Macromolecules最新文献

{"title":"Phase Transitions of Anionic Block Copolymers with Modulated Charge Density","authors":"Yue Zhou,&nbsp;Lei Shen,&nbsp;Miaohong Wang,&nbsp;Weichao Shi","doi":"10.1021/acs.macromol.6c01628","DOIUrl":"10.1021/acs.macromol.6c01628","url":null,"abstract":"<p>Ionic block copolymers have great potential for diverse applications. Their phase behaviors have been intensively studied at limited charge densities and remain to be explored toward the high-density limit. Here, we establish a synthetic method to modulate the charge density of sulfonate groups in a broad range and study its effect on phase behaviors systematically. Incorporation of a low charge density is found to improve the long-range order of microphase separation significantly. In comparison, high charge density hinders the ordering process and traps the microphase separation in less ordered state, due to associated ionic clusters and crystallization of sulfonate groups. The crystallinity of sulfonates increases with charge density, while the dissociation of charge pairs decreases. The strong electrostatic cohesion of dense charges maintains the phase structures above the melting temperature and improves the thermal stability of block copolymers. These findings are validated in sulfonated block copolymers with sodium and lithium as counterions. This work provides an efficient chemical approach to modulate the charge density of block polymers and sheds insights into the physical mechanism of phase behaviors, which are very useful for exploring high-density ionic materials.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"11115–11126"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049798","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}

{"title":"Entropic Phase Separation in Polymer–Vitrimer Melts","authors":"Alexandros A. Rispo Constantinou,&nbsp;Bálint Magyari,&nbsp;Giovanni Ianniruberto,&nbsp;Evelyne van Ruymbeke,&nbsp;Daniel J. Read","doi":"10.1021/acs.macromol.6c00893","DOIUrl":"10.1021/acs.macromol.6c00893","url":null,"abstract":"<p>Traditional plastics demand a choice between durability (thermosets) and reprocessability (thermoplastics). Vitrimers are a recent class of polymer network combining both of these qualities. Their increased cost of production can be offset by mixing them with a traditional thermoplastic; however, phase separation in such blends can lead to inhomogenous materials. In this paper, we adapt an existing model for the free energy of dissociative polymer networks to their associative, vitrimeric counterpart. We test the accuracy of the model’s predictions by comparing them with the results of novel molecular-dynamics simulations. We demonstrate that such melts can undergo phase separation even in the absence of energetic interactions between the components, with a phase diagram qualitatively similar to that of dissociative systems. We furthermore find that—for equal-length chains in the limit of highly functionalized vitrimers—entropic phase separation sets in as soon as two function sites per chain are cross-linked to other chains, such that only loosely cross-linked networks are stable.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"10615–10630"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049982","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}

{"title":"Phase Behavior of Pentablock Terpolymers Differing in Molecular Architecture and Modified with a Block-Selective Oil","authors":"Kacie M. Wells,&nbsp;Alexey A. Gavrilov,&nbsp;Ivan Kuzmenko,&nbsp;Fontaine E. McFeaters,&nbsp;Artem M. Rumyantsev,&nbsp;Richard J. Spontak","doi":"10.1021/acs.macromol.6c01692","DOIUrl":"10.1021/acs.macromol.6c01692","url":null,"abstract":"<p>Thermoplastic elastomer gels constitute a valuable class of composition-tunable materials that are typically fabricated from styrenic ABA triblock copolymers (<em>i</em>) possessing a morphology with A-dispersions in a B-matrix and (<em>ii</em>) physically modified with a B-selective, low-volatility oil to controllably alter mechanical properties such as modulus and extensibility. In this work, we extend these earlier studies by investigating the phase behavior of two chemically-identical pentablock terpolymers differing primarily in molecular architecture—ABCBA vs ACBCA—in the presence of a B-selective oil at different loading levels. Our reason for studying these polymers is that they constitute the precursors to anionic block polymers (with a sulfonated C-block) that have emerged as amphiphilic block polymers with remarkably versatile bulk and surface properties. Morphological characteristics are experimentally interrogated here by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS), and are complemented by dissipative particle dynamics (DPD) simulations. By changing the block sequence, the morphologies of the neat polymers are observed and predicted to be considerably different. Addition of oil is found to promote vastly dissimilar blend morphologies, along with macrophase separation at moderate oil concentrations. The experimental and simulation results reported here are in generally favorable agreement and clearly demonstrate that the molecular architecture of multicomponent block polymers plays a critical role in the morphological development of these blends.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"11156–11169"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149003526","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}

