The kinetics of ureate anion-catalyzed ring-opening polymerization (ROP) of 3,6-diethyltetrahydro-2H-pyran-2-one () and 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one (), CO2-derived lactones, is reported. Polymerization rates were significantly enhanced by matching the pKa of a particular urea and the pKa-H of the base, with stronger bases and more weakly acidic ureas leading to universally fast catalysis—reducing reaction times from earlier-reported days to minutes/seconds. In parallel, 2-ethylheptanoic acid (), a byproduct from monomer synthesis, was discovered to completely suppress polymerization, even in trace amounts. This highlights the need for rigorous purification protocols to ensure high monomer purity. These results demonstrate the dual importance of chemical purity and rational catalyst design for achieving rapid ROP of CO2-derived and offer a framework for advancing sustainable polymer synthesis.
{"title":"Ureate anion-catalyzed ring-opening polymerization (ROP) of CO2-derived lactones: rapid catalysis through pKa matching","authors":"Madhur M. Bhatt , Arron C. Deacy , Ian A. Tonks","doi":"10.1039/d5py00950b","DOIUrl":"10.1039/d5py00950b","url":null,"abstract":"<div><div>The kinetics of ureate anion-catalyzed ring-opening polymerization (ROP) of 3,6-diethyltetrahydro-2<em>H</em>-pyran-2-one () and 3-ethyl-6-vinyltetrahydro-2<em>H</em>-pyran-2-one (), CO<sub>2</sub>-derived lactones, is reported. Polymerization rates were significantly enhanced by matching the p<em>K</em><sub>a</sub> of a particular urea and the p<em>K</em><sub>a-H</sub> of the base, with stronger bases and more weakly acidic ureas leading to universally fast catalysis—reducing reaction times from earlier-reported days to minutes/seconds. In parallel, 2-ethylheptanoic acid (), a byproduct from monomer synthesis, was discovered to completely suppress polymerization, even in trace amounts. This highlights the need for rigorous purification protocols to ensure high monomer purity. These results demonstrate the dual importance of chemical purity and rational catalyst design for achieving rapid ROP of CO<sub>2</sub>-derived and offer a framework for advancing sustainable polymer synthesis.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 47","pages":"Pages 5064-5069"},"PeriodicalIF":3.9,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145448193","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}
Marta Pacheco-Romeralo , Eva Hernández-García , Antxon Martínez de Ilarduya , Ronak Janani , Chris Sammon , Sergio Torres-Giner
Acting on the Bioeconomy strategy, this study has developed fully bio-based copolyamide 1010/410 (PA1010/410) from “nylon salts” derived from renewable putrescine, decamethylenediamine, and sebacic acid monomers. Different fully bio-based copolyamides were synthetized by the polycondensation reaction of nylon 1010 salt with 12.5, 25, and 37.5 mol% of nylon 410 salt. Thereafter, the resultant PA1010/410 grades were shaped into 150-µm films by thermo-compression and characterized. Results showed that the putrescine content presents a strong influence on the molecular weight, crystallinity and, hence, thermal, mechanical, and barrier properties of PA1010/410. In particular, it was observed that the introduction of nylon 410 contents at 25 and 37.5 mol% resulted in PA1010/410 grades in the 2–3 × 104 g mol−1 range, with a crystallinity as low as ∼15%. Interestingly, these copolyamide compositions led to transparent films melting at nearly 180 °C, being highly ductile with elongation at break of up to 130% and improved barrier to oxygen with a permeability as low as 5.3 × 10−19 m3 m m−2 Pa−1 s−1. These green nylons were finally applied as lid films in trays to preserve beef meat, and were shown to successfully extend food shelf life beyond those of current commercial monolayer solutions based on petrochemical polymers, thereby showing their potential for use in sustainable food packaging.
