Jing Yi Chin,Nur Hashimah Alias,Muhd Izzudin Fikry Zainuddin,Adeline Seak May Chua,Chong Yang Chuah,Euntae Yang
Physical aging in high-free-volume glassy polymers progressively reduces gas permeability, limiting the long-term performance of gas separation membranes. The incorporation of nanoporous fillers into mixed-matrix membranes (MMMs) and thin-film nanocomposite (TFN) membranes has emerged as a promising strategy to mitigate aging while preserving high gas transport performance. This perspective outlines the fundamental characteristics of physical aging, including its underlying mechanisms, recovery approaches, and key factors governing its progression, followed by a review of the techniques used to quantify aging and their associated limitations. The central focus of this perspective is a mechanistic evaluation of how nanoporous fillers suppress physical aging, moving beyond the conventional free-volume spacer concept to structural pillaring effects, interfacial rigidification through chain adsorption, and direct suppression of segmental chain mobility. Evidence across diverse polymer systems indicates that aging resistance is governed by filler properties rather than matrix chemistry. The analysis also highlights the coupled influence of filler loading and selective-layer thickness in TFC membranes on aging behaviour. A critical inconsistency in current reporting practices is identified, where variations in observation time, membrane format and performance metrics prevent meaningful cross-study comparison. To address this issue, minimum reporting standards are proposed, with aging-corrected performance as the primary benchmark for filler effectiveness evaluation. Broader adoption of broadband dielectric spectroscopy is also advocated to directly probe chain dynamics, while nanoporous engineering of gutter layers in TFC membranes is identified as a promising yet underexplored pathway toward durable membrane performance.
{"title":"Physical aging in glassy polymer gas separation membranes: mechanistic insights into filler mitigation strategies","authors":"Jing Yi Chin,Nur Hashimah Alias,Muhd Izzudin Fikry Zainuddin,Adeline Seak May Chua,Chong Yang Chuah,Euntae Yang","doi":"10.1039/d6py00588h","DOIUrl":"https://doi.org/10.1039/d6py00588h","url":null,"abstract":"Physical aging in high-free-volume glassy polymers progressively reduces gas permeability, limiting the long-term performance of gas separation membranes. The incorporation of nanoporous fillers into mixed-matrix membranes (MMMs) and thin-film nanocomposite (TFN) membranes has emerged as a promising strategy to mitigate aging while preserving high gas transport performance. This perspective outlines the fundamental characteristics of physical aging, including its underlying mechanisms, recovery approaches, and key factors governing its progression, followed by a review of the techniques used to quantify aging and their associated limitations. The central focus of this perspective is a mechanistic evaluation of how nanoporous fillers suppress physical aging, moving beyond the conventional free-volume spacer concept to structural pillaring effects, interfacial rigidification through chain adsorption, and direct suppression of segmental chain mobility. Evidence across diverse polymer systems indicates that aging resistance is governed by filler properties rather than matrix chemistry. The analysis also highlights the coupled influence of filler loading and selective-layer thickness in TFC membranes on aging behaviour. A critical inconsistency in current reporting practices is identified, where variations in observation time, membrane format and performance metrics prevent meaningful cross-study comparison. To address this issue, minimum reporting standards are proposed, with aging-corrected performance as the primary benchmark for filler effectiveness evaluation. Broader adoption of broadband dielectric spectroscopy is also advocated to directly probe chain dynamics, while nanoporous engineering of gutter layers in TFC membranes is identified as a promising yet underexplored pathway toward durable membrane performance.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858076","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}
Ahmad Alsholi,Shreya Tiwari,Jiyizhe Zhang,Marloes Peeters
Molecularly imprinted polymers (MIPs) are porous materials generated by templated polymerisation, in which functional and crosslinking monomers are organised around a target molecule and fixed within a polymer network to create high-affinity, selective recognition sites for the chosen analyte. The appeal of MIPs lies in their robustness, low-cost and chemically versatile nature, in addition to directly encoding selective molecular recognition into polymer networks while retaining the thermal, mechanical, and processing advantages of synthetic materials. Yet, despite being discovered a century ago, MIP development remains dominated by empirical, target-by-target optimisation. The field therefore presents a compelling challenge for data science and machine learning: MIP performance emerges from a high-dimensional coupling of material, polymer synthesis and processing parameters but this complex design space is still only sparsely sampled. In this Perspective, we argue that the next step for MIPs is not simply better prediction of pre-polymerisation interactions, which is traditionally used to predict optimal composition. Pre-polymerisation metrics are weak predictors of functional performance once MIPs are synthesized and applied; therefore, a broader shift towards data-driven polymer design which considers manufacturing constraints from the outset is needed. We discuss our future vision for the field and how structured datasets, high-throughput screening, computational modelling, Bayesian optimisation and interpretable machine learning enable the move from empirical recipes towards programmable synthetic receptors. Sensing and sustainable manufacturing routes will be covered, placing particular emphasis routes on exploiting the robustness of MIPs to facilitate high-throughput production and biocompatibility challenges.
