We report a solvent-free melt polycondensation strategy for synthesizing a partially biodegradable isosorbide-based polycarbonate (ISB-based PC) incorporating ethylene oxide (EO)-functionalized comonomers. The incorporation of a minor fraction of EO-modified bisphenol A (5 mol%) significantly enhanced polymerizability, yielding PC with enhanced molecular weight (Mw up to 64 360; dispersity (Đ) ≈ 1.80), improved tensile strength (up to 71.7 MPa, surpassing conventional non-degradable biomass-based PCs at ∼60 MPa), and excellent optical transparency (90.3–93.0%). The polymer exhibited a high glass transition temperature (Tg = 135.7 °C) and enhanced mechanical flexibility due to EO-containing segments. ISO 14855-1-based biodegradation tests revealed 16.7% mineralization over 70 days, significantly exceeding the rates of both petroleum-derived and biomass-based non-degradable polycarbonates. MTT assays confirmed negligible cytotoxicity toward HaCaT keratinocytes, affirming the material's biocompatibility. Green chemistry metrics (E-factor = 0.98, PMI = 1.98, atom economy = 50.5%) demonstrate the environmental efficiency of the process, outperforming conventional phosgene-based approaches. This study presents a scalable and sustainable approach for designing bio-based polycarbonates combining partial biodegradability, cytocompatibility, and desirable material properties. Strategic inclusion of a minimal amount of BPA-EO facilitates bridging high performance with green design, laying a foundation for future development toward fully bio-based systems. The results align with green chemistry principles, highlighting ISB-based PC as a promising candidate for applications in packaging, coatings, and medical devices.
{"title":"An effective strategy to synthesize a novel biodegradable isosorbide-based polycarbonate","authors":"Won-Bin Lim, Gang-Young Lee, Jin-Sik Choi, Jae-Ryong Lee, Jin-Gyu Min, Ju-Hong Lee, Ji-Hong Bae, PilHo Huh","doi":"10.1039/d5py01100k","DOIUrl":"https://doi.org/10.1039/d5py01100k","url":null,"abstract":"We report a solvent-free melt polycondensation strategy for synthesizing a partially biodegradable isosorbide-based polycarbonate (ISB-based PC) incorporating ethylene oxide (EO)-functionalized comonomers. The incorporation of a minor fraction of EO-modified bisphenol A (5 mol%) significantly enhanced polymerizability, yielding PC with enhanced molecular weight (<em>M</em><small><sub>w</sub></small> up to 64 360; dispersity (<em>Đ</em>) ≈ 1.80), improved tensile strength (up to 71.7 MPa, surpassing conventional non-degradable biomass-based PCs at ∼60 MPa), and excellent optical transparency (90.3–93.0%). The polymer exhibited a high glass transition temperature (<em>T</em><small><sub>g</sub></small> = 135.7 °C) and enhanced mechanical flexibility due to EO-containing segments. ISO 14855-1-based biodegradation tests revealed 16.7% mineralization over 70 days, significantly exceeding the rates of both petroleum-derived and biomass-based non-degradable polycarbonates. MTT assays confirmed negligible cytotoxicity toward HaCaT keratinocytes, affirming the material's biocompatibility. Green chemistry metrics (<em>E</em>-factor = 0.98, PMI = 1.98, atom economy = 50.5%) demonstrate the environmental efficiency of the process, outperforming conventional phosgene-based approaches. This study presents a scalable and sustainable approach for designing bio-based polycarbonates combining partial biodegradability, cytocompatibility, and desirable material properties. Strategic inclusion of a minimal amount of BPA-EO facilitates bridging high performance with green design, laying a foundation for future development toward fully bio-based systems. The results align with green chemistry principles, highlighting ISB-based PC as a promising candidate for applications in packaging, coatings, and medical devices.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145893797","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}
Gaoyang Du, Yurong Xue, Hemin Zhang, Xiaoyu Huang, Sen Zhang, Guolin Lu
