post-consumer blend, scanning electron microscopy (SEM) showed progressive coalescence of LDPE droplets, contributing to reduced interfacial area and decreased impact resistance. In general, the results showed that virgin PA 11 retains acceptable performance up to three cycles, while the post-consumer blend exhibits faster and more pronounced degradation driven by both chemical and morphological changes particularly due to droplet coalescence and loss of interfacial area.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111541"},"PeriodicalIF":6.3,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144633943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Bio-based benzoxazine containing phthalonitrile: Nonsolvent synthesis, curing behavior and pyrolysis mechanism 含邻苯二腈生物基苯并恶嗪：非溶剂合成、固化行为及热解机理

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-10 DOI: 10.1016/j.polymdegradstab.2025.111542

Ya Xue , Ying Li , Fei Zhong , Zhongxiang Bai , Pan Wang , Kui Li , Fan Lei , Zhoukun He , Yang Yang , Wei Feng , Xulin Yang

{"title":"Bio-based benzoxazine containing phthalonitrile: Nonsolvent synthesis, curing behavior and pyrolysis mechanism","authors":"Ya Xue , Ying Li , Fei Zhong , Zhongxiang Bai , Pan Wang , Kui Li , Fan Lei , Zhoukun He , Yang Yang , Wei Feng , Xulin Yang","doi":"10.1016/j.polymdegradstab.2025.111542","DOIUrl":"10.1016/j.polymdegradstab.2025.111542","url":null,"abstract":"<div><div>Traditional benzoxazines are largely constrained by the dependence on non-renewable resources, solvent-based synthesis, and insufficient thermal resistance. This study presents a novel high-performance bio-based benzoxazine containing phthalonitrile (BZPN), synthesized via melt condensation using eugenol, 3-aminophenoxyphthalonitrile, and paraformaldehyde. The chemical formula of BZPN was validated by FTIR, ¹H and ¹³C NMR analyses. The curing of BZPN involves ring-opening polymerization of oxazine group and ring-forming polymerization from phthalonitrile unit, yielding polybenzoxazines and heteroaromatics respectively. Combined TG-DTG, TG-FTIR with TG-MS technique, the three-stage thermal pyrolysis mechanism of BZPN was proposed. The initial decomposition (<em>T<sub>dm1</sub></em>=395 °C) occurs through the cleavage of C<img>N, C<img>O, and C<img>C bonds in the polybenzoxazine, releasing NH₃, H₂O, CH₄, and CO₂. The second stage (<em>T<sub>dm2</sub></em>=485 °C) involves the cleavage of C<img>O and C<img>C bonds in the heteroaromatic networks by releasing NH₃, H₂O, CH₄, and CO₂. The final carbonization stage (<em>T<sub>dm3</sub></em>=615 °C) includes the transformation of highly aromatic compounds into graphite. With the facile solvent-less synthesis method and superior comprehensive properties (compressive strength: >220 MPa, <em>T<sub>g</sub></em>: >375 °C, <em>T<sub>d5</sub></em>: >390 °C, and <em>C<sub>y</sub></em>: 72 % at 800 °C), bio-based BZPN is a promising high-performance thermosetting resin for advanced industrial and engineering applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111542"},"PeriodicalIF":6.3,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144614721","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Inspired by the shell of an armadillo-black phosphorus nanosheets weared Ar plasma protective clothing to enhance the fire safety of epoxy resin 受犰狳壳的启发，黑色磷纳米片穿上了Ar等离子防护服，增强了环氧树脂的防火安全性

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-10 DOI: 10.1016/j.polymdegradstab.2025.111533

Renjian Xie , Xiu-e Li , Xiaohong Liu , Jialin Li , Shanshan Zhou , Yumei Li , Hui Yang , Guoming Yuan , Kun Wu , Kunxin Wang