{"title":"From empirical imprinting to programmable synthetic receptors: A perspective on data science and machine learning for molecularly imprinted polymers","authors":"Ahmad Alsholi,Shreya Tiwari,Jiyizhe Zhang,Marloes Peeters","doi":"10.1039/d6py00493h","DOIUrl":"https://doi.org/10.1039/d6py00493h","url":null,"abstract":"Molecularly imprinted polymers (MIPs) are porous materials generated by templated polymerisation, in which functional and crosslinking monomers are organised around a target molecule and fixed within a polymer network to create high-affinity, selective recognition sites for the chosen analyte. The appeal of MIPs lies in their robustness, low-cost and chemically versatile nature, in addition to directly encoding selective molecular recognition into polymer networks while retaining the thermal, mechanical, and processing advantages of synthetic materials. Yet, despite being discovered a century ago, MIP development remains dominated by empirical, target-by-target optimisation. The field therefore presents a compelling challenge for data science and machine learning: MIP performance emerges from a high-dimensional coupling of material, polymer synthesis and processing parameters but this complex design space is still only sparsely sampled. In this Perspective, we argue that the next step for MIPs is not simply better prediction of pre-polymerisation interactions, which is traditionally used to predict optimal composition. Pre-polymerisation metrics are weak predictors of functional performance once MIPs are synthesized and applied; therefore, a broader shift towards data-driven polymer design which considers manufacturing constraints from the outset is needed. We discuss our future vision for the field and how structured datasets, high-throughput screening, computational modelling, Bayesian optimisation and interpretable machine learning enable the move from empirical recipes towards programmable synthetic receptors. Sensing and sustainable manufacturing routes will be covered, placing particular emphasis routes on exploiting the robustness of MIPs to facilitate high-throughput production and biocompatibility challenges.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858213","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}
The photoredox-catalyzed postfunctionalization of polymers bearing N-hydroxyphthalimide (NHPI) ester moieties via radical-polar crossover (RPC) is a promising strategy for introducing phosphonate groups into polymer backbones, as we previously reported. However, the degree of functionalization (DOF) in the phosphonylation of methyl acrylate copolymers has been limited to 15% owing to competition between the RPC process and hydrogen atom transfer. In this study, we demonstrate that the rational selection of an organic photocatalyst on the basis of three key features, i.e., oxidation power, photostability, and excited-state lifetime, substantially improves the RPC efficiency in the phosphonylation of methyl acrylate copolymers containing NHPI ester moieties. Systematic screening of eight organic photocatalysts revealed that 2,4,5,6-tetrakis(3,6-di-tert-butyl-9H-carbazol-9-yl)isophthalonitrile (4CzIPN-tBu), operating via a reductive quenching mechanism, affords a DOF of 28%. The approach was extended to various phosphite nucleophiles and NHPI estercontaining polymer substrates, all of which afforded higher DOFs than those reported in our previous work. In addition, computational studies revealed for the first time the role of neighboring group participation in RPC-based polymer reactions: the ester groups of the methyl acrylate units form stable cyclic intermediates with the carbocation intermediates generated via RPC, effectively suppressing undesired back electron transfer and enabling efficient phosphonylation even from inherently unstable secondary carbocations. This study establishes rational design principles for enhancing RPC efficiency in postfunctionalization reactions, thereby contributing to the development of a broader range of functional polymer architectures.
