Polymer Chemistry最新文献

{"title":"Ion Mobility Mass Spectrometry Coupled with Molecular Dynamics Simulations: In-depth Structural Analysis of Polystyrene-based Au-Containing Copolymers","authors":"Sarajit Naskar, Aidan Izuagbe, Vincent Lemaur, Quentin Duez, Andrea Minoia, Julien De Winter, Stephen Blanksby, Jerome Cornil, Christopher Barner-Kowollik, Pascal Gerbaux","doi":"10.1039/d5py00194c","DOIUrl":"https://doi.org/10.1039/d5py00194c","url":null,"abstract":"Artificial enzymes based on polystyrene copolymers featuring a metal complex within their structure, so-called Single Chain Nanoparticles (SCNPs), are currently discussed as hybrid heterogeneous/homogeneous catalysts. Using styrene (derivative) building blocks, SCNP pre-cursor copolymers decorated with pendent triphenylphosphine ligands complexed with catalytically active gold motifs have recently been reported. It is highly challenging to determine the location and orientation of the functional groups – including the catalytic center – the coil geometry, and even the macromolecular architecture within these complex precursors via conventional analytical techniques. The use of ion mobility mass spectrometry (IMS-MS) combined with molecular dynamics (MD) simulations is emerging as a way to establish the structure of gaseous ions, including the description of the secondary interactions responsible of the folding. IMS-MS is used to separate intricate polymer mixtures, while providing structural information through collisional cross section (CCS) determination. MD simulations are used to assign a detailed internal structure to the conformations sampled by IMS-MS by comparing the experimental CCS to the theoretical values computed for the MD structures. In the present contribution, we provide an in-depth investigation of the conformation of gaseous Au-functionalized copolymer ions composed of three different monomer units, i.e., styrene, styrene-CH2-OH and styrene-PPh2-AuCl, and bearing a TEMPO unit as the initiator end group. For the styrene/styrene-CH2-OH copolymer ions, an H-bond associating protonated TEMPO and a styrene-CH2-OH unit is responsible for the ultimate folding of the polymer ions with the charge settled at the center of the globular ions. When incorporating the triphenylphosphine-AuCl unit, a strong H-bond associating the chlorine atom with protonated TEMPO is detected. However, the steric hindrance around the triphenylphosphine ligand prevents the charge from being incorporated in the core of the globular ions.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"30 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723498","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":"Design of degradable, intrinsically flame-retardant and high-performance tung-oil-based epoxy vitrimers","authors":"Qianyong Chang, Kun Zhang, Wenbin Li, Yanqing Wang, Ke Li, Yigang Wang, Xiaoan Nie, Jie Chen","doi":"10.1039/d5py00141b","DOIUrl":"https://doi.org/10.1039/d5py00141b","url":null,"abstract":"The performance of carbon fiber-reinforced composites (CFRCs) is mainly influenced by the resin matrix. In this study, eleostearic acid was utilized as the raw material, with DOPO serving as the flame-retardant functional group, and dynamic ester bonds were introduced to construct tung oil-based flame-retardant epoxy vitrimers (DGEBA-MSPDGE), which were subsequently applied in the preparation of CFRCs. This approach was aimed to address two major challenges of CFRCs: flammability and recyclability. With DGEBA-MNA cured with commercial methyl nadic anhydride (MNA) as a control, DGEBA-MSPDGE-1 exhibited excellent mechanical properties, and achieved a tensile strength of 81.4 MPa and an elongation at break of 3.83%, which were both superior to those of DGEBA-MNA (76.1 MPa and 2.86%, respectively). DGEBA-MSPDGE attained a limiting oxygen index of 36.4% and a UL-94 V-0 rating in a vertical burning test, and demonstrated blow-off effects during evaluation. The peak heat release rate and total heat release for DGEBA-MSPDGE-1 compared to those of DGEBA-MNA were reduced by 40% and 46%, respectively, which indicate excellent flame retardancy properties. It displayed excellent chemical degradability by completely degrading within five hours under mild conditions. Notably, the recovered carbon fibers (CFs) retained their original chemical structure, mechanical properties, and surface morphology, which facilitated non-destructive recycling of CFs. Therefore, this research provides a viable strategy for fabricating high-performance, fire-safe and recyclable CFRCs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713388","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":"Plastic-Rubber