Yao Ding,Xin Li,Mengjie Zhou,Junle Zhang,Yanjie He,Wenjie Zhang,Xue-Jing Zhai,Ge Shi,Xiaoguang Qiao,Xinchang Pang
As important industrial raw materials, amines usually display strict structural effect on the resulting material properties, indicating the great significance of selective and sensitive probing for amines. However, it is still challenging to qualitatively and quantitatively detect amines with similar structures and physicochemical properties, especially for the multi-substituted derivatives and their mixtures. Herein, the first facile amine recognition based on acid-base complexes comprising achiral poly(phenylacetylene)s, chiral amines and achiral amine analytes was achieved. The induction of one-handed dominant helicity in the mainchain via carboxyl-amino interactions, displayed normal or anomalous “Sergeants-and-Soldiers” effects which was depended on the amine structure. Such distinctive chiral amplification provided three indicators (absorption, Cotton peak and asymmetric factors) for the discrimination between aliphatic and aromatic amines, as well as the qualitative and quantitative analysis on mixtures of structurally similar amines. The ambiguous mechanism and induction model were further investigated using the Ising model, DFT, and Materials Studio, indicating the electrostatic and structural effects on the evolution of chiroptical activities. In addition, circularly polarized luminescence switching triggered by the identical chiral source can also be realized in this system, which opens up a new route for molecular sensing.
{"title":"The Mechanism and Facile Amine Recognition of Anomalous Induction between Sergeants and Soldiers in Poly(phenylacetylene)s","authors":"Yao Ding,Xin Li,Mengjie Zhou,Junle Zhang,Yanjie He,Wenjie Zhang,Xue-Jing Zhai,Ge Shi,Xiaoguang Qiao,Xinchang Pang","doi":"10.1039/d6py00654j","DOIUrl":"https://doi.org/10.1039/d6py00654j","url":null,"abstract":"As important industrial raw materials, amines usually display strict structural effect on the resulting material properties, indicating the great significance of selective and sensitive probing for amines. However, it is still challenging to qualitatively and quantitatively detect amines with similar structures and physicochemical properties, especially for the multi-substituted derivatives and their mixtures. Herein, the first facile amine recognition based on acid-base complexes comprising achiral poly(phenylacetylene)s, chiral amines and achiral amine analytes was achieved. The induction of one-handed dominant helicity in the mainchain via carboxyl-amino interactions, displayed normal or anomalous “Sergeants-and-Soldiers” effects which was depended on the amine structure. Such distinctive chiral amplification provided three indicators (absorption, Cotton peak and asymmetric factors) for the discrimination between aliphatic and aromatic amines, as well as the qualitative and quantitative analysis on mixtures of structurally similar amines. The ambiguous mechanism and induction model were further investigated using the Ising model, DFT, and Materials Studio, indicating the electrostatic and structural effects on the evolution of chiroptical activities. In addition, circularly polarized luminescence switching triggered by the identical chiral source can also be realized in this system, which opens up a new route for molecular sensing.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"67 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067372","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}
Özgün Dağlar,Patrick Schara,Christos Pantazidis,Anna Maria Cristadoro,Martin Linnenbrink,Željko Tomović
Thermosetting aliphatic polyurethanes are highly attractive for transparent coating applications owing to their excellent optical clarity and superior UV resistance; however, their intrinsically low reactivity generally requires prolonged curing times or the use of external catalysts. Herein, a series of self-catalytic liquid polyols were developed through solvent-free aza-Michael reactions between the multifunctional Michael acceptor 1,3,5-triacryloylhexahydro-1,3,5-triazine (TAHT) and secondary aminoalcohols, simultaneously generating tertiary amine-containing polyol structures capable of intrinsically catalyzing urethane formation. The resulting polyols enabled fast catalyst-free curing of hexamethylene diisocyanate isocyanurate trimer (HDI trimer)-based aliphatic polyurethane thermosets under mild conditions, exhibiting dramatically accelerated curing behavior compared with conventional non-catalytic systems. The obtained transparent thermoset showed excellent optical clarity together with robust thermomechanical and coating performance. Furthermore, efficient debonding-on-demand behavior was achieved using citric acid-catalyzed hydrolysis, enabling complete coating debonding and substrate recovery without damaging the underlying aluminum substrate. These findings demonstrate a versatile molecular design strategy for aliphatic polyurethane coating systems that are rapidly curable without external catalysts, transparent, and selectively removable on demand.
