Christophe Pauly, Lisa Schlichter, Bart Jan Ravoo, Armido Studer
In polymer science, mechanochemistry is emerging as a powerful tool for materials science and molecular synthesis, offering novel avenues for controlled polymerization and post-synthetic modification. Building upon the previous research, nitroxide-mediated polymerization (NMP) is merged with mechanochemistry through the design of nitroxide-based mechanophore macroinitiators, pioneering the first instance of a sonochemical nitroxide-mediated-type polymerization. As NMP usually requires high temperatures, this study demonstrates that a sonochemical NMP-type process allows polymerization under reduced temperatures down to 55 °C. Moreover, depending on the nature of the employed monomers, gelated networks are obtained, demonstrating the adaptability of the mechanophore system. This study elucidates the potential of mechanochemistry in polymer synthesis, offering insights into manipulating polymerization kinetics and advancing materials science applications.
在聚合物科学领域,机械化学正成为材料科学和分子合成的有力工具,为受控聚合和合成后改性提供了新的途径。在前人研究的基础上,通过设计基于硝基氧化物的机械骨架大引发剂,将硝基氧化物介导聚合(NMP)与机械化学相结合,开创了声化学硝基氧化物介导型聚合的先河。由于 NMP 通常需要较高的温度,这项研究表明,声化学 NMP 型工艺可以在低至 55 °C 的温度下进行聚合。此外,根据所使用单体的性质,还可获得凝胶状网络,这证明了机械发泡体系的适应性。这项研究阐明了机械化学在聚合物合成中的潜力,为操纵聚合动力学和推进材料科学应用提供了见解。
{"title":"Sonochemical Nitroxide-Mediated Polymerization: Harnessing Sonochemistry for Polymer Synthesis.","authors":"Christophe Pauly, Lisa Schlichter, Bart Jan Ravoo, Armido Studer","doi":"10.1002/marc.202400732","DOIUrl":"https://doi.org/10.1002/marc.202400732","url":null,"abstract":"<p><p>In polymer science, mechanochemistry is emerging as a powerful tool for materials science and molecular synthesis, offering novel avenues for controlled polymerization and post-synthetic modification. Building upon the previous research, nitroxide-mediated polymerization (NMP) is merged with mechanochemistry through the design of nitroxide-based mechanophore macroinitiators, pioneering the first instance of a sonochemical nitroxide-mediated-type polymerization. As NMP usually requires high temperatures, this study demonstrates that a sonochemical NMP-type process allows polymerization under reduced temperatures down to 55 °C. Moreover, depending on the nature of the employed monomers, gelated networks are obtained, demonstrating the adaptability of the mechanophore system. This study elucidates the potential of mechanochemistry in polymer synthesis, offering insights into manipulating polymerization kinetics and advancing materials science applications.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2400732"},"PeriodicalIF":4.2,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alexandros Petropoulos, Laurence Charles, Jean-Michel Becht, Michael Schmitt, Jacques Lalevée, Jean-François Lutz
A photo-assisted process is explored for improving the synthesis of oligo(triazole amide)s, which are prepared by solid phase synthesis using a repeated cycle of two reactions: amine-carboxylic acid coupling and copper-catalyzed azide-alkyne cycloaddition (CuAAC). The improvement of the second reaction is investigated herein. A catalytic system involving Cu(II)Cl2, N,N,N',N″,N″-pentamethyldiethylenetriamine (PMDETA) and a titanocene photoinitiator is explored for reducing the reaction time of CuAAC. This catalyst is first tested on a model reaction involving phenylacetylene and ethyl azidoacetate in DMSO. The kinetics of these model experiments are monitored by 1H NMR in the presence of different concentrations of the photoinitiator. It is found that 30 mol% of photoinitiator leads to quantitative reactions in only 8 min. These conditions are then applied to the solid phase synthesis of oligo(triazole amide)s, performed on a glycine-loaded Wang resin. The backbone of the oligomers is constructed using 6-heptynoic acid and 1-amino-11-azido-3,6,9-trioxaundecane as submonomers. Due to slow reagent diffusion, the CuAAC step required more time in the solid phase than in solution. Yet, one hour only is necessary to achieve quantitative CuAAC on the resin, which is twice as fast as previously-reported conditions. Using these optimized conditions, oligo(triazole amide)s of different length are prepared.