Diblock Copolymer from Copolymerization of Dimethyl-1,3-butadiene and Butadiene by Rare-earth Metal Catalyst","authors":"Jiao Zong, Benmin Hu, Lei Li, Shihui Li, Bo Liu, Dongmei Cui","doi":"10.1039/d4py01446d","DOIUrl":"https://doi.org/10.1039/d4py01446d","url":null,"abstract":"Coordination polymerization of 2,3-dimethyl-1,3-butadiene (DMB) has been investigated by using rare-earth metal catalysts. Of which the ligand-free gadolinium dibenzyl chloride precursor exhibits the highest activity and perfect cis-1,4 selectivity for DMB homopolymerization and copolymerization with butadiene (BD) to afford plastic poly(2,3-dimethyl-1,3-butadiene) (PDMB) and plastic-rubber diblock copolymer PDMB-b-PBD, respectively. In solution PDMB-b-PBD self-assembles into “core-shell” morphology with the crystalline cis-1,4 regulated PDMB segment as the core and the amorphous cis-1,4 stereoregular PBD unit as the shell, whilst in melt, PDMB block forms physical cross-linking in PBD rubbery matrix, endowing the material with an unusual high stress accompanied by excellent elongation.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"287 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703326","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":"Effect of biphenyl groups on the properties of poly(fluorenylidene piperidinium) based anion exchange membranes for applications to water electrolyzers","authors":"Ahmed Mohamed Ahmed Mahmoud, Kenji Miyatake, Fanghua Liu, Vikrant Yadav, Fang Xian, Lin Guo, Chun Yik Wong, Toshio Iwataki, Makoto Uchida, Katsuyoshi Kakinuma","doi":"10.1039/d5py00210a","DOIUrl":"https://doi.org/10.1039/d5py00210a","url":null,"abstract":"A series of quaternized poly(arylene fluorenylidene piperidinium)-based copolymers were synthesized using different hydrophobic components, including biphenyl, m- or p-terphenyl, and 9,9-dimethylfluorenyl groups. Among them, the quaternized poly(biphenylene fluorenylidene piperidinium) had the best solvent solubility and membrane formability. Transmission electron microscopy showed that poly(biphenylene fluorenylidene piperidinium) (QBPh-Pip) had a well-interconnected nanoscale phase-separated morphology. The QBPh-Pip membrane with an ion exchange capacity of 1.9 mequiv. g−1 exhibited the most balanced properties, with low water uptake (95% at 80°C), low swelling (45%), and high hydroxide ion conductivity (160 mS cm−1 at 80°C). Despite the low water absorption, rapid ion mobility led to high ion conductivity, as calculated using normalized diffusion coefficients. Furthermore, the QBPh-Pip membrane exhibited excellent alkaline stability (91.5% (141 mS cm-1) of the initial conductivity after 1,000 h in 8 M potassium hydroxide at 80°C) and excellent mechanical properties (29.0 MPa of maximum stress and 134% elongation at break). In a water electrolysis cell using a nickel iron oxide anode catalyst, the QBPh-Pip membrane achieved a low cell voltage (1.7 V at 1.0 A cm−2) with 72% efficiency. The QBPh-Pip cell was durable for 1,000 h at a constant current density of 1.0 A cm−2 with minor voltage decay of 70 μV h−1.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"47 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703318","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":"Effect of Fluorine Substitution on Tetraphenylethene-Benzothiadiazole Based AIE-active Copolymers","authors":"Chih-Hsien Chen, Yen-Ting Cao, Yi-Ting Ou, Man-Hsin Hsieh","doi":"10.1039/d5py00049a","DOIUrl":"https://doi.org/10.1039/d5py00049a","url":null,"abstract":"The influence of fluorine substitution on the aggregation-induced emission enhancement of alternating tetraphenylethene-benzothiadiazole copolymers pBTPE and pBFTPE is investigated. The presence of difluorobenzothiadiazole in pBFTPE significantly enhances the intensity of emission upon aggregation, whereas pBTPE without fluorinated substituents exhibits relatively weak aggregation-enhanced emission. Furthermore, both TEM image and 2-D GIWAXS reveal denser packing for pBFTPE. The fluorine atoms on the polymer backbone may promote more pronounced inter-polymer interactions, improving molecular packing and resulting in conformational difference. It may dictate the nature of aggregation between polymers and resulting photophysical behavior.