Heterogeneous photocatalytic polymerization has emerged as a promising strategy for developing greener reversible complexation-mediated polymerization (RCMP) systems. In this study, a bio-based heterogeneous photocatalyst was prepared by anchoring betaine onto hydroxyethyl cellulose via esterification, aiming to address the drawbacks of homogeneous photo-RCMP systems and inorganic support catalysts, and thereby enabling photoinduced RCMP under white LED irradiation. This system enabled the synthesis of well-defined polymethacrylates with controlled molecular weights and narrow dispersity (Đ < 1.2). Upon light exposure, photoinduced energy transfer from the catalyst to alkyl iodide initiators promoted carbon-iodine bond cleavage, generating radicals to initiate polymerization. Density functional theory calculations revealed that electrostatic interactions between the iodide anion and the quaternary ammonium cation, together with halogen bonding between the catalyst and alkyl iodide, significantly lower the bond dissociation energy, thereby enhancing polymerization efficiency. Kinetic studies and light on/off experiments confirmed good temporal control, while chain-extension experiments demonstrated high chain-end fidelity. Furthermore, the photocatalyst exhibited broad monomer compatibility, retained over 90% of its activity after three recycling cycles, and performed effectively under natural sunlight. Overall, this work provides a sustainable and recyclable strategy for visible-light-induced RCMP by integrating renewable materials with efficient photocatalytic functionality.
{"title":"Bio-Based Cellulose-Supported Photocatalyst Enabling Reversible Complexation-Mediated Polymerization via Energy Transfer under White LED Irradiation","authors":"Huirong Li, Chen Zhou, Rui Zhao, Shumin Chen, Danni Tang, Longqiang Xiao, Linxi Hou","doi":"10.1039/d5py01228g","DOIUrl":"https://doi.org/10.1039/d5py01228g","url":null,"abstract":"Heterogeneous photocatalytic polymerization has emerged as a promising strategy for developing greener reversible complexation-mediated polymerization (RCMP) systems. In this study, a bio-based heterogeneous photocatalyst was prepared by anchoring betaine onto hydroxyethyl cellulose via esterification, aiming to address the drawbacks of homogeneous photo-RCMP systems and inorganic support catalysts, and thereby enabling photoinduced RCMP under white LED irradiation. This system enabled the synthesis of well-defined polymethacrylates with controlled molecular weights and narrow dispersity (Đ < 1.2). Upon light exposure, photoinduced energy transfer from the catalyst to alkyl iodide initiators promoted carbon-iodine bond cleavage, generating radicals to initiate polymerization. Density functional theory calculations revealed that electrostatic interactions between the iodide anion and the quaternary ammonium cation, together with halogen bonding between the catalyst and alkyl iodide, significantly lower the bond dissociation energy, thereby enhancing polymerization efficiency. Kinetic studies and light on/off experiments confirmed good temporal control, while chain-extension experiments demonstrated high chain-end fidelity. Furthermore, the photocatalyst exhibited broad monomer compatibility, retained over 90% of its activity after three recycling cycles, and performed effectively under natural sunlight. Overall, this work provides a sustainable and recyclable strategy for visible-light-induced RCMP by integrating renewable materials with efficient photocatalytic functionality.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"120 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489353","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}
Degradable aliphatic long-chain polyesters (ALCPEs), obtained from the ring-opening polymerization (ROP) of macrolactones (MLs), have emerged as a promising degraddable polymers, as they combine the mechanical and thermal properties of polyethylene with the degradability of polyesters. Herein, we report a highly efficient MeAl(BHT)2 catalyst for facile ROP of the bio-based macrolactone ω-pentadecalactone (PDL) and ω-dodecalactone (DDL). This system also enables the one-pot random copolymerization of MLs with ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL), allowing for good control of the melting temperature (Tm) of the resulting copolyesters over a range of 48-95 °C by adjusting the monomer feed ratios. More importantly, well-defined block copolymers such as PDDL-b-PLLA, PDDL-b-PCL, and PDDL-b-PVL can be prepared using a sequential monomer addition strategy. The structures and compositions of these polymers were confirmed by nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry (DSC), and gel permeation chromatography (GPC).
