Polymer Degradation and Stability最新文献_第3页

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}

引用次数: 0

Investigating the effects of furan ring substitution and network position on char formation in intrinsically flame-retardant epoxy resins 研究呋喃环取代和网络位置对环氧树脂本质阻燃成焦的影响

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-08 DOI: 10.1016/j.polymdegradstab.2025.111538

Amy Honnig Bassett , Alexander B. Morgan , Giuseppe R. Palmese

{"title":"Investigating the effects of furan ring substitution and network position on char formation in intrinsically flame-retardant epoxy resins","authors":"Amy Honnig Bassett , Alexander B. Morgan , Giuseppe R. Palmese","doi":"10.1016/j.polymdegradstab.2025.111538","DOIUrl":"10.1016/j.polymdegradstab.2025.111538","url":null,"abstract":"<div><div>Flame-retardant chemicals are often added to epoxy resins to decrease their flammability. However, there is an increasing interest in transitioning from these chemicals to intrinsically flame-retardant epoxies. One promising approach involves incorporating furan into polymers, which is known to enhance char formation. Nonetheless, the chemical reactions that allow furan to convert from five-membered rings to six-membered rings in the final carbon structure remain poorly understood. In this work, three furan-based epoxy resins were developed to explore how furan ring substitution and network positioning affect char formation: furan diepoxy (FDE), methyl furan diepoxy (MethylFDE), and tetraglycidyl amine of difuran diamine (TGDFDA). Thermogravimetric analysis (TGA) and evolved gas analysis showed that the network position of the furan ring has a greater impact on char formation than ring substitution. PolyTGDFDA, which has main-chain furan rings, had the highest char yield of 44.0 ± 0.6 % at 1000 °C in a nitrogen atmosphere. In contrast, PolyFDE, containing pendant, monosubstituted furan rings, displayed a char yield of 38.6 ± 0.7 %, while PolyMethyl-FDE, with pendant, disubstituted furan rings, yielded 22.4 ± 2.1 %. The influence of furan ring substitution and network position significantly impacted the char yield, but not the type of carbon formed, as shown by Raman spectroscopy. The enhanced char yields positively affected the flammability performance, as evaluated by micro-combustion calorimetry (MCC). These furan-based epoxies showed a path toward developing intrinsically flame-retardant polymers without needing flame-retardant chemicals. Furthermore, insights into the role of furan rings during char formation were developed.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111538"},"PeriodicalIF":6.3,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144633946","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

Preparation of core-shell hybrid particles based on biomass resveratrol and phosphazene molecules co-assisted bimetallic ZIF achieves efficient flame-retardant modification and mechanical property enhancement of polyurea 基于生物质白藜芦醇和磷腈分子共助双金属ZIF制备核壳杂化颗粒，实现了聚脲的高效阻燃改性和力学性能增强

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-07 DOI: 10.1016/j.polymdegradstab.2025.111536

Jing Qiao , Guanyue Zeng , Lingfeng Cui , Hua Wang , Hanhua Tan , Fuping Dong , Yuzhu Xiong

