Hongyu Jiang, Haotian Yang, Siyue Qiu, Jialiang Nie, Meizhu Qin, Zihan Wang, Xinfeng Yang, Shaohua Zhang, Gang Liu, Wenlong Xu
Hydrogels, renowned for their exceptional mechanical properties, superior swelling capacity, excellent biocompatibility, and notable ionic conductivity, have demonstrated significant potential across diverse fields, including biomedicine, food industry, and flexible electronics. However, conventional hydrogels face a significant limitation in cold environments: the internal water within these materials tends to freeze at low temperatures. This freezing process not only compromises the structural integrity of the hydrogels but also drastically reduces their performance, severely limiting their utility in cold environments. As a result, the development of antifreeze hydrogels has become a critical area of research. These advanced hydrogels are designed to effectively inhibit the formation and growth of ice crystals, enabling them to maintain optimal performance even under low-temperature conditions. This article provides a comprehensive and in-depth review of the current research progress on antifreeze hydrogels, meticulously analyzing their antifreeze mechanisms and synthesis strategies. Furthermore, we systematically discuss the unique properties of antifreeze hydrogels and their specific applications across various fields. Finally, we present insights into the current challenges and future directions for the development of antifreeze hydrogels.
{"title":"Synthesis Strategy and Application of Multifunctional Antifreeze Hydrogels","authors":"Hongyu Jiang, Haotian Yang, Siyue Qiu, Jialiang Nie, Meizhu Qin, Zihan Wang, Xinfeng Yang, Shaohua Zhang, Gang Liu, Wenlong Xu","doi":"10.1039/d5py00346f","DOIUrl":"https://doi.org/10.1039/d5py00346f","url":null,"abstract":"Hydrogels, renowned for their exceptional mechanical properties, superior swelling capacity, excellent biocompatibility, and notable ionic conductivity, have demonstrated significant potential across diverse fields, including biomedicine, food industry, and flexible electronics. However, conventional hydrogels face a significant limitation in cold environments: the internal water within these materials tends to freeze at low temperatures. This freezing process not only compromises the structural integrity of the hydrogels but also drastically reduces their performance, severely limiting their utility in cold environments. As a result, the development of antifreeze hydrogels has become a critical area of research. These advanced hydrogels are designed to effectively inhibit the formation and growth of ice crystals, enabling them to maintain optimal performance even under low-temperature conditions. This article provides a comprehensive and in-depth review of the current research progress on antifreeze hydrogels, meticulously analyzing their antifreeze mechanisms and synthesis strategies. Furthermore, we systematically discuss the unique properties of antifreeze hydrogels and their specific applications across various fields. Finally, we present insights into the current challenges and future directions for the development of antifreeze hydrogels.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"109 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866148","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}
Azalea Uva, Yaejin Kim, Sofia Michailovich, Sung Yuan Hsu, David C. Bain, Shine Han Huang, Andrew J Musser, Helen Tran
Carotenoids are ideal building blocks for degradable π-conjugated polymers due to their intrinsic single-molecule conductance and well-documented degradation pathways. Previously, we reported a carotenoid-based polymer, p(CP-hexyl), which incorporated a cleavable imine linker enabling degradation via acid hydrolysis or sunlight; however, there was limited insight into its electronic properties. In this current study, we compare the optoelectronic and photophysical properties of p(CP-hexyl) with a structural analog, caro-PPV, which replaces the imine bonds with vinylene groups, to improve charge transport while maintaining degradability. Ultraviolet-visible (UV-Vis) spectroscopy, density functional theory (DFT), and transient absorption (TA) spectroscopy provided a comprehensive understanding of these polymers’ optoelectronic properties. Further, chemical doping and oxidative degradation were evaluated using FeCl3 and trifluoroacetic acid (TFA), unveiling differences in radical formation and degradation mechanisms for both carotenoid-based polymers. Lastly, charge carrier mobility measurements in organic field-effect transistors (OFETs) unveiled caro-PPV’s superior semiconductor performance, with mobilities 103 -104 times greater than p(CP-hexyl). These findings highlight the potential of carotenoid monomers in the design of π-conjugated polymers for degradable electronics.
