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Summary: A dual-dynamic cross-linked network composed of dynamic covalent and non-covalent bonds was proposed for closed-loop recovery of epoxy thermosets/composites. The cooperative effects of hydrogen-bond interactions and molecular interlocking of rigid-flexible molecular chains enhanced the stiffness and ductility, and enabled the material to have excellent fracture toughness. Importantly, driven by the pH-sensitive feature, the material could be completely degraded within 3 hours. The recovered oligomer showed potential in toughening brittle materials, and the CF cloths could be re-prepared into new high-performance composites.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
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Summary: Thermosetting polymers are difficult to recycle due to their permanently cross-linked networks. This mini-review summarizes the recent progress and future prospects in upcycling thermosetting polymers.
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(2023)
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Summary: This study incorporates dynamic covalent boronic ester linkages with internal B-N coordination into a commercial epoxy matrix to prepare room-temperature phosphorescence (RTP) polymers. The obtained polymers show enhanced mechanical toughness, ultralong RTP, shape memory behavior, and excellent durability in various solvents. These novel properties make them suitable for potential applications in information encryption and anti-counterfeiting.
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Tingting Lian et al.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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Summary: A reactive blending strategy was proposed to develop a thermoplastic-thermoset blend with enhanced compatibility based on dynamic covalent chemistry. Polybutylene terephthalate (PBT) and polymerized epoxy vitrimer were melt blended and the bond exchange facilitated the grafting of PBT and epoxy vitrimer chains, resulting in improved interfacial compatibility and thermal stability. The obtained blend achieved a balance between the strength and stretchability of PBT and epoxy vitrimer, leading to enhanced toughness.
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Solene Guggari et al.
Summary: Epoxy vitrimers, containing dynamic reversible covalent bonds, have advantages over traditional epoxy materials, such as recyclability, repairability, and reprocessability. The development of eco-friendly epoxy materials has been expanded by incorporating dynamic aromatic disulfide bridges. In this study, a bio-based aliphatic disulfide based on cystamine was used as a hardener with a vanillin-derived bio-sourced epoxy to prepare fully bio-based epoxy vitrimer. The presence of the aliphatic hardener significantly influenced the reactivity and dynamic properties of the epoxy vitrimer.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
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(2023)
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ACS APPLIED POLYMER MATERIALS
(2023)
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Huawei Qiao et al.
Summary: This study systematically reveals the role of a hyperbranched polysiloxane (PBPS) with boron in the curing kinetics of epoxy resin. Boron efficiently reduces the induction time of curing and increases the reaction rate in the non-catalytic stage. The addition of PBPS also affects the activation energy of the viscous flow stage, resulting in excellent toughening effects. This study fills the knowledge gap regarding the mechanism and influence of hyperbranched polysiloxane in the curing of epoxy resin.
CHEMICAL ENGINEERING JOURNAL
(2023)
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Qi Zhang et al.
Summary: This article discusses the dynamic chemical properties of 1,2-dithiolanes as a versatile structural unit for the design of smart materials. It summarizes the latest research progress in this field and provides an overview of the challenges and potential future directions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
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Liuyue Zhong et al.
Summary: This study synthesized a ferulic acid-based hyperbranched epoxy resin (FEHBP) to produce closed-loop recyclable and catalyst-free epoxy vitrimers with improved mechanical performance. The incorporation of FEHBP enhanced the tensile strength and toughness of the epoxy vitrimers through an in situ reinforcing and toughening mechanism. The hydroxyls of FEHBP catalyzed the dynamic transesterification and accelerated the reprocessing of epoxy vitrimers.
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Yingchun Sun et al.
Summary: Developing amine-cured epoxy vitrimers is more significant than conventional epoxy-carboxylic acid vitrimers due to the wider usage of amines as curing agents. By synthesizing aliphatic and aromatic glycidyl esters and curing them with amine-curing agents containing disulfide bonds, dual dynamic vitrimers with integrated hydroxyl esters and disulfide bonds in the cross-linked network can be obtained. The properties of these vitrimers can be easily adjusted by changing the proportion of aromatic and aliphatic glycidyl esters, and the addition of aromatic glycidyl esters can enhance and toughen the materials without sacrificing their curing activity and reprocessing property.
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Alaitz Ruiz de Rekondo et al.