{"title":"Catalytically Active Polyols for Fast-Curing Aliphatic Polyurethane Coatings with On-Demand Debonding","authors":"Özgün Dağlar,Patrick Schara,Christos Pantazidis,Anna Maria Cristadoro,Martin Linnenbrink,Željko Tomović","doi":"10.1039/d6py00683c","DOIUrl":"https://doi.org/10.1039/d6py00683c","url":null,"abstract":"Thermosetting aliphatic polyurethanes are highly attractive for transparent coating applications owing to their excellent optical clarity and superior UV resistance; however, their intrinsically low reactivity generally requires prolonged curing times or the use of external catalysts. Herein, a series of self-catalytic liquid polyols were developed through solvent-free aza-Michael reactions between the multifunctional Michael acceptor 1,3,5-triacryloylhexahydro-1,3,5-triazine (TAHT) and secondary aminoalcohols, simultaneously generating tertiary amine-containing polyol structures capable of intrinsically catalyzing urethane formation. The resulting polyols enabled fast catalyst-free curing of hexamethylene diisocyanate isocyanurate trimer (HDI trimer)-based aliphatic polyurethane thermosets under mild conditions, exhibiting dramatically accelerated curing behavior compared with conventional non-catalytic systems. The obtained transparent thermoset showed excellent optical clarity together with robust thermomechanical and coating performance. Furthermore, efficient debonding-on-demand behavior was achieved using citric acid-catalyzed hydrolysis, enabling complete coating debonding and substrate recovery without damaging the underlying aluminum substrate. These findings demonstrate a versatile molecular design strategy for aliphatic polyurethane coating systems that are rapidly curable without external catalysts, transparent, and selectively removable on demand.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"192 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149019676","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 Rezaie,Gity Mir Mohamad Sadeghi,Seyed Morteza Ghasemi
Polyurethanes (PUs) represent one of the most versatile classes of polymers, yet their conventional synthesis relies on toxic isocyanates, posing challenges for sustainable development. Here, we present a scalable and environmentally benign strategy for producing multifunctional non-isocyanate polyurethanes (NIPUs) with performance competitive with that of isocyanate-based analogues. Using a simple, solvent-free, two-step process and commodity monomers, the materials were obtained in quantitative yields (>98%) without hazardous reagents or complex catalysts. Structural and thermal analyses confirmed well-defined nanophase separation and tunable crystallinity, enabling precise control over the mechanical and functional properties. The NIPUs demonstrated tensile strengths of up to 8.93 MPa and elongations at break exceeding 240%, together with remarkable self-healing efficiencies (up to 98%) and excellent shape-memory behavior, with shape-fixity and shape-recovery ratios above 90%. Dynamic interfacial processes associated with the softening of the semicrystalline PCL domains, together with reversible hydrogen bonding, shape-memory-assisted crack closure, and the likely contribution of dynamic disulfide exchange, collectively contributed to the excellent self-healing performance. By uniting green chemistry with advanced performance, this work narrows the long-standing gap between NIPUs and conventional PUs, establishing a sustainable platform for next-generation smart materials for adaptive coatings and flexible electronics.
