Macromolecules最新文献

{"title":"Narrowing Molecular-Weight Distribution via Regulating the Prepolymers in Linear Polycondensation Reaction: Multiscale Simulation Study for the Case of Polyether Ether Ketone","authors":"Zhi-Yong Dong,&nbsp;Yu-Qing Li,&nbsp;Xu-Ze Zhang,&nbsp;Ming-Yang Li,&nbsp;Duo Liu,&nbsp;Rui Shi,&nbsp;Xuanbo Zhu*,&nbsp;Jianxin Mu and Hu-Jun Qian*,&nbsp;","doi":"10.1021/acs.macromol.4c0281010.1021/acs.macromol.4c02810","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02810https://doi.org/10.1021/acs.macromol.4c02810","url":null,"abstract":"<p >Molecular-weight distribution (MWD) is a key factor determining the wide spectra of polymer properties. Especially for special engineering plastics (SEPs), experimental characterization and therefore a precise optimization of the MWD remain a long-standing challenge. Here, we take polyether ether ketone (PEEK) as a model system, and a multiscale theoretical simulation strategy is developed for its synthesis procedure. We found that controlling the MWD of prepolymers at the initial stage is the key to the final product. Based on this understanding, we proposed a “two-pots” strategy and a stepwise addition strategy. Both of them are started from end-capping reactions of the prepolymers, which can effectively reduce the dispersity (<i>Đ</i>) of the prepolymer and therefore that of the resulted final PEEK products. The resulting <i>Đ</i> from both proposed strategies are much lower than the conventional one-pot process. We believe that both strategies can enable the customized optimization of the MWD for polymers synthesized from polycondensation reactions.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 10","pages":"4889–4898 4889–4898"},"PeriodicalIF":5.1,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cyclic Poly(Thioester Amide)s via Ring-Opening Copolymerization of Aziridines and Phthalic Thioanhydride: Mechanistic Insights and Enhanced Properties for Sustainable Materials","authors":"Jiaojiao Qin, Zhun Xu, Huan Wang, Xiaoyan Tang","doi":"10.1021/acs.macromol.5c00511","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00511","url":null,"abstract":"Ring-opening copolymerization renders aziridines promising candidates for constructing <i>N</i>-containing polymers; however, producing polymers with predicted molar masses and defined sequence structures remains challenging. Here, we present a strategy for synthesizing poly(thioester amide)s (PTEAs) via ROCOP of <i>N</i>-alkyl aziridines and phthalic thioanhydride. Remarkably, perfectly alternating copolymerization was achieved by the synergistic catalysis of a phosphazene base and a protic initiator, delivering cyclic PTEAs with a molar mass of up to 188.4 kDa. Model reaction and chain extension experiments supported the rapid <i>S</i>-to-<i>N</i> acyl shift after aziridine ring-opening and spontaneous ring-closure upon applying an external stimulus. Notably, liquid-phase transmission electron microscopy confirmed the linear or cyclic topology before or after the postprocessing by spatially resolving the morphology of transient conformations. The in-chain thioester bonds endow polymers with enhanced thermal and optical properties compared to their poly(ester amide) counterparts, along with desirable degradability and biocompatibility, establishing a robust foundation for developing PTEAs as sustainable and functional biomedical materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"22 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915985","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Model Polymer Systems Replicate the Experimental Features of the Slow Arrhenius Process","authors":"Chun Li,&nbsp; and ,&nbsp;Simone Napolitano*,&nbsp;","doi":"10.1021/acs.macromol.5c0092110.1021/acs.macromol.5c00921","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00921https://doi.org/10.1021/acs.macromol.5c00921","url":null,"abstract":"<p >We identify the dynamic signatures of the slow Arrhenius process (SAP), which is a relaxation mechanism experimentally observed in polymers and small organic molecules. By applying these criteria to the analysis of the desorption of 1,4-polybutadiene (PB) chains from a series of flat substrates, an archetypal system to investigate interfacial equilibration mechanisms, we verify that molecular dynamics (MD) simulations can reproduce the characteristic features of the SAP. By systematically exploring the role of the different components of the force field, we build up a class of model polymer systems that can be employed to study equilibration mechanisms mediated by the SAP. Our work sheds light on the molecular origin of the SAP and elucidates the role of intramolecular interactions in the relaxation of polymer melts.