Pub Date : 2026-02-04DOI: 10.1021/acs.macromol.5c02877
Jelle De Ceulaer,Ruth Cardinaels,Peter Van Puyvelde
Dynamic covalent networks (DCNs) combine thermoset-like performance with thermoplastic reprocessability through dynamic covalent chemistry. Their properties are dictated by their microstructure, which is determined by the interplay between reversible covalent reactions and fixation mechanisms, such as crystallization. Here, the interplay of crystallization and cross-linking in poly(ε-caprolactone)-based DCNs is investigated by varying PCL precursor functionality from linear 2-functional to star-shaped 4- and 6-functional architectures. This design enables distinct cases ranging from linear chain extension to network formation occurring on similar time scales as crystallization. Nonisothermal and isothermal studies reveal that cross-linking slows down crystallization, lowers crystallization peak temperatures, and promotes secondary crystallization. Morphological analysis shows more irregular spherulites, while kinetic evaluation confirms adverse effects of cross-linking on both nucleation and crystal growth, except in short linear chains where nucleation is enhanced. In that case, molecular weight effects during cross-linking are likely to dominate the crystallization behavior. These results provide structural insight into tailoring crystallizable DCNs.
{"title":"Competing Crystallization and Cross-Linking Behavior in Multifunctional Poly(ε-Caprolactone)-Based Dynamic Covalent Networks","authors":"Jelle De Ceulaer,Ruth Cardinaels,Peter Van Puyvelde","doi":"10.1021/acs.macromol.5c02877","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02877","url":null,"abstract":"Dynamic covalent networks (DCNs) combine thermoset-like performance with thermoplastic reprocessability through dynamic covalent chemistry. Their properties are dictated by their microstructure, which is determined by the interplay between reversible covalent reactions and fixation mechanisms, such as crystallization. Here, the interplay of crystallization and cross-linking in poly(ε-caprolactone)-based DCNs is investigated by varying PCL precursor functionality from linear 2-functional to star-shaped 4- and 6-functional architectures. This design enables distinct cases ranging from linear chain extension to network formation occurring on similar time scales as crystallization. Nonisothermal and isothermal studies reveal that cross-linking slows down crystallization, lowers crystallization peak temperatures, and promotes secondary crystallization. Morphological analysis shows more irregular spherulites, while kinetic evaluation confirms adverse effects of cross-linking on both nucleation and crystal growth, except in short linear chains where nucleation is enhanced. In that case, molecular weight effects during cross-linking are likely to dominate the crystallization behavior. These results provide structural insight into tailoring crystallizable DCNs.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"24 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111074","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.5c02754
Mokun Chen, Marc C. A. Stuart, Kubra Kalayci, Vincent S. D. Voet, Rudy Folkersma, Katja Loos
Stimuli-responsive glycosylated nanoparticles hold great promise for mimicking complex biological glycans, yet current fabrication methods often lack versatility in tuning the morphology and responsiveness. Here, we report a solvent-selective self-assembly approach using multiresponsive glycosylated triblock tercopolymers designed with pH- and temperature-responsive segments. These polymers form well-defined nanoparticles, including spheres, cylinders, and worm-like aggregates, which can be modulated under external stimuli. Furthermore, we fabricated a diverse range of glycosylated nanoparticles by altering the sequence of the blocks within the terpolymers. Their well-defined morphologies were visualized via cryogenic transmission electron microscopy (cryo-TEM), and their size distributions were analyzed via dynamic light scattering (DLS). Our results demonstrate that integrating multiple stimuli-responsive elements in triblock terpolymers enables structural control of glycosylated nanoparticles. The morphological evolution of these nanoparticles corresponds to changes in the macromolecular configuration triggered by variations in the pH, temperature, and block sequence. This approach offers new opportunities for developing biomimetic materials for targeted delivery and glycan-based sensing.
