Polymer Chemistry最新文献

{"title":"Mitigating the – trade-off in D–A conjugated polymer thermoelectrics doping-induced microstructural reconfiguration","authors":"Huanbiao Zeng,Jinjia Xu,Chengjun Pan","doi":"10.1039/d6py00556j","DOIUrl":"https://doi.org/10.1039/d6py00556j","url":null,"abstract":"Achieving simultaneous enhancement of electrical conductivity (σ) and the Seebeck coefficient (S) remains a central challenge in developing high-performance organic thermoelectrics (OTEs). Here, we demonstrate that this trade-off can be mitigated in a novel donor–acceptor (D–A) conjugated polymer, PDPPEDOT, through the precise control of microstructural evolution induced by F4TCNQ doping. Spectroscopic analyses (UV-vis-NIR, Raman, and XPS) confirm efficient charge transfer between the PDPPEDOT backbone and F4TCNQ. Microstructural characterization via GIWAXS and AFM reveals that moderate doping (10 mg mL−1) acts as a structural template, promoting ordered molecular packing and uniform nanocrystalline domain formation, whereas excessive doping disrupts this structural integrity. Benefiting from optimized microstructural packing, the PDPPEDOT thin film can achieve a high electrical conductivity of 10.71 S cm−1 while maintaining a Seebeck coefficient of 76.75 μV K−1, yielding a maximum power factor of 6.31 μW m−1 K−2 with a characteristic “volcano-shaped” trend. This study highlights doping-induced microstructural regulation as an efficient strategy for mitigating the trade-off between thermoelectric parameters and advancing next-generation high-performance D–A-type organic thermoelectric materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148703497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and polymerization of an AB-type cage silsesquioxane monomer","authors":"Naoki Yamaguchi,Cashew Nagashima,Takahiro Iwamoto,Kensuke Naka,Hiroaki Imoto","doi":"10.1039/d6py00597g","DOIUrl":"https://doi.org/10.1039/d6py00597g","url":null,"abstract":"An AB2-type polyhedral oligomeric silsesquioxane (POSS) monomer was synthesized from heptaisobutyl-POSS trisilanol as an isomeric mixture and polymerized via Pt-catalyzed hydrosilylation. The reaction afforded polymeric, oligomeric, and cyclic products, which were separated using preparative high-performance liquid chromatography. The polymeric and oligomeric products formed transparent, homogeneous, and amorphous films, whereas the monomer mixture and cyclic product formed turbid films because of the POSS aggregation. The polymeric and oligomeric products also exhibited high thermal stability. These results demonstrate that AB2-type POSS monomers are useful building blocks for soluble, transparent, and thermally stable organic–inorganic hybrid polymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858080","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Smart gels reversible deactivation radical polymerization: design, synthesis, and applications","authors":"Ankit Kumar Kaushik,Koushik Mahata,Sudipta Paul,Sanjib Banerjee","doi":"10.1039/d6py00504g","DOIUrl":"https://doi.org/10.1039/d6py00504g","url":null,"abstract":"Smart polymer gels have emerged as an important class of adaptive materials owing to their ability to respond to external stimuli and exhibit tunable physicochemical properties. Hydrogels, organogels, ionogels, nanogels, and hybrid gel and other systems have attracted significant attention for applications in wearable electronics, soft robotics, tissue engineering, sensing, environmental remediation, and energy storage. The performance of these systems is strongly governed by polymer network architecture, crosslink distribution, and molecular-level structural precision, which collectively determine mechanical integrity, swelling behavior, transport properties, responsiveness, and long-term stability. This review critically examines the role of reversible deactivation radical polymerization (RDRP) in enabling structurally controlled smart gel systems. Particular emphasis is placed on atom transfer radical polymerization (ATRP), reversible addition–fragmentation chain transfer (RAFT), nitroxide-mediated polymerization (NMP), and emerging photo-mediated and advanced RDRP strategies, together with their mechanisms, kinetics, molecular design principles, and influence on gel network formation. Compared with conventional free radical polymerization (FRP), RDRP enables improved control over molecular weight, dispersity, chain-end fidelity, topology, and crosslink homogeneity, resulting in more predictable and multifunctional gel systems. To establish this transition, comparative discussions between FRP and RDRP derived gels are incorporated throughout the review, highlighting differences in structural defects, swelling predictability, mechanical behaviour, and stimuli responsiveness. This review further correlates polymerization strategies with structure–property relationships and discusses the emerging integration of RDRP with additive manufacturing approaches such as digital light processing (DLP) and direct ink writing (DIW). Overall, this review provides a method-focused perspective connecting controlled radical polymerization with the rational design of next-generation smart gels possessing enhanced structural precision, responsiveness, and application-specific functionality.