{"title":"Ring-opening (Co)Polymerization of Macrolactones Catalyzed by a Simple Organoaluminum Complex of MeAl(BHT)2","authors":"Rui Han, Zheng Li, Zhibo Li","doi":"10.1039/d6py00054a","DOIUrl":"https://doi.org/10.1039/d6py00054a","url":null,"abstract":"Degradable aliphatic long-chain polyesters (ALCPEs), obtained from the ring-opening polymerization (ROP) of macrolactones (MLs), have emerged as a promising degraddable polymers, as they combine the mechanical and thermal properties of polyethylene with the degradability of polyesters. Herein, we report a highly efficient MeAl(BHT)2 catalyst for facile ROP of the bio-based macrolactone ω-pentadecalactone (PDL) and ω-dodecalactone (DDL). This system also enables the one-pot random copolymerization of MLs with ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL), allowing for good control of the melting temperature (Tm) of the resulting copolyesters over a range of 48-95 °C by adjusting the monomer feed ratios. More importantly, well-defined block copolymers such as PDDL-b-PLLA, PDDL-b-PCL, and PDDL-b-PVL can be prepared using a sequential monomer addition strategy. The structures and compositions of these polymers were confirmed by nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry (DSC), and gel permeation chromatography (GPC).","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"2 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489352","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}
Sebastian Leeming, Samuel Fryer, Georgina L. Gregory
Conjugated polyelectrolytes (CPEs) combine ionic conductivity from tethered ionic groups with electronic conductivity from intrinsically-doped π-conjugated backbones, enabling applications in energy storage, bioelectronics, and neuromorphic computing. Conjugated block polyelectrolytes (CBEs), in which the conjugated and ionic functions are spatially segregated into distinct blocks, represent an emerging and underexplored variant of this materials class. Despite multiple studies of various pendant ionic groups, neither borate ionic functionalisation nor block copolymer architectures bearing non-sulfonate ionic groups have been explored. Here, we report CBEs, accessible through controlled Suzuki–Miyaura catalyst-transfer polymerisation (SCTP) and cyclic carbonate ring-opening polymerisation (ROP), incorporating alkali metal borate polycarbonate segments: poly(3-hexylthiophene)-block-poly(ethylene oxide-graft-poly(ethylene glycol))-block-polycarbonate bearing lithium, sodium, or potassium borate moieties. Systematic variation of P3HT chain length (DP = 35 and 110) and content (10–50 wt%) reveals distinct cation-dependent transport behaviour. Electrochemical characterisation via impedance spectroscopy, chronoamperometry, and linear sweep voltammetry demonstrates purely ionic conduction at low applied potentials, with p-type electronic transport activated above 1–1.5 V. Notably, lithium-ion conductivity remains independent of P3HT incorporation, whereas sodium transport improves with longer conjugated blocks and potassium conductivity is enhanced with shorter segments. Thermal analysis, DFT calculations, rheological and tensile measurements establish structure–property relationships linking polymer ionic networking to mechanical and ionic-electronic transport properties. These findings position anionic borate CBEs as a promising addition to the mixed ionic-electronic conductor platform, with tuneable properties for emerging electrochemical technologies and a modular synthetic approach expected to extend to alternative conjugated backbones and other polyelectrolyte groups easily installed by ligand coordination chemistry.
{"title":"Alkali Metal Borate Conjugated Block Polyelectrolytes as Tuneable Mixed Ionic-Electronic Conductors","authors":"Sebastian Leeming, Samuel Fryer, Georgina L. Gregory","doi":"10.1039/d6py00119j","DOIUrl":"https://doi.org/10.1039/d6py00119j","url":null,"abstract":"Conjugated polyelectrolytes (CPEs) combine ionic conductivity from tethered ionic groups with electronic conductivity from intrinsically-doped π-conjugated backbones, enabling applications in energy storage, bioelectronics, and neuromorphic computing. Conjugated block polyelectrolytes (CBEs), in which the conjugated and ionic functions are spatially segregated into distinct blocks, represent an emerging and underexplored variant of this materials class. Despite multiple studies of various pendant ionic groups, neither borate ionic functionalisation nor block copolymer architectures bearing non-sulfonate ionic groups have been explored. Here, we report CBEs, accessible through controlled Suzuki–Miyaura catalyst-transfer polymerisation (SCTP) and cyclic carbonate ring-opening polymerisation (ROP), incorporating alkali metal borate polycarbonate segments: poly(3-hexylthiophene)-block-poly(ethylene oxide-graft-poly(ethylene glycol))-block-polycarbonate bearing lithium, sodium, or potassium borate moieties. Systematic variation of P3HT chain length (DP = 35 and 110) and content (10–50 wt%) reveals distinct cation-dependent transport behaviour. Electrochemical characterisation via impedance spectroscopy, chronoamperometry, and linear sweep voltammetry demonstrates purely ionic conduction at low applied potentials, with p-type electronic transport activated above 1–1.5 V. Notably, lithium-ion conductivity remains independent of P3HT incorporation, whereas sodium transport improves with longer conjugated blocks and potassium conductivity is enhanced with shorter segments. Thermal analysis, DFT calculations, rheological and tensile measurements establish structure–property relationships linking polymer ionic networking to mechanical and ionic-electronic transport properties. These findings position anionic borate CBEs as a promising addition to the mixed ionic-electronic conductor platform, with tuneable properties for emerging electrochemical technologies and a modular synthetic approach expected to extend to alternative conjugated backbones and other polyelectrolyte groups easily installed by ligand coordination chemistry.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147447859","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}
