Pub Date : 2026-02-05DOI: 10.1021/acs.macromol.5c03222
Junsu Kim, Seungjae Lee, Yeongsik Kim, Jeonghun Kim, Thomas P. Russell, Du Yeol Ryu
In strongly segregated block copolymers (BCPs), amorphous–liquid crystalline (LC) BCPs provide access to unconventional mesophases owing to the configurational anisotropy and conformational asymmetry (ε) between the two blocks. The BCPs of polydimethylsiloxane-b-poly((4(phenyldiazenyl)phenoxy)hexyl acrylate) (PDMS-b-PPHAs) are composed of amorphous and LC blocks containing side-chain azobenzene units. Various self-assembled morphologies were obtained by adjusting the volume fraction of the PPHA block and its photoisomerization. The trans-isomeric PDMS-b-PPHAs enable the π–π stacking of the azobenzene units in the PPHA block, that generates a variety of mesophases, including A15, columnar rectangular (Colr), columnar hexagonal (Colh), and lamellar (LAM) phases. The A15 and Colr phases are stabilized by the planar mesogenic packing of azobenzene units at low temperatures, and a Colr–Colh transition occurs upon heating. Particularly, the high ε between the two blocks leads to highly asymmetric LAM phase. However, the cis-isomeric PDMS-b-PPHAs show mostly the non-LC driven Colh phases with limited access to the highly asymmetric LAM phases. These findings highlight a versatile design platform for configurational mesophases using amorphous–LC BCPs, which, together with the discovery of a Colr phase with large microdomains, produces a new paradigm for self-assembled mesophases of side-chain LC BCPs.
{"title":"Configurational Mesophases in Amorphous–Azobenzene-Containing LC Block Copolymers: A15, Columnar Rectangular, and Highly Asymmetric Lamellar Phases","authors":"Junsu Kim, Seungjae Lee, Yeongsik Kim, Jeonghun Kim, Thomas P. Russell, Du Yeol Ryu","doi":"10.1021/acs.macromol.5c03222","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03222","url":null,"abstract":"In strongly segregated block copolymers (BCPs), amorphous–liquid crystalline (LC) BCPs provide access to unconventional mesophases owing to the configurational anisotropy and conformational asymmetry (ε) between the two blocks. The BCPs of polydimethylsiloxane-<i>b</i>-poly((4(phenyldiazenyl)phenoxy)hexyl acrylate) (PDMS-<i>b</i>-PPHAs) are composed of amorphous and LC blocks containing side-chain azobenzene units. Various self-assembled morphologies were obtained by adjusting the volume fraction of the PPHA block and its photoisomerization. The trans-isomeric PDMS-<i>b</i>-PPHAs enable the π–π stacking of the azobenzene units in the PPHA block, that generates a variety of mesophases, including A15, columnar rectangular (Col<sub>r</sub>), columnar hexagonal (Col<sub>h</sub>), and lamellar (LAM) phases. The A15 and Col<sub>r</sub> phases are stabilized by the planar mesogenic packing of azobenzene units at low temperatures, and a Col<sub>r</sub>–Col<sub>h</sub> transition occurs upon heating. Particularly, the high ε between the two blocks leads to highly asymmetric LAM phase. However, the cis-isomeric PDMS-<i>b</i>-PPHAs show mostly the non-LC driven Col<sub>h</sub> phases with limited access to the highly asymmetric LAM phases. These findings highlight a versatile design platform for configurational mesophases using amorphous–LC BCPs, which, together with the discovery of a Col<sub>r</sub> phase with large microdomains, produces a new paradigm for self-assembled mesophases of side-chain LC BCPs.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"28 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122234","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}
Pub Date : 2026-02-05DOI: 10.1021/acs.macromol.5c03140
Jianjun Li, Deyu Niu, Weijun Yang, Pengwu Xu, Piming Ma
Traditional bisphenol A-based polycarbonate (BPA-PC) has been restricted in food contact materials, particularly those for infants and babies, which has the potential chronic toxicity and estrogenic activity due to the presence of bisphenol A. In this study, a series of high-performance isosorbide (ISB)-based polyester-polycarbonates (PIs-PCLCs) were prepared using ISB, poly(caprolactone) diol, and diphenyl carbonate via melt transesterification polycondensation as a potential alternative to BPA-PC. The properties of the PIs-PCLC samples, such as strength, elongation, and glass transition temperature, gradually varied as increasing the polycaprolactone (PCL)-diol content from 0 to 10 mol %, and a good balance in performance was obtained at around 6.25% of the PCL-diol content. Notably, the PIs-PCLC-6.25 (6.25 represents the molar percentage of PCL diol) sample exhibited a tensile strength of 74.6 MPa, an elongation at break of 83%, a high glass transition temperature (Tg) of 122 °C, and an optical transmittance of 89.2% at 550 nm. This overall combination of properties was comparable to that of certain commercial engineering plastics. The small-angle X-ray scattering results obtained during tensile stretching reveal a transition in the deformation mechanism. While the poly(isosorbide carbonate) homopolymer exhibits craze-dominated fracture characteristics, the PIs-PCLC-6.25 sample demonstrates a shear band-mediated deformation process. This is attributed to the incorporation of flexible PCL diol chain segments, which leads to ductile fracture behavior. In summary, this study presents an efficient and viable strategy for fabricating high-performance PIs-PCLCs, thereby broadening the practical application prospects of high-performance biobased polymeric materials in areas such as food-contact packaging and medical devices.