Summary: Aromatic disulfides containing epoxy vitrimers are versatile materials with potential for industrial applications. This study investigated the effect of different hardener structures, free pending amine groups, and catalysts on the mechanical and dynamic properties of vitrimers. The results showed that the relaxation time and activation energy varied depending on the regioisomerism of the aromatic hardener, stoichiometry, and presence of catalysts. The presence of free pending amine groups or imidazole catalysts reduced the stress relaxation time, making them suitable for processing techniques.
Article
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Xiaoguang Li et al.
Summary: This study demonstrates a method to incorporate dynamic silyl ether linkages into rubber matrix, allowing for the tunability of mechanical and dynamic properties of the material. By adjusting the content and functionality of silyl ether cross-linkers, the resulting networks exhibit thermally-activated malleability and reprocessability.
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Xiaohong Liu et al.
Summary: In this study, a high-strength epoxy resin EP-SeSe with self-healing and shape memory properties was designed, which exhibited excellent shape memory performance, self-healing performance, high mechanical strength, and exceptional thermal stability. Through the [2 + 1] radical-mediated mechanism of the dynamic diselenide bonds, EP-SeSe displayed fast stress relaxation, self-healing, remodeling, and weldability above the glass transition temperature. This study provided a facile method for constructing robust epoxy resins with self-healing and shape memory properties, with great potential applications.
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Radhika Wazalwar et al.
Summary: Surface-modified Ti3C2 nanosheets were studied as toughening agents for aerospace-grade epoxy composites. The nanosheets improved the curing behavior and mechanical properties of the composites, resulting in increased compressive strength and fracture properties. The functionalization of the nanosheets was crucial in achieving uniform filler dispersion and favorable filler-matrix interaction.
ACS APPLIED POLYMER MATERIALS
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Amber M. Hubbard et al.
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Shipeng Xiang et al.
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Huan Zhang et al.
Summary: This article introduces a new type of aromatic disulfide epoxy vitrimer packaged electronic devices, which have nondestructive healing and recycling properties, effectively reducing the generation of e-waste and promoting resource recycling and environmentally friendly development of electronic devices.
Review
Chemistry, Multidisciplinary
Filip Van Lijsebetten et al.
Summary: Dynamic covalent polymer networks are an interesting solution for the recyclability of thermosets and elastomers, but balancing thermal reprocessability and dimensional stability remains a challenge. Disconnecting chemical reactivity at low and high temperatures can achieve creep resistance and high dynamism in polymer networks.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
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Haojie Gong et al.
Summary: Predicting barely visible damage on high-performance glass-fiber-reinforced composites is essential in preventing material failure. This study demonstrates the synthesis of a self-reporting and recyclable composite material through the use of a disulfide bond-tailored epoxy matrix.
CHEMICAL ENGINEERING JOURNAL
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Fanlong Meng et al.
Summary: In this paper, we provide a comprehensive description of the rheological behavior of vitrimers, ranging from small deformation to large deformation. We propose concise analytical expressions to assist in data analysis and clarify emerging insights and concepts in the field. Additionally, we identify the elastic-plastic transition at a timescale comparable to the lifetime of exchangeable bonds in the vitrimer network and propose a new method to deduce material parameters. Furthermore, we investigate partial vitrimers and present a phase diagram of their strain response under different applied loads.
NATURE COMMUNICATIONS
(2022)
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Amber M. Hubbard et al.
Summary: Vitrimers are a type of covalent adaptable networks that have self-healing and shape reprocessing capabilities. This study investigates the influence of fillers on the thermomechanical properties, self-healing, and shape processing capabilities of vitrimer composites. The results show that the concentration and dispersion of fillers play a significant role in creep suppression, increased topology freezing temperature, and improved mechanical properties.
ACS APPLIED POLYMER MATERIALS
(2022)
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Yan Ma et al.
Summary: A new dynamic polyurea network with highly cross-linked inner cores and flexible outer branches was designed and synthesized. This network provides resistance to creep and chemical corrosion, as well as reprocessability.
JOURNAL OF MATERIALS CHEMISTRY A
(2022)
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Jing Chen et al.
Summary: This study proposes a design for stretchable ionic conductors called dynamic supramolecular ionic conductive elastomers (DSICE), using a phase-locked strategy. The soft phase polyether backbone conducts lithium-ion transport, while the combination of dynamic disulfide metathesis and supramolecular quadruple hydrogen bonds in the hard domains contributes to self-healing capacity and mechanical versatility. The well-designed DSICE exhibits high ionic conductivity, transparency, stretchability, strength, toughness, self-healing capability, and recyclability.
