Polymer Journal最新文献

{"title":"Special issue: Advanced polymers in renewable energy systems and sustainability","authors":"Cheng-Liang Liu, Takuma Yasuda, Keun Hyung Lee, Keiji Tanaka","doi":"10.1038/s41428-026-01215-z","DOIUrl":"10.1038/s41428-026-01215-z","url":null,"abstract":"","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 9","pages":"987-988"},"PeriodicalIF":3.1,"publicationDate":"2026-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-026-01215-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148904464","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sustainable valorization of organic solid wastes: macromolecular humic acid-stabilized cinnamon essential oil emulsions with enhanced antibacterial properties","authors":"Zhimin Duan, Liu Yang, Z M WANG, Zhanming Liang, Lanlan Wang, Qiqi Huang, Song Wang, Xiaodong Ye, Zeng Lh, Liangzhi Hong","doi":"10.1038/s41428-026-01231-z","DOIUrl":"https://doi.org/10.1038/s41428-026-01231-z","url":null,"abstract":"","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148672195","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrolytic behavior of dihydroxy-functionalized poly(trimethylene carbonate) analogs with amide linkers","authors":"Hyung Ju Lee, Yukiko Tanaka, Masaru Tanaka, Kazuki Fukushima","doi":"10.1038/s41428-026-01226-w","DOIUrl":"10.1038/s41428-026-01226-w","url":null,"abstract":"Global environmental issues drive the development of sustainable materials. Water-soluble polymers with tunable degradability have the potential to displace conventional nondegradable counterparts. Poly(trimethylene carbonate) (PTMC) analogs are promising candidates for functionalized hydrolyzable polymers, including those with water-soluble functionality. Recently, the hydration properties conferred by side chains have been shown to promote the hydrolysis of PTMC analogs. Additionally, the amide linker in the side chain facilitates interactions with water and may catalyze hydrolysis via hydrogen-bond activation of water and main-chain carbonate bonds. Herein, we report the hydrolytic behavior of previously developed water-soluble PTMC analogs and discuss their relationship to their hydration properties. The PTMC analogs are designed to have two hydroxy groups on the side chain arranged in different configurations, thereby enabling high water solubility. The dihydroxy-functionalized PTMC analogs degrade in water within a few days in phosphate-buffered saline (PBS), whereas under alkaline conditions, the polymers degrade within 1 h. Differential scanning calorimetry of the hydrated PTMC analogs indicates that dihydroxy side chains efficiently facilitate the formation of intermediate water. This study demonstrates that enhancing hydration through side-chain engineering promotes the hydrolysis of PTMC analogs, thereby enabling the polymer lifetime to be tuned from hours to weeks. The hydrolysis behavior and thermal properties of dihydroxy-functionalized PTMC analogs with different geometries of the hydroxy groups on the side chains were examined. The polymers are highly water soluble because of the dihydroxy side groups and degrade in water within a few days under neutral conditions. Differential scanning calorimetry revealed that dihydroxy side chains efficiently facilitated the formation of intermediate water. This study supports the promotion of the hydrolysis of PTMC analogs by enhancing hydration via side-chain engineering.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 9","pages":"1173-1184"},"PeriodicalIF":3.1,"publicationDate":"2026-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-026-01226-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148904468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multichromic polymers based on 5-[3,5-di(carbazol-9-yl)phenyl]benzene-1,3-dicarbonitrile and dithiophene derivatives for rapid switching electrochromic devices","authors":"Chung-Wen Kuo, Pei-Ying Lee, Pei-Jun Sun, Yuan-Chung Lin, Tzi-Yi Wu","doi":"10.1038/s41428-026-01222-0","DOIUrl":"10.1038/s41428-026-01222-0","url":null,"abstract":"A dicarbonitrile-substituted homopolymer (P(dCzCN)) and four dCzCN-containing copolymers (P(dCzCN-co-bTP), P(dCzCN-co-TF), P(dCzCN-co-CPDT), P(dCzCN-co-CPDTK)) were polymerized electrochemically on an indium tin oxide (ITO) glass substrate. The P(dCzCN) film was light gray, yellowish gray, and greenish gray at 0.0 V, 1.2 V, and 1.5 V, respectively. The electrochromic switching of the polymer films revealed that P(dCzCN-co-bTP) showed a high transmittance change (ΔT = 61.0% at 1000 nm), and P(dCzCN-co-CPDTK) exhibited a high coloration efficiency (η = 292.4 cm2 C−1 at 