{"title":"Architecting Well-Defined Glyco-Nanoparticles from pH- and Temperature-Responsive Glycosylated Triblock Terpolymers","authors":"Mokun Chen, Marc C. A. Stuart, Kubra Kalayci, Vincent S. D. Voet, Rudy Folkersma, Katja Loos","doi":"10.1021/acs.macromol.5c02754","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02754","url":null,"abstract":"Stimuli-responsive glycosylated nanoparticles hold great promise for mimicking complex biological glycans, yet current fabrication methods often lack versatility in tuning the morphology and responsiveness. Here, we report a solvent-selective self-assembly approach using multiresponsive glycosylated triblock tercopolymers designed with pH- and temperature-responsive segments. These polymers form well-defined nanoparticles, including spheres, cylinders, and worm-like aggregates, which can be modulated under external stimuli. Furthermore, we fabricated a diverse range of glycosylated nanoparticles by altering the sequence of the blocks within the terpolymers. Their well-defined morphologies were visualized via cryogenic transmission electron microscopy (cryo-TEM), and their size distributions were analyzed via dynamic light scattering (DLS). Our results demonstrate that integrating multiple stimuli-responsive elements in triblock terpolymers enables structural control of glycosylated nanoparticles. The morphological evolution of these nanoparticles corresponds to changes in the macromolecular configuration triggered by variations in the pH, temperature, and block sequence. This approach offers new opportunities for developing biomimetic materials for targeted delivery and glycan-based sensing.","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":"146122087","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 continuous network with short-range aggregation structures in an amorphous matrix is widely recognized for achieving optimal electronic and mechanical performance of conjugated polymer films. The size and structural order of these aggregates critically determine the ability to accommodate and dissipate strain without disrupting the charge transport pathways. Here, we systematically investigated the effect of polymer chain dynamics on the evolution of aggregation structure for the conjugated polymer poly(indacenodithiophene-co-benzothiadiazole) (IDTBT) by controlling the annealing temperature (Ta). In the as-cast film, the polymer backbone remains kinetically trapped in a distorted conformation, leading to a loosely packed and disordered morphology. Thermal annealing at 100 °C, between the backbone glass transition temperatures (Tg) and the disaggregation temperature (Tdisagg), activates the segment motion, enabling reorganization into small, short-range ordered aggregates with an extended conformation. When annealed at 260 °C (Ta > Tdisagg), full chain mobility permits assembly into larger, more ordered aggregates with dense molecular packing. Consequently, the charge mobility increases from 0.92 cm2 V–1 s–1 in the as-cast film to 3.14 cm2 V–1 s–1 after annealing at 260 °C. Under strain, the film annealed at 100 °C retains its short-range aggregates, which facilitates efficient stress dissipation through interlayer slip and preserves charge mobility. In contrast, the film annealed at 260 °C exhibits premature fracture of the large ordered aggregates accompanied by restricted chain alignment. As a result, the film annealed at 100 °C maintains a charge mobility of 0.86 cm2 V–1 s–1 under 100% strain, whereas the 260 °C-annealed film exhibits a substantially lower mobility of 0.14 cm2 V–1 s–1. These results underscore the critical role of short-range aggregation structures in achieving high-performance stretchable conjugated polymer films.
{"title":"The Short-Range Ordered Aggregation Structures Obtained by Controlling the Chain Segment Movement for Stretchable IDTBT Films","authors":"Junhang Li,Zicheng Ding,Zehao Wang,Yiting Liu,Tianya Jin,Xueting Yi,Rui Chen,Zhongxiang Peng,Rui Zhang,Yanchun Han","doi":"10.1021/acs.macromol.5c03533","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03533","url":null,"abstract":"A continuous network with short-range aggregation structures in an amorphous matrix is widely recognized for achieving optimal electronic and mechanical performance of conjugated polymer films. The size and structural order of these aggregates critically determine the ability to accommodate and dissipate strain without disrupting the charge transport pathways. Here, we systematically investigated the effect of polymer chain dynamics on the evolution of aggregation structure for the conjugated polymer poly(indacenodithiophene-co-benzothiadiazole) (IDTBT) by controlling the annealing temperature (Ta). In the as-cast film, the polymer backbone remains kinetically trapped in a distorted conformation, leading to a loosely packed and disordered morphology. Thermal annealing at 100 °C, between the backbone glass transition temperatures (Tg) and the disaggregation temperature (Tdisagg), activates the segment motion, enabling reorganization into small, short-range ordered aggregates with an extended conformation. When annealed at 260 °C (Ta > Tdisagg), full chain mobility permits assembly into larger, more ordered aggregates with dense molecular packing. Consequently, the charge mobility increases from 0.92 cm2 V–1 s–1 in the as-cast film to 3.14 cm2 V–1 s–1 after annealing at 260 °C. Under strain, the film annealed at 100 °C retains its short-range aggregates, which facilitates efficient stress dissipation through interlayer slip and preserves charge mobility. In contrast, the film annealed at 260 °C exhibits premature fracture of the large ordered aggregates accompanied by restricted chain alignment. As a result, the film annealed at 100 °C maintains a charge mobility of 0.86 cm2 V–1 s–1 under 100% strain, whereas the 260 °C-annealed film exhibits a substantially lower mobility of 0.14 cm2 V–1 s–1. These results underscore the critical role of short-range aggregation structures in achieving high-performance stretchable conjugated polymer films.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"8 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111072","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.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}
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