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 10","pages":"5377–5383 5377–5383"},"PeriodicalIF":5.1,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137396","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular Insights into Interfacial Dynamics and Toughening Mechanisms for Poly(lactic acid)-Grafted Cellulose Nanocrystal Composites","authors":"Yang Wang, Wenjie Xia","doi":"10.1021/acs.macromol.4c03064","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03064","url":null,"abstract":"Cellulose nanocrystals (CNCs) are highly regarded as one of the most promising natural biomass-based nanofillers for enhancing poly(lactic acid) (PLA) nanocomposites due to their biocompatibility and high specific modulus. This study presents a temperature-transferable and chemistry-specific coarse-grained (CG) model of PLA developed by using the well-established energy-renormalization (ER) framework. The ER-corrected PLA CG model accurately captures the temperature-dependent dynamics, density, mechanical properties, and conformational characteristics of its all-atom (AA) counterpart. It predicts an accurate glass transition temperature (326 K) and precise tensile and shear moduli, which agree with the AA model and experimental data. Additionally, taking PLA grafted to high-aspect-ratio CNCs as a model nanocomposite, we examine the interfacial behavior of the CNC/PLA nanocomposite and explore the effect of grafted chain length (<i>n</i>) on its mechanical properties under the same CNC content. The results demonstrate a constant Young’s modulus but a higher toughness of CNC/PLA nanocomposites with a longer <i>n</i> due to sufficient chain slippage and crazing fiber formation. The structural evolution during stretching, like chain alignment, bond, and angle, follows the same trend as the stress–strain curve. Furthermore, the dynamics of PLA at a segmental scale are slowed down in proximity to the CNC interface, gradually intensifying as the depth into the matrix increases, thereby revealing a consistent interfacial thickness of 3 nm in the system without grafting, as confirmed by molecular stiffness measurements. Increasing <i>n</i> leads to a greater interfacial thickness. These findings offer valuable insights into the mechanical properties of CNC/PLA systems and valuable guidance for designing and characterizing high-performance CNC-reinforced polymer nanocomposites.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"115 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910821","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular Insights into Interfacial Dynamics and Toughening Mechanisms for Poly(lactic acid)-Grafted Cellulose Nanocrystal Composites","authors":"Yang Wang*,&nbsp; and ,&nbsp;Wenjie Xia*,&nbsp;","doi":"10.1021/acs.macromol.4c0306410.1021/acs.macromol.4c03064","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03064https://doi.org/10.1021/acs.macromol.4c03064","url":null,"abstract":"<p >Cellulose nanocrystals (CNCs) are highly regarded as one of the most promising natural biomass-based nanofillers for enhancing poly(lactic acid) (PLA) nanocomposites due to their biocompatibility and high specific modulus. This study presents a temperature-transferable and chemistry-specific coarse-grained (CG) model of PLA developed by using the well-established energy-renormalization (ER) framework. The ER-corrected PLA CG model accurately captures the temperature-dependent dynamics, density, mechanical properties, and conformational characteristics of its all-atom (AA) counterpart. It predicts an accurate glass transition temperature (326 K) and precise tensile and shear moduli, which agree with the AA model and experimental data. Additionally, taking PLA grafted to high-aspect-ratio CNCs as a model nanocomposite, we examine the interfacial behavior of the CNC/PLA nanocomposite and explore the effect of grafted chain length (<i>n</i>) on its mechanical properties under the same CNC content. The