Macromolecules最新文献_第4页

Azide-Capped Poly(alkoxycarbonylmethylene)s for Click Chemistry: Their Syntheses by 2-Bromoethanol-Mediated Chain Transfer Polymerization of Diazoacetate Followed by Azidation 2-溴乙醇介导的重氮乙酸酯链转移聚合-叠氮化反应合成叠氮化包覆的聚烷氧羰基亚甲基

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-16 DOI: 10.1021/acs.macromol.6c01954

Hiroaki Shimomoto,Momoe Kawata,Yusuke Kuzukawa,Rika Okawaki,Kaori Miyahara,Tomomichi Itoh,Eiji Ihara

引用次数: 0

Hierarchical Ion-Conducting Materials Based on Polymer-Aligned Nanoparticles within Poly(vinyl benzyl methoxy poly(ethylene oxide) ether)- block -polystyrene Diblock Copolymer 基于聚（乙烯基苄基甲氧基聚（环氧乙烷）醚）-嵌段-聚苯乙烯二嵌段共聚物内聚合物取向纳米颗粒的分级离子导电材料

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-16 DOI: 10.1021/acs.macromol.6c01855

Leire Unanue,Monika Król,Gabriele Lingua,Jorge L. Olmedo-Martínez,Alejandro Herranz Berzosa,Sven Schneider,Agnieszka Tercjak,Janne Ruokolainen,Patrick Théato,Alejandro J. Müller,David Mecerreyes

{"title":"Hierarchical Ion-Conducting Materials Based on Polymer-Aligned Nanoparticles within Poly(vinyl benzyl methoxy poly(ethylene oxide) ether)-\u0000 block\u0000 -polystyrene Diblock Copolymer","authors":"Leire Unanue,Monika Król,Gabriele Lingua,Jorge L. Olmedo-Martínez,Alejandro Herranz Berzosa,Sven Schneider,Agnieszka Tercjak,Janne Ruokolainen,Patrick Théato,Alejandro J. Müller,David Mecerreyes","doi":"10.1021/acs.macromol.6c01855","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01855","url":null,"abstract":"Abstract Solid polymer electrolytes based on poly(ethylene oxide) (PEO) are promising alternatives to liquid electrolytes for safer lithium-ion batteries. Here, we report hierarchical solid polymer electrolytes obtained by selectively incorporating lithium sulfonamide-functionalized polymer nanoparticles (LiNPs) into a microphase-separated poly(vinyl benzyl methoxy poly(ethylene oxide) ether)-block-polystyrene block copolymer. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and small-angle X-ray scattering (SAXS) demonstrate that the phase-segregated lamellar morphology of the block copolymer is preserved upon nanoparticle incorporation. Notably, the LiNPs preferentially localize within the poly(ethylene glycol)-rich lamellae, generating hierarchical structures with ordering across multiple length scales arising from block copolymer self-assembly, selective nanoparticle organization, and poly(ethylene glycol) crystallization. Differential scanning calorimetry (DSC) reveals that the crystallinity of the poly(ethylene glycol) phase depends strongly on nanoparticle loading and plasticizer content. These hierarchical electrolytes exhibit high ionic conductivity, which is further enhanced by the addition of sulfolane as a plasticizer. These results elucidate the interplay between hierarchical morphology, phase crystallinity, and ion transport in block copolymer-based solid electrolytes, providing design guidelines for mechanically robust solid electrolytes with enhanced transport performance.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"1 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209822","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}

引用次数: 0

Red-Light-Activated Dual Photocatalytic ATRP of Methacrylates and Acrylates Enabled by Copper Phthalocyanines 酞菁铜催化甲基丙烯酸酯和丙烯酸酯的红光活化双光催化ATRP

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-16 DOI: 10.1021/acs.macromol.6c01816

Edina Rusen,Cristina Stavarache,Aurel Diacon,Alexandra Mocanu,Gabriela Toader,Oana Brincoveanu,Ana-Mihaela Gavrila,Livia Alexandra Dinu