Poly(methyl methacrylate) (PMMA) is widely studied for its attractive properties, including good processability, excellent optical characteristics and low cost. Nevertheless, a persistent challenge for PMMA-based materials is their limited thermal stability. Herein, a series of PMMA copolymers containing perfluorocyclobutyl (PFCB) aryl ether groups were prepared to enhance the heat resistance of PMMA-based materials via the introduction of rigid PFCB aryl ether moieties and the formation of a cross-linked network. PFCBMA, a methacrylamide monomer consisting of PFCB aryl ether moiety, was firstly synthesized and copolymerized with MMA to give PFCB-containing PMMA copolymers (PPFCBMA-co-PMMA), which exhibit higher glass transition (Tg) and thermal decomposition (Td) temperature than PMMA. Subsequently, a dimethacrylamide monomer bearing PFCB aryl ether moiety (MAPFCBMA) was synthesized and copolymerized with MMA to afford crosslinked PMMA copolymers (Cross-PFCB-PMMA) with PFCB units serving as crosslinking points. These Cross-PFCB-PMMA polymers show much higher thermal decomposition temperatures than pure PMMA and PPFCBMA-PMMA. Furthermore, no glass transition was observed below 250°C in DSC analysis of Cross-PFCB-PMMA polymers. This work demonstrates that incorporating PFCB aryl ether moieties, introducing amide bonds and constructing a crosslinked network are effective strategies for improving the thermal stability of PMMA-based polymers.
{"title":"Heat-Resistant Poly(methyl methacrylate) by Modification with Perfluorocyclobutyl Methacrylamide Monomers","authors":"Gaoyang Du, Yurong Xue, Hemin Zhang, Xiaoyu Huang, Sen Zhang, Guolin Lu","doi":"10.1039/d5py01014d","DOIUrl":"https://doi.org/10.1039/d5py01014d","url":null,"abstract":"Poly(methyl methacrylate) (PMMA) is widely studied for its attractive properties, including good processability, excellent optical characteristics and low cost. Nevertheless, a persistent challenge for PMMA-based materials is their limited thermal stability. Herein, a series of PMMA copolymers containing perfluorocyclobutyl (PFCB) aryl ether groups were prepared to enhance the heat resistance of PMMA-based materials via the introduction of rigid PFCB aryl ether moieties and the formation of a cross-linked network. PFCBMA, a methacrylamide monomer consisting of PFCB aryl ether moiety, was firstly synthesized and copolymerized with MMA to give PFCB-containing PMMA copolymers (PPFCBMA-co-PMMA), which exhibit higher glass transition (Tg) and thermal decomposition (Td) temperature than PMMA. Subsequently, a dimethacrylamide monomer bearing PFCB aryl ether moiety (MAPFCBMA) was synthesized and copolymerized with MMA to afford crosslinked PMMA copolymers (Cross-PFCB-PMMA) with PFCB units serving as crosslinking points. These Cross-PFCB-PMMA polymers show much higher thermal decomposition temperatures than pure PMMA and PPFCBMA-PMMA. Furthermore, no glass transition was observed below 250°C in DSC analysis of Cross-PFCB-PMMA polymers. This work demonstrates that incorporating PFCB aryl ether moieties, introducing amide bonds and constructing a crosslinked network are effective strategies for improving the thermal stability of PMMA-based polymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145893806","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}
Ionic liquid crystals have various potential applications enabling selective and effective transportation. Herein, we report the development of a separation membrane prepared by fixing the liquid-crystalline (LC) columnar (Col) nanostructures through in situ polymerization of the film states formed by imidazolium-sulfobetaine ionic liquid crystals. We compared the properties of the nanostructured betaine liquid crystals with those of analogous Col structures containing mono-ionic groups such as imidazolium and trialkyl ammonium moieties. The betaine LC compounds formed more thermally stable LC phases than the mono-ionic LC compounds having analogous structures. For salt permeation in water treatment, the betaine LC membrane exhibited ion selectivity, that was different from those of the mono-ionic LC membranes. During the virus filtration, the water flux of the betaine membrane was the highest among other analogous nanostructured Col membranes. For gas separation, these Col LC membranes showed selective CO2 permeation properties and exhibited the αCO2/N2 selectivity of about 30 under highly humidified conditions.