{"title":"Preparation of core-shell hybrid particles based on biomass resveratrol and phosphazene molecules co-assisted bimetallic ZIF achieves efficient flame-retardant modification and mechanical property enhancement of polyurea","authors":"Jing Qiao , Guanyue Zeng , Lingfeng Cui , Hua Wang , Hanhua Tan , Fuping Dong , Yuzhu Xiong","doi":"10.1016/j.polymdegradstab.2025.111536","DOIUrl":"10.1016/j.polymdegradstab.2025.111536","url":null,"abstract":"<div><div>The evolution of Spray Polyurea Elastomer (SPUA) technology has revolutionized protective coating materials. While market demands have accelerated polyurea (PUA) development, achieving high-performance fire-resistant formulations remains a critical challenge. In this study, a novel core-shell hybrid flame-retardant particle, FPM@ZIF-67/ZIF-8, was successfully synthesized through the precise assembly of bimetallic ZIF onto functional polyphosphazene microspheres (FPM). By strategically incorporating biomass-derived resveratrol and phosphazene molecules to introduce flame-retardant features, such as phosphorus-nitrogen heterocycles and aromatic rings, and capitalizing on the synergistic interaction between these structures and the smoke-suppressing properties of ZIFs, highly efficient flame-retardant PUA composites were successfully prepared. Specifically, the 5 wt % FPM@ZIF-67/ZIF-8 composite achieves UL-94 V-0 rating with limiting oxygen index (LOI) increasing from 20.3 % to 28.4 %. Relative to pure PUA, reductions of 41.6 %, 40.9 %, and 37.8 % were observed in pHRR, THR, and TSP, respectively. Furthermore, robust interfacial adhesion between FPM@ZIF-67/ZIF-8 particles and the PUA matrix, combined with efficient energy dissipation mechanisms, resulted in enhanced tensile strength (20.8 MPa) and elongation at break (1014.6 %). This study advances the design of bio-derived core-shell flame-retardant hybrids, facilitating the creation of high-performance PUA elastomers with balanced fire resistance and mechanical integrity. These findings hold substantial implications for broadening PUA applications in fire-sensitive domains.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111536"},"PeriodicalIF":6.3,"publicationDate":"2025-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604280","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-reconstruction-functional enhancement coupled upcycling of waste PET into recycled thermoplastic polyurethane with P-N synergistic flame retardancy 降解-重建-功能增强耦合再生PET成P-N协同阻燃的再生热塑性聚氨酯

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-07 DOI: 10.1016/j.polymdegradstab.2025.111537

Zhenlin Jiang , Jizhe Liu , Wanyu Xie , Yi Song , Ning Liu , Jiaguo Li , Baoxiu Wang , Jiapeng Chen , Shiqiang Song , Peng Ji

{"title":"Degradation-reconstruction-functional enhancement coupled upcycling of waste PET into recycled thermoplastic polyurethane with P-N synergistic flame retardancy","authors":"Zhenlin Jiang , Jizhe Liu , Wanyu Xie , Yi Song , Ning Liu , Jiaguo Li , Baoxiu Wang , Jiapeng Chen , Shiqiang Song , Peng Ji","doi":"10.1016/j.polymdegradstab.2025.111537","DOIUrl":"10.1016/j.polymdegradstab.2025.111537","url":null,"abstract":"<div><div>Functional regeneration of waste plastics is a pivotal strategy for sustainable development. This study has developed a method for functional and collaborative upgrading recycling of waste PET. By using chemical alcoholysis and copolymerization techniques, the waste PET is chemically modified into flame-retardant polyester polyols (rFR POL). It is then used as functional soft segments to polymerize, resulting in the synthesis of recycled high transparency, weather-resistant, and flame-retardant thermoplastic polyurethane (rFR TPU). Research shows using rFR POL as a soft segment cuts petroleum-based material use by 57 % in TPU production. And this enhances the transparency, hydrolysis resistance and flame retardancy of TPU films. After 14 days of hydrolysis and thermal weight loss tests, it was found that the molecular weight of rFR50 % TPU remains almost unchanged, with a high T<sub>5wt %</sub> (225 °C). For rFR100 % TPU, the phosphorus content increases to 19,680 ppm, the LOI reaches 35.30 %, and the vertical burning is rated V-0. The flame retardancy mechanism is attributed to the synergistic gas phase and condensed phase flame retardant effects of P-N. The total GWP of this process is 2800 kg CO<sub>2</sub> equivalent, and the total cost is $1342 per ton, which is 37.8 % and 42 % lower than traditional petroleum-based TPU production, respectively. This process reduces polyester fire risks, fundamentally solves functional chain migration and excessive modifier issues. It also achieves upgraded recycling of non-biodegradable polyester, providing an innovative solution for green flame-retardant polymer development.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111537"},"PeriodicalIF":6.3,"publicationDate":"2025-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604283","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

Effect of hydrotalcite on the thermal stabilization performance of natural antioxidant vitamin E in Ziegler-Natta polyethylene 水滑石对Ziegler-Natta聚乙烯天然抗氧化剂维生素E热稳定性能的影响

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-06 DOI: 10.1016/j.polymdegradstab.2025.111534

