Pub Date : 2026-02-04DOI: 10.1021/acs.macromol.5c02445
Chengwang Shi,Xiaodong Li,Hao Jiang,Xing Su,Xiaoxuan Wang,Xufeng Zhang,Meishuai Zou
Imine-functionalized epoxy resins have become a research hotspot due to their degradable and recyclable properties. However, the inherent thermodynamic instability of imine bonds poses a challenge in developing multifunctional novel epoxy resins that exhibit high strength and toughness, low-temperature resistance, and environmental stability. In this study, a molecular structure engineering strategy was employed to construct a dual-dynamic supramolecular acylhydrazone-functionalized epoxy network-EPCAN-5. Benefiting from the synergistic cross-linking effect between the reversible hydrogen-bonding network in the gradient-energy structure and the covalent cross-linking network with a rigid-flexible design, this material exhibits ultrahigh strength and toughness (tensile strength of 115 MPa, elongation at break of 12.3%, toughness of 11.01 MJ/m3). It maintains a tensile strength of 140 MPa with 6% elongation even at an extremely low temperature of −50 °C, and retains excellent mechanical stability and flexibility even when immersed in liquid nitrogen (−196 °C). Furthermore, it demonstrates outstanding resistance to water and weak acids, addressing the technical challenge of performance degradation in imine-based epoxy materials under service conditions. The gradient-energy hydrogen-bonding structure endows EPCAN-5 with excellent programmable heat-driven shape memory functionality; a designed hook structure can lift up to 5000 times its own weight and automatically release the load upon reaching the temperature threshold. Additionally, the material can be fully recovered via a catalyst-free closed-loop process, with the repolymerized material retaining 99% of the original mechanical properties. In summary, this work successfully constructed a covalent cross-linking system that integrates gradient hydrogen bonds, reversible covalent bonds, and a balanced combination of rigidity and flexibility. This system exhibits notable advantages, including high strength and toughness, low-temperature resistance, shape memory capability, and environmental stability.
{"title":"Highly Robust and Ultralow Temperature Resistant Epoxy Network Based on Acylhydrazone Bonds: Water Resistant, Shape Memory and Closed-Loop Recyclable","authors":"Chengwang Shi,Xiaodong Li,Hao Jiang,Xing Su,Xiaoxuan Wang,Xufeng Zhang,Meishuai Zou","doi":"10.1021/acs.macromol.5c02445","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02445","url":null,"abstract":"Imine-functionalized epoxy resins have become a research hotspot due to their degradable and recyclable properties. However, the inherent thermodynamic instability of imine bonds poses a challenge in developing multifunctional novel epoxy resins that exhibit high strength and toughness, low-temperature resistance, and environmental stability. In this study, a molecular structure engineering strategy was employed to construct a dual-dynamic supramolecular acylhydrazone-functionalized epoxy network-EPCAN-5. Benefiting from the synergistic cross-linking effect between the reversible hydrogen-bonding network in the gradient-energy structure and the covalent cross-linking network with a rigid-flexible design, this material exhibits ultrahigh strength and toughness (tensile strength of 115 MPa, elongation at break of 12.3%, toughness of 11.01 MJ/m3). It maintains a tensile strength of 140 MPa with 6% elongation even at an extremely low temperature of −50 °C, and retains excellent mechanical stability and flexibility even when immersed in liquid nitrogen (−196 °C). Furthermore, it demonstrates outstanding resistance to water and weak acids, addressing the technical challenge of performance degradation in imine-based epoxy materials under service conditions. The gradient-energy hydrogen-bonding structure endows EPCAN-5 with excellent programmable heat-driven shape memory functionality; a designed hook structure can lift up to 5000 times its own weight and automatically release the load upon reaching the temperature threshold. Additionally, the material can be fully recovered via a catalyst-free closed-loop process, with the repolymerized material retaining 99% of the original mechanical properties. In summary, this work successfully constructed a covalent cross-linking system that integrates gradient hydrogen bonds, reversible covalent bonds, and a balanced combination of rigidity and flexibility. This system exhibits notable advantages, including high strength and toughness, low-temperature resistance, shape memory capability, and environmental stability.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"19 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111075","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.5c03218
Hao Cai, Huan Gao, Zhe Ma, Li Pan, Yuesheng Li
Polypropylene-based elastomers (PP-Es) offer superior mechanical properties, heat resistance, and compatibility with PP matrices compared to polyethylene-based elastomers (PE-Es). This study developed high-performance PP-Es with low α-olefin consumption through catalyst selection and chain structure design. Employing a moderately stereo- and regioselective bis(phenolate-ether) hafnium catalyst, as opposed to a highly selective metallocene catalyst, afforded PP-Es with higher molecular weight, enhanced mechanical properties, and similar crystallinity at a reduced comonomer requirement. When used as tougheners for brittle iPP, PP-Es significantly enhance tensile performance, markedly increasing elongation at break, far exceeding commercial PE-E systems (e.g., Engage 7447 and 8842), while maintaining high strength and transparency. Added to incompatible HDPE/iPP blends (30/70 and 50/50), PP-Es effectively compatibilized the phases, significantly increasing elongation at break while largely retaining strength. Furthermore, the compatibilization behaviors of PP-Es and PE-Es were compared across different HDPE/iPP ratios, together with their tensile and impact properties, establishing a clear link between compatibilizer chain structure, phase composition, and performance enhancement.