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703317","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 water-soluble, highly branched arborescent poly(acrylate)s: a colloid-macromolecule chimera","authors":"Jonas Quandt, Rustam A. Gumerov, Timon Kratzenberg, Max Hohenschutz, David Kulczycki, Walter Richtering, Igor Potemkin, Cesar Rodriguez-Emmenegger","doi":"10.1039/d5py00104h","DOIUrl":"https://doi.org/10.1039/d5py00104h","url":null,"abstract":"Arborescent (dendrigraft) polymers are high-molecular-weight dendritic macromolecules with a regular, multilevel branched topology and a high density of functional end groups in their periphery. Their well-defined architecture, devoid of cross-links or loops, imparts a particle-macromolecule duality that becomes particularly pronounced at interfaces. However, the underlying mechanisms governing their interfacial behavior remain largely unexplored. Here, we elucidate how the unique topology dictates the interfacial organization of water-soluble arborescent polymers. Using an iterative grafting-from approach via single-electron transfer living radical polymerization, we synthesized narrowly dispersed polymers with controlled branching and ultra-high molecular weight of 6.2·10⁶ g·mol⁻¹. These polymers transition from spherical rigid particles in solution, to highly flexible, two-dimensional conformations upon interfacial adsorption. At solid interfaces, increasing segment density shifts surface morphologies from quasi-2D discs to fried-egg-like structures, as observed by atomic force microscopy and corroborated by dissipative particle dynamics simulations. At liquid-liquid interfaces, the absence of substrate constraints facilitates complete spreading into uniform 2D discs, driven by the energy gain due to polymer-segment adsorption. Furthermore, we uncover that macromolecular crowding and topological constraints inherent to the arborescent architecture dictate the response to compression of the adsorbed polymer layer, contrasting sharply with the behavior of conventional flexible linear or star polymers. The combination of high interfacial activity, spatially adaptable end groups, and extreme molecular flexibility will enable arborescent polymers to adapt to complex interfaces, acting as versatile platform for multivalent and superselective interactions. These properties open new avenues for designing multivalent nanocarriers and adaptive interfacial materials with cooperative binding effects.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695113","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":"Tunable Organo-catalysed Ring-opening Polymerization of ω-Dodecalactone Macrolactone by Cyclic Triphosphazene Base","authors":"Rui Han, Xiangyu Miao, Dongfang Zhao, Zheng Li, Zhibo Li","doi":"10.1039/d5py00001g","DOIUrl":"https://doi.org/10.1039/d5py00001g","url":null,"abstract":"Degradable aliphatic long-chain polyesters (ALCPEs) with properties comparable to polyolefins are desirable as alternative substitute for polyethylene. The preparation of ALCPEs by ring-opening polymerization (ROP) of macrolactones has the advantages of atom economy and controllable molecular weight in contrast to the polycondensation strategy. ω-Dodecalactone (DDL) is a derivative from the terpolymerization of 1, 3-butadiene and has the potential to be produced on a large scale. Here, we demonstrated that the organobase cyclic triphosphazene base (CTPB) can serve as an efficient catalyst for the ROP of DDL. A high conversion of 95% can be achieved in less than 50 min at 80 °C and 1.0 M monomer concentration. Moreover, the ROP of DDL at 80 °C showed first-order kinetics and exhibited a controlled ROP behavior. Poly(ω-dodecalactone-block-L-lactide) (PDDL-b-PLLA) block copolymers were obtained by sequential addition of DDL and L-lactide (L-LA), and validated by NMR, DSC, and GPC. The synthesized poly(ω-dodecalactone-random-ε-caprolactone) (PDDL-r-PCL) random copolyester have adjustable melting point (Tm). The PDDL-b-PCL block copolymer was also successfully obtained by reducing the basicity of CTPB by adding benzoic acid to decrease the activity of CTPB. The present work provides an efficient catalytic system for the facial synthesis of degradable ALCPEs materials via ROP of DDL.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695114","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":"Polymer-metal nanocomposites with bi- or tri-metallic compositions exhibiting catalytic properties","authors":"Nicholas Kai Shiang Teo, Yi Huang, San Thang","doi":"10.1039/d5py00113g","DOIUrl":"https://doi.org/10.1039/d5py00113g","url":null,"abstract":"Heterogenous catalysis using hybrid materials such as polymer-metal nanocomposites (PMNCs) are rapidly gaining attention in recent years for their enhanced catalytic performance due to their significantly different physicochemical properties compared to their larger counterparts. Traditional techniques of preparing PMNCs uses capping/stabilising agents which wraps around metal nanoparticles (MNPs), forming a barrier that