{"title":"Photo-Accelerated Synthesis of Oligo(triazole amide)s.","authors":"Alexandros Petropoulos, Laurence Charles, Jean-Michel Becht, Michael Schmitt, Jacques Lalevée, Jean-François Lutz","doi":"10.1002/marc.202400759","DOIUrl":"https://doi.org/10.1002/marc.202400759","url":null,"abstract":"<p><p>A photo-assisted process is explored for improving the synthesis of oligo(triazole amide)s, which are prepared by solid phase synthesis using a repeated cycle of two reactions: amine-carboxylic acid coupling and copper-catalyzed azide-alkyne cycloaddition (CuAAC). The improvement of the second reaction is investigated herein. A catalytic system involving Cu(II)Cl<sub>2</sub>, N,N,N',N″,N″-pentamethyldiethylenetriamine (PMDETA) and a titanocene photoinitiator is explored for reducing the reaction time of CuAAC. This catalyst is first tested on a model reaction involving phenylacetylene and ethyl azidoacetate in DMSO. The kinetics of these model experiments are monitored by <sup>1</sup>H NMR in the presence of different concentrations of the photoinitiator. It is found that 30 mol% of photoinitiator leads to quantitative reactions in only 8 min. These conditions are then applied to the solid phase synthesis of oligo(triazole amide)s, performed on a glycine-loaded Wang resin. The backbone of the oligomers is constructed using 6-heptynoic acid and 1-amino-11-azido-3,6,9-trioxaundecane as submonomers. Due to slow reagent diffusion, the CuAAC step required more time in the solid phase than in solution. Yet, one hour only is necessary to achieve quantitative CuAAC on the resin, which is twice as fast as previously-reported conditions. Using these optimized conditions, oligo(triazole amide)s of different length are prepared.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2400759"},"PeriodicalIF":4.2,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613251","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This comprehensive review addresses the self-healing phenomenon in perovskite solar cells (PSCs), emphasizing the reversible reactions of dynamic bonds as the pivotal mechanism. The crucial role of polymers in both enhancing the inherent properties of perovskite and inducing self-healing phenomena in grain boundaries of perovskite films are exhibited. The review initiates with an exploration of the various stability problems that PSCs encounter, underscoring the imperative to develop PSCs with extended lifespans capable of self-heal following damage from moisture and mechanical stress. Owing to the strong compatibility brought by polymer characteristics, many additive strategies can be employed in self-healing PSCs through artful molecular design. These strategies aim to limit ion migration, prevent moisture ingress, alleviate mechanical stress, and enhance charge carrier transport. By scrutinizing the conditions, efficiency, and types of self-healing behavior, the review encapsulates the principles of dynamic bonds in the polymers of self-healing PSCs. The meticulously designed polymers not only improve the lifespan of PSCs through the action of dynamic bonds but also enhance their environmental stability through functional groups. In addition, an outlook on self-healing PSCs is provided, offering strategic guidance for future research directions in this specialized area.
