Jason Kaff, Mercie N. Hodges, Abdul Moeez, Sarah Zeitler, Lilo Pozzo, Matthew Golder
Integral aspects of what is considered green chemistry include minimizing solvent use and utilizing energy-efficient methods to synthesize target materials. For polymer synthesis in particular, accessing copolymer sequences derived from immiscible feedstocks and masses in the ultra-high molecular weight regime (>1 MDa) often require specialized methods, extensive optimization, and may consume large amounts of energy. In this work, we report on the synthesis of diverse polyacrylates inspired by the principles of green chemistry using a streamlined ball mill grinding methodology. Mechanoredox reversible addition–fragmentation chain-transfer (MR-RAFT) polymerizations are used herein to synthesize multiblock copolymers from immiscible monomers and overcome viscosity restraints to reach ultra-high molecular weights. The ability to access these traditionally challenging-to-synthesize polymers using a (nearly) solvent-free method will enable the discovery of novel materials with minimal environmental impact.
{"title":"Pushing the Limits of Mechanoredox RAFT Polymerization Methods","authors":"Jason Kaff, Mercie N. Hodges, Abdul Moeez, Sarah Zeitler, Lilo Pozzo, Matthew Golder","doi":"10.1039/d5py01061f","DOIUrl":"https://doi.org/10.1039/d5py01061f","url":null,"abstract":"Integral aspects of what is considered green chemistry include minimizing solvent use and utilizing energy-efficient methods to synthesize target materials. For polymer synthesis in particular, accessing copolymer sequences derived from immiscible feedstocks and masses in the ultra-high molecular weight regime (>1 MDa) often require specialized methods, extensive optimization, and may consume large amounts of energy. In this work, we report on the synthesis of diverse polyacrylates inspired by the principles of green chemistry using a streamlined ball mill grinding methodology. Mechanoredox reversible addition–fragmentation chain-transfer (MR-RAFT) polymerizations are used herein to synthesize multiblock copolymers from immiscible monomers and overcome viscosity restraints to reach ultra-high molecular weights. The ability to access these traditionally challenging-to-synthesize polymers using a (nearly) solvent-free method will enable the discovery of novel materials with minimal environmental impact.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146160778","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}
George Britovsek, Sami Gesslbauer, Daniel Dalland, Pimpisa Titipunya, Molly Parry, Christopher Wallis, Gavin Hill, Sarah K. Y. Ho, Giovanni Santagiuliana, Tian Sang
The proliferation of waste plastic is a growing environmental concern due to its harmful effects on ecosystems, wildlife and human health. Here we have investigated the introduction of photolabile carbonyl and dicarbonyl units into polyethylene terephthalate (PET) with the aim to enhance the degradability of PET in the natural environment. Single carbonyl units have been introduced using 1,3-dihydroxyacetone as the diol component in place of ethylene glycol. Studies on the thermal behaviour of molecular polymer models have shown insufficient stability of the dihydroxyacetone unit under typical PET polymerisation conditions (~ 270 ˚C). The introduction of dicarbonyl units into PET was achieved using a dimethyl dicarbonyl ester (DDE) or di(hydroxyethyl) dicarbonyl ester (BHEDE) which have been incorporated into PET through transesterification methods. Effective removal of methanol or glycol is extremely difficult under these conditions and can lead to reductions in molecular weight due to transesterification. A series of copolymers using various ratios of additive/PET has been prepared through melt processing. The degradability of the resulting polymer films has been investigated using artificial weathering during a 14-day cycle with controlled temperature, humidity and UV irradiation. A lowering of the molecular weight was observed in all cases, most likely due to hydrolysis of the ester linkages, although oxidative cleavage of the dicarbonyl units could also have taken place, but the end-groups would be indistinguishable.