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"32 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858081","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modular amine-catalyzed inverse vulcanization for sulfur-rich functional films","authors":"Sumin Choi,Sanghoon Song,Jeewoo Lim","doi":"10.1039/d6py00580b","DOIUrl":"https://doi.org/10.1039/d6py00580b","url":null,"abstract":"Inverse vulcanization (IV) enables the solvent-free synthesis of sulfur-rich polymers with tunable optical and electrochemical properties, yet their integration into flexible electronic substrates is currently restricted by the limited development of free-standing films in the sub-millimeter thickness range and a lack of systematic data regarding their dielectric and mechanical properties. We report herein an amine-catalyzed modular synthetic platform for sulfur-rich terpolymers that utilize elemental sulfur, allyl glycidyl ether (AGE), and diverse epoxy crosslinkers. Tertiary amine catalysis facilitates concurrent sulfur and epoxide ring opening, yielding a homogeneous network architecture that enables the fabrication of uniform, free-standing films in the thickness range of 350 to 500 μm via hot-press molding. These materials exhibit tunable glass transition temperatures in the range of 10 to 33 °C, resulting in a viscoelastic mechanical response at ambient temperature that combines high tensile strength of up to 13 MPa with ductility (up to 70% elongation). Systematic dielectric characterization establishes a quantitative correlation between network connectivity and dielectric response, identifying a controllable permittivity (ε′) in the range of 4.3 to 5.0. This work establishes a scalable processing route for sulfur-rich dielectrics, providing a framework for their implementation in various electronic and sensing applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"211 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858078","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Y-shaped PCL-PLA copolymer-based all-solid electrolyte with enhanced Li ion conduction and stable cycling performance","authors":"Shan Qian,Limin You,Yunjie Zhang,Xiaoting Huang,Jingfan Zou,Zhaoying Chen,Rui Ma","doi":"10.1039/d6py00048g","DOIUrl":"https://doi.org/10.1039/d6py00048g","url":null,"abstract":"In recent years, solid polymer electrolytes (SPEs) have attracted much attention because of their good safety, good thermal stability and environmental stability. In this study, PLA-DMPA was synthesized by amidation after terminal group modification of PLA. A Y-shaped poly(ε-caprolactone)-poly(l-lactide) (Y-PCL-PLA) copolymer was delicately tailored by ring-opening copolymerization of PLA-DMPA and the ε-CL monomer, and the utilization rate of the terminal group (-DMPA) reached 83.7%. The Y-shaped structure can effectively decrease the crystallinity of PCL by 18.3%, improve the molecular chain movement ability and enhance the mechanical properties at high temperature. LFP/Y-PCL-PLA/Li batteries exhibit high ionic conductivity (1.64 × 10−4 S cm−1 at 60 °C), a wide electrochemical stability window (∼5.65 V), and a high lithium ion transfer number (tLi+ = 0.72). At 0.5C, the LFP/Y-PCL-PLA/Li battery can maintain a long-term stable cycle of 500 cycles, and the Coulombic efficiency is maintained above 99.7%. The discharge capacity is high (132 mAh g−1), the capacity retention rate can reach 75.8%, and the polarization voltage is very small (0.08 V). These data illustrate the excellent performance of Y-PCL-PLA as an all-solid electrolyte.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148672101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of pH-responsive statistical polyampholytes by PET-RAFT polymerization of protected monomers","authors":"Hadley A. Johnston,Genevieve C. Thomas,Tianyu Zhang,Conner H. Chee,Jennifer E. Laaser","doi":"10.1039/d6py00400h","DOIUrl":"https://doi.org/10.1039/d6py00400h","url":null,"abstract":"Synthetic polymers have emerged as powerful models for investigating drivers of liquid–liquid phase separation in biological materials. However, synthesizing polymers with “protein-like” distributions of cationic, anionic, hydrophilic, hydrophobic, and aromatic sidechains has remained a significant challenge. Here, we demonstrate that this problem