results demonstrate a constant Young’s modulus but a higher toughness of CNC/PLA nanocomposites with a longer <i>n</i> due to sufficient chain slippage and crazing fiber formation. The structural evolution during stretching, like chain alignment, bond, and angle, follows the same trend as the stress–strain curve. Furthermore, the dynamics of PLA at a segmental scale are slowed down in proximity to the CNC interface, gradually intensifying as the depth into the matrix increases, thereby revealing a consistent interfacial thickness of 3 nm in the system without grafting, as confirmed by molecular stiffness measurements. Increasing <i>n</i> leads to a greater interfacial thickness. These findings offer valuable insights into the mechanical properties of CNC/PLA systems and valuable guidance for designing and characterizing high-performance CNC-reinforced polymer nanocomposites.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 10","pages":"5318–5328 5318–5328"},"PeriodicalIF":5.1,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137594","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and Morphological Analysis of Well-Defined Poly(2,6-dimethyl-1,4-phenylene ether)-b-Poly(dimethylsiloxane)","authors":"Riku Takahashi, Kan Hatakeyama-Sato, Yuta Nabae, Teruaki Hayakawa","doi":"10.1021/acs.macromol.5c00730","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00730","url":null,"abstract":"Microphase-separated structures of block copolymers have been leveraged in advanced functional materials. However, such unique morphologies have not been extensively studied for block copolymers comprising poly(2,6-dimethyl-1,4-phenylene ether) (PPE), although PPE is a commonly utilized engineering plastic. Herein, based on precisely prepared PPE, we have developed PPE-containing block copolymers, exhibiting various microphase-separated structures such as spheres, lamellae, and cylinders. As the second block component, poly(dimethylsiloxane) (PDMS) was synthesized via living ring-opening polymerization. Block copolymers (PPE-<i>b</i>-PDMS) with different compositions were efficiently obtained by employing hydrosilylation using Karstedt’s catalyst. Additionally, it was found that PPE-<i>b</i>-PDMS followed different pathways of microphase-separated structure formation depending on the solvent used for sample preparation. The developed morphologies are expected to enhance the properties of PPE through the combination with other block components and the control of nanometer-scale internal structures.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"139 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910823","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Using Vinyl Cyclicsiloxane as a Scaffold to Prepare Tetraborane Lewis Acid as a Synergistic Catalyst for the Ring-Opening Polymerization of Epoxides","authors":"Zhenwei Zhou,&nbsp;Xiaowu Wang*,&nbsp;Xinyuan Song,&nbsp;Ronglin Zhong* and Zhibo Li*,&nbsp;","doi":"10.1021/acs.macromol.5c0033810.1021/acs.macromol.5c00338","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00338https://doi.org/10.1021/acs.macromol.5c00338","url":null,"abstract":"<p >The development of efficient metal-free catalyst systems for the ring-opening polymerization (ROP) of epoxides is essential for producing functional polyethers with controlled molecular weights, low dispersity, and precise main-chain sequences. In this study, we present a binary system comprising tetravinyltetramethylcyclotetrasiloxane-based tetraboranes (<b>V4B</b>) as the catalyst and tetrabutyl ammonium succinic salt (TBASA) as the initiator for the ROP of epoxides to precisely synthesize polyethers. The binary <b>V4B</b>/TBASA system demonstrates high activity (TOF = 1500 h^–1 per borane) under mild conditions, enabling polyethers with predictable molecular weights and moderate dispersity (<i>D̵</i> = 1.32). Notably, this binary system exhibits living polymerization characteristics, allowing the preparation of multiblock polyethers. Kinetic studies and density functional theory (DFT) calculations suggested that a synergistic intramolecular PO activation from symmetric tetraborane centers with suitably spatial proximity was critical for the high activity of <b>V4B</b> as compared to the triborane substituted counterpart. This work provides valuable insights into designing advanced multiborane catalysts for highly efficient and precise polymerization processes.