{"title":"Designing Resource-Efficient Polypropylene-Based Elastomers via Moderately Selective Catalyst for Toughening and Compatibilization","authors":"Hao Cai, Huan Gao, Zhe Ma, Li Pan, Yuesheng Li","doi":"10.1021/acs.macromol.5c03218","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03218","url":null,"abstract":"Polypropylene-based elastomers (PP-Es) offer superior mechanical properties, heat resistance, and compatibility with PP matrices compared to polyethylene-based elastomers (PE-Es). This study developed high-performance PP-Es with low α-olefin consumption through catalyst selection and chain structure design. Employing a moderately stereo- and regioselective bis(phenolate-ether) hafnium catalyst, as opposed to a highly selective metallocene catalyst, afforded PP-Es with higher molecular weight, enhanced mechanical properties, and similar crystallinity at a reduced comonomer requirement. When used as tougheners for brittle <i>i</i>PP, PP-Es significantly enhance tensile performance, markedly increasing elongation at break, far exceeding commercial PE-E systems (e.g., Engage 7447 and 8842), while maintaining high strength and transparency. Added to incompatible HDPE/<i>i</i>PP blends (30/70 and 50/50), PP-Es effectively compatibilized the phases, significantly increasing elongation at break while largely retaining strength. Furthermore, the compatibilization behaviors of PP-Es and PE-Es were compared across different HDPE/<i>i</i>PP ratios, together with their tensile and impact properties, establishing a clear link between compatibilizer chain structure, phase composition, and performance enhancement.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"19 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116085","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.5c03531
Jens Van Hoorde,Quinten Thijssen,Nezha Badi,Filip E. Du Prez
Sequence-defined macromolecules provide uniform chain composition and precise control over monomer order, yet their implementation in materials science has been constrained by challenges in achieving their scalable synthesis. Here, we report the multigram-scale (i.e., 120 g) preparation of telechelic sequence-defined oligourethanes incorporating distinct hydrogen-bonding motifs and their subsequent cross-linking into structurally well-defined model networks. This scalable access to such uniform structures enables comprehensive structural, thermal, and mechanical characterization, including precise analysis of network integrity through network-disassembly spectrometry. This in-depth analysis revealed clear correlations between the molecular design of the cross-linker and bulk network properties, including swelling behavior, hydrophilicity, and Young’s modulus. Importantly, the scalability of these macromolecules also allowed integration with volumetric 3D printing as a representative high-volume fabrication method, demonstrating that molecular-level sequence control can be reliably translated into advanced manufacturing applications.
