Polymer Chemistry最新文献

{"title":"Solvent and temperature effects in the photoiniferter RAFT polymerisation of PEG methacrylate†","authors":"Roujia Chang ,&nbsp;Bryn D. Monnery ,&nbsp;Inge S. Zuhorn","doi":"10.1039/d5py00300h","DOIUrl":"10.1039/d5py00300h","url":null,"abstract":"<div><div>Photoiniferter (PI)-RAFT polymerization is a promising approach to synthesise a broad range of (meth)acrylic and styrenic polymers because of its highly ‘living’ nature. The lack of an imbalance between initiating and chain-transfer fragments minimises the inherent bimolecular termination of conventional RAFT. Poly(poly(ethylene glycol) methyl ether methacrylate) (P(PEGMA)) is a potential biocompatible material for biomedical applications, but the highly reactive free radical of PEGMA makes control of its polymerisation challenging. In this study, we investigated the synthesis of P(PEGMA) through PI-RAFT. Current studies on the PI-RAFT mechanisms are limited and the effect of solvents on kinetics has not been reported. We varied several reaction conditions: excitation wavelengths, monomer concentrations, temperatures, and solvents. The propagation constant (<em>k</em>_p) values were affected by the RAFT main equilibrium. We calculated the Arrhenius parameters, enthalpy of activation (Δ<em>H</em>^‡), and entropy of activation (Δ<em>S</em>^‡) for polymerization in various solvents. Regression analysis was conducted to fit the results with extinction coefficients of CTA in seven common solvents, solvent physical properties, and solvatochromic scales. The effective collision factor <em>A</em> had a good fitting with an exponential regression model of the extinction coefficients, indicating a strong relationship between the reaction rate and excitation of the CTA. Solvent polarity scales, such as Kalmet–Abraham–Taft (KAT) and Catalan parameters, failed to predict <em>k</em>_p, Arrhenius parameters, Δ<em>H</em>^‡, and Δ<em>S</em>^‡. A chain transfer constant <em>C</em>_tr &gt; 1 for all syntheses indicated relatively good control over the polymerization through degenerative chain transfer with CTA radicals. In general, <em>C</em>_tr decreased with increasing temperatures, a result of the rate of excitation by photon absorption being constant, but the <em>k</em>_p being increased by the temperature. Anisole was the best solvent, able to keep <em>Đ</em> = 1.30 even at 40 °C.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 25","pages":"Pages 2952-2961"},"PeriodicalIF":4.1,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154087","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":"Supramolecular polymerization and self-assembly of transition metal complexes","authors":"Merlin R. Stühler ,&nbsp;Alex J. Plajer","doi":"10.1039/d5py00315f","DOIUrl":"10.1039/d5py00315f","url":null,"abstract":"<div><div>Metallo-supramolecular polymers (MSPs) have emerged as a dynamic field in soft materials and nanomaterials over the past three decades. The unique interplay of ligands and metal ions plays a crucial role in defining their properties, such as binding strength and topology, making these systems distinct from their all-organic counterparts. Furthermore, the incorporation of metal centers introduces redox activity, unique photophysical properties, and electronic functionality. As a result, these systems can exhibit stimuli-responsive behavior, essential for applications in optoelectronics and biology. However, challenges remain in achieving precise control over self-assembly, morphology, and spatiotemporal responsiveness, as well as a clear rationale between coordination and self-assembly behavior. Our review, therefore, summarizes recent advances in ligand design, coordination modulation, and polymerization techniques, offering new strategies to rationally develop MSPs with tailored functionalities.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 24","pages":"Pages 2799-2810"},"PeriodicalIF":4.1,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104079","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":"Tuning the linkage microenvironment in imine-based covalent organic frameworks for enhanced photocatalytic hydrogen production†","authors":"Hao Li ,&nbsp;Bin Zheng ,&nbsp;Ming Wang ,&nbsp;Xiaofang Su ,&nbsp;Hui Hu ,&nbsp;Jianyi Wang ,&nbsp;Huanjun Xu ,&nbsp;Jingying Shi ,&nbsp;Yanan Gao","doi":"10.1039/d5py00361j","DOIUrl":"10.1039/d5py00361j","url":null,"abstract":"<div><div>Rational design of covalent organic frameworks (COFs) at the molecular level is necessary to improve the photocatalytic hydrogen evolution (PHE) performance. Herein, a photosensitive two-dimensional (2D) COF, namely Im_TF–PD, is first constructed through the condensation of 1,3,6,8-tetra(4-formylphenyl)pyrene (TFPPy) and <em>p</em>-phenylenediamine (PD) under solvothermal conditions. The photocatalytic activity of Im_TF–PD is regulated by transforming imine linkages