can be addressed by polymerizing protected amine- and acid-functionalized monomers, along with a wide variety of nonionic comonomers, under photoinduced electron/energy transfer reversible addition–fragmentation chain transfer polymerization (PET-RAFT) conditions. We show that PET-RAFT enables controlled polymerization of tert-butyl (2-acrylamidoethyl)carbamate (Boc-AEAm) and tert-butyl acryloylglycinate (tBu-AG). Copolymerization of these monomers proceeds with reactivity ratios close to one, and deprotection with trifluoroacetic acid yields polyampholytes with pH-dependent phase behavior consistent with expected changes in the polymers’ isoelectric points as the cation : anion ratio is varied. We further show that a 50 : 50 mixture of these monomers can be copolymerized with hydrophilic (acrylamide, hydroxyethyl acrylamide), hydrophobic (n-butyl acrylamide), and aromatic (benzyl acrylamide) comonomers, which in turn significantly impact the pH-dependent phase behavior of the materials. This approach is both high-throughput and scalable, and promises to offer new opportunities both for understanding composition–property relationships in polyampholyte materials and for preparing polyampholytes with targeted properties and functions for a wide range of applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"6 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148672103","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effects of polymer backbone connectivity on ion conduction in polymers bearing oligo(ethylene glycol) side chains","authors":"Davide Savi,Francesco M. Ara,Giulio Torboli,Alessandro Magro,Alessandro Bertolo,Alessio Lo Bocchiaro,Alessandra Lorenzetti,Edmondo M. Benetti,Francesca Lorandi","doi":"10.1039/d6py00475j","DOIUrl":"https://doi.org/10.1039/d6py00475j","url":null,"abstract":"Polymer electrolytes (PEs) based on graft polymers bearing oligo(ethylene glycol) side chains are promising materials for Li-ion batteries. While ion transport in poly(meth)acrylate-based systems has been extensively investigated, the use of poly(vinyl ester) backbones remains unexplored. Herein, we compare the ion-transport properties of poly[di(ethylene glycol)]vinyl ester (PDEGVE), acrylate (PDEGA), and methacrylate (PDEGMA) blended with LiTFSI. PDEGVE-based PE shows the highest conductivity, nearly twice that of PDEGA and one order of magnitude higher than that of PDEGMA. Structural, thermal and electrochemical characterizations reveal that the low conductivity of PDEGMA originates from its relatively low dielectric constant, which promotes Li-TFSI ion pairing, together with the reduced mobility of EO units. In contrast, the enhanced conductivity of PDEGVE arises from greater mobility of EO units and distinct polymer-ion interactions induced by the vinyl ester backbone connectivity. These findings elucidate the influence of backbone chemistry on the ion-transport ability of graft polymers and identify poly[oligo(ethylene glycol)]vinyl esters as a promising platform for optimizing the ionic conductivity of graft PEs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148672106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of novel non-glycidyl ether epoxy resins the Corey–Chaykovsky reaction and preparation of high heat-resistant cured products by their curing reaction","authors":"Hiroyuki Maekawa,Seiryu Umetani,Naoya Yamaguchi,Toshiyuki Oyama","doi":"10.1039/d6py00315j","DOIUrl":"https://doi.org/10.1039/d6py00315j","url":null,"abstract":"In this study, three types of non-glycidyl ether epoxy resins, namely, 2,2′-(1,4-phenylene)bisoxirane (PBOX), 1,7-dioxadispiro[2.2.2.2]decane (DCD), and 1,1′-dioxa-6,6′-bispiro[2.5]octane (DBO), were synthesized via a peroxide-free route using the Corey–Chaykovsky reaction between carbonyl compounds and methylsulfonium methylide. Differential scanning calorimetry measurements indicated that the reactivity of PBOX was comparable to that of its glycidyl ether analogue and that DCD and DBO have larger strain energy than their glycidyl ether counterparts. The non-glycidyl ether epoxy resins were found to be curable with phenol novolak and m-phenylenediamine (MPDA) as curing agents, and the thermal stability of the resulting cured products was compared with that of the corresponding glycidyl-ether-type cured derivatives. The PBOX-derived cured product exhibited higher physical thermal stability than its glycidyl ether counterpart, and the DCD- and DBO-derived cured products showed higher physical/chemical thermal stability than the corresponding glycidyl ether cured derivatives. The DBO-derived cured product showed the highest thermal stability among the compounds evaluated, with a 5% weight loss temperature of 408 °C and a glass transition temperature of 291 °C. These results suggest that non-glycidyl ether epoxy resins are promising highly heat-resistant thermosetting resins suitable for various applications, such as encapsulation of next-generation power devices for high-temperature operation.