950 nm). Moreover, dual-layer electrochromic devices (ECDs) were constructed using P(dCzCN), P(dCzCN-co-bTP), P(dCzCN-co-TF), P(dCzCN-co-CPDT), and P(dCzCN-co-CPDTK) as the anodic layers and PEDOT as the cathodic layer. The P(dCzCN-co-bTP)/PEDOT ECD revealed a high ΔT (38.0% at 630 nm), a high coloration efficiency (η = 531.4 cm2 C−1 at 630 nm) and a fast switching time ( ≤0.3 s). The abovementioned electrochromic performances imply that dicarbonitrile-substituted polycarbazoles provide high transmittance changes and fast switching in electrodes for ECDs. P(dCzCN-co-bTP) copolymers were electrocoated onto ITO-coated glass substrates. A dual-type complementary electrochromic device (ECD) was fabricated using P(dCzCN-co-bTP) as anodically coloring electrochromes and PEDOT as the cathodically coloring electrochrome. The P(dCzCN-co-bTP)/PEDOT ECD revealed a high ΔT (38.0% at 630 nm), a high coloration efficiency (η = 531.4 cm2 C−1 at 630 nm) and a fast switching time ( ≤ 0.3 s). P(dCzCN-co-bTP)/PEDOT ECD showed yellow at 0.0 V and blue at 1.8 V.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 9","pages":"1067-1082"},"PeriodicalIF":3.1,"publicationDate":"2026-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-026-01222-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148904483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Silica nanofiber-reinforced carbonate-based composite polymer electrolytes: interfacial effects on Li-ion transport","authors":"Pa Do Kim, Hidetoshi Matsumoto, Nantapat Soontornnon, Kento Kimura, Yoichi Tominaga","doi":"10.1038/s41428-026-01210-4","DOIUrl":"10.1038/s41428-026-01210-4","url":null,"abstract":"Polymer electrolytes have been actively investigated as safer alternatives to liquid electrolytes; however, their electrochemical performance often remains limited. In this study, carbonate-based composite polymer electrolytes (CPEs) were prepared using a PEC-LiFSI matrix with two types of silica fillers: SiO2 nanoparticles and electrospun silica nanofibers (SNFs). Filler contents of 1, 5, and 10 wt% were used to examine the morphology and interface-related effects. Compared with the filler-free PEC-LiFSI electrolyte (SPE), both fillers increased thermal stability. FT-IR analysis of the carbonyl stretching region revealed changes with filler addition, indicating changes in the Li+ coordination environment. The ionic conductivity exhibited an optimum at 5 wt% loading for both fillers, followed by a decrease at 10 wt%. Linear sweep voltammetry further indicated improved oxidation stability with the addition of silica, with the highest oxidation onset potential observed at 5 wt% SNFs. The mechanical properties were enhanced much more strongly by SNFs than by SiO2, especially at high loadings. The capacity of the battery increased during the initial cycles and approached approximately 140 mAh g−1. Overall, these results highlight that the surface/interface effects and loading of silica fillers together influence key thermal, mechanical, and electrochemical properties of carbonate-based CPEs and that SNFs are an effective filler for mechanically robust PEC-LiFSI-based CPEs. PEC-based composite polymer electrolytes (CPEs) reinforced by electrospun silica nanofibers (SNFs), prepared without calcination. SNF incorporation enhances both ionic conductivity and mechanical strength, with an optimal conductivity observed at 5 wt% loading. The high-aspect-ratio fibrous morphology and polar surface groups (Si-OH and aminopropyl) promote effective filler–electrolyte interactions, resulting in improved overall performance of carbonate-based CPEs.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 9","pages":"1153-1162"},"PeriodicalIF":3.1,"publicationDate":"2026-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-026-01210-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148904451","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Confinement-controlled redox behavior in viologen-functionalized polymer brushes","authors":"Hongyao Zhou, Hiromu Moku, Koshiro Tamashima, Mizuha Ujita, Masayuki Morimoto, Hitoshi Asakawa, Teppei Yamada","doi":"10.1038/s41428-026-01221-1","DOIUrl":"10.1038/s41428-026-01221-1","url":null,"abstract":"Viologen derivatives are widely used redox-active motifs whose reversible redox chemistry between the dication (V2+) and the radical cation (V•+) is often accompanied by the formation of a π-bonded dimer. While such aggregation has been extensively studied in molecular systems and polymer solutions, the influence of spatial confinement on the redox behavior of viologen-functionalized polymers remains poorly