Polymer Chemistry最新文献

{"title":"Tunable organo-catalysed ring-opening polymerization of ω-dodecalactone macrolactone by the cyclic triphosphazene base†","authors":"Rui Han ,&nbsp;Xiangyu Miao ,&nbsp;Dongfang Zhao ,&nbsp;Zheng Li ,&nbsp;Zhibo Li","doi":"10.1039/d5py00001g","DOIUrl":"10.1039/d5py00001g","url":null,"abstract":"<div><div>Degradable aliphatic long-chain polyesters (ALCPEs) with properties comparable to polyolefins are desirable as alternative substitutes 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 of 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 follows first-order kinetics. Poly(ω-dodecalactone-<em>block</em>-<span>l</span>-lactide) (PDDL-<em>b</em>-PLLA) block copolymers were obtained by the sequential addition of DDL and <span>l</span>-lactide (<span>l</span>-LA) and validated by NMR, DSC, and GPC. The synthesized poly(ω-dodecalactone-<em>random</em>-ε-caprolactone) (PDDL-<em>r</em>-PCL) random copolyester has an adjustable melting point (<em>T</em>_m). The PDDL-<em>b</em>-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 facile synthesis of degradable ALCPE materials <em>via</em> the ROP of DDL, which is beneficial for promoting the large-scale production of ALCPEs.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 17","pages":"Pages 1939-1948"},"PeriodicalIF":4.1,"publicationDate":"2025-03-19","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":"Synthesis of water-soluble, highly branched arborescent poly(acrylate)s: a colloid-macromolecule chimera†","authors":"Jonas Quandt ,&nbsp;Rustam A. Gumerov ,&nbsp;Timon Kratzenberg ,&nbsp;Max Hohenschutz ,&nbsp;David Kulczycki ,&nbsp;Walter Richtering ,&nbsp;Igor I. Potemkin ,&nbsp;Cesar Rodriguez-Emmenegger","doi":"10.1039/d5py00104h","DOIUrl":"10.1039/d5py00104h","url":null,"abstract":"<div><div>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 <em>via</em> 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 platforms for multivalent and superselective interactions. These properties open new avenues for designing multivalent nanocarriers and adaptive interfacial materials with cooperative binding effects.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 17","pages":"Pages 2007-2022"},"PeriodicalIF":4.1,"publicationDate":"2025-03-19","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":"Polymer–metal nanocomposites with bi- or tri-metallic compositions exhibiting catalytic properties†","authors":"Nicholas Kai Shiang Teo ,&nbsp;Yi Huang ,&nbsp;San H. Thang","doi":"10.1039/d5py00113g","DOIUrl":"10.1039/d5py00113g","url":null,"abstract":"<div><div>The use of hybrid materials such as polymer–metal nanocomposites (PMNCs) in heterogeneous catalysis has rapidly gained attention in recent years due to their enhanced catalytic performance and significantly different physicochemical properties compared to their larger counterparts. Traditional techniques for preparing PMNCs involve the use of capping/stabilising agents that wrap around metal nanoparticles (MNPs), forming a barrier that limits active site availability and reduces catalytic efficiency. This paper presents an approach for preparing gold (Au), palladium (Pd) and silver (Ag)-based PMNCs <em>in situ via</em> 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 the aerobic oxidation of 1-phenylethanol 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 a concentration of 0.02 mol%. Additionally, the catalytic performance of the trimetallic Ag–Au–Pd PMNC was discovered to be 39.8% and 96.0%, respectively, for both reactions at the same concentration. This work aims to expand the knowledge of PMNCs and promote their utility as advanced heterogeneous catalysts in organic reactions.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 17","pages":"Pages 1969-1980"},"PeriodicalIF":4.1,"publicationDate":"2025-03-19","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":"Effect of fluorine substitution on tetraphenylethene-benzothiadiazole based AIE-active copolymers†","authors":"Chih-Hsien Chen ,&nbsp;Yen-Ting Cao ,&nbsp;Yi-Ting Ou ,&nbsp;Man-Hsin Hsieh","doi":"10.1039/d5py00049a","DOIUrl":"10.1039/d5py00049a","url":null,"abstract":"<div><div>The influence of fluorine substitution on the aggregation-induced emission enhancement of alternating tetraphenylethene–benzothiadiazole copolymers and is investigated. The presence of difluorobenzothiadiazole in significantly enhances the intensity of emission upon aggregation, whereas without fluorinated substituents exhibits relatively weak aggregation-enhanced emission. Furthermore, both the TEM image and 2-D GIWAXS reveal a denser packing for . The fluorine atoms on the polymer backbone may promote more pronounced inter-polymer interactions, improving molecular packing and resulting in a conformational difference. It may dictate the nature of aggregation between polymers and the resulting photophysical behavior.