{"title":"Linking Molecular Sequence to Material Performance: Model Networks and Volumetric 3D Printing of Sequence-Defined Oligourethanes","authors":"Jens Van Hoorde,Quinten Thijssen,Nezha Badi,Filip E. Du Prez","doi":"10.1021/acs.macromol.5c03531","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03531","url":null,"abstract":"Sequence-defined macromolecules provide uniform chain composition and precise control over monomer order, yet their implementation in materials science has been constrained by challenges in achieving their scalable synthesis. Here, we report the multigram-scale (i.e., 120 g) preparation of telechelic sequence-defined oligourethanes incorporating distinct hydrogen-bonding motifs and their subsequent cross-linking into structurally well-defined model networks. This scalable access to such uniform structures enables comprehensive structural, thermal, and mechanical characterization, including precise analysis of network integrity through network-disassembly spectrometry. This in-depth analysis revealed clear correlations between the molecular design of the cross-linker and bulk network properties, including swelling behavior, hydrophilicity, and Young’s modulus. Importantly, the scalability of these macromolecules also allowed integration with volumetric 3D printing as a representative high-volume fabrication method, demonstrating that molecular-level sequence control can be reliably translated into advanced manufacturing applications.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"41 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111071","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}
Liquid-crystalline block copolymers (LC-BCPs) typically form structurally precise one-dimensional assemblies via nucleation–epitaxial growth, whereas constructing hierarchical structures generally relies on fusion–rearrangement processes. However, effectively balancing polymer chain mobility and LC order to direct such fusion–rearrangement pathways remains challenging, particularly when targeting multicomponent hierarchical heterostructures. Here, we synthesized a series of poly(cyclopropane-1,1-dicarboxylate)-based BCPs (PEG45-b-P(m)Choln) featuring asymmetric dicarboxylate pendent groups that enhance chain mobility while maintaining LC order. These BCPs self-assembled into bamboo-like hierarchical micelles through a fusion–rearrangement pathway characterized by perpendicular lamellar LC domains and multilayered surface structures. Upon coassembly with an amino acid-derived chiral amphiphile bearing a homologous mesogen, the micelles undergo a similar pathway, during which molecular chirality is transferred and amplified, ultimately evolving into well-defined superhelical fibers. This work highlights the cooperative roles of LC ordering and fusion–rearrangement and provides a versatile strategy for constructing hierarchical and biomimetic architectures from LC-BCPs.
{"title":"Balancing Chain Mobility and Liquid-Crystalline Order in Block Copolymers Enables Fusion–Rearrangement-Driven Hierarchical Assemblies","authors":"Juanjuan Gao, Yue Lu, Yangge Ren, Yujia Guo, Hao Huang, Lin Jia","doi":"10.1021/acs.macromol.5c02992","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02992","url":null,"abstract":"Liquid-crystalline block copolymers (LC-BCPs) typically form structurally precise one-dimensional assemblies via nucleation–epitaxial growth, whereas constructing hierarchical structures generally relies on fusion–rearrangement processes. However, effectively balancing polymer chain mobility and LC order to direct such fusion–rearrangement pathways remains challenging, particularly when targeting multicomponent hierarchical heterostructures. Here, we synthesized a series of poly(cyclopropane-1,1-dicarboxylate)-based BCPs (PEG<sub>45</sub>-<i>b</i>-P(<i>m</i>)Chol<sub><i>n</i></sub>) featuring asymmetric dicarboxylate pendent groups that enhance chain mobility while maintaining LC order. These BCPs self-assembled into bamboo-like hierarchical micelles through a fusion–rearrangement pathway characterized by perpendicular lamellar LC domains and multilayered surface structures. Upon coassembly with an amino acid-derived chiral amphiphile bearing a homologous mesogen, the micelles undergo a similar pathway, during which molecular chirality is transferred and amplified, ultimately evolving into well-defined superhelical fibers. This work highlights the cooperative roles of LC ordering and fusion–rearrangement and provides a versatile strategy for constructing hierarchical and biomimetic architectures from LC-BCPs.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"21 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111009","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}
A PBAT film is generally fabricated through blown film processing, during which the thermal-force fields strongly regulate the final performance. However, the underlying mechanism remains unclear because there is little quantitative analysis due to the high blowing speed. Here, a self-developed blown film system equipped with an infrared thermal camera is used to monitor the temperature, and both the blow-up ratio and the take-up ratio are used to regulate the magnitude of the force field. The results show that a dominant transverse force field promotes isotropic lamellar crystal formation, resulting in mechanical isotropy with excellent water barrier properties. Conversely, a stronger vertical force field enhances the molecular chain orientation, leading to mechanical anisotropy with enhanced strength. Additionally, the steep temperature gradients amplify the regulatory force fields. These findings may provide guidelines for optimizing processing parameters to achieve the targeted macroproperties of PBAT industrially.