Milena Jäger, Michael Agyemang, Wanja Timm Schulze, Julian Kimmig, Thomas Bätz, Chiara Wondraczek, Stefan Zechel, Alexander Croy, Michael Schmitt, Juergen Popp, Stefanie Gräfe, Martin D. Hager, Ulrich S. Schubert
In this study, we investigate the structural changes in dynamic metallopolymers during stimulus application, i.e. thermal treatment. For this purpose, we focused on the synthesis of polymers containing terpyridine moieties as ligands in the side chains that were complexed with either iron(II) or zinc(II) salts. The resulting crosslinked metallopolymers were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and elemental analysis (EA). Rheology experiments, including dynamic mechanical thermal analysis (DMTA), frequency sweeps, stress relaxation and time-temperature superposition were conducted to study the stimuli-responsive mechanical properties. Hereby, the activation energy as a combination of the metal complex and the polymer matrix could be determined. Additionally, computational master curves were obtained and the resulting relaxation spectra were analyzed. Beside the macroscopic material properties, temperature-dependent Raman spectroscopy and density functional theory (DFT) calculations were utilized to gain information on the changes on the molecular level. In this context, morphological changes in the polymer matrix were observed, which might be correlated to the presence of supramolecular aggregates. The changes on the molecular level could be linked to the macroscopic properties.
{"title":"Investigation of the dynamic behavior of metallopolymers by combined experimental and theoretical methods","authors":"Milena Jäger, Michael Agyemang, Wanja Timm Schulze, Julian Kimmig, Thomas Bätz, Chiara Wondraczek, Stefan Zechel, Alexander Croy, Michael Schmitt, Juergen Popp, Stefanie Gräfe, Martin D. Hager, Ulrich S. Schubert","doi":"10.1039/d6py00053c","DOIUrl":"https://doi.org/10.1039/d6py00053c","url":null,"abstract":"In this study, we investigate the structural changes in dynamic metallopolymers during stimulus application, i.e. thermal treatment. For this purpose, we focused on the synthesis of polymers containing terpyridine moieties as ligands in the side chains that were complexed with either iron(II) or zinc(II) salts. The resulting crosslinked metallopolymers were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and elemental analysis (EA). Rheology experiments, including dynamic mechanical thermal analysis (DMTA), frequency sweeps, stress relaxation and time-temperature superposition were conducted to study the stimuli-responsive mechanical properties. Hereby, the activation energy as a combination of the metal complex and the polymer matrix could be determined. Additionally, computational master curves were obtained and the resulting relaxation spectra were analyzed. Beside the macroscopic material properties, temperature-dependent Raman spectroscopy and density functional theory (DFT) calculations were utilized to gain information on the changes on the molecular level. In this context, morphological changes in the polymer matrix were observed, which might be correlated to the presence of supramolecular aggregates. The changes on the molecular level could be linked to the macroscopic properties.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"42 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147440351","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}
Aline Rebejac, Nathan Wybo, Luc Avérous, Antoine Duval
This work reports the synthesis of lignin-based non-isocyanate polyurethanes (NIPU) via transurethanisation (TU), aiming to develop biobased and recyclable covalent adaptable networks (CANs). A kinetic study of a model TU reaction enabled the selection of four catalysts for the preparation of crosslinked NIPU from a Kraft lignin-derived polyol and hexamethylene dicarbamate. All these aromatic materials exhibited dynamic covalent behavior, allowing stress relaxation and efficient recycling through multiple thermomechanical cycles. The catalyst choice significantly influenced network architecture, mechanical performance, and recyclability. Iron and bismuth/zinc catalysts emerged as promising non-toxic alternatives to conventional tin-based catalysts, promoting efficient TU while limiting side reactions such as urea formation, which otherwise can compromise the reprocessability. Chemical recycling was also demonstrated as a potential option for the end-of-life valorization. Indeed, TU emerges as a robust and versatile framework for the synthesis of biobased and circular NIPUs. This approach clearly emphasizes how strategic catalyst selection is fundamental to tailoring material properties and ensuring recyclability.