{"title":"Rational photocatalyst selection for efficient radical-polar crossover phosphonylation of -hydroxyphthalimide ester-containing polymers","authors":"Yoichiro Eriguchi,Kohei Taniguchi,Tomohiro Tamano,Kosuke Sato,Shinsuke Inagi","doi":"10.1039/d6py00581k","DOIUrl":"https://doi.org/10.1039/d6py00581k","url":null,"abstract":"The photoredox-catalyzed postfunctionalization of polymers bearing N-hydroxyphthalimide (NHPI) ester moieties via radical-polar crossover (RPC) is a promising strategy for introducing phosphonate groups into polymer backbones, as we previously reported. However, the degree of functionalization (DOF) in the phosphonylation of methyl acrylate copolymers has been limited to 15% owing to competition between the RPC process and hydrogen atom transfer. In this study, we demonstrate that the rational selection of an organic photocatalyst on the basis of three key features, i.e., oxidation power, photostability, and excited-state lifetime, substantially improves the RPC efficiency in the phosphonylation of methyl acrylate copolymers containing NHPI ester moieties. Systematic screening of eight organic photocatalysts revealed that 2,4,5,6-tetrakis(3,6-di-tert-butyl-9H-carbazol-9-yl)isophthalonitrile (4CzIPN-tBu), operating via a reductive quenching mechanism, affords a DOF of 28%. The approach was extended to various phosphite nucleophiles and NHPI estercontaining polymer substrates, all of which afforded higher DOFs than those reported in our previous work. In addition, computational studies revealed for the first time the role of neighboring group participation in RPC-based polymer reactions: the ester groups of the methyl acrylate units form stable cyclic intermediates with the carbocation intermediates generated via RPC, effectively suppressing undesired back electron transfer and enabling efficient phosphonylation even from inherently unstable secondary carbocations. This study establishes rational design principles for enhancing RPC efficiency in postfunctionalization reactions, thereby contributing to the development of a broader range of functional polymer architectures.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858211","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}
Redox-active enzymes efficiently catalyze a wide range of (bio)chemical reactions using their unique metalloporphyrin catalytic centers that are coordinated with proximal amino acid residues from surrounding polypeptide chains. Chemical synthesis of catalysts that mimic such effective catalytic motifs has long been pursued but remains challenging. Current designs can typically reproduce only selected features of natural enzymes. Here, we present a strategy for synthesizing polymer-supported metalloporphyrin catalysts through the precise design of a norbornene-based monomer bearing a TPP-Co catalytic center and an imidazole axial ligand. This three-in-one strategy enables one-step polymerization to produce a polymer-supported TPP-based catalyst in which a proximal ligand is axially coordinated to the metal center. Spectroscopic characterization revealed the axial-ligand interaction. Compared with the ligand-free polymer P1-Co, which exhibits a Tafel slope of 279 mV dec−1 for the oxygen evolution reaction (OER), the target polymer catalyst P2-Co shows a substantially higher catalytic current, a reduced Tafel slope of 157 mV dec−1, and nearly tenfold higher activity than its monomeric counterpart. This work demonstrates a new strategy for the molecular design of polymer-based, enzyme-mimicking catalysts.
