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}
Sobin Alosious, Jiaxin Xu, Meng Jiang, Tengfei Luo
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":"https://doi.org/10.1039/d5py01039j","url":null,"abstract":"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.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"90 1","pages":""},"PeriodicalIF":4.6,"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}
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":"https://doi.org/10.1039/d6py00091f","url":null,"abstract":"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.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"46 1","pages":""},"PeriodicalIF":4.6,"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}
Nishant Chaudhary, A. Stephen K. Hashmi, Jean-François Carpentier, Sophie M Guillaume
Ring-opening copolymerization (ROCOP) of CO 2 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 CO 2 -based polycarbonates. Herein, the CO 2 /benzyl glycidyl ether (BnGE) or CO 2 /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 (BEt 3 ) as catalyst, combined with bis(triphenylphosphoranylidene)ammonium chloride (PPNCl) as initiator. While the Al/Febased catalyst systems selectively returned the corresponding benzyloxymethylene five-membered cyclic carbonate (5CC) with poor activity in the copolymerization of CO 2 /BnGE, the {Salphen}CoCl/PPNCl and BEt 3 /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 BEt 3 /PPNCl catalytic systems in the ROCOP of CO 2 /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 >15mol%. Depolymerization of PBnGEC, PCHC and P(BnGEC-co-CHC) using 1,5,7triazabicyclo[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.
{"title":"CO2/Epoxides Ring-Opening Copolymerization Towards Hydroxy-Functionalized Polycarbonates","authors":"Nishant Chaudhary, A. Stephen K. Hashmi, Jean-François Carpentier, Sophie M Guillaume","doi":"10.1039/d5py01191d","DOIUrl":"https://doi.org/10.1039/d5py01191d","url":null,"abstract":"Ring-opening copolymerization (ROCOP) of CO 2 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 CO 2 -based polycarbonates. Herein, the CO 2 /benzyl glycidyl ether (BnGE) or CO 2 /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 (BEt 3 ) as catalyst, combined with bis(triphenylphosphoranylidene)ammonium chloride (PPNCl) as initiator. While the Al/Febased catalyst systems selectively returned the corresponding benzyloxymethylene five-membered cyclic carbonate (5CC) with poor activity in the copolymerization of CO 2 /BnGE, the {Salphen}CoCl/PPNCl and BEt 3 /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 BEt 3 /PPNCl catalytic systems in the ROCOP of CO 2 /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 >15mol%. Depolymerization of PBnGEC, PCHC and P(BnGEC-co-CHC) using 1,5,7triazabicyclo[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.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"46 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116030","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}
Yuki Horino, Ryota Kobayashi, Toshiko Mizokuro, Hiromitsu Sogawa, Fumio Sanda
Ring-opening metathesis polymerization of norbornene derivatives is useful for preparing thermally stable and transparent polymeric materials with excellent moldability. The present paper deals with the ring-opening metathesis copolymerization of a norbornene monomer tethering a platinum (Pt) arylacetylide complex moiety and a norbornene monomer tethering 9,10-diphenylanthracene (DPA) moiety, and investigation of the photoluminescent properties.All the copolymers luminesced brightly in N 2 . The copolymers did not exhibit triplet-triplet annihilation upconversion without the addition of DPA, but did with DPA present. This result indicates that it is necessary not only for the sensitizing Pt moiety and emitting DPA moiety to be present in the polynorbornene side chain, but also for the relative positions of the two moieties to be appropriately controlled.
{"title":"Synthesis and photoluminescent properties of polynorbornenes bearing platinum complex and diphenylanthracene moieties in the side chains","authors":"Yuki Horino, Ryota Kobayashi, Toshiko Mizokuro, Hiromitsu Sogawa, Fumio Sanda","doi":"10.1039/d5py00874c","DOIUrl":"https://doi.org/10.1039/d5py00874c","url":null,"abstract":"Ring-opening metathesis polymerization of norbornene derivatives is useful for preparing thermally stable and transparent polymeric materials with excellent moldability. The present paper deals with the ring-opening metathesis copolymerization of a norbornene monomer tethering a platinum (Pt) arylacetylide complex moiety and a norbornene monomer tethering 9,10-diphenylanthracene (DPA) moiety, and investigation of the photoluminescent properties.All the copolymers luminesced brightly in N 2 . The copolymers did not exhibit triplet-triplet annihilation upconversion without the addition of DPA, but did with DPA present. This result indicates that it is necessary not only for the sensitizing Pt moiety and emitting DPA moiety to be present in the polynorbornene side chain, but also for the relative positions of the two moieties to be appropriately controlled.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"61 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102026","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}
Lei Lei, Thi Phuong Thu Nguyen, Yoann de Rancourt de Mimérand, Daniel Grande, Benjamin Le Droumaguet, Yves Gnanou, Benoit Couturaud
We report in this study the synthesis of core-degradable spherical nanoparticles via reverse-sequence polymerization-induced self-assembly (PISA) under aqueous conditions. A hydrophobic poly [(ethylene carbonate)-co-( ethylene oxide)] (PECEO) copolymer sample was utilized to synthesize the PECEO macro chain-transfer agent (PECEO macro-CTA), which was subsequently chain-extended with N,N'-dimethylacrylamide (DMAA) via reversible addition-fragmentation chain transfer (RAFT) polymerization, leading to the formation of stable spherical nanoparticles. In all cases, near-quantitative monomer conversion was achieved, as confirmed by ¹H NMR spectroscopy. Dynamic light scattering (DLS) analysis confirmed the formation of spherical nanoparticles with diameters in the 20-30 nm range. The incorporation of carbonate units within the polymer backbone conferred degradability to the nanoparticle, as further demonstrated by size exclusion chromatography (SEC) and 1 H NMR analyses when those nanoparticle suspensions were subjected to basic conditions.