{"title":"Synthesis and characterization of copolyamide 1010/410 with varying putrescine contents for meat packaging applications","authors":"Marta Pacheco-Romeralo , Eva Hernández-García , Antxon Martínez de Ilarduya , Ronak Janani , Chris Sammon , Sergio Torres-Giner","doi":"10.1039/d5py00766f","DOIUrl":"10.1039/d5py00766f","url":null,"abstract":"<div><div>Acting on the Bioeconomy strategy, this study has developed fully bio-based copolyamide 1010/410 (PA1010/410) from “nylon salts” derived from renewable putrescine, decamethylenediamine, and sebacic acid monomers. Different fully bio-based copolyamides were synthetized by the polycondensation reaction of nylon 1010 salt with 12.5, 25, and 37.5 mol% of nylon 410 salt. Thereafter, the resultant PA1010/410 grades were shaped into 150-µm films by thermo-compression and characterized. Results showed that the putrescine content presents a strong influence on the molecular weight, crystallinity and, hence, thermal, mechanical, and barrier properties of PA1010/410. In particular, it was observed that the introduction of nylon 410 contents at 25 and 37.5 mol% resulted in PA1010/410 grades in the 2–3 × 10<sup>4</sup> g mol<sup>−1</sup> range, with a crystallinity as low as ∼15%. Interestingly, these copolyamide compositions led to transparent films melting at nearly 180 °C, being highly ductile with elongation at break of up to 130% and improved barrier to oxygen with a permeability as low as 5.3 × 10<sup>−19</sup> m<sup>3</sup> m m<sup>−2</sup> Pa<sup>−1</sup> s<sup>−1</sup>. These green nylons were finally applied as lid films in trays to preserve beef meat, and were shown to successfully extend food shelf life beyond those of current commercial monolayer solutions based on petrochemical polymers, thereby showing their potential for use in sustainable food packaging.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 47","pages":"Pages 5040-5063"},"PeriodicalIF":3.9,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145448198","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}
Shilei Qu , Wuyan Liu , Lili An , Xinyu Liu , Zhongyi Wang , Zezhou Liang , Chunyan Yang , Junfeng Tong
Constructing asymmetric polymeric semiconductors was proved to be an effective strategy for preparing key photoactive layer materials for high-performing organic solar cells. In this investigation, two region-asymmetric medium bandgap (MBG) type conjugated copolymers (CPs), namely PFBDT-TBT and PFBDT-TClBT, in which electron-rich 4,8-bis(4-fluoro-5-(2-butyloctyl)thien-2-yl)benzo[1,2-b:4,5-b′]dithiophene (FBDT) and electron-deficient benzothiadiazole (BT)/5-chlorobenzothiadiazole (ClBT), in conjunction with 3-octylthiophene, were sequentially designated as donors, acceptors, and π-conjugated bridging moieties, were developed, with the primary objective of investigating the role of monochlorination. Monochlorinated PFBDT-TClBT possessed lower thermal stability but better photostability. Monochlorination induced slightly blue-shifted absorption and an unchanged optical bandgap, weakened aggregation both in the solution and thin-film states, deepened EHOMO, resulted in greater twisting geometry, and markedly increased the natural dipole moment. Influenced by this, a chlorine-free PFBDT-TBT:Y6-based device delivered a PCE of 7.77%, with a VOC of 0.80 V, a JSC of 18.67 mA cm−2 and an FF of 51.9%. In contrast, monochlorination facilitated the PFBDT-TClBT-based device to acquire a 0.07 V elevated VOC of 0.87 V, a 5.78% heightened JSC of 19.75 mA cm−2, and a 7.32% increased FF of 55.7%, collectively contributing to an 22.65% increased PCE to 9.53 %. This increase in PCE after monochlorination was mainly due to the deepened EHOMO, better exciton dissociation, suppressed bimolecular recombination and a more balanced μe/µh ratio originating from the desired predominant face-on molecular orientation and reduced aggregation, better miscibility and smoother surface morphology. This finding demonstrated that monochlorination was an effective and promising design approach for improving photovoltaic performance by regulating the molecular structure, energy levels, packing and microstructural morphology.