{"title":"Synthesis of polymer catalysts with tailored metalloporphyrin–ligand proximity by precision monomer design","authors":"Imogen Smith,Martin R. Johnston,Zhongfan Jia","doi":"10.1039/d6py00620e","DOIUrl":"https://doi.org/10.1039/d6py00620e","url":null,"abstract":"Redox-active enzymes efficiently catalyze a wide range of (bio)chemical reactions using their unique metalloporphyrin catalytic centers that are coordinated with proximal amino acid residues from surrounding polypeptide chains. Chemical synthesis of catalysts that mimic such effective catalytic motifs has long been pursued but remains challenging. Current designs can typically reproduce only selected features of natural enzymes. Here, we present a strategy for synthesizing polymer-supported metalloporphyrin catalysts through the precise design of a norbornene-based monomer bearing a TPP-Co catalytic center and an imidazole axial ligand. This three-in-one strategy enables one-step polymerization to produce a polymer-supported TPP-based catalyst in which a proximal ligand is axially coordinated to the metal center. Spectroscopic characterization revealed the axial-ligand interaction. Compared with the ligand-free polymer P1-Co, which exhibits a Tafel slope of 279 mV dec−1 for the oxygen evolution reaction (OER), the target polymer catalyst P2-Co shows a substantially higher catalytic current, a reduced Tafel slope of 157 mV dec−1, and nearly tenfold higher activity than its monomeric counterpart. This work demonstrates a new strategy for the molecular design of polymer-based, enzyme-mimicking catalysts.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148821694","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}
Azine-based conjugated polymers were synthesised via a metal-free dehydration polycondensation of diformyl monomers with hydrazine, and the relationship between monomer structure and product topology was systematically investigated. Depending on the monomer structure, the polymerisation afforded either linear polymers or cyclic oligomers, revealing a clear structure–product correlation. Rigid monomers with linearly aligned formyl groups preferentially yielded high-molecular-weight polymers, whereas rotationally flexible thiophene-containing and donor–acceptor monomers promoted the formation of cyclic species. Optical and electronic characterisation demonstrated that incorporation of different π-spacers modulates the HOMO/LUMO energy levels. In particular, an azine polymer incorporating a naphthalene diimide unit exhibited a markedly lowered LUMO level (−3.87 eV), suitable for electron injection. Thin films of this polymer showed smooth morphology and an edge-on orientation, enabling its application in organic field-effect transistors (OFETs), where n-type semiconducting behaviour was confirmed. These findings establish molecular design guidelines for selectively obtaining linear azine-based polymers and highlight the potential of metal-free synthesised conjugated polymers as sustainable n-type semiconductors.
{"title":"Structure–product relationships in azine-based conjugated polymers: linear cyclic topologies and n-type semiconducting properties","authors":"Hidetoyo Kanzawa,Kyoya Kobayashi,Keita Suzuki,Yusei Kubota,Hiroki Murakami,Ziwei Hu,Takeshi Yasuda,Takaki Kanbara,Junpei Kuwabara","doi":"10.1039/d6py00649c","DOIUrl":"https://doi.org/10.1039/d6py00649c","url":null,"abstract":"Azine-based conjugated polymers were synthesised via a metal-free dehydration polycondensation of diformyl monomers with hydrazine, and the relationship between monomer structure and product topology was systematically investigated. Depending on the monomer structure, the polymerisation afforded either linear polymers or cyclic oligomers, revealing a clear structure–product correlation. Rigid monomers with linearly aligned formyl groups preferentially yielded high-molecular-weight polymers, whereas rotationally flexible thiophene-containing and donor–acceptor monomers promoted the formation of cyclic species. Optical and electronic characterisation demonstrated that incorporation of different π-spacers modulates the HOMO/LUMO energy levels. In particular, an azine polymer incorporating a naphthalene diimide unit exhibited a markedly lowered LUMO level (−3.87 eV), suitable for electron injection. Thin films of this polymer showed smooth morphology and an edge-on orientation, enabling its application in organic field-effect transistors (OFETs), where n-type semiconducting behaviour was confirmed. These findings establish molecular design guidelines for selectively obtaining linear azine-based polymers and highlight the potential of metal-free synthesised conjugated polymers as sustainable n-type semiconductors.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148821663","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}