{"title":"Polyesters with Inbuilt Photolabile Units for Degradation of PET in the Natural Environment","authors":"George Britovsek, Sami Gesslbauer, Daniel Dalland, Pimpisa Titipunya, Molly Parry, Christopher Wallis, Gavin Hill, Sarah K. Y. Ho, Giovanni Santagiuliana, Tian Sang","doi":"10.1039/d5py00992h","DOIUrl":"https://doi.org/10.1039/d5py00992h","url":null,"abstract":"The proliferation of waste plastic is a growing environmental concern due to its harmful effects on ecosystems, wildlife and human health. Here we have investigated the introduction of photolabile carbonyl and dicarbonyl units into polyethylene terephthalate (PET) with the aim to enhance the degradability of PET in the natural environment. Single carbonyl units have been introduced using 1,3-dihydroxyacetone as the diol component in place of ethylene glycol. Studies on the thermal behaviour of molecular polymer models have shown insufficient stability of the dihydroxyacetone unit under typical PET polymerisation conditions (~ 270 ˚C). The introduction of dicarbonyl units into PET was achieved using a dimethyl dicarbonyl ester (DDE) or di(hydroxyethyl) dicarbonyl ester (BHEDE) which have been incorporated into PET through transesterification methods. Effective removal of methanol or glycol is extremely difficult under these conditions and can lead to reductions in molecular weight due to transesterification. A series of copolymers using various ratios of additive/PET has been prepared through melt processing. The degradability of the resulting polymer films has been investigated using artificial weathering during a 14-day cycle with controlled temperature, humidity and UV irradiation. A lowering of the molecular weight was observed in all cases, most likely due to hydrolysis of the ester linkages, although oxidative cleavage of the dicarbonyl units could also have taken place, but the end-groups would be indistinguishable.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"173 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146184262","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 streamlined catalytic system to produce high-cis polybutadiene (PBD), consisting of neodymium carboxylate and a halogenated MAO-derived activator, was developed. Halogenated MAO was synthesized via the replacement of methyl groups of commercial MAO with chlorides using BCl3. The polymerization of butadiene in optimal conditions (Al/Nd = 50 and Cl/Nd = 2.1) at 25 °C resulted in nearly complete conversion, producing PBD with a high molecular weight (Mn > 105), a narrow distribution (Đ ~ 2), and a high cis- content (> 98%). Cl incorporation into both the MAO framework and active species was confirmed by X-ray total scattering analysis, which showed that halogenated MAO functions as both an alkylating and halogenating agent of neodymium salt. Halogenated MAO may replace traditional ternary cocatalyst systems, giving a simpler catalyst composition and higher stereoregularity.
{"title":"One-shot activating reagent of neodymium carboxylate for highly cis-1,4 specific butadiene polymerization","authors":"Yu Jia, Toru Wada, Yuushou Nakayama, Takeshi Shiono, Ryo Tanaka","doi":"10.1039/d6py00007j","DOIUrl":"https://doi.org/10.1039/d6py00007j","url":null,"abstract":"A streamlined catalytic system to produce high-cis polybutadiene (PBD), consisting of neodymium carboxylate and a halogenated MAO-derived activator, was developed. Halogenated MAO was synthesized via the replacement of methyl groups of commercial MAO with chlorides using BCl3. The polymerization of butadiene in optimal conditions (Al/Nd = 50 and Cl/Nd = 2.1) at 25 °C resulted in nearly complete conversion, producing PBD with a high molecular weight (Mn > 105), a narrow distribution (Đ ~ 2), and a high cis- content (> 98%). Cl incorporation into both the MAO framework and active species was confirmed by X-ray total scattering analysis, which showed that halogenated MAO functions as both an alkylating and halogenating agent of neodymium salt. Halogenated MAO may replace traditional ternary cocatalyst systems, giving a simpler catalyst composition and higher stereoregularity.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"2 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116125","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}
Heat capacity (Cp) of polymers is an essential property for diverse applications, such as energy storage systems, electronics thermal management, and thermal insulation. In this study, we explore a transfer learning framework to predict polymer Cp, where models are first pretrained on large datasets generated from molecular dynamics (MD) simulations and group contribution (GC) calculations, and then fine-tuned using experimental data. We evaluate multiple machine learning (ML) models, including multilayer perceptrons and graph neural networks, using various molecular fingerprints and structural descriptors. The trained models are applied to existing polymers and virtual polymers to enable large-scale Cp prediction and screening. We analyze structure–property relationships to identify key molecular features influencing Cp and propose an updated GC model through a data-driven regression for quick Cp evaluation. Using the predicted Cp, in combination with thermal conductivity and glass transition temperature, we search polymers for four functional categories relevant to thermal applications: thermal interface materials, insulators, buffers, and heat spreaders. Representative polymer candidates are identified for each category based on the combined thermal property thresholds, demonstrating the practical relevance of predicted values for real-world material selection. This integrated approach enables targeted selection of polymer materials for specific thermal applications.