{"title":"Charge Separation Length of Zwitterions Dictates Coacervation-Mediated Microphase Separation of Zwitterionic Double Hydrophilic Block Copolymers in Water","authors":"Yuji Higaki,&nbsp;Yuri Mitsunobu,&nbsp;Ayuho Miyamoto,&nbsp;Yasuhiro Eguchi,&nbsp;Saya Maeda","doi":"10.1021/acs.macromol.6c02087","DOIUrl":"10.1021/acs.macromol.6c02087","url":null,"abstract":"<p>Aqueous mesoscopic compartments produced by the microphase separation of double hydrophilic block copolymers serve as adaptive molecular compartments driven by thermodynamic imbalances. The impact of the inter-zwitterion interaction strength, modulated by the charge separation length (CSL) in zwitterions, on the microphase separation behavior of poly(carboxybetaine methacrylate)-<em>block</em>-poly(sulfobetaine methacrylate) (PCB2-<em>b</em>-PSBX) aqueous solutions was investigated. We demonstrate that longer CSLs significantly enhance the cohesive energy between sulfobetaine pairs, effectively deepening the thermodynamic potential well for phase separation. This enhancement reduces the threshold degree of polymerization required for ordering and promotes the formation of an ordered lattice at lower concentrations. Conversely, the resulting increase in the effective transient crosslink density led to the suppression of the water-uptake capacity of the PSBX-rich phase and the promotion of selective water partitioning into the PCB2-rich phase. The associated increase in interfacial stiffness and elastic constraint facilitates phase separation but can also lead to a kinetically arrested disordered state by inhibiting structural relaxation towards ordered lattices at high polymer concentrations. These findings highlight the importance of precise control of the inter-zwitterion interaction energies and the resulting interfacial mechanics for designing molecular systems with programmable, adaptive mesoscopic architectures.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"11127–11136"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091704","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}

{"title":"Form II to Form I Transition in Butene-1/Ethylene Copolymer at Isothermal Crystallization Temperatures","authors":"Meilin An,&nbsp;Dong Lyu,&nbsp;Jiahao Li,&nbsp;Pan Chen,&nbsp;Ying Lu,&nbsp;Yongfeng Men","doi":"10.1021/acs.macromol.6c01764","DOIUrl":"10.1021/acs.macromol.6c01764","url":null,"abstract":"<p>By means of differential scanning calorimetry and wide-angle X-ray diffraction techniques, the form II to form I polymorphic transition in a butene-1/ethylene random copolymer (9.88 mol % ethylene co-units) under isothermal crystallization conditions was discovered. The results indicated that this peculiar phase transition at the isothermal crystallization temperature was driven by the local internal stress due to the formation of less-stable form I′ in amorphous regions between existing form II lamellae via a confined crystallization process. Such internal stress was then transmitted to the form II crystals by intercrystalline links of tie molecules and entangled loops, effectively overcoming the nucleation barrier and accelerating the phase transition from form II to form I. A sufficient amount of the less-stable form I′ generated after the sample had completed the form II isothermal crystallization was necessary to accelerate this phase transition. Consequently, a higher proportion of form II was observed to undergo phase transition to form I in samples that started from a melt at a lower temperature or crystallized at a lower temperature.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"11061–11071"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149003528","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}

{"title":"Polymer Nanosphere-Induced Heterogeneous Crosslinking toward Robust Anion Exchange Membranes for Water Electrolysis","authors":"Qiuxing Zhang,&nbsp;Linghan Kong,&nbsp;Wei Yuan,&nbsp;Xuedong Zhang,&nbsp;Lingping Zeng,&nbsp;Jianchuan Wang,&nbsp;Zidong Wei","doi":"10.1021/acs.macromol.6c02180","DOIUrl":"10.1021/acs.macromol.6c02180","url":null,"abstract":"<p>Anion exchange membranes (AEMs) frequently face trade-off between high hydroxide conductivity and dimensional stability under hydration. Conventional homogeneous crosslinking improves the dimensional stability and mechanical strength of AEMs. However, an excessively high crosslink density may compromise hydroxide conductivity. Here, we propose a polymer nanosphere-induced heterogeneous crosslinking strategy that spatially confines crosslinking to the nanosphere-matrix interfaces, enabling comparable enhancement of dimensional stability with a substantially reduced conductivity penalty relative to conventional homogeneous crosslinking. The ∼16 nm nanospheres, which possess benzyl chloride-rich surfaces, are embedded in a rigid aromatic cationic polymer matrix, where interfacial reactions lead to interface-localized crosslinking at the nanosphere-matrix boundary. The optimized membrane shows a strongly suppressed swelling ratio (SR) of 5.0% at 80 °C (∼70% lower than that of the control) together with a markedly enhanced wet tensile strength of 55.1 MPa (fully hydrated state; 2.7 times that of the control), without compromising hydroxide conductivity (205.7 mS cm^–1 at 80 °C) or alkaline stability. In anion exchange membrane water electrolysis (AEMWE), the optimized membrane delivers 5.29 A cm^–2 at 2.0 V in 1 M KOH at 80 °C.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"11217–11228"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010362","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}

