Viraj P Nirwan, Altangerel Amarjargal, Rebecca Hengsbach, Amir Fahmi
Smart electrospun hybrid nanofibers represent a cutting-edge class of functional nanostructured materials with unique collective properties. This review aims to provide a comprehensive overview of the applications of smart electrospun hybrid nanofibers in the fields of energy, catalysis, and biomedicine. Electrospinning is a powerful tool to fabricate different types of nanofibers' morphologies with precise control over structure and compositions. Through the incorporation of various functional components, such as nanoparticles, nanomoieties, and biomolecules, into the (co)polymer matrix, nanofibers can be tailored into smart hybrid materials exhibiting responsiveness to external stimuli such as temperature, pH, or light among others. Herein recent advancements in fabrication strategies for electrospun smart hybrid nanofibers are discussed, focusing on different electrospinning tools aimed at tailoring and developing smart hybrid nanofibers. These strategies include surface functionalization, doping, and templating, which enable fine-tuning of mechanical strength, conductivity, and biocompatibility. The review explores the challenges and recent progress in the development of smart hybrid nanofibers. Issues such as scalability, reproducibility, biocompatibility, and environmental sustainability are identified as key for improvement. Furthermore, the applications of smart nanofibers in biomedicine, environment, energy storage, and smart textiles underscore their potential to address the challenges in development of nanostructured materials for emerging technologies.
{"title":"Electrospun Smart Hybrid Nanofibers for Multifaceted Applications.","authors":"Viraj P Nirwan, Altangerel Amarjargal, Rebecca Hengsbach, Amir Fahmi","doi":"10.1002/marc.202400617","DOIUrl":"https://doi.org/10.1002/marc.202400617","url":null,"abstract":"<p><p>Smart electrospun hybrid nanofibers represent a cutting-edge class of functional nanostructured materials with unique collective properties. This review aims to provide a comprehensive overview of the applications of smart electrospun hybrid nanofibers in the fields of energy, catalysis, and biomedicine. Electrospinning is a powerful tool to fabricate different types of nanofibers' morphologies with precise control over structure and compositions. Through the incorporation of various functional components, such as nanoparticles, nanomoieties, and biomolecules, into the (co)polymer matrix, nanofibers can be tailored into smart hybrid materials exhibiting responsiveness to external stimuli such as temperature, pH, or light among others. Herein recent advancements in fabrication strategies for electrospun smart hybrid nanofibers are discussed, focusing on different electrospinning tools aimed at tailoring and developing smart hybrid nanofibers. These strategies include surface functionalization, doping, and templating, which enable fine-tuning of mechanical strength, conductivity, and biocompatibility. The review explores the challenges and recent progress in the development of smart hybrid nanofibers. Issues such as scalability, reproducibility, biocompatibility, and environmental sustainability are identified as key for improvement. Furthermore, the applications of smart nanofibers in biomedicine, environment, energy storage, and smart textiles underscore their potential to address the challenges in development of nanostructured materials for emerging technologies.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142454311","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}
Haozhe Wang, Dan Li, Qingyao Meng, Xue Li, Kangle Guo, Zehua Zou, Jinsong Peng, Yuan Sun, Tiedong Sun
Bacterial infection of wound surfaces has posed a significant threat to human health and represents a formidable challenge in the clinical treatment. In this study, a novel antimicrobial hydrogel utilizing POM is synthesized as the primary component, with gelatin and sodium alginate as the structural framework. The resultant hydrogel demonstrates exceptional mechanical properties and viscoelasticity attributed to the hydrogen-bonded cross-linking between POM and gelatin, as well as the ionic cross-linking between sodium alginate and Ca2+. In addition, the integration of CuS nanoparticles conferred photothermal properties to the hydrogel system. To address the concerns regarding the potential thermal damage to the surrounding normal cells, this study employs a LT-PTT combined with CDT approach to achieve the enhanced antimicrobial efficacy while minimizing the inadvertent harm to the healthy cells. The findings suggested that POM-based hydrogels, serving as an inorganic-organic hybrid material, will represent a promising antimicrobial solution and offer valuable insights for the development of the non-antibiotic materials.
