Polymer Chemistry最新文献

{"title":"Photomediated Cationic RAFT (Co)Polymerisation for Precision Engineering of Macromolecules","authors":"Amit Kumar,Pratibha Sharma,Janah Shaya,Andrew B. Lowe","doi":"10.1039/d6py00745g","DOIUrl":"https://doi.org/10.1039/d6py00745g","url":null,"abstract":"Cationic RAFT (CAT-RAFT) polymerisation has emerged as a convenient and comparatively facile approach for the controlled polymerisation of electron-rich vinyl monomers such as the vinyl ether family. It enables precise control of molar mass, dispersity and end-group fidelity by combining reversible addition-fragmentation chain transfer with cationic propagation. Compared with conventional cationic polymerisation, CAT-RAFT offers improved robustness and greater flexibility in designing and synthesising (co)polymers with advanced architectures. Integrating light as an activation trigger in CAT-RAFT has added new dimensions of precision and versatility. Photomediated CAT-RAFT polymerisation uses light to control the formation and exchange of cationic active species. This gives the polymerisation process exceptional spatiotemporal control. This light-mediated approach not only regulates polymerisation rates but also enables on-demand activation and deactivation under mild, environmentally friendly conditions. These advancements have enabled the synthesis of complex macromolecular structures. Herein, we highlight recent advances in photocatalyst development, stereochemical control, monomer scope, combination with other polymerisations, continuous-flow systems, 3D printing, and emerging applications enabled by light-driven regulation.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149229981","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":"In Situ Asymmetric Photo-polymerization via the Coupling of Chiral Au Nanoparticles and Circularly Polarized Visible Light","authors":"Gang Zou,Chutian Zhang,Qiankun Chen,Di Wang,Liyu Gan,Jingang Hu,Yifan Xie,Douguo Zhang,Jingguo Li,Hongli Zhang","doi":"10.1039/d6py00766j","DOIUrl":"https://doi.org/10.1039/d6py00766j","url":null,"abstract":"Chiral noble metal nanoparticles hold great promise in asymmetric photochemical reactions owing to their distinctive chiral near-field enhancement and intense chiral light-matter interactions. Although numerous studies have reported enantioselective catalysis by chiral Au nanoparticles (AuNPs), the coupling between chiral AuNPs and the spin angular momentum of excitation light remains poorly understood in asymmetric photocatalysis, particularly in enantioselective photo-polymerization. Here, we systematically investigate the asymmetric photo-polymerization of achiral diacetylene (DA) monomers assisted by chiral AuNPs in conjunction with visible light of various polarization states. We find that synergistic chiral amplification is achieved when the handedness of circularly polarized visible light (CPVL) matches that of the AuNPs, whereas mismatched CPVL can offset or even reverse the chiral bias originating from the AuNPs. This enables the fabrication of polydiacetylene (PDA) micropatterns with programmable chiral distributions using a homogeneous vector light field generated by a spatial light modulator (SLM), establishing a viable strategy for information storage and encryption.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"6 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149230021","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":"Fast Curing Green Phenolic Honeymoon Adhesive through A Highly Efficient Polycondensation Reaction","authors":"Yaojie Yu,Junpo He","doi":"10.1039/d6py00732e","DOIUrl":"https://doi.org/10.1039/d6py00732e","url":null,"abstract":"A fast polycondensation reaction between 3,5-Dimethoxyphenol (DMP-3,5) and glutaraldehyde (GA) was developed. Benefiting from the synergistic electron-donating effect of dimethoxy and hydroxy substituents, DMP-3,5 exhibited superior reactivity towards GA compared with other phenolic derivatives, achieving very fast curing within seconds in the presence of p-toluenesulfonic acid (p-TSA) as the catalyst. The reaction mechanism, kinetic behavior, and structural evolution of the DMP-3,5/GA system were systematically explored using nuclear magnetic resonance spectroscopy (NMR), Fourier transform infra-red spectroscopy (FTIR), size exclusion chromatography (SEC), and rheological measurements. Two key diadduct intermediates were isolated and identified, clarifying the stepwise protonation and hydroxyalkylation pathway. It was found that the reaction temperature, time, the feeding monomer molar ratio, and catalyst concentration effectively regulated the molecular weight and bonding performance of polymer networks. The polycondensation reaction was applied as a high-performance honeymoon adhesive. Using the optimized DMP-3,5/GA system at a molar ratio of 1.5:1, the adhesive exhibited satisfactory instant bonding strength and bonding durability. The prepared three-layered plywood achieved a maximum bonding strength of 9.99 MPa, with reliable instant and aged adhesion. The work provides a facile and sustainable strategy for developing bio-sourced green phenolic adhesives as an alternative to traditional formaldehyde-based products.