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 10","pages":"5049–5057 5049–5057"},"PeriodicalIF":5.1,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137637","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tuning Copolymer Microstructure Using Ring-Opening Cross-Metathesis Polymerization","authors":"Jeffrey C. Foster, Isaiah T. Dishner","doi":"10.1021/acs.macromol.5c00659","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00659","url":null,"abstract":"The capability of ring-opening cross-metathesis (RO/CM) polymerization to produce alternating copolymers was studied. By treating commercial polybutadiene (PB) with bulky oxanorbornene monomers and Ru-based olefin metathesis catalysts, alternating copolymers were produced under mild conditions with high sequence fidelities. We found that alternating copolymers could be produced starting from a variety of butadiene sources including PB, cyclooctadiene (COD), or <i>t</i>,<i>t</i>,<i>t</i>-1,5,9-cyclododecatriene (CDT), highlighting for the first time the kinetic pathway independence of this process. Kinetic copolymerization analysis of an oxanorbonene monomer with CDT revealed that much higher monomer conversions were obtained compared with the analogous homopolymerizations and showed evidence of alternating monomer incorporation. Copolymerization of these monomers also enabled good control when targeting different molecular weights. Copolymer thermal analysis revealed a strong correlation between thermal behavior and alternating sequence fidelity, providing a second lever beyond composition to tune thermal behavior. These data demonstrate that a broad variety of polymer microstructures can be accessed via RO/CM polymerization and highlight the potential of CDT in alternating copolymer synthesis.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"19 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910822","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of a Double-Hydrophilic Block Copolymer with a Multifunctional Block: Spontaneous Formation of Polyion Complex Micelles from a Single Cationic–Anionic Copolymer","authors":"Ananthapadmanabhan Unnikrishnan,&nbsp;Mateus Garcia Rodolfo,&nbsp;Najet Mahmoudi,&nbsp;Gaulthier Rydzek*,&nbsp;Julien Schmitt*,&nbsp;Ralf Schweins and Corine Gérardin,&nbsp;","doi":"10.1021/acs.macromol.4c0288410.1021/acs.macromol.4c02884","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02884https://doi.org/10.1021/acs.macromol.4c02884","url":null,"abstract":"&lt;p &gt;A double-hydrophilic block copolymer (DHBC) exhibiting a multifunctional block was obtained via a multistep synthesis. First, the parent copolymer, Par. Pol., P(OEGMEA)-&lt;i&gt;b&lt;/i&gt;-PAA, composed of a neutral block of poly(oligo(ethylene glycol))-methyl ether acrylate (P(OEGMEA)) and a weak polyacid block of poly(acrylic acid) (PAA), was synthesized by RAFT polymerization. Then, the PAA block was modified via the activation/amidation route, using &lt;i&gt;N&lt;/i&gt;-(3-(dimethylamino)propyl)-&lt;i&gt;N&lt;/i&gt;′-ethylcarbodiimide (EDC) and &lt;i&gt;N&lt;/i&gt;-hydroxysuccinimide (NHS) to activate the DHBC, yielding the activated copolymer Act. Pol., before reaction with &lt;i&gt;N&lt;/i&gt;-Boc ethylenediamine. The resulting amidated copolymer, named Ami. Pol., composed of P(OEGMEA)-&lt;i&gt;b&lt;/i&gt;-P(AA-&lt;i&gt;s&lt;/i&gt;-(Acyl urea)-&lt;i&gt;s&lt;/i&gt;-(N-Boc)), exhibits several functional groups on the second block: acrylates from the PAA backbone, pending &lt;i&gt;N&lt;/i&gt;-Acyl urea, and finally pending &lt;i&gt;N&lt;/i&gt;-Boc ethylenediamine. &lt;i&gt;N&lt;/i&gt;-Acyl urea exhibits tertiary amines, while &lt;i&gt;N&lt;/i&gt;-boc ethylenediamine adds primary amines protected by a &lt;i&gt;tert&lt;/i&gt;-butyl group, which can later be removed by a deprotection step using trichloroacetic acid (TCA), yielding the final P(OEGMEA)-&lt;i&gt;b&lt;/i&gt;-P(AA-&lt;i&gt;s&lt;/i&gt;-(Acyl urea)-&lt;i&gt;s&lt;/i&gt;-(AA/NH&lt;sub&gt;2&lt;/sub&gt;)) copolymer, labeled De. Pol. We characterized the DHBC at every stage of the modification (i.e., parent copolymer, activated copolymer, amidated copolymer, and deprotected copolymer) using a combination of NMR and elemental analysis to assess the number of units of each group in the second