{"title":"Design and characterization of self-healing, shape-memory non-isocyanate polyurethanes with tunable nanostructure and mechanical properties","authors":"Reza Rezaie,Gity Mir Mohamad Sadeghi,Seyed Morteza Ghasemi","doi":"10.1039/d6py00534a","DOIUrl":"https://doi.org/10.1039/d6py00534a","url":null,"abstract":"Polyurethanes (PUs) represent one of the most versatile classes of polymers, yet their conventional synthesis relies on toxic isocyanates, posing challenges for sustainable development. Here, we present a scalable and environmentally benign strategy for producing multifunctional non-isocyanate polyurethanes (NIPUs) with performance competitive with that of isocyanate-based analogues. Using a simple, solvent-free, two-step process and commodity monomers, the materials were obtained in quantitative yields (>98%) without hazardous reagents or complex catalysts. Structural and thermal analyses confirmed well-defined nanophase separation and tunable crystallinity, enabling precise control over the mechanical and functional properties. The NIPUs demonstrated tensile strengths of up to 8.93 MPa and elongations at break exceeding 240%, together with remarkable self-healing efficiencies (up to 98%) and excellent shape-memory behavior, with shape-fixity and shape-recovery ratios above 90%. Dynamic interfacial processes associated with the softening of the semicrystalline PCL domains, together with reversible hydrogen bonding, shape-memory-assisted crack closure, and the likely contribution of dynamic disulfide exchange, collectively contributed to the excellent self-healing performance. By uniting green chemistry with advanced performance, this work narrows the long-standing gap between NIPUs and conventional PUs, establishing a sustainable platform for next-generation smart materials for adaptive coatings and flexible electronics.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"57 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149019709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The curing of gel precursors containing alkene groups typically relies on photoinitiation, thermal initiation, or redox initiation. Here, we show that concentrated metal salt solutions can induce the gelation of poly(ethylene glycol) diacrylate (PEGDA) and investigate the factors affecting this gelation behavior. The results show that gel precursors represented by PEGDA can undergo alkene polymerization and form gels under specific metal salt conditions, particularly in the presence of Cu and Fe nitrate or sulfate salts, indicating a clear dependence of this phenomenon on both the metal species and its chemical environment. The gelation behavior is also strongly influenced by the metal–salt solution concentration and its volume fraction in the formulation (φsalt). At φsalt values close to 0.50, increasing the metal–salt solution concentration shortens the gelation time and increases the gel modulus, whereas lower concentrations or φsalt values farther from 0.50 lead to slower gelation and lower modulus. Infrared and Raman spectroscopy, together with cyclic water washing, indicate that the gel network primarily arises from chemical crosslinking through alkene conversion rather than from permanent coordination by metal ions. In addition, similar gelation behavior was applicable to other hydrophilic gel precursors containing alkene groups. These results show that concentrated metal salt solutions can induce gelation of alkene-containing precursors under specific formulation conditions.
{"title":"Gelation of hydrophilic unsaturated precursors induced by concentrated metal salt solutions","authors":"Kaiyuan Zhu","doi":"10.1039/d6py00451b","DOIUrl":"https://doi.org/10.1039/d6py00451b","url":null,"abstract":"The curing of gel precursors containing alkene groups typically relies on photoinitiation, thermal initiation, or redox initiation. Here, we show that concentrated metal salt solutions can induce the gelation of poly(ethylene glycol) diacrylate (PEGDA) and investigate the factors affecting this gelation behavior. The results show that gel precursors represented by PEGDA can undergo alkene polymerization and form gels under specific metal salt conditions, particularly in the presence of Cu and Fe nitrate or sulfate salts, indicating a clear dependence of this phenomenon on both the metal species and its chemical environment. The gelation behavior is also strongly influenced by the metal–salt solution concentration and its volume fraction in the formulation (φsalt). At φsalt values close to 0.50, increasing the metal–salt solution concentration shortens the gelation time and increases the gel modulus, whereas lower concentrations or φsalt values farther from 0.50 lead to slower gelation and lower modulus. Infrared and Raman spectroscopy, together with cyclic water washing, indicate that the gel network primarily arises from chemical crosslinking through alkene conversion rather than from permanent coordination by metal ions. In addition, similar gelation behavior was applicable to other hydrophilic gel precursors containing alkene groups. These results show that concentrated metal salt solutions can induce gelation of alkene-containing precursors under specific formulation conditions.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149013616","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}