{"title":"A New Structure of High-Performance Isosorbide-Based Polyester-Polycarbonates and Its Mechanical Behavior","authors":"Jianjun Li, Deyu Niu, Weijun Yang, Pengwu Xu, Piming Ma","doi":"10.1021/acs.macromol.5c03140","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03140","url":null,"abstract":"Traditional bisphenol A-based polycarbonate (BPA-PC) has been restricted in food contact materials, particularly those for infants and babies, which has the potential chronic toxicity and estrogenic activity due to the presence of bisphenol A. In this study, a series of high-performance isosorbide (ISB)-based polyester-polycarbonates (PIs-PCLCs) were prepared using ISB, poly(caprolactone) diol, and diphenyl carbonate via melt transesterification polycondensation as a potential alternative to BPA-PC. The properties of the PIs-PCLC samples, such as strength, elongation, and glass transition temperature, gradually varied as increasing the polycaprolactone (PCL)-diol content from 0 to 10 mol %, and a good balance in performance was obtained at around 6.25% of the PCL-diol content. Notably, the PIs-PCLC-6.25 (6.25 represents the molar percentage of PCL diol) sample exhibited a tensile strength of 74.6 MPa, an elongation at break of 83%, a high glass transition temperature (<i>T</i><sub>g</sub>) of 122 °C, and an optical transmittance of 89.2% at 550 nm. This overall combination of properties was comparable to that of certain commercial engineering plastics. The small-angle X-ray scattering results obtained during tensile stretching reveal a transition in the deformation mechanism. While the poly(isosorbide carbonate) homopolymer exhibits craze-dominated fracture characteristics, the PIs-PCLC-6.25 sample demonstrates a shear band-mediated deformation process. This is attributed to the incorporation of flexible PCL diol chain segments, which leads to ductile fracture behavior. In summary, this study presents an efficient and viable strategy for fabricating high-performance PIs-PCLCs, thereby broadening the practical application prospects of high-performance biobased polymeric materials in areas such as food-contact packaging and medical devices.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146121948","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}
Pub Date : 2026-02-05DOI: 10.1021/acs.macromol.5c03645
Fen You, Hui Liu, Yanan Zhao, Xiaochao Shi
Cationic rare-earth metal alkyl complexes have proven to be outstanding single-site catalysts, particularly for the coordination polymerization of 1,3-dienes with high catalytic activity and stereoselectivity. Unprecedentedly, the polymerization of the novel bioderived 1,3-diene, namely 2-allylidene-6,6-dimethylbicyclo[3.1.1]heptane (ADH), catalyzed by a cationic scandium alkyl complex, proceeded via a ring-opening cationic mechanism rather than a coordination–insertion pathway. Detailed studies indicated that during the initiation step, the coordination-induced steric repulsion between the catalyst and ADH was critical for generating the active tertiary carbocation, which was formed by the ring-opening of the fused cyclobutane unit in ADH. Density functional theory (DFT) calculations revealed that both coordination polymerization and ring-opening cationic polymerization of ADH can be energetically competitive, and the steric hindrance of the catalyst may play a critical role in determining the polymerization outcome. The resulting poly(ADH) (PADH) exhibited a high glass transition temperature, excellent thermostability, optical transparency, and potential for postmodification.