构造不对称聚合物半导体是制备高性能有机太阳能电池关键光活性层材料的有效策略。本文研究了两种区域不对称介质带隙（MBG）型共轭共聚物PFBDT-TBT和PFBDT-TClBT，其中富电子的4,8-二（4-氟-5-（2-丁基辛基）噻吩-2-基）苯并[1,2-b:4,5-b ']二噻吩（FBDT）、缺电子的苯并噻唑(BT)/5-氯并噻唑（ClBT）与3-辛基噻吩依次被指定为给体、受体和共轭桥接基团。主要目的是研究沿聚合物主链的单氯化修饰的功能作用。单氯化PFBDT-TClBT的热稳定性下降，但光稳定性较好。单氯化作用使其吸收发生轻微蓝移，光学带隙不变，溶液态和薄膜态的聚集现象减弱，EHOMO加深，分子几何扭曲加剧，自然偶极矩明显增加。受此影响，无氯PFBDT-TBT: y6基器件的PCE为7.77%，VOC为0.80 V， JSC为18.67 mA cm-2， FF为51.9%。相比之下，单氯化处理使基于PFBDT-TClBT的器件VOC提高了0.07 V，达到0.87 V， JSC提高了5.78%，达到19.75 mA cm-2， FF提高了7.32%，达到55.7%，PCE提高了11.52%，达到9.53%。单氯化后PCE的增加主要是由于EHOMO加深，激子解离更好，双分子重组受到抑制，μe/µh比更平衡，这是由于所期望的主要面朝分子取向和聚集减少，更好的混溶性和更光滑的表面形貌。这一发现表明，单氯化是一种有效的、有前途的设计方法，可以通过调节分子结构、能级、填料和微观结构形态来提高PV的性能。
{"title":"Monochlorination-enabled elevated solar cell performance in region-asymmetric benzothiadiazole-based medium bandgap conjugated copolymers","authors":"Shilei Qu , Wuyan Liu , Lili An , Xinyu Liu , Zhongyi Wang , Zezhou Liang , Chunyan Yang , Junfeng Tong","doi":"10.1039/d5py00928f","DOIUrl":"10.1039/d5py00928f","url":null,"abstract":"<div><div>Constructing asymmetric polymeric semiconductors was proved to be an effective strategy for preparing key photoactive layer materials for high-performing organic solar cells. In this investigation, two region-asymmetric medium bandgap (MBG) type conjugated copolymers (CPs), namely PFBDT-TBT and PFBDT-TClBT, in which electron-rich 4,8-bis(4-fluoro-5-(2-butyloctyl)thien-2-yl)benzo[1,2-<em>b</em>:4,5-<em>b</em>′]dithiophene (FBDT) and electron-deficient benzothiadiazole (BT)/5-chlorobenzothiadiazole (ClBT), in conjunction with 3-octylthiophene, were sequentially designated as donors, acceptors, and π-conjugated bridging moieties, were developed, with the primary objective of investigating the role of monochlorination. Monochlorinated PFBDT-TClBT possessed lower thermal stability but better photostability. Monochlorination induced slightly blue-shifted absorption and an unchanged optical bandgap, weakened aggregation both in the solution and thin-film states, deepened <em>E</em><sub>HOMO</sub>, resulted in greater twisting geometry, and markedly increased the natural dipole moment. Influenced by this, a chlorine-free PFBDT-TBT:Y6-based device delivered a PCE of 7.77%, with a <em>V</em><sub>OC</sub> of 0.80 V, a <em>J</em><sub>SC</sub> of 18.67 mA cm<sup>−2</sup> and an <em>FF</em> of 51.9%. In contrast, monochlorination facilitated the PFBDT-TClBT-based device to acquire a 0.07 V elevated <em>V</em><sub>OC</sub> of 0.87 V, a 5.78% heightened <em>J</em><sub>SC</sub> of 19.75 mA cm<sup>−2</sup>, and a 7.32% increased FF of 55.7%, collectively contributing to an 22.65% increased PCE to 9.53 %. This increase in PCE after monochlorination was mainly due to the deepened <em>E</em><sub>HOMO</sub>, better exciton dissociation, suppressed bimolecular recombination and a more balanced <em>μ</em><sub>e</sub>/<em>µ</em><sub>h</sub> ratio originating from the desired predominant face-on molecular orientation and reduced aggregation, better miscibility and smoother surface morphology. This finding demonstrated that monochlorination was an effective and promising design approach for improving photovoltaic performance by regulating the molecular structure, energy levels, packing and microstructural morphology.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 47","pages":"Pages 5079-5092"},"PeriodicalIF":3.9,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145455376","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}
This study systematically investigates the kinetics and selectivity of photoinduced reversible addition–fragmentation chain-transfer single unit monomer insertion (RAFT SUMI) reactions in different solvents. The thiocarbonylthio-based chain transfer agent (CTA) was directly activated by visible light, enabling the incorporation of vinyl monomers. Although the SUMI reaction provides a potential way to precisely control the sequence of oligomers, it usually suffers from a slow reaction rate and low product selectivity. We found that these challenges could be overcome by simply performing the SUMI reaction in a deep eutectic solvent composed of tetrabutylammonium chloride and ethylene glycol. Compared to common organic solvents, acetonitrile (ACN) and dimethyl sulfoxide (DMSO), the photoinduced SUMI reaction in DES exhibited a significantly enhanced reaction rate and selectivity. Nearly full conversion of the initial CTA could be achieved in only 60 min of green light irradiation under N2-degassed conditions in DES, while 120 min was required for the reaction in ACN. Furthermore, the SUMI reaction in DES showed a high oxygen tolerance. In particular, the reaction in ACN under open-to-air conditions led to a significant degradation of CTA. In contrast, the degradation of CTA in DES was much less pronounced. Finally, DES is applicable to a wide range of monomers and the SUMI reaction of a second building block. These findings highlight the value of DES in developing green and sequence-controlled polymerization platforms.