understood. Here, we report the synthesis of a viologen-functionalized polymer, poly(4-vinylpyridine-N-diethylviologen) (P4VP-V), prepared via atom-transfer radical polymerization followed by postpolymerization functionalization and investigate its electrochemical behavior in aqueous solution and as a surface-grafted polymer brush. In solution, electrochemical reduction of viologen units increases the hydrophobicity of the polymer chains, leading to reversible coil–globule transition and aggregation. Cyclic voltammetry reveals that the apparent number of electrons transferred increases at slower scan rates, which is consistent with cooperative electron transfer associated with viologen radical dimerization. In contrast, when P4VP-V is confined within a polymer brush on an indium tin oxide (ITO) substrate, the viologen units undergo only a single-electron redox process. These observations indicate that spatial confinement and chain crowding within the polymer brush limit the association of the viologen units required for radical dimerization, demonstrating that nanoscale confinement fundamentally alters intermolecular interactions and electron-transfer behavior. Viologen-functionalized polymer brushes exhibit fundamentally different electrochemical behaviors than their solution-phase counterparts. In solution, poly(4-vinylpyridine-N-diethylviologen) (P4VP-V) undergoes reversible coil–globule transitions upon reduction, with cyclic voltammetry revealing cooperative multielectron transfer driven by radical dimerization. When confined as a surface-grafted brush on ITO, chain crowding suppresses viologen radical dimerization, yielding only single-electron redox processes. These findings demonstrate that nanoscale spatial confinement in polymer brushes provides a powerful means to modulate the intermolecular interactions and electron-transfer behavior of pendant redox-active groups.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 9","pages":"1119-1126"},"PeriodicalIF":3.1,"publicationDate":"2026-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-026-01221-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148904462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Uncertainty-aware prediction of the glass transition temperature of aliphatic polycarbonates using ensemble machine learning","authors":"Yoshifumi Amamoto, Ryunosuke Ito, Mikako Murakami, Kohzo Ito, Kazuki Fukushima","doi":"10.1038/s41428-026-01208-y","DOIUrl":"10.1038/s41428-026-01208-y","url":null,"abstract":"Sustainable polymers are often designed to be degradable or recyclable via low-energy, low-CO₂-emission pathways while demonstrating high physical properties comparable to those of conventional plastics. Aliphatic polycarbonates (APCs), studied as functionalized degradable polymers, are promising candidates for use as sustainable materials. However, enhancing their physical properties remains essential. Polymer properties depend on various factors, including chemical structure, molecular weight and its distribution, branching, higher-order structures, and thermal history, and are therefore not uniquely determined. Machine learning models are powerful tools for predicting polymer properties with associated uncertainty, particularly for polymers absent from open datasets. Herein, we investigate uncertainty-aware predictions of the glass transition temperature (Tg) of APCs using ensembles of multiple molecular descriptors and machine learning methods. The Tg data for more than 50 APCs were collected from previous experimental studies. Prediction models for Tg were constructed using more than 100 combinations of molecular descriptors and machine learning algorithms based on datasets of common polymers. The top five models, selected by coefficients of determination, exhibited moderate predictive performance for APCs. The mean values and standard deviations of the predictions obtained from the top five models provide Tg predictions with quantified uncertainty. This ensemble-based framework will be extended to uncertainty-aware prediction of various polymer properties. Aliphatic polycarbonates (APCs) are promising sustainable polymers, but improving their physical properties remains a challenge. Here, uncertainty-aware machine learning was applied to predict the glass transition temperature (Tg) of APCs using ensembles of molecular descriptors and algorithms. Tg data from over 50 APCs were analyzed, and the top five models provided moderate predictive accuracy with quantified uncertainty. This ensemble-based framework enables reliable prediction of polymer properties and supports the design of high-performance sustainable polymers.