{"title":"Coordination-Induced Ring-Opening Cationic Polymerization of Bioderived 1,3-Diene by Cationic Rare-Earth Metal Alkyl Complexes","authors":"Fen You, Hui Liu, Yanan Zhao, Xiaochao Shi","doi":"10.1021/acs.macromol.5c03645","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03645","url":null,"abstract":"Cationic rare-earth metal alkyl complexes have proven to be outstanding single-site catalysts, particularly for the coordination polymerization of 1,3-dienes with high catalytic activity and stereoselectivity. Unprecedentedly, the polymerization of the novel bioderived 1,3-diene, namely 2-allylidene-6,6-dimethylbicyclo[3.1.1]heptane (<b>ADH</b>), catalyzed by a cationic scandium alkyl complex, proceeded via a ring-opening cationic mechanism rather than a coordination–insertion pathway. Detailed studies indicated that during the initiation step, the coordination-induced steric repulsion between the catalyst and <b>ADH</b> was critical for generating the active tertiary carbocation, which was formed by the ring-opening of the fused cyclobutane unit in <b>ADH</b>. Density functional theory (DFT) calculations revealed that both coordination polymerization and ring-opening cationic polymerization of <b>ADH</b> can be energetically competitive, and the steric hindrance of the catalyst may play a critical role in determining the polymerization outcome. The resulting poly(<b>ADH</b>) (PADH) exhibited a high glass transition temperature, excellent thermostability, optical transparency, and potential for postmodification.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"76 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122086","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}
Pub Date : 2026-02-05DOI: 10.1021/acs.macromol.5c01752
Tianyi Jin, Connor W. Coley, Alfredo Alexander-Katz
Synthetic random heteropolymers (RHPs) offer a versatile platform for mimicking protein-like functions through their sequence and structure ensembles, providing a cost-effective and scalable alternative to natural proteins. Unlike the well-studied energy landscapes of protein folding, the energy landscape of RHP folding, or more generally, collapse, remains largely unexplored. Here, we investigate the energy landscape and structural stability of a recently emergent class of methyl methacrylate-based RHPs. By conducting microsecond-scale atomistic molecular dynamics simulations with umbrella sampling, we propose a hierarchically rugged free energy landscape characterized by high energy barriers separating broad minima with internally rugged basins that permit local structural fluctuations. Identical local sequences are found to be able to adopt diverse conformations. Using XGBoost and SHAP analysis, we identify key contact patterns critical for structural stability. These include specific residue–residue contacts reminiscent of those observed in protein folding, and position-nonspecific interactions, such as contacts between backbone and polar or hydrophobic side groups, which are related to monomer miscibility. This latter relationship resembles the design rules in plastics. Moreover, the inherent diversity of microenvironments in RHPs highlights their potential to incorporate functional ligands, enabling versatile applications such as catalysis. This work elucidates both the similarities and differences among RHPs, proteins, and plastics, providing fundamental insight into the collapse free energy landscape, structural stability, and functional adaptability of RHPs.
{"title":"Energy Landscape and Stability in Random Heteropolymers: Somewhere Between Protein Folding and Plastic Miscibility","authors":"Tianyi Jin, Connor W. Coley, Alfredo Alexander-Katz","doi":"10.1021/acs.macromol.5c01752","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01752","url":null,"abstract":"Synthetic random heteropolymers (RHPs) offer a versatile platform for mimicking protein-like functions through their sequence and structure ensembles, providing a cost-effective and scalable alternative to natural proteins. Unlike the well-studied energy landscapes of protein folding, the energy landscape of RHP folding, or more generally, collapse, remains largely unexplored. Here, we investigate the energy landscape and structural stability of a recently emergent class of methyl methacrylate-based RHPs. By conducting microsecond-scale atomistic molecular dynamics simulations with umbrella sampling, we propose a hierarchically rugged free energy landscape characterized by high energy barriers separating broad minima with internally rugged basins that permit local structural fluctuations. Identical local sequences are found to be able to adopt diverse conformations. Using XGBoost and SHAP analysis, we identify key contact patterns critical for structural stability. These include specific residue–residue contacts reminiscent of those observed in protein folding, and position-nonspecific interactions, such as contacts between backbone and polar or hydrophobic side groups, which are related to monomer miscibility. This latter relationship resembles the design rules in plastics. Moreover, the inherent diversity of microenvironments in RHPs highlights their potential to incorporate functional ligands, enabling versatile applications such as catalysis. This work elucidates both the similarities and differences among RHPs, proteins, and plastics, providing fundamental insight into the collapse free energy landscape, structural stability, and functional adaptability of RHPs.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"287 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116120","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}
Pub Date : 2026-02-05DOI: 10.1021/acs.macromol.5c02814
Jaechul Ju, Ryan C. Hayward