{"title":"A transfer learning framework integrating molecular dynamics and group contribution methods for predicting polymer specific heat capacity","authors":"Sobin Alosious , Jiaxin Xu , Meng Jiang , Tengfei Luo","doi":"10.1039/d5py01039j","DOIUrl":"10.1039/d5py01039j","url":null,"abstract":"<div><div>Heat capacity (<em>C</em><sub>p</sub>) of polymers is an essential property for diverse applications, such as energy storage systems, electronics thermal management, and thermal insulation. In this study, we explore a transfer learning framework to predict polymer <em>C</em><sub>p</sub>, where models are first pretrained on large datasets generated from molecular dynamics (MD) simulations and group contribution (GC) calculations, and then fine-tuned using experimental data. We evaluate multiple machine learning (ML) models, including multilayer perceptrons and graph neural networks, using various molecular fingerprints and structural descriptors. The trained models are applied to existing polymers and virtual polymers to enable large-scale <em>C</em><sub>p</sub> prediction and screening. We analyze structure–property relationships to identify key molecular features influencing <em>C</em><sub>p</sub> and propose an updated GC model through a data-driven regression for quick <em>C</em><sub>p</sub> evaluation. Using the predicted <em>C</em><sub>p</sub>, in combination with thermal conductivity and glass transition temperature, we search polymers for four functional categories relevant to thermal applications: thermal interface materials, insulators, buffers, and heat spreaders. Representative polymer candidates are identified for each category based on the combined thermal property thresholds, demonstrating the practical relevance of predicted values for real-world material selection. This integrated approach enables targeted selection of polymer materials for specific thermal applications.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"17 10","pages":"Pages 1028-1051"},"PeriodicalIF":3.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116143","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}
Pub Date : 2026-02-04Epub Date: 2026-02-17DOI: 10.1039/d5py01156f
Rachel H. Bianculli , Connor M. B. Gallagher , Zhen Shi , Rhone B. Jenkins , Timothy D. Ermolaev , Michael D. Schulz
High-throughput polymer synthesis enables rapid exploration of chemical space but remains limited by batch-to-batch inconsistencies that can obscure structure–property relationship trends. To address this challenge, we developed a synthetic approach to produce multifunctional copolymers using post-polymerization modification of activated ester modular polymers with commercially available amines. Easily derivitized parent polymers—poly(tetrafluorophenyl acrylate) and poly(tetrafluorophenyl styrene sulfonate)—were synthesized by RAFT polymerization to yield single polymer batches containing highly reactive tetrafluorophenyl esters or sulfonate esters on each repeat unit. Tuning post-polymerization modification reaction conditions enabled the addition of sub-stoichiometric amounts of amines (relative to the repeat unit) to yield partially functionalized intermediates that could then be further derivatized. Reaction monitoring by 19F NMR spectroscopy confirmed good control over these sequential post-polymerization modifications. This synthetic route produced a variety of copolymers with defined comonomer ratios while preserving the underlying polymer structure (degree of polymerization, dispersity, tacticity) for both the acrylate and styrene sulfonate backbones. We further applied this approach in a divergent manner to create a small library of structurally distinct copolymers from a single parent batch in three synthetic steps. This modular, divergent synthesis demonstrates a general route to structurally consistent copolymer libraries that enable systematic studies of structure–property relationships and can accelerate functional materials discovery.