{"title":"Self-assembled nanostructured membranes with an imidazolium-sulfonate betaine group: Ionic columnar liquid crystals on water treatment and CO2 gas separation properties","authors":"Takeshi Sakamoto, Kyoya Adachi, Kazushi Imamura, Yu Hoshino, Miaomiao Liu, Shotaro Torii, Hiroyuki Katayama, Takashi Kato","doi":"10.1039/d5py00995b","DOIUrl":"https://doi.org/10.1039/d5py00995b","url":null,"abstract":"Ionic liquid crystals have various potential applications enabling selective and effective transportation. Herein, we report the development of a separation membrane prepared by fixing the liquid-crystalline (LC) columnar (Col) nanostructures through in situ polymerization of the film states formed by imidazolium-sulfobetaine ionic liquid crystals. We compared the properties of the nanostructured betaine liquid crystals with those of analogous Col structures containing mono-ionic groups such as imidazolium and trialkyl ammonium moieties. The betaine LC compounds formed more thermally stable LC phases than the mono-ionic LC compounds having analogous structures. For salt permeation in water treatment, the betaine LC membrane exhibited ion selectivity, that was different from those of the mono-ionic LC membranes. During the virus filtration, the water flux of the betaine membrane was the highest among other analogous nanostructured Col membranes. For gas separation, these Col LC membranes showed selective CO<small><sub>2</sub></small> permeation properties and exhibited the αCO<small><sub>2</sub></small>/N<small><sub>2</sub></small> selectivity of about 30 under highly humidified conditions.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"94 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145893801","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}
Juan-Juan Feng, Yuman Guo, Qian Song, Ze-Cheng Guo, Feng-Shou Liu
Dibenzobarrelene-based N-heterocyclic carbenes (NHCs) offer tunable steric and electronic properties, making them attractive ligands for Pd catalysis. Herein, we report a family of "large-but-flexible" Pd-NHC precatalysts that enable roomtemperature Suzuki-Miyaura polycondensations (SMPs) of sterically hindered and electronically deactivated aryl dichlorides. Key features include 2,6-diethylphenyl-substituted NHCs and 3-chloropyridine, which cooperatively promote C-Cl activation. Structural and variable-temperature-NMR analyses reveal suppressed C Ar -N bond rotation and a conformationally adaptive ligand environment. The system affords high-molecular-weight π-conjugated polymers with broad monomer scope and good solubility. Significantly, it achieves electrophile-selective coupling of aryl chlorides to construct sequence-defined polymers, offering a more practical alternative to traditional nucleophile-based strategies.Mechanistic studies suggest a dynamic ligand exchange equilibrium that stabilizes the active Pd(0) species. These findings establish a robust and versatile platform for low-temperature polycondensation of unactivated aryl dichlorides.