{"title":"Lignin-based Non-Isocyanate Polyurethanes by transurethanisation: catalyst selection towards Covalent Adaptable Networks","authors":"Aline Rebejac, Nathan Wybo, Luc Avérous, Antoine Duval","doi":"10.1039/d6py00044d","DOIUrl":"https://doi.org/10.1039/d6py00044d","url":null,"abstract":"This work reports the synthesis of lignin-based non-isocyanate polyurethanes (NIPU) via transurethanisation (TU), aiming to develop biobased and recyclable covalent adaptable networks (CANs). A kinetic study of a model TU reaction enabled the selection of four catalysts for the preparation of crosslinked NIPU from a Kraft lignin-derived polyol and hexamethylene dicarbamate. All these aromatic materials exhibited dynamic covalent behavior, allowing stress relaxation and efficient recycling through multiple thermomechanical cycles. The catalyst choice significantly influenced network architecture, mechanical performance, and recyclability. Iron and bismuth/zinc catalysts emerged as promising non-toxic alternatives to conventional tin-based catalysts, promoting efficient TU while limiting side reactions such as urea formation, which otherwise can compromise the reprocessability. Chemical recycling was also demonstrated as a potential option for the end-of-life valorization. Indeed, TU emerges as a robust and versatile framework for the synthesis of biobased and circular NIPUs. This approach clearly emphasizes how strategic catalyst selection is fundamental to tailoring material properties and ensuring recyclability.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147439752","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}
Hyperbranched polyethylenes synthesized via Pd-diimine chain walking polymerization possess distinctive structural features. Incorporation of fluorine is anticipated to further enhance their performance by imparting valuable attributes and thereby expanding their potential applications. In this work, we present the synthesis of a new series of fluorinated hyperbranched polyethylenes through chain walking copolymerization of ethylene with various fluorinated comonomers. The comonomers investigated include hexafluoroisopropyl acrylate (HFIPA), allylpentafluorobenzene (APFB), tridecafluorooctyl(allyl) ether (13FOAE), and 1H,1H,2H-perfluoro-1-hexene (PFH), with APFB, 13FOAE, and PFH employed for the first time in this polymerization system. The choice of comonomers markedly influenced catalyst activity and incorporation efficiency. Three comonomers, i.e., HFIPA, APFB, and 13FOAE, were found to be copolymerizable under the reaction conditions, with APFB delivering the highest catalytic activity and 13FOAE rendering highest comonomer incorporation at identical feed concentrations. Notably, even a low-level incorporation of fluorinated comonomers substantially reduced the surface energy of the resulting copolymers, while retaining their hyperbranched topology and low glass-transition temperature (ca. -69 °C).