{"title":"POM-Based Hydrogels for Efficient Synergistic Chemodynamic/Low-Temperature Photothermal Antibacterial Therapy.","authors":"Haozhe Wang, Dan Li, Qingyao Meng, Xue Li, Kangle Guo, Zehua Zou, Jinsong Peng, Yuan Sun, Tiedong Sun","doi":"10.1002/marc.202400415","DOIUrl":"https://doi.org/10.1002/marc.202400415","url":null,"abstract":"<p><p>Bacterial infection of wound surfaces has posed a significant threat to human health and represents a formidable challenge in the clinical treatment. In this study, a novel antimicrobial hydrogel utilizing POM is synthesized as the primary component, with gelatin and sodium alginate as the structural framework. The resultant hydrogel demonstrates exceptional mechanical properties and viscoelasticity attributed to the hydrogen-bonded cross-linking between POM and gelatin, as well as the ionic cross-linking between sodium alginate and Ca<sup>2+</sup>. In addition, the integration of CuS nanoparticles conferred photothermal properties to the hydrogel system. To address the concerns regarding the potential thermal damage to the surrounding normal cells, this study employs a LT-PTT combined with CDT approach to achieve the enhanced antimicrobial efficacy while minimizing the inadvertent harm to the healthy cells. The findings suggested that POM-based hydrogels, serving as an inorganic-organic hybrid material, will represent a promising antimicrobial solution and offer valuable insights for the development of the non-antibiotic materials.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142454318","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}
Yang Zong, Run-Tan Gao, Na Liu, Jing Luo, Zheng Chen, Zong-Quan Wu
Polyallenes with appropriate pendants can form stable helices and exhibit significant optical activity. These helical polyallenes contain reactive double bonds that allow for further functionalization, making them a class of chiral functional materials with broad application prospects. This review article delves into the intricacies of synthesizing well-defined helical polyallenes through controlled synthetic methodologies, including helix-sense selective living polymerization, regioselective and asymmetric living polymerization, and one-pot block copolymerization of allenes with aryl monomers. The systemically outlined characteristics of the resulting helical polyallenes and related copolymers are summarized include their unique chiroptical properties, stimuli-responsiveness, helix-induced chiral self-assembly, and circularly polarized luminescence (CPL). Additionally, current challenges and future perspectives in the research of controlled synthesis, functionalities, and applications of helical polyallenes are discussed in detail.
{"title":"Helical Polyallenes: From Controlled Synthesis to Distinct Properties.","authors":"Yang Zong, Run-Tan Gao, Na Liu, Jing Luo, Zheng Chen, Zong-Quan Wu","doi":"10.1002/marc.202400671","DOIUrl":"https://doi.org/10.1002/marc.202400671","url":null,"abstract":"<p><p>Polyallenes with appropriate pendants can form stable helices and exhibit significant optical activity. These helical polyallenes contain reactive double bonds that allow for further functionalization, making them a class of chiral functional materials with broad application prospects. This review article delves into the intricacies of synthesizing well-defined helical polyallenes through controlled synthetic methodologies, including helix-sense selective living polymerization, regioselective and asymmetric living polymerization, and one-pot block copolymerization of allenes with aryl monomers. The systemically outlined characteristics of the resulting helical polyallenes and related copolymers are summarized include their unique chiroptical properties, stimuli-responsiveness, helix-induced chiral self-assembly, and circularly polarized luminescence (CPL). Additionally, current challenges and future perspectives in the research of controlled synthesis, functionalities, and applications of helical polyallenes are discussed in detail.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398850","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}
Adrian Wolf, Lea Pursche, Laura Boskamp, Katharina Koschek
Bisfunctional benzoxazine and polyether diamine-based polymers show Arrhenius-like stress-relaxation varying with stoichiometry and polymerization temperatures proving vitrimeric behavior. Molecular structural investigations reveal the presence of different aminoalkylated phenols occurring at varying ratios depending on polymer composition and polymerization conditions. The vitrimeric mechanism is found to involve an amine exchange reaction of aminoalkylated phenols in an equilibrium reaction like a nucleophilic substitution reaction. As determined by molecular studies and dissolution experiments in reactive solvents, aliphatic and aromatic primary as well as aliphatic secondary amines in the polybenzoxazine structure can act as nucleophiles in reaction with electrophilic methylene bridges. Thus, aminoalkylated phenols proved to be a relevant structural motif resulting in a vitrimeric polybenzoxazine due to amine exchange reaction.
