Shweta Gaikwad , Argha Bhattacharjee , Stanley Baldwin , Steven Huss , Anna Griggs , Michael Spicuzza , Elizabeth Elacqua
Iridium-based polypyridyl complexes have gained recent attention in photoredox catalysis, with the potential for enhanced efficiency across a variety of applications. However, challenges such as poor recyclability, catalyst loss, and high costs can hinder their practical utility. Herein, we report the synthesis and characterization of three poly(methyl methacrylate)s featuring pendant cyclometalated iridium complexes based upon [Ir(df(CF3)ppy)2(dmbpy)](PF6), [Ir(ppy)2(dmbpy)](PF6), and fac-Ir(ppy)3. Our homogeneous polymer catalysts exhibited exceptional performance across a diverse array of photoredox-mediated transformations, including Birch-type photo-reduction, cycloaddition reactions, dual catalytic cross-coupling systems, and regioselective alkene functionalizations, while closely mimicking the catalytic and photophysical properties of their small-molecule counterparts. The new polymer photocatalyst maintained fidelity during reactions, enabling it to be recycled and reused up to at least five cycles. This approach combines high performance with sustainability, offering a promising pathway toward greener photoredox catalysts while broadening the practical applications of iridium-based systems.
{"title":"Recyclable iridium-containing copolymers for homogeneous photoredox catalysis†","authors":"Shweta Gaikwad , Argha Bhattacharjee , Stanley Baldwin , Steven Huss , Anna Griggs , Michael Spicuzza , Elizabeth Elacqua","doi":"10.1039/d4py01391c","DOIUrl":"10.1039/d4py01391c","url":null,"abstract":"<div><div>Iridium-based polypyridyl complexes have gained recent attention in photoredox catalysis, with the potential for enhanced efficiency across a variety of applications. However, challenges such as poor recyclability, catalyst loss, and high costs can hinder their practical utility. Herein, we report the synthesis and characterization of three poly(methyl methacrylate)s featuring pendant cyclometalated iridium complexes based upon [Ir(df(CF<sub>3</sub>)ppy)<sub>2</sub>(dmbpy)](PF<sub>6</sub>), [Ir(ppy)<sub>2</sub>(dmbpy)](PF<sub>6</sub>), and <em>fac</em>-Ir(ppy)<sub>3</sub>. Our homogeneous polymer catalysts exhibited exceptional performance across a diverse array of photoredox-mediated transformations, including Birch-type photo-reduction, cycloaddition reactions, dual catalytic cross-coupling systems, and regioselective alkene functionalizations, while closely mimicking the catalytic and photophysical properties of their small-molecule counterparts. The new polymer photocatalyst maintained fidelity during reactions, enabling it to be recycled and reused up to at least five cycles. This approach combines high performance with sustainability, offering a promising pathway toward greener photoredox catalysts while broadening the practical applications of iridium-based systems.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 15","pages":"Pages 1704-1712"},"PeriodicalIF":4.1,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599137","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}
Donglai Tian , Bin Huang , Huanghao Pan , Yanchen Deng , Guiyou Wang , Aiguo Hu
Despite significant advancements in the synthesis of block copolymers featuring conjugated segments for crystallization-driven self-assembly (CDSA), the effective realization of functional systems remains to be limited to a select number of meticulously engineered conjugated polymers. Current methodologies for controlled/living chain-growth polymerization do not extend to a diverse array of conjugated polymer systems, as most are synthesized through step-growth polymerization techniques. To this end, this research introduces a novel approach for the synthesis of conjugated polymers via controlled step-growth polymerization, facilitating their application in synthesizing narrowly distributed triblock copolymers and further investigation in CDSA. The study demonstrates the formation of rod-like micelles when the conjugated segment exhibits crystallinity, and spherical micelles when the conjugated segment is noncrystalline. This method presents several advantages over traditional techniques, including a broader selection of monomers and streamlined post-processing procedures. Consequently, it holds the potential to incorporate a wider variety of conjugated polymer systems into CDSA, thereby broadening the range of possible applications.