{"title":"Red-Light-Activated Dual Photocatalytic ATRP of Methacrylates and Acrylates Enabled by Copper Phthalocyanines","authors":"Edina Rusen,Cristina Stavarache,Aurel Diacon,Alexandra Mocanu,Gabriela Toader,Oana Brincoveanu,Ana-Mihaela Gavrila,Livia Alexandra Dinu","doi":"10.1021/acs.macromol.6c01816","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01816","url":null,"abstract":"Abstract Copper phthalocyanines (Pc) represent a promising yet underexplored class of low-cost and photostable dyes for visible-light-mediated polymerizations. In this study, we demonstrate that copper phthalocyanine (CuPc) and its derivatives efficiently mediate dual photocatalyst/copper atom transfer radical polymerization (PC/Cu-ATRP) of acrylates and methacrylates under red-light irradiation (λ = 628 nm). Using methyl acrylate (MA) as a model monomer, CuPc and its chlorinated derivative (CuPc-Cl) enable controlled polymerization in DMSO at ambient temperature, whereas the aminated analogue (CuPc-NH2) exhibits substantially lower activity. Kinetic analysis reveals apparent first-order behavior with respect to the monomer, with higher polymerization rates observed for CuPc compared to CuPc-Cl, consistent with differences in solubility. The resulting polymers display predictable molar mass evolution, low dispersity (Đ &lt; 1.3), and good temporal control under intermittent irradiation. High chain-end fidelity is confirmed by successful chain extension, affording PMA-b-PMMA block copolymers. Molecular weight can be readily tuned by varying the monomer-to-initiator ratio. As a practical demonstration, CuPc was applied in the suspension polymerization of methyl methacrylate (MMA), yielding polymer particles (3–20 μm) incorporating the dye, as confirmed by optical microscopy and scanning electron microscopy (SEM). These findings establish copper phthalocyanines as efficient and accessible photocatalysts for red-light-driven controlled radical polymerization.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"37 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209817","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}

引用次数: 0

One-Pot Barbier Polymerization-Induced Emission toward Stimuli-Responsive Luminescent Borinic Acid Polymers with Aggregation-Induced Emission-Type Clusteroluminescence 具有聚集致发射型团簇发光的刺激响应发光硼酸聚合物的一锅Barbier聚合诱导发射

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-16 DOI: 10.1021/acs.macromol.6c02005

Wen-Hui Liu,Yan-Shu Liu,Dong-Ming Liu,Zhen Lv,Qiu-Xia Xie,Xiao-Li Sun,Wen-Ming Wan

{"title":"One-Pot Barbier Polymerization-Induced Emission toward Stimuli-Responsive Luminescent Borinic Acid Polymers with Aggregation-Induced Emission-Type Clusteroluminescence","authors":"Wen-Hui Liu,Yan-Shu Liu,Dong-Ming Liu,Zhen Lv,Qiu-Xia Xie,Xiao-Li Sun,Wen-Ming Wan","doi":"10.1021/acs.macromol.6c02005","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c02005","url":null,"abstract":"Abstract A stimuli-responsive luminescent polymer is a promising smart material, which, however, suffers from multiple synthetic procedures involving the general preparation of a stimuli-responsive moiety, a luminescent moiety, and a polymer chain. Here, a one-pot polymerization-induced emission strategy is demonstrated for the synthesis of a stimuli-responsive luminescent polymer. Through Barbier hyperbranching polymerization of 4,4’-dichlorobenzophenone in the presence of trimethyl borate in one pot, a borinic acid moiety is successfully incorporated into the polymer chain through carbon–boron bond formation. This modification endows the polymer with both stimuli-responsive and luminescent functionalities simultaneously, resulting in the preparation of a stimuli-responsive luminescent polymer in one pot. In comparison with borinic acid polymers with an aggregation-caused quenching effect reported in the literature, borinic acid-containing hyperbranched polytriphenylmethanol (HPTPM-BA) exhibits intriguing aggregation-induced emission-type clusteroluminescence. Attributed to the borinic acid moiety, further stimuli-responsive luminescent behavior of HPTPM-BA is carried out for the luminescent detection of 8-hydroxyquinoline (HQ) and fluoride ions. Due to the strong dative N-&gt;B bond, the HPTPM-BA-HQ complex is prepared by complexation of HPTPM-BA with HQ, which exhibits interesting dual-state emission (luminescent both in solution and in the solid state) and distinct solvent-polarity-dependent luminescence, as well as polarity-sensitive luminescence in different polymer matrices. These results therefore confirm that the borinic acid moiety is versatile in stimuli-responsive luminescent polymers and opens a new avenue for the molecular design of a stimuli-responsive clusteroluminescent polymer in one pot.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"11 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209820","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}