Herein, a reactive phosphorus–nitrogen–silicon-containing hardener (FAD) was synthesized from aminopropyl polysiloxane, 1-formylpiperazine, and DOPO to prepare high-performance EP thermosets. The design integrates P/N-assisted flame inhibition with a rigid-flexible molecular architecture: DOPO-derived rigid aromatic phosphate units promote char formation and mechanical reinforcement, piperazine nitrogen contributes to flame dilution and network formation, and Si–O–Si segments increase the free volume, improve toughness, and suppress dielectric polarization. The optimized EP-FAD-2 thermoset, containing 43.42 g of FAD per 100 g of DGEBA (2.0 wt% P), achieved a UL-94 V-0 rating and an LOI of 29%. Compared with those of the neat EP, its pHRR, THR, and TSP decreased by 45.6%, 27.2%, and 45.5%, respectively. EP-FAD-2 also showed enhanced tensile strength (37.3 to 51.7 MPa), impact strength (9.5 to 18.3 kJ m−2), and flexural strength (85.1 to 145.6 MPa). Moreover, the dielectric constant and loss at 1 MHz decreased to 2.326 and 0.0181, respectively, while the transmittance remained above 80% in the 400–500 nm region. This work demonstrates a molecular design strategy for resolving the performance trade-offs of epoxy thermosets for advanced electronic packaging and optical coating applications.
{"title":"Novel P/N/Si-containing hardener-cured epoxy thermoset with simultaneously improved flame retardancy, transparency, dielectric stability and mechanical strength and toughness","authors":"Yu-Ting Yang,Yu Li,Yuan Hu,Amirbek Bekeshev,Zukhra Aimaganbetova,Gulbanu Serikbaeva,Zamzagul Kuatovna Shanina,Bin Yu,Xin Wang","doi":"10.1039/d6py00544f","DOIUrl":"https://doi.org/10.1039/d6py00544f","url":null,"abstract":"Herein, a reactive phosphorus–nitrogen–silicon-containing hardener (FAD) was synthesized from aminopropyl polysiloxane, 1-formylpiperazine, and DOPO to prepare high-performance EP thermosets. The design integrates P/N-assisted flame inhibition with a rigid-flexible molecular architecture: DOPO-derived rigid aromatic phosphate units promote char formation and mechanical reinforcement, piperazine nitrogen contributes to flame dilution and network formation, and Si–O–Si segments increase the free volume, improve toughness, and suppress dielectric polarization. The optimized EP-FAD-2 thermoset, containing 43.42 g of FAD per 100 g of DGEBA (2.0 wt% P), achieved a UL-94 V-0 rating and an LOI of 29%. Compared with those of the neat EP, its pHRR, THR, and TSP decreased by 45.6%, 27.2%, and 45.5%, respectively. EP-FAD-2 also showed enhanced tensile strength (37.3 to 51.7 MPa), impact strength (9.5 to 18.3 kJ m−2), and flexural strength (85.1 to 145.6 MPa). Moreover, the dielectric constant and loss at 1 MHz decreased to 2.326 and 0.0181, respectively, while the transmittance remained above 80% in the 400–500 nm region. This work demonstrates a molecular design strategy for resolving the performance trade-offs of epoxy thermosets for advanced electronic packaging and optical coating applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148821671","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}
Hannah de Fontaine,George Wan,Mia Wetzel,Irene Lim,Dylan J. Freas
Polyethylene glycol (PEG) is widely used in biomaterials due to its water solubility and biocompatibility, which has motivated the development of degradable PEG analogs. Herein, we report a scalable and operationally straightforward method for the direct functionalization of PEG with carboxylic acids to generate hydrolytically degradable α-acyloxy ethers. The transformation employs N-chlorosuccinimide (NCS) as an inexpensive and comparatively safe oxidant and proceeds with minimal polymer chain scission or cross-linking. A broad range of alkyl- and aryl-substituted carboxylic acids bearing diverse functional groups and bioactive motifs were successfully incorporated into the PEG backbone. The method is also compatible with PEG samples of varying molecular weights and can be conducted on a gram scale. While the resulting PEG derivatives are stable during storage under ambient conditions, they undergo hydrolytic degradation in aqueous solutions at 37 °C over two weeks. This approach offers a practical route to degradable PEG-based materials using readily available reagents and mild conditions, which may facilitate the development of advanced biomaterials.