{"title":"Photoinduced single unit monomer insertion promoted by deep eutectic solvents","authors":"Bo-Rong Hung , Ting-En Kung , Sheng-Sheng Yu","doi":"10.1039/d5py00848d","DOIUrl":"10.1039/d5py00848d","url":null,"abstract":"<div><div>This study systematically investigates the kinetics and selectivity of photoinduced reversible addition–fragmentation chain-transfer single unit monomer insertion (RAFT SUMI) reactions in different solvents. The thiocarbonylthio-based chain transfer agent (CTA) was directly activated by visible light, enabling the incorporation of vinyl monomers. Although the SUMI reaction provides a potential way to precisely control the sequence of oligomers, it usually suffers from a slow reaction rate and low product selectivity. We found that these challenges could be overcome by simply performing the SUMI reaction in a deep eutectic solvent composed of tetrabutylammonium chloride and ethylene glycol. Compared to common organic solvents, acetonitrile (ACN) and dimethyl sulfoxide (DMSO), the photoinduced SUMI reaction in DES exhibited a significantly enhanced reaction rate and selectivity. Nearly full conversion of the initial CTA could be achieved in only 60 min of green light irradiation under N<sub>2</sub>-degassed conditions in DES, while 120 min was required for the reaction in ACN. Furthermore, the SUMI reaction in DES showed a high oxygen tolerance. In particular, the reaction in ACN under open-to-air conditions led to a significant degradation of CTA. In contrast, the degradation of CTA in DES was much less pronounced. Finally, DES is applicable to a wide range of monomers and the SUMI reaction of a second building block. These findings highlight the value of DES in developing green and sequence-controlled polymerization platforms.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 47","pages":"Pages 5070-5078"},"PeriodicalIF":3.9,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145448195","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}
Aya Saruwatari, Yuji Kamiyama, Jun Nakanishi, Ryota Tamate and Takeshi Ueki
Cell culture at liquid|liquid interfaces has gained attention from the perspective of the mechanobiology. We recently reported cell culture at water-immiscible ionic liquids (ILs) interface, which have an advantage of polymer compatibility over the conventional non-polar liquid scaffold capable of interfacial cell culturing. Herein, we report a light-responsive polymer solution in a noncytotoxic IL (NCIL) that reversibly changes its viscosity. Methoxyazobenzene (mAzoA) was selected as the chromophore for reversible photoisomerization under non-phototoxic visible light. For a main polymer, poly(methyl methacrylate) (PMMA) was chosen because of exhibiting upper critical solution temperature (UCST) type phase transition in an NCIL ([P8,8,8,8][TFSI]) near cell culturing temperature. We successfully demonstrated that the loss modulus of the polymer solution was switched reversibly triggered by visible light photochromism of mAzoA. We also revealed that the polymer solution showed no cytotoxicity, confirming that they can be applied to liquid cell scaffold materials. Furthermore, the thermal isomerization of cis-mAzoA to trans-mAzoA was extremely slowed down in [P8,8,8,8][TFSI] (τ1/2 = 2911 h at 37 °C), suggesting the avoidance of undesired aging degradation during cell culturing operation. The system ability to switch between higher and lower viscoelasticity offers a powerful tool for real-time control of the cellular environment.
