Polymer Degradation and Stability最新文献

{"title":"Enhanced recyclability of polycaprolactone via precisely defined incorporation of acetal bonds","authors":"Marta Socka,&nbsp;Bartłomiej Kost","doi":"10.1016/j.polymdegradstab.2025.111635","DOIUrl":"10.1016/j.polymdegradstab.2025.111635","url":null,"abstract":"<div><div>Here, we report the synthesis of polycaprolactone with enhanced recyclability without losing its thermal properties. Firstly, we synthesised reactive telechelic polycaprolactones with hydroxyl end-groups, with molar masses in the 1000–4000 g/mol range. Then, homo polycaprolactone was reacted with a model aldehyde (paraformaldehyde) in the presence of a weak acid catalyst to demonstrate the possibility of obtaining high-molecular-weight PCL with modified degradability from a high molecular mass polycaprolactone. The materials were evaluated for their recyclability through the hydrolysis of the acetal bond in the presence of water and the presence of acids of different strengths. The best result was obtained for the solution of hydrochloric acid, leading to the recovery of the reactive polycaprolactone block. The introduction of acetal bonds to the polycaprolactone macromolecules in a strictly defined way improved the chemical recyclability of prepared polymers, retaining their crystallinity and crystallisation temperature unchanged. Furthermore, we demonstrated that the recovered polycaprolactone block can be successfully repolymerized to obtain a material with the same thermal properties as the starting materials.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"242 ","pages":"Article 111635"},"PeriodicalIF":7.4,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145004853","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}

{"title":"Thermal decomposition of cellulosic materials: Insights into mechanisms and product evolution","authors":"Elisabetta Ranucci,&nbsp;Jenny Alongi","doi":"10.1016/j.polymdegradstab.2025.111629","DOIUrl":"10.1016/j.polymdegradstab.2025.111629","url":null,"abstract":"<div><div>This review provides an in-depth exploration of the thermal decomposition behavior of cellulose and cellulosic materials such as cotton and paper, with a focus on the underlying reaction mechanisms. Following a brief overview of the motivations behind studying cellulose decomposition, it introduces key concepts in thermal decomposition, specifically pyrolysis – namely in inert atmosphere – and thermo-oxidation. It then delves into the detailed pathways involved in cellulose decomposition, with special emphasis on the formation of volatile compounds, tar and char – carbon-rich residue. To offer a comprehensive understanding of this complex process, the review also examines the critical factors that influence the balance between volatilization and charring, including heating rate, moisture content, presence of metal ions, cellulose morphology and treatment with functional additives such as flame retardants. These elements are thoroughly discussed to present a complete and nuanced view of cellulose thermal decomposition.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"242 ","pages":"Article 111629"},"PeriodicalIF":7.4,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144919875","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}

{"title":"New insights into solid state phosphorylation of cellulose for the development of bio-based flame retardant","authors":"Sophie Dropsit,&nbsp;Jevgenij Lazko,&nbsp;Nicolas Landercy,&nbsp;Philippe Dubois,&nbsp;Fouad Laoutid","doi":"10.1016/j.polymdegradstab.2025.111632","DOIUrl":"10.1016/j.polymdegradstab.2025.111632","url":null,"abstract":"<div><div>The phosphorylation of microcrystalline cellulose (MCC) has been investigated as a strategy to develop bio-based flame retardants, aiming to enhance their charring ability and thermal stability. The modification process was performed using solid-state mechanochemistry, employing varying excesses of phosphorus pentoxide (P₂O₅) to optimize the phosphorus grafting rate. It was discovered that, with a significant P₂O₅ excess, contact of the recovered blend with a small amount of water induces a vigorous reaction. This reaction leads to cellulose expansion and its conversion into a graphitic structure, while also allowing for the grafting of a high phosphorus content. This phosphorylated graphitic cellulose demonstrated a superior flame retardant effect in polypropylene (PP), achieving a 55 % reduction in peak heat release rate (pHRR) even at a relatively low incorporation content (12.5 wt.%), while also conserving composite ductility.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"242 ","pages":"Article 111632"},"PeriodicalIF":7.4,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020117","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}