{"title":"PEG-based Core-Degradable Nanoparticles via RAFT-Mediated Reverse-Sequence PISA","authors":"Lei Lei, Thi Phuong Thu Nguyen, Yoann de Rancourt de Mimérand, Daniel Grande, Benjamin Le Droumaguet, Yves Gnanou, Benoit Couturaud","doi":"10.1039/d5py01119a","DOIUrl":"https://doi.org/10.1039/d5py01119a","url":null,"abstract":"We report in this study the synthesis of core-degradable spherical nanoparticles via reverse-sequence polymerization-induced self-assembly (PISA) under aqueous conditions. A hydrophobic poly [(ethylene carbonate)-co-( ethylene oxide)] (PECEO) copolymer sample was utilized to synthesize the PECEO macro chain-transfer agent (PECEO macro-CTA), which was subsequently chain-extended with N,N'-dimethylacrylamide (DMAA) via reversible addition-fragmentation chain transfer (RAFT) polymerization, leading to the formation of stable spherical nanoparticles. In all cases, near-quantitative monomer conversion was achieved, as confirmed by ¹H NMR spectroscopy. Dynamic light scattering (DLS) analysis confirmed the formation of spherical nanoparticles with diameters in the 20-30 nm range. The incorporation of carbonate units within the polymer backbone conferred degradability to the nanoparticle, as further demonstrated by size exclusion chromatography (SEC) and 1 H NMR analyses when those nanoparticle suspensions were subjected to basic conditions.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"98 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098188","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}
Natalia Oleszko-Torbus, Barbara Mendrek, Agnieszka Fus-Kujawa, Agnieszka Kowalczuk, Marcelina Bochenek
This study reports the synthesis of core crosslinked star-shaped poly(2-oxazoline)s (CC-sPOxs) via an “arm first” approach combining cationic ring opening polymerization (CROP) with a thiol–ene click reaction. The resulting polymers consist of hydrophilic poly(2-ethyl-2-oxazoline) (PEtOx) arms and a poly(2-(3-butenyl)-2-oxazoline) (PButEnOx) core. First, a series of linear block copolymers PEtOx-b-PButEnOx was synthesized by CROP. These copolymers were subsequently crosslinked through a thiol–ene reaction using the crosslinker 2,2′-(ethylenedioxy)diethanethiol, yielding CC-sPOxs. To optimize the formation of star-shaped polymers, the thiol–ene reaction was carried out with varying amounts of the crosslinking agent and different amounts of comonomers. The resulting polymers were characterized in terms of their molar mass, composition, and solution behaviour and their cytotoxicity was assessed, confirming their potential suitability in biology and medicine. A novel method for synthesizing non-toxic poly(2-oxazoline)s with a non-linear macromolecular topology, with a precisely defined molar mass and number of arms, is presented in this work.