{"title":"Revealing the Microstructural Evolution under the Blown Film Processing for PBAT Materials","authors":"Weiyouran Hong,Huan Li,Gang li,Zhenkun Wang,Guiying Yu,Yanshan Feng,Haoran Wang,Jiang Li,Shaoyun Guo,Chunhai Li","doi":"10.1021/acs.macromol.5c03152","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03152","url":null,"abstract":"A PBAT film is generally fabricated through blown film processing, during which the thermal-force fields strongly regulate the final performance. However, the underlying mechanism remains unclear because there is little quantitative analysis due to the high blowing speed. Here, a self-developed blown film system equipped with an infrared thermal camera is used to monitor the temperature, and both the blow-up ratio and the take-up ratio are used to regulate the magnitude of the force field. The results show that a dominant transverse force field promotes isotropic lamellar crystal formation, resulting in mechanical isotropy with excellent water barrier properties. Conversely, a stronger vertical force field enhances the molecular chain orientation, leading to mechanical anisotropy with enhanced strength. Additionally, the steep temperature gradients amplify the regulatory force fields. These findings may provide guidelines for optimizing processing parameters to achieve the targeted macroproperties of PBAT industrially.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"1 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111076","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 : 2026-02-03DOI: 10.1021/acs.macromol.5c03130
Jie Qiu, Yan Sui, Wei Wang, Xiang Liu, Yanan Zhang, Xian Kong, Tao Wen
In this study, phase separation of long-chain polyurethanes (LCPUs) induced by evaporation of mixed “nonsolvents” was investigated. The amphiphilic nature of LCPUs, consisting of alternating high-polar segments (urethane groups) and low-polar segments (alkyl chains), allows their dissolution in a mixture of high-polarity solvent and low-polarity solvent; both of which are nonsolvents of LCPUs when used individually. The sequential evaporation of two nonsolvents triggers phase separation of LCPU solutions, namely, “mixed 'nonsolvents' evaporation induced phase separation” (MNEIPS). The dependence of pore sizes and porosities of LCPU membranes on the length of alkyl chains, the initial polymer concentration, and the solvent compositions was investigated in detail. In addition, we demonstrated the application of LCPU membranes as separators in both lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). This work expands the scope of amphiphilic polymers and provides unique insights into the development of functional long-chain polycondensates.
{"title":"Mixed “Nonsolvents” Induced Phase Separation of Amphiphilic Long-Chain Polyurethanes","authors":"Jie Qiu, Yan Sui, Wei Wang, Xiang Liu, Yanan Zhang, Xian Kong, Tao Wen","doi":"10.1021/acs.macromol.5c03130","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03130","url":null,"abstract":"In this study, phase separation of long-chain polyurethanes (LCPUs) induced by evaporation of mixed “nonsolvents” was investigated. The amphiphilic nature of LCPUs, consisting of alternating high-polar segments (urethane groups) and low-polar segments (alkyl chains), allows their dissolution in a mixture of high-polarity solvent and low-polarity solvent; both of which are nonsolvents of LCPUs when used individually. The sequential evaporation of two nonsolvents triggers phase separation of LCPU solutions, namely, “mixed 'nonsolvents' evaporation induced phase separation” (MNEIPS). The dependence of pore sizes and porosities of LCPU membranes on the length of alkyl chains, the initial polymer concentration, and the solvent compositions was investigated in detail. In addition, we demonstrated the application of LCPU membranes as separators in both lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). This work expands the scope of amphiphilic polymers and provides unique insights into the development of functional long-chain polycondensates.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"17 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110992","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 : 2026-02-02DOI: 10.1021/acs.macromol.5c02807
Jingtao Wu, Baoli Wang
Disentangled ultrahigh-molecular-weight polyethylene (dis-UHMWPE) is of fundamental interest and practical importance due to its high crystallinity and facile processing. However, the synthesis of dis-UHMWPE has still been seriously restricted by few catalysts until now, and the molecular weight is limited. Herein, we report the synthesis of a series of half-sandwich titanium complexes and their catalytic performance toward ethylene polymerization activated by less amounts of alkyl aluminum. The catalyst structure (bulky steric hindrance and fluorine atoms on the ligand) and polymerization conditions play important roles in controlling for molecular weight and the disentangled state of polyethylene. The resultant polyethylene showed ultrahigh molecular weight ranging from 3.16 × 106 g·mol–1 to 7.15 × 106 g·mol–1 with a narrow polydispersity index (Mw/Mn < 2.6) and high linearity, and the disentangled state was studied by compression molding and differential scanning calorimetry (DSC) annealing experiments. The formation of active species was also proposed according to electron paramagnetic resonance (EPR) and in situ 1H NMR experiments.