{"title":"Advances in Self-Healing Perovskite Solar Cells Enabled by Dynamic Polymer Bonds.","authors":"Qisong Yuan, Juxiang Chen, Chengyu Shi, Xiangrong Shi, Chenyu Sun, Bo Jiang","doi":"10.1002/marc.202400630","DOIUrl":"https://doi.org/10.1002/marc.202400630","url":null,"abstract":"<p><p>This comprehensive review addresses the self-healing phenomenon in perovskite solar cells (PSCs), emphasizing the reversible reactions of dynamic bonds as the pivotal mechanism. The crucial role of polymers in both enhancing the inherent properties of perovskite and inducing self-healing phenomena in grain boundaries of perovskite films are exhibited. The review initiates with an exploration of the various stability problems that PSCs encounter, underscoring the imperative to develop PSCs with extended lifespans capable of self-heal following damage from moisture and mechanical stress. Owing to the strong compatibility brought by polymer characteristics, many additive strategies can be employed in self-healing PSCs through artful molecular design. These strategies aim to limit ion migration, prevent moisture ingress, alleviate mechanical stress, and enhance charge carrier transport. By scrutinizing the conditions, efficiency, and types of self-healing behavior, the review encapsulates the principles of dynamic bonds in the polymers of self-healing PSCs. The meticulously designed polymers not only improve the lifespan of PSCs through the action of dynamic bonds but also enhance their environmental stability through functional groups. In addition, an outlook on self-healing PSCs is provided, offering strategic guidance for future research directions in this specialized area.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2400630"},"PeriodicalIF":4.2,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613165","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Muhammad Atif, Gizem Babuççu, Martijn Riool, Sebastian Zaat, Ulrich Jonas
Antimicrobial peptides (AMPs) are promising alternatives to traditional antibiotics for treating skin wound infections. Nonetheless, their short half-life in biological environments restricts clinical applicability. Covalent immobilization of AMPs onto suitable substrates offers a comprehensive solution, creating contact-killing surfaces with long-term functionality. Here, a copolymer of poly[(hydroxy ethyl acrylamide)-co-(4-benzophenone acrylamide)-co-(pentafluorophenyl acrylate)-co-(ECOSURF EH-3 acrylate)], in short poly(HEAAm-co-BPAAm-co-PFPA-co-EH3A), is synthesized by free radical polymerization. Subsequent modification of active ester groups with the amine groups of SAAP-148, results in a copolymer, that is non-cytotoxic to human lung fibroblasts. UV photocrosslinking of the benzophenone units yields a polymer network that forms a hydrogel after swelling with aqueous medium. Both the SAAP-148-modified polymer in solution and the photocrosslinked hydrogels show good antimicrobial activity against strains of Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Acinetobacter baumannii, including multidrug-resistant strains, frequently found in wound infections. The covalent attachment of SAAP-148 prevents leaching, ensuring sustained antimicrobial activity for at least 48 h in diluted human blood plasma and 14 days in PBS. This prolonged retention of antimicrobial activity in human blood plasma significantly enhances its clinical potential. Overall, this study shows the potential of the AMP-functionalized photocrosslinkable polymer as antimicrobial wound dressings, providing an effective alternative to antibiotics.
{"title":"Antimicrobial Peptide SAAP-148-Functionalized Hydrogels from Photocrosslinkable Polymers with Broad Antibacterial Activity.","authors":"Muhammad Atif, Gizem Babuççu, Martijn Riool, Sebastian Zaat, Ulrich Jonas","doi":"10.1002/marc.202400785","DOIUrl":"https://doi.org/10.1002/marc.202400785","url":null,"abstract":"<p><p>Antimicrobial peptides (AMPs) are promising alternatives to traditional antibiotics for treating skin wound infections. Nonetheless, their short half-life in biological environments restricts clinical applicability. Covalent immobilization of AMPs onto suitable substrates offers a comprehensive solution, creating contact-killing surfaces with long-term functionality. Here, a copolymer of poly[(hydroxy ethyl acrylamide)-co-(4-benzophenone acrylamide)-co-(pentafluorophenyl acrylate)-co-(ECOSURF EH-3 acrylate)], in short poly(HEAAm-co-BPAAm-co-PFPA-co-EH3A), is synthesized by free radical polymerization. Subsequent modification of active ester groups with the amine groups of SAAP-148, results in a copolymer, that is non-cytotoxic to human lung fibroblasts. UV photocrosslinking of the benzophenone units yields a polymer network that forms a hydrogel after swelling with aqueous medium. Both the SAAP-148-modified polymer in solution and the photocrosslinked hydrogels show good antimicrobial activity against strains of Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Acinetobacter baumannii, including multidrug-resistant strains, frequently found in wound infections. The covalent attachment of SAAP-148 prevents leaching, ensuring sustained antimicrobial activity for at least 48 h in diluted human blood plasma and 14 days in PBS. This prolonged retention of antimicrobial activity in human blood plasma significantly enhances its clinical potential. Overall, this study shows the potential of the AMP-functionalized photocrosslinkable polymer as antimicrobial wound dressings, providing an effective alternative to antibiotics.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2400785"},"PeriodicalIF":4.2,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qian Zhong, Siqi Huo, Cheng Wang, Guofeng Ye, Qi Zhang, Hao Wang, Zhitian Liu