{"title":"Poly(2-oxazoline)-based core crosslinked star polymers via a combined cationic ring opening polymerization and click chemistry approach","authors":"Natalia Oleszko-Torbus, Barbara Mendrek, Agnieszka Fus-Kujawa, Agnieszka Kowalczuk, Marcelina Bochenek","doi":"10.1039/d5py01158b","DOIUrl":"https://doi.org/10.1039/d5py01158b","url":null,"abstract":"This study reports the synthesis of core crosslinked star-shaped poly(2-oxazoline)s (CC-sPOxs) <em>via</em> an “arm first” approach combining cationic ring opening polymerization (CROP) with a thiol–ene click reaction. The resulting polymers consist of hydrophilic poly(2-ethyl-2-oxazoline) (PEtOx) arms and a poly(2-(3-butenyl)-2-oxazoline) (PButEnOx) core. First, a series of linear block copolymers PEtOx-<em>b</em>-PButEnOx was synthesized by CROP. These copolymers were subsequently crosslinked through a thiol–ene reaction using the crosslinker 2,2′-(ethylenedioxy)diethanethiol, yielding CC-sPOxs. To optimize the formation of star-shaped polymers, the thiol–ene reaction was carried out with varying amounts of the crosslinking agent and different amounts of comonomers. The resulting polymers were characterized in terms of their molar mass, composition, and solution behaviour and their cytotoxicity was assessed, confirming their potential suitability in biology and medicine. A novel method for synthesizing non-toxic poly(2-oxazoline)s with a non-linear macromolecular topology, with a precisely defined molar mass and number of arms, is presented in this work.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102027","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}
Achieving intrinsic conductivity, excellent mechanical properties, and self-adhesiveness simultaneously in a stretchable ionic hydrogel is critical for ionotronics, yet it continues to be a major hurdle in the field. Here, gluconate-regulated polydopamine-polyacrylamide hydrogels (PDA-PAM-X) are developed for simultaneously improving the mechanical robustness, self-adhesion, and ionic conductivity. The gluconate induces the formation of dynamic crosslinked structure strengthening the mechanical properties and provides high ionic conductivity, whereas the dopamine endows hydrogels with self-adhesive properties. Based on these integrated effects, the optimized zinc gluconate-regulated polydopamine-polyacrylamide hydrogel (PDA-PAM-Zn) exhibits 75.04% enhanced mechanical strength (59.5 kPa), toughness (198.84 kJ/m³), Young's modulus (19.351 kPa), and ionic conductivity (2.05 S/m). Furthermore, PDA-PAM-Zn hydrogel exhibits strong adhesion with various substrates (plastics, metals, glass).
{"title":"Mechanically robust gluconate-regulated polydopamine-polyacrylamide hydrogel with exceptional adhesion","authors":"Zhongyang Wang, Chengcheng Yin, Qiaoyu Ma, Songfang Zhao, Guanbin Duan, Degang Zhao, Shuhua Yang","doi":"10.1039/d5py01049g","DOIUrl":"https://doi.org/10.1039/d5py01049g","url":null,"abstract":"Achieving intrinsic conductivity, excellent mechanical properties, and self-adhesiveness simultaneously in a stretchable ionic hydrogel is critical for ionotronics, yet it continues to be a major hurdle in the field. Here, gluconate-regulated polydopamine-polyacrylamide hydrogels (PDA-PAM-X) are developed for simultaneously improving the mechanical robustness, self-adhesion, and ionic conductivity. The gluconate induces the formation of dynamic crosslinked structure strengthening the mechanical properties and provides high ionic conductivity, whereas the dopamine endows hydrogels with self-adhesive properties. Based on these integrated effects, the optimized zinc gluconate-regulated polydopamine-polyacrylamide hydrogel (PDA-PAM-Zn) exhibits 75.04% enhanced mechanical strength (59.5 kPa), toughness (198.84 kJ/m³), Young's modulus (19.351 kPa), and ionic conductivity (2.05 S/m). Furthermore, PDA-PAM-Zn hydrogel exhibits strong adhesion with various substrates (plastics, metals, glass).","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"285 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098189","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}
Radical copolymerization of vinyl- and isopropenyl-type boron monomers followed by side-chain oxidation enabled the synthesis of α-methylated poly(vinyl alcohol)s (PVAs), which are difficult to obtain by conventional methods. The composition ratio of the resulting vinyl alcohol (VA)–isopropenyl alcohol (IPA) copolymers was tunable in a wide range (VA/IPA = 84/16 – 7/93 mol%) by adjusting monomer feed ratios in the copolymerization step. All copolymers were amorphous in the bulk state regardless of their composition ratios, despite the semi-crystalline natures of both VA and IPA homopolymers. In solution, copolymers with specific compositions exhibited solvent-dependent thermal-responsive behavior: lower critical solution temperature (LCST)-type transitions in water and upper critical solution temperature (UCST)-type transitions in acetone.