{"title":"Preparation of Disentangled Ultrahigh-Molecular-Weight Polyethylene by Using Half-Sandwich Titanium Catalysts","authors":"Jingtao Wu, Baoli Wang","doi":"10.1021/acs.macromol.5c02807","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02807","url":null,"abstract":"Disentangled ultrahigh-molecular-weight polyethylene (dis-UHMWPE) is of fundamental interest and practical importance due to its high crystallinity and facile processing. However, the synthesis of dis-UHMWPE has still been seriously restricted by few catalysts until now, and the molecular weight is limited. Herein, we report the synthesis of a series of half-sandwich titanium complexes and their catalytic performance toward ethylene polymerization activated by less amounts of alkyl aluminum. The catalyst structure (bulky steric hindrance and fluorine atoms on the ligand) and polymerization conditions play important roles in controlling for molecular weight and the disentangled state of polyethylene. The resultant polyethylene showed ultrahigh molecular weight ranging from 3.16 × 10<sup>6</sup> g·mol<sup>–1</sup> to 7.15 × 10<sup>6</sup> g·mol<sup>–1</sup> with a narrow polydispersity index (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> < 2.6) and high linearity, and the disentangled state was studied by compression molding and differential scanning calorimetry (DSC) annealing experiments. The formation of active species was also proposed according to electron paramagnetic resonance (EPR) and in situ <sup>1</sup>H NMR experiments.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"80 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098000","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}
In the original version of this article on p. 377, errors appeared in the authors’ affiliation information. The corrected affiliation is provided below to accurately reflect the authors’ institutional associations. This correction does not affect the scientific content or the conclusions of this work. Mizuki Kishimoto – Mitsui Chemicals Inc., 580–32 Nagaura, Sodegaura, Chiba 299–0265, Japan Kiminori Uchida – Mitsui Chemicals Inc., 580–32 Nagaura, Sodegaura, Chiba 299–0265, Japan This article has not yet been cited by other publications.
{"title":"Correction to “STXM Studies on the Changes in the Spatial Distribution of Density and Chain Orientation of LLDPE with Strain”","authors":"Masato Arakawa, Mizuki Kishimoto, Kiminori Uchida, Yohei Nakanishi, Mikihito Takenaka","doi":"10.1021/acs.macromol.6c00224","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c00224","url":null,"abstract":"In the original version of this article on p. 377, errors appeared in the authors’ affiliation information. The corrected affiliation is provided below to accurately reflect the authors’ institutional associations. This correction does not affect the scientific content or the conclusions of this work. Mizuki Kishimoto – Mitsui Chemicals Inc., 580–32 Nagaura, Sodegaura, Chiba 299–0265, Japan Kiminori Uchida – Mitsui Chemicals Inc., 580–32 Nagaura, Sodegaura, Chiba 299–0265, Japan This article has not yet been cited by other publications.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"41 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110994","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 : 2026-02-02DOI: 10.1021/acs.macromol.5c02859
Zhou-Liang Wu, Hao-Jia Guo, Ling-Rui Li, Shuangquan Liao, Ming-Chao Luo
The recyclability of vulcanized rubbers remains a critical challenge due to the irreversibility of conventional covalent cross-linking networks. Here, we report a hybrid cross-linking point strategy that integrates conventional vulcanization bonds with reversible β-hydroxy ester bonds within a single cross-linking point, enabling the simultaneous achievement of mechanical robustness, reprocessability, and creep resistance, and overcoming the trade-offs typically observed in conventional hybrid networks. Copolymers of sulfur and vinylacetic acid (CSVA), synthesized via inverse vulcanization, are employed to cross-link epoxidized natural rubber (ENR). In this system, CSVA functions as a dual cross-linker: sulfur units form vulcanization networks, while carboxyl groups react with epoxidation groups of ENR to generate dynamic β-hydroxy ester bonds. These hybrid cross-linking points ensure dimensional stability at service temperatures through permanent bonds, while facilitating network flow at elevated temperatures via dynamic ester bonds. Notably, increasing the CSVA content leads to simultaneous improvements in the mechanical performance, reprocessability, and creep resistance. Rheological results show thermally activated rearrangements of the networks. This study demonstrates that hybrid cross-linking points offer a generalizable design principle for creating vulcanized rubbers that are both mechanically robust and malleable, providing a viable pathway toward sustainable elastomer development.