{"title":"Direct synthesis of fluorinated hyperbranched polyethylenes by chain walking copolymerization","authors":"Peishuai Dai, Naiheng Song, Zhibin Ye","doi":"10.1039/d5py01150g","DOIUrl":"https://doi.org/10.1039/d5py01150g","url":null,"abstract":"Hyperbranched polyethylenes synthesized via Pd-diimine chain walking polymerization possess distinctive structural features. Incorporation of fluorine is anticipated to further enhance their performance by imparting valuable attributes and thereby expanding their potential applications. In this work, we present the synthesis of a new series of fluorinated hyperbranched polyethylenes through chain walking copolymerization of ethylene with various fluorinated comonomers. The comonomers investigated include hexafluoroisopropyl acrylate (HFIPA), allylpentafluorobenzene (APFB), tridecafluorooctyl(allyl) ether (13FOAE), and 1H,1H,2H-perfluoro-1-hexene (PFH), with APFB, 13FOAE, and PFH employed for the first time in this polymerization system. The choice of comonomers markedly influenced catalyst activity and incorporation efficiency. Three comonomers, i.e., HFIPA, APFB, and 13FOAE, were found to be copolymerizable under the reaction conditions, with APFB delivering the highest catalytic activity and 13FOAE rendering highest comonomer incorporation at identical feed concentrations. Notably, even a low-level incorporation of fluorinated comonomers substantially reduced the surface energy of the resulting copolymers, while retaining their hyperbranched topology and low glass-transition temperature (ca. -69 °C).","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"299 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383907","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}
Richard Ngulube, Jiancheng Zhou, Huaiyuan Zhu, Zhiwei Fu, Naixu Li
The performance of thermoregulated-phase separable catalysis-based initiators for continuous activator regeneration atom transfer radical polymerization (TPSC-based ICAR ATRP) system depends on the judicious selection of solvents that fully dissolve polymers while enabling efficient catalyst separation and recycling after polymerization. Herein, an active poly(ionic liquid) macroligand, PILLL1, was synthesized via free-radical polymerization of active ATRP ligand, poly(ethylene glycol)-300-methyl methacrylate and alkyl ammonium bromide–based ionic liquid monomers, with anisole employed as a solvent pair to broaden the solubility range and improve the sustainability of the TPSC-based ICAR ATRP system. The assessment of this system's kinetic studies at 5000 ppm CuBr2 catalyst loading exhibited excellent polymerization control, reaching 92% monomer conversion in 7 h and narrow Mw/Mn ≤ 1.38 at 80 ℃. However, catalyst leaching remained relatively high, ranging from 141 to 189 ppm with a recycling efficiency of 83.9% after five cycles. Interestingly, further optimization at a reduced CuBr2 loading of 125 ppm significantly decreased leached metal residue from 10.3 to 3.4 ppm, although the recycling efficiency declined further to 73.2% after five cycles. Meanwhile, at higher AIBN concentrations, polymerization control slightly decreased, as indicated by moderate deviations of Mn,GPC from Mn,th despite maintaining narrow Mw/Mn ˂ 1.5. These results have the potential for developing TPSC-based ATRP systems with high control and recyclability at low catalyst loadings using greener, highly soluble organic solvents as sustainable alternatives.
{"title":"Investigating Anisole/Cu(II)-Macroligand-complex Pair to Broaden Solubility Scope and Catalyst Recycling for Atom Transfer Radical Polymerization","authors":"Richard Ngulube, Jiancheng Zhou, Huaiyuan Zhu, Zhiwei Fu, Naixu Li","doi":"10.1039/d5py01106j","DOIUrl":"https://doi.org/10.1039/d5py01106j","url":null,"abstract":"The performance of thermoregulated-phase separable catalysis-based initiators for continuous activator regeneration atom transfer radical polymerization (TPSC-based ICAR ATRP) system depends on the judicious selection of solvents that fully dissolve polymers while enabling efficient catalyst separation and recycling after polymerization. Herein, an active poly(ionic liquid) macroligand, PILLL1, was synthesized via free-radical polymerization of active ATRP ligand, poly(ethylene glycol)-300-methyl methacrylate and alkyl ammonium bromide–based ionic liquid monomers, with anisole employed as a solvent pair to broaden the solubility range and improve the sustainability of the TPSC-based ICAR ATRP system. The assessment of this system's kinetic studies at 5000 ppm CuBr2 catalyst