{"title":"Impact of imine bonds on the electronic properties of degradable carotenoid-based conjugated polymers","authors":"Azalea Uva, Yaejin Kim, Sofia Michailovich, Sung Yuan Hsu, David C. Bain, Shine Han Huang, Andrew J Musser, Helen Tran","doi":"10.1039/d5py00235d","DOIUrl":"https://doi.org/10.1039/d5py00235d","url":null,"abstract":"Carotenoids are ideal building blocks for degradable π-conjugated polymers due to their intrinsic single-molecule conductance and well-documented degradation pathways. Previously, we reported a carotenoid-based polymer, p(CP-hexyl), which incorporated a cleavable imine linker enabling degradation via acid hydrolysis or sunlight; however, there was limited insight into its electronic properties. In this current study, we compare the optoelectronic and photophysical properties of p(CP-hexyl) with a structural analog, caro-PPV, which replaces the imine bonds with vinylene groups, to improve charge transport while maintaining degradability. Ultraviolet-visible (UV-Vis) spectroscopy, density functional theory (DFT), and transient absorption (TA) spectroscopy provided a comprehensive understanding of these polymers’ optoelectronic properties. Further, chemical doping and oxidative degradation were evaluated using FeCl3 and trifluoroacetic acid (TFA), unveiling differences in radical formation and degradation mechanisms for both carotenoid-based polymers. Lastly, charge carrier mobility measurements in organic field-effect transistors (OFETs) unveiled caro-PPV’s superior semiconductor performance, with mobilities 10<small><sup>3</sup></small> -10<small><sup>4</sup></small> times greater than p(CP-hexyl). These findings highlight the potential of carotenoid monomers in the design of π-conjugated polymers for degradable electronics.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"2 1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A study of the collapse of bisdiazo compounds with different terminal groups upon heating, to generate reactive biscarbene intermediates has provided evidence for homopolymerization, in a process which proceeds in the absence of catalysts and is tolerant of oxygen. This polymerization behavior was monitored spectroscopically through UV-Vis kinetic analysis with various combinations of temperature and solvent, and clear evidence for dimer and trimer formation was found by Field Desorption Mass Spectrometry. Oligomerisation may involve the formation of C=C and C=N-N=C linkage, as studied validified by molecular dynamic (MD) calculations, before reaching macromolecular size. In the presence of terminal NH2 groups, cross-linking resulting from carbene insertion, is also observed. This unusual polymerization of diazo monomers, when conducted on a polyvinyl alcohol (PVA) surface in the open-air upon heating, creates a highly crosslinked structure which changes surface properties.