{"title":"Property Modulation of Poly(vinyl alcohol)s via Controlled Incorporation of α-Methyl Groups Using Alkenylboron Monomers","authors":"Hiroshi Suzuki, Tsuyoshi Nishikawa, Makoto Ouchi","doi":"10.1039/d5py01168j","DOIUrl":"https://doi.org/10.1039/d5py01168j","url":null,"abstract":"Radical copolymerization of vinyl- and isopropenyl-type boron monomers followed by side-chain oxidation enabled the synthesis of α-methylated poly(vinyl alcohol)s (PVAs), which are difficult to obtain by conventional methods. The composition ratio of the resulting vinyl alcohol (VA)–isopropenyl alcohol (IPA) copolymers was tunable in a wide range (VA/IPA = 84/16 – 7/93 mol%) by adjusting monomer feed ratios in the copolymerization step. All copolymers were amorphous in the bulk state regardless of their composition ratios, despite the semi-crystalline natures of both VA and IPA homopolymers. In solution, copolymers with specific compositions exhibited solvent-dependent thermal-responsive behavior: lower critical solution temperature (LCST)-type transitions in water and upper critical solution temperature (UCST)-type transitions in acetone.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"30 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089800","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}
Jennifer C. Hughes, James A. Wilson, Devanshi Singh, Nick Hawkins, Yi. Zhang, Chris Holland, Andrew T. Slark
Here we report a facile, efficient strategy to prepare dual-dynamic networks (DDNs) comprising both thermally reversible Diels–Alder (DA) covalent bonds and non-covalent hydrogen bonds which combine excellent mechanical properties and creep resistance with facile processability at mild temperatures. A series of DDNs was synthesised via the copolymerisation of maleimide-terminated poly(ε-caprolactone urethane) or poly(1,4-butadiene urethane) prepolymers with multifunctional furan crosslinkers containing ester, urethane or urea functional groups. The mechanical properties of the resulting DDNs are enhanced by increasing the strength of crosslinker hydrogen bonding or reducing the polarity of the bismaleimide backbone, achieving a broad range of tensile strength (11.7–26.5 MPa), elongation (210–690%) and toughness (14.4–75.7 MJ m−3) values. DDNs comprising crosslinkers with stronger hydrogen bonding groups produced higher gel transition temperatures (Tgel), creep-resistance and tensile strength, implying synergistic network reinforcement. Furthermore, DDNs comprising the non-polar poly(1,4-butadiene) also presented improved creep resistance. For these materials, rubbery plateaus extended over broader temperature ranges resulting in higher Tgel up to 150 °C. Poly(ε-caprolactone) conferred networks with superior Young's modulus, tensile strength, toughness and flexibility. We have shown that materials can be thermally reprocessed multiple times whilst maintaining high stress recovery efficiencies and display rapid healing abilities under mild temperatures. This work highlights the crucial role of crosslinked network reinforcement via hydrogen bonding interactions to design high-performance yet recyclable polymer networks with tailored properties.
{"title":"Synergistic reinforcement of Diels–Alder cycloadducts with hydrogen bonding interactions in recyclable dual-dynamic polyurethane networks","authors":"Jennifer C. Hughes, James A. Wilson, Devanshi Singh, Nick Hawkins, Yi. Zhang, Chris Holland, Andrew T. Slark","doi":"10.1039/d5py00347d","DOIUrl":"https://doi.org/10.1039/d5py00347d","url":null,"abstract":"Here we report a facile, efficient strategy to prepare dual-dynamic networks (DDNs) comprising both thermally reversible Diels–Alder (DA) covalent bonds and non-covalent hydrogen bonds which combine excellent mechanical properties and creep resistance with facile processability at mild temperatures. A series of DDNs was synthesised <em>via</em> the copolymerisation of maleimide-terminated poly(ε-caprolactone urethane) or poly(1,4-butadiene urethane) prepolymers with multifunctional furan crosslinkers containing ester, urethane or urea functional groups. The mechanical properties of the resulting DDNs are enhanced by increasing the strength of crosslinker hydrogen bonding or reducing the polarity of the bismaleimide backbone, achieving a broad range of tensile strength (11.7–26.5 MPa), elongation (210–690%) and toughness (14.4–75.7 MJ m<small><sup>−3</sup></small>) values. DDNs comprising crosslinkers with stronger hydrogen bonding groups produced higher gel transition temperatures (<em>T</em><small><sub>gel</sub></small>), creep-resistance and tensile strength, implying synergistic network reinforcement. Furthermore, DDNs comprising the non-polar poly(1,4-butadiene) also presented improved creep resistance. For these materials, rubbery plateaus extended over broader temperature ranges resulting in higher <em>T</em><small><sub>gel</sub></small> up to 150 °C. Poly(ε-caprolactone) conferred networks with superior Young's modulus, tensile strength, toughness and flexibility. We have shown that materials can be thermally reprocessed multiple times whilst maintaining high stress recovery efficiencies and display rapid healing abilities under mild temperatures. This work highlights the crucial role of crosslinked network reinforcement <em>via</em> hydrogen bonding interactions to design high-performance yet recyclable polymer networks with tailored properties.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"67 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098190","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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