loading exhibited excellent polymerization control, reaching 92% monomer conversion in 7 h and narrow Mw/Mn ≤ 1.38 at 80 ℃. However, catalyst leaching remained relatively high, ranging from 141 to 189 ppm with a recycling efficiency of 83.9% after five cycles. Interestingly, further optimization at a reduced CuBr2 loading of 125 ppm significantly decreased leached metal residue from 10.3 to 3.4 ppm, although the recycling efficiency declined further to 73.2% after five cycles. Meanwhile, at higher AIBN concentrations, polymerization control slightly decreased, as indicated by moderate deviations of Mn,GPC from Mn,th despite maintaining narrow Mw/Mn ˂ 1.5. These results have the potential for developing TPSC-based ATRP systems with high control and recyclability at low catalyst loadings using greener, highly soluble organic solvents as sustainable alternatives.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383947","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}
Chenxi Sheng, Meng Huang, Andrew P. Dove, Linjiang Chen
The development of sustainably sourced polymers with robust mechanical properties is an important aspect of the challenge to mitigate the impact of plastic waste on the environment. However, with a wide range of potential bio-derivable building blocks and chemicals with which to construct polymers, predicting their thermomechanical properties is challenging. To address this challenge, here we established an integrated computational framework to relate chemical design to mechanics in isohexide-based polyurethanes (PUs). We combined and varied three structural motifs: (i) dynamic-bond moieties in the backbone, (ii) hydrogen-bonding moieties that mediate interchain cohesion, and (iii) stereochemical ring configurations. Density functional theory with the “External Force is Explicitly Included” (EFEI) formalism quantified how different dynamic bonds control single-chain scission forces, while semiempirical EFEI calculations and classical molecular dynamics (MD) revealed how the number and arrangement of hydrogen bond sites govern double-chain shear forces. Reactive MD with ReaxFF was used to probe uniaxial tensile deformation of amorphous PU bulk systems. Sulfur-containing dynamic-bond moieties markedly reduced single-chain scission forces, consistent with their use in self-healing and reprocessable PUs, whereas nitrogen-containing motifs combined with highly multidentate hydrogen-bonding groups maximized both intrachain strength and interchain cohesion. A representative design (NO5M) achieved a substantially higher peak stress than a disulfide-rich analogue (SS4I) under tensile loading. This multiscale framework yields chemically interpretable design rules for high-performance, recyclable PUs and illustrates the synergistic use of EFEI and MD simulations in polymer mechanochemistry.
开发具有强大机械性能的可持续来源聚合物是减轻塑料废物对环境影响的一个重要方面。然而，由于有广泛的潜在的生物衍生构建模块和化学物质用于构建聚合物，预测它们的热机械性能是具有挑战性的。为了应对这一挑战，我们建立了一个集成的计算框架，将化学设计与基于异己烷的聚氨酯（pu）的力学联系起来。我们结合并改变了三种结构基序：(i)主链上的动态键基，（ii）介导链间内聚的氢键基，以及（iii）立体化学环构型。采用“明确包含外力”（External Force is explicit Included， EFEI）形式的密度泛函数理论量化了不同动态键如何控制单链剪切力，而半经验EFEI计算和经典分子动力学（classical molecular dynamics， MD）揭示了氢键位点的数量和排列如何控制双链剪切力。用ReaxFF反应MD对非晶PU块体体系的单轴拉伸变形进行了研究。含硫动态键显著降低单链断裂力，这与它们在自我修复和可再加工pu中的应用一致，而含氮基序与高度多齿氢键基团结合，使链内强度和链间内聚力最大化。在拉伸载荷下，典型设计（NO5M）的峰值应力明显高于富二硫化物类似物（SS4I）。这种多尺度框架为高性能、可回收的pu提供了化学上可解释的设计规则，并说明了EFEI和MD模拟在聚合物力学化学中的协同应用。
{"title":"A computational framework for tuning intra- and intermolecular ductility in polyurethanes","authors":"Chenxi Sheng, Meng Huang, Andrew P. Dove, Linjiang Chen","doi":"10.1039/d5py01221j","DOIUrl":"https://doi.org/10.1039/d5py01221j","url":null,"abstract":"The development of sustainably sourced polymers with robust mechanical properties is an important aspect of the challenge to mitigate the impact of plastic waste on the environment. However, with a wide range of potential bio-derivable building blocks and chemicals with which to construct polymers, predicting their thermomechanical properties is challenging. To address this challenge, here we established an integrated computational framework to relate chemical design to mechanics in isohexide-based polyurethanes (PUs). We combined and varied three structural motifs: (i) dynamic-bond moieties in the backbone, (ii) hydrogen-bonding moieties that mediate interchain cohesion, and (iii) stereochemical ring configurations. Density functional theory with the “External Force is Explicitly Included” (EFEI) formalism quantified how different dynamic bonds control single-chain scission forces, while semiempirical