Cocontinuous polymeric nanomaterials have gained attention for their ability to preserve distinct properties of constituent microphases within a single material. Randomly linked copolymer networks have shown very wide stability windows for disordered cocontinuous phases (extending over ≈ 30 wt % in composition), but the reliance on a network architecture prevents subsequent solution- or melt-processing. Furthermore, the key factors contributing to cocontinuity have remained unclear. We recently found that randomly linked star copolymers (RSCs) can exhibit a cocontinuous window as wide as 25 wt % in the case of 4-arm stars, suggesting that while a network architecture is not essential for the formation of disordered cocontinuous phases, the presence of random elastic forces in such architectures may indeed facilitate their formation. In addition, the behavior was found to be highly sensitive to arm number, with 6-arm RSCs exhibiting almost no cocontinuous phase. These results raised a key mechanistic question regarding the contribution of random elastic forces, originating from strands that bridge between junctions, in stabilizing disordered cocontinuous phases. In the current study, we synthesized randomly linked branched copolymers (RBCs) of polystyrene (PS) and poly(D,L-lactic acid) (PLA), which represent an intermediate architecture between networks and stars. This approach allows for the introduction of elastic contributions from strands bridging between different junctions, while still maintaining the processability advantages of a non-network architecture. The cocontinuous regions of the PS/PLA RBCs, with varying polymer and linker functionalities (fp and fl, respectively), were characterized by small-angle X-ray scattering, gravimetry, and scanning electron microscopy. We found that the cocontinuous windows of RBCs typically expanded with increasing elastic contributions and exhibited reduced sensitivity to junction-functionality compared to RSCs. Notably, RBCs with fp = 1.50 and fl = 3, which had large molecular weights due to proximity to the gel point, achieved a cocontinuous window of ≈ 34 wt %, which is almost twice as wide as analogous 3-arm RSCs and comparable to randomly linked networks. Leveraging this robust cocontinuity and solution-processability, we fabricated a film of interconnected nanoporous PS.
{"title":"Microphase Separation of Randomly Linked Branched Polystyrene/Polylactic Acid for Formation of Cocontinuous Nanostructures","authors":"Jaechul Ju, Ryan C. Hayward","doi":"10.1021/acs.macromol.5c02814","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02814","url":null,"abstract":"Cocontinuous polymeric nanomaterials have gained attention for their ability to preserve distinct properties of constituent microphases within a single material. Randomly linked copolymer networks have shown very wide stability windows for disordered cocontinuous phases (extending over ≈ 30 wt % in composition), but the reliance on a network architecture prevents subsequent solution- or melt-processing. Furthermore, the key factors contributing to cocontinuity have remained unclear. We recently found that randomly linked star copolymers (RSCs) can exhibit a cocontinuous window as wide as 25 wt % in the case of 4-arm stars, suggesting that while a network architecture is not essential for the formation of disordered cocontinuous phases, the presence of random elastic forces in such architectures may indeed facilitate their formation. In addition, the behavior was found to be highly sensitive to arm number, with 6-arm RSCs exhibiting almost no cocontinuous phase. These results raised a key mechanistic question regarding the contribution of random elastic forces, originating from strands that bridge between junctions, in stabilizing disordered cocontinuous phases. In the current study, we synthesized randomly linked branched copolymers (RBCs) of polystyrene (PS) and poly(D,L-lactic acid) (PLA), which represent an intermediate architecture between networks and stars. This approach allows for the introduction of elastic contributions from strands bridging between different junctions, while still maintaining the processability advantages of a non-network architecture. The cocontinuous regions of the PS/PLA RBCs, with varying polymer and linker functionalities (<i>f</i><sub>p</sub> and <i>f</i><sub>l</sub>, respectively), were characterized by small-angle X-ray scattering, gravimetry, and scanning electron microscopy. We found that the cocontinuous windows of RBCs typically expanded with increasing elastic contributions and exhibited reduced sensitivity to junction-functionality compared to RSCs. Notably, RBCs with <i>f</i><sub>p</sub> = 1.50 and <i>f</i><sub>l</sub> = 3, which had large molecular weights due to proximity to the gel point, achieved a cocontinuous window of ≈ 34 wt %, which is almost twice as wide as analogous 3-arm RSCs and comparable to randomly linked networks. Leveraging this robust cocontinuity and solution-processability, we fabricated a film of interconnected nanoporous PS.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"159 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116084","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}
Pub Date : 2026-02-05DOI: 10.1021/acs.macromol.5c02733
Ioannis Tzourtzouklis, Tobias Gäb, Marianna Spyridakou, Holger Frey, George Floudas
A new family of block copolymer electrolytes, where the “soft” block is synthesized via anionic ring opening copolymerization of ethylene oxide (EO) and glycidyl methyl ether (GME) and the “hard” block is glassy polystyrene (PS), overcomes many of the limitations of poly(ethylene oxide) (PEO) for battery applications. Two block copolymer systems, PS-b-P(EO-co-GME) with a GME content of 21% and PS-b-PGME containing a pure PGME block, were prepared, both with narrow dispersity (Đ = 1.03–1.15). All polyether blocks are structural isomers of PEO. Yet, in both structures, the polyether block is fully amorphous at all temperatures. When doped with LiN(SO2CF3) (LiTFSI) at different ratios, the materials provide superior dc-conductivity values in comparison to the established dual ion conductors PS-b-PEO doped with LiTFSI or with LiCF3SO3 (LiTf). In addition, PS-b-PGME doped with (LiTFSI) has a higher conductivity (∼1 × 10–5 S·cm–1 at the PS glass temperature) than PS-b-P(EO-co-GME) and a higher conductivity than the structurally similar single ion conductor polystyrene-b-poly(ethylene oxide-co-(lithium trifluoromethane-sulfonamide)ethyl glycidyl ether) (PS-b-P(EO-co-LiTFSAEGE). PGME best combines favorable properties required for the design of the soft block in SPEs based on block copolymers: low liquid-to-glass temperature (Tg) nearly independent of molar mass, favorable molecular structure that can solubilize alkali metal salts, higher dielectric permittivity than PEO, and the absence of crystallization. These results suggest that PGME or PGME-containing polyether copolymers can replace PEO as the “soft” block in future SPEs.