{"title":"Synthesis and crystallization-driven self-assembly of triblock copolymers based on narrowly distributed α,ω-bifunctionalized conjugated polymers†","authors":"Donglai Tian , Bin Huang , Huanghao Pan , Yanchen Deng , Guiyou Wang , Aiguo Hu","doi":"10.1039/d5py00053j","DOIUrl":"10.1039/d5py00053j","url":null,"abstract":"<div><div>Despite significant advancements in the synthesis of block copolymers featuring conjugated segments for crystallization-driven self-assembly (CDSA), the effective realization of functional systems remains to be limited to a select number of meticulously engineered conjugated polymers. Current methodologies for controlled/living chain-growth polymerization do not extend to a diverse array of conjugated polymer systems, as most are synthesized through step-growth polymerization techniques. To this end, this research introduces a novel approach for the synthesis of conjugated polymers <em>via</em> controlled step-growth polymerization, facilitating their application in synthesizing narrowly distributed triblock copolymers and further investigation in CDSA. The study demonstrates the formation of rod-like micelles when the conjugated segment exhibits crystallinity, and spherical micelles when the conjugated segment is noncrystalline. This method presents several advantages over traditional techniques, including a broader selection of monomers and streamlined post-processing procedures. Consequently, it holds the potential to incorporate a wider variety of conjugated polymer systems into CDSA, thereby broadening the range of possible applications.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 15","pages":"Pages 1685-1691"},"PeriodicalIF":4.1,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143590168","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}
Chuncai Zhao , Nan Nie , Wenmin Pang , Dan Peng , Menghe Xu
Polar norbornene-based monomers represent an important class of comonomers in ethylene copolymerization, and their exo/endo isomers usually exhibit different reactivity during the polymerization process. In this contribution, we first report that the exo-isomer of 5-norbornene-2,3-dicarboxylic anhydride (CA) can be more efficiently copolymerized with ethylene than its endo-isomer and exhibit higher polymerization activities, higher incorporations and higher molecular weights using phosphine-sulfonate palladium catalysts. Kinetic studies further confirmed that the polymerization rate of the exo-isomer of CA was faster than that of the corresponding endo-isomer. In addition, the properties of the obtained copolymers were investigated, including surface, mechanical, adhesive and compatibilizing properties. In particular, the copolymer of ethylene and the exo-isomer of CA with an incorporation of 6.0 mol% exhibited a better compatibilizing performance than the commercial compatibilizer for polyamide-6 and polyolefin elastomer blends.
{"title":"Investigation of exo- and endo-isomers of 5-norbornene-2,3-dicarboxylic anhydride in ethylene copolymerization†","authors":"Chuncai Zhao , Nan Nie , Wenmin Pang , Dan Peng , Menghe Xu","doi":"10.1039/d5py00087d","DOIUrl":"10.1039/d5py00087d","url":null,"abstract":"<div><div>Polar norbornene-based monomers represent an important class of comonomers in ethylene copolymerization, and their <em>exo</em>/<em>endo</em> isomers usually exhibit different reactivity during the polymerization process. In this contribution, we first report that the <em>exo</em>-isomer of 5-norbornene-2,3-dicarboxylic anhydride (CA) can be more efficiently copolymerized with ethylene than its <em>endo</em>-isomer and exhibit higher polymerization activities, higher incorporations and higher molecular weights using phosphine-sulfonate palladium catalysts. Kinetic studies further confirmed that the polymerization rate of the <em>exo</em>-isomer of CA was faster than that of the corresponding <em>endo</em>-isomer. In addition, the properties of the obtained copolymers were investigated, including surface, mechanical, adhesive and compatibilizing properties. In particular, the copolymer of ethylene and the <em>exo</em>-isomer of CA with an incorporation of 6.0 mol% exhibited a better compatibilizing performance than the commercial compatibilizer for polyamide-6 and polyolefin elastomer blends.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 15","pages":"Pages 1680-1684"},"PeriodicalIF":4.1,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143590238","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}
Designing non-toxic, non-hemolytic, selective antimicrobials remains an important and challenging research problem. Herein, we report an affordable synthetic route to prepare a series of ten multifunctional polyethylene glycols (PEGs) via a cascade reaction approach involving aza-Michael polyaddition followed by post-polymerization modifications using triazolinedione-based click reactions. All polymers are characterized by NMR, IR, SEC, DSC and TG analyses. Antimicrobial and hemolytic studies reveal that structure plays a pivotal role in tuning the antimicrobial efficacy and selectivity (HC/MIC) of the functional PEGs. The selectivity (HC/MIC) reported for the best prototype (InPEG700-C12-TAD) is 129, 33 and 39 against P. aeruginosa, E. coli and S. aureus, respectively. Additionally, all the polymers are non-cytotoxic, as revealed by the MTT assay, and exhibit excellent antibiofilm activity.
