Macromolecules最新文献_第10页

Active Segment Polymerization of 1,3-Propanediamine Enables Low-Melting-Point Polyamides for High-Precision 3D Printing 1,3-丙二胺的活性段聚合使低熔点聚酰胺用于高精度3D打印

IF 5.7 1区化学

Macromolecules Pub Date : 2026-10-13 Epub Date: 2026-09-29 DOI: 10.1021/acs.macromol.6c01525

Lurong Zhang, Hangtao Song, Yang Zhou, Like Hou, Heng Li, Jin Cheng, Yidi Wang, Changhai Cao, Biao Zhao, Kai Pan

{"title":"Active Segment Polymerization of 1,3-Propanediamine Enables Low-Melting-Point Polyamides for High-Precision 3D Printing","authors":"Lurong Zhang, Hangtao Song, Yang Zhou, Like Hou, Heng Li, Jin Cheng, Yidi Wang, Changhai Cao, Biao Zhao, Kai Pan","doi":"10.1021/acs.macromol.6c01525","DOIUrl":"10.1021/acs.macromol.6c01525","url":null,"abstract":"The preparation of ultra-short-chain diamine-based polyamides by melt polycondensation remains a formidable challenge in polyamide synthesis, with 1,3-propanediamine (DAP) serving as a representative monomer. To date, the fundamental reasons why this monomer fails to yield satisfactory polymeric products via melt polycondensation remain unclear. Here, we employed quantum chemical calculations to identify DAP polymerization transition states, reaction pathways, and energy barriers, thereby elucidating the molecular origins of the polymerization challenges. The theoretical predictions were further validated by experimental results. Based on the above mechanistic insights, we developed a living chain-segment polymerization strategy that effectively suppresses side reactions, enabling the facile synthesis of a novel structurally tunable low-melting-point polyamide (LMPA), PAX(12312). These LMPAs exhibit exceptional mechanical properties, including a tensile strength of 55 MPa, an elongation at break exceeding 500%, and an impact strength retention of 13.9 kJ/m2 at –30 °C, along with a tunable melting range. Notably, they also feature a low saturated water absorption of 1.25%, a narrow molecular weight distribution of 1.6–2.0, and superior processability. The low processing temperature and high melt stability of these LMPAs confer unique advantages for 3D printing, enabling the fabrication of warp-free, high-precision components.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"11205–11216"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093006","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

Anomalous Thermotropic Cylinder-to-Gyroid Transition in Polystyrene- block -poly(ethylene oxide)/Ionic Liquid Blends 聚苯乙烯-嵌段-聚（环氧乙烷）/离子液体共混物的反常热致圆柱体-陀螺转变

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-12 DOI: 10.1021/acs.macromol.6c01448

Sumana Bandyopadhyay,Aditya Sahare,Sarin Sajjadu Krishna,Tzu-Chien Wei,Hsin-Lung Chen

{"title":"Anomalous Thermotropic Cylinder-to-Gyroid Transition in Polystyrene-\u0000 block\u0000 -poly(ethylene oxide)/Ionic Liquid Blends","authors":"Sumana Bandyopadhyay,Aditya Sahare,Sarin Sajjadu Krishna,Tzu-Chien Wei,Hsin-Lung Chen","doi":"10.1021/acs.macromol.6c01448","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01448","url":null,"abstract":"Abstract Accessing complex morphologies in polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymers at high PEO volume fractions is often hindered by PEO crystallization and relatively weak segregation strength. Here, we report an anomalous thermotropic transition from hexagonally packed cylinders (HEX) to a double gyroid (DG) network in PEO-rich PS-b-PEO/ionic liquid (IL) blends, where a strongly PEO-selective IL suppresses crystallization, swells the PEO domains, and increases the effective segregation strength (χeff) with increasing IL concentration. At low temperatures, strong PEO-IL hydrogen-bonding interactions promote anisotropic conformations of the PEO blocks and stabilize a frustrated HEX morphology under vitrified PS domains. Upon heating above the glass transition temperature of the PS block (Tg,PS), increased segmental mobility enables chain relaxation, while possible weakening of directional PEO-IL interactions may further reduce the tendency toward locally constrained chain extension. The swollen PEO/IL domain is consequently accommodated through an increase in the interfacial area per chain (Σ) and reduced chain stretching. The cylindrical geometry cannot accommodate this enlarged Σ without imposing severe packing constraints on the PS domains. The system therefore undergoes a HEX→DG transition, wherein the bicontinuous DG morphology redistributes interfacial area and chain conformations in three dimensions to relieve packing frustration under incompressibility. The DG structure can be kinetically trapped upon cooling, resulting in a robust three-dimensional ion-conducting network that exhibits higher conductivity than the cylindrical and lamellar phases.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"14 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151095","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