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 9","pages":"1059-1066"},"PeriodicalIF":3.1,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-026-01208-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148904489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Preparation of regenerable polymeric adsorbents functionalized with β-cyclodextrin moieties for selective recovery of bisphenol A.","authors":"Haruki Hoshino, Masayuki Yokoyama, Azumi Akiyama, Daisuke Aoki, Tatsuo Taniguchi","doi":"10.1038/s41428-026-01196-z","DOIUrl":"10.1038/s41428-026-01196-z","url":null,"abstract":"Bisphenol A (BPA), widely used in polycarbonate plastics and epoxy resins, is a well-known endocrine-disrupting compound. Although numerous β-cyclodextrin (βCD)-based adsorbents for BPA removal have been reported, challenges in adsorbent synthesis and regeneration remain. This study reports the synthesis of porous polymer particles (several hundred micrometers in size) functionalized with βCD derivatives for industrial column applications. Porous polymer particles (SDG) were synthesized by suspension polymerization of styrene, divinylbenzene, and glycidyl methacrylate, yielding a specific surface area of 103.15 m²/g, as determined by mercury intrusion porosimetry. The primary hydroxy groups of βCD were brominated to obtain per(6-bromo-6-deoxy)cyclodextrin (PB-βCD). The adsorbent (SDG-EDA-βCD) was obtained via a reaction between PB-βCD and SDG aminated with ethylenediamine (EDA). Elemental analysis indicated a βCD loading of 239 µmol/g, corresponding to a theoretical BPA adsorption capacity of 54.5 mg/g. Batch adsorption experiments revealed that BPA adsorption kinetics followed the Weber–Morris model, and the maximum adsorption capacity at 293 K determined from the Langmuir isotherm was 55.6 mg/g. Repeated adsorption–desorption cycles using methanol demonstrated quantitative BPA recovery and efficient adsorbent regeneration. Thermodynamic analysis confirmed that BPA adsorption was spontaneous and exothermic, indicating that SDG-EDA-βCD is a promising adsorbent for BPA removal from aqueous media. A selective adsorbent (SDG-EDA-βCD) for bisphenol A (BPA) was synthesized by chemically bonding per(6-bromo-6-deoxy)-β-cyclodextrin onto polymer particles prepared via suspension polymerization of styrene, divinylbenzene, and glycidyl methacrylate, followed by amination with ethylenediamine. The adsorption behavior of BPA was well described by the Weber–Morris kinetic model and the Langmuir isotherm model. Thermodynamic analysis revealed that the adsorption process was spontaneous and exothermic. Furthermore, SDG‑EDA‑βCD was readily regenerated by methanol-induced desorption of BPA. These results highlight the potential of SDG-EDA-βCD for the efficient and sustainable removal of BPA from aqueous solutions.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 10","pages":"1293-1305"},"PeriodicalIF":3.1,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-026-01196-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148928138","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigating the synergistic effects of hybrid and bimodal filler networks on the out-of-plane thermal conductivity of polymer composites","authors":"Yonghyun Albert Kwon, Jaeyeon Kim, Jiseon Choi, Soojeong Jeong, Yunchan Lee, Ho Sun Lim, Jeong Ho Cho","doi":"10.1038/s41428-026-01220-2","DOIUrl":"10.1038/s41428-026-01220-2","url":null,"abstract":"As 3D-integrated architectures such as high-bandwidth memory (HBM) increase in power density, managing vertical heat dissipation during burn-in testing (when temperatures can reach 280 °C) is critical. Traditional prepregs frequently lack sufficient thermal conductivity, causing thermal warpage or false device failures. In this study, we investigated monofiller, hybrid filler, and bimodal-morphology filler systems to increase the out-of-plane thermal conductivity (K⊥) of styrene–ethylene–butylene–styrene (SEBS)-based polymer composites and prepregs at low filler loadings. While hybrid systems (h-BN/Al2O3) provide isotropic thermal bridges, they are hindered by high interfacial thermal resistance (Rint) at heterogeneous contacts. To address this issue, we developed a bimodal system using chemically identical h-BN fillers with different morphologies. This configuration facilitates an isotropic conduction network while reducing Rint through homogeneous filler-to-filler interfaces. At a total loading of 25 wt%, the aggregated bimodal prepreg achieved a K⊥ of 0.56 W/m·K, which is an increase of 31% over the baselines of the monofiller. These results indicate that