{"title":"Conversion of oligo(ethyleneglycol)s into non-toxic highly selective biocompatible poly(ethyleneglycol)s: synthesis, antimicrobial and antibiofilm activity†","authors":"Sulbha Kumari , Arpita Halder , Aayush Anand , Oindrilla Mukherjee , Subrata Chattopadhyay","doi":"10.1039/d4py01302f","DOIUrl":"10.1039/d4py01302f","url":null,"abstract":"<div><div>Designing non-toxic, non-hemolytic, selective antimicrobials remains an important and challenging research problem. Herein, we report an affordable synthetic route to prepare a series of ten multifunctional polyethylene glycols (PEGs) <em>via</em> a cascade reaction approach involving aza-Michael polyaddition followed by post-polymerization modifications using triazolinedione-based click reactions. All polymers are characterized by NMR, IR, SEC, DSC and TG analyses. Antimicrobial and hemolytic studies reveal that structure plays a pivotal role in tuning the antimicrobial efficacy and selectivity (HC/MIC) of the functional PEGs. The selectivity (HC/MIC) reported for the best prototype (InPEG<sub>700</sub>-C<sub>12</sub>-TAD) is 129, 33 and 39 against <em>P. aeruginosa</em>, <em>E. coli</em> and <em>S. aureus</em>, respectively. Additionally, all the polymers are non-cytotoxic, as revealed by the MTT assay, and exhibit excellent antibiofilm activity.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 14","pages":"Pages 1584-1594"},"PeriodicalIF":4.1,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495695","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}
Chenhui Cui , Xiejun Zhao , Xinyi Wang , Yinzhou Guo , Kexiang Chen , Jia Ma , Xueping Yan , Yilong Cheng , Zhishen Ge , Yanfeng Zhang
The extensive development of polymer materials from fossil resources poses serious environmental challenges. Therefore, developing recyclable functional materials from biomass is crucial. Here, we confirmed the reversible exchange ability of dithioacetal bonds through a model compound exchange reaction. Crosslinked polydithioacetal (PDTA) was prepared via solvent-free polycondensation of biomass benzaldehyde and tetra-thiol monomers at room temperature. Self-healing and multi-mode recycling, including mechanical reprocessing, chemical recycling, and back-to-monomer recycling, were achieved under mild conditions with no mechanical performance reduction. The solid-state plasticity due to the dynamic nature of polydithioacetal endowed PDTA with reconfigurable shape memory capability, which ensured the flexible application of PDTA by allowing reconfiguration of its permanent shape and recovery route direction. Moreover, the activation temperature for shape memory can be facilely tuned by adjusting the crosslinking densities of PDTA to meet medical application needs. With its facile tunability, great hydrolytic resistance and biocompatibility, PDTA exhibited outstanding performance in a vascular stent demonstration experiment, in which a shrunken stent made of body temperature-responsive PDTA expanded and provided support within the vessel, showing the promise of PDTA as an environmentally and biologically friendly material for the implanted biomedical stent.
{"title":"Bio-based recyclable polydithioacetal covalent adaptable networks with activation-temperature-tunable shape memory properties†","authors":"Chenhui Cui , Xiejun Zhao , Xinyi Wang , Yinzhou Guo , Kexiang Chen , Jia Ma , Xueping Yan , Yilong Cheng , Zhishen Ge , Yanfeng Zhang","doi":"10.1039/d4py01280a","DOIUrl":"10.1039/d4py01280a","url":null,"abstract":"<div><div>The extensive development of polymer materials from fossil resources poses serious environmental challenges. Therefore, developing recyclable functional materials from biomass is crucial. Here, we confirmed the reversible exchange ability of dithioacetal bonds through a model compound exchange reaction. Crosslinked polydithioacetal (PDTA) was prepared <em>via</em> solvent-free polycondensation of biomass benzaldehyde and tetra-thiol monomers at room temperature. Self-healing and multi-mode recycling, including mechanical reprocessing, chemical recycling, and back-to-monomer recycling, were achieved under mild conditions with no mechanical performance reduction. The solid-state plasticity due to the dynamic nature of polydithioacetal endowed PDTA with reconfigurable shape memory capability, which ensured the flexible application of PDTA by allowing reconfiguration of its permanent shape and recovery route direction. Moreover, the activation temperature for shape memory can be facilely tuned by adjusting the crosslinking densities of PDTA to meet medical application needs. With its facile tunability, great hydrolytic resistance and biocompatibility, PDTA exhibited outstanding performance in a vascular stent demonstration experiment, in which a shrunken stent made of body temperature-responsive PDTA expanded and provided support within the vessel, showing the promise of PDTA as an environmentally and biologically friendly material for the implanted biomedical stent.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 14","pages":"Pages 1595-1602"},"PeriodicalIF":4.1,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495694","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 development of materials from laboratory research to industrial production is a complex, challenging, but significant process. Polysulfamates have not been industrially available to date because of the absence of efficient and economical synthetic methods. Herein, a comprehensive process for the development of novel polysulfamate (PSA) materials from laboratory research to industrial manufacture is reported. PSAs were prepared with high molecular weight and narrow polydispersity through nucleophilic polycondensation between aryl bisphenols and disulfamoyl difluorides in the presence of an inorganic base. The polymerization process was stable in moisture and air. The industrial production of PSAs was achieved on 100 kg scale with the assistance of a cooperative factory for the first time. The PSAs displayed excellent solvent tolerance, acid/base resistance, thermal stability, machinability and mechanical properties, which were promising for their application in the area of engineering plastics, as well as high-performance resins.
