ACS Applied Polymer Materials
·
2023
·
IF 5
Jiaming Liu,Xiaohong Liu,Xiaohua Cui,Jingjing Qin,Min Shi,Dingsong Wang,Liyan Liang,Chaolong Yang
Vitrimers are polymers possessing a covalent adaptable network (CANs) that can undergo a topological structural transformation under specific conditions, enabling material reprocessing. In this study, an active ester hardener containing imine bonds (TAI) was synthesized, and subsequently, epoxy resin with CANs (epoxy vitrimer, DGEBA/TAI) was prepared, which exhibited excellent thermal stability (initial degradation temperature of 364 °C and char yield at 800 °C of 30%), low water absorption (0.25 wt %), and good dielectric properties (dielectric constant of 3.37 and dielectric loss of 0.013). A comparative scratch healing test between the epoxy vitrimer and conventional epoxy resin showed that the hard vitrimer could not demonstrate self-healing ability and that scratch healing was derived from deformation recovery. The performance of such hard vitrimers should focus on recycling and reprocessing rather than a self-healing capability. Thus, the resin could be effectively recycled and reused by a hot pressing or solvent method, resulting in recycled resins with good tensile strength (70 MPa for hot-press welding and 58 MPa for solvent recycling) compared to the originals (69 MPa). In addition, the vitrimer materials allow shape reconfiguration through a network structure transformation, and an alternative analytical method was proposed to obtain the relaxation time of the vitrimer by fitting the equation of the stress relaxation curve, which could mitigate some of the interferences and provide a method for data reliability verification of the viscoelastic properties of the vitrimer.
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高影响因子
ADVANCED ENGINEERING MATERIALS
·
2023
·Vol. 25
·期 13
·2300031
·
IF 3.6
Zhiqiang Chen,Chenyu Jin,Zhen Li,Xiuzhao Li,Liuyu Yang,Tiejun Wang
Progress in the ever-growing vitrimer chemistry opens up great opportunities for a sustainable society by producing reprocessable thermosets. However, most vitrimers suffer from the conflict between mechanical performance and dynamic reactivity, hindering the development of industrial applications. Herein, a facile but universal material design strategy is proposed to yield tough epoxy vitrimers while preserving excellent reprocessability. Copolymerization and bond exchange reactions can build covalent bridges between heterogeneous polymer networks, thus leading to a hybrid dynamic covalent polymer network containing hard and soft segments. Tailorable mechanical and thermal properties are obtained by controlling the ratio of hard-to-soft components. The resulting epoxy vitrimer can balance strength and stretchability while exhibiting brittle-to-ductile transformation in tensile tests. Enhanced fracture toughness is achieved compared to both pristine hard and soft vitrimers. The resulting vitrimers exhibit excellent processability and potential applications in composite fabrication, welding and reshaping, and multiple shape memory functions. This work presents a feasible approach to satisfying the demands of mechanical performance and dynamic reactivity in the design of epoxy vitrimers. The material design principle will be applicable to a wide range of vitrimer systems to pursue desirable properties.
研究领域:
材料科学
·
高分子化学
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Mingzhuan Li,Haitao Yu,Xingyao Liu,Qinghua Zhang,Peifeng Feng,Yongbo Chi,Xigao Jian,Yujie Song,Jian Xu
Traditional carbon fiber reinforced epoxy composites (CFRECs) pose significant challenges to sustainable development due to their non-self-healable and non-recyclable nature, which causes environmental pollutions . To address these challenges, our research focuses on the design of carbon fiber reinforced vitrimer (CF/vitrimer) composites system with dual self-healing properties (self-healing resin and self-healing interface) and dual recyclable capabilities (recycling vitrimer resin and recycling CF). On the one hand, the scratch on the vitrimer resin exhibited rapid self-healing properties (achieving ˃ 95 % recovery within 5 min). Additionally, the self-healing interface was constructed between the functionalized CF and the vitrimer resin, and even after undergoing five self-healing cycles, the self-healing interface maintained a self-healing efficiency of 77.4 %. On the other hand, the CF/vitrimer composites could be easily and effectively degraded in ethylene glycol , resulting in recycled vitrimer resin and recycled CF. These results not only indicate the potential for developing other types of self-healing CF/vitrimer composites but also highlight their contributions to sustainable development.