Polysiloxane Supramolecular Elastomers via Programmable Ionic-Hydrogen-Bonded Aggregates 通过可编程离子-氢键聚集体制备聚硅氧烷超分子弹性体

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-12 DOI: 10.1021/acs.macromol.6c02125

Yaping Sheng,Weiguang Jia,Anqiang Zhang,Yaling Lin

{"title":"Polysiloxane Supramolecular Elastomers via Programmable Ionic-Hydrogen-Bonded Aggregates","authors":"Yaping Sheng,Weiguang Jia,Anqiang Zhang,Yaling Lin","doi":"10.1021/acs.macromol.6c02125","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c02125","url":null,"abstract":"While nanoscale aggregates as dynamic crosslinks enhance supramolecular elastomers, systematically elucidating how aggregate parameters are regulated and dictate mechanical responses remains challenging. Here, we fabricate polysiloxane-based supramolecular elastomers with varied aggregate structural parameters by leveraging the thermodynamic incompatibility between strongly associative ion pairs and the weakly polar siloxane backbone, driving spontaneous microphase separation. Three primary design parameters influence aggregate structure and dictate mechanical behavior and failure mechanisms: interaction strength, spacer length, and preparation methods (direct, stepwise, and simultaneous crosslinking). SAXS, TEM, and AFM reveal clear differences in aggregate structures, a trend consistent with rheological and relaxation behavior. Interaction strength drives phase separation, governing aggregate formation and stability. Spacer length governs interaggregate distance (d) and chain mobility, balancing modulus, energy dissipation, and creep recovery. Preparation methods dictate the spatial distribution of aggregates. Compared with the direct (AU) and simultaneous (AX) crosslinked networks, the stepwise crosslinked network (AUU) promotes a transition from discrete, island-like aggregates to locally interconnected, percolating aggregate networks, which fundamentally alters the stress-transfer mechanism and leads to a distinct trade-off: enhanced static load-bearing capacity and dynamic adaptability at the cost of increased notch sensitivity. This work establishes systematic correlations between tunable aggregate parameters (d, size, and connectivity) and the dynamic/static properties, providing guidelines for the design of supramolecular elastomers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"53 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152087","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

Quantifying the Impacts of Junction Functionality on Primary Loop Formation in Linear Polymers and Polymer Networks 线性聚合物和聚合物网络中结功能对初级环形成的量化影响

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-12 DOI: 10.1021/acs.macromol.6c01583

Juan A. Cintron-Cruz,Devosmita Sen,Bradley D. Olsen,Jeremiah A. Johnson

{"title":"Quantifying the Impacts of Junction Functionality on Primary Loop Formation in Linear Polymers and Polymer Networks","authors":"Juan A. Cintron-Cruz,Devosmita Sen,Bradley D. Olsen,Jeremiah A. Johnson","doi":"10.1021/acs.macromol.6c01583","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01583","url":null,"abstract":"Abstract Most polymer networks formed from flexible precursors contain elastically inactive primary loops that significantly impact macroscopic material properties. While primary loop formation is known to decrease with increasing strand concentration and length, the role of junction functionality (f), defined by the number of strands connected to each junction, remains poorly understood. Here, we use network disassembly spectrometry (NDS) to experimentally quantify primary loops in end-linked poly(ethylene glycol) (PEG) networks with f = 3–6 as well as linear step-growth polymers (f = 2). Our results reveal that f governs the sensitivity of primary loop formation to synthesis conditions. Step-growth polymerizations (f = 2) show the strongest dependence, with 1° loop formation strongly suppressed at high concentrations and chain lengths. As f increases, sensitivity to concentration and chain length decreases progressively, showing an initial odd–even effect that plateaus at the highest functionality investigated (f = 6). Comparing against four different computational simulation algorithms, Kinetic Monte Carlo (KMC) simulations and Annable’s coarse-grained model are shown to agree best with NDS results. These findings establish junction functionality as a key parameter for engineering the cyclic topology of polymeric materials and provide experimental guidance that informs the selection of computational models for the design and prediction of polymer network topology in the future.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"6 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151455","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

Anisotropic Thermal Conductivity of Poly(lactic acid) Polymers Subjected to Uniaxial Elongation 单轴拉伸下聚乳酸聚合物的各向异性热导率

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-12 DOI: 10.1021/acs.macromol.6c02061

Oscar Sanchez Pinosa,David C. Venerus

引用次数: 0

Catalyst-free Polyannulations of Potassium Sulfide and Unactivated Alkynes toward Multifunctional Thiophene-Containing Polymers 无催化剂硫化钾和非活化炔对多功能含噻吩聚合物的聚环反应