{"title":"Stimuli-responsive liquid cell scaffold: reversible viscoelasticity switching of a polymer in an ionic liquid by visible-light","authors":"Aya Saruwatari, Yuji Kamiyama, Jun Nakanishi, Ryota Tamate and Takeshi Ueki","doi":"10.1039/D5PY00876J","DOIUrl":"10.1039/D5PY00876J","url":null,"abstract":"<p >Cell culture at liquid|liquid interfaces has gained attention from the perspective of the mechanobiology. We recently reported cell culture at water-immiscible ionic liquids (ILs) interface, which have an advantage of polymer compatibility over the conventional non-polar liquid scaffold capable of interfacial cell culturing. Herein, we report a light-responsive polymer solution in a noncytotoxic IL (NCIL) that reversibly changes its viscosity. Methoxyazobenzene (mAzoA) was selected as the chromophore for reversible photoisomerization under non-phototoxic visible light. For a main polymer, poly(methyl methacrylate) (PMMA) was chosen because of exhibiting upper critical solution temperature (UCST) type phase transition in an NCIL ([P8,8,8,8][TFSI]) near cell culturing temperature. We successfully demonstrated that the loss modulus of the polymer solution was switched reversibly triggered by visible light photochromism of mAzoA. We also revealed that the polymer solution showed no cytotoxicity, confirming that they can be applied to liquid cell scaffold materials. Furthermore, the thermal isomerization of <em>cis</em>-mAzoA to <em>trans</em>-mAzoA was extremely slowed down in [P8,8,8,8][TFSI] (<em>τ</em><small><sub>1/2</sub></small> = 2911 h at 37 °C), suggesting the avoidance of undesired aging degradation during cell culturing operation. The system ability to switch between higher and lower viscoelasticity offers a powerful tool for real-time control of the cellular environment.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 3","pages":" 310-324"},"PeriodicalIF":3.9,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145448197","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 C. Sheers , Melissa K. Stanfield , Jason A. Smith , Stuart C. Thickett
As the world seeks to reduce its reliance on petrochemicals, the search for renewable polymers with equal or enhanced performance compared to conventional fossil fuel-based materials is crucial. In this study we utilized the readily accessible platform molecule levoglucosenone (LGO) as a renewable feedstock for the synthesis of bio-derived acrylic polymers. LGO, was used in the preparation of the bio-based monomer LGO-acrylate (LGOA), possessing an internal unsaturated carbon–carbon bond within the LGO ring. The as-synthesized monomer was subject to PET-RAFT polymerization with 95% conversion of the acrylate group in 6 hours, with only a small fraction of the internal unsaturated bond in the LGO bicyclic ring pendant group consumed during the course of the polymerization. The homopolymer possessed a high glass transition temperature (up to 118 °C) and excellent thermal stability, and was successfully copolymerized with n-butyl acrylate (BA) both in the bulk and in emulsion, to form polymers with glass transitions below room temperature. Thiol–ene ‘click’ chemistry as a post-polymerization modification approach was performed using the double bonds within LGO pendant groups, enabling convenient polymer functionalization and the formation of crosslinked networks and films via a post-polymerization approach. The formation of thiol functionalized and crosslinked polymers demonstrates the ability to produce tailorable bio-derived polymer networks, identifying LGO as an attractive scaffold for the synthesis of polymers from renewable starting materials.