基于二苯二苯二烯的n -杂环碳化合物（NHCs）具有可调节的空间和电子性质，使其成为Pd催化的有吸引力的配体。在这里，我们报道了一个“大而灵活”的Pd-NHC预催化剂家族，使空间阻碍和电子失活的芳基二氯化物在室温下发生Suzuki-Miyaura缩聚（SMPs）。主要特征包括2,6-二乙基苯基取代NHCs和3-氯吡啶，它们共同促进C-Cl活化。结构和变温核磁共振分析表明，C - Ar -N键旋转受到抑制，构象适应配体环境。该体系提供了单体范围广、溶解性好的高分子量π共轭聚合物。值得注意的是，它实现了芳酰氯的亲电选择性偶联，以构建序列定义的聚合物，为传统的亲核基策略提供了更实用的替代方案。机制研究表明，动态配体交换平衡稳定活性Pd(0)物种。这些发现建立了一个强大的和通用的平台低温缩聚非活化芳基二氯化合物。
{"title":"Room-Temperature Suzuki-Miyaura Polycondensation of Aryl Dichloride Monomers Enabled by 'Large-but-Flexible' Pd-NHC Precatalysts","authors":"Juan-Juan Feng, Yuman Guo, Qian Song, Ze-Cheng Guo, Feng-Shou Liu","doi":"10.1039/d5py01111f","DOIUrl":"https://doi.org/10.1039/d5py01111f","url":null,"abstract":"Dibenzobarrelene-based N-heterocyclic carbenes (NHCs) offer tunable steric and electronic properties, making them attractive ligands for Pd catalysis. Herein, we report a family of \"large-but-flexible\" Pd-NHC precatalysts that enable roomtemperature Suzuki-Miyaura polycondensations (SMPs) of sterically hindered and electronically deactivated aryl dichlorides. Key features include 2,6-diethylphenyl-substituted NHCs and 3-chloropyridine, which cooperatively promote C-Cl activation. Structural and variable-temperature-NMR analyses reveal suppressed C Ar -N bond rotation and a conformationally adaptive ligand environment. The system affords high-molecular-weight π-conjugated polymers with broad monomer scope and good solubility. Significantly, it achieves electrophile-selective coupling of aryl chlorides to construct sequence-defined polymers, offering a more practical alternative to traditional nucleophile-based strategies.Mechanistic studies suggest a dynamic ligand exchange equilibrium that stabilizes the active Pd(0) species. These findings establish a robust and versatile platform for low-temperature polycondensation of unactivated aryl dichlorides.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145893662","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}
Dachuan Zhang, Ni Yang, Yang Zhou, Haomin Yu, Jingning Cao, Minghao Wang, Si Wu
Photoresponsive gels exhibit various applications because they can change their structures and properties under the stimulation of light. However, the use of photoresponsive gels is limited by solvent evaporation, which compromises their longevity and functionality. Herein, we design a metallopolymer organogel to overcome this challenge. The organo-gel incorporates metal-ligand coordination bonds as reversible, photoswitchable crosslinks within a polyacrylamide network, using high-boiling-point 1,2-propanediol as the solvent. This system exhibits excellent stability against solvent loss and displays fully reversible and photoresponsive behaviors, including gel-to-sol transitions, color change and volumetric expansion/contraction. We use these properties to demonstrate rewritable photopatterning and shape reconfiguration. We also demonstrate that the organogel maintains low solvent evaporation and stable performance even under hightemperature conditions. The metallopolymer organogel design opens avenues for the development of long-lasting, intelligent soft matter for use in demanding applications.
{"title":"Visible-light-responsive gels with long-lasting functions via combining metallopolymers and coordination solvents with reduced volatilization","authors":"Dachuan Zhang, Ni Yang, Yang Zhou, Haomin Yu, Jingning Cao, Minghao Wang, Si Wu","doi":"10.1039/d5py01126d","DOIUrl":"https://doi.org/10.1039/d5py01126d","url":null,"abstract":"Photoresponsive gels exhibit various applications because they can change their structures and properties under the stimulation of light. However, the use of photoresponsive gels is limited by solvent evaporation, which compromises their longevity and functionality. Herein, we design a metallopolymer organogel to overcome this challenge. The organo-gel incorporates metal-ligand coordination bonds as reversible, photoswitchable crosslinks within a polyacrylamide network, using high-boiling-point 1,2-propanediol as the solvent. This system exhibits excellent stability against solvent loss and displays fully reversible and photoresponsive behaviors, including gel-to-sol transitions, color change and volumetric expansion/contraction. We use these properties to demonstrate rewritable photopatterning and shape reconfiguration. We also demonstrate that the organogel maintains low solvent evaporation and stable performance even under hightemperature conditions. The metallopolymer organogel design opens avenues for the development of long-lasting, intelligent soft matter for use in demanding applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"56 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145893815","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}
Ryohei Kakuchi, Koki Kasai, Kiho Matsubara, Hideki Amii
Post-polymerization modification (PPM) has become a pivotal strategy in modern polymer chemistry, enabling the late-stage functionalization of pre-formed polymer backbones. Among the many reactive motifs employed, fluorinated units have played a central role due to their exceptional electronic properties and chemical robustness. While perfluorinated motifs have traditionally been utilized in polymer materials and PPMs, the exploration of partially fluorinated units remains limited. In this Mini-Review, we highlight recent advances in PPMs in the context of existing methodologies and emphasize the synthetic utility of fluorine-containing units in PPM design. Particular attention is given to α,α-difluoroacetates, a class of partially fluorinated esters that uniquely combine carbonyl activation with α-position masking. The recent integration of α,α-difluoroacetates has enabled efficient aminolysis-based PPMs and, remarkably, has allowed for the regeneration of activated ester polymers. These findings establish the first example of a regenerable aminolysis PPM, marking a conceptual shift toward dynamic and recyclable polymer modifications.