High-performance, versatile epoxy resins (EPs) are used in a variety of fields, but the manufacture of transparent, fireproof, and strong EPs remains a major challenge. The hyperbranched, multifunctional flame retardant (DSi) is prepared by using diethanolamine, polyformaldehyde, diphenylphosphine oxide, and phenyltrimethoxysilane as raw materials in this work. When the additional amount of DSi is only 2 wt.%, the EP-DSi2 sample reaches a vertical burning (UL-94) V-0, and its limiting oxygen index (LOI) is 32.8%. When the content of DSi is 3 wt.%, the peak heat release rate (PHRR) and total smoke production (TSP) of EP-DSi samples are 43.8% and 21.4% lower than those of EP. The good compatibility of DSi and EP endows EP-DSi with high transparency, and the hyperbranched structure of DSi makes EP-DSi have obviously enhanced mechanical strength and toughness. The enhanced fire safety of EP-DSi is mainly due to the promoting carbonization and radical quenching effects of DSi. This paper offers a comprehensive design concept aimed at creating high-performance epoxy resins with good optical, mechanical, and flame-retardant properties, which have broad application prospects.
{"title":"A Hyperbranched Phosphorus/Nitrogen/Silicon-Containing Polymer as a Multifunctional Additive for Epoxy Resins.","authors":"Qian Zhong, Siqi Huo, Cheng Wang, Guofeng Ye, Qi Zhang, Hao Wang, Zhitian Liu","doi":"10.1002/marc.202400801","DOIUrl":"https://doi.org/10.1002/marc.202400801","url":null,"abstract":"<p><p>High-performance, versatile epoxy resins (EPs) are used in a variety of fields, but the manufacture of transparent, fireproof, and strong EPs remains a major challenge. The hyperbranched, multifunctional flame retardant (DSi) is prepared by using diethanolamine, polyformaldehyde, diphenylphosphine oxide, and phenyltrimethoxysilane as raw materials in this work. When the additional amount of DSi is only 2 wt.%, the EP-DSi<sub>2</sub> sample reaches a vertical burning (UL-94) V-0, and its limiting oxygen index (LOI) is 32.8%. When the content of DSi is 3 wt.%, the peak heat release rate (PHRR) and total smoke production (TSP) of EP-DSi samples are 43.8% and 21.4% lower than those of EP. The good compatibility of DSi and EP endows EP-DSi with high transparency, and the hyperbranched structure of DSi makes EP-DSi have obviously enhanced mechanical strength and toughness. The enhanced fire safety of EP-DSi is mainly due to the promoting carbonization and radical quenching effects of DSi. This paper offers a comprehensive design concept aimed at creating high-performance epoxy resins with good optical, mechanical, and flame-retardant properties, which have broad application prospects.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2400801"},"PeriodicalIF":4.2,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613162","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Özgün Dağlar, Tankut Türel, Christos Pantazidis, Željko Tomović
Epoxy systems are essential in numerous industrial applications due to their exceptional mechanical properties, thermal stability, and chemical resistance. Yet, recycling epoxy networks and reinforcing materials in epoxy composites remains challenging, raising environmental concerns. The critical challenge is the recovery of well-defined molecules upon depolymerization. To address these issues, an innovative strategy is developed utilizing imine-containing secondary amine hardener (M1). The reaction of M1 with DGEBA produced high-performance epoxy thermoset P1, which exhibits Young's modulus of 2.18 GPa and tensile strength of 63.4 MPa, and excellent stability in neutral aqueous conditions. Upon carbon-fiber reinforcement, Young's modulus and tensile strength are significantly elevated to 10.99 GPa and 328.3 MPa, respectively. The reactive secondary amine functionalities enabled the tailored network to display a well-defined growth pattern, yielding only well-defined molecules and intact carbon fibers upon acidic depolymerization. Consequently, the recycled polymers retained properties identical to those of P1. Notably, it is discovered that despite the cross-linked nature of the epoxy networks, complete dissolution in dichloromethane facilitated straightforward solvent-based recycling, allowing the recovery of undamaged carbon fibers and an epoxy thermoset with properties matching the virgin material. Presented novel monomer design and approach showcased two important and efficient recycling options for epoxy systems.