{"title":"Amine Exchange of Aminoalkylated Phenols as Dynamic Reaction in Benzoxazine/Amine-Based Vitrimers.","authors":"Adrian Wolf, Lea Pursche, Laura Boskamp, Katharina Koschek","doi":"10.1002/marc.202400557","DOIUrl":"https://doi.org/10.1002/marc.202400557","url":null,"abstract":"<p><p>Bisfunctional benzoxazine and polyether diamine-based polymers show Arrhenius-like stress-relaxation varying with stoichiometry and polymerization temperatures proving vitrimeric behavior. Molecular structural investigations reveal the presence of different aminoalkylated phenols occurring at varying ratios depending on polymer composition and polymerization conditions. The vitrimeric mechanism is found to involve an amine exchange reaction of aminoalkylated phenols in an equilibrium reaction like a nucleophilic substitution reaction. As determined by molecular studies and dissolution experiments in reactive solvents, aliphatic and aromatic primary as well as aliphatic secondary amines in the polybenzoxazine structure can act as nucleophiles in reaction with electrophilic methylene bridges. Thus, aminoalkylated phenols proved to be a relevant structural motif resulting in a vitrimeric polybenzoxazine due to amine exchange reaction.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398848","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}
Lijie Yin, Wei Li, Yichen Lu, Liang He, Ming Tian, Nanying Ning, Wencai Wang
Ultrahigh molecular weight polyethylene (UHMWPE) fibers possess excellent mechanical properties, yet their applications are severely limited by surface inertness and low melting points. To enhance surface activity and temperature resistance, soluble polyimide (PI) is applied to the surface of UHMWPE fibers. A mussel-inspired biomimetic polycatechol/polyamine (PA) coating is initially constructed on the UHMWPE fiber surface by oxidative self-polymerization, serving as a secondary reaction platform. Subsequently, multifunctional UHMWPE-PA-PI fibers are prepared by depositing soluble PI on the fiber surface via impregnation. The PA and PI layers are firmly bonded by hydrogen bonding interactions and physical adhesion. The results show that the PI-coated UHMWPE fiber surface exhibits enhanced chemical activity, hydrophilicity, and thermal stability, with an increased thermal decomposition temperature of approximately 30 °C. Compared to pristine UHMWPE, the breaking force of UHMWPE-PA-PI fibers increases by 14.9%, and the interfacial adhesion strength between the fiber and rubber improves by 65.5%. The PI coatings also provide thermal insulation, acid resistance, and erasability functionalities. This modification strategy is highly efficient, simple, and less damaging, offering a novel solution to address UHMWPE fibers' surface inertness and temperature intolerance.
超高分子量聚乙烯(UHMWPE)纤维具有优异的机械性能,但其应用却受到表面惰性和低熔点的严重限制。为了提高表面活性和耐温性,可溶性聚酰亚胺(PI)被应用于超高分子量聚乙烯纤维的表面。受贻贝启发的仿生物聚邻苯二酚/聚胺(PA)涂层最初是通过氧化自聚合作用在超高分子量聚乙烯纤维表面构建的,作为二级反应平台。随后,通过浸渍法在纤维表面沉积可溶性 PI,制备出多功能 UHMWPE-PA-PI 纤维。PA 层和 PI 层通过氢键相互作用和物理粘附牢固地结合在一起。结果表明,涂有 PI 的超高分子量聚乙烯纤维表面具有更高的化学活性、亲水性和热稳定性,热分解温度提高了约 30 °C。与原始 UHMWPE 相比,UHMWPE-PA-PI 纤维的断裂力提高了 14.9%,纤维与橡胶之间的界面粘附强度提高了 65.5%。PI 涂层还具有隔热、耐酸和可擦除功能。这种改性策略高效、简单、损伤小,为解决超高分子量聚乙烯纤维的表面惰性和温度不耐受性问题提供了一种新的解决方案。
{"title":"Soluble Polyimide Coated UHMWPE Fibers with Multiple Property Enhancements: Surface Activity, Tensile Strength, Heat Resistance, Acid Resistance, and Erasability.","authors":"Lijie Yin, Wei Li, Yichen Lu, Liang He, Ming Tian, Nanying Ning, Wencai Wang","doi":"10.1002/marc.202400682","DOIUrl":"https://doi.org/10.1002/marc.202400682","url":null,"abstract":"<p><p>Ultrahigh molecular weight polyethylene (UHMWPE) fibers possess excellent mechanical properties, yet their applications are severely limited by surface inertness and low melting points. To enhance surface activity and temperature resistance, soluble polyimide (PI) is applied to the surface of UHMWPE fibers. A mussel-inspired biomimetic polycatechol/polyamine (PA) coating is initially constructed on the UHMWPE fiber surface by oxidative self-polymerization, serving as a secondary reaction platform. Subsequently, multifunctional UHMWPE-PA-PI fibers are prepared by depositing soluble PI on the fiber surface via impregnation. The PA and PI layers are firmly bonded by hydrogen bonding interactions and physical adhesion. The results show that the PI-coated UHMWPE fiber surface exhibits enhanced chemical activity, hydrophilicity, and thermal stability, with an increased thermal decomposition temperature of approximately 30 °C. Compared to pristine UHMWPE, the breaking force of UHMWPE-PA-PI fibers increases by 14.9%, and the interfacial adhesion strength between the fiber and rubber improves by 65.5%. The PI coatings also provide thermal insulation, acid resistance, and erasability functionalities. This modification strategy is highly efficient, simple, and less damaging, offering a novel solution to address UHMWPE fibers' surface inertness and temperature intolerance.