{"title":"Bridging the Reactivity Discrepancy: Model Molecules vs. Polymers in Polyurethane Recycling","authors":"Lei Yan,&nbsp;Junming Yang,&nbsp;Wenhao Xu,&nbsp;Junyan Li,&nbsp;Shumin Li,&nbsp;Danxuan Fang,&nbsp;Xuehui Liu,&nbsp;Yong Zeng,&nbsp;Shimei Xu,&nbsp;Yu-zhong Wang","doi":"10.1021/acs.macromol.6c01275","DOIUrl":"10.1021/acs.macromol.6c01275","url":null,"abstract":"<p>The prevailing approach to polymer recycling relies on small-molecule analogs to predict cleavage behavior, implicitly assuming that functional group reactivity translates directly from molecular to macromolecular systems. Here, we challenge this assumption by demonstrating diverged hydrolysis reactivities of carbamate and urea groups in polyurethanes from their small-molecule counterparts under Lewis acid-catalyzed, water-lean conditions. We trace this discrepancy to the distinct microenvironments surrounding each linkage within the polymer matrix: adjacent ether groups promote carbamate cleavage via a thermal decomposition pathway, while urea hydrolysis proceeds through a nucleophilic mechanism. The reactivity can be rationally regulated by Lewis acids and water-lean solvent selection. Furthermore, we uncover that the generated aniline can further react with carbamate groups to yield urea, while also coordinating with the Lewis acid catalyst, enabling its precipitation and thereby simplifying product separation. This fundamental understanding offers a new paradigm for chemical recycling that leverages the unique influence of the macromolecular microenvironment and enables the selective and efficient depolymerization of PUs.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"10864–10874"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091700","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}

{"title":"Coil- to Worm-like Transition for Short Side chain Polymers: Impact on the Design of High-χ, Low-N Block Copolymers for High-Resolution Patterning","authors":"Kyunghyeon Lee,&nbsp;Ki Hyun Kim,&nbsp;Joshua Mysona,&nbsp;Daniel F. Sunday,&nbsp;Jong Dae Jang,&nbsp;Sang Ho Lee,&nbsp;Ji Sung Park,&nbsp;In Beom Heo,&nbsp;Gordon S. W. Craig,&nbsp;Hyeong Min Jin,&nbsp;Paul F. Nealey","doi":"10.1021/acs.macromol.6c00983","DOIUrl":"10.1021/acs.macromol.6c00983","url":null,"abstract":"<p>As block copolymers (BCPs) are designed to self-assemble with smaller feature sizes, the requirement for a lower degree of polymerization (<em>N</em>) inevitably brings the contour length (<em>L</em>_c) closer to the persistence length (<em>L</em>_p). As <em>L</em>_c approaches <em>L</em>_p, even relatively short side groups on chain segments can drive the system away from flexible chain behavior toward worm-like and rod-like conformations. Here, we demonstrate that side groups consisting of only 8–12 carbon units induce worm-like chain (WLC) behavior at length scales relevant to 16–28 nm BCP domain spacings (<em>L</em>₀). We investigate thiol-modified poly(glycidyl methacrylate) (PGMA), a versatile platform for post-polymerization functionalization that has played a key role in the development of BCPs with A-<em>b</em>-(B-<em>r</em>-C) architectures for applications in directed self-assembly. Small-angle neutron scattering from PGMA-modified 4-methoxythiophenol (4MTP), trifluoroethanethiol (TFET), or mixtures of the thiols reveals rod-like scaling in the high-<em>q</em> regime and a relatively large <em>L</em>_p (2–3 nm), consistent with WLC behavior over block lengths relevant to these systems. All-atom simulation further corroborates reduced conformational flexibility with slower relaxation dynamics for the thiol-modified PGMA. These results provide fundamental insights into the onset of deviations in behavior compared to coil-coil BCPs as a function of <em>N</em> and side group lengths, including changes in scaling, with <em>v</em> &gt; 2/3 for <em>L</em>₀ ∼ <em>N</em>^<em>v</em>, and narrower interfacial widths, and reveal chain stiffness as an additional design parameter for high-χ, low-<em>N</em> block copolymers in high-resolution patterning applications.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"10781–10793"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092468","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}