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-12 DOI: 10.1021/acs.macromol.6c01108

Qingqing Gao,Ruoyao Zhang,Junkai Liu,Dongyang Fan,Zheng Zhao,Haoke Zhang,Jun Zhang,Ting Han,Jacky W. Y. Lam,Ben Zhong Tang

{"title":"Catalyst-free Polyannulations of Potassium Sulfide and Unactivated Alkynes toward Multifunctional Thiophene-Containing Polymers","authors":"Qingqing Gao,Ruoyao Zhang,Junkai Liu,Dongyang Fan,Zheng Zhao,Haoke Zhang,Jun Zhang,Ting Han,Jacky W. Y. Lam,Ben Zhong Tang","doi":"10.1021/acs.macromol.6c01108","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01108","url":null,"abstract":"Abstract Facile and efficient transformation of inexpensive inorganic sulfides into high-value polymer materials is of great academic and industrial significance. Herein, we report a catalyst-free polyannulation strategy between potassium sulfide and internal diynes, which can efficiently produce thiophene-containing polymers (TCPs) in N,N-dimethylformamide under mild conditions. The reaction may proceed via a trisulfur radical anion-mediated mechanism, generating thiophene units in situ without the need for thiophene-containing monomers, additives, or transition metals. The resulting TCPs exhibit high molecular weights (up to 16,300 g/mol), excellent solubility and film-forming ability, and remarkable thermal stability. Their thin films display high refractive indices (n589.2 = 1.6579–1.8078) and UV-tunable optical properties. Post-oxidation transforms the polymers into aggregation-induced emission-active materials with remarkably enhanced fluorescence quantum yields in aggregate and solid states. The aggregate-state luminescent TCPs and their S,S-dioxide derivatives demonstrate organelle-specific imaging capabilities and excellent biocompatibility, highlighting their potential for advanced optical and bioimaging applications.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"33 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151453","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

Directional Nanoparticle Migration Driven by Mobility Gradient in Glassy Polymers 玻璃聚合物中迁移率梯度驱动的纳米颗粒定向迁移

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-12 DOI: 10.1021/acs.macromol.6c02053

Yu Li,Mingshu Yang,Xia Dong,Guoming Liu,Dujin Wang

引用次数: 0

Sequence-Controlled Copolymerization of 6-/7-Membered Cyclic Carbonates with l-Lactide: Wide-Range Regulation of Copolymer Properties 6-/7元环碳酸盐与l-丙交酯的序控共聚：共聚物性能的大范围调控

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-12 DOI: 10.1021/acs.macromol.6c01662

Shuming Dai,Mingqian Wang,Zhiqiang Ding,Honggang Xia,Dongbin Wang,Zhe Ma,Bin Wang

{"title":"Sequence-Controlled Copolymerization of 6-/7-Membered Cyclic Carbonates with l-Lactide: Wide-Range Regulation of Copolymer Properties","authors":"Shuming Dai,Mingqian Wang,Zhiqiang Ding,Honggang Xia,Dongbin Wang,Zhe Ma,Bin Wang","doi":"10.1021/acs.macromol.6c01662","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01662","url":null,"abstract":"The synthesis of sequence-controlled poly(lactide-carbonate) copolymers via ring-opening copolymerization (ROCOP) of l-lactide (l-LA) with cyclic carbonates under industrially relevant conditions (in bulk and melt) is highly challenging owing to the lack of highly active and thermally stable catalysts. Herein, we systematically investigated the melt and bulk ROCOPs of l-LA with 6-membered trimethylene carbonate (TMC) and 7-membered cyclic 1,4-butylene carbonate (CBC), respectively, using the (amidoalkyl)pyridine–phenolate aluminum methyl complexes as catalysts. The kinetic differentiation and reactivity ratios for l-LA/TMC and l-LA/CBC monomer mixtures were determined in solution polymerization to deeply understand the catalyst-dependent ROCOP behavior. Poly(LA-TMC) and poly(LA-CBC) copolymers with varying comonomer incorporation ratios and tunable sequence length of PLA segments were further synthesized under bulk and melt conditions with different catalysts. The thermal/mechanical properties and degradation behavior of the resulting poly(LA-TMC) and poly(LA-CBC) samples were thoroughly investigated to elucidate the significant effects of comonomer distribution and chain sequences on material properties. Notably, the aluminum complexes exhibited a higher degree of control over the ROCOP process compared with stannous octoate (Sn(Oct)2), affording poly(LA-TMC) and poly(LA-CBC) copolymers with higher molecular weights and superior thermal/mechanical properties under identical conditions. This systematic investigation of the relationships between catalyst/monomer structure, chain composition, and material properties provides valuable insights into the development of high-performance aliphatic copolyesters and the optimization of their practical application performance.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"9 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152086","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