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398862","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}
Akmal Z Umarov, Joseph Collins, Evgeniia A Nikitina, Ioannis Moutsios, Martin Rosenthal, Andrey V Dobrynin, Sergei S Sheiko, Dimitri A Ivanov
Self-assembled networks of bottlebrush copolymers are promising materials for biomedical applications due to a unique combination of ultra-softness and strain-adaptive stiffening, characteristic of soft biological tissues. Transitioning from ABA linear-brush-linear triblock copolymers to A-g-B bottlebrush graft copolymer architectures allows significant increasing the mechanical strength of thermoplastic elastomers. Using real-time synchrotron small-angle X-ray scattering, it is shown that annealing of A-g-B elastomers in a selective solvent for the linear A blocks allows for substantial network reconfiguration, resulting in an increase of both the A domain size and the distance between the domains. The corresponding increases in the aggregation number and extension of bottlebrush strands lead to a significant increase of the strain-stiffening parameter up to 0.7, approaching values characteristic of the brain and skin tissues. Network reconfiguration without disassembly is an efficient approach to adjusting the mechanical performance of tissue-mimetic materials to meet the needs of diverse biomedical applications.
瓶丛共聚物的自组装网络具有软生物组织所特有的超柔软性和应变适应刚性的独特组合,是一种很有前景的生物医学应用材料。从 ABA 线性-毛刷线性三嵌段共聚物过渡到 A-g-B 瓶丛接枝共聚物结构,可以显著提高热塑性弹性体的机械强度。研究利用实时同步加速器小角 X 射线散射技术表明,在线性 A 嵌段的选择性溶剂中对 A-g-B 弹性体进行退火处理,可大幅重构网络,从而增加 A 结构域的尺寸和结构域之间的距离。聚集数的相应增加和底层链的延伸导致应变刚度参数显著增加,最高可达 0.7,接近大脑和皮肤组织的特征值。无需拆卸的网络重组是调整组织模拟材料机械性能的有效方法,可满足各种生物医学应用的需要。
{"title":"Enhancing the Biomimetic Mechanics of Bottlebrush Graft-Copolymers through Selective Solvent Annealing.","authors":"Akmal Z Umarov, Joseph Collins, Evgeniia A Nikitina, Ioannis Moutsios, Martin Rosenthal, Andrey V Dobrynin, Sergei S Sheiko, Dimitri A Ivanov","doi":"10.1002/marc.202400569","DOIUrl":"https://doi.org/10.1002/marc.202400569","url":null,"abstract":"<p><p>Self-assembled networks of bottlebrush copolymers are promising materials for biomedical applications due to a unique combination of ultra-softness and strain-adaptive stiffening, characteristic of soft biological tissues. Transitioning from ABA linear-brush-linear triblock copolymers to A-g-B bottlebrush graft copolymer architectures allows significant increasing the mechanical strength of thermoplastic elastomers. Using real-time synchrotron small-angle X-ray scattering, it is shown that annealing of A-g-B elastomers in a selective solvent for the linear A blocks allows for substantial network reconfiguration, resulting in an increase of both the A domain size and the distance between the domains. The corresponding increases in the aggregation number and extension of bottlebrush strands lead to a significant increase of the strain-stiffening parameter up to 0.7, approaching values characteristic of the brain and skin tissues. Network reconfiguration without disassembly is an efficient approach to adjusting the mechanical performance of tissue-mimetic materials to meet the needs of diverse biomedical applications.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398849","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}
Se Jong Kim, Eun Ji Hong, Nuri Kim, Nuri Kim, Minseong Kim, Aram Shin, Byeong-Su Kim, Dong Won Lee, Jeung Gon Kim