into quinoline through the Povarov reaction between the imine groups and phenylacetylene and 4-ethynylbenzonitrile, respectively. Such a post-synthetic modification (PSM) process enables the modulation of π-conjugation and simultaneously the introduction of the electron-deficient nitrile group improves the local electron delocalization of the skeleton of Im_TF–PD. As a result, the modified quinoline based COF (Qu-CN) exhibited outstanding and steady hydrogen production with a maximum hydrogen production rate of 245.17 mmol g⁻¹ h⁻¹ under visible-light irradiation (<em>λ</em> ≥ 420 nm). Experimental and computational results revealed that Qu-CN with better electron–hole separation and lower band gap significantly improved the catalytic activity regarding kinetics and thermodynamics. This study reveals that enhancing π-conjugation and tuning the local electronic environment of COF-based photocatalysts provide a convenient and effective approach for the development of new efficient photocatalysts.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 24","pages":"Pages 2870-2877"},"PeriodicalIF":4.1,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145872","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":"Yttrium-mediated ring-opening polymerization of functionalizable dihydrocarvide: tunable terpene-based polyesters using grafting from and block copolymerization strategies†","authors":"Lea-Sophie Hornberger ,&nbsp;Julian Fischer ,&nbsp;Alexandra Friedly ,&nbsp;Ingo Hartenbach ,&nbsp;Thomas Sottmann ,&nbsp;Friederike Adams","doi":"10.1039/d5py00322a","DOIUrl":"10.1039/d5py00322a","url":null,"abstract":"<div><div>Poly(dihydrocarvide) (PDHC) is synthesized through ring-opening polymerization (ROP) of terpene-based 7-membered lactone dihydrocarvide (DHC) using an amino-alkoxy-bis(phenolate) yttrium amido catalyst and isopropanol (iPrOH) as a chain transfer agent while retaining the pendant-group double bond in the monomer unit. Polymerization under conditions found to be favorable (60 °C, 1 eq. iPrOH) yielding PDHC with tunable molecular weights and low to moderate polydispersities (<em>Đ</em> = 1.2–1.5). Crystalline fractions are introduced into amorphous PDHC by producing block copolymers with 16-membered ω-pentadecalactone (PDL) or 4-membered racemic β-butyrolactone (BBL) <em>via</em> sequential addition following the coordination strength hierarchy (PDL &lt; DHC &lt; BBL). This resulted in semi-crystalline renewable block copolymers P(PDL-<em>b</em>-DHC) and P(DHC-<em>b</em>-PHB) that were further analyzed by PXRD and SAXS measurements. Additionally, PDHC is functionalized <em>via</em> thiol–ene reaction with 2-mercaptoethanol, introducing hydroxyl functionality and opening up a multitude of functionalization possibilities. As one example, atom transfer radical polymerization (ATRP) initiators are attached, and SARA and ARGET ATRP techniques are employed to graft poly(ethyl acrylate) (PEA) as model compound, forming PDHC-<em>g</em>-PEA brush polymers. The TPMA^NMe₂-based ARGET ATRP system demonstrates superior control over molecular weight and polydispersity compared to SARA ATRP, though both methods yield well-defined polymer brushes with molecular weight growth correlating with the initial amount of ethyl acrylate. This approach demonstrates the potential of PDHC for constructing diverse polymer architectures from different types of lactones or vinyl monomers by combining ROP and ATRP.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 25","pages":"Pages 2910-2922"},"PeriodicalIF":4.1,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933282","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":"5-Ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) based alicyclic polyols for the synthesis of polyesters†","authors":"Brigita Bratić ,&nbsp;Peter Altenbuchner ,&nbsp;Thomas Heuser ,&nbsp;Bernhard Rieger","doi":"10.1039/d5py00247h","DOIUrl":"10.1039/d5py00247h","url":null,"abstract":"<div><div>Amorphous polyesters derived from rigid alicyclic monomers with high glass transition temperatures are of great interest as potential substitutes for poly(carbonate)s. Therefore, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) were identified as interesting diol monomer precursors to enhance the thermal properties of polyesters. The regioselective synthesis of the corresponding diols from ENB and VNB was optimized and the first scale-up experiments gave promising results for a potential large-scale production of these polyester monomers. Moreover, for proof of concept, an alternative procedure was established to synthesize exclusively <em>branched</em> diols. Polymerization experiments were conducted with dimethyl terephthalate (DMT) as a model compound to compare the polyesters with commonly used poly(ethylene terephthalate)s. Therefore, a series of polyesters containing <em>branched</em> or <em>linear</em> regioisomers or a mixture of both regioisomers were produced, and structure–property relationships were investigated using GPC, TGA and DSC analyses. The <em>T</em>_g values ranged from 75 to 103 °C, depending on the <em>branched</em> and <em>linear</em> moieties in the polyester microstructure and their molecular weights. Moreover, isosorbide (IS) was introduced as a biobased comonomer, resulting in amorphous copolyesters with promising <em>T</em>_gs ranging from 81 to 97 °C.