{"title":"Supramolecular Janus Nanocylinders: Solvent-Induced Hydrogen-Bond Modulation Yields Structures under Thermodynamic Equilibrium","authors":"Rihab Zguir,&nbsp;Mingsheng Ji,&nbsp;Irene Antignano,&nbsp;Bochra Seaali,&nbsp;Jean-Michel Guigner,&nbsp;Christophe Sinturel,&nbsp;Ralf Schweins,&nbsp;Marylene Vayer,&nbsp;Frédérick Niepceron,&nbsp;Sandrine Pensec,&nbsp;Jutta Rieger,&nbsp;Laurent Bouteiller,&nbsp;Erwan Nicol,&nbsp;Olivier Colombani","doi":"10.1021/acs.macromol.6c01809","DOIUrl":"10.1021/acs.macromol.6c01809","url":null,"abstract":"<p>Janus nanocylinders (JNCs) are anisotropic, non-centrosymmetric colloids composed of two different faces, making them attractive for advanced functional materials. However, their nanometric dimensions and pronounced anisotropy complexify their preparation. Recently, a versatile supramolecular strategy has emerged that enables JNCs to be formed without the need for incompatible polymer arms. It occurs in water via the self-assembly of two polymers end-functionalized with complementary, non-symmetrical, hydrogen-bonding motifs. However, assembly in water is driven by a combination of hydrogen bonds and strong hydrophobic effects, yielding kinetically frozen nanostructures whose amount and dimensions depend on the assembly process. Here, we show that supramolecular assembly in toluene overcomes these limitations. In contrast to aqueous systems, solvophobic effects are negligible in toluene, and supramolecular assembly is predominantly driven by the formation of hydrogen bonds between urea-associating units. Consequently, reorganization of the assemblies is possible in toluene at room temperature and a pathway-independent supramolecular organization can be achieved by modulating intermolecular interactions through heating or by the addition of a moderate hydrogen-bond competitor. These results hint at the formation of supramolecular Janus nanocylinders at thermodynamic equilibrium, which can be formed in a very straightforward direct dispersion approach with repeatable characteristics (length, diameter).</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"10892–10902"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092760","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}

{"title":"Microgels Based on Amphiphilic Polymer Conetworks at a Liquid–Liquid Interface: Microphase Segregation in Swollen Particles","authors":"Nikita V. Bushuev,Rustam A. Gumerov,Andrey A. Rudov,Stepan I. Zholudev,Igor I. Potemkin","doi":"10.1021/acs.macromol.6c01005","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01005","url":null,"abstract":"Amphiphilic microgels with a diblock copolymer-like network architecture (each subchain of the network is a diblock copolymer chain) were studied at the interface of two immiscible liquids (oil and water) using mesoscopic computer simulations. It was shown that adsorption of microgels to the interface causes not only deformation of the soft particles, which is primarily controlled by their cross-linking density and incompatibility of the liquids but also microphase separation inside them. One of the blocks is considered to be water-soluble and the other as soluble in oil only, i.e., both liquids are selective solvents for the copolymer. In contrast to dense block copolymer systems, where microphase separation is driven by the incompatibility of the blocks, the microphase separation within the microgel swollen at the interface is solely caused by the incompatibility of the different liquids. Water-soluble blocks uptake water from the water phase, and water-insoluble blocks uptake oil from the oil phase in a proportion, which is determined by a composition of the copolymer. Therefore, the location of the different blocks determines the location of the different liquids, whose incompatibility stabilizes nanodomains. Thus, the subchains remain swollen (each block is swollen in the corresponding liquid) and the incompatibility between blocks alone does not cause microphase separation. Under uniaxial compression of monolayers of such microgels, the morphology of the interfacial ensemble was found to vary from elongated lamellar domains oriented along the compression axis for highly cross-linked particles to onion-like structures for weakly cross-linked particles. Finally, using one-dimensional structure factor analysis and two-dimensional diffraction patterns, the evolution of nanoscale ordering in monolayers during compression was tracked, confirming the emergence of lamellar nanodomains.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"9 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152088","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}