{"title":"Chemical and Solvent-Based Recycling of DGEBA-Based Epoxy Thermoset and Carbon-Fiber Reinforced Epoxy Composite Utilizing Imine-Containing Secondary Amine Hardener.","authors":"Özgün Dağlar, Tankut Türel, Christos Pantazidis, Željko Tomović","doi":"10.1002/marc.202400678","DOIUrl":"https://doi.org/10.1002/marc.202400678","url":null,"abstract":"<p><p>Epoxy systems are essential in numerous industrial applications due to their exceptional mechanical properties, thermal stability, and chemical resistance. Yet, recycling epoxy networks and reinforcing materials in epoxy composites remains challenging, raising environmental concerns. The critical challenge is the recovery of well-defined molecules upon depolymerization. To address these issues, an innovative strategy is developed utilizing imine-containing secondary amine hardener (M1). The reaction of M1 with DGEBA produced high-performance epoxy thermoset P1, which exhibits Young's modulus of 2.18 GPa and tensile strength of 63.4 MPa, and excellent stability in neutral aqueous conditions. Upon carbon-fiber reinforcement, Young's modulus and tensile strength are significantly elevated to 10.99 GPa and 328.3 MPa, respectively. The reactive secondary amine functionalities enabled the tailored network to display a well-defined growth pattern, yielding only well-defined molecules and intact carbon fibers upon acidic depolymerization. Consequently, the recycled polymers retained properties identical to those of P1. Notably, it is discovered that despite the cross-linked nature of the epoxy networks, complete dissolution in dichloromethane facilitated straightforward solvent-based recycling, allowing the recovery of undamaged carbon fibers and an epoxy thermoset with properties matching the virgin material. Presented novel monomer design and approach showcased two important and efficient recycling options for epoxy systems.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2400678"},"PeriodicalIF":4.2,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613171","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Artificial light-harvesting systems (LHSs) are of growing interest for their potential in energy capture and conversion, but achieving efficient fluorescence in aqueous environments remains challenging. In this study, a novel tetraphenylethylene (TPE) derivative, TPEN, is synthesized and co-assembled with poly(sodium 4-styrenesulfonate) (PSS) to enhance its fluorescence via electrostatic interactions. The resulting PSS⊃TPEN network significantly increased blue emission, which is further harnessed by an energy-matched dye, 4,7-di(2-thienyl)benzo[2,1,3]thiadiazole (DBT), to produce an efficient LHS with yellow emission. Moreover, this system is successfully applied to develop color-tunable light-emitting diode (LED) devices. The findings demonstrate a cost-effective and environmentally friendly approach to designing tunable luminescent materials, with promising potential for future advancements in energy-efficient lighting technologies.