引用次数: 0

Influence of Solvents on Acrylate-Methacrylate Copolymerization Chain Growth Kinetics: From Bulk to Dilute Aqueous Solution 溶剂对丙烯酸酯-甲基丙烯酸酯共聚链生长动力学的影响：从散装水溶液到稀水溶液

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-16 DOI: 10.1021/acs.macromol.6c02258

Fatemeh Salarhosseini,Noushin Rajabalinia,Ankita Meena,Miroslav Janata,Vladimír Raus,Igor Lacík,Robin A. Hutchinson

{"title":"Influence of Solvents on Acrylate-Methacrylate Copolymerization Chain Growth Kinetics: From Bulk to Dilute Aqueous Solution","authors":"Fatemeh Salarhosseini,Noushin Rajabalinia,Ankita Meena,Miroslav Janata,Vladimír Raus,Igor Lacík,Robin A. Hutchinson","doi":"10.1021/acs.macromol.6c02258","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c02258","url":null,"abstract":"Abstract The PLP–SEC technique, i.e., pulsed-laser polymerization coupled with size-exclusion chromatographic analysis of the resulting copolymer molar mass distributions, is used to investigate the effects of solvent polarity (ethanol/water mixtures varying from pure ethanol to pure water) and monomer concentrations (1 wt % to bulk) on composition-averaged propagation rate coefficients (kpcop) at 60 °C for methyl acrylate (MA) copolymerized in solution with di(ethylene glycol) methyl ether methacrylate (DEGMEMA), methacrylic acid (MAA) and methyl methacrylate (MMA), as well as for acrylic acid (AA) copolymerized with DEGMEMA. The kpcop values increase with increasing water content in the alcohol-water solvent mixtures, becoming more than an order of magnitude higher in dilute aqueous solution than in bulk across the full range of comonomer composition. Values for all four systems converge as the solvent environment shifts from bulk (i.e., as in emulsion polymerization particles) to aqueous, despite significant differences in monomer polarity and aqueous solubility between AA vs MA and MAA vs DEGMEMA vs MMA. These profound differences in chain-growth kinetics in bulk and aqueous solution should be accounted for when modeling emulsion copolymerization kinetics.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"51 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209821","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}

引用次数: 0

Design and Performance of Salami-Structured Polymer Alloys by Reactive Blending: Toward Light-Weight, Superior-Toughness, and High-Strength Materials 反应共混的萨拉米结构聚合物合金的设计和性能：向轻质、高韧性和高强度材料的方向发展

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-16 DOI: 10.1021/acs.macromol.6c01642

Hengti Wang,Xiao Wang,Yan Xia,Yao Zhang,Zhihui Li,Xin Yang,Yongjin Li

{"title":"Design and Performance of Salami-Structured Polymer Alloys by Reactive Blending: Toward Light-Weight, Superior-Toughness, and High-Strength Materials","authors":"Hengti Wang,Xiao Wang,Yan Xia,Yao Zhang,Zhihui Li,Xin Yang,Yongjin Li","doi":"10.1021/acs.macromol.6c01642","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01642","url":null,"abstract":"Abstract Design of polymer alloys that combine lightweight, high-strength, and superior toughness has been a long-standing motivation toward emerging technologies while still facing ongoing challenges. Inspired by the unique salami microstructure in commercial HIPS, here, we present a feasible strategy to construct salami morphology by exploiting the disparities in melting points (Tm) of polymers using conventional reactive processing method. Taking maleic anhydride-grafted poly(styrene-ethylene/butyl diene-styrene) (SEBS-g-MAH) toughened polypropylene (PP) system as an example, we attempt to use polyamide 6 (PA6), with its higher Tm (220 °C), as the rigid multicores within soft SEBS-shells by processing at an intermediate temperature between the Tm of matrix and subinclusions. Specifically, the premade SEBS-g-PA6 via reactive blending was incorporated into PP via melt compounding at 190 °C. Distinct from the traditional procedure, PA6 grafts exhibited solid-like behaviors during blending, effectively “locking” the migrations of PA6 segments to achieve multiple cores within the elastomeric particles. Through the introduction of subinclusions, we demonstrate a synergistic improvement of toughness (51.4 kJ/m2), stiffness (0.86 GPa), and desirable strength (33.6 MPa) while maintaining lightweight (low density of 0.92 g/cm3) for the salami structured alloys. This work resolves the challenge of the persistent performance trade-off of materials, providing a versatile and efficient paradigm for designing high-performance all-polymer alloys.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"236 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209818","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}