{"title":"Introducing hydrolytic degradability to PEG C–H oxidation by -chlorosuccinimide","authors":"Hannah de Fontaine,George Wan,Mia Wetzel,Irene Lim,Dylan J. Freas","doi":"10.1039/d6py00554c","DOIUrl":"https://doi.org/10.1039/d6py00554c","url":null,"abstract":"Polyethylene glycol (PEG) is widely used in biomaterials due to its water solubility and biocompatibility, which has motivated the development of degradable PEG analogs. Herein, we report a scalable and operationally straightforward method for the direct functionalization of PEG with carboxylic acids to generate hydrolytically degradable α-acyloxy ethers. The transformation employs N-chlorosuccinimide (NCS) as an inexpensive and comparatively safe oxidant and proceeds with minimal polymer chain scission or cross-linking. A broad range of alkyl- and aryl-substituted carboxylic acids bearing diverse functional groups and bioactive motifs were successfully incorporated into the PEG backbone. The method is also compatible with PEG samples of varying molecular weights and can be conducted on a gram scale. While the resulting PEG derivatives are stable during storage under ambient conditions, they undergo hydrolytic degradation in aqueous solutions at 37 °C over two weeks. This approach offers a practical route to degradable PEG-based materials using readily available reagents and mild conditions, which may facilitate the development of advanced biomaterials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148821666","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}
Living ring-opening polymerization (ROP) of 2,2-dimethylpropiolactone [(Me)2PL] has never been achieved because the resulting polymer, poly(3-hydroxy-2,2-dimethylpropionate) [P3H(Me)2P], has poor solubility in common organic solvents due to its high crystallinity, similar to polyglycolide (PGA). In previous work, we reported the first living anionic ROP of glycolide in strong protic fluorinated alcohols (FAs) as cosolvents, which were conventionally considered incompatible with anionic polymerization. In this work, we implemented the strategy of FAs as cosolvents to achieve living/controlled ROP of (Me)2PL. Well-defined P3H(Me)2P (Ð < 1.19) were obtained at room temperature. Various initiators, including primary alcohols, primary amines, and alkylammonium halides, were used to initiate the ROP. The thermal properties of the isolated P3H(Me)2Ps were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and X-ray diffraction (XRD), confirming the highly crystalline nature and excellent thermal stability of P3H(Me)2P.
{"title":"Living/Controlled Ring-Opening Polymerization of 2,2-Dimethylpropiolactone in Fluoroalcohols","authors":"viko ladelta,Jiaxi Xu,Bhagyasree Kulkarni,Nikos Hadjichristidis","doi":"10.1039/d6py00701e","DOIUrl":"https://doi.org/10.1039/d6py00701e","url":null,"abstract":"Living ring-opening polymerization (ROP) of 2,2-dimethylpropiolactone [(Me)2PL] has never been achieved because the resulting polymer, poly(3-hydroxy-2,2-dimethylpropionate) [P3H(Me)2P], has poor solubility in common organic solvents due to its high crystallinity, similar to polyglycolide (PGA). In previous work, we reported the first living anionic ROP of glycolide in strong protic fluorinated alcohols (FAs) as cosolvents, which were conventionally considered incompatible with anionic polymerization. In this work, we implemented the strategy of FAs as cosolvents to achieve living/controlled ROP of (Me)2PL. Well-defined P3H(Me)2P (Ð < 1.19) were obtained at room temperature. Various initiators, including primary alcohols, primary amines, and alkylammonium halides, were used to initiate the ROP. The thermal properties of the isolated P3H(Me)2Ps were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and X-ray diffraction (XRD), confirming the highly crystalline nature and excellent thermal stability of P3H(Me)2P.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"271 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858073","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}
Yulu Liu,Yi Liu,Hengfeng Yu,Hongkun Tian,Xiaofu Wu,Hui Tong,Lixiang Wang