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 25","pages":"Pages 2933-2942"},"PeriodicalIF":4.1,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104077","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":"Impact of imine bonds on the electronic properties of degradable carotenoid-based conjugated polymers†","authors":"Azalea Uva ,&nbsp;Yaejin Kim ,&nbsp;Sofia Michailovich ,&nbsp;Nathan S. Y. Hsu ,&nbsp;David C. Bain ,&nbsp;Shine H. Huang ,&nbsp;Andrew J. Musser ,&nbsp;Helen Tran","doi":"10.1039/d5py00235d","DOIUrl":"10.1039/d5py00235d","url":null,"abstract":"<div><div>Carotenoids are suitable building blocks for degradable π-conjugated polymers due to their intrinsic single-molecule conductance and well-documented degradation pathways. Previously, we reported a carotenoid-based polymer, p(CP-hexyl), which incorporated a cleavable imine linker enabling degradation <em>via</em> acid hydrolysis or sunlight; however, there was limited insight into its electronic properties. In this current study, we compare the optoelectronic and photophysical properties of p(CP-hexyl) with a structural analog, caro-PPV, which replaces the imine bonds with vinylene groups, to improve charge transport while maintaining degradability. Ultraviolet–visible spectroscopy, density functional theory, and transient absorption spectroscopy provided a comprehensive understanding of these polymers’ optoelectronic properties. Further, chemical doping and oxidative degradation were evaluated using FeCl₃ and trifluoroacetic acid, unveiling differences in radical formation and degradation mechanisms for both carotenoid-based polymers. Lastly, charge carrier mobility measurements in organic field-effect transistors unveiled caro-PPV's superior semiconductor performance, with mobilities 10³–10⁴ times greater than p(CP-hexyl). These findings highlight the potential of carotenoid monomers in the design of π-conjugated polymers for degradable electronics.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 24","pages":"Pages 2817-2828"},"PeriodicalIF":4.1,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866146","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":"Innovative synthesis of PPC-P-co-PLA multi-block copolymers via one-pot copolymerization and transesterification catalysed by alkyl boron and diverse Lewis bases†","authors":"Mei Meng ,&nbsp;Min Xiao ,&nbsp;Jintao Wang ,&nbsp;Peiyuan Li ,&nbsp;Xianli Wu ,&nbsp;Yuezhong Meng","doi":"10.1039/d5py00272a","DOIUrl":"10.1039/d5py00272a","url":null,"abstract":"<div><div>Carbon dioxide (CO₂) has been utilized for synthesizing biodegradable polymers to promote sustainable energy conservation and mitigate emissions. Nonetheless, the low glass transition temperature of amorphous CO₂-based polyester–polycarbonate (PPC-P) significantly impedes its practical application. Herein, semi-crystalline copolymers, PPC-P-<em>co</em>-PLA, were successfully synthesized <em>via</em> copolymerization of propylene oxide (PO), phthalic anhydride (PA), and CO₂ in combination with PLA through transesterification catalysed by Lewis acid–base pairs in a one-pot/one-step method. Metal-free catalysts were utilized for the first time to catalyse both ring-opening copolymerization and transesterification reactions for copolymer synthesis. The mechanism study of PLA transesterification catalysed by triethyl borane (TEB)/Lewis bases revealed that effective depolymerization and transesterification of PLA hinge on α-H chemical shift alterations induced by the Lewis bases. Lewis acid–base pairs facilitate the formation of PPC-P-<em>co</em>-PLA multi-block copolymers by terminating one end of PPC-P with PLA segments <em>via</em> continuous transesterification reactions. Compared to PPC-P, the copolymers exhibit an increase in glass transition temperature by 5–7 °C and an elevation in thermal decomposition temperature by 18–45 °C. The optimal mechanical and rheological properties of PPC-P-<em>co</em>-PLA multi-block copolymers are achieved at a PLA concentration of 8 wt%. This study opens new avenues for the synthesis of semi-crystalline polyester–polycarbonate-based copolymers with high glass transition temperatures, thereby enriching the theoretical foundation for the synthesis of block copolymers.