Polyglycerol (PG) is a versatile polyether whose properties strongly depend on its molecular weight and constitutional architecture. However, detailed characterization of its molecular constitution remains challenging due to its inherent heterogeneity and the resulting spectral overlap in NMR experiments. In this work, we present an approach for the assignment and quantitative analysis of PG substructures using NMR spectroscopy. A detailed assignment of 13C NMR signals was achieved, enabling identification of glycerol units based on both connectivity (terminal, linear, dendritic) and linkage type (via primary or secondary carbons). The assignments further reveal the identities of connected glycerol units, enabling characterization of local constitutional environments in addition to individual glycerol substructures. This provides a more comprehensive description than conventional methods. Based on these assignments, a user-friendly protocol was established to quantify the relative abundance of PG substructures. Applying this methodology to four oligomeric PG samples (PG2-PG6) reveals an increasing proportion of linear units with molecular size and a predominance of primary linkages, consistent with mostly linear molecules. The results also reveal an increasing diversity of constitutional substructures with increasing molecular size. A simplified H NMR approach is further introduced for rapid estimation of terminal and linear content. This work provides a broadly applicable framework for quantitative constitutional characterization of polyglycerol, enabling improved understanding of its structure and supporting future studies of structure-property relationships.
{"title":"Determination of polyglycerol substructures and their connectivity by multidimensional and quantitative NMR spectroscopy","authors":"Frida Bilén,Nasim Nahavandizadeh,Moa Larsson,Sami Zeliouche,Romain Bordes,Lars Evenäs","doi":"10.1039/d6py00638h","DOIUrl":"https://doi.org/10.1039/d6py00638h","url":null,"abstract":"Polyglycerol (PG) is a versatile polyether whose properties strongly depend on its molecular weight and constitutional architecture. However, detailed characterization of its molecular constitution remains challenging due to its inherent heterogeneity and the resulting spectral overlap in NMR experiments. In this work, we present an approach for the assignment and quantitative analysis of PG substructures using NMR spectroscopy. A detailed assignment of 13C NMR signals was achieved, enabling identification of glycerol units based on both connectivity (terminal, linear, dendritic) and linkage type (via primary or secondary carbons). The assignments further reveal the identities of connected glycerol units, enabling characterization of local constitutional environments in addition to individual glycerol substructures. This provides a more comprehensive description than conventional methods. Based on these assignments, a user-friendly protocol was established to quantify the relative abundance of PG substructures. Applying this methodology to four oligomeric PG samples (PG2-PG6) reveals an increasing proportion of linear units with molecular size and a predominance of primary linkages, consistent with mostly linear molecules. The results also reveal an increasing diversity of constitutional substructures with increasing molecular size. A simplified H NMR approach is further introduced for rapid estimation of terminal and linear content. This work provides a broadly applicable framework for quantitative constitutional characterization of polyglycerol, enabling improved understanding of its structure and supporting future studies of structure-property relationships.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148993839","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 series of novel (arylimido)vanadium(V) complexes bearing tridentate ligands with -SPh side arm has been synthesized and structurally characterized {V(N-2,6-Me2C6H3)Cl2{O-2-R1-4-R2-6-[(2-C6H5SC6H4)N=CH]C6H3}: 2a, R1=R2 =tBu; 2b, R1=tBu, R2=H; 2c, R1=R2=H; 2d, R1=R2=I; 2e, R1=R2=Cl; 2f, R1=CF3, R2=H; 2g, R1=Ph, R2=H}. These complexes were meticulously characterized by 1H, 13C and 51V NMR analysis. The structure of complex 2b was further confirmed via X-ray crystallographic analysis. On activation with Et2AlCl, complexes 2a-g exhibited rather high catalytic activities toward ethylene polymerization (up to 285 kgPE/mmolV·h, even at high temperature, suggesting the wisdom of introducing the -SPh as a side arm. Moreover, high molecular weight polymers with unimodal molecular weight distribution can be obtained, indicating the single site behaviors of these catalysts. Catalytic activity and polymer molecular weight can be controlled over a wide range by the variation of catalyst structures and the reaction parameters, including the Al/V molar ratio and polymerization temperature. Furthermore, the investigation into the copolymerization of ethylene with norbornene (NBE) revealed that these (arylimido)vanadium(V) complexes maintained substantial activity and thermal stability and afforded cyclic olefin copolymers (COCs) with even up to 43.7% NBE incorporation.