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149230018","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":"gpcML: A Comprehensive Data Standard for Size-Exclusion Chromatography","authors":"Oliver Cruse,Tanja Junkers","doi":"10.1039/d6py00930a","DOIUrl":"https://doi.org/10.1039/d6py00930a","url":null,"abstract":"Modern data driven chemistry requires chemical information to be available in machine-readable formats. This requires setup of universal data standards that allow to save data in structured, non-proprietor formats. Here, we suggest a data standard for the saving and processing of size exclusion chromatography data for polymers, gpcML. Based on the XML format, gpcML stores all required data around a chromatogram of a polymer sample, including mass calibrations, instrument and sample information and processing history that allows to connect the primary measurement data with the evaluated mass distributions. Next to the standard itself, we also include an online platform that allows to validate files based on gpcML, and a rudimentary function to visualise gpcML data (www.gpcml.com). The data format can be viewed as an advanced alpha version of the data standard, and this description will form the start of community consultation for further development of the standard.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149230019","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":"Microscopic Structure and Dynamics in Metallo-Supramolecular Polymer Gels with Heterocomplementary Network Connectivity","authors":"Yasothaa Thavayogarajah,Niels Giesselmann,Lynn Zank,Louisa Elisabeth Kraft,Mostafa Ahmadi,Katrin Amann Winkel,Sebastian Seiffert","doi":"10.1039/d6py00682e","DOIUrl":"https://doi.org/10.1039/d6py00682e","url":null,"abstract":"Supramolecular polymer networks combine the adaptability of reversible interactions with the structural integrity of conventional elastomers or gels, giving rise to soft materials with tunable mechanical properties. Their mechanical appearance is governed by the interplay of transient connectivity, nano- and mesoscale structure, and chain dynamics, making it challenging to directly relate molecular processes to macroscopic mechanics. Here, we present metallo-supramolecular tetra-arm poly(ethylene glycol) (tetra-PEG) networks as model systems that enable a systematic investigation of structure–dynamics–mechanics relationships. Using transition metal-mediated linking of monodisperse tetra-PEG precursors, the network architecture and crosslink lifetime are controlled through the choice of the coordinating ligands and metal ions, explicitly including homoleptic and heteroleptic coordination. Small-angle X-ray scattering (SAXS) largely denotes structural homogeneity on length scales of 31 nm to 900 nm, while rheology reveals differences in macroscopic viscoelastic response and relaxation dynamics. In contrast, fluorescence recovery after photobleaching (FRAP) provides direct access to molecular-scale transport processes and uncovers distinct qualitative differences. Whereas terpyridine-based networks exhibit multi-component diffusion with finite immobile fractions, phenanthroline-based systems display well-defined single-component diffusion. Based on these findings, the tetra-PEG metallo-supramolecular network can be designed to approach a structurally controlled reference network exhibiting single-mode transport dynamics and well-defined transient mechanical response.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149230020","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":"Local Cross-Linking Structure Regulates Active Site Mobility and Molecular Accessibility in Polymer-Bound Photocatalysts","authors":"Hikaru Matsumoto,Masanori Nagao,Yoshiko Miura","doi":"10.1039/d6py00862c","DOIUrl":"https://doi.org/10.1039/d6py00862c","url":null,"abstract":"Engineering reaction microenvironment in immobilized molecular catalysts is essential for programmable catalytic performance. Herein, we introduce a molecular strategy to regulate the reaction microenvironment based on cross-linking structure of polymer-bound catalysts. A series of polymer-bound tris(2,2′-bipyridine)Ru(II) complexes are synthesized by systematically varying the number and position of covalent anchor points between the Ru complex and polymer chains. Photoluminescence lifetime and absolute quantum yield measurements reveal that increasing the covalent anchors progressively suppresses structural mobility of the Ru core. Stern-Volmer quenching analysis shows that excessive local cross-linking lowers diffusional accessibility of dissolved O2 to the Ru complex due to sterically hindered polymer network. We elucidated that photocatalytic kinetics in a 1O2-mediated anthracene oxidation are determined by both the catalyst mobility and molecular accessibility, which correlates with energy transfer probability from a photoexcited Ru complex to dissolved O2. These findings identify the local cross-linking structure surrounding the active site as a molecular design parameter for engineering the reaction microenvironment in immobilized catalysis.