{"title":"Hindered phenolic antioxidant with high transamidation reactivity for the long-term thermo-oxidative stabilization of polyamide 6,6","authors":"Jiacheng Zhang ,&nbsp;Alex Zharikov ,&nbsp;Xiaohan Liu ,&nbsp;Juan Chen ,&nbsp;Yanfen Ding ,&nbsp;Haijun Fan ,&nbsp;Mingshu Yang","doi":"10.1016/j.polymdegradstab.2025.111630","DOIUrl":"10.1016/j.polymdegradstab.2025.111630","url":null,"abstract":"<div><div>A hindered phenolic antioxidant (AO) based on a 1,3,5-triazine-2,4,6-N amide structure was synthesized. The resonance energy (<em>E_R</em>) and a theoretical reactivity descriptor for intermolecular reactivity analysis, namely local hyper-softness (<em>s</em>⁽²⁾(<strong>r</strong>)), were calculated by computational methods to assess the transamidation reactivity of the AO. The <em>E_R</em> of the amide bond in the AO was determined to be only 6–7 kcal/mol, which can be attributed to the electron-withdrawing effect of the triazine ring. Owing to this characteristic, the AO exhibits high transamidation reactivity, which allowed us to effectively graft the hindered phenol functional groups to the polyamide 66 (PA66) molecular chain with a grafting rate of almost 60 % through a facile twin-screw extrusion process. The results of accelerated aging experiments demonstrated that the PA66/AO samples, which were grafted with 5.97 μmol/g of the hindered phenol functional groups, exhibited thermo-oxidative stability comparable to that of the PA66 samples containing 8.30 μmol/g of the commercial hindered phenolic antioxidant Irganox 1098. Furthermore, the grafting process effectively prevented the loss of the antioxidant, allowing PA66/AO to maintain good thermo-oxidative stability even after extraction with organic solvents such as ethanol or ethylene glycol. In contrast, PA66/1098 was susceptible to thermo-oxidative degradation due to the physical loss of Irganox 1098 during the extraction experiment.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"242 ","pages":"Article 111630"},"PeriodicalIF":7.4,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144988921","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}

{"title":"Aminotrimethylene phosphonic acid and 1,10-diaminodecane modified ammonium polyphosphate for polypropylene composites with satisfactory flame retardancy and mechanical properties while maintaining transparency","authors":"Xinyu Chen ,&nbsp;Pengyu Wang ,&nbsp;Shuang Qiu ,&nbsp;Xiaowei Su ,&nbsp;Jun Sun ,&nbsp;Xiaoyu Gu ,&nbsp;Hanwei Wang ,&nbsp;Sheng Zhang","doi":"10.1016/j.polymdegradstab.2025.111628","DOIUrl":"10.1016/j.polymdegradstab.2025.111628","url":null,"abstract":"<div><div>Ammonium polyphosphate (APP) is a halogen-free flame retardant with good thermal stability and char-forming ability. However, APP often leads to interface incompatibility, reducing the strength and transparency of the polymer. In this study, a surface modification strategy has been designed and applied in APP to address these challenges. APP is modified with aminotrimethylene phosphonic acid (ATMP) and long-chain alkane 1,10-diaminodecane (DAD) to obtain APP-DA. The prepared APP-DA is then introduced into polypropylene (PP) through melt blending. The flammability tests demonstrate that the APP-DA greatly enhances the fire resistance of PP. Compared with the control PP, the incorporation of 25 wt.% APP-DA into PP increases the limiting oxygen index (LOI) value to 26.7 %, achieves a UL-94 V-0 rating. In addition, the peak heat release rate (pHRR) and the smoke release rate (SPR) are decreased by 66.2 % and 40.0 %, respectively. Moreover, the presence of APP-DA increases the mechanical properties and maintains good transparency. Compared with PP, the impact strength of PP/APP-DA (25 %) sample increases by 19.6 %, and the transparency retains 91.2 %. This APP surface modification strategy offers a practical method for preparing PP composites to meet industrial application requirements.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"242 ","pages":"Article 111628"},"PeriodicalIF":7.4,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144919873","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}

{"title":"Biodegradability of polyisoprene rubber cross-linked with poly(L-cysteine) cross-linker","authors":"Kousuke Tsuchiya ,&nbsp;Yui Tsuji ,&nbsp;Kayo Terada ,&nbsp;Yoko Horii ,&nbsp;Keiji Numata","doi":"10.1016/j.polymdegradstab.2025.111624","DOIUrl":"10.1016/j.polymdegradstab.2025.111624","url":null,"abstract":"<div><div>Polyisoprene is biodegradable bio-based polymer as a main component of natural rubber. Cross-linking such as vulcanization enhances physical properties of natural rubber materials, while the cross-linked network structure severely deteriorates biodegradability. In this study, we synthesized a biodegradable polypeptide cross-linker to fabricate cross-linked polyisoprene. The cross-linked polyisoprene was prepared by thiol–ene reaction with poly(<span>l</span>-cysteine). The mechanical properties of the cross-linked polyisoprene ring sample were comparable to that of conventional peroxide-mediated cross-linked polyisoprene. The biodegradability of the cross-linked polyisoprenes was evaluated by biochemical oxygen demand test in the presence of <em>Nocardia takedensis</em>, a rubber degrading bacterium. The cross-linked polyisoprene with poly(<span>l</span>-cysteine) cross-linked structure showed higher biodegradability compared to peroxide-cross-linked one, indicating that the combination of polyisoprene backbone and polypeptide cross-linking structures facilitated biodegradation.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"242 ","pages":"Article 111624"},"PeriodicalIF":7.4,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144913450","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}