{"title":"Inspired by the shell of an armadillo-black phosphorus nanosheets weared Ar plasma protective clothing to enhance the fire safety of epoxy resin","authors":"Renjian Xie , Xiu-e Li , Xiaohong Liu , Jialin Li , Shanshan Zhou , Yumei Li , Hui Yang , Guoming Yuan , Kun Wu , Kunxin Wang","doi":"10.1016/j.polymdegradstab.2025.111533","DOIUrl":"10.1016/j.polymdegradstab.2025.111533","url":null,"abstract":"<div><div>Black phosphorous (BP) nanosheets as a novel two-dimensional material have revealed dramatically fire safety promotion in polymer nanocomposite. Herein, plasma cleaning machine (PC), equiped with Ar plasma, was applied to protect BP (PCBP) to enhance the environmental stability of BP. Further, the fire safety of epoxy resin (EP) was enhanced. The molecular dynamics simulation (MDS) results indicate that the values of binding energy between Ar plasma and BP at 0 K, 200 K, 400 K, 600 K, and 800 K were -847.0148, -847.3044, -847.3012, -847.2975, and -847.3035 eV, respectively. It meant that there was a strong electrostatic interaction between BP and Ar plasma, and it was not affected by temperature. Electron Paramagnetic Resonance (EPR) test revealed that the free radical strength of PCBP decreased than BP, suggesting that the environmental stability of PCBP was better than that of BP. The results of cone calorimetry test (CCT) displayed that the flame retardant ability of EP was enormously improved through the addition amount of 1.5 wt % PCBP nanosheets, for instance, the peak heat release rate (pHRR) and the total heat release (THR) were descended by 22.98 % and 16.24 %, respectively. Epoxy nanocomposite with 1.5 wt% PCBP nanosheets can achieve UL-94 V-0 rating level with a limit oxygen index (LOI) of 30.4. Thermogravimetric analysis (TGA) result displayed that the residual weight rate increased by 23.27 %. Raman test of the residual char layer proved that the value of I<sub>D</sub>/I<sub>G</sub> declined from 4.021 to 3.098, indicating a promotion in the degree of graphitization. These were attributable to the cooperation effect of physical barrier, free radicals trapping and catalytic conversion into char of PCBP.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111533"},"PeriodicalIF":6.3,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144633945","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Thermal decomposition mechanisms of phosphorus flame retardants: A combined theoretical and experimental approach 磷系阻燃剂的热分解机理：理论与实验相结合的方法

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-10 DOI: 10.1016/j.polymdegradstab.2025.111543

Jiuke Chen , Sandro Lehner , Sin Yong Teng , Sabyasachi Gaan , Daniele Passerone , Manfred Heuberger , Ali Gooneie

{"title":"Thermal decomposition mechanisms of phosphorus flame retardants: A combined theoretical and experimental approach","authors":"Jiuke Chen , Sandro Lehner , Sin Yong Teng , Sabyasachi Gaan , Daniele Passerone , Manfred Heuberger , Ali Gooneie","doi":"10.1016/j.polymdegradstab.2025.111543","DOIUrl":"10.1016/j.polymdegradstab.2025.111543","url":null,"abstract":"<div><div>Phosphorus flame retardants (PFRs) are one of the main candidates for a fully organic, sustainable replacement to traditional halogenated FRs. However, their unexpected decomposition remains an open challenge hindering their full potential for sustainable applications in polymers. To address this issue, thermal decomposition of two common PFRs, namely 6H-Dibenz[c,e][1,2]oxaphosphorin, 6-[(1-oxido-2,6,7-trioxa-1-phospha bicyclo[2.2.2]oct‑4-yl)methoxy]-, 6-oxide (DOPO-PEPA) and Aflammit PCO 900 (AF), was studied using density functional theory (DFT) coupled with experimental methods, particularly the direct inlet probe-mass spectrometry (DIP-MS). The DIP-MS spectra were processed and analyzed using algorithms to identify potential decomposition products of DOPO-PEPA and AF. Under inert atmospheric conditions, bond dissociation and proton attack were identified as the predominant decomposition pathways. Geometries of intermediates, transition states, and products along potential energy surfaces were identified through DFT calculations. For DOPO-PEPA, the dissociation of the C<img>O bond linking the DOPO and PEPA moieties was identified as the most kinetically favored dissociation pathway; while for AF, bond dissociation was found energetically demanding. On the other hand, protonation processes demonstrate more dependence on the availability of protons. Cross-validating computational results with experimental observations verified the pathways through which DOPO-PEPA and AF release phosphorus-containing species and other decomposition products. Benefitting from a combination of fundamental molecular models and experimental evidence, this study provides new insights into the molecular mechanisms of thermal degradation of PFRs, thus providing a template for developing new FRs with enhanced thermal stability.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111543"},"PeriodicalIF":6.3,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144654087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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