Guangxin Zhao , Fushan Wang , Jiachun Feng

{"title":"Effect of hydrotalcite on the thermal stabilization performance of natural antioxidant vitamin E in Ziegler-Natta polyethylene","authors":"Guangxin Zhao , Fushan Wang , Jiachun Feng","doi":"10.1016/j.polymdegradstab.2025.111534","DOIUrl":"10.1016/j.polymdegradstab.2025.111534","url":null,"abstract":"<div><div>Residual catalysts in Ziegler-Natta (ZN) polyolefins usually significantly impair the effectiveness of antioxidants and the incorporation of acid scavengers is an effective method to mitigate these detrimental effects. With the increasing use of natural antioxidants like vitamin E (VE) in human-safety applications, whether their stabilizing effectiveness is affected by catalyst residues and whether traditional acid scavengers remain effective have become key issues requiring urgent resolution. This study systematically investigated the impact of hydrotalcite, a conventional acid scavenger, on VE's thermal stabilization performance in ZN polyethylene (ZN-PE). The results demonstrated that combining 500 ppm VE with 500 ppm hydrotalcite significantly extended the oxidation induction time of ZN-PE to 55.7 min at 190 °C, which surpassed the 30.7 min achieved by 1000 ppm VE alone. The changes in chemical structure, mechanical properties, and color of different samples after multiple extrusions and accelerated aging further confirmed the strong synergistic effect of VE and hydrotalcite in enhancing the thermal-oxidative stability of ZN-PE. Mechanistic investigations revealed that hydrotalcite primarily functioned by eliminating the impairment of VE’s antioxidant efficiency caused by the ZN catalyst. Additionally, hydrotalcite exhibited a certain adsorption effect on VE, which could control the release of VE, thereby extending its antioxidant efficiency in ZN-PE. These findings highlight the critical role of acid scavengers in optimizing VE performance, providing an effective strategy to optimize the use of natural antioxidants in ZN polyolefin stabilization.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111534"},"PeriodicalIF":6.3,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144587442","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

Antioxidant depletion in polyethylene used in chlorinated seawater: from accelerated ageing to modelling 氯化海水中使用的聚乙烯抗氧化剂损耗：从加速老化到建模

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-06 DOI: 10.1016/j.polymdegradstab.2025.111535

R Laot , P-Y․Le Gac , M․Le Gall , M. Broudin , C. Ovalle , L. Laiarinandrasana

{"title":"Antioxidant depletion in polyethylene used in chlorinated seawater: from accelerated ageing to modelling","authors":"R Laot , P-Y․Le Gac , M․Le Gall , M. Broudin , C. Ovalle , L. Laiarinandrasana","doi":"10.1016/j.polymdegradstab.2025.111535","DOIUrl":"10.1016/j.polymdegradstab.2025.111535","url":null,"abstract":"<div><div>This study focuses on the loss of stabilizers used in polyethylene (PE) formulations exposed to chlorinated seawater. A PE model containing antioxidants is aged in three different environments: deoxygenated water, oxygenated water and chlorinated seawater with oxygen. To elucidate slow-occurring phenomena, accelerated ageing experiments were performed across a range of chlorine concentrations and temperatures. Additionally, ageing tests are performed on samples of different thicknesses to distinguish between surface processes, reaction-based mechanisms and diffusion-involved mechanisms. In all cases, the loss of stabilizers is monitored by measuring the oxidation induction time. The results show that the physical extraction of stabilizers (leaching) can be described using existing theories from the literature, with the extraction constants identified based on tests in deoxygenated water at 60, 80 and 90 °C. It appears that the presence of oxygen in water leads to a faster decrease in stabilizers over time, explained by the reaction of these molecules with free radicals formed during the oxidation process. Kinetic rates associated with this process were determined at 40, 60, 80 and 90 °C. Finally, for the first time, the kinetics of stabilizer loss in chlorinated seawater are identified for two pro-oxidant concentrations at 21 °C. Based on theoretical considerations from the literature, a kinetic model of stabilizer loss is proposed to describe the results obtained in this study.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111535"},"PeriodicalIF":6.3,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604281","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