Large-Strain Viscoelasticity of Partial Vitrimer Silicone Rubber Networks with Stress-Assisted Bond Exchange and Topological Constraints 具有应力辅助键交换和拓扑约束的部分玻璃体硅橡胶网络的大应变粘弹性

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-12 DOI: 10.1021/acs.macromol.6c01730

Guifa Xu,Shensheng Chen,Jun Wang

{"title":"Large-Strain Viscoelasticity of Partial Vitrimer Silicone Rubber Networks with Stress-Assisted Bond Exchange and Topological Constraints","authors":"Guifa Xu,Shensheng Chen,Jun Wang","doi":"10.1021/acs.macromol.6c01730","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01730","url":null,"abstract":"Abstract Partial vitrimer elastomers that combine static and dynamic covalent crosslinks provide a promising route to reconcile creep resistance with network reconfigurability; however, the mechanistic understanding of their cooperative roles under large deformation remains limited. Here, we report a high-performance silicone rubber system based on polymethylvinylsiloxane (PMVS) incorporating dynamic boronic ester bonds and static covalent crosslinks with tunable compositions. The resulting materials exhibit exceptional stretchability (&gt;1200%) together with enhanced tensile strength and improved elastic recovery under large strains. Rheological and mechanical analyses reveal that dynamic covalent crosslinks (DCCs) enable topological rearrangement, leading to enhanced damping, extensibility, and rate-dependent response, while static covalent crosslinks (SCCs) provide a persistent elastic backbone and impose topological constraints that suppress long-time flow and delay DCC-mediated relaxation. To quantitatively describe this behavior, we develop a constitutive model that integrates non-Gaussian chain elasticity with finite extensibility, stress-assisted bond-exchange kinetics, and static-crosslink induced topological constraints. The model accurately reproduces rate- and strain-dependent mechanical behavior and enables direct partitioning of viscoelastic contributions from the static and dynamic subnetworks. This work establishes a quantitative constitutive framework linking effective bond exchange kinetics and hybrid network topology to the macroscopic nonlinear mechanics of partial vitrimer elastomers under large strains.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"42 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151452","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

Tuning the Architecture of High-Density Bottlebrush Block Copolymers to Control Their Photonic Properties 调整高密度瓶刷嵌段共聚物的结构以控制其光子特性

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-09 DOI: 10.1021/acs.macromol.6c01001

Joanna N. Vo,Haisu Kang,Xiao Huan,Ying Diao,Charles E. Sing,Damien Guironnet

{"title":"Tuning the Architecture of High-Density Bottlebrush Block Copolymers to Control Their Photonic Properties","authors":"Joanna N. Vo,Haisu Kang,Xiao Huan,Ying Diao,Charles E. Sing,Damien Guironnet","doi":"10.1021/acs.macromol.6c01001","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01001","url":null,"abstract":"Abstract The backbone rigidity of bottlebrush block copolymers (BBCPs) induced by the dense branches distributed along their polymeric backbones has made them materials of interest for fast self-assembly of photonic materials. Today, the rigidity of BBCPs is limited by the maximum number of branches per backbone repeating unit synthetically accessible (≤2). Here, we report a methodology to yield polystyrene-b-poly(lactic acid) BBCP with five PLA branches per backbone repeating unit (PS-b-PLA5). A graft-through ring-opening metathesis polymerization (ROMP) of PS macromonomer followed by the addition of a norbornene-based monomer bearing five hydroxyl groups (M(OH)5) yields a block copolymer with a bottlebrush block and a linear polyol block (PS-b-PM(OH)5). A graft-from ring-opening polymerization of lactide initiated by the polyol macroinitiator then affords the desired PS-b-PLA5. Monitoring the monomer consumptions for the three polymerizations supports the successful synthesis of the targeted high-branch-density BBCP. The low solubility of the growing PS-b-PM(OH)5 favored a termination of the ROMP via recombination, which results in the formation of triblock PS-b-PM(OH)5-b-PS (that can subsequently be converted into PS-b-PLA5-b-PS). Simple manipulation of the solvent composition for the ROMP provides control over the fraction of triblock BBCPs present in the final material. The self-assembly structures of the polymers containing different ratios of diblock to triblock were compared experimentally by SEM and UV–vis diffusion reflectance spectroscopy. All materials showed similar domain spacings, which is consistent with predictions obtained from coarse-grained simulation. Overall, this work showcases the broad application of the GT-GF methodology in the synthesis of high-density BBCPs and the control we have over the synthesized product.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"167 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151456","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