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 17","pages":"Pages 1961-1968"},"PeriodicalIF":4.1,"publicationDate":"2025-03-19","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":"Facile synthesis of functionalized high vinyl polybutadiene by using 1,2-dipiperidinoethane derivatives as polar modifiers†","authors":"Qiqi Dai ,&nbsp;Yao Long ,&nbsp;Xupeng Han ,&nbsp;Yang Yang ,&nbsp;Yi Yang ,&nbsp;Yawen Fu ,&nbsp;Wenjun Yi ,&nbsp;Xiaoxing Gu ,&nbsp;Kun Liu ,&nbsp;Lijun Li","doi":"10.1039/d5py00227c","DOIUrl":"10.1039/d5py00227c","url":null,"abstract":"<div><div>Polydiene-based liquid rubber can be used to prepare high-frequency copper-clad plates, and it is also the most critical raw material for photosensitive elastomers used in flexible resin plates. The molecular structure control requirements of high-performance liquid rubber are very high, and special living anionic initiation systems and polymerization processes need to be developed to achieve stable control of the product structure. In this study, a series of novel polar modifiers were synthesized by introducing alkyl substituents and N/O-containing heteroatoms into the cycloamine ring (1,2-dipiperidinoethane (DPE) derivatives). High vinyl polybutadiene (90% &lt; 1,2-units &lt; 99%) with quantitative tertiary-amine functionalization (0%–25% molar ratio) was synthesized by <em>in situ</em> copolymerization using 4-dimethylaminomethylstyrene (VBA) as a comonomer. The polymerization process has obvious characteristics of being controllable and living under mild conditions. The fine structure of the product was analyzed by ¹H NMR, FTIR, GPC, and DSC. <em>In situ</em> anionic copolymerization provides a new way for developing high-performance liquid rubber.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 17","pages":"Pages 1997-2006"},"PeriodicalIF":4.1,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654032","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":"Reviving recovered carbon black as a reinforcement for natural rubber by utilizing acylhydrazine-functionalized polysulfide as an intelligent interfacial modifier†","authors":"Senmao Yu ,&nbsp;Zhenghai Tang ,&nbsp;Dong Wang ,&nbsp;Siwu Wu ,&nbsp;Fei Chen ,&nbsp;Baochun Guo ,&nbsp;Liqun Zhang","doi":"10.1039/d5py00111k","DOIUrl":"10.1039/d5py00111k","url":null,"abstract":"<div><div>Recovered carbon black (rCB), a regenerative product from the thermal pyrolysis of waste tires, can be reused as a reinforcement for rubbers, with the goal of achieving high-value utilization of resources and promoting sustainable development. However, the inert surface of rCB causes poor compatibility with rubbers and results in low reinforcement efficiency. In this work, we synthesized acylhydrazine-functionalized polysulfide (SPT) and utilized it as an interfacial modifier for demineralized rCB (drCB)-filled natural rubber (NR) composites. SPT was synthesized through a one-pot sequential copolymerization of sulfur, styrene and thioctic acylhydrazine. The acylhydrazine moieties of SPT have multiple interactions with the oxygen-containing groups on the drCB surface, while the polysulfide segments are able to graft onto NR chains, thereby creating a molecular bridge between drCB and NR. Morphological and interfacial studies show that drCB dispersion is remarkably improved and interfacial adhesion is greatly enhanced upon the addition of SPT. As a consequence, the reinforcement efficiency of drCB is improved and the hysteresis loss of the resulting composites is significantly decreased.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 17","pages":"Pages 1949-1960"},"PeriodicalIF":4.1,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660669","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":"Revisiting polymer coatings on nanoparticles: correlation between molecular weight and coating thickness in chain transfer polymerizations†","authors":"Daniel Döpping, Andreas Stihl, Dominik Voll, Felix H. Schacher and Patrick Théato","doi":"10.1039/D5PY00081E","DOIUrl":"10.1039/D5PY00081E","url":null,"abstract":"<p >Various poly(methyl methacrylate) (PMMA) and poly(acrylonitrile) (PAN) coated silica nanoparticles were synthesized <em>via</em> chain transfer polymerization with the goal to assess the coating behavior and characterization of polymer coated silica nanoparticles with monomers of different reactivities. The particles were characterized by TGA, EDXS, TEM and correlated to the free PMMA/PAN formed in the crude reaction mixture characterized with SEC. It was found that the mass loss observed in TGA and coating thickness obtained from TEM micrographs correlate strongly with the average polymer chain-length in the crude reaction mixture.