This study presents an organocatalytic C-H functionalization approach for postpolymerization modification (PPM) of poly(ethylene oxide) (PEO). Most of PEO PPM is previously processed at the end hydroxy group, but recent advances in C-H functionalization open a way to modify the backbone position. Structurally diverse carboxylic acids are attached to PEO through a cascade process of radical generation by peroxide and oxidation to oxocarbenium by tertiary butylammonium iodide. Attaching carboxylic acids yields a series of functionalize PEO with acetal units (2-5 mol%) in a backbone, which is not accessible via conventional copolymerization of epoxides. The optimized conditions minimizes the uncontrolled degradation or crosslinking from the highly reactive radical and oxocarbenium intermediate. The newly introduced acetal units bring degradability of PEO as well as delivery of carboxylic acid molecules. Hydrolysis studies with high molecular weight functionalization PEO (Mn = 13.0 kg mol-1) confirm the steady release of fragmented PEO (Mn ∼ 2.0 kg mol-1) and carboxylic acid over days and the process rate is not sensitive to pH variation between pH 5 and 9. The presented method offers a versatile and efficient way to modify PEO with potential energy and medical applications.
{"title":"C-H Functionalization of Poly(ethylene oxide) - Embracing Functionality, Degradability, and Molecular Delivery.","authors":"Se Jong Kim, Eun Ji Hong, Nuri Kim, Nuri Kim, Minseong Kim, Aram Shin, Byeong-Su Kim, Dong Won Lee, Jeung Gon Kim","doi":"10.1002/marc.202400613","DOIUrl":"https://doi.org/10.1002/marc.202400613","url":null,"abstract":"<p><p>This study presents an organocatalytic C-H functionalization approach for postpolymerization modification (PPM) of poly(ethylene oxide) (PEO). Most of PEO PPM is previously processed at the end hydroxy group, but recent advances in C-H functionalization open a way to modify the backbone position. Structurally diverse carboxylic acids are attached to PEO through a cascade process of radical generation by peroxide and oxidation to oxocarbenium by tertiary butylammonium iodide. Attaching carboxylic acids yields a series of functionalize PEO with acetal units (2-5 mol%) in a backbone, which is not accessible via conventional copolymerization of epoxides. The optimized conditions minimizes the uncontrolled degradation or crosslinking from the highly reactive radical and oxocarbenium intermediate. The newly introduced acetal units bring degradability of PEO as well as delivery of carboxylic acid molecules. Hydrolysis studies with high molecular weight functionalization PEO (M<sub>n</sub> = 13.0 kg mol<sup>-1</sup>) confirm the steady release of fragmented PEO (M<sub>n</sub> ∼ 2.0 kg mol<sup>-1</sup>) and carboxylic acid over days and the process rate is not sensitive to pH variation between pH 5 and 9. The presented method offers a versatile and efficient way to modify PEO with potential energy and medical applications.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386783","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}
Xiang Liu, Mei Fang, Yuezhan Feng, Ming Huang, Chuntai Liu, Changyu Shen
Diglycidyl ether of bisphenol A crosslinking with glutaric anhydride is used to form the conventional "covalent adaptive network", polyether sulfone (PES) by coiling and aggregating on the adaptive network is used to significantly increase the uncured resin viscosity for improving the processability of epoxy resin, but inevitably affecting the curing reaction and dynamic transesterification reaction. This study investigates the crucial roles of PES in curing dynamics and stress relaxation behavior. The results indicate that although PES does not directly participate in the crosslinking reaction of polyester-based epoxy vitrimers. Moreover, the isothermal curing studies reveal that the addition of PES can greatly bring forward the reaction rate peak from conversion α = 0.6 to α = 0.2, meaning that the curing mechanism transfers from chemical control to diffusion control. Dynamic property analysis shows that the addition of PES significantly accelerates stress relaxation, especially at lower temperatures, leading to low viscous flow activation energy Eτ and relatively insensitive stress relaxation behavior to temperature. Introducing PES into vitrimer resin greatly improves crosslinking density (2.31 × 10⁴ mol m-3), enhancing glass transition temperature (82.68 °C), tensile strength (68.66 MPa), and fracture toughness (6.25%). Additionally, the modified vitrimer resin exhibits satisfying shape memory performance and reprocessing capability.