引用次数: 0

From α-Helices to Mesoscale Order: Structure–Packing Relationships in Polypeptide Block Copolymer Films 从α-螺旋到中尺度秩序：多肽嵌段共聚物薄膜的结构-填充关系

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-15 DOI: 10.1021/acs.macromol.6c01769

Yupei Ma,Sifan Ji,Alexia Araujo,Arnaud Hemmerle,Florian Le Goupil,Cédric Le Coz,Sébastien Lecommandoux,Colin Bonduelle,Guillaume Fleury

{"title":"From α-Helices to Mesoscale Order: Structure–Packing Relationships in Polypeptide Block Copolymer Films","authors":"Yupei Ma,Sifan Ji,Alexia Araujo,Arnaud Hemmerle,Florian Le Goupil,Cédric Le Coz,Sébastien Lecommandoux,Colin Bonduelle,Guillaume Fleury","doi":"10.1021/acs.macromol.6c01769","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01769","url":null,"abstract":"Abstract Polypeptide-based block copolymers are promising platforms for creating hierarchical nanostructures because their secondary structures can direct mesoscale self-assembly. This study investigates how polypeptide chain length and thermal annealing govern the hierarchical organization of poly(ethylene glycol)-b-poly(ε-benzyloxycarbonyl-l-lysine) (PEG-b-PZLL) thin films. Combined FTIR, AFM, AFM-IR, and synchrotron GIWAXS/GISAXS analyses reveal that PZLL segments predominantly form α-helical conformations that assemble into hexagonally packed domains with nearly constant lattice parameters across compositions. Increasing the PZLL degree of polymerization stabilizes the α-helical structure, promotes preferential in-plane orientation of cylindrical domains, and enables the formation of long-range ordered fibrillar morphologies, whereas short PZLL chains partially transform into β-sheet structures during film formation and after high-temperature annealing. These findings establish a direct relationship between the secondary structure, orientational ordering, and mesoscale morphology in self-assembled polypeptide block copolymer films.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"39 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209825","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}

引用次数: 0

Unexpected Two-Step Crystallization in Polyethylene with Isolated In-Chain Functional Groups 具有分离链内官能团的聚乙烯的意外两步结晶

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-15 DOI: 10.1021/acs.macromol.6c01886

Nontarin Roopsung,Yipu Lu,Kohei Takahashi,Kyoko Nozaki,Naoko Yoshie,Shintaro Nakagawa

{"title":"Unexpected Two-Step Crystallization in Polyethylene with Isolated In-Chain Functional Groups","authors":"Nontarin Roopsung,Yipu Lu,Kohei Takahashi,Kyoko Nozaki,Naoko Yoshie,Shintaro Nakagawa","doi":"10.1021/acs.macromol.6c01886","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01886","url":null,"abstract":"Abstract Polyethylene (PE) functionalization is a promising route to expand material performance while preserving the favorable properties of PE, such as mechanical robustness. However, the influence of isolated in-chain functional groups embedded in the PE backbone on the crystallization of PE remains poorly understood. Herein, we investigate the crystallization behavior of polyethylene bearing in-chain carbonyl (PE-CO) and amide (PE-CONH) groups that are embedded randomly in the PE backbone in a highly isolated manner. PE-CONH was obtained from PE-CO via main-chain editing, ensuring closely matched in-chain group distributions. Strikingly, PE-CO and PE-CONH showed a distinct two-step evolution of crystallinity during cooling at a constant rate. Such a two-step crystallization phenomenon was found in random copolymers for the first time. A comprehensive multiscale analysis revealed the molecular mechanism of the two-step crystallization: the in-chain groups were rejected from the PE crystalline phase in the first step but were later incorporated into the crystal lattice in the second step. Amide groups induced a more pronounced delay in the onset of the second step than carbonyl groups did. The discovery of the two-step crystallization offers a new opportunity for designing advanced PE-derived materials through precise main-chain modification.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"13 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209824","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}

引用次数: 0

Liquid-Crystalline Polymer Alloy Design through Interfacial Reactions Enabled by In Situ Polymerization and Reactive Blending 基于原位聚合和反应共混界面反应的液晶聚合物合金设计

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-15 DOI: 10.1021/acs.macromol.6c01698

Gosuke Washino,Kyoya Tachibana,Keiichi Kuboyama,Juri Asada,Tsuyoshi Takano,Ryoyu Hifumi,Ikuyoshi Tomita,Toshiaki Ougizawa