Flammability of flax plant fractions: a whole-plant study from micro- to bench-scale 亚麻植物组分的可燃性：从微观到实验规模的全植物研究

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-04 DOI: 10.1016/j.polymdegradstab.2025.111532

Solène Galinier , Clément Brendlé , Johnny Beaugrand , Antoine Barbulée , Nicolas Le Moigne , Rodolphe Sonnier

{"title":"Flammability of flax plant fractions: a whole-plant study from micro- to bench-scale","authors":"Solène Galinier , Clément Brendlé , Johnny Beaugrand , Antoine Barbulée , Nicolas Le Moigne , Rodolphe Sonnier","doi":"10.1016/j.polymdegradstab.2025.111532","DOIUrl":"10.1016/j.polymdegradstab.2025.111532","url":null,"abstract":"<div><div>The flammability of a large set of 7 flax plant fractions, namely roots, shives, scutched fibres, tows, fines, seeds and capsules, has been studied using pyrolysis-combustion flow calorimetry and cone calorimetry in order to characterize the most performant fractions in terms of fire reaction. In addition, scutched fibres from twelve flax varieties with different growth locations and retting conditions have been considered to assess the variability of flammability properties and understand the scattering of results observed in the literature. The fines, produced in small amounts and rich in minerals, are the least flammable fraction, with a low heat release (6.1 kJ/g after anaerobic pyrolysis at microscale) and a high content of mineral-enriched residue (45 wt %). On the contrary, seeds release a large amount of energy (19.6 kJ/g) during combustion due to their oil-rich composition (> 30 wt %). In addition, variables such as flax variety, growth location and retting have a significant influence on the flammability properties of scutched fibres although the respective contributions of these factors cannot be easily discriminated.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111532"},"PeriodicalIF":6.3,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144632150","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

Efficient polyphosphazene covalent triazine flame retardants for epoxy resin: Double-faced role of benzene ring and flame-ratardant mechanism 环氧树脂用高效聚磷腈共价三嗪阻燃剂：苯环的双面作用及阻燃机理

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-04 DOI: 10.1016/j.polymdegradstab.2025.111530

Yu Feng , Doudou Li , Weiwei He , Lifen Zhang , Zhenping Cheng

{"title":"Efficient polyphosphazene covalent triazine flame retardants for epoxy resin: Double-faced role of benzene ring and flame-ratardant mechanism","authors":"Yu Feng , Doudou Li , Weiwei He , Lifen Zhang , Zhenping Cheng","doi":"10.1016/j.polymdegradstab.2025.111530","DOIUrl":"10.1016/j.polymdegradstab.2025.111530","url":null,"abstract":"<div><div>Despite significant progress has been made, fabricating organic flame retardants with excellent fire resistance at low level addition remains a challenging task. In this work, four polyphosphazene covalent triazine (PCT) flame retardants which are named as MTP, B-MTP, CTP and B-CTP respectively, are synthesized through simple precipitation polymerization, and introduced into epoxy resin (EP) to investigate the anti-flammability. An addition of 3 wt% B-MTP significantly improves the char residue at 800 °C and enhances the thermal stability of EP. In addition, the peak heat release rate (p-HRR), fire growth index (FGI), total smoke production (TSP), and total heat release (THR) decrease by 40.2 %, 64.9 %, 32.3 %, and 28.8 %, respectively. Subsequently, the flame-ratardant mechanisms of PCT with different structures are studied in detail using thermogravimetric analysis-Fourier transform infrared, X-ray photoelectron, and Raman spectroscopy. Interestingly, for the first time the double-faced role of benzene ring in the flame-ratardant performance of the prepared PCT flame retardants is discovered, probably due to the delayed noncombustible gas generation mechanism. This work provides theoretical support for future construction of efficient PCT based flame retardants.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111530"},"PeriodicalIF":6.3,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144587441","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

Depolymerisation of polyisoprene by olefin cross-metathesis at equilibrium 在平衡状态下烯烃交叉复分解聚异戊二烯的解聚合

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-03 DOI: 10.1016/j.polymdegradstab.2025.111529