一种新的嵌段共聚物电解质，其中“软”嵌段是通过环氧乙烷（EO）和缩水甘油酯甲基醚（GME）的阴离子开环共聚合成的，“硬”嵌段是玻璃状聚苯乙烯（PS），克服了聚环氧乙烷（PEO）在电池应用中的许多限制。制备了两种嵌段共聚物体系，GME含量为21%的PS-b-P（EO-co-GME）和含有纯PGME嵌段的PS-b-PGME，分散性均较窄（Đ = 1.03-1.15）。所有聚醚嵌段都是PEO的结构异构体。然而，在这两种结构中，聚醚块在所有温度下都是完全无定形的。当以不同比例掺杂LiN(SO2CF3) （LiTFSI）时，与已建立的掺杂LiTFSI或LiCF3SO3 （LiTf）的双离子导体PS-b-PEO相比，材料具有更好的直流电导率值。此外，掺杂（LiTFSI）的PS-b- pgme具有比PS-b- p （EO-co-GME）更高的电导率（在PS玻璃温度下为1 × 10-5 S·cm-1），并且比结构相似的单离子导体聚苯乙烯-b-聚（环氧乙烷-co-（三氟甲烷-磺胺锂）乙基甘油醚）(PS-b- p （EO-co-LiTFSAEGE）更高的电导率。PGME最好地结合了基于嵌段共聚物的spe中软嵌段设计所需的有利性能：低的液-玻璃温度（Tg）几乎与摩尔质量无关，有利的分子结构可以溶解碱金属盐，比PEO更高的介电常数，并且没有结晶。这些结果表明，PGME或含PGME的聚醚共聚物可以在未来的spe中取代PEO作为“软”嵌段。
{"title":"On Replacing Poly(ethylene oxide) in Solid Block Copolymer Electrolytes by Poly(glycidyl methyl ether): Morphology and Ionic Conductivity","authors":"Ioannis Tzourtzouklis, Tobias Gäb, Marianna Spyridakou, Holger Frey, George Floudas","doi":"10.1021/acs.macromol.5c02733","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02733","url":null,"abstract":"A new family of block copolymer electrolytes, where the “soft” block is synthesized via anionic ring opening copolymerization of ethylene oxide (EO) and glycidyl methyl ether (GME) and the “hard” block is glassy polystyrene (PS), overcomes many of the limitations of poly(ethylene oxide) (PEO) for battery applications. Two block copolymer systems, PS-<i>b</i>-P(EO-<i>co</i>-GME) with a GME content of 21% and PS-<i>b</i>-PGME containing a pure PGME block, were prepared, both with narrow dispersity (<i>Đ</i> = 1.03–1.15). All polyether blocks are structural isomers of PEO. Yet, in both structures, the polyether block is fully amorphous at all temperatures. When doped with LiN(SO<sub>2</sub>CF<sub>3</sub>) (LiTFSI) at different ratios, the materials provide superior dc-conductivity values in comparison to the established dual ion conductors PS-<i>b</i>-PEO doped with LiTFSI or with LiCF<sub>3</sub>SO<sub>3</sub> (LiTf). In addition, PS-<i>b</i>-PGME doped with (LiTFSI) has a higher conductivity (∼1 × 10<sup>–5</sup> S·cm<sup>–1</sup> at the PS glass temperature) than PS-<i>b</i>-P(EO-<i>co</i>-GME) and a higher conductivity than the structurally similar single ion conductor polystyrene-<i>b</i>-poly(ethylene oxide-<i>co</i>-(lithium trifluoromethane-sulfonamide)ethyl glycidyl ether) (PS-<i>b</i>-P(EO-<i>co</i>-LiTFSAEGE). PGME best combines favorable properties required for the design of the soft block in SPEs based on block copolymers: low liquid-to-glass temperature (<i>T</i><sub>g</sub>) nearly independent of molar mass, favorable molecular structure that can solubilize alkali metal salts, higher dielectric permittivity than PEO, and the absence of crystallization. These results suggest that PGME or PGME-containing polyether copolymers can replace PEO as the “soft” block in future SPEs.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"69 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122232","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}
Pub Date : 2026-02-05DOI: 10.1021/acs.macromol.5c03346
Xin-Lei Li, Wen-Da Shang, Tie-Qi Xu
Although recyclable polymers have offered a promising solution to concerns about our environment and sustainability, developing elastomeric materials that simultaneously possess strong toughness and excellent resilience remains a significant challenge. To address this, a recyclable polyester elastomer is reported by the strategic Diels–Alder reaction between a furan-based amorphous polyester copolymer and a maleimide cross-linker, thereby overcoming the traditional trade-off between mechanical strength and resilience. The resulting elastomer exhibits ultratoughness (201 MJ m–3) and resilience in the first extension stress (89%), which are 2–3.3 times and 1.4–1.6 times higher than those of commercial polyolefin-based TPEs, respectively. In addition, the cyclohexene linkage moieties endow the elastomers with unique dynamic characteristics, including self-healing capabilities and shape reconfigurability, thus significantly increasing the design flexibility and versatility of complex structures. They also have wide service temperature ranges (−50–105 °C), high temperature stability (Td,5% = 358 °C), and reasonably wide thermal reprocessing windows (105–358 °C). Thermolysis of the bulk elastomer at 150 °C can recover 95 wt % of the material, allowing reuse without losing value and achieving a successful closed-loop life cycle.
{"title":"Super-Tough and Resilient Recyclable Polyester Elastomers Enabled by Dynamic Cross-Linking","authors":"Xin-Lei Li, Wen-Da Shang, Tie-Qi Xu","doi":"10.1021/acs.macromol.5c03346","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03346","url":null,"abstract":"Although recyclable polymers have offered a promising solution to concerns about our environment and sustainability, developing elastomeric materials that simultaneously possess strong toughness and excellent resilience remains a significant challenge. To address this, a recyclable polyester elastomer is reported by the strategic Diels–Alder reaction between a furan-based amorphous polyester copolymer and a maleimide cross-linker, thereby overcoming the traditional trade-off between mechanical strength and resilience. The resulting elastomer exhibits ultratoughness (201 MJ m<sup>–3</sup>) and resilience in the first extension stress (89%), which are 2–3.3 times and 1.4–1.6 times higher than those of commercial polyolefin-based TPEs, respectively. In addition, the cyclohexene linkage moieties endow the elastomers with unique dynamic characteristics, including self-healing capabilities and shape reconfigurability, thus significantly increasing the design flexibility and versatility of complex structures. They also have wide service temperature ranges (−50–105 °C), high temperature stability (<i>T</i><sub>d,5%</sub> = 358 °C), and reasonably wide thermal reprocessing windows (105–358 °C). Thermolysis of the bulk elastomer at 150 °C can recover 95 wt % of the material, allowing reuse without losing value and achieving a successful closed-loop life cycle.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"12 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122529","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}
Pub Date : 2026-02-05DOI: 10.1021/acs.macromol.5c03609
Zixiao Liu, Fumi Ishizuka, Masayoshi Ido, Shunsuke Chatani, Per B. Zetterlund
Covalent cross-linking has been widely employed to stabilize the morphology of worm-like polymer nanoparticles. However, conventional qualitative evaluations of cross-linking efficiency are insufficient for further optimization of cross-linking conditions. In this study, a novel solvent-exchange method has been developed to quantitatively estimate the cross-linking efficiency of worm-like nanoparticles synthesized via reversible addition–fragmentation chain transfer (RAFT)-mediated aqueous emulsion polymerization-induced self-assembly (PISA). By integrating quantitative and qualitative analyses, the cross-linking efficiency and morphological stability of both in situ and post-cross-linking approaches were systematically compared. The results showed that in situ cross-linking consistently yielded high efficiency and better-preserved worm-like structures at lower cross-linker ratios. The present work provides a practical methodology for evaluation and optimization of cross-linking strategies in polymer nanoparticle synthesis.