{"title":"The Alchemy of Fluorine: α,α-Difluoroacetates Unlocking Regenerable Post-Polymerization Modification","authors":"Ryohei Kakuchi, Koki Kasai, Kiho Matsubara, Hideki Amii","doi":"10.1039/d5py00967g","DOIUrl":"https://doi.org/10.1039/d5py00967g","url":null,"abstract":"Post-polymerization modification (PPM) has become a pivotal strategy in modern polymer chemistry, enabling the late-stage functionalization of pre-formed polymer backbones. Among the many reactive motifs employed, fluorinated units have played a central role due to their exceptional electronic properties and chemical robustness. While perfluorinated motifs have traditionally been utilized in polymer materials and PPMs, the exploration of partially fluorinated units remains limited. In this Mini-Review, we highlight recent advances in PPMs in the context of existing methodologies and emphasize the synthetic utility of fluorine-containing units in PPM design. Particular attention is given to α,α-difluoroacetates, a class of partially fluorinated esters that uniquely combine carbonyl activation with α-position masking. The recent integration of α,α-difluoroacetates has enabled efficient aminolysis-based PPMs and, remarkably, has allowed for the regeneration of activated ester polymers. These findings establish the first example of a regenerable aminolysis PPM, marking a conceptual shift toward dynamic and recyclable polymer modifications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"36 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145893665","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}
Zhihao Wang, En Fang, Liangyu Chen, Zhiqiang Fan, Shaofei Song
Plastics have been indispensable in modern society since their large-scale production commenced in the 1950s. However, their massive accumulation of post-consumption has led to severe environmental pollution. This review summarizes recent advances in plastic waste management technologies, encompassing mechanical recycling, biodegradation, and chemical recycling. Mechanical recycling remains the most prevalent industrial practice due to its operational simplicity and relatively low cost. Biodegradation, which leverages microorganisms or enzymes, offers a promising eco-friendly alternative. Chemical recycling breaks the constraints of conventional end-of-life treatments (e.g., landfill and incineration) by depolymerizing or degrading plastics into valuable chemical feedstocks such as monomers. Despite significant progress, these technologies still face considerable challenges: the gradual deterioration of material properties during mechanical recycling, unintended environmental impacts such as the release of toxic additives during biodegradation, and the high energy and economic costs hindering the large-scale application of chemical recycling. This review aims to provide a comprehensive methodological perspective to advance solutions for the global plastic waste crisis.