Donor–acceptor conjugated polymers have attracted wide attention as photocatalysts for photocatalytic water splitting. However, most of these polymeric photocatalysts are based on conjugated polymers with both donor and acceptor units within their main chains, despite the fact that the distribution of donor and acceptor units can greatly influence the optoelectronic properties. Herein, by introducing two acceptor units (cyano and cyanoacrylate groups) onto the orthogonal side chains of spirobifluorene, respectively, two donor–orthogonal acceptor conjugated polymers (SPCN-3T and SPCNE-3T) based on poly(spirobifluorene-terthiophene) (SP-3T) backbones were obtained via Stille coupling reactions. In contrast to the highly overlapped HOMO and LUMO orbitals observed for SP-3T, the introduction of orthogonal acceptor units achieved spatial separation of the HOMO and LUMO distributions, which not only resulted in stronger built-in electric fields, but also effectively enhanced electron–hole separation in the excited state. In particular, SPCNE-3T with the strongest electron-withdrawing acceptor unit, possessed the largest dipole moment, the longest excited-state lifetime, and the most efficient charge separation and transport. Consequently, single-component photocatalysts based on SPCNE-3T achieved the highest hydrogen evolution rate (HER) of 51.9 mmol g−1 h−1, approximately 10 times higher than that of SP-3T (4.9 mmol g−1 h−1). Our findings demonstrate that constructing donor–orthogonal acceptor conjugated polymers to achieve spatially orthogonal separation of HOMO and LUMO orbitals represents an effective strategy for designing photocatalysts with high photocatalytic activity.
{"title":"Spirobifluorene-based conjugated polymers with donor–orthogonal acceptor structures for boosting photocatalytic hydrogen evolution","authors":"Yulu Liu,Yi Liu,Hengfeng Yu,Hongkun Tian,Xiaofu Wu,Hui Tong,Lixiang Wang","doi":"10.1039/d6py00454g","DOIUrl":"https://doi.org/10.1039/d6py00454g","url":null,"abstract":"Donor–acceptor conjugated polymers have attracted wide attention as photocatalysts for photocatalytic water splitting. However, most of these polymeric photocatalysts are based on conjugated polymers with both donor and acceptor units within their main chains, despite the fact that the distribution of donor and acceptor units can greatly influence the optoelectronic properties. Herein, by introducing two acceptor units (cyano and cyanoacrylate groups) onto the orthogonal side chains of spirobifluorene, respectively, two donor–orthogonal acceptor conjugated polymers (SPCN-3T and SPCNE-3T) based on poly(spirobifluorene-terthiophene) (SP-3T) backbones were obtained via Stille coupling reactions. In contrast to the highly overlapped HOMO and LUMO orbitals observed for SP-3T, the introduction of orthogonal acceptor units achieved spatial separation of the HOMO and LUMO distributions, which not only resulted in stronger built-in electric fields, but also effectively enhanced electron–hole separation in the excited state. In particular, SPCNE-3T with the strongest electron-withdrawing acceptor unit, possessed the largest dipole moment, the longest excited-state lifetime, and the most efficient charge separation and transport. Consequently, single-component photocatalysts based on SPCNE-3T achieved the highest hydrogen evolution rate (HER) of 51.9 mmol g−1 h−1, approximately 10 times higher than that of SP-3T (4.9 mmol g−1 h−1). Our findings demonstrate that constructing donor–orthogonal acceptor conjugated polymers to achieve spatially orthogonal separation of HOMO and LUMO orbitals represents an effective strategy for designing photocatalysts with high photocatalytic activity.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"154 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148821660","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}
Anjali Nambidiyattil,Maryam F. Abdollahi,Adrian A. Lorenzana,Pinelopi A. Tsami,Tanner George,Saurabh S. Chitnis