{"title":"Polymerization Behavior of Biscarbenes Derived by Thermolysis of Bisdiazo Compounds","authors":"Mark G Moloney, Xiaosong Liu, Koji Okuda","doi":"10.1039/d4py01474j","DOIUrl":"https://doi.org/10.1039/d4py01474j","url":null,"abstract":"A study of the collapse of bisdiazo compounds with different terminal groups upon heating, to generate reactive biscarbene intermediates has provided evidence for homopolymerization, in a process which proceeds in the absence of catalysts and is tolerant of oxygen. This polymerization behavior was monitored spectroscopically through UV-Vis kinetic analysis with various combinations of temperature and solvent, and clear evidence for dimer and trimer formation was found by Field Desorption Mass Spectrometry. Oligomerisation may involve the formation of C=C and C=N-N=C linkage, as studied validified by molecular dynamic (MD) calculations, before reaching macromolecular size. In the presence of terminal NH2 groups, cross-linking resulting from carbene insertion, is also observed. This unusual polymerization of diazo monomers, when conducted on a polyvinyl alcohol (PVA) surface in the open-air upon heating, creates a highly crosslinked structure which changes surface properties.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"91 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866149","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}
Naralyne Pesqueira, Fabrice Morlet-Savary, Michael Schmitt, Valdemiro P. Carvalho, Jr., Beatriz Eleutério Goi, Jacques Lalevée
The evaluation of NiII complexes bearing bidentate N-heterocyclic carbene (NHC) ligands has shown great potential as catalysts in various reactions. However, their luminescence properties and photocatalytic applications remain underexplored. Two novel nickel-based NHC complexes, [Ni(py-NHC)2](PF6)2 (NiC1) and [Ni(ph-NHC)2] (NiC2), were synthesized with ligands N-Mesityl-N’-2-pyridylimidazolium Tetrafluorophosphate and 1-Mesityl-3-phenyl-1H-imidazol-3-ium Tetrafluorophosphate, respectively. The complexes were thoroughly characterized using spectroscopy techniques, including FTIR, UV-Vis, 1H NMR, and fluorescence, along with elemental analysis, cyclic voltammetry, and mass spectrometry. NiC1 and NiC2 exhibited emission properties and lifetime ranging of 3.8 and 9.1 ns, respectively. The photocatalytic properties of NiC1 and NiC2 were investigated for initiating free radical photopolymerization of ethoxylated trimethylolpropane triacrylate under violet light. This process incorporated di-tert-butyl-diphenyl iodonium hexafluorophosphate and ethyl dimethylaminobenzoate as additives. NiC2 achieved the highest monomer conversion under air or in laminate and was effective in on-off LED irradiation. Proposed oxidative and reductive mechanisms were supported by photolysis, fluorescence quenching, and electron spin resonance data. The optimized system was applied in 3D printing, producing smooth-surfaced, high-resolution patterns.
{"title":"Visible Light-Promoted Nickel-NHC Photocatalysts for Free Radical Photopolymerization and 3D Printing Application","authors":"Naralyne Pesqueira, Fabrice Morlet-Savary, Michael Schmitt, Valdemiro P. Carvalho, Jr., Beatriz Eleutério Goi, Jacques Lalevée","doi":"10.1039/d4py01252f","DOIUrl":"https://doi.org/10.1039/d4py01252f","url":null,"abstract":"The evaluation of NiII complexes bearing bidentate N-heterocyclic carbene (NHC) ligands has shown great potential as catalysts in various reactions. However, their luminescence properties and photocatalytic applications remain underexplored. Two novel nickel-based NHC complexes, [Ni(py-NHC)2](PF6)2 (NiC1) and [Ni(ph-NHC)2] (NiC2), were synthesized with ligands N-Mesityl-N’-2-pyridylimidazolium Tetrafluorophosphate and 1-Mesityl-3-phenyl-1H-imidazol-3-ium Tetrafluorophosphate, respectively. The complexes were thoroughly characterized using spectroscopy techniques, including FTIR, UV-Vis, 1H NMR, and fluorescence, along with elemental analysis, cyclic voltammetry, and mass spectrometry. NiC1 and NiC2 exhibited emission properties and lifetime ranging of 3.8 and 9.1 ns, respectively. The photocatalytic properties of NiC1 and NiC2 were investigated for initiating free radical photopolymerization of ethoxylated trimethylolpropane triacrylate under violet light. This process incorporated di-tert-butyl-diphenyl iodonium hexafluorophosphate and ethyl dimethylaminobenzoate as additives. NiC2 achieved the highest monomer conversion under air or in laminate and was effective in on-off LED irradiation. Proposed oxidative and reductive mechanisms were supported by photolysis, fluorescence quenching, and electron spin resonance data. The optimized system was applied in 3D printing, producing smooth-surfaced, high-resolution patterns.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862166","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}
Zahra Sekhavat Pour, Pravin S. Shinde, Jun Wang, Cameron Woods, Seth Taylor, Sourav Chatterjee, Jason Edward Bara