{"title":"Recent Developments in the Recycling Technologies of Polymeric Plastics","authors":"Zhihao Wang, En Fang, Liangyu Chen, Zhiqiang Fan, Shaofei Song","doi":"10.1039/d5py01031d","DOIUrl":"https://doi.org/10.1039/d5py01031d","url":null,"abstract":"Plastics have been indispensable in modern society since their large-scale production commenced in the 1950s. However, their massive accumulation of post-consumption has led to severe environmental pollution. This review summarizes recent advances in plastic waste management technologies, encompassing mechanical recycling, biodegradation, and chemical recycling. Mechanical recycling remains the most prevalent industrial practice due to its operational simplicity and relatively low cost. Biodegradation, which leverages microorganisms or enzymes, offers a promising eco-friendly alternative. Chemical recycling breaks the constraints of conventional end-of-life treatments (e.g., landfill and incineration) by depolymerizing or degrading plastics into valuable chemical feedstocks such as monomers. Despite significant progress, these technologies still face considerable challenges: the gradual deterioration of material properties during mechanical recycling, unintended environmental impacts such as the release of toxic additives during biodegradation, and the high energy and economic costs hindering the large-scale application of chemical recycling. This review aims to provide a comprehensive methodological perspective to advance solutions for the global plastic waste crisis.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145893816","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}
Anna Stasiuk, Alexis Millan, Elena Rigo, Mathias Destarac, Marc Guerre
Covalent adaptable networks (CANs) offer an appealing alternative to traditional thermosets by combining mechanical robustness with reprocessability through dynamic covalent chemistry. Thiol–thioester CANs are particularly promising, but their reliance on free thiols to enable network rearrangement also promotes creep and permanent deformation. Here, we present a simple reversible thiol-protection strategy to overcome this issue. Free thiols are temporarily “masked” via a reversible thiol–Michael reaction, limiting chain mobility and improving mechanical resistance while preserving network dynamics. To demonstrate this concept, we developed a thioester-based CAN in which thiols are trapped as dithioacetal groups. Model studies confirmed that the masked thiols can be released on demand and participate in thiol–thioester exchanges, with both steps catalysed by TBD. A reference network with unprotected thiols (C-FT) was compared to the protected analogue (C-BT). Although thiol protection slowed down relaxation due to incomplete dissociation, increasing catalyst concentration compensated for this effect, enabling similar relaxation kinetics while preserving enhanced mechanical resistance. This reversible thiol-protection strategy provides a simple and effective approach to mitigate creep in thioester-based CANs without compromising reprocessability, and could be extended to other nucleophile-activated dynamic chemistries.
{"title":"Enhancing the robustness of thiol–thioester covalent adaptable networks through reversible thiol–Michael masking","authors":"Anna Stasiuk, Alexis Millan, Elena Rigo, Mathias Destarac, Marc Guerre","doi":"10.1039/d5py01081k","DOIUrl":"https://doi.org/10.1039/d5py01081k","url":null,"abstract":"Covalent adaptable networks (CANs) offer an appealing alternative to traditional thermosets by combining mechanical robustness with reprocessability through dynamic covalent chemistry. Thiol–thioester CANs are particularly promising, but their reliance on free thiols to enable network rearrangement also promotes creep and permanent deformation. Here, we present a simple reversible thiol-protection strategy to overcome this issue. Free thiols are temporarily “masked” via a reversible thiol–Michael reaction, limiting chain mobility and improving mechanical resistance while preserving network dynamics. To demonstrate this concept, we developed a thioester-based CAN in which thiols are trapped as dithioacetal groups. Model studies confirmed that the masked thiols can be released on demand and participate in thiol–thioester exchanges, with both steps catalysed by TBD. A reference network with unprotected thiols (C-FT) was compared to the protected analogue (C-BT). Although thiol protection slowed down relaxation due to incomplete dissociation, increasing catalyst concentration compensated for this effect, enabling similar relaxation kinetics while preserving enhanced mechanical resistance. This reversible thiol-protection strategy provides a simple and effective approach to mitigate creep in thioester-based CANs without compromising reprocessability, and could be extended to other nucleophile-activated dynamic chemistries.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"94 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145823685","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}
Yueping Mao, Yingrui Zhu, Lin Zheng, Ruiting Ni, Jianming Pan, Qian Wang, Fu Yang
Poly(ionic liquid)s (PILs), with their inherent ionic functional moieties and tunable macromolecular architectures, exhibit distinct advantages in heterogeneous catalysis, including high charge density, customizable porous frameworks, and abundant active sites. However, no comprehensive review systematically summarized task-specific PILs for heterogeneous catalytic applications to date. This review provides a critical overview of three representative synthetic strategies for PIL-based catalysts: (1) one-pot ionomerization polymerization of functional ionic liquids with special monomers, (2) post-polymerization functionalization to achieve precise introduction of functional groups for spatial control of active sites, (3) confined-space encapsulation (“ship-in-bottle” strategy) to realize restricted growth of active species and enhance catalytic stability. These well-defined PILs can directly serve as task-specific heterogeneous catalysts for esterification, CO2 cycloaddition, and biomass conversion through synergistic ionic interactions, or be integrated with heteropoly acids, noble metal nanoparticles, metal oxides, and enzymes to construct synergistic/tandem catalytic systems. The review further highlights paramount challenges in achieving precise structural control of PILs, improving recycling stability, and developing multi-component synergistic catalysis platforms, thereby offering novel perspectives for the rational design of advanced heterogeneous catalysts.