{"title":"Ethylene (Co)Polymerization Catalyzed by Highly-Active Arylimido-Vanadium(V) Complexes Bearing Tridentate Ligands","authors":"Lingpan Lu,Haoyang Wu,Biao Li,Li Pan,Yuesheng Li","doi":"10.1039/d6py00722h","DOIUrl":"https://doi.org/10.1039/d6py00722h","url":null,"abstract":"A series of novel (arylimido)vanadium(V) complexes bearing tridentate ligands with -SPh side arm has been synthesized and structurally characterized {V(N-2,6-Me2C6H3)Cl2{O-2-R1-4-R2-6-[(2-C6H5SC6H4)N=CH]C6H3}: 2a, R1=R2 =tBu; 2b, R1=tBu, R2=H; 2c, R1=R2=H; 2d, R1=R2=I; 2e, R1=R2=Cl; 2f, R1=CF3, R2=H; 2g, R1=Ph, R2=H}. These complexes were meticulously characterized by 1H, 13C and 51V NMR analysis. The structure of complex 2b was further confirmed via X-ray crystallographic analysis. On activation with Et2AlCl, complexes 2a-g exhibited rather high catalytic activities toward ethylene polymerization (up to 285 kgPE/mmolV·h, even at high temperature, suggesting the wisdom of introducing the -SPh as a side arm. Moreover, high molecular weight polymers with unimodal molecular weight distribution can be obtained, indicating the single site behaviors of these catalysts. Catalytic activity and polymer molecular weight can be controlled over a wide range by the variation of catalyst structures and the reaction parameters, including the Al/V molar ratio and polymerization temperature. Furthermore, the investigation into the copolymerization of ethylene with norbornene (NBE) revealed that these (arylimido)vanadium(V) complexes maintained substantial activity and thermal stability and afforded cyclic olefin copolymers (COCs) with even up to 43.7% NBE incorporation.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"39 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148980709","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}
Muhammad Faizan,Dongjoo Lee,Sujitkumar Bontapalle,Rafael Verduzco,Mohammad Nahid Siddiqui
The escalating environmental impact of conventional plastics necessitates the development of sustainable alternatives. This review presents an interdisciplinary analysis of degradable polymer-based composites, highlighting their pivotal role in achieving circular economy and low-carbon goals. Focusing on biodegradable and biobased polymers such as PLA, PHA, PBS, and PCL, the study explores their integration with natural fibers, agro-waste fillers, and nanomaterials to produce high-performance, eco-friendly composites. Design strategies including compatibilization, hybrid reinforcement, and advanced processing methods like extrusion and 3D printing are discussed. Emphasis is placed on the degradation mechanisms, structure–property relationships, and environmental fate under real conditions, including soil, marine, and composting scenarios. These applications range from packaging, biomedical, agricultural, and automotive fields, whose efficacy has been proved via life cycle assessment as well as mechanical, thermal, and dielectric characterization. Collectively, this review provides a critical perspective on structure–property–process relationships in sustainable polymer composites and demonstrates routes towards multifunctional scalable materials that comply with global objectives of carbon neutralization, waste minimization, and resource management.