{"title":"Liquid-Crystalline Polymer Alloy Design through Interfacial Reactions Enabled by\u0000 In Situ\u0000 Polymerization and Reactive Blending","authors":"Gosuke Washino,Kyoya Tachibana,Keiichi Kuboyama,Juri Asada,Tsuyoshi Takano,Ryoyu Hifumi,Ikuyoshi Tomita,Toshiaki Ougizawa","doi":"10.1021/acs.macromol.6c01698","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01698","url":null,"abstract":"Abstract Liquid-crystalline polymers (LCPs), an important class of super engineering thermoplastics, exhibit outstanding melt processability and are attractive materials for designing high-performance polymer alloys. However, the fundamental insights required to overcome macroscopic phase separation arising from the intrinsic structural disparity between liquid-crystalline and isotropic polymers, and the design guidelines built on these insights, have not yet been clearly established. Here, we investigated an alloy design strategy for LCP-based systems through an interfacial-reaction approach, using poly(phenylene ether) (PPE) as a dispersed phase capable of copolymer formation with the LCP matrix. First, in melt-mixed LCP/PPE blends prepared by twin-screw extrusion, the PPE domain size was minimized when the viscosity ratio between the liquid-crystalline matrix and the isotropic dispersed phase approached unity. We then constructed LCP/PPE alloys through two reactive routes: in situ polymerization of the LCP in the presence of PPE and reactive melt blending of LCP and PPE. The results collectively indicate that copolymer formation at the liquid-crystalline/isotropic interface reduces melt-state interfacial tension while reinforcing the interface in the solid state, thereby enabling fine dispersion and enhanced mechanical performance. These findings highlight the central role of interfacial engineering beyond differences in higher-order structure and provide a general route to tough, highly processable LCP-based alloys.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"13 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209829","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}

引用次数: 0

Time-Resolved Synchrotron WAXD/SAXS Analysis of Mechanical Deformation and Viscoelastic Relaxation of the Crystalline Phase in Uniaxially Oriented Polymers 时间分辨同步加速器WAXD/SAXS分析单轴取向聚合物中结晶相的力学变形和粘弹性松弛

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-15 DOI: 10.1021/acs.macromol.6c01731

Kohji Tashiro,Yoshihiro Yamashita,Hiroshi Sekiguchi,Koki Aoyama

{"title":"Time-Resolved Synchrotron WAXD/SAXS Analysis of Mechanical Deformation and Viscoelastic Relaxation of the Crystalline Phase in Uniaxially Oriented Polymers","authors":"Kohji Tashiro,Yoshihiro Yamashita,Hiroshi Sekiguchi,Koki Aoyama","doi":"10.1021/acs.macromol.6c01731","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01731","url":null,"abstract":"Abstract The crystallite modulus, commonly referred to as Young's modulus in the crystalline phase of a polymer, is determined by analyzing the strain and stress within the crystalline region through the X-ray method. Traditional experiments utilizing X-ray diffraction require several tens of hours to accurately assess the crystalline strain. In the present study, we have developed a synchrotron system that enables the collection of X-ray data in just a few minutes. However, since the crystalline stress is fundamentally unknown, it must be assumed that the crystal stress is equivalent to that of the bulk sample, which contradicts the conventional understanding of heterogeneous stress distribution. As a result, the crystallite modulus obtained is still an apparent value. To accurately ascertain the ‘true’ crystallite modulus, it is essential to create a sophisticated mechanical model that incorporates both crystalline and amorphous regions as elastic components, considering the heterogeneous stress distribution. Nevertheless, the current rapid-scan synchrotron system has provided new insights into the stress relaxation behavior of the crystalline component, which should be regarded as a viscoelastic entity rather than as a conventional simple elastic body. These two concepts—heterogeneous stress distribution and the viscoelastic nature of the crystalline (and amorphous) phase—are crucial for developing a new mechanical model, which has allowed us to estimate the ‘true’ crystallite moduli and relaxation behavior of various representative polymers such as polyethylene, nylon-6, cellulose, and silk. Throughout the extensive history of this research theme, establishing the true crystallite moduli has been challenging due to various unresolved factors. The present study has addressed these issues and introduced a new concept for treating the crystalline phase as a viscoelastic entity in the interpretation of semicrystalline polymers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"12 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209827","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}

引用次数: 0