研究领域:
材料科学
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环境科学
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高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2023
·Vol. 58
·期 46
·17470-17482
·
IF 4.5
Li Zi-Xia,Xiang Yong-Sheng,Ran Yin
Realizing nano-filler well dispersed in epoxy matrix is essential for the fabrication of high-performance epoxy composites. However, the aggregation of untreated nano-filler in epoxy resin during static curing greatly reduces the material performance. Herein, we report an effective and facile approach to fabricate well-dispersed silica nanoparticle (SiNP)-reinforced epoxy composites through dynamic crosslinking depending on vitrimer chemistry. The epoxy vitrimer synthesized by dynamic crosslinking method was named as EVD, and the epoxy vitrimer synthesized by static curing method was named as EVS. EVD/SiO 2 nanocomposites were prepared by dynamic crosslinking technology with unmodified nano-SiO 2 as a reinforcement filler, sebacic acid as a curing agent, diglycidyl ether of bisphenol A (DGEBA) as an epoxy monomer, zinc acetylacetonate as a transesterification catalyst, and a torque rheometer (internal mixer) as a dynamic crosslinking equipment, and EVS/SiO 2 nanocomposites were prepared by traditional static curing method as counterparts. The structure, properties, and stress relaxation of the EVD/SiO 2 and EVS/SiO 2 were comparatively investigated in detail. When the loading amount of SiO 2 was 5 wt%, EVD/SiO 2 -5 indicated 2.38 times tensile strength and 2.06 times elongation at break of EVS/SiO 2 -5. The Young's modulus of EVD/SiO 2 -5 (6.76 ± 1.07 MPa) was slightly higher than that of EVS/SiO 2 -5 (5.81 ± 1.06 MPa), which was attributed to more well-dispersed SiNP in EVD/SiO 2 -5. Moreover, the amount of SiO 2 can be filled up to 40 wt% in epoxy vitrimer to obtain high-modulus (1001 times of pure vitrimer) composite. We believe that this study provides a new idea for the preparation of other vitrimer composites with desired properties. Graphical abstract
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高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2021
·Vol. 138
·期 39
·51010
·
IF 3.125
Yue Yin,Jian Yang,Linghui Meng
Poly(butylene succinate) (PBS) refers to a high-performance biodegradable polymer employed to substitute petroleum polymers that cause environmental issues. However, PBS exhibits the defect of flowing above the melting point and rapid dripping for its poor melt strength. Accordingly, this study proposed a novel method to fabricate PBS vitrimer by exploiting reactive extrusion technology to mix diepoxide with PBS and then by employing zinc acetate as a catalyst to crosslink the PBS. Therefore, after the reaction extrusion blending, the blend still has a lower viscosity and high processing performance; in the subsequent curing process, the polymer undergoes a transesterification reaction and the viscosity increases. Via transesterification to form a cross-linked network, the storage modulus, and loss modulus of PBS vitrimer at 140°C reach 55,800% and 3500% of pure PBS, respectively. At this time, the crystallinity of PBS vitrimer is still as high as 56.9% (The crystallinity of pure PBS is 47.4%). And the shape stability of PBS at high temperatures was significantly improved. Moreover, PBS vitrimer could still be reshaped after the cross-linking process. This study proposed a facile method to produce PBS materials exhibiting high thermal shape stability.
研究领域:
材料科学
·
高分子化学
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高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2024
·Vol. 141
·期 29
·e55684
·
IF 2.7
Tong Yan,Hao Jiang,Wuting Pang,Tinglei He,Meng Cheng,Zhikun Wang,Chunling Li,Shuangqing Sun,Songqing Hu
Vitrimer materials have machinability and stability because of their shape remodeling and self-healing properties at high temