Polymer Degradation and Stability最新文献

{"title":"Phosphorus-derived imidazolium salts with varied oxidation states: Tailoring latency, mechanical properties, and flame retardancy in single-component epoxy resins","authors":"Jingsheng Wang ,&nbsp;Jun Wang ,&nbsp;Shuang Yang ,&nbsp;Guoping Ding ,&nbsp;Renxin Xu ,&nbsp;Wei Liu ,&nbsp;Jiuxiao Sun ,&nbsp;Kaiwen Chen ,&nbsp;Liu Duan ,&nbsp;Jiaqi Wang ,&nbsp;Hao Wang ,&nbsp;Siqi Huo","doi":"10.1016/j.polymdegradstab.2025.111325","DOIUrl":"10.1016/j.polymdegradstab.2025.111325","url":null,"abstract":"<div><div>Single-component epoxy resin (EP) is the premix of EP and latent curing agent, which is highly demanded in industries. However, current single-component EPs struggle to balance storage stability with mechanical properties and flame retardancy. To address this issue, three phosphorus-derived imidazolium salts (MPOx, x = 2, 3, 4) were synthesized using 2-ethyl-4-methylimidazole (EMI) and phosphorus-containing acids with different oxidation states (diphenylphosphinic acid, phenyl hydrogen phenylphosphonate, and diphenyl phosphate). The oxidation state of phosphorus significantly influenced thermal latency of MPOx, with higher oxidation states leading to improved latency. EP/MPO4 achieved the longest shelf life of 42 d at 25 °C. EP/MPO3 and EP/MPO4 exhibited enhanced tensile strength, modulus, and impact resistance compared to EP/EMI, but EP/MPO2 showed poor mechanical properties due to phase separation. All EP/MPOx achieved limiting oxygen index (LOI) exceeding 30 %, with EP/MPO3 showing the highest LOI of 34.0 % and significant reductions in heat release and smoke production. Flame-retardant mechanistic studies revealed a shift from gaseous-phase flame inhibition to condensed-phase promoting carbonization with increasing phosphorus oxidation state. Obviously, MPOx provides a tailored balance of latency, mechanical strength, and flame retardancy, making it a promising solution for advanced single-component EPs in aerospace, electronics, and optical applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111325"},"PeriodicalIF":6.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629255","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":"High performance polyurethanes with extraordinary hydrolytic resistance prepared from bio-renewable alkyl-δ-lactones: Synthesis, properties and chemical recycling","authors":"Min Zhang ,&nbsp;Qin Yan ,&nbsp;Xinxin Yu ,&nbsp;Yong Shen ,&nbsp;Zhibo Li","doi":"10.1016/j.polymdegradstab.2025.111322","DOIUrl":"10.1016/j.polymdegradstab.2025.111322","url":null,"abstract":"<div><div>Despite the great advancements achieved for the chemically recyclable polymers in recent years, it remains as a challenge to develop chemically recyclable polyurethanes from bio-renewable monomers with thermal and mechanical properties that compare with petroleum-based polyurethanes. In this contribution, we present the successful preparation of a series of chemically recyclable polyurethanes from the ring-opening polymerization of bio-renewable alkyl-δ-lactones followed by the tandem polycondensation with diisocyanate and a chain extender. The thermal and mechanical properties of the obtained polyurethanes can be easily tailored by adjusting the molar mass of soft segment, the hard segment content as well as the length of the pendent alkyl group of the poly(alkyl-δ-lactone) polyol precursor. The obtained polyurethanes behave as thermoplastic elastomers with excellent tensile strength and elasticity that compare with commodity petroleum-based polyurethanes. Remarkably, the obtained polyurethanes exhibit extraordinary hydrolytic resistance and remain intact up to 5 months in acidic or basic aqueous solution. The chemical recycling of polyurethanes to recover clean alkyl-δ-lactones with high yield (&gt; 95 %) can be easily achieved by simple heating the materials in bulk under reduced pressure.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111322"},"PeriodicalIF":6.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143621205","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":"A novel P-N structure modified halloysite nanotube for simultaneously enhancing flame retardancy and mechanical properties of unsaturated polyester resin","authors":"Hang-Ping Fang ,&nbsp;Ying-Ming Li ,&nbsp;Dan-Ping Zhu ,&nbsp;Yao Deng ,&nbsp;De-Yi Wang","doi":"10.1016/j.polymdegradstab.2025.111324","DOIUrl":"10.1016/j.polymdegradstab.2025.111324","url":null,"abstract":"<div><div>Unsaturated polyester resin (UPR) is highly flammable due to its long-chain polymer structure composed of hydrocarbon elements, which significantly restricts its application. In this study, an organic-inorganic hybrid flame retardant was developed by using siloxane (KH-560) as a bridging agent to graft bio-based P-N structure (the salt formation of diphenyl phosphoric acid and cytosine) onto the surface of halloysite nanotubes (HNT), resulting in the synthesis of HNT-Si-DC. Experimental results demonstrated that the UPR composite containing 15 wt% HNT-Si-DC achieved a UL-94 V-0 rating, with a limiting oxygen index (LOI) of 33.2 %. Compared to pure UPR, the peak of heat release rate (PHRR) of the composite decreased by 49.8 %. Furthermore, the mechanical properties of the UPR/HNT-Si-DC₁₅ composite were significantly enhanced, with the tensile modulus increasing by 38.7 % and the flexural strength improving by 21.3 % compared to those of pure UPR, indicating high mechanical performance. Additionally, the dense and continuous carbon layer preferentially enhanced the flame retardancy. This work presents a highly efficient approach to designing organic-inorganic hybrid modified HNT for the development of UPR composites with excellent fire resistance and high mechanical properties.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111324"},"PeriodicalIF":6.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143628939","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":"Novel one-pot recovery and in-situ crystallization of polyhydroxybutyrate and hydroxyapatite/tricalcium phosphate biocomposite microparticles with comparative life cycle assessment","authors":"Anuchan Panaksri ,&nbsp;Pasin Kuncharin ,&nbsp;Purin Neerawong ,&nbsp;Taranuch Panthong ,&nbsp;Thanadol Thanakornkriengkrai ,&nbsp;Sani Boonyagul ,&nbsp;Woradej Pichaiaukrit ,&nbsp;Sutee Wangtueai ,&nbsp;Nuankanya Sathirapongsasuti ,&nbsp;Kittisak Jantanasakulwong ,&nbsp;Pornchai Rachtanapun ,&nbsp;Patnarin Worajittiphon ,&nbsp;Phavit Wongsirichot ,&nbsp;Nuttapol Tanadchangsaeng","doi":"10.1016/j.polymdegradstab.2025.111321","DOIUrl":"10.1016/j.polymdegradstab.2025.111321","url":null,"abstract":"<div><div>Formation of polyhydroxybutyrate (PHB) biopolymer composites with bioceramics such as hydroxyapatite (HA) and tricalcium phosphate (TCP) is essential in achieving mechanical properties needed for novel bone tissue engineering using PHB. However, composite microparticle synthesis typically requires multiple steps, including 1) PHB recovery and purification, 2) dispersion of HA and TCP particles in the melt or solvent-dissolved polymer liquid, and 3) micro-droplet drying. In this study, PHB/HA/TCP composite microparticles were successfully produced by one-pot biosynthesis. This was achieved during acid-based PHB recovery by utilizing the crystallization of native-amorphous granule PHB within <em>Cupriavidus necator</em>. In-situ PHB crystallization was successfully monitored by real-time attenuated total reflection-Fourier transform infrared (ATR-FTIR). Additionally, the in-situ crystallization behavior was elucidated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The most suitable conditions for synthesis of the PHB/HA/TCP composite were pH 2, and 20 min of reaction time, which capitalizes on the amorphous nature of the in-situ PHB during recovery. The HA and TCP did not function as nucleating agents, thereby not impacting accumulation and homogeneity. This allows HA/TCP bioceramics to be inserted into the polymer during the PHB recovery period, and after the crystallization step is completed, the composite microparticles could facilely form. The crystallization mechanism was found to be sporadic, and the morphology was a disc with two dimensions. Additionally, the life cycle assessment (LCA) revealed that the one-pot method reduced global warming potential (GWP) emissions by 50% and non-renewable energy use (NREU) by a comparable margin, compared to the conventional multi-step method for HA/TCP (20:80) production. These findings emphasize the environmental advantages of the one-pot approach alongside its cost and process efficiency. The demonstrated one-pot synthesis method would allow for more streamlined and cost-effective production of PHB/HA/TCP biocomposites. The materials produced and insights gained will be beneficial for future development of biopolymer composite processing and biomedical applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111321"},"PeriodicalIF":6.3,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654881","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":"How does DOPO flame retard polybutylene succinate? An in-depth mechanism investigation","authors":"Chi Hu ,&nbsp;Serge Bourbigot ,&nbsp;Gaëlle Fontaine","doi":"10.1016/j.polymdegradstab.2025.111318","DOIUrl":"10.1016/j.polymdegradstab.2025.111318","url":null,"abstract":"<div><div>9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is an efficient phosphorus-based flame retardant which may act in the gas phase to flame retard polyesters. When it was incorporated at 10wt% loading in polybutylene succinate (PBS), it was observed, in mass loss cone test (MLC) that the time to ignition (TTI) was dramatically increased from 119 s to 467 s and 2206 s under a heat flux of 35 kW/m² and 25 kW/m² respectively. Various techniques have been used to investigate its mode of action. Mass spectra (MS) results indicate that the sublimation and thermal decomposition products of DOPO are formed in the gas phase. A large quantity of combustible gases (mainly tetrahydrofuran and succinic anhydride) was observed before ignition by an in-situ infrared spectra combining with MLC (IR-MLC). Therefore, decomposition/sublimation products of DOPO have a strong flame poisoning effect that prevents the material's ignition until the combustible gases reach a critical concentration and ignite.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"236 ","pages":"Article 111318"},"PeriodicalIF":6.3,"publicationDate":"2025-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609771","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":"Degradation behavior of nitrocellulose in imidazole aqueous solution","authors":"Huihui Xue ,&nbsp;Alei Zhang ,&nbsp;Xinguang Wu ,&nbsp;Yajun Ding ,&nbsp;Zhongliang Xiao","doi":"10.1016/j.polymdegradstab.2025.111300","DOIUrl":"10.1016/j.polymdegradstab.2025.111300","url":null,"abstract":"<div><div>Nitrocellulose (NC)-based materials can take years to degrade considerably in nature. One of the most promising NC waste treatment methods is inorganic base hydrolysis. In this work, the degradation mechanism of NC in an aqueous solution of imidazole, an organic base, had been constructed. The results showed that imidazole can cause denitration, ring opening, and oxygen bridge breaking in NC; eventually, NC was completely degraded. In this process, the denitration of vicinal nitrates generated nitrite and carbonyl groups, while the denitration of isolated nitrates produced nitrate and hydroxyl groups. The molar ratio of nitrite to nitrate in the reaction solution increased from 2.77 to 4.44 and finally decreased to 1.97 with time. The reaction rate of the nitrate group and oxygen bridge at the early stages of the reaction was as follows: vicinal nitrate's denitrification &gt; isolated nitrate's denitrification &gt; oxygen bridge breaking. Moreover, imidazole's diffusion rate gradually decreased as the reaction progressed, eventually balancing with the rate for complete degradation of NC. Meanwhile, the degree of crystallinity of remaining NC gradually increased, whereas the nitrogen content and relative number-average molecular weight of remaining NC gradually decreased from 13.52 % and 139,212 to 11.57 % and 3721; they ultimately maintained balance. The apparent morphology of NC fibers changed as cracks initially formed, then cracks progressively enlarged to produce fiber fragments, and eventually NC vanished entirely in the solution. The degradation of NC by imidazole potentially supports the one-step biochemical treatment of NC waste.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111300"},"PeriodicalIF":6.3,"publicationDate":"2025-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143621206","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":"Behavior of poly(methyl methacrylate) exposed to extreme ultraviolet laser radiation: A relationship between the high-energy photo-decomposition of the polymer and the mass spectra of emitted ions","authors":"L. Vyšín ,&nbsp;J. Chalupský ,&nbsp;L.A. Rush ,&nbsp;L. Fekete ,&nbsp;J. Bulička ,&nbsp;P. Mojzeš ,&nbsp;Z. Kuglerová ,&nbsp;J. Krása ,&nbsp;L. Juha ,&nbsp;J.J. Rocca ,&nbsp;C.S. Menoni","doi":"10.1016/j.polymdegradstab.2025.111298","DOIUrl":"10.1016/j.polymdegradstab.2025.111298","url":null,"abstract":"<div><div>This study investigates the fluence-dependent fragmentation of poly(methyl methacrylate) (PMMA) when irradiated with focused extreme ultraviolet (EUV) 26.4-eV photons, using an extreme ultraviolet laser ablation mass spectrometer (EUV LA-MS). Our findings reveal two critical fluence thresholds: the ablation threshold fluence (<em>F_th</em>=9 mJ·cm⁻²), after which the material begins to desorb and ionize nonthermally, and the transition fluence (<em>F_tr</em>=110 mJ·cm⁻²), where the interaction shifts to a thermal regime characterized by a nonlinear response in crater formation. The new nonlinear response function recovery (NoReFry) algorithm was used to reconstruct the dose-response curve, using detailed topographical data from atomic force microscopy scans of the ablated craters, enhancing estimation of beam fluence during the experiments. The mass spectra obtained during ablation showed distinct fragmentation pathways that evolve with fluence. Nonthermal conditions primarily produce small fragments, including short-chain ions and gaseous species, while the thermal regime allows for greater fragmentation complexity and the formation of higher molecular weight species. Using experimental data and Monte Carlo simulations, we compared the effects of nano- and femtosecond pulses on the ablation threshold of PMMA. Comprehensive analysis of the mass spectra highlights the dynamics of photoinduced processes, providing insight into the ablation and ionization mechanisms critical for applications in materials processing with EUV radiation.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"236 ","pages":"Article 111298"},"PeriodicalIF":6.3,"publicationDate":"2025-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143580434","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fluorescent starch/chitosan composites as safe and photoprotective coverings for perishable food products","authors":"Dagmara Bajer","doi":"10.1016/j.polymdegradstab.2025.111317","DOIUrl":"10.1016/j.polymdegradstab.2025.111317","url":null,"abstract":"<div><div>Perishable product quality and shelf life (e.g., fresh fruit and vegetables) may be partially controlled process by employing intelligent packaging. Protecting food from light, which quickly initiates food spoilage, prompting its chemical, enzymatic, and physical modification, plays a crucial role in packaging functions. In the present research, environmentally safe starch-chitosan films enriched with dialdehyde starch and fluorescent dyes (fluorescein/Rose Bengal) exhibiting UV radiation absorption properties were designed. Such networks formed of biopolymers and fluorescein/Rose Bengal may limit direct ¹O₂ attacks. The starch changes its crystallinity degree (X_c) from 17.4 % in starch film, to 19.6 % for starch-chitosan (SCh) film and 26,4 % for starch-chitosan-dialdehyde starch (SChDS) mixture. When modified with dyes its maximal drop was 13.9 % (Starch/chitosan/dialdehyde starch/Rose Bengal film; RSChDS), and the increase to 24 % for starch/chitosan/dialdehyde starch/fluorescein film (FSChDS) was observed. Mixtures with fluorescein were more resistant to bending than those with Rose Bengal. SEM images demonstrate good structural integrity of the samples (with the exception of starch/chitosan/ Rose Bengal film, RSCh). Spectroscopic studies (UV–Vis, FTIR-ATR, Raman, XRD, NMR) confirmed the interaction between blend components (covalent, ionic, and hydrogen bonding). Competitive oxidation reactions, chromophore formation, dye photolysis, and conformational changes of starch were observed after prolonged UV-light irradiation. The type of dye and irradiation insignificantly modify the thermal resistance of the samples. UV-light influenced increased surface roughness of the FS and FSChDS samples, and the opposite effect (smoothing the surface) for RS and RSChDS blends. Dialdehyde starch (DS) promoted cross-linking between the mixture components. It improved the flexibility of the films (most in the case of samples with fluorescein) but also limited the susceptibility to UV radiation. Coatings of starch/chitosan/dialdehyde starch/fluorescein (FSChDS) appear to be good blockers for sunlight, protecting food products against accelerated spoilage. Such coatings may be applied to the broadly understood packaging industry for light-sensitive and perishable food, cosmetics, and medicine products, such as lipids and vitamins, to protect against UV radiation and the influence of microorganisms.