{"title":"Efficient and simplified strategy to access novel polysulfamate materials: from laboratory research to industrial production†","authors":"Xingyu Ma , Pengqiang Liang , Zhongqiang Zhao , Jinwei Chen , Xueqing Wang , Yunbin Zhou , Xianxing Jiang , Weiwei Zhu","doi":"10.1039/d4py01383b","DOIUrl":"10.1039/d4py01383b","url":null,"abstract":"<div><div>The development of materials from laboratory research to industrial production is a complex, challenging, but significant process. Polysulfamates have not been industrially available to date because of the absence of efficient and economical synthetic methods. Herein, a comprehensive process for the development of novel polysulfamate (PSA) materials from laboratory research to industrial manufacture is reported. PSAs were prepared with high molecular weight and narrow polydispersity through nucleophilic polycondensation between aryl bisphenols and disulfamoyl difluorides in the presence of an inorganic base. The polymerization process was stable in moisture and air. The industrial production of PSAs was achieved on 100 kg scale with the assistance of a cooperative factory for the first time. The PSAs displayed excellent solvent tolerance, acid/base resistance, thermal stability, machinability and mechanical properties, which were promising for their application in the area of engineering plastics, as well as high-performance resins.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 14","pages":"Pages 1578-1583"},"PeriodicalIF":4.1,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495809","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}
Haidong Zhang , Xiuhui Zhang , Hao Zheng , Feng Wang , Xindi Wei , Xuequan Zhang , Heng Liu
Tapping facile and efficient strategies for preparing α,ω-end hetero-functionalized polyisoprene (PIp) that mimics the chain structure of natural rubber (NR) has been a long-standing pursuit in polymer science. In this study, we present a novel approach utilizing neodymium-catalyzed coordinative chain transfer polymerization (CCTP) to construct end-functionalized PIps with distinct functional groups at the α- and ω-termini. The α-end functionalization was achieved by incorporating copolymerizable heteroatomic 1-substituted dienes (BdPhX) during the aging stage of polymerization. By varying the type and feed ratio of BdPhX, a diverse array of α-functional moieties with tunable incorporation levels was readily obtained. Detailed kinetic studies revealed that the presence of α-functional BdPhX moieties exerted minimal impact on the CCTP process, maintaining highly reactive allyl–metal bonds (predominantly allyl–Al bonds) crucial for subsequent ω-end functionalizations. The ω-end functionalization was realized through two complementary strategies: (1) the incorporation of copolymerizable diene derivatives and (2) in situ reactions with reactive small molecules. The first approach was achieved by introducing BdPhX monomers, while in the second approach, reactive small molecules such as isothiocyanates and oxygen, were employed to construct thioamide and hydroxyl end-functional groups, respectively. The synthesized polymers were comprehensively characterized to confirm their structures and functionalities, highlighting the versatility and efficiency of this strategy for designing α,ω-end hetero-functionalized PIps.