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 24","pages":"Pages 2851-2869"},"PeriodicalIF":4.1,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144097063","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":"Preparation and properties of stretchable low temperature resistant flexible epoxy resin curing agent†","authors":"Hao Li ,&nbsp;Qiang Liu ,&nbsp;Yiming Du ,&nbsp;Yanyan Liu ,&nbsp;Wei Zhang ,&nbsp;Xingyou Tian ,&nbsp;Hua Wang","doi":"10.1039/d5py00254k","DOIUrl":"10.1039/d5py00254k","url":null,"abstract":"<div><div>Two innovative molecular design strategies for epoxy curing agents to address the inherent brittleness and cryogenic limitations of conventional epoxy systems are introduced. A silane-modified curing agent (DETA-Si) and a flexible-chain-engineered curing agent (NBO_<em>n</em>) were synthesized to achieve unprecedented mechanical–electrical–thermal synergies. The DETA-Si/EP composite demonstrates a record-breaking elongation at break of 125% (22× improvement over unmodified systems) while maintaining ultralow dielectric loss (tan <em>δ</em> &lt; 0.04) and thermal stability (<em>T</em>_d = 236 °C). The NBO_<em>n</em> series, incorporating rigid benzene rings and tunable aliphatic chains, exhibits exceptional cryogenic resilience: 18% elongation at 298 K with &gt;50% ductility retention after 24-hour immersion in liquid nitrogen (77 K). Conductive composites cured with EP/NBO₁₀ show stable resistance (±5%) under 30-day cryogenic exposure. Free volume engineering, validated <em>via</em> WLF modeling, underpins the enhanced low-temperature performance. These advancements establish a paradigm for epoxy resins in flexible electronics operating under extreme conditions, such as flexible sensors and polar climate devices.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 24","pages":"Pages 2878-2886"},"PeriodicalIF":4.1,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145870","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":"Preparation of high-performance one-component polysulfide adhesives and modification by silane side chains†","authors":"Xu Han ,&nbsp;Le Chang ,&nbsp;Zeqian Wang ,&nbsp;Feng Liu","doi":"10.1039/d5py00314h","DOIUrl":"10.1039/d5py00314h","url":null,"abstract":"<div><div>One-component polysulfide adhesive preparation by diisocyanate-terminated prepolymers and 1,4-butanedithiol (BSO) can provide convenient moisture curing and excellent mechanical properties, but the formation of polysulfide-urea (–NHCOS–) groups causes some reduction in solvent resistance limiting their further application in aircraft fuel tank sealing. Introducing silane side chains into polysulfide adhesive systems is a viable approach to improving the solvent resistance. In this work, a series of novel silane side chain-modified one-component polysulfide adhesives were synthesized by using chain extenders in different proportions of BSO and (3-(2-aminoethyl)aminopropyl)trimethoxysilane (AEAPTMS). The results showed that a moderate amount of silane side chains and restricting the formation of Si–O–Si crosslinked networks can effectively enhance the elongation, interfacial interaction and solvent resistance. The optimal overall performance was obtained when the mass ratio of BSO and AEAPTMS was 7 : 1 (Si-OCPS3). Conversely, the oil and water absorption content after 21 days of Si-OCPS3 were 2.21 ± 0.06% and 2.81 ± 0.31%, being 20.50% and 43.57% lower than before modification (Si-OCPS0), respectively. Moreover, Si-OCPS3 exhibited higher tensile strength of 17.34 ± 0.66 MPa (oil) and 15.67 ± 0.32 MPa (water) than Si-OCPS0. We believe our paradigm can provide a feasible approach for designing high-performance one-component polysulfide adhesives.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 24","pages":"Pages 2887-2896"},"PeriodicalIF":4.1,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154088","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":"Photothermally-driven cobalt catalysed atom transfer radical polymerisation enables isocyanide copolymer synthesis†","authors":"Cristina Preston-Herrera ,&nbsp;Erin E. Stache","doi":"10.1039/d5py00422e","DOIUrl":"10.1039/d5py00422e","url":null,"abstract":"<div><div>Design and synthesis of degradable polymers is a burgeoning area of research to combat plastic waste buildup. Here, a cobalt-catalysed atom transfer radical polymerisation (ATRP) turned on by photothermal conversion is used to synthesize photodegradable non-alternating acrylate-isocyanide copolymers. A simple one-step protocol enables control over copolymerisation with good chain-end fidelity under mild conditions. Although fundamentally a ground state reaction, we demonstrate temporal control <em>via</em> a unique localized heating strategy. Lastly, we demonstrate the advantage of this polymerisation compared to more traditional ATRP protocols.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 24","pages":"Pages 2811-2816"},"PeriodicalIF":4.1,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177341","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}