{"title":"Quantitative Evaluation of Cross-Linking Efficiency in Worm-like Nanoparticles Prepared via RAFT-Mediated Aqueous Emulsion PISA","authors":"Zixiao Liu, Fumi Ishizuka, Masayoshi Ido, Shunsuke Chatani, Per B. Zetterlund","doi":"10.1021/acs.macromol.5c03609","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03609","url":null,"abstract":"Covalent cross-linking has been widely employed to stabilize the morphology of worm-like polymer nanoparticles. However, conventional qualitative evaluations of cross-linking efficiency are insufficient for further optimization of cross-linking conditions. In this study, a novel solvent-exchange method has been developed to quantitatively estimate the cross-linking efficiency of worm-like nanoparticles synthesized via reversible addition–fragmentation chain transfer (RAFT)-mediated aqueous emulsion polymerization-induced self-assembly (PISA). By integrating quantitative and qualitative analyses, the cross-linking efficiency and morphological stability of both in situ and post-cross-linking approaches were systematically compared. The results showed that in situ cross-linking consistently yielded high efficiency and better-preserved worm-like structures at lower cross-linker ratios. The present work provides a practical methodology for evaluation and optimization of cross-linking strategies in polymer nanoparticle synthesis.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122470","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}
Pub Date : 2026-02-05DOI: 10.1021/acs.macromol.5c02263
Antonio Baldanza, Cosimo Brondi, Giuseppe Mensitieri, Pellegrino Musto, Marianna Pannico, Andrea Correa, Antonio De Nicola, Giuseppe Milano, Giuseppe Scherillo
The objectives of this work are 2-fold. First, we aim to provide a comprehensive description of the poly(ether imide) (PEI)–methanol system, linking atomistic insights to macroscopic thermodynamic behavior, with explicit consideration of the hydrogen-bonding interactions governing the system. Second, by presenting this paradigmatic case, we intend to illustrate how a microscopic description validated through vibrational spectroscopy can be effectively exploited to establish a sound physical basis for developing a predictive macroscopic thermodynamic model. Sorption thermodynamics of methanol vapor in poly(ether imide) (Ultem 1000) has been thoroughly investigated through a synergistic multiscale theoretical approach combined with in situ FTIR spectroscopy. Density Functional Theory (DFT) calculations provided estimates of methanol–methanol and PEI–methanol interaction energies as well as simulated FTIR spectra. These results showed good agreement with the experimental outcomes of in situ FTIR spectroscopy, both in terms of the collected spectra and of the energies of hydrogen bond formation within the methanol-PEI system exposed to methanol vapor at different pressures and at a temperature of 30 °C. The analysis of the experimental FTIR spectra of the polymer phase enabled a quantitative assessment of the concentration of methanol molecules hydrogen-bonded to imide groups of the polymer and of methanol molecules hydrogen-bonded to the former methanol molecule (the so-called “first-shell” and ‘second-shell’ methanol molecules, respectively). The presence of these two “populations” was quantitatively confirmed by Molecular Dynamics (MD) simulations. The detailed picture emerging from these complementary approaches was then exploited to refine the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) equation of state model, which was used to interpret the sorption thermodynamics of methanol in PEI. In particular, the PC-SAFT model was extended, adopting the Dry Glass Reference Perturbation Theory (DGRPT), to address the nonequilibrium nature of the glassy PEI-methanol system and to account for the swelling associated with methanol sorption. Predictions made using the DGRPT-PC-SAFT theoretical framework showed a very good agreement with both the FTIR experimental results and the MD simulations, successfully predicting the concentrations of first- and second-shell methanol molecules in PEI as a function of methanol activity in the vapor phase.