bimodal h-BN architectures comprise an effective method for developing high-performance, reliable substrates for next-generation semiconductor testing. We report a highly effective approach to improve the out-of-plane thermal conductivity of polymer prepregs by optimizing filler networks. Comparing monofiller, hybrid (h-BN/Al2O3), and bimodal (h-BN aggregates/powders) systems reveal that bimodal architectures successfully balance isotropic phonon transport with minimized interfacial thermal resistance. By utilizing chemically identical h-BN fillers with distinct morphologies, the composites construct a robust, multidimensional conduction network. The optimized bimodal prepreg yielded a thermal conductivity of 0.56 W/m·K at just 25 wt% filler loading.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 9","pages":"1163-1172"},"PeriodicalIF":3.1,"publicationDate":"2026-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-026-01220-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148904467","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of poly(acetoacetoxyethyl methacrylate-b-dimethylsiloxane-b-acetoacetoxyethyl methacrylate) triblock copolymers via SARA ATRP for reaction-mediated microphase separation of sustainable vitrimers","authors":"Yi-Shen Huang, Shibiru Yadeta Ejeta, Shiao-Wei Kuo, Yeo-Wan Chiang, Yasuyuki Nakamura, Chih-Feng Huang","doi":"10.1038/s41428-026-01205-1","DOIUrl":"10.1038/s41428-026-01205-1","url":null,"abstract":"Vitrimers offer a sustainable route to covalently crosslinked polymer networks with processability enabled by thermally activated bond-exchange reactions. However, the integration of programmable nanostructures into vitrimer networks remains challenging because of the competition between phase behavior and the curing process. Here, we report an environmentally conscious synthesis of ABA-type triblock copolymers (tBCPs), poly(acetoacetoxyethyl methacrylate-b-dimethylsiloxane-b-acetoacetoxyethyl methacrylate) (P(AAEMA-b-DMS-b-AAEMA)), using a supplemental activator and reducing agent (SARA) atom transfer radical polymerization (ATRP) technique. In this approach, a Br–poly(dimethylsiloxane)–Br (Br–PDMS–Br) macroinitiator and a low-concentration (ppm-level) CuBr2 catalyst were used. The resulting high-χ tBCPs exhibited facile composition-dependent bulk morphologies spanning spheres, cylinders, and lamellae on a scale of approximately 30 nm, as confirmed by small-angle X-ray scattering (SAXS). Subsequently, vinylogous urethane vitrimer networks were prepared by crosslinking the β-ketoester (β-KE) units with hexamethylenediamine (HMDA) at 80 °C, followed by postcuring via hot-pressing at 160 °C. Compared with the tBCP precursor, vitrimerization markedly enhances the thermal resistance, thereby increasing the 5% weight-loss temperature (Td,5%) by 51 °C. The results of SAXS analysis before and after vitrimer formation revealed that curing/processing largely suppresses higher-order reflections and yields broadened primary maxima, indicating the formation of less long-range order and primarily nonordered microphase-separated structures. Mediating the NH2/β-KE ratio (1 vs. 2) induces modest but systematic changes in the peak position and width, suggesting that the crosslink density affects segregation/coherence, while the reaction-mediated microphase separation (REMPS) pathway during curing governs primarily the loss of tBCP-derived lattice order. This study presents a scalable ATRP-to-vitrimer strategy for preparing PDMS-containing nanostructured networks and provides mechanistic insight into morphology evolution during vitrimerization. Sustainable SARA ATRP with ppm-level copper enables the efficient synthesis of nanostructured P(AAEMA-b-DMS-b-AAEMA) tBCPs. These precursors exhibit tunable morphologies, including spheres, cylinders, and lamellae at the 30 nm scale. Crosslinking with hexamethylene diamine forms vinylogous urethane vitrimers, boosting thermal stability. SAXS studies reveal that vitrification via the Reaction-mEdiated MicroPhase Separation (REMPS) pathway suppresses long-range order nanostructured networks. This strategy provides a scalable route to PDMS-containing vitrimers, offering key mechanistic insights into the structural evolution of programmable, processable, and sustainable covalently crosslinked polymer networks","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 9","pages":"1225-1235"},"PeriodicalIF":3.1,"publicationDate":"2026-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-026-01205-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148904494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}