{"title":"The renewable feedstock levoglucosenone as a building block for the development of bio-derived, functional acrylic polymers","authors":"Hannah C. Sheers , Melissa K. Stanfield , Jason A. Smith , Stuart C. Thickett","doi":"10.1039/d5py00509d","DOIUrl":"10.1039/d5py00509d","url":null,"abstract":"<div><div>As the world seeks to reduce its reliance on petrochemicals, the search for renewable polymers with equal or enhanced performance compared to conventional fossil fuel-based materials is crucial. In this study we utilized the readily accessible platform molecule levoglucosenone (LGO) as a renewable feedstock for the synthesis of bio-derived acrylic polymers. LGO, was used in the preparation of the bio-based monomer LGO-acrylate (LGOA), possessing an internal unsaturated carbon–carbon bond within the LGO ring. The as-synthesized monomer was subject to PET-RAFT polymerization with 95% conversion of the acrylate group in 6 hours, with only a small fraction of the internal unsaturated bond in the LGO bicyclic ring pendant group consumed during the course of the polymerization. The homopolymer possessed a high glass transition temperature (up to 118 °C) and excellent thermal stability, and was successfully copolymerized with <em>n</em>-butyl acrylate (BA) both in the bulk and in emulsion, to form polymers with glass transitions below room temperature. Thiol–ene ‘click’ chemistry as a post-polymerization modification approach was performed using the double bonds within LGO pendant groups, enabling convenient polymer functionalization and the formation of crosslinked networks and films <em>via</em> a post-polymerization approach. The formation of thiol functionalized and crosslinked polymers demonstrates the ability to produce tailorable bio-derived polymer networks, identifying LGO as an attractive scaffold for the synthesis of polymers from renewable starting materials.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 47","pages":"Pages 5093-5105"},"PeriodicalIF":3.9,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536197","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}
Reza Razavi, Alireza Shakeri, Hasan Salehi, Rozgol Bonsale, Amir Jangizehi and Sebastian Seiffert
Forward osmosis (FO), a pressure-free membrane process, holds significant promise for water purification and seawater desalination. However, its efficiency is often limited by internal concentration polarization (ICP). To address this challenge, high-performance thin-film nanocomposite (TFN) membranes were developed by modifying poly(ethersulfone) (PES) substrates with varying amounts of graphene oxide-graft-poly(2-dimethylaminoethyl methacrylate) (GO-g-PDMA) nanoplates. The PDMA polymer is synthesized via atom transfer radical polymerization (ATRP) and covalently grafted onto azide-functionalized GO via click chemistry. This study systematically investigates the effects of GO-g-PDMA loading on substrate morphology, polyamide (PA) active layer formation, and overall membrane performance. Compared to bare GO, GO-g-PDMA significantly enhances the PES substrate's hydrophilicity, porosity, and water permeability. The optimally loaded TFN membrane (0.5 wt% GO-g-PDMA) exhibits superior FO performance, achieving water fluxes of 27.8 ± 1.9 L m−2 h−1 (LMH) in FO mode and 52.1 ± 1.5 LMH in PRO mode. Importantly, this membrane also demonstrates a 53.4% reduction in the structural parameter (S) relative to the unmodified TFC membrane, underscoring its improved resistance to ICP. These findings highlight the potential of GO-g-PDMA-functionalized substrates for enhancing FO membrane performance through synergistic improvements in the structure and function.
{"title":"Graphene oxide-graft-poly(2-(dimethylamino)ethyl methacrylate) as a functional additive for structurally tuned and high-performance thin-film composite membranes","authors":"Reza Razavi, Alireza Shakeri, Hasan Salehi, Rozgol Bonsale, Amir Jangizehi and Sebastian Seiffert","doi":"10.1039/D5PY00605H","DOIUrl":"10.1039/D5PY00605H","url":null,"abstract":"<p >Forward osmosis (FO), a pressure-free membrane process, holds significant promise for water purification and seawater desalination. However, its efficiency is often limited by internal concentration polarization (ICP). To address this challenge, high-performance thin-film nanocomposite (TFN) membranes were developed by modifying poly(ethersulfone) (PES) substrates with varying amounts of graphene oxide-<em>graft</em>-poly(2-dimethylaminoethyl methacrylate) (GO-<em>g</em>-PDMA) nanoplates. The PDMA polymer is synthesized <em>via</em> atom transfer radical polymerization (ATRP) and covalently grafted onto azide-functionalized GO <em>via</em> click chemistry. This study systematically investigates the effects of GO-<em>g</em>-PDMA loading on substrate morphology, polyamide (PA) active layer formation, and overall membrane performance. Compared to bare GO, GO-<em>g</em>-PDMA significantly enhances the PES substrate's hydrophilicity, porosity, and water permeability. The optimally loaded TFN membrane (0.5 wt% GO-<em>g</em>-PDMA) exhibits superior FO performance, achieving water fluxes of 27.8 ± 1.9 L m<small><sup>−2</sup></small> h<small><sup>−1</sup></small> (LMH) in FO mode and 52.1 ± 1.5 LMH in PRO mode. Importantly, this membrane also demonstrates a 53.4% reduction in the structural parameter (<em>S</em>) relative to the unmodified TFC membrane, underscoring its improved resistance to ICP. These findings highlight the potential of GO-<em>g</em>-PDMA-functionalized substrates for enhancing FO membrane performance through synergistic improvements in the structure and function.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 2","pages":" 216-235"},"PeriodicalIF":3.9,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/py/d5py00605h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145448196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Govinda Prasad Devkota , Carter K. Dauenhauer , Jizhou Jiang , Jennifer L. Schaefer
While single-ion conducting polymer electrolytes (SICPEs) are highly promising candidates for safer polymer electrolytes due to their stability and high transference number, their practical application is often hindered by substantially lower ionic conductivities. In this study, we investigate morphology and dynamics of a family of SICPEs based on a side-chain ionomer blended with poly(ethylene oxide) (PEO) at various ratios. In the pure state, the side-chain ionomer is liquid crystalline with dense ionic layers. PEO addition reduced the primary glass transition temperature, accompanied by the emergence of a new glass transition attributed to the ionomer's polystyrene backbone. Morphologically, blends with lower PEO content maintained the lamellar structure of the pure ionomer, while higher PEO ratios resulted in increased disorder. The ionic conductivity of the blend at high PEO content (EO–Li ratio of 20–1) reached 7.9 × 10−5 S cm−1 at 90 °C, approximately four orders of magnitude greater than that of pure ionomer and similar to that of other PEO-ionomer blends containing tethered –sulfonyl(trifluoromethylsulfonyl)imide (–TFSI−) anions. Dielectric spectroscopy revealed that PEO addition leads to increased coupling between dielectric relaxation and long-range ion transport.