NATURE COMMUNICATIONS
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Junheng Zhang et al.
Summary: In this study, a hyperbranched polymer based on itaconic acid was synthesized and incorporated into the preparation of epoxy vitrimers. The resulting epoxy vitrimers showed excellent mechanical properties and malleability, and could be efficiently degraded and recycled for environmental-friendly reprocessing.
Review
Chemistry, Multidisciplinary
Yanlin Liu et al.
Summary: This review discusses the closed-loop recycling of novel thermosets, including hydrolysis recycling and dynamic reaction recycling. Hydrolysis recycling allows recovered thermosets to have the same structure and properties as the original resin, but improving monomer recovery remains a challenge. Dynamic reaction recycling enables 100% recovery rate, but at the cost of lower performance of the recovered resin.
Article
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Lin Wang et al.
Summary: By incorporating hydrogen bonds and functional groups into elastomer vitrimers, the mechanical performance and stability of the elastomer can be improved. The reversible breakage and recombination characteristics of hydrogen bonds, as well as the microphase-separated structure formed by functional groups, can enhance the creep resistance. The reprocessability of the network is not affected.
Review
Chemistry, Multidisciplinary
Xiao-Li Zhao et al.
Summary: Biobased covalent adaptable networks (CANs) provide a sustainable alternative to traditional thermosetting polymers and exhibit attractive functionalities such as reprocessing, recyclability, and self-healing. Significant progress has been made in the design and synthesis of biobased CANs using biomass-derived chemicals and dynamic covalent bonds.
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Polymer Science
Stephanie Engelen et al.
Summary: Research on bio-based covalent adaptable networks is popular nowadays for finding an optimal implementation of thermoset materials and composites in a circular context. In this study, a vanillin derivative is integrated into vitrimers to create materials with promising properties.
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Haojie Gong et al.
Summary: This study introduces a novel high-performance GFRCs material with pre-damage indication and recyclability.
CHEMICAL ENGINEERING JOURNAL
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Yang Yang et al.
Summary: Epoxy vitrimers offer reprocessability, self-healing, welding, reshaping, and recycling properties to epoxy resins, providing hope for replacing traditional thermosets in a wide range of applications in aerospace materials, electronic devices, and consumer products of daily life.
PROGRESS IN MATERIALS SCIENCE
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Jianfan Qiu et al.
Summary: This research successfully transformed poly(ethylene terephthalate) (PET) into continuously reprocessable vitrimers through a specific method, improving the mechanical properties and processability of PET for industrial production.
Article
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Ibon Aranberri et al.
Summary: In this study, a recyclable and reprocessable vitrimer suitable for pultrusion process was developed and used to manufacture a pultruded profile reshaped by thermoforming. The material showed good thermal stability and mechanical properties, and demonstrated the ability for mechanical recycling and thermoforming.
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Qiong Li et al.
Summary: The research team synthesized a novel acetal precursor from abundant and renewable furfural to produce PU covalent adaptable networks for the first time, combining excellent reprocessability and controlled degradability. Through a series of reaction processes, the properties of the materials can be adjusted, promoting the development of advanced thermosets from renewable bioresources.
Review
Polymer Science
Jingkai Liu et al.
Summary: The development of sustainable thermosetting resins is a contemporary research objective, requiring renewable feedstocks, comprehensive properties, and recyclability. This systematic overview discusses recent advances in bio-based thermosetting resins, including the application of bio-based platform compounds, synthesis of typical bio-based thermosets, and strategies for recycling waste products.
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Itxaso Azcune et al.
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EUROPEAN POLYMER JOURNAL
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Qiong Li et al.
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Polymer Science
Wenbin Li et al.
Summary: The research focuses on bio-based multifunctional self-repairing and cross-linking epoxy resins with excellent mechanical properties. A biobased double functional epoxy monomer modified with organosilicon was derived and cured to form dynamic epoxy resins with lower glass transition temperature and tensile strength, but higher elongation at break compared to traditional thermosets. The resins exhibited self-repairing, shape memory, and reprocessing ability, as well as complete degradation, showing promise for sustainable development.
Editorial Material
Chemistry, Multidisciplinary
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Xiwei Xu et al.
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