{"title":"Degradable polymer composites for circular and sustainable materials engineering","authors":"Muhammad Faizan,Dongjoo Lee,Sujitkumar Bontapalle,Rafael Verduzco,Mohammad Nahid Siddiqui","doi":"10.1039/d6py00621c","DOIUrl":"https://doi.org/10.1039/d6py00621c","url":null,"abstract":"The escalating environmental impact of conventional plastics necessitates the development of sustainable alternatives. This review presents an interdisciplinary analysis of degradable polymer-based composites, highlighting their pivotal role in achieving circular economy and low-carbon goals. Focusing on biodegradable and biobased polymers such as PLA, PHA, PBS, and PCL, the study explores their integration with natural fibers, agro-waste fillers, and nanomaterials to produce high-performance, eco-friendly composites. Design strategies including compatibilization, hybrid reinforcement, and advanced processing methods like extrusion and 3D printing are discussed. Emphasis is placed on the degradation mechanisms, structure–property relationships, and environmental fate under real conditions, including soil, marine, and composting scenarios. These applications range from packaging, biomedical, agricultural, and automotive fields, whose efficacy has been proved via life cycle assessment as well as mechanical, thermal, and dielectric characterization. Collectively, this review provides a critical perspective on structure–property–process relationships in sustainable polymer composites and demonstrates routes towards multifunctional scalable materials that comply with global objectives of carbon neutralization, waste minimization, and resource management.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"76 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148980710","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}
Donya Ramimoghadam,Richard A Evans,Graeme Moad,Susan Holmes,Melissa Skidmore,Ranya Simons
A dynamic acylhydrazone-enabled thermoset polyurethane (TriHydPU) was synthesized using a tri-isocyanate crosslinker and a low molar mass diol containing an acylhydrazone linkage. The resulting polymer and derived films demonstrate a range of desirable properties, making them highly suitable for high-performance applications. TriHydPU undergoes dynamic bond exchange under acidic conditions in the presence of acetone (hydrazone exchange partner) and acetic acid (acid catalyst), thereby enabling controlled degradation and chemical recycling. TriHydPU films combine strong mechanical performance (maximum tensile strength of 28.07 MPa), solvent-resistance, and excellent thermal stability similar to a non-dynamic control polymer (TriHeptPU). Importantly, the TriHydPU films additionally display stimuli-assisted-healing properties effectively repairing surface micro-fractures under mild conditions. Quantitative coating assessments revealed exceptional substrate adhesion (crosscut: 4B) and high surface durability (pencil hardness: 2H), validating the potential application of TriHydPU in advanced protective and functional coatings.
{"title":"Dynamic Polyurethane Thermosets based on an Acylhydrazone Diol: Degradable High-Performance Coatings","authors":"Donya Ramimoghadam,Richard A Evans,Graeme Moad,Susan Holmes,Melissa Skidmore,Ranya Simons","doi":"10.1039/d5py01199j","DOIUrl":"https://doi.org/10.1039/d5py01199j","url":null,"abstract":"A dynamic acylhydrazone-enabled thermoset polyurethane (TriHydPU) was synthesized using a tri-isocyanate crosslinker and a low molar mass diol containing an acylhydrazone linkage. The resulting polymer and derived films demonstrate a range of desirable properties, making them highly suitable for high-performance applications. TriHydPU undergoes dynamic bond exchange under acidic conditions in the presence of acetone (hydrazone exchange partner) and acetic acid (acid catalyst), thereby enabling controlled degradation and chemical recycling. TriHydPU films combine strong mechanical performance (maximum tensile strength of 28.07 MPa), solvent-resistance, and excellent thermal stability similar to a non-dynamic control polymer (TriHeptPU). Importantly, the TriHydPU films additionally display stimuli-assisted-healing properties effectively repairing surface micro-fractures under mild conditions. Quantitative coating assessments revealed exceptional substrate adhesion (crosscut: 4B) and high surface durability (pencil hardness: 2H), validating the potential application of TriHydPU in advanced protective and functional coatings.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"35 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973499","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}
Jessica Garcia,Magomed M. Anikin,Alina V. Maryasevskaya,Alexey A. Piryazev,Akmal Z. Umarov,Zilu Wang,Andrey V. Dobrynin,Dimitri A. Ivanov,Sergei S. Sheiko