{"title":"Methanol Sorption in Poly(ether imide): Molecular Insights from a Multiscale Study Combining Experiments, Theory, and Simulations","authors":"Antonio Baldanza, Cosimo Brondi, Giuseppe Mensitieri, Pellegrino Musto, Marianna Pannico, Andrea Correa, Antonio De Nicola, Giuseppe Milano, Giuseppe Scherillo","doi":"10.1021/acs.macromol.5c02263","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02263","url":null,"abstract":"The objectives of this work are 2-fold. First, we aim to provide a comprehensive description of the poly(ether imide) (PEI)–methanol system, linking atomistic insights to macroscopic thermodynamic behavior, with explicit consideration of the hydrogen-bonding interactions governing the system. Second, by presenting this paradigmatic case, we intend to illustrate how a microscopic description validated through vibrational spectroscopy can be effectively exploited to establish a sound physical basis for developing a predictive macroscopic thermodynamic model. Sorption thermodynamics of methanol vapor in poly(ether imide) (<i>Ultem</i> 1000) has been thoroughly investigated through a synergistic multiscale theoretical approach combined with in situ FTIR spectroscopy. Density Functional Theory (DFT) calculations provided estimates of methanol–methanol and PEI–methanol interaction energies as well as simulated FTIR spectra. These results showed good agreement with the experimental outcomes of in situ FTIR spectroscopy, both in terms of the collected spectra and of the energies of hydrogen bond formation within the methanol-PEI system exposed to methanol vapor at different pressures and at a temperature of 30 °C. The analysis of the experimental FTIR spectra of the polymer phase enabled a quantitative assessment of the concentration of methanol molecules hydrogen-bonded to imide groups of the polymer and of methanol molecules hydrogen-bonded to the former methanol molecule (the so-called “first-shell” and ‘second-shell’ methanol molecules, respectively). The presence of these two “populations” was quantitatively confirmed by Molecular Dynamics (MD) simulations. The detailed picture emerging from these complementary approaches was then exploited to refine the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) equation of state model, which was used to interpret the sorption thermodynamics of methanol in PEI. In particular, the PC-SAFT model was extended, adopting the Dry Glass Reference Perturbation Theory (DGRPT), to address the nonequilibrium nature of the glassy PEI-methanol system and to account for the swelling associated with methanol sorption. Predictions made using the DGRPT-PC-SAFT theoretical framework showed a very good agreement with both the FTIR experimental results and the MD simulations, successfully predicting the concentrations of first- and second-shell methanol molecules in PEI as a function of methanol activity in the vapor phase.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122515","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}
Pub Date : 2026-02-04DOI: 10.1021/acs.macromol.5c03180
Somesh Kurahatti,Mariano E. Brito,David Beyer,Christian Holm
Elastic modulus, G, and equilibrium swelling ratio, QV, are two properties of hydrogels, which are linked by the scaling law G ∼ QVβ, where β = −1 and −9/4 in the low- and high-salt limits, respectively. Tuning them independently would enable the optimization of the material design for a wide variety of distinct applications. In this work, we investigate several possibilities to achieve this using various network heterogeneities. We employ implicit solvent coarse-grained molecular dynamics simulations to explore mechanical, structural, and thermodynamic properties of hydrogels with varying topologies in comparison to a regular reference gel. We explore regular gels with tetrafunctional cross-linkers arranged in a diamond-lattice fashion, which we take as a reference gel, together with bottlebrush gels, gels with dangling ends, and gels coexisting with floating chains. We observe that incorporating dangling ends changes the swelling ratio and bulk modulus following the relation obtained from the regular reference gel, whereas the bottlebrush and floating-chain gels show stronger deviations. Specifically, floating-chain gels resulted in higher moduli and higher swelling ratios, while bottlebrush gels resulted in lower moduli and lower swelling ratios than the regular counterparts. Concomitantly, a clear change in salt partitioning was observed for various hydrogel architectures. Our results show new ways to optimize the elastic modulus of gels with respect to their swelling behavior and allow for the optimization and on-demand design of hydrogels.
{"title":"Effect of Different Network Topologies on Swelling and Mechanical Properties of Polyelectrolyte Hydrogels","authors":"Somesh Kurahatti,Mariano E. Brito,David Beyer,Christian Holm","doi":"10.1021/acs.macromol.5c03180","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03180","url":null,"abstract":"Elastic modulus, G, and equilibrium swelling ratio, QV, are two properties of hydrogels, which are linked by the scaling law G ∼ QVβ, where β = −1 and −9/4 in the low- and high-salt limits, respectively. Tuning them independently would enable the optimization of the material design for a wide variety of distinct applications. In this work, we investigate several possibilities to achieve this using various network heterogeneities. We employ implicit solvent coarse-grained molecular dynamics simulations to explore mechanical, structural, and thermodynamic properties of hydrogels with varying topologies in comparison to a regular reference gel. We explore regular gels with tetrafunctional cross-linkers arranged in a diamond-lattice fashion, which we take as a reference gel, together with bottlebrush gels, gels with dangling ends, and gels coexisting with floating chains. We observe that incorporating dangling ends changes the swelling ratio and bulk modulus following the relation obtained from the regular reference gel, whereas the bottlebrush and floating-chain gels show stronger deviations. Specifically, floating-chain gels resulted in higher moduli and higher swelling ratios, while bottlebrush gels resulted in lower moduli and lower swelling ratios than the regular counterparts. Concomitantly, a clear change in salt partitioning was observed for various hydrogel architectures. Our results show new ways to optimize the elastic modulus of gels with respect to their swelling behavior and allow for the optimization and on-demand design of hydrogels.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"1 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111073","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}
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