The abundance of glycerol associated with biofuel production makes it an interesting substrate for a variety of new molecules. Our prior works have demonstrated the controlled and scalable synthesis of symmetric and asymmetric 1,3-diether-2-propanol compounds with a glycerol skeleton, which serve as versatile intermediates for further chemical modifications. Now we demonstrate that 1,3-diether-2-propanol compounds are useful building blocks to synthesize corresponding methacrylate monomers via Steglich esterification with methacrylic anhydride under mild catalytic conditions. The resulting methacrylate monomers were then successfully 3D printed as neat resins using a consumer-level printer. The thermal and mechanical properties of the printed materials were thoroughly investigated. The 3D-printed samples of 1,3-diethoxypropan-2-yl methacrylate (MAA-DEP) possessed good combinations of mechanical and thermal properties, with a tensile strength of 1.61 MPa, elongation at break of 143%, and a glass transition temperature (Tg) near 0 °C. A notable feature of the MAA-DEP monomer is its ability to dissolve polystyrene (PS). Thus, glycerol-based (meth)acrylate monomers present not only new molecules for 3D printing resins with tunable properties but also offer advancements in additive manufacturing by demonstrating how glycerol-derived acrylates also have solvating power to incorporate (waste) thermoplastics into SLA-printable formulations.
{"title":"1,3-Diether-2-Methacrylates with Glycerol Skeletons: Tunable Resins for Stereolithography 3D Printing","authors":"Zahra Sekhavat Pour, Pravin S. Shinde, Jun Wang, Cameron Woods, Seth Taylor, Sourav Chatterjee, Jason Edward Bara","doi":"10.1039/d5py00198f","DOIUrl":"https://doi.org/10.1039/d5py00198f","url":null,"abstract":"The abundance of glycerol associated with biofuel production makes it an interesting substrate for a variety of new molecules. Our prior works have demonstrated the controlled and scalable synthesis of symmetric and asymmetric 1,3-diether-2-propanol compounds with a glycerol skeleton, which serve as versatile intermediates for further chemical modifications. Now we demonstrate that 1,3-diether-2-propanol compounds are useful building blocks to synthesize corresponding methacrylate monomers via Steglich esterification with methacrylic anhydride under mild catalytic conditions. The resulting methacrylate monomers were then successfully 3D printed as neat resins using a consumer-level printer. The thermal and mechanical properties of the printed materials were thoroughly investigated. The 3D-printed samples of 1,3-diethoxypropan-2-yl methacrylate (MAA-DEP) possessed good combinations of mechanical and thermal properties, with a tensile strength of 1.61 MPa, elongation at break of 143%, and a glass transition temperature (Tg) near 0 °C. A notable feature of the MAA-DEP monomer is its ability to dissolve polystyrene (PS). Thus, glycerol-based (meth)acrylate monomers present not only new molecules for 3D printing resins with tunable properties but also offer advancements in additive manufacturing by demonstrating how glycerol-derived acrylates also have solvating power to incorporate (waste) thermoplastics into SLA-printable formulations.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862442","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}
Maxime Michelas, Nathaniel Corrigan, Cyrille Boyer
Polymerization-induced microphase separation (PIMS) is a versatile technique for manufacturing nanostructured materials. Combining PIMS with 3D printing enables the fabrication of complex objects with nanoscale features, opening possibilities in diverse applications, including nanostructured ceramics, solid polymer electrolytes, and ion-exchange materials. Traditionally, PIMS utilizes polymers synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization (macromolecular Chain Transfer Agents, macroCTAs). However, RAFT-based PIMS can introduce undesirable color and odor into the final materials. To address these limitations, this study explores the use of macromonomers, polymers terminated with acrylate or methacrylate groups, as alternatives to macroCTAs. We synthesized a series of polycaprolactone (PCL) variants with identical molecular weights but differing terminal functionalities: acrylate, methacrylate, trithiocarbonate, and dithiobenzoate. This library enabled a direct comparison of macromonomer and macroCTA approaches for nanostructured material fabrication via PIMS. Small-angle X-ray scattering (SAXS) was employed to determine nanodomain sizes. Notably, both acrylate and trithiocarbonate-terminated PCLs yielded comparable nanodomain sizes. Exploiting PCL degradation, we fabricated nanoporous, 3D-printed objects by selectively etching the PCL from materials formed with both trithiocarbonate and acrylate-terminated PCL. Critically, the acrylate-terminated macromonomer-based PIMS system produced transparent, colorless materials with well-defined microstructures. This work demonstrates the potential of macromonomers to overcome the inherent limitations of RAFT-PIMS, providing a cleaner and more versatile pathway to advanced nanostructured materials.