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 18","pages":" 2075-2082"},"PeriodicalIF":4.1,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d5py00081e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640364","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ring-opening metathesis polymerization of (oxa)norbornenes with sulfonate, sulfone, and sulfoxide sidechains†","authors":"Oliver Paul Clarke ,&nbsp;Abdulrahman Bashir ,&nbsp;Sophie Wazlowski ,&nbsp;Sara Ptaszynska ,&nbsp;Brian Hale Northrop ,&nbsp;Benjamin Ross Elling","doi":"10.1039/d4py01307g","DOIUrl":"10.1039/d4py01307g","url":null,"abstract":"<div><div>Sulphur-containing polymers are utilized in applications ranging from vulcanized rubbers to optical materials and proton conducting membranes. Typically, sulphur-containing polymers are synthesized <em>via</em> condensation methods. While ring-opening metathesis polymerization is a useful tool for polymerizing functional monomers, previous reports have shown difficulties incorporating sulphur-containing functional groups due to Ru–S interactions. In this work, we report the synthesis and polymerization of a number of poly(oxa)norobornenes containing sulfonate, sulfone, and sulfoxide sidechains. We demonstrate the effects of the identity of the bridge group, sidechain R groups, and substituent stereochemistry on polymerization rates, molecular weight distributions, and thermal properties. Interestingly, while the <em>exo</em>-norbornene phenyl sulfoxide monomer was effectively polymerized, the <em>endo</em> isomer resulted in exclusive single addition to the Ru catalyst due to sulphur chelation to the metal centre. This monomer could however be used for alternating copolymerization with other cyclic olefins.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 15","pages":"Pages 1653-1658"},"PeriodicalIF":4.1,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654031","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 lactate amide acrylic polymers developed from PLA bags†","authors":"Marc Palà ,&nbsp;Alina Ismagilova ,&nbsp;Adrian Moreno ,&nbsp;Jorge Plaza ,&nbsp;Juan C. Ronda ,&nbsp;Marina Galià ,&nbsp;Lauri Vares ,&nbsp;Gerard Lligadas","doi":"10.1039/d5py00070j","DOIUrl":"10.1039/d5py00070j","url":null,"abstract":"<div><div>The growing global demand for sustainable products, driven by the depletion of fossil resources and mounting environmental concerns, has amplified interest in transforming lignocellulosic biomass into bio-based solvents, fine chemicals, and polymers. Among these, lactic acid has emerged as a pivotal platform chemical for synthesizing high-value derivatives. The chemical depolymerization of polylactic acid (PLA) into lactate esters and amides represents a straightforward and efficient strategy for upcycling PLA waste into specialty polymers. In this study, we developed a mini-library of lactate amide-based acrylic monomers using commercially available PLA bags as feedstock. These monomers were polymerized into homo, statistical, and block copolymers <em>via</em> Cu(<span>ii</span>)Br₂/Me₆TREN-mediated polymerization under UV light. The resulting polymers exhibited water solubility adjustable through amide <em>N</em>-substitution combined with low ecotoxicity. This innovative approach not only advances sustainable PLA waste management but also opens new possibilities for designing advanced thermoresponsive polymers with single or double phase separation behaviors—an underexplored frontier in biobased synthetic polymer research.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 15","pages":"Pages 1692-1703"},"PeriodicalIF":4.1,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143507204","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":"Developing conjugated polymers with broad-band absorption covering visible and near-infrared regions for electrochromism†","authors":"Guoqiang Kuang ,&nbsp;Hongbin Yin ,&nbsp;Chenming Li ,&nbsp;Yijie Tao ,&nbsp;Yafei Guo ,&nbsp;Shiguo Zhang","doi":"10.1039/d4py01461h","DOIUrl":"10.1039/d4py01461h","url":null,"abstract":"<div><div>Conjugated polymers containing donor (D) and acceptor (A) units exhibit intramolecular charge transfer (ICT), which results in lower bandgaps and facilitates a red shift of the absorption peaks. Utilizing the conjugated backbone structure and ICT mechanisms, several D–A-type polymers were designed and synthesized using thiophene, strong fused-ring thiophene donors (IDT or IDTT), ultrastrong acceptor units (benzobisthiadiazole derivatives (SNT) or benzothiadiazolo[3,4-<em>g</em>]quinoxaline (TQX)), and acceptor benzothiadiazole (TZ) as the building blocks for constructing broad-band absorption electrochromic polymers. The incorporation of SNT (or TQX) units into the polymer chain induces the near-infrared (NIR) modulation, while the combination of TZ units fulfils long-wave visible absorption for synergistic visible and near-infrared modulation of the polymers. Consequently, the synthesized polymers and derived electrochromic devices demonstrate ultra-broad electrochromism from 350 nm to 1000 nm with high optical contrast, swift switching response, and good stability, which show great application potential in smart windows.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 15","pages":"Pages 1659-1668"},"PeriodicalIF":4.1,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546979","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}