利用双酚 A 的二缩水甘油醚与戊二酸酐交联形成传统的 "共价自适应网络",利用聚醚砜(PES)在自适应网络上的盘绕和聚集显著提高树脂的未固化粘度,从而改善环氧树脂的加工性能,但不可避免地会影响固化反应和动态酯交换反应。本研究探讨了 PES 在固化动力学和应力松弛行为中的关键作用。研究结果表明,虽然 PES 并不直接参与聚酯基环氧树脂玻璃体的交联反应,但它在固化过程中对应力松弛行为起着至关重要的作用。此外,等温固化研究表明,PES 的加入可大大提高反应速率峰值,从转化率 α = 0.6 提高到 α = 0.2,这意味着固化机理从化学控制转变为扩散控制。动态特性分析表明,PES 的加入大大加快了应力松弛,尤其是在较低温度下,从而导致较低的粘流活化能 Eτ 和对温度相对不敏感的应力松弛行为。在玻璃树脂中加入聚醚砜可大大提高交联密度(2.31 × 10⁴ mol m- 3),从而提高玻璃化转变温度(82.68 °C)、拉伸强度(68.66 兆帕)和断裂韧性(6.25%)。此外,改性后的三聚氰酸酯树脂还具有令人满意的形状记忆性能和再加工能力。
{"title":"Investigation on Polyether Sulfone Toughening Epoxy Vitrimer: Curing and Dynamic Properties.","authors":"Xiang Liu, Mei Fang, Yuezhan Feng, Ming Huang, Chuntai Liu, Changyu Shen","doi":"10.1002/marc.202400540","DOIUrl":"https://doi.org/10.1002/marc.202400540","url":null,"abstract":"<p><p>Diglycidyl ether of bisphenol A crosslinking with glutaric anhydride is used to form the conventional \"covalent adaptive network\", polyether sulfone (PES) by coiling and aggregating on the adaptive network is used to significantly increase the uncured resin viscosity for improving the processability of epoxy resin, but inevitably affecting the curing reaction and dynamic transesterification reaction. This study investigates the crucial roles of PES in curing dynamics and stress relaxation behavior. The results indicate that although PES does not directly participate in the crosslinking reaction of polyester-based epoxy vitrimers. Moreover, the isothermal curing studies reveal that the addition of PES can greatly bring forward the reaction rate peak from conversion α = 0.6 to α = 0.2, meaning that the curing mechanism transfers from chemical control to diffusion control. Dynamic property analysis shows that the addition of PES significantly accelerates stress relaxation, especially at lower temperatures, leading to low viscous flow activation energy E<sub>τ</sub> and relatively insensitive stress relaxation behavior to temperature. Introducing PES into vitrimer resin greatly improves crosslinking density (2.31 × 10⁴ mol m<sup>-</sup> <sup>3</sup>), enhancing glass transition temperature (82.68 °C), tensile strength (68.66 MPa), and fracture toughness (6.25%). Additionally, the modified vitrimer resin exhibits satisfying shape memory performance and reprocessing capability.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386784","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}
Front Cover: In the cover image of article 2400343, Levent Kamil Toppare, Ali Cirpan, and co-workers basically bridge the nature of chemistry and renewable energy. The round-bottomed flask encapsulates a solar cell, symbolizing the bond of energy with wet lab chemistry. The molecular orbitals surrounding showcase the synergy between molecular design and computational chemistry.