EFEI calculations and classical molecular dynamics (MD) revealed how the number and arrangement of hydrogen bond sites govern double-chain shear forces. Reactive MD with ReaxFF was used to probe uniaxial tensile deformation of amorphous PU bulk systems. Sulfur-containing dynamic-bond moieties markedly reduced single-chain scission forces, consistent with their use in self-healing and reprocessable PUs, whereas nitrogen-containing motifs combined with highly multidentate hydrogen-bonding groups maximized both intrachain strength and interchain cohesion. A representative design (NO5M) achieved a substantially higher peak stress than a disulfide-rich analogue (SS4I) under tensile loading. This multiscale framework yields chemically interpretable design rules for high-performance, recyclable PUs and illustrates the synergistic use of EFEI and MD simulations in polymer mechanochemistry.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"45 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383908","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}
Thermosetting epoxy resins typically struggle to achieve high strength and high toughness simultaneously. Furthermore, the difficulty of recycling of epoxy resin/carbon fiber (EP/CF) composites after use poses severe environmental pollution issues. The preparation of EP/CF composites that simultaneously exhibit high strength, toughness, elongation at break, and recyclability remains a significant challenge. We synthesized bio-based hyperbranched epoxy resins (BAFI-n, n = 6, 12, 24) by combining hyperbranched topological networks with rigid–flexible units. BAFI-n demonstrates exceptional performance in simultaneously enhancing the strength, toughness, and degradability of diglycidyl ether of bisphenol A (DGEBA). Specifically, the tensile strength, elongation at break, and tensile toughness of the cured 12 wt% BAFI-12/DGEBA copolymer increased significantly by 58.46%, 166.67%, and 361.15%, respectively. Optimal mechanical properties were achieved at maximum crosslinking density and minimum free volume fraction, attributed to the synergistic interaction between rigid and flexible structures within the crosslinked network. The prepared TCF-BAFI-12/DGEBA composites exhibit superior mechanical properties compared to the original PCF/DGEBA composites, with tensile strength, flexural strength, and interlaminar shear strength increasing by 65.66%, 58.62%, and 84.21%, respectively. The enhanced properties stem from an interfacial reinforcement mechanism: the hyperbranched topology enables efficient load transfer, while the crosslinked network forms mechanical interlocking. Furthermore, the TCF-BAFI-12/DGEBA composites completely degrade under acidic conditions, allowing for damage-free recovery of the carbon fiber fabric. The resins achieve a 96% recovery rate, enabling high-value recycling. The strategy of combining rigid–flexible structures with hyperbranched topological crosslinking networks provides a pathway for designing high-strength, high-toughness, and recyclable EP/CF composites.
热固性环氧树脂通常难以同时达到高强度和高韧性。此外，环氧树脂/碳纤维（EP/CF）复合材料使用后难以回收，造成了严重的环境污染问题。制备同时具有高强度、韧性、断裂伸长率和可回收性的EP/CF复合材料仍然是一个重大挑战。我们将超支化拓扑网络与刚柔单元结合，合成了生物基超支化环氧树脂（BAFI-n, n = 6,12,24）。BAFI-n在同时增强双酚A二缩水甘油酯醚（DGEBA）的强度、韧性和可降解性方面表现出优异的性能。其中，12 wt% BAFI-12/DGEBA共聚物的抗拉强度、断裂伸长率和拉伸韧性分别显著提高了58.46%、166.67%和361.15%。在最大的交联密度和最小的自由体积分数下，由于交联网络中刚性和柔性结构之间的协同作用，获得了最佳的力学性能。制备的TCF-BAFI-12/DGEBA复合材料的力学性能优于原PCF/DGEBA复合材料，抗拉强度、抗折强度和层间剪切强度分别提高了65.66%、58.62%和84.21%。增强的性能源于界面增强机制：超支化拓扑结构实现了有效的负载传递，而交联网络形成了机械联锁。此外，TCF-BAFI-12/DGEBA复合材料在酸性条件下完全降解，允许碳纤维织物的无损伤恢复。树脂回收率达到96%，实现高价值回收。刚柔结构与超支化拓扑交联网络相结合的策略为设计高强度、高韧性、可回收的EP/CF复合材料提供了一条途径。
{"title":"Ultrastrong and high-elongation degradable bio-based hyperbranched epoxy resins and carbon fiber composites","authors":"Xue Wang, Yu Wu, Sufang Chen, Zejun Xu, Yu Jiang, Xudong Chen, Daohong Zhang","doi":"10.1039/d6py00076b","DOIUrl":"https://doi.org/10.1039/d6py00076b","url":null,"abstract":"Thermosetting epoxy resins typically struggle to achieve high strength and high toughness simultaneously. Furthermore, the difficulty of recycling of epoxy resin/carbon fiber (EP/CF) composites after use poses severe environmental pollution issues. The preparation of EP/CF composites that simultaneously exhibit high strength, toughness, elongation at break, and recyclability remains a significant challenge. We synthesized bio-based hyperbranched epoxy resins (BAFI-<em>n</em>, <em>n</em> = 6, 12, 24) by combining hyperbranched topological networks with rigid–flexible units. BAFI-<em>n</em> demonstrates exceptional