{"title":"Synthesis of α,ω-end hetero-functionalized polyisoprene via neodymium-mediated coordinative chain transfer polymerization†","authors":"Haidong Zhang , Xiuhui Zhang , Hao Zheng , Feng Wang , Xindi Wei , Xuequan Zhang , Heng Liu","doi":"10.1039/d4py01452a","DOIUrl":"10.1039/d4py01452a","url":null,"abstract":"<div><div>Tapping facile and efficient strategies for preparing α,ω-end hetero-functionalized polyisoprene (PIp) that mimics the chain structure of natural rubber (NR) has been a long-standing pursuit in polymer science. In this study, we present a novel approach utilizing neodymium-catalyzed coordinative chain transfer polymerization (CCTP) to construct end-functionalized PIps with distinct functional groups at the α- and ω-termini. The α-end functionalization was achieved by incorporating copolymerizable heteroatomic 1-substituted dienes (Bd<sub>PhX</sub>) during the aging stage of polymerization. By varying the type and feed ratio of Bd<sub>PhX</sub>, a diverse array of α-functional moieties with tunable incorporation levels was readily obtained. Detailed kinetic studies revealed that the presence of α-functional Bd<sub>PhX</sub> moieties exerted minimal impact on the CCTP process, maintaining highly reactive allyl–metal bonds (predominantly allyl–Al bonds) crucial for subsequent ω-end functionalizations. The ω-end functionalization was realized through two complementary strategies: (1) the incorporation of copolymerizable diene derivatives and (2) <em>in situ</em> reactions with reactive small molecules. The first approach was achieved by introducing Bd<sub>PhX</sub> monomers, while in the second approach, reactive small molecules such as isothiocyanates and oxygen, were employed to construct thioamide and hydroxyl end-functional groups, respectively. The synthesized polymers were comprehensively characterized to confirm their structures and functionalities, highlighting the versatility and efficiency of this strategy for designing α,ω-end hetero-functionalized PIps.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 14","pages":"Pages 1556-1567"},"PeriodicalIF":4.1,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538680","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}
Herein, a new type of supramolecular cross-linker was successfully constructed through host–guest interactions between the cationic pillar[5]arene and a sulfonate-functionalized acrylate, leading to the formation of a supramolecular polymeric hydrogel using photopolymerization of acrylamide, acrylic acid and twisted intramolecular charge transfer fluorescent moieties. This obtained hydrogel is a novel multicolor fluorescent functional hydrogel integrating pH-responsiveness, self-healing, electrical conductivity, and stretchability. Moreover, this hydrogel can effectively detect iron ions (Fe3+) through fluorescence.
{"title":"Supramolecular multicolor fluorescent hydrogels with a single fluorescent group based on host–guest interactions†","authors":"Shunli Jiang , Xinglin Chen , Ping Geng , Huijing Han , Meiran Xie , Xiaojuan Liao","doi":"10.1039/d5py00086f","DOIUrl":"10.1039/d5py00086f","url":null,"abstract":"<div><div>Herein, a new type of supramolecular cross-linker was successfully constructed through host–guest interactions between the cationic pillar[5]arene and a sulfonate-functionalized acrylate, leading to the formation of a supramolecular polymeric hydrogel using photopolymerization of acrylamide, acrylic acid and twisted intramolecular charge transfer fluorescent moieties. This obtained hydrogel is a novel multicolor fluorescent functional hydrogel integrating pH-responsiveness, self-healing, electrical conductivity, and stretchability. Moreover, this hydrogel can effectively detect iron ions (Fe<sup>3+</sup>) through fluorescence.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 14","pages":"Pages 1537-1545"},"PeriodicalIF":4.1,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486562","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}
Niccolò Braidi , Aitor Hernández , Giulia Scurani , Francesca Parenti , Nezha Badi , Filip E. Du Prez
In this study, a primary amine-terminated star-shaped polystyrene (PS) was synthesized using an Activators Regenerated by Electron Transfer Atom Transfer Radical Polymerization (ARGET ATRP) protocol, yielding products with low dispersity (<1.2) and molar masses in the range of 2 to 12 kDa. The influence of the trifunctional initiator's reactivity on the resulting polymer topology was investigated. The bromo-terminated PS was efficiently converted to its azide-terminated counterpart as confirmed by online ATR FT-IR and NMR spectroscopy. The targeted amine-terminated PS was then obtained by a Staudinger reduction of the azide groups using tributylphosphine. To assess the applicability of these novel amine-terminated PSs as well-defined trifunctional crosslinking agents, traditional epoxy thermoset networks and covalent adaptable networks (CANs) were synthesized using diepoxides or diacetoacetates, respectively. The resulting materials exhibited excellent thermal resistance, attributed to the high PS content. Moreover, by making use of the option of tuning the molar mass of such macromolecular crosslinkers, the network's crosslinking density could be tailored, enabling control over swelling degree, glass transition temperature, and, in the case of the obtained vinylogous urethane vitrimers, even reprocessability.