limit active site availability and reduce catalytic efficiency. This paper presents an approach to prepare gold (Au), palladium (Pd) and silver (Ag)-based PMNCs in situ via ultrasonic treatment with unobstructed MNPs attached to amine functionalities located on the surface of polymeric chains synthesised from reversible addition−fragmentation chain-transfer (RAFT) polymerisation-induced self-assembly (RAFT-PISA). High resolution transmission electron microscopy (HR-TEM) imaging and energy-dispersive x-ray (EDX) mapping confirmed the successful preparation of these PMNCs. The catalytic performances of these PMNCs are evaluated against well-known organic reactions such as 1-phenylethanol aerobic oxidation and the Suzuki-Miyaura cross-coupling reaction between 4-iodophenol and phenylboronic acid, where the performance of the bimetallic Au-Pd PMNC and the bimetallic Ag-Au PMNC reached as high as 94% and 98.5% for each respective reaction at 0.02 mol% concentration. Additionally, the catalytic performance of the trimetallic Ag-Au-Pd PMNC was discovered to be 39.8% and 96.0% respectively for both reaction at the same concentration. This work aims to expand on the knowledge of PMNCs and promote their utility as advanced heterogenous catalysts in organic reactions.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695115","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":"Towards degradable and functionalizable polymers: alternating ring-opening metathesis copolymerization of oxanorbornadiene dicarboxylate and 2,3-dihydrofuran†","authors":"Tarek Ibrahim, Kaia Kendzulak, Syrena Carver, Tamara Perez and Hao Sun","doi":"10.1039/D5PY00176E","DOIUrl":"10.1039/D5PY00176E","url":null,"abstract":"<p >Here we report the design and synthesis of acid-degradable and functionalizable polymers <em>via</em> alternating ring-opening metathesis copolymerization of oxanorbornadiene dicarboxylate and 2,3-dihydrofuran. The resulting polymers can undergo post-polymerization modification through aza-Michael and thia-Michael additions, leading to a diverse set of degradable polymer structures with various functional groups and tunable properties.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 15","pages":" 1647-1652"},"PeriodicalIF":4.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695086","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":"The origin of the thermally stable white-light emission property of POSS-conjugated polymer hybrid films","authors":"Satoru Saotome, Masayuki Gon, Kazuo Tanaka","doi":"10.1039/d5py00144g","DOIUrl":"https://doi.org/10.1039/d5py00144g","url":null,"abstract":"We have previously reported thermally stable white-light luminescence from polymer hybrid films consisting of tetraphenylethene (TPE)-tethered polyhedral oligomeric silsesquioxane (POSS) and poly(1,4-phenylenevinylene) (PPV). We observed that the intensity ratios between the dual emission bands from the POSS and the conjugated polymer, and thus the color balance, were maintained even in the higher-temperature region. In this paper, the origin of the thermally stable dual-emission properties of these white-light-emitting hybrid films is investigated using a series of POSS derivatives with different tethered luminophores and various conjugated polymer matrices. We obtained homogeneous hybrid films and revealed that one of the key factors for the expression of dual-emission properties is the relationship between the photoluminescence quantum yields of the energy donors (fillers) (<em>Φ</em><small>_D</small>) and acceptors (polymers) (<em>Φ</em><small>_A</small>). When the emission quantum yield of either the donor or acceptor molecules is high, only an emission band originating from the molecule with the higher emission quantum yield can be observed. Dual emission from both the donor and acceptor is detectable only when the <em>Φ</em><small>_D</small> is as high as the <em>Φ</em><small>_A</small> or slightly higher than the <em>Φ</em><small>_A</small>. Based on these findings, we have demonstrated a logical design for dual-emissive materials. We also found that the affinity between POSS and polymers is responsible for maintaining the emission color balance at high temperatures. It was observed that POSS substituted with bulky groups can hybridize with conjugated polymer chains, and that the thermal behavior of the polymer is dominated by the POSS. As a result, the thermal stability can be enhanced. We revealed the origin of the thermally stable white-light luminesce properties of POSS hybrids based on two aspects.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666397","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}