{"title":"A divergent synthetic route to functional copolymer libraries via modular polymers","authors":"Rachel H. Bianculli , Connor M. B. Gallagher , Zhen Shi , Rhone B. Jenkins , Timothy D. Ermolaev , Michael D. Schulz","doi":"10.1039/d5py01156f","DOIUrl":"10.1039/d5py01156f","url":null,"abstract":"<div><div>High-throughput polymer synthesis enables rapid exploration of chemical space but remains limited by batch-to-batch inconsistencies that can obscure structure–property relationship trends. To address this challenge, we developed a synthetic approach to produce multifunctional copolymers using post-polymerization modification of activated ester modular polymers with commercially available amines. Easily derivitized parent polymers—poly(tetrafluorophenyl acrylate) and poly(tetrafluorophenyl styrene sulfonate)—were synthesized by RAFT polymerization to yield single polymer batches containing highly reactive tetrafluorophenyl esters or sulfonate esters on each repeat unit. Tuning post-polymerization modification reaction conditions enabled the addition of sub-stoichiometric amounts of amines (relative to the repeat unit) to yield partially functionalized intermediates that could then be further derivatized. Reaction monitoring by <sup>19</sup>F NMR spectroscopy confirmed good control over these sequential post-polymerization modifications. This synthetic route produced a variety of copolymers with defined comonomer ratios while preserving the underlying polymer structure (degree of polymerization, dispersity, tacticity) for both the acrylate and styrene sulfonate backbones. We further applied this approach in a divergent manner to create a small library of structurally distinct copolymers from a single parent batch in three synthetic steps. This modular, divergent synthesis demonstrates a general route to structurally consistent copolymer libraries that enable systematic studies of structure–property relationships and can accelerate functional materials discovery.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"17 10","pages":"Pages 1052-1058"},"PeriodicalIF":3.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146205723","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}
Pub Date : 2026-02-04Epub Date: 2026-02-17DOI: 10.1039/d5py01070e
Mengying Yang , Thomas H. Epps
Solvent-free, solid polymer electrolytes (SPEs) are promising candidates for next-generation, electrochemical energy storage systems due to their potential to enhance safety and performance, enable flexible device architectures, and streamline manufacturing processes. Conventional SPEs suffer from limited ionic conductivity due to the strong coupling between ion transport and (generally slow) polymer segmental relaxation. The realization of superionic conduction in SPEs, in which ions move faster than the structural relaxation of the polymers, requires a shift in design principles to promote this type of decoupled ion motion. In this perspective, we discuss how polymer architecture, ion–ion correlations, and ion–polymer interactions can unlock superionic behavior. We highlight several key design features, such as crystallinity, bulky side groups, high molecular weight, and percolating ionic aggregation, with a focus on creating low-barrier transport pathways in various polymer systems. We also demonstrate opportunities to combine polymer chemistry and data science through high-throughput and automated screening approaches to reveal how phase behavior, ion dynamics, and ionic interactions govern transport, thereby potentially enabling data-driven discovery of superionic polymer electrolyte materials.
{"title":"Superionic conduction in solid polymer electrolytes – decoupling ion transport from segmental relaxation","authors":"Mengying Yang , Thomas H. Epps","doi":"10.1039/d5py01070e","DOIUrl":"10.1039/d5py01070e","url":null,"abstract":"<div><div>Solvent-free, solid polymer electrolytes (SPEs) are promising candidates for next-generation, electrochemical energy storage systems due to their potential to enhance safety and performance, enable flexible device architectures, and streamline manufacturing processes. Conventional SPEs suffer from limited ionic conductivity due to the strong coupling between ion transport and (generally slow) polymer segmental relaxation. The realization of superionic conduction in SPEs, in which ions move faster than the structural relaxation of the polymers, requires a shift in design principles to promote this type of decoupled ion motion. In this perspective, we discuss how polymer architecture, ion–ion correlations, and ion–polymer interactions can unlock superionic behavior. We highlight several key design features, such as crystallinity, bulky side groups, high molecular weight, and percolating ionic aggregation, with a focus on creating low-barrier transport pathways in various polymer systems. We also demonstrate opportunities to combine polymer chemistry and data science through high-throughput and automated screening approaches to reveal how phase behavior, ion dynamics, and ionic interactions govern transport, thereby potentially enabling data-driven discovery of superionic polymer electrolyte materials.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"17 10","pages":"Pages 971-983"},"PeriodicalIF":3.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146231098","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}
Robert D. Murphy , Thiago Ouriques Machado , Carlo Gonzato , Fernando Vidal , Ander Leiza , Oihane Varela , Haritz Sardon , Olivier Soppera , Andreas Heise
Conventional resin systems for 3D object fabrication rely predominantly on non-degradable (meth)acrylate networks, despite global concerns about microplastic persistence. Polypeptide-based networks offer an attractive alternative due to their inherent biocompatibility and degradability, yet efficient methods to photochemically access such materials remain severely underdeveloped. In this contribution, photobase generators (PBGs) are introduced as efficient initiating systems for photo-induced N-carboxyanhydride (NCA) ring-opening polymerization (ROP), enabling rapid (<10 min) and spatiotemporally controlled polypeptide synthesis using ultraviolet (365 nm) and visible (405 nm) light irradiation. Incorporation of disulfide-containing difunctional NCA monomers enables photostructuring of crosslinked polymer networks, which can be readily degraded on demand using chemical reductants. This strategy represents the first demonstration of light-triggered NCA ROP by PBGs to provide direct access to photocurable, degradable polypeptide networks. The combination of rapid photopolymerization and reductive degradability shown here may truly expand the utility of NCA ROP systems as next-generation resins for manufacture of 3D structures with on-demand degradability.