{"title":"Synthesis of triamine-functionalized rigid crosslinkers for materials science†","authors":"Niccolò Braidi , Aitor Hernández , Giulia Scurani , Francesca Parenti , Nezha Badi , Filip E. Du Prez","doi":"10.1039/d5py00098j","DOIUrl":"10.1039/d5py00098j","url":null,"abstract":"<div><div>In this study, a primary amine-terminated star-shaped polystyrene (PS) was synthesized using an Activators Regenerated by Electron Transfer Atom Transfer Radical Polymerization (ARGET ATRP) protocol, yielding products with low dispersity (<1.2) and molar masses in the range of 2 to 12 kDa. The influence of the trifunctional initiator's reactivity on the resulting polymer topology was investigated. The bromo-terminated PS was efficiently converted to its azide-terminated counterpart as confirmed by online ATR FT-IR and NMR spectroscopy. The targeted amine-terminated PS was then obtained by a Staudinger reduction of the azide groups using tributylphosphine. To assess the applicability of these novel amine-terminated PSs as well-defined trifunctional crosslinking agents, traditional epoxy thermoset networks and covalent adaptable networks (CANs) were synthesized using diepoxides or diacetoacetates, respectively. The resulting materials exhibited excellent thermal resistance, attributed to the high PS content. Moreover, by making use of the option of tuning the molar mass of such macromolecular crosslinkers, the network's crosslinking density could be tailored, enabling control over swelling degree, glass transition temperature, and, in the case of the obtained vinylogous urethane vitrimers, even reprocessability.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 14","pages":"Pages 1546-1555"},"PeriodicalIF":4.1,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486564","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}
Jiayi Zhang , Ruyue Cao , Xiaowei Wang , Yixuan Wang , Anchao Feng
This study introduces a novel approach combining reversible addition–fragmentation chain transfer (RAFT) polymerization and hetero-Diels–Alder (HDA) reactions to efficiently synthesize hyperbranched polymers (HBPs) with controlled topology. The traditional ABn monomer methods for creating HBPs face limitations due to random polymerization and the risk of gelation. By optimizing the ABn system into an ABx macromonomer framework, this new RAFT–HDA method enables controlled polymerization, reducing intramolecular cyclization and topological defects and broadening the range of possible polymer architectures. Additionally, more readily available and widely used novel dienes and dienophiles have been identified for the HDA reaction. The versatility of this approach was demonstrated by synthesizing a variety of HBPs with different branching degrees and molecular weights, which were thoroughly characterized by NMR, FTIR, GPC, and DLS techniques. This study provides a robust and efficient pathway for synthesizing complex polymer structures, demonstrating that the RAFT–HDA strategy enables the production of well-defined hyperbranched polymers with significant potential for applications in nanomaterials, biomedicine, and advanced functional materials.
{"title":"Regioselective RAFT–HDA: a new approach to synthesize hyperbranched polymers with precise topology control†","authors":"Jiayi Zhang , Ruyue Cao , Xiaowei Wang , Yixuan Wang , Anchao Feng","doi":"10.1039/d4py01376j","DOIUrl":"10.1039/d4py01376j","url":null,"abstract":"<div><div>This study introduces a novel approach combining reversible addition–fragmentation chain transfer (RAFT) polymerization and hetero-Diels–Alder (HDA) reactions to efficiently synthesize hyperbranched polymers (HBPs) with controlled topology. The traditional AB<sub><em>n</em></sub> monomer methods for creating HBPs face limitations due to random polymerization and the risk of gelation. By optimizing the AB<sub><em>n</em></sub> system into an AB<sub><em>x</em></sub> macromonomer framework, this new RAFT–HDA method enables controlled polymerization, reducing intramolecular cyclization and topological defects and broadening the range of possible polymer architectures. Additionally, more readily available and widely used novel dienes and dienophiles have been identified for the HDA reaction. The versatility of this approach was demonstrated by synthesizing a variety of HBPs with different branching degrees and molecular weights, which were thoroughly characterized by NMR, FTIR, GPC, and DLS techniques. This study provides a robust and efficient pathway for synthesizing complex polymer structures, demonstrating that the RAFT–HDA strategy enables the production of well-defined hyperbranched polymers with significant potential for applications in nanomaterials, biomedicine, and advanced functional materials.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 14","pages":"Pages 1527-1536"},"PeriodicalIF":4.1,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486568","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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