{"title":"Enhanced Emission in Polyelectrolyte Assemblies for the Development of Artificial Light-Harvesting Systems and Color-Tunable LED Device.","authors":"Qunpeng Duan, Xiuxiu Li, Zhiying Wu, Shihao Lin, Rong Zeng, Tangxin Xiao","doi":"10.1002/marc.202400752","DOIUrl":"https://doi.org/10.1002/marc.202400752","url":null,"abstract":"<p><p>Artificial light-harvesting systems (LHSs) are of growing interest for their potential in energy capture and conversion, but achieving efficient fluorescence in aqueous environments remains challenging. In this study, a novel tetraphenylethylene (TPE) derivative, TPEN, is synthesized and co-assembled with poly(sodium 4-styrenesulfonate) (PSS) to enhance its fluorescence via electrostatic interactions. The resulting PSS⊃TPEN network significantly increased blue emission, which is further harnessed by an energy-matched dye, 4,7-di(2-thienyl)benzo[2,1,3]thiadiazole (DBT), to produce an efficient LHS with yellow emission. Moreover, this system is successfully applied to develop color-tunable light-emitting diode (LED) devices. The findings demonstrate a cost-effective and environmentally friendly approach to designing tunable luminescent materials, with promising potential for future advancements in energy-efficient lighting technologies.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2400752"},"PeriodicalIF":4.2,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The copolymerization of two or more monomers produces polymeric materials with unique properties that cannot be achieved with homopolymers. However, precise control over the polymer sequence remains challenging because the sequence is determined by the inherent reactivity of comonomers. Therefore, only limited methods using modified monomers or supramolecular interactions are reported. In this study, the sequence control of acrylate-styrene copolymerization using multinuclear zinc complexes is reported. The copolymerization of the zinc acrylate complex with a polymeric sheet-like structure and styrene in benzene affords a copolymer with a higher content of acrylate triad than calculated for the statistical random model, whereas tetranuclear zinc acrylate (TZA) affords a copolymer with fewer adjacent acrylate sequences. The copolymer with a higher content of acrylate triad exhibits a lower glass transition temperature because of the higher mobility of the longer polystyrene segments. These results highlight the promise of multinuclear zinc acrylate complexes as monomers for sequence-controlled copolymerization.
{"title":"Sequence-Controlled Copolymerization of Structurally Well-Defined Multinuclear Zinc Acrylate Complexes and Styrene.","authors":"Takanori Iwasaki, Gaito Suehisa, Ryo Mandai, Kyoko Nozaki","doi":"10.1002/marc.202400742","DOIUrl":"https://doi.org/10.1002/marc.202400742","url":null,"abstract":"<p><p>The copolymerization of two or more monomers produces polymeric materials with unique properties that cannot be achieved with homopolymers. However, precise control over the polymer sequence remains challenging because the sequence is determined by the inherent reactivity of comonomers. Therefore, only limited methods using modified monomers or supramolecular interactions are reported. In this study, the sequence control of acrylate-styrene copolymerization using multinuclear zinc complexes is reported. The copolymerization of the zinc acrylate complex with a polymeric sheet-like structure and styrene in benzene affords a copolymer with a higher content of acrylate triad than calculated for the statistical random model, whereas tetranuclear zinc acrylate (TZA) affords a copolymer with fewer adjacent acrylate sequences. The copolymer with a higher content of acrylate triad exhibits a lower glass transition temperature because of the higher mobility of the longer polystyrene segments. These results highlight the promise of multinuclear zinc acrylate complexes as monomers for sequence-controlled copolymerization.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2400742"},"PeriodicalIF":4.2,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142613253","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Manon Jouanlanne, Antoine Egelé, Wiebke Drenckhan, Jean Farago, Aurélie Hourlier-Fargette
Front Cover: The generation of model monodisperse polyurethane foams with controlled morphology is achieved via the drainage from a secondary foam containing catalyst into a first foam produced without catalyst, and the homogeneity and reproducibility of the final foams is revealed via detailed structural characterization using X-ray microtomography. More details can be found in article 2400254 by Aurélie Hourlier-Fargette and co-workers.