{"title":"Recent Advances in the Synthesis and Application of Task-Specific Porous Poly(ionic liquid)s for Heterogeneous Catalysis","authors":"Yueping Mao, Yingrui Zhu, Lin Zheng, Ruiting Ni, Jianming Pan, Qian Wang, Fu Yang","doi":"10.1039/d5py00974j","DOIUrl":"https://doi.org/10.1039/d5py00974j","url":null,"abstract":"Poly(ionic liquid)s (PILs), with their inherent ionic functional moieties and tunable macromolecular architectures, exhibit distinct advantages in heterogeneous catalysis, including high charge density, customizable porous frameworks, and abundant active sites. However, no comprehensive review systematically summarized task-specific PILs for heterogeneous catalytic applications to date. This review provides a critical overview of three representative synthetic strategies for PIL-based catalysts: (1) one-pot ionomerization polymerization of functional ionic liquids with special monomers, (2) post-polymerization functionalization to achieve precise introduction of functional groups for spatial control of active sites, (3) confined-space encapsulation (“ship-in-bottle” strategy) to realize restricted growth of active species and enhance catalytic stability. These well-defined PILs can directly serve as task-specific heterogeneous catalysts for esterification, CO2 cycloaddition, and biomass conversion through synergistic ionic interactions, or be integrated with heteropoly acids, noble metal nanoparticles, metal oxides, and enzymes to construct synergistic/tandem catalytic systems. The review further highlights paramount challenges in achieving precise structural control of PILs, improving recycling stability, and developing multi-component synergistic catalysis platforms, thereby offering novel perspectives for the rational design of advanced heterogeneous catalysts.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"7 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145823686","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}
Mahsaalsadat Rokni, Zoran Dusan Zujovic, Erin M. Leitao
In this study, pendant vinyl functionalised polysiloxane oils were converted into dynamic, self healing elastomers after crosslinking with elemental sulfur through vulcanisation. Three polysiloxanes with varying vinyl content, chain length, and functional groups were directly reacted with elemental sulfur (S₈), generating three different crosslinked materials: X-poly(PDMS-PVMS-r-S), X-poly(PVMS-r-S), and X-poly(PPMS-PPVS-r-S), where X is wt% sulfur. The reactions were monitored by solution state ¹H NMR spectroscopy, confirming progressive vinyl consumption by the decrease in vinyl proton signals (H = 5.7–6.2 ppm), and simultaneous appearance of CH/CH2–S bonds (H = 2.0–3.0 ppm). Vitrification times varied across the three polymers, primarily influenced by the polysiloxane chain length, vinyl content, other pendant functional groups, and sulfur loading, with higher sulfur content generally leading to shorter times. Solid state NMR spectroscopy on the final cured elastomers confirmed vinyl consumption and CH/CH2–S bond formation, and thermogravimetric analysis (TGA) showed a lower char yield with higher sulfur incorporation, consistent with the increased proportion of thermally labile polysulfide linkages. Glass transition temperatures measured via DSC were higher in the phenyl containing polysiloxane, up to –3°C, compared to the methyl rich polysiloxanes (Tg < –70°C) due to the reduced backbone mobility from the bulky phenyl substituents. Contact angle measurements confirmed that all elastomers remained highly hydrophobic (104–111°). Rheological analysis demonstrated increasing tan δ values with sulfur content, attributed to a higher density of dynamic crosslinks. After physically damaging the materials and thermal healing, efficient S–S bond reformation restored mechanical integrity, while minor irreversible changes modestly influenced viscoelasticity. In addition, DMF enabled a solvent-based route to depolymerisation–recrosslinking. 10-poly(PPMS-PPVS-r-S) dissolved fully in DMF, whereas 10-poly(PVMS-r-S) and 7-poly(PDMS-PVMS-r-S) were only partially soluble. After removing DMF and briefly annealing (140°C, 1 h) the elastomers were regenerated, providing chemical recyclability alongside thermal healing. These results show that pendant-vinyl polysiloxanes can be directly converted into dynamic, repairable elastomers through catalyst and solvent-free vulcanisation using elemental sulfur, a refinery by-product, as the sole crosslinker. The process is 100% atom economical and generates materials which extend silicone lifetimes while valorising industrial sulfur waste.