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"45 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148672105","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Controlling crystallinity in degradable poly(ethylene carbonate) polymers by precision carbonate placement","authors":"Rachel H. Bianculli,He Sun,Ani N. Davis,Joshua D. Marquez,Kenneth B. Wagener,Summer J. Brown,Eva Vásquez-Barillas,Kathryn R. Williams,Austin M. Evans","doi":"10.1039/d6py00452k","DOIUrl":"https://doi.org/10.1039/d6py00452k","url":null,"abstract":"In this report, we show that precision placement of hydrolyzable carbonate units enables chemical deconstruction without compromising crystallinity. The crystallinity of polyethylene underlies its exceptional mechanical, thermal, and barrier properties. However, the non-polar, crystalline structure of polyethylene materials renders it resistant to backbone degradation. Incorporating degradable functionalities along the backbone offers a potential solution, provided crystallinity can be retained. Here we report the synthesis of precision carbonate-containing polyethylene-like (PE-like) polymers by acyclic diene metathesis (ADMET) polymerization followed by mild hydrogenation. This generates PE-like materials where the density and placements of carbonate units is precisely controlled. Thermal analysis shows that the melting behavior and crystallinity are retained by the methylene-rich domains, where melting temperatures increase (35, 50, 76 °C) as uninterrupted methylene sequences lengthen (PCO3-10C, PCO3-14C, and PCO3-18C, respectively). X-ray scattering reveals that carbonates are excluded from the interior of lamellae and are positioned at the termini of orthorhombic crystallites, indicating that the carbonates are the dominant source of chain-folding in these semicrystalline materials. Surface-localized carbonates provide a route for acid-catalyzed hydrolytic cleavage, which we exploit to degrade these materials into small molecules. These results provide a mechanistic understanding of how dipolar, hydrolyzable groups interact with polyethylene domains and offer design principles for embedding degradable units into polyolefins without compromising bulk crystallinity. We expect that future efforts to control the crystallinity of polyethylene materials could provide a route to sustainable materials with tunable thermal, mechanical, or chemical characteristics.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"19 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148672099","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pressure-sensitive adhesives with squaramide as a building block","authors":"Tielei Li,Kaini Yang,Yachun Su,Baochen Wang,Zhengqing Kong,Jin Zhu","doi":"10.1039/d6py00407e","DOIUrl":"https://doi.org/10.1039/d6py00407e","url":null,"abstract":"Pressure-sensitive adhesives (PSAs) with squaramide as a building block are reported herein, presenting a modular approach to the rational design of supramolecular adhesives. A poly(butyl acrylate-co-ethyl squaramate methacrylate) scaffold is synthesized and quantitatively functionalized with a library of primary amines (alkyl, mono-hydroxyl, and di-hydroxyl) through highly selective squaramate aminolysis to install diverse side-chain squaramide hydrogen-bonding networks. With the main-chain sequence distribution and molecular weight fixed, the macroscopic viscoelasticity of the resulting squaramide PSAs is directly dictated by the side-chain hydrogen-bonding capacity. As such, the balance between adhesion and cohesion is tuned through the side-chain structure across the functionalized series. Macroscopic evaluations reveal that the alkyl (propylamine) modification provides moderate cohesive enhancement through the squaramide hydrogen-bonding network, the mono-hydroxyl (ethanolamine) modification affords a favorable adhesion–cohesion balance with high lap shear strength (183.3 kPa), high static shear resistance (7920 min under 500 g loading), and high 180° peel strength (11.1 N/25 mm), and the extended mono-hydroxyl (4-amino-1-butanol) and di-hydroxyl (3-amino-1,2-propanediol) modifications furnish high lap shear strength (197.8 and 265.6 kPa) and high cohesive shear resistance (no failure after 7 days under 500 g loading). The squaramide PSAs developed herein showcase squaramide as a versatile and modular building block for the rational design of supramolecular adhesives.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"54 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148672098","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}