Most synthetic polymers are constructed from linear or cyclic (aromatic) building blocks. The controlled use of bicyclic, three-dimensional organic monomers remains synthetically challenging. In contrast, incorporating unstrained inorganic cages like polyhedral oligomeric silsesquioxanes (POSS) and carboranes into polymer backbones is facile, and has been used to make materials with exceptional stability and mechanical properties. But besides these two classes, inorganic cages are minimally explored as monomers in polymer chemistry. In this study, a phosphorus–nitrogen (PN) bicyclo[2.2.2]octane was converted via Staudinger reactions with azido alcohols to cage-containing aromatic (PNBP) and aliphatic (PNBH) diols, making monomers analogous to organic diols commonly used in polycondensation. Crystallographic analysis reveals how functional-group identity and conformational freedom influence intermolecular association and solubility. Attempted addition of these diols to diisocyanates does not yield polyurethanes, showing evidence of side-reactions involving an aza-Wittig pathway instead. On the other hand, polycondensations with Me2SiCl2 yields the first examples of main chain alternating phosphazene–organosiloxane copolymers. The aromatic derivative exhibits low solubility, pronounced crystallinity as measured by X-ray diffraction, melting and crystallization transitions at Tm = 96 °C and Tc = 66 °C, and a high decomposition temperature (Tdec,50% = 524 °C). The aliphatic analogue exhibits higher solubility, lower melting and crystallization temperatures (Tm = 60 °C, Tc = 45 °C), a glass-transition temperature of −32 °C, and a lower Tdec,50% value of 357 °C. Thermal stability and preliminary combustion analyses show that the polymers possess favourable prospects as halogen-free flame retardants. These results establish PN cage-based diols as versatile building blocks for cage-dense hybrid polymers and a platform for next-generation high-performance materials.
{"title":"Phosphaza-bicyclo[2.2.2]octane diols as monomers for organosiloxane-based hybrid materials","authors":"Anjali Nambidiyattil,Maryam F. Abdollahi,Adrian A. Lorenzana,Pinelopi A. Tsami,Tanner George,Saurabh S. Chitnis","doi":"10.1039/d6py00557h","DOIUrl":"https://doi.org/10.1039/d6py00557h","url":null,"abstract":"Most synthetic polymers are constructed from linear or cyclic (aromatic) building blocks. The controlled use of bicyclic, three-dimensional organic monomers remains synthetically challenging. In contrast, incorporating unstrained inorganic cages like polyhedral oligomeric silsesquioxanes (POSS) and carboranes into polymer backbones is facile, and has been used to make materials with exceptional stability and mechanical properties. But besides these two classes, inorganic cages are minimally explored as monomers in polymer chemistry. In this study, a phosphorus–nitrogen (PN) bicyclo[2.2.2]octane was converted via Staudinger reactions with azido alcohols to cage-containing aromatic (PNBP) and aliphatic (PNBH) diols, making monomers analogous to organic diols commonly used in polycondensation. Crystallographic analysis reveals how functional-group identity and conformational freedom influence intermolecular association and solubility. Attempted addition of these diols to diisocyanates does not yield polyurethanes, showing evidence of side-reactions involving an aza-Wittig pathway instead. On the other hand, polycondensations with Me2SiCl2 yields the first examples of main chain alternating phosphazene–organosiloxane copolymers. The aromatic derivative exhibits low solubility, pronounced crystallinity as measured by X-ray diffraction, melting and crystallization transitions at Tm = 96 °C and Tc = 66 °C, and a high decomposition temperature (Tdec,50% = 524 °C). The aliphatic analogue exhibits higher solubility, lower melting and crystallization temperatures (Tm = 60 °C, Tc = 45 °C), a glass-transition temperature of −32 °C, and a lower Tdec,50% value of 357 °C. Thermal stability and preliminary combustion analyses show that the polymers possess favourable prospects as halogen-free flame retardants. These results establish PN cage-based diols as versatile building blocks for cage-dense hybrid polymers and a platform for next-generation high-performance materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148821667","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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