{"title":"Silicone vitrimers prepared by vulcanisation of pendant vinylpolysiloxanes with elemental sulfur","authors":"Mahsaalsadat Rokni, Zoran Dusan Zujovic, Erin M. Leitao","doi":"10.1039/d5py01118c","DOIUrl":"https://doi.org/10.1039/d5py01118c","url":null,"abstract":"In this study, pendant vinyl functionalised polysiloxane oils were converted into dynamic, self healing elastomers after crosslinking with elemental sulfur through vulcanisation. Three polysiloxanes with varying vinyl content, chain length, and functional groups were directly reacted with elemental sulfur (S₈), generating three different crosslinked materials: X-poly(PDMS-PVMS-r-S), X-poly(PVMS-r-S), and X-poly(PPMS-PPVS-r-S), where X is wt% sulfur. The reactions were monitored by solution state ¹H NMR spectroscopy, confirming progressive vinyl consumption by the decrease in vinyl proton signals (H = 5.7–6.2 ppm), and simultaneous appearance of CH/CH2–S bonds (H = 2.0–3.0 ppm). Vitrification times varied across the three polymers, primarily influenced by the polysiloxane chain length, vinyl content, other pendant functional groups, and sulfur loading, with higher sulfur content generally leading to shorter times. Solid state NMR spectroscopy on the final cured elastomers confirmed vinyl consumption and CH/CH2–S bond formation, and thermogravimetric analysis (TGA) showed a lower char yield with higher sulfur incorporation, consistent with the increased proportion of thermally labile polysulfide linkages. Glass transition temperatures measured via DSC were higher in the phenyl containing polysiloxane, up to –3°C, compared to the methyl rich polysiloxanes (Tg < –70°C) due to the reduced backbone mobility from the bulky phenyl substituents. Contact angle measurements confirmed that all elastomers remained highly hydrophobic (104–111°). Rheological analysis demonstrated increasing tan δ values with sulfur content, attributed to a higher density of dynamic crosslinks. After physically damaging the materials and thermal healing, efficient S–S bond reformation restored mechanical integrity, while minor irreversible changes modestly influenced viscoelasticity. In addition, DMF enabled a solvent-based route to depolymerisation–recrosslinking. 10-poly(PPMS-PPVS-r-S) dissolved fully in DMF, whereas 10-poly(PVMS-r-S) and 7-poly(PDMS-PVMS-r-S) were only partially soluble. After removing DMF and briefly annealing (140°C, 1 h) the elastomers were regenerated, providing chemical recyclability alongside thermal healing. These results show that pendant-vinyl polysiloxanes can be directly converted into dynamic, repairable elastomers through catalyst and solvent-free vulcanisation using elemental sulfur, a refinery by-product, as the sole crosslinker. The process is 100% atom economical and generates materials which extend silicone lifetimes while valorising industrial sulfur waste.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796303","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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