block. After activation/amidation, &lt;i&gt;N&lt;/i&gt;-Acyl urea groups represent ca. 13–32% of the second block, depending on the activation conditions, while the amount of &lt;i&gt;N&lt;/i&gt;-Boc ethylenediamine groups is ca. 8–34%, depending on the amidation conditions. We demonstrated the efficient removal of the &lt;i&gt;tert&lt;/i&gt;-butyl protection groups after deprotection without any damage to the DHBC. Due to the presence of acrylates and amine functions, the activated, amidated, and deprotected copolymers exhibit pH-tunable self-assembling properties. Samples were studied at pH values ranging from 2 to 9, using dynamic light scattering (DLS), ζ-potential measurements, and ATR-FTIR, and well-defined micelles were observed at pH values ranging from 4–9. The combination of measurements, coupled with DLS studies as a function of salt, provided evidence that micelles were formed by electrostatic complexation between the positively charged &lt;i&gt;N&lt;/i&gt;-Acyl urea pending groups and the unmodified negatively charged acrylate species. Micelles were then characterized using a combination of light and small-angle neutron scattering (SANS). Notably, an optimum pH range for micellization of 5–7 with a single population was obtained by dynamic light scattering (DLS). SANS data were successfully fitted using a model of polymer micelles, which provided information about the core radius of the micelles &lt;i&gt;R&lt;/i&gt; (6.3 ± 0.1 nm for amidated cop","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 10","pages":"5110–5134 5110–5134"},"PeriodicalIF":5.1,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137588","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Phase Behavior and Thermal Properties of Precision Polyelectrolyte Blends: The Dilute Charge Regime","authors":"Michael Patrick Blatt,&nbsp;Cecilia Hansen,&nbsp;Victoria Horton,&nbsp;Nam Nguyen,&nbsp;Justin G. Kennemur,&nbsp;Rufina G. Alamo and Daniel T. Hallinan Jr.*,&nbsp;","doi":"10.1021/acs.macromol.4c0323110.1021/acs.macromol.4c03231","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03231https://doi.org/10.1021/acs.macromol.4c03231","url":null,"abstract":"<p >In this work, miscibility and thermal properties were studied in blends of poly(ethylene oxide) (PEO) and a precision polyanion of linear polyethylene hosting a phenyl-4-[sulfonyl(trifluoromethylsulfonyl)imide-Li] at every fifth carbon (<i>p5</i>). Blends were found to be miscible at low to moderate PEO concentrations ranging from 10 to 80 wt % PEO. However, in blends with high PEO weight fraction (≥90 wt % PEO), visible, macroscopic phase separation was observed. Differential scanning calorimetry was used to study trends in the primary and secondary phase transitions of each blend to better understand the phase boundaries and interactions underpinning phase behavior. A single glass transition temperature (<i>T</i>_g) was identified for each blend composition. Within the miscible range, the <i>T</i>_g values were well fit by the Kwei model and a modified Fox model with a single fitting parameter, but significant disagreement between models and experiment was observed for two-phase blends (&gt;80 wt % PEO). In miscible semicrystalline blends, PEO melting point depression was clearly observed due to the presence of <i>p5</i> as a diluent. In contrast, the PEO melting temperature of two-phase blends was a nonmonotonic function of <i>p5</i> content. This evidence agrees well with predictions from theory and modeling by Sing and Olvera de la Cruz (10.1021/mz500202n) for blends with strong ion correlations, indicating that charge plays a significant and complex role in blend phase behavior especially in the dilute charge regime. Furthermore, a modified Fox equation was developed to model blend <i>T</i>_g as a function of blend composition that performed comparably to the Kwei model (a model with 2 adjustable parameters), despite only requiring one fitting parameter. Both findings provide key insight into the prospective design of polyanion-based polymer blend electrolytes as miscibility and flexibility are essential in these materials.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 10","pages":"5071–5079 5071–5079"},"PeriodicalIF":5.1,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137636","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}