虽然单离子导电聚合物电解质（SICPEs）由于其稳定性和高转移数而成为更安全的聚合物电解质的极有希望的候选者，但它们的实际应用往往受到离子电导率大幅降低的阻碍。在这项研究中，我们研究了基于侧链离聚物与聚环氧乙烷（PEO）以不同比例共混的sicpe家族的形态和动力学。在纯态下，侧链离聚体是具有致密离子层的液晶。PEO的加入降低了一次玻璃化转变温度，同时由于离聚体的聚苯乙烯主链产生了新的玻璃化转变。从形貌上看，PEO含量较低的共混物保持了纯离聚体的层状结构，而PEO含量较高的共混物无序性增加。在90°C时，高PEO含量（EO-Li比为20-1）的共混物的离子电导率达到7.9 × 10−5 S cm−1，比纯离聚体的离子电导率高约4个数量级，与其他含有系链-磺酰（三氟甲基磺酰）亚胺（-TFSI−）阴离子的PEO-离聚体共混物的离子电导率相似。电介质谱分析表明，PEO的加入增加了介质弛豫和远程离子输运之间的耦合。
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Loc Tan Nguyen , Adithya Tharayil , Nezha Badi , Johan M. Winne , Filip E. Du Prez
The growing environmental challenge of non-recyclable thermosets underscores the urgent need for sustainable alternatives. Covalent adaptable networks (CANs) containing dynamic β-amino amide moieties have emerged as promising reprocessable polymer networks, combining mechanical robustness with recyclability. In this work, we elucidate the exchange kinetics of both the well-established (retro)-aza-Michael addition and a newly identified transamidation pathway that is operative in β-amino amides. Systematic catalyst screening reveals that acidic catalysts significantly enhance viscoelastic control, thereby improving (re)processing efficiency. Furthermore, we introduce a chemical recycling protocol that enables the recovery of the original amino building blocks with up to 86% purity, demonstrating their direct use as feedstock in material (re)synthesis. These insights advance the fundamental understanding of dynamic bond exchange in β-amino amide based CANs and establish a viable route towards circular thermoset materials for numerous applications.