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"57 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218278","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":"Non-Ideal Radical Copolymerization of Lignin-Based Guaiacyl Itaconate with Methyl Methacrylate: Chain Heterogeneity and Self-Assembly Consequences","authors":"Althea Carstens,Ndumiso Sibanda,Susanne Boye,Helen Pfukwa,Albena Lederer","doi":"10.1039/d6py00882h","DOIUrl":"https://doi.org/10.1039/d6py00882h","url":null,"abstract":"Lignin-derived phenolic monomers provide a structurally rich platform for designing functional polymers, yet their radical copolymerisation and consequences for chain architecture remain insufficiently understood. In this work, guaiacyl itaconate (IAnG), a fully bio-derivable monomer obtained from guaiacol and itaconic anhydride, is investigated as a bulky aromatic itaconate comonomer for radical copolymerisation with methyl methacrylate (MMA). IAnG was synthesised via a solvent-free, atom-efficient ring-opening reaction, in which the reaction temperature controlled α/β regioisomer formation with β-IAnG favoured under mild conditions.Copolymerisation with MMA revealed that IAnG does not behave as a passive renewable comonomer.Instead, increasing IAnG feed content leads to reduced conversion, lower molar mass, and non-linear comonomer incorporation and pronounced chain-to-chain compositional heterogeneity. SEC-UV-MALS-dRI and DOSY NMR confirmed the presence of an IAnG-rich oligomeric population alongside longer MMA-rich copolymer chains, indicating a secondary growth pathway parallel to conventional copolymerisation. This compositional heterogeneity directly affected thermal and selfassembly behaviour: IAnG incorporation reduces thermal stability, broadens the glass transition and enables aqueous self-assembly. The resulting assemblies displayed a composition-dependent evolution from spherical to more asymmetric morphologies, as shown by transmission electron microscopy (TEM) and multidetector asymmetrical flow field-flow fractionation (AF4-MD).This study demonstrates that lignin-derived itaconates can actively reshape radical copolymerisation pathways, chain composition and nanoscale organisation, highlighting both their potential and the need for polymerisation strategies adapted to their intrinsic propagation constraints.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"9 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149230044","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":"Anionic Polymerization of Terpene-derived Monomers in Polar Solvents: A Comprehensive Kinetic Study","authors":"Frédéric Petrov,Moritz M. Simon,Jonas Allebrand,Manfred Wagner,Holger Frey,Axel Muller","doi":"10.1039/d6py00824k","DOIUrl":"https://doi.org/10.1039/d6py00824k","url":null,"abstract":"The growing interest in bio-based diene monomers as a sustainable alternative to petrochemical feedstocks has renewed attention for anionic polymerization, owing to its unmatched control over molar mass and microstructure. However, comprehensive datasets remain scarce, particularly for terpene-derived dienes and alternative ether solvents. The propagation kinetics of isoprene, β-myrcene, and trans-β-farnesene initiated by sec-butyllithium were investigated in situ in tetrahydrofuran (THF) and additionally methyl tert-butyl ether (MTBE), a solvent of intermediate polarity. To benchmark these findings against a well-established model system, the anionic polymerization kinetics of styrene, extensively characterized in numerous solvents but not yet in MTBE, were additionally investigated. Using in situ near-infrared and 1H NMR spectroscopy, kinetics, aggregation, and dissociation parameters were determined under comparable experimental conditions. For all investigated monomers, THF promotes predominantly unimeric ion pairs as active species, enabling direct comparison of propagation reactivity. Under these conditions, propagation rate constants decrease with increasing steric demand of the monomer, following the order isoprene > myrcene > farnesene, which is the inverse order in comparison to the use of nonpolar solvents. In contrast, MTBE exhibits intermediate aggregation behavior, indicating a dynamic equilibrium between unimeric and aggregated species existing in comparable proportions, thus resulting in markedly reduced propagation rates. Kinetics results for polymerizations of isoprene and myrcene in MTBE could be described using a non-linear fit, enabling the determination of dissociation constants and ion pair propagation. The activation energies of propagation further reveal significant solvent-dependent differences in the energetic barriers of propagation. These results establish a consistent kinetic reference dataset for structurally related dienes and demonstrate how solvent-controlled aggregation governs the transition between aggregation-dominated and sterically controlled propagation in living anionic polymerization.