{"title":"Photobase generators for amino acid N-carboxyanhydride ring-opening photopolymerization: rapid access to degradable polypeptide-based networks","authors":"Robert D. Murphy , Thiago Ouriques Machado , Carlo Gonzato , Fernando Vidal , Ander Leiza , Oihane Varela , Haritz Sardon , Olivier Soppera , Andreas Heise","doi":"10.1039/d6py00091f","DOIUrl":"10.1039/d6py00091f","url":null,"abstract":"<div><div>Conventional resin systems for 3D object fabrication rely predominantly on non-degradable (meth)acrylate networks, despite global concerns about microplastic persistence. Polypeptide-based networks offer an attractive alternative due to their inherent biocompatibility and degradability, yet efficient methods to photochemically access such materials remain severely underdeveloped. In this contribution, photobase generators (PBGs) are introduced as efficient initiating systems for photo-induced <em>N</em>-carboxyanhydride (NCA) ring-opening polymerization (ROP), enabling rapid (<10 min) and spatiotemporally controlled polypeptide synthesis using ultraviolet (365 nm) and visible (405 nm) light irradiation. Incorporation of disulfide-containing difunctional NCA monomers enables photostructuring of crosslinked polymer networks, which can be readily degraded on demand using chemical reductants. This strategy represents the first demonstration of light-triggered NCA ROP by PBGs to provide direct access to photocurable, degradable polypeptide networks. The combination of rapid photopolymerization and reductive degradability shown here may truly expand the utility of NCA ROP systems as next-generation resins for manufacture of 3D structures with on-demand degradability.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"17 10","pages":"Pages 989-994"},"PeriodicalIF":3.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116121","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}
Pub Date : 2026-02-04Epub Date: 2026-02-20DOI: 10.1039/d5py01173f
Michael-Phillip Smith , Lauren E. Ball , Ilanie Wessels , Bert Klumperman
Dimethylformamide (DMF), a commonly employed solvent during poly(styrene-alt-maleic anhydride) (SMAnh) functionalization, was noted to decompose and chemically modify the copolymer under laboratory relevant conditions. The in situ generation of dimethylamine resulted in modification of anhydride repeat units, highlighting an undocumented reactivity of DMF with SMAnh which could influence copolymer identity and reactivity.
{"title":"The amidation of poly(styrene-alt-maleic anhydride) via N,N-dimethylformamide decomposition","authors":"Michael-Phillip Smith , Lauren E. Ball , Ilanie Wessels , Bert Klumperman","doi":"10.1039/d5py01173f","DOIUrl":"10.1039/d5py01173f","url":null,"abstract":"<div><div>Dimethylformamide (DMF), a commonly employed solvent during poly(styrene-<em>alt</em>-maleic anhydride) (SMAnh) functionalization, was noted to decompose and chemically modify the copolymer under laboratory relevant conditions. The <em>in situ</em> generation of dimethylamine resulted in modification of anhydride repeat units, highlighting an undocumented reactivity of DMF with SMAnh which could influence copolymer identity and reactivity.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"17 10","pages":"Pages 984-988"},"PeriodicalIF":3.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146223305","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}
Pub Date : 2026-02-04Epub Date: 2025-12-03DOI: 10.1039/d5py01063b
Xuzheng Guo , Wenhua Peng , Wenjie Zhang , Chengli Wang , Xiaomeng Zhang , Zhe Cui , Peng Fu , Minying Liu , Ge Shi , Shuang Liang , Yanjie He , Xinchang Pang
Degradation of mass-manufactured acrylate/methyl acrylate polymers is considered to be a promising path to alleviate the growing and alarming plastic waste issue. However, deconstruction of such stable polymers remains a daunting challenge due to their stable saturated backbone, with previous strategies primarily relying on harsh reaction conditions or cumbersome synthetic polymers that are not suitable for practical implementation and industrialization. Herein, we report a main chain-initiated, visible light-induced degradation methodology under mild conditions, which is applicable to various categories of acrylate or methacrylate copolymers. These acrylate or methacrylate copolymers could be readily prepared by copolymerizing diverse acrylate/methacrylate monomers with low mol% acrylic acid/methacrylic acid (AA/MAA), which could serve as degradable triggers. These triggers consisting of COOH groups could generate –COOCeIV species by coordinating with a cerium catalyst followed by oxidation in the presence of O2, thereby initiating the ligand-to-metal charge transfer process and decarboxylation under visible light irradiation to produce alkyl radicals to trigger degradation via backbone scission. More importantly, this efficient degradation could be accomplished regardless of the synthetic routes, pendant groups, chain-end functionalities, molecular weights, topological architectures and concentrations of polymers, rendering this strategy a robust route to degrade diverse acrylate/methacrylate polymers.