{"title":"Properties and mechanism of high-performance flame retardant thermoplastic vulcanizate with silicon-based alkenyl-crosslinking molecule","authors":"Siqi Chen ,&nbsp;Yihuimeng Xiong ,&nbsp;Lijun Qian ,&nbsp;Lijie Qu ,&nbsp;Jingyu Wang ,&nbsp;Wei Tang","doi":"10.1016/j.polymdegradstab.2025.111627","DOIUrl":"10.1016/j.polymdegradstab.2025.111627","url":null,"abstract":"<div><div>A novel flame retardant was synthesized by introducing tetramethyl tetravinyl cyclotetrasiloxane (MVC) into the alkenyl-crosslinking structure formed by anhydrous piperazine and vinyl phosphoric acid, resulting in a silicon-based alkenyl-crosslinking molecule GMA-nMVC. The GMA-15 %MVC, with an optimal component ratio, enhanced the flame retardancy and mechanical properties of thermoplastic vulcanizate (TPV) composites. At 20 wt.% loading, the limiting oxygen index of the GMA-15 %MVC/MPP/TPV system reached 30.2 %, and both 3.2 mm and 1.6 mm samples passed UL 94 V-0. Compared to GMA/MPP/TPV and pure TPV, GMA-15 %MVC significantly reduced the peak heat release rate, total heat release, smoke release, and effective combustion heat, while increasing residual char yield and promoting a denser char layer. The tensile strength of GMA-15 %MVC/MPP/TPV system reached 17.2 MPa, with an increase of 48.3 % and 23.7 % compared to GMA/MPP/TPV and pure TPV, respectively. The corresponding elongation at break reached 987.7 %, surpassing GMA/MPP/TPV and pure TPV. Siloxane’s flexible chain segments and strong char-forming ability led to excellent synergistic effects, offering a new approach for developing TPV materials with high flame retardancy and superior mechanical properties.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"242 ","pages":"Article 111627"},"PeriodicalIF":7.4,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144907244","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}

{"title":"Biodepolymerisations of intracellular and extracellular polyhydroxyalkanoates: Methodological approaches and current update on biotechnological applications","authors":"Nur Hanani Arif Shah ,&nbsp;Siti Nor Syairah Anis ,&nbsp;Amirul Al-Ashraf Abdullah ,&nbsp;Mohamad Suffian Mohamad Annuar ,&nbsp;Khanom Simarani ,&nbsp;Ida Idayu Muhamad ,&nbsp;Sevakumaran Vigneswari","doi":"10.1016/j.polymdegradstab.2025.111626","DOIUrl":"10.1016/j.polymdegradstab.2025.111626","url":null,"abstract":"<div><div>Polyhydroxyalkanoates (PHAs) are microbial polyesters synthesised as intracellular carbon and energy storage compounds, with significant potential as sustainable and biodegradable alternatives to petroleum-based plastics. Their degradation, or depolymerisation, occurs through both intracellular and extracellular mechanisms, each offering unique methodological challenges and opportunities. This review provides a comprehensive overview of current methodological approaches for studying PHA depolymerisation via enzymatic hydrolysis, encompassing <em>in vivo</em> and <em>in vitro</em> intracellular depolymerisation, as well as environmental, <em>in vivo</em>, and <em>in vitro</em> extracellular depolymerisation processes. Furthermore, recent advances in the biotechnological applications of PHA depolymerisation products, especially enantiomerically pure (<em>R</em>)-3-hydroxyalkanoates, are discussed. These monomers are increasingly exploited in the production of versatile chiral building blocks with diverse applications, ranging from pharmaceuticals and food additives to biodegradable plastics and plant protection. This review aims to consolidate the current knowledge base and highlight emerging methodological approaches in studying PHA depolymerisation and applications of its depolymerised products.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"242 ","pages":"Article 111626"},"PeriodicalIF":7.4,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144913451","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}