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111317"},"PeriodicalIF":6.3,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143628938","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":"Development of a DOPO-based flame retardant with pendant chains for enhanced polyurethane elastomers","authors":"Yiqing Yao ,&nbsp;Jing Man ,&nbsp;Xi Wang ,&nbsp;Xiaoyu Gu ,&nbsp;Zefu Zheng ,&nbsp;Hongfei Li ,&nbsp;Jun Sun ,&nbsp;Dan Meng ,&nbsp;Sheng Zhang ,&nbsp;Quanxiao Dong","doi":"10.1016/j.polymdegradstab.2025.111302","DOIUrl":"10.1016/j.polymdegradstab.2025.111302","url":null,"abstract":"<div><div>Polyurethane elastomers (PUE) with viscoelastic properties are extensively used in rail transit due to their versatility. However, enhancing their flame retardancy and damping performance remains a challenge, particularly when relying on the introduction of additives. In this work, we synthesized a novel reactive flame retardant, 1,4-bis-DOPO- (1,4-bis(((1‑hydroxy-2-ethylethyl) amino) methyl) benzene) (PABD), which incorporates both phosphorus (P) and nitrogen (N) elements, along with pendant chains. PABD was then used to produce high-performance flame-retardant polyurethane elastomers (PUE-PABD). Flammability testing revealed that PUE-PABD₁₅ achieved excellent flame retardancy, passing the UL-94 V-0 rating with a limiting oxygen index (LOI) of 29.1 %. Compared to that of unmodified PUE, the peak heat release rate and total heat release of PUE-PABD₁₅ were reduced by 82.6 % and 49.5 %, respectively, while the peak smoke production rate and total smoke production were lowered by 70.7 %. The dynamic mechanical analysis showed an increase in tanδmax from 0.39 to 0.74, with the effective damping temperature range broadening from 29.3 °C to 54.1 °C. This improvement was attributed to the pendant chains, which reduced phase separation between hard and soft segments. Moreover, the incorporation of 15.0 wt. % PABD increased the tensile strength of PUE by 108.5 %, which was due to enhanced hydrogen bonding and π-π stacking from the benzene ring groups. This work lays a foundation for the development of high-performance polyurethane materials suitable for advanced rail transit applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"236 ","pages":"Article 111302"},"PeriodicalIF":6.3,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143580430","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":"Biomass-derived poly(lactic acid) and poly(3-methyl-1,5-pentanediol sebacate) alternating multiblock copolymers with improved marine biodegradability and mechanical properties","authors":"Atsuki Takagi ,&nbsp;Yu-I Hsu ,&nbsp;Hiroshi Uyama","doi":"10.1016/j.polymdegradstab.2025.111301","DOIUrl":"10.1016/j.polymdegradstab.2025.111301","url":null,"abstract":"<div><div>The reliance on fossil resources and the mismanagement of waste owing to the rapid increase in plastic production have led to serious environmental problems, particularly global marine pollution. In recent years, poly(lactic acid) (PLA) has been widely used as a biomass plastic to replace petroleum-based materials. However, the biodegradation of PLA is limited to composting environments and its brittle nature limits its application. This study aimed to synthesize a biomass-based PLA and poly(3-methyl-1,5-pentanediol sebacic acid) (PMPDSe)-diol copolymer and evaluate its marine biodegradability and mechanical properties. PLA was copolymerized with PMPDSe-diol to obtain the triblock copolymer PLA-PMPDSe-PLA, which was then chain-extended with hexamethylene diisocyanate to form an alternating multiblock (PLA-<em>alt</em>-PMPDSe) copolymer. Because of their regular arrangement, the thermal and mechanical properties could be controlled by varying the length of the PLA chains, compared with random multiblock (PLA-<em>ran</em>-PMPDSe) copolymers. In particular, when 61 % or 71 % PLA was included, the films had higher elongation at break (331 %–518 %) and toughness than PLA and PLA-<em>ran</em>-PMPDSe copolymers. Biodegradability was the highest when 54 % PLA was used, and the films disintegrated in compost and seawater. In seawater, the molecular weight decreased to 45 % in three months, and the biodegradability was confirmed to be &gt;17 % in two months. Furthermore, the PLA-<em>alt</em>-PMPDSe copolymer exhibited a contact angle of over 83°, which is equivalent to that of PLA and could be used as a film. This polymer has a wide range of applications and will contribute to the development of sustainable bioplastics and address plastic waste.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"236 ","pages":"Article 111301"},"PeriodicalIF":6.3,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143580433","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}