{"title":"A Hybrid Cross-Linking Point Strategy To Reconcile Reprocessability and Creep Resistance in Mechanically Robust Rubbers","authors":"Zhou-Liang Wu, Hao-Jia Guo, Ling-Rui Li, Shuangquan Liao, Ming-Chao Luo","doi":"10.1021/acs.macromol.5c02859","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02859","url":null,"abstract":"The recyclability of vulcanized rubbers remains a critical challenge due to the irreversibility of conventional covalent cross-linking networks. Here, we report a hybrid cross-linking point strategy that integrates conventional vulcanization bonds with reversible β-hydroxy ester bonds within a single cross-linking point, enabling the simultaneous achievement of mechanical robustness, reprocessability, and creep resistance, and overcoming the trade-offs typically observed in conventional hybrid networks. Copolymers of sulfur and vinylacetic acid (CSVA), synthesized via inverse vulcanization, are employed to cross-link epoxidized natural rubber (ENR). In this system, CSVA functions as a dual cross-linker: sulfur units form vulcanization networks, while carboxyl groups react with epoxidation groups of ENR to generate dynamic β-hydroxy ester bonds. These hybrid cross-linking points ensure dimensional stability at service temperatures through permanent bonds, while facilitating network flow at elevated temperatures via dynamic ester bonds. Notably, increasing the CSVA content leads to simultaneous improvements in the mechanical performance, reprocessability, and creep resistance. Rheological results show thermally activated rearrangements of the networks. This study demonstrates that hybrid cross-linking points offer a generalizable design principle for creating vulcanized rubbers that are both mechanically robust and malleable, providing a viable pathway toward sustainable elastomer development.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"23 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098001","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 : 2026-02-02DOI: 10.1021/acs.macromol.5c02303
Hongxing Lin, Jie Jiang, Taoheng Zhang, Xiaodi Cui, Chenyang Li, Jinjin Li, Ling Zhao, Zhenhao Xi
Polymer thermal properties, including glass transition (Tg), melting (Tm), decomposition (Td), and crystallization (Tc) temperatures, alongside the softening point (SP), are pivotal for material design yet challenging to determine efficiently via laborious experiments or computationally intensive simulations. To leverage the complementary strengths of diverse molecular representations, this work introduces a deep learning framework featuring a gated fusion mechanism that integrates molecular graph representations and hybrid fingerprint descriptors. Evaluation on five thermal properties demonstrates that the proposed model shows improved performance over traditional benchmarks in single-task learning. Ablation studies and gating mechanism analysis reveal that the model adaptively prioritizes graph or fingerprint features, enabling effective multimodal fusion. Furthermore, a multitask learning strategy exploits latent correlations to reduce prediction errors for properties with limited data, offering an efficient and unified framework. This dual approach provides a competitive tool for accelerating data-driven material discovery.
{"title":"Adaptive Fusion of Graph Neural Networks and Fingerprints via Gating for Multitask Prediction of Polymer Thermal Properties","authors":"Hongxing Lin, Jie Jiang, Taoheng Zhang, Xiaodi Cui, Chenyang Li, Jinjin Li, Ling Zhao, Zhenhao Xi","doi":"10.1021/acs.macromol.5c02303","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02303","url":null,"abstract":"Polymer thermal properties, including glass transition (<i>T</i><sub>g</sub>), melting (<i>T</i><sub>m</sub>), decomposition (<i>T</i><sub>d</sub>), and crystallization (<i>T</i><sub>c</sub>) temperatures, alongside the softening point (SP), are pivotal for material design yet challenging to determine efficiently via laborious experiments or computationally intensive simulations. To leverage the complementary strengths of diverse molecular representations, this work introduces a deep learning framework featuring a gated fusion mechanism that integrates molecular graph representations and hybrid fingerprint descriptors. Evaluation on five thermal properties demonstrates that the proposed model shows improved performance over traditional benchmarks in single-task learning. Ablation studies and gating mechanism analysis reveal that the model adaptively prioritizes graph or fingerprint features, enabling effective multimodal fusion. Furthermore, a multitask learning strategy exploits latent correlations to reduce prediction errors for properties with limited data, offering an efficient and unified framework. This dual approach provides a competitive tool for accelerating data-driven material discovery.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"275 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097999","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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