{"title":"3D Printing via Polymerization-Induced Microphase Separation using Acrylate Macromonomers instead of MacroRAFT Agents","authors":"Maxime Michelas, Nathaniel Corrigan, Cyrille Boyer","doi":"10.1039/d5py00226e","DOIUrl":"https://doi.org/10.1039/d5py00226e","url":null,"abstract":"Polymerization-induced microphase separation (PIMS) is a versatile technique for manufacturing nanostructured materials. Combining PIMS with 3D printing enables the fabrication of complex objects with nanoscale features, opening possibilities in diverse applications, including nanostructured ceramics, solid polymer electrolytes, and ion-exchange materials. Traditionally, PIMS utilizes polymers synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization (macromolecular Chain Transfer Agents, macroCTAs). However, RAFT-based PIMS can introduce undesirable color and odor into the final materials. To address these limitations, this study explores the use of macromonomers, polymers terminated with acrylate or methacrylate groups, as alternatives to macroCTAs. We synthesized a series of polycaprolactone (PCL) variants with identical molecular weights but differing terminal functionalities: acrylate, methacrylate, trithiocarbonate, and dithiobenzoate. This library enabled a direct comparison of macromonomer and macroCTA approaches for nanostructured material fabrication via PIMS. Small-angle X-ray scattering (SAXS) was employed to determine nanodomain sizes. Notably, both acrylate and trithiocarbonate-terminated PCLs yielded comparable nanodomain sizes. Exploiting PCL degradation, we fabricated nanoporous, 3D-printed objects by selectively etching the PCL from materials formed with both trithiocarbonate and acrylate-terminated PCL. Critically, the acrylate-terminated macromonomer-based PIMS system produced transparent, colorless materials with well-defined microstructures. This work demonstrates the potential of macromonomers to overcome the inherent limitations of RAFT-PIMS, providing a cleaner and more versatile pathway to advanced nanostructured materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857305","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 review comprehensively assesses recent advancements in the utilization of cation-π interactions in high-performance polymers, a unique form of point-to-face non-covalent bonding with significant implications in both biological systems and materials science. We begin by exploring the fundamental properties of cation-π interactions, including their nature, influencing factors, and various classifications. The review then delves into specific types of high-performance polymer materials, such as films, porous materials, hydrogels, composites, and storage materials, each illustrating how cation-π interactions influence their structure and properties. Particular emphasis is placed on the challenges of precise molecular design, stability under diverse conditions, multifunctionality, and managing competing interactions. Through selected examples, we highlight strategies to regulate and enhance these interactions, offering insights into the future trajectories of research in this rapidly evolving field.