{"title":"Visible light-induced degradation of acrylate/methacrylate copolymers with comonomer triggers","authors":"Xuzheng Guo , Wenhua Peng , Wenjie Zhang , Chengli Wang , Xiaomeng Zhang , Zhe Cui , Peng Fu , Minying Liu , Ge Shi , Shuang Liang , Yanjie He , Xinchang Pang","doi":"10.1039/d5py01063b","DOIUrl":"10.1039/d5py01063b","url":null,"abstract":"<div><div>Degradation of mass-manufactured acrylate/methyl acrylate polymers is considered to be a promising path to alleviate the growing and alarming plastic waste issue. However, deconstruction of such stable polymers remains a daunting challenge due to their stable saturated backbone, with previous strategies primarily relying on harsh reaction conditions or cumbersome synthetic polymers that are not suitable for practical implementation and industrialization. Herein, we report a main chain-initiated, visible light-induced degradation methodology under mild conditions, which is applicable to various categories of acrylate or methacrylate copolymers. These acrylate or methacrylate copolymers could be readily prepared by copolymerizing diverse acrylate/methacrylate monomers with low mol% acrylic acid/methacrylic acid (AA/MAA), which could serve as degradable triggers. These triggers consisting of COOH groups could generate –COOCe<sup>IV</sup> species by coordinating with a cerium catalyst followed by oxidation in the presence of O<sub>2</sub>, thereby initiating the ligand-to-metal charge transfer process and decarboxylation under visible light irradiation to produce alkyl radicals to trigger degradation <em>via</em> backbone scission. More importantly, this efficient degradation could be accomplished regardless of the synthetic routes, pendant groups, chain-end functionalities, molecular weights, topological architectures and concentrations of polymers, rendering this strategy a robust route to degrade diverse acrylate/methacrylate polymers.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"17 10","pages":"Pages 995-1004"},"PeriodicalIF":3.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145665225","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}
Nishant Chaudhary , A. Stephen K. Hashmi , Jean-François Carpentier , Sophie M. Guillaume
Ring-opening copolymerization (ROCOP) of CO2 and epoxides witnesses continued interest to access sustainable polycarbonates. Introduction of an exocyclic functional group onto the epoxides enables to tune and diversify the properties of the resulting CO2-based polycarbonates. Herein, the CO2/benzyl glycidyl ether (BnGE) or CO2/cyclohexene oxide (CHO) ROCOP has been performed, using a bicomponent catalyst system composed of either a {diamino-bisphenolate}MCl (Al, Fe) or {Salphen}CoCl complex or triethylborane (BEt3) as catalyst, combined with bis(triphenylphosphoranylidene)ammonium chloride (PPNCl) as initiator. While the Al/Fe-based catalyst systems selectively returned the corresponding benzyloxymethylene five-membered cyclic carbonate (5CCOBn) with poor activity in the copolymerization of CO2/BnGE, the {Salphen}CoCl/PPNCl and BEt3/PPNCl systems produced poly(benzyl glycidyl ether carbonate) (PBnGEC) with high chemoselectivity (∼80% and >98%) and regioselectivity (>99% and ∼84%), featuring >99% and ∼85% of carbonate linkages, respectively. Investigation of the {Salphen}CoCl/PPNCl and BEt3/PPNCl catalytic systems in the ROCOP of CO2/BnGE/CHO with different comonomers loadings, enabled to prepare a series of tunable P(BnGEC-co-CHC) terpolymers with similar selectivities. Subsequent hydrogenolysis of these hydrophobic polymers using Pd/C resulted in the deprotection of the side-chain benzyloxy moieties, affording the corresponding hydrophilic P(GC-co-CHC) polymers featuring hydroxyl pendant groups; yet, significant degradation of the polycarbonate main chain was observed for hydroxyl contents >15 mol%. Depolymerization of PBnGEC, PCHC and P(BnGEC-co-CHC) using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst quantitatively returned both corresponding 5CCs. In-depth characterizations by NMR spectroscopy, mass spectrometry, SEC, TGA, and DSC analyses supported well-defined protected and deprotected terpolymers with tunable chemical and thermal properties, providing opportunities for biomedical and/or industrial outcomes.
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