Controlling degradation kinetics and pathways in polymeric materials typically relies on altering chemical composition, often coupling degradation behavior to changes in mechanical and thermal properties. Here, we show that molecular architecture provides an alternative route to degradation control without modifying the underlying chemistry. Using bottlebrush polycaprolactone (PCL) elastomers with systematically varied side-chain lengths, we tune crystallinity, melting temperature, and solvent accessibility to regulate degradation kinetics and pathways independently of chemical composition. Compared to rigid, highly crystalline linear PCL analogs, bottlebrush architecture suppresses crystallization, lowers the melting temperature, and accelerates degradation through surface erosion. Incorporation of a controlled fraction of hydrophilic polyethylene glycol (PEG) side chains introduces a complementary mechanism for tuning degradation by enhancing water uptake and inducing a transition from surface to bulk erosion. X-ray scattering and coarse-grained molecular dynamics simulations reveal distinct degradation pathways in pure PCL and PCL–PEG bottlebrushes, arising from limited versus enhanced solvent penetration and the corresponding differences in network fragmentation. At physiological temperature, these materials exist in a melt state and exhibit soft elastic moduli (∼10–100 kPa). Together, these findings establish bottlebrush architecture as a general molecular design strategy for independently regulating degradation kinetics, erosion mode, and mechanical properties in degradable polymer materials.
{"title":"Accelerating polycaprolactone degradation through bottlebrush architecture","authors":"Jessica Garcia,Magomed M. Anikin,Alina V. Maryasevskaya,Alexey A. Piryazev,Akmal Z. Umarov,Zilu Wang,Andrey V. Dobrynin,Dimitri A. Ivanov,Sergei S. Sheiko","doi":"10.1039/d6py00549g","DOIUrl":"https://doi.org/10.1039/d6py00549g","url":null,"abstract":"Controlling degradation kinetics and pathways in polymeric materials typically relies on altering chemical composition, often coupling degradation behavior to changes in mechanical and thermal properties. Here, we show that molecular architecture provides an alternative route to degradation control without modifying the underlying chemistry. Using bottlebrush polycaprolactone (PCL) elastomers with systematically varied side-chain lengths, we tune crystallinity, melting temperature, and solvent accessibility to regulate degradation kinetics and pathways independently of chemical composition. Compared to rigid, highly crystalline linear PCL analogs, bottlebrush architecture suppresses crystallization, lowers the melting temperature, and accelerates degradation through surface erosion. Incorporation of a controlled fraction of hydrophilic polyethylene glycol (PEG) side chains introduces a complementary mechanism for tuning degradation by enhancing water uptake and inducing a transition from surface to bulk erosion. X-ray scattering and coarse-grained molecular dynamics simulations reveal distinct degradation pathways in pure PCL and PCL–PEG bottlebrushes, arising from limited versus enhanced solvent penetration and the corresponding differences in network fragmentation. At physiological temperature, these materials exist in a melt state and exhibit soft elastic moduli (∼10–100 kPa). Together, these findings establish bottlebrush architecture as a general molecular design strategy for independently regulating degradation kinetics, erosion mode, and mechanical properties in degradable polymer materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"60 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973500","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}
Recently, the development of thermosetting polymers that combine high performance with chemical recyclability has received intense attention. In this work, a fully chemically recyclable, ternary cross-linked elastomer was synthesized via ring-opening metathesis polymerization (ROMP) from three cyclic monomers, including cis-cyclooctene (COE, providing elasticity), dicyclopentadiene (DCPD, imparting cross-linking and strength), and 2,3-dihydrofuran (DHF, introducing degradable linkages). The resulting elastomers exhibit an excellent combination of properties, including high elasticity (elongation at break >500%), a remarkable shape memory effect, and good thermal stability (onset decomposition temperature >400 °C). Most importantly, this material can be completely degraded within 24 hours in a 0.05 M HCl/THF solution at room temperature. By employing norbornene alcohol as a nucleophile during degradation, the resulting oligomers were successfully functionalized and regained ROMP reactivity, enabling a chemical recycling process (polymer-to-functionalized oligomer-to-polymer) for up to five generations. The recycled materials retained satisfactory mechanical properties (elongation at break: 600–900%). These results not only provide an innovative strategy for designing sustainable, recyclable high-performance thermoset elastomers but also demonstrate a universal concept: the integration of degradable units as intrinsic design elements can synergistically optimize material processing, performance, and end-of-life management.