{"title":"Cation-π Interactions in Polymer Science: From Fundamental Insights to Material Applications","authors":"Tianhang Zhou, Ning Wang, Yang Gao, Xiaoan Li","doi":"10.1039/d5py00232j","DOIUrl":"https://doi.org/10.1039/d5py00232j","url":null,"abstract":"This review comprehensively assesses recent advancements in the utilization of cation-π interactions in high-performance polymers, a unique form of point-to-face non-covalent bonding with significant implications in both biological systems and materials science. We begin by exploring the fundamental properties of cation-π interactions, including their nature, influencing factors, and various classifications. The review then delves into specific types of high-performance polymer materials, such as films, porous materials, hydrogels, composites, and storage materials, each illustrating how cation-π interactions influence their structure and properties. Particular emphasis is placed on the challenges of precise molecular design, stability under diverse conditions, multifunctionality, and managing competing interactions. Through selected examples, we highlight strategies to regulate and enhance these interactions, offering insights into the future trajectories of research in this rapidly evolving field.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857301","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}
Tomohito Inoue, Sota Saito, Akihiro Nishioka, Hideharu Mori
The use of ion-conductive organic–inorganic hybrids with high ionic conductivity, suitable flexibility/viscosity, and good thermal and mechanical properties is a promising approach for the development of next-generation, safer solid-state electrolytes. In this study, a series of new deep eutectic silsesquioxane (SQ) hybrids (DESQs) were developed by simply mixing hydroxyl-functionalized SQ acting as a polyol-type hydrogen bond donor (HBD) with imidazolium- and ammonium-based organic salts acting as hydrogen bond acceptors (HBAs) in the presence of a small amount of difunctional HBAs without the use of volatile organic solvents. The use of cross-linkable HBAs results in improved thermal stability and tunable flexibility (glass transition temperature and viscosity). The combination of hydroxyl-functionalized SQs and imidazolium salt-based mono-/difunctional HBAs afforded hybrids with hydrogen bond networks, showing a suitable balance between thermal properties and high ionic conductivity (4.17 × 10−4 S cm−1 at 25 °C), while maintaining reasonable viscosity (5.62 × 106 mPa S at 25 °C). The ionic conductivity can be improved by adding a lithium salt, allowing for an efficient approach for obtaining safer, greener, and cost-effective electrolytes with good ionic conductivity.
{"title":"Deep eutectic ion-conductive hybrids produced by combining hydroxyl-functionalized silsesquioxane and mono-/difunctional hydrogen bond acceptors","authors":"Tomohito Inoue, Sota Saito, Akihiro Nishioka, Hideharu Mori","doi":"10.1039/d5py00192g","DOIUrl":"https://doi.org/10.1039/d5py00192g","url":null,"abstract":"The use of ion-conductive organic–inorganic hybrids with high ionic conductivity, suitable flexibility/viscosity, and good thermal and mechanical properties is a promising approach for the development of next-generation, safer solid-state electrolytes. In this study, a series of new deep eutectic silsesquioxane (SQ) hybrids (DESQs) were developed by simply mixing hydroxyl-functionalized SQ acting as a polyol-type hydrogen bond donor (HBD) with imidazolium- and ammonium-based organic salts acting as hydrogen bond acceptors (HBAs) in the presence of a small amount of difunctional HBAs without the use of volatile organic solvents. The use of cross-linkable HBAs results in improved thermal stability and tunable flexibility (glass transition temperature and viscosity). The combination of hydroxyl-functionalized SQs and imidazolium salt-based mono-/difunctional HBAs afforded hybrids with hydrogen bond networks, showing a suitable balance between thermal properties and high ionic conductivity (4.17 × 10<small><sup>−4</sup></small> S cm<small><sup>−1</sup></small> at 25 °C), while maintaining reasonable viscosity (5.62 × 10<small><sup>6</sup></small> mPa S at 25 °C). The ionic conductivity can be improved by adding a lithium salt, allowing for an efficient approach for obtaining safer, greener, and cost-effective electrolytes with good ionic conductivity.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857302","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}
Gregor M. Linden, Sandra Schüttner, Nora Fribiczer, Sebastian Seiffert, Holger Frey
Oleyl glycidyl ether (OlGE) is a highly hydrophobic monomer synthesized from a biobased fatty alcohol and epichlorohydrin. When combined with hydrophilic monomethoxy poly(ethylene glycol) (mPEG) macroinitiators, well-defined, highly amphiphilic AB block copolymers are obtained via anionic ring-opening polymerization (Đ ≤ 1.08). Surprisingly, an investigation of the copolymerization kinetics of OlGE and ethylene oxide revealed an almost ideally random copolymerization (rEO = 1.27, rOlGE = 0.78) despite the significant structural differences. Both statistical and block copolymers were investigated regarding their behavior in aqueous solution. The block copolymers of the type mPEG-b-POlGE featured two distinct melting temperatures (Tms). Besides a melting transition of mPEG, a second Tm is attributed to the crystallization of the cis-alkenyl side chain of the OlGE units. Varying degrees of side chain hydrogenation of the POlGE homopolymer using potassium azodicarboxylate (PADA) allowed for tailoring of the Tm. The thiol-ene click reaction allowed subsequent functionalization. This work not merely highlights the prospect of novel polyether surfactants, it also suggests the potential of biobased long-chain polyethers for the development of drug delivery systems featuring temperature-controlled release.