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"75 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149230016","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":"Accessing block copolymers with independently modulated tacticities using sequential cationic–anionic polymerization of vinyl ethers and thiiranes","authors":"William Ramos,Nicholas M. Legaux,Brandon M. Hosford,Hanlin M. Wang,Elizabeth A. Murphy,Alicia C. Huggett,Frank A. Leibfarth,Jessica R. Lamb","doi":"10.1039/d6py00788k","DOIUrl":"https://doi.org/10.1039/d6py00788k","url":null,"abstract":"Tacticity can have profound effects on the physical properties of polymers, such as self-assembly of block copolymers (BCPs). Despite its promise, previous reports on changing tacticity of BCPs have primarily focused on changing a single block or comparing fully isotactic to fully atactic copolymers. Herein, we report a platform to easily access fully atactic, fully isotactic, and mixed tacticity poly(vinyl ether)-block-poly(thiirane) BCPs. Isotacticity was independently accessed via stereoselective polymerization of vinyl ethers and by using enantiopure thiirane monomers, respectively. Thermal analyses of these materials were performed and semi-crystallinity was observed in aryl-containing isotactic blocks. For BCPs with alkyl side chains or atactic aryl side chains, fractionation on the basis of composition was performed to accelerate self-assembly studies. These fractionated BCPs were characterized via small-angle X-ray scattering (SAXS), where we observed hexagonally-packed cylinder or lamellar morphologies for some fractions. The development of this framework of selective tacticity modulation opens up facile access to diverse BCPs with varying thermal, solution-state, and bulk properties.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218276","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":"Thermoresponsive Behaviour of PEG-Based Methacrylate Polymers: Influence of Linear and Star Architectures","authors":"Jiahe Wang,Arkadios Marathianos,Minen Cao,Xu Liu,Theoni K Georgiou","doi":"10.1039/d6py00821f","DOIUrl":"https://doi.org/10.1039/d6py00821f","url":null,"abstract":"Thermoresponsive polymers based on poly(ethylene glycol) (PEG) have attracted significant attention in various applications, especially in biomedical fields, because of their excellent biocompatibility and high tunability which can be controlled by varying the molecular mass (MM), architecture, and monomer composition. In this study, the monomers oligo(ethylene glycol) methyl ether methacrylate (OEGMA300, average MM = 300 g mol-1) and di(ethylene glycol) methyl ether methacrylate (DEGMA) were selected. OEGMA300, with its longer EG side chains, is more hydrophilic than the relatively hydrophobic DEGMA. Linear copolymers based on these monomers have been investigated, whereas star-shaped polymers have not, and more importantly, a direct comparison of linear and star-shaped polymers as thermogels has not previously been reported. Thus, in this investigation, a series of linear and star polymers composed of OEGMA300 and DEGMA were synthesised via group transfer polymerisation (GTP) with the concentration of the OEGMA300 content ranging from 65 wt% to 35 wt %. Star polymers of different architectures and monomer sequences were synthesised, and their thermal behaviour was investigated. Gel permeation chromatography (GPC) and proton nuclear magnetic resonance (NMR) spectroscopy were used to determine the MMs and compositions of the obtained polymers. Two important transition temperatures, cloud point temperature (Tcp) and gelation temperature (Tgel), were identified through characterisation techniques, including turbidimetry, dynamic light scattering (DLS), visual tests, and rheology. The star polymer which exhibited the best gelation behaviour was the heteroarm star containing 35 wt% OEGMA300 and 65 wt% DEGMA. VT-1H NMR was also performed to investigate the dual-transition behaviour observed in DEGMA-first diblock linear polymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173148","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}