近年来，结合高性能和化学可回收性的热固性聚合物的发展受到了广泛的关注。在这项工作中，通过开环复分解聚合（ROMP）由三个环单体合成了一种完全化学可回收的三元交联弹性体，包括顺式环烯（COE，提供弹性）、双环戊二烯（DCPD，提供交联和强度）和2,3-二氢呋喃（DHF，引入可降解的键）。所得弹性体表现出优异的综合性能，包括高弹性（断裂伸长率>500%）、显著的形状记忆效应和良好的热稳定性（开始分解温度>400°C）。最重要的是，这种材料可以在室温下0.05 M HCl/THF溶液中在24小时内完全降解。通过在降解过程中使用降冰片烯醇作为亲核试剂，得到的低聚物被成功功能化并恢复了ROMP反应性，从而实现了长达五代的化学循环过程（聚合物-功能化低聚物-聚合物）。回收材料保持了令人满意的力学性能（断裂伸长率：600-900%）。这些结果不仅为设计可持续、可回收的高性能热固性弹性体提供了一种创新策略，而且还展示了一个普遍的概念：将可降解单元作为内在设计元素的整合可以协同优化材料加工、性能和报废管理。
{"title":"A chemically recyclable thermosetting elastomer ring-opening metathesis polymerization","authors":"Yifan Gao,Xinyu Zhao,Lishan Lei,Jianhua Cheng","doi":"10.1039/d6py00530f","DOIUrl":"https://doi.org/10.1039/d6py00530f","url":null,"abstract":"Recently, the development of thermosetting polymers that combine high performance with chemical recyclability has received intense attention. In this work, a fully chemically recyclable, ternary cross-linked elastomer was synthesized via ring-opening metathesis polymerization (ROMP) from three cyclic monomers, including cis-cyclooctene (COE, providing elasticity), dicyclopentadiene (DCPD, imparting cross-linking and strength), and 2,3-dihydrofuran (DHF, introducing degradable linkages). The resulting elastomers exhibit an excellent combination of properties, including high elasticity (elongation at break >500%), a remarkable shape memory effect, and good thermal stability (onset decomposition temperature >400 °C). Most importantly, this material can be completely degraded within 24 hours in a 0.05 M HCl/THF solution at room temperature. By employing norbornene alcohol as a nucleophile during degradation, the resulting oligomers were successfully functionalized and regained ROMP reactivity, enabling a chemical recycling process (polymer-to-functionalized oligomer-to-polymer) for up to five generations. The recycled materials retained satisfactory mechanical properties (elongation at break: 600–900%). These results not only provide an innovative strategy for designing sustainable, recyclable high-performance thermoset elastomers but also demonstrate a universal concept: the integration of degradable units as intrinsic design elements can synergistically optimize material processing, performance, and end-of-life management.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"36 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973578","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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