{"title":"Triethanolamine copolymerization of degradable polyesters for enhanced degradation, oxidation-accelerated hydrolysis and fiber formation","authors":"Chaochen Xu ,&nbsp;Weicheng Yang ,&nbsp;Shaojie Shi ,&nbsp;Wufeng Shen ,&nbsp;Chao Zeng ,&nbsp;Shengming Zhang ,&nbsp;Peng Ji ,&nbsp;Chaosheng Wang ,&nbsp;Huaping Wang","doi":"10.1016/j.polymdegradstab.2025.111625","DOIUrl":"10.1016/j.polymdegradstab.2025.111625","url":null,"abstract":"<div><div>The development of degradable plastics is crucial for addressing the issue of plastic pollution. Although poly(butylene adipate terephthalate) (PBAT) is a degradable polyester, it has stringent environmental requirements for degradation and necessitates urgent modification. Triethanolamine (TEOA), an inexpensive industrial product, was introduced into the molecular chain of PBAT to facilitate branching and enhance catalytic synergy. poly(butylene adipate terephthalate - triethanolamine) (PBAT-TEOA) with TEOA contents ranging from 0.25% to 4% were synthesized. The results indicate that the introduction of triethanolamine significantly shortens the polycondensation time while maintaining favorable coloration (b value &lt; 10). Additionally, the mechanical properties of the copolyester can be slightly improved with minimal TEOA incorporation. Specifically, PBAT-TEOA_0.5 exhibits a tensile strength of 20.96 MPa. However, this strength declines rapidly when TEOA content exceeds 1%. Furthermore, TEOA enhances both the hydrophilicity and enzymatic as well as hydrolytic properties of the copolyester. Notably, PBAT-TEOA_0.25 underwent hydrolysis in PBS buffer over a period of 49 days, resulting in a mass residual rate of 89.86%. The branched structure can be disrupted through the Cope elimination reaction, thereby accelerating degradation following treatment with hydrogen peroxide (H₂O₂). The number average molecular weight of PBAT-TEOA₂ decreases by 35.53% after the oxidative treatment. Finally, melt spinning was conducted on PBAT-TEOAs to prepare degradable polyester fibers with a fiber strength of 1.98 cN/dtex. This work presents a straightforward, efficient and cost-effective strategy for enhancing both the degradation performance and spinnability of PBAT with good coloration.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111625"},"PeriodicalIF":7.4,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144907102","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}

{"title":"Sub-atmospheric pressure environment enabled flame-retardant MXene-Al2O3 nanohybrid for polyethylene composites","authors":"Hongsheng Xu ,&nbsp;Hankun Lv ,&nbsp;Wenbin Ye,&nbsp;Yanbei Hou,&nbsp;Fukai Chu,&nbsp;Weizhao Hu,&nbsp;Lei Song,&nbsp;Yuan Hu","doi":"10.1016/j.polymdegradstab.2025.111623","DOIUrl":"10.1016/j.polymdegradstab.2025.111623","url":null,"abstract":"<div><div>Low-pressure environments significantly compromise the performance of conventional intumescent flame-retardant systems by accelerating ignition and inducing excessive yet fragile char expansion, which easily cracks and compromises its protective function. To overcome these challenges, MXene has attracted considerable attention due to its ability to promote char layer formation and serve as an effective physical barrier. In this work, a novel flame-retardant PE composite was developed by incorporating a silane-coupling-agent-modified Al₂O₃-supported MXene nanohybrid (MXene@Al₂O₃). The nanohybrid exhibited uniform morphology, strong interfacial bonding, and excellent dispersion within the PE matrix, significantly reducing the fire risk of PE under sub-atmospheric conditions. With only 1 wt% of MXene@Al₂O₃, the composite achieved a 26.9 % and 31.8 % reduction in peak heat release rate and total heat release, respectively, along with a 25.9 % decrease in maximum smoke density and significant suppression of carbon monoxide evolution. Under reduced pressures (55–99 kPa), the system formed more graphitized and compact char layers, demonstrating enhanced thermal stability and suppressed volatile release. Mechanistic insights obtained via synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) revealed a shift from oxygen-driven oxidation to condensed-phase carbonization under low pressure. These improvements are attributed to the early char templating and barrier-forming capabilities of MXene, while Al₂O₃ contributes by catalyzes carbonization reactions and suppresses smoke precursors. This work demonstrates a pressure-adaptive flame-retardant strategy for polyolefin materials and offers theoretical guidance for designing next-generation nanohybrid flame-retardant systems for sub-atmospheric pressure environments.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111623"},"PeriodicalIF":7.4,"publicationDate":"2025-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144907103","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}