{"title":"Exploring transamidation and chemical recycling of β-amino amide-derived covalent adaptable networks","authors":"Loc Tan Nguyen , Adithya Tharayil , Nezha Badi , Johan M. Winne , Filip E. Du Prez","doi":"10.1039/d5py00959f","DOIUrl":"10.1039/d5py00959f","url":null,"abstract":"<div><div>The growing environmental challenge of non-recyclable thermosets underscores the urgent need for sustainable alternatives. Covalent adaptable networks (CANs) containing dynamic β-amino amide moieties have emerged as promising reprocessable polymer networks, combining mechanical robustness with recyclability. In this work, we elucidate the exchange kinetics of both the well-established (retro)-aza-Michael addition and a newly identified transamidation pathway that is operative in β-amino amides. Systematic catalyst screening reveals that acidic catalysts significantly enhance viscoelastic control, thereby improving (re)processing efficiency. Furthermore, we introduce a chemical recycling protocol that enables the recovery of the original amino building blocks with up to 86% purity, demonstrating their direct use as feedstock in material (re)synthesis. These insights advance the fundamental understanding of dynamic bond exchange in β-amino amide based CANs and establish a viable route towards circular thermoset materials for numerous applications.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 46","pages":"Pages 5009-5018"},"PeriodicalIF":3.9,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145442039","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}
Erika Saito, Taeka Yonekura, Shuji Okada, Shotaro Nishitsuji, Jun Matsui and Ryohei Yamakado
In this study, π-conjugated anions were used as counterions in poly(4-vinyl-N-alkylpyridinium) (P4VCxP+) to construct highly ordered ionic microstructures. Nuclear magnetic resonance, Fourier transform infrared, and ultraviolet–visible spectroscopies, and differential scanning calorimetry were employed to characterize the resulting ion-pair polymers. Furthermore, thin films were fabricated and subjected to humidity annealing above the glass transition temperature. Grazing-incidence small-angle X-ray scattering showed that humidity annealing promoted the formation of hexagonally packed cylindrical microdomains in P4VCxP+ with π-conjugated anions. The π-conjugated anions increased the effective hydrophilic volume and facilitated the structural alignment via π–π and dipole–dipole interactions. Optical absorption analysis indicated that both pyridinium and π-conjugated anions exhibited end-on orientations and revealed the dynamic behavior of 7,7,8,8-tetracyanoquinodimethane radical anion, including dimerization and charge-transfer complex formation. Thus, π-conjugated ion pairs show significant promise for the controlled self-assembly and functional optical properties of polymeric materials.
在本研究中，π共轭阴离子作为反离子在聚（4-乙烯基- n -烷基吡啶）（P4VC x P +）中构建了高度有序的离子微结构。采用核磁共振、傅里叶变换红外光谱、紫外可见光谱和差示扫描量热法对所得离子对聚合物进行表征。此外，制备薄膜并在玻璃化转变温度以上进行湿度退火。掠入射小角度x射线散射表明，湿度退火促进了P4VC x P +中π共轭阴离子的六边形填充柱状微畴的形成。π共轭阴离子增加了有效亲水性体积，并通过π-π和偶极子-偶极子相互作用促进了结构取向。光学吸收分析表明，吡啶和π共轭阴离子均呈现端对取向，揭示了7,7,8,8-四氰喹啉二甲烷自由基阴离子的动力学行为，包括二聚化和电荷转移配合物的形成。因此，π共轭离子对在高分子材料的控制自组装和功能光学性质方面显示出重要的前景。
{"title":"Construction of higher-ordered structures in alkylpyridinium-based polymers via π-conjugated anion pairing and humidity annealing","authors":"Erika Saito, Taeka Yonekura, Shuji Okada, Shotaro Nishitsuji, Jun Matsui and Ryohei Yamakado","doi":"10.1039/D5PY00879D","DOIUrl":"10.1039/D5PY00879D","url":null,"abstract":"<p >In this study, π-conjugated anions were used as counterions in poly(4-vinyl-<em>N</em>-alkylpyridinium) (<strong>P4VC<small><sub><em>x</em></sub></small>P<small><sup>+</sup></small></strong>) to construct highly ordered ionic microstructures. Nuclear magnetic resonance, Fourier transform infrared, and ultraviolet–visible spectroscopies, and differential scanning calorimetry were employed to characterize the resulting ion-pair polymers. Furthermore, thin films were fabricated and subjected to humidity annealing above the glass transition temperature. Grazing-incidence small-angle X-ray scattering showed that humidity annealing promoted the formation of hexagonally packed cylindrical microdomains in <strong>P4VC<small><sub><em>x</em></sub></small>P<small><sup>+</sup></small></strong> with π-conjugated anions. The π-conjugated anions increased the effective hydrophilic volume and facilitated the structural alignment <em>via</em> π–π and dipole–dipole interactions. Optical absorption analysis indicated that both pyridinium and π-conjugated anions exhibited end-on orientations and revealed the dynamic behavior of 7,7,8,8-tetracyanoquinodimethane radical anion, including dimerization and charge-transfer complex formation. Thus, π-conjugated ion pairs show significant promise for the controlled self-assembly and functional optical properties of polymeric materials.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 1","pages":" 27-34"},"PeriodicalIF":3.9,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145442042","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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