{"title":"Biobased Oleyl Glycidyl Ether: Copolymerization with Ethylene Oxide, Postmodification, Thermal Properties, and Micellization Behavior","authors":"Gregor M. Linden, Sandra Schüttner, Nora Fribiczer, Sebastian Seiffert, Holger Frey","doi":"10.1039/d5py00159e","DOIUrl":"https://doi.org/10.1039/d5py00159e","url":null,"abstract":"Oleyl glycidyl ether (OlGE) is a highly hydrophobic monomer synthesized from a biobased fatty alcohol and epichlorohydrin. When combined with hydrophilic monomethoxy poly(ethylene glycol) (mPEG) macroinitiators, well-defined, highly amphiphilic AB block copolymers are obtained via anionic ring-opening polymerization (Đ ≤ 1.08). Surprisingly, an investigation of the copolymerization kinetics of OlGE and ethylene oxide revealed an almost ideally random copolymerization (rEO = 1.27, rOlGE = 0.78) despite the significant structural differences. Both statistical and block copolymers were investigated regarding their behavior in aqueous solution. The block copolymers of the type mPEG-b-POlGE featured two distinct melting temperatures (Tms). Besides a melting transition of mPEG, a second Tm is attributed to the crystallization of the cis-alkenyl side chain of the OlGE units. Varying degrees of side chain hydrogenation of the POlGE homopolymer using potassium azodicarboxylate (PADA) allowed for tailoring of the Tm. The thiol-ene click reaction allowed subsequent functionalization. This work not merely highlights the prospect of novel polyether surfactants, it also suggests the potential of biobased long-chain polyethers for the development of drug delivery systems featuring temperature-controlled release.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853393","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}
Exploring monomers that undergo polymerization–depolymerization processes is of great importance for constructing closed-loop chemical recycling systems. In this study, six-membered 1,3-dioxa-2-silacycloalkanes were demonstrated to undergo ring-opening polymerization with 1,5,7-triazabicyclo[4.4.0]dec-5-ene as a catalyst. Moreover, monomer regeneration via polymer degradation was achieved by a distillation-combined reaction with an acid catalyst.
{"title":"Ring-opening polymerization of six-membered 1,3-dioxa-2-silacycloalkanes by an organobase catalyst: precision polymerization and monomer regeneration by polymer degradation","authors":"Ikuto Tanaka, Sadahito Aoshima, Arihiro Kanazawa","doi":"10.1039/d5py00204d","DOIUrl":"https://doi.org/10.1039/d5py00204d","url":null,"abstract":"Exploring monomers that undergo polymerization–depolymerization processes is of great importance for constructing closed-loop chemical recycling systems. In this study, six-membered 1,3-dioxa-2-silacycloalkanes were demonstrated to undergo ring-opening polymerization with 1,5,7-triazabicyclo[4.4.0]dec-5-ene as a catalyst. Moreover, monomer regeneration via polymer degradation was achieved by a distillation-combined reaction with an acid catalyst.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853392","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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