performance in simultaneously enhancing the strength, toughness, and degradability of diglycidyl ether of bisphenol A (DGEBA). Specifically, the tensile strength, elongation at break, and tensile toughness of the cured 12 wt% BAFI-12/DGEBA copolymer increased significantly by 58.46%, 166.67%, and 361.15%, respectively. Optimal mechanical properties were achieved at maximum crosslinking density and minimum free volume fraction, attributed to the synergistic interaction between rigid and flexible structures within the crosslinked network. The prepared TCF-BAFI-12/DGEBA composites exhibit superior mechanical properties compared to the original PCF/DGEBA composites, with tensile strength, flexural strength, and interlaminar shear strength increasing by 65.66%, 58.62%, and 84.21%, respectively. The enhanced properties stem from an interfacial reinforcement mechanism: the hyperbranched topology enables efficient load transfer, while the crosslinked network forms mechanical interlocking. Furthermore, the TCF-BAFI-12/DGEBA composites completely degrade under acidic conditions, allowing for damage-free recovery of the carbon fiber fabric. The resins achieve a 96% recovery rate, enabling high-value recycling. The strategy of combining rigid–flexible structures with hyperbranched topological crosslinking networks provides a pathway for designing high-strength, high-toughness, and recyclable EP/CF composites.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147360297","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}
Yun-Cong Ye, Yong-Hong Luo, Min Xie, Qing Cao, Zhongzheng Cai, Jian-Bo Zhu
The development of closed-loop recyclable thermoplastic elastomers (TPEs) represents a promising solution to address the serious plastic pollution. However, the traditional synthetic and chemical recycling pathways of triblock TPEs still face significant challenge due to their intrinsic complex multicomponent. Herein, we create a one-pot sequence-controlled copolymerization platform towards chemically recyclable TPEs. The distinct polymerization reactivity of aliphatic caprolactone-based monomer MTO and the benzo-fused or naphthalene-fused caprolactone-based monomer DHB or DHN allowed us to construct ABA triblock TPE products where the low-Tg PMTO segment served as the soft midblock and the high-Tm P(DHB) block or high-Tg P(DHN) block as the hard end segments. Remarkably, these resulting TPE products showcased tunable material properties by altering their compositions. TPE4 with FDHN = 0.21 demonstrated outstanding tensile strength, ductility, impressive toughness (UT = 133 ± 14 MJ/m 3 ), and high elastic recovery (>90%). More importantly, these synthesized TPE materials were able to depolymerize back to their monomers in presence of Sn(Oct)2 at 160-200 °C, establishing an efficient closed-loop recycling.
{"title":"Selectively Controlled Ring-Opening Copolymerization to Chemically Recyclable Thermoplastic Elastomers","authors":"Yun-Cong Ye, Yong-Hong Luo, Min Xie, Qing Cao, Zhongzheng Cai, Jian-Bo Zhu","doi":"10.1039/d6py00127k","DOIUrl":"https://doi.org/10.1039/d6py00127k","url":null,"abstract":"The development of closed-loop recyclable thermoplastic elastomers (TPEs) represents a promising solution to address the serious plastic pollution. However, the traditional synthetic and chemical recycling pathways of triblock TPEs still face significant challenge due to their intrinsic complex multicomponent. Herein, we create a one-pot sequence-controlled copolymerization platform towards chemically recyclable TPEs. The distinct polymerization reactivity of aliphatic caprolactone-based monomer MTO and the benzo-fused or naphthalene-fused caprolactone-based monomer DHB or DHN allowed us to construct ABA triblock TPE products where the low-Tg PMTO segment served as the soft midblock and the high-Tm P(DHB) block or high-Tg P(DHN) block as the hard end segments. Remarkably, these resulting TPE products showcased tunable material properties by altering their compositions. TPE4 with FDHN = 0.21 demonstrated outstanding tensile strength, ductility, impressive toughness (UT = 133 ± 14 MJ/m 3 ), and high elastic recovery (>90%). More importantly, these synthesized TPE materials were able to depolymerize back to their monomers in presence of Sn(Oct)2 at 160-200 °C, establishing an efficient closed-loop recycling.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"283 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358903","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}
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