Alexis Perrot, Julien Renault, Isabelle Dez

{"title":"Depolymerisation of polyisoprene by olefin cross-metathesis at equilibrium","authors":"Alexis Perrot, Julien Renault, Isabelle Dez","doi":"10.1016/j.polymdegradstab.2025.111529","DOIUrl":"10.1016/j.polymdegradstab.2025.111529","url":null,"abstract":"<div><div>Chemical valorisation of polymers gained a massive interest in the recent years, as it represents a more sustainable approach for the management of plastic waste. In particular, depolymerisation of polydienes by olefin cross metathesis is a powerful strategy to access telechelic oligomers with a variety of end groups. Despite the multiplication of investigations aimed at developing new materials from these oligomers, there has been little interest in the prediction of their molecular weight after depolymerisation, even though it represents a major parameter influencing macromolecular properties; in fact, most studies only rely on a kinetic approach to obtain a targeted molar mass. Here, we demonstrate that the equilibrium molecular weight of the oligodienes can be calculated from the amount of chain-transfer agent incorporated in the polymer. Equilibrium was achieved by performing several additions of catalyst, and the molar mass could be predicted from a simple statistical model. While we could not predict the conversion of chain-transfer agent beforehand, this statistical approach still provides an easy tool to establish the degree of polymerization of the products and, hence, have a better control over the final materials properties.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111529"},"PeriodicalIF":6.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144571434","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

Preparation of a durable flame-retardant regenerated cellulose fiber with enhanced mechanical properties 增强机械性能的耐用阻燃再生纤维素纤维的制备

IF 6.3 2区化学

Polymer Degradation and Stability Pub Date : 2025-07-02 DOI: 10.1016/j.polymdegradstab.2025.111523

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

{"title":"Preparation of a durable flame-retardant regenerated cellulose fiber with enhanced mechanical properties","authors":"Guangming Sun, Jieyu Wei, Hejun Li, Tian Li, Hui Xu, Fayu Sun, Guangxian Zhang","doi":"10.1016/j.polymdegradstab.2025.111523","DOIUrl":"10.1016/j.polymdegradstab.2025.111523","url":null,"abstract":"<div><div>The incorporation of flame retardants into regenerated cellulose spinning solutions is a crucial approach for producing flame-retardant regenerated cellulose fibers. However, this method often encounters challenges such as poor compatibility and inadequate dispersion of the flame retardants within the matrix. In this study, a novel flame retardant (P-TSDPAH) was synthesized using ordinary materials such as tetramethylphosphonium sulfate, dimethyl phosphite, and ammonia solution. The P-TSDPAH contains a lot of -NH- bonds, exhibits compatibility with cellulose and N-methylmorpholine N-oxide (NMMO), and remains good dispersion in the cellulose spinning solution. SEM analysis revealed that the P-TSDPAH was uniformly distributed within the FR-fiber 15 % without aggregation, and EDS results confirmed the presence of substantial phosphorus content. FTIR analysis confirmed the presence of characteristic P-C-O, C<img>N, and N<img>H structures within the FR-fiber 15 %. XRD analysis revealed an enhanced crystallinity in the FR-fiber 15 % upon incorporation of the P-TSDPAH. Compared with pure regenerated cellulose fibers, the peak heat release rate and total heat release of FR-fiber 15 % were reduced by 88.61 % and 30.50 %, respectively, while the char residue at 700 °C increased by 142.79 %. TG and TG-IR analyses demonstrated the flame retardancy of the FR-fiber 15 %, revealing condensed-phase flame retardant mechanism, while limiting oxygen index (LOI) remained at 35.0 % even after 50 washing cycles (NFPA 2112–2012 standard), demonstrating durable performance. Additionally, the incorporation of the P-TSDPAH enhanced the mechanical properties of the regenerated cellulose fibers, which the relative breaking strength and elongation increased by 31.16 % and 48.05 %, respectively. Therefore, the synthesized P-TSDPAH demonstrates application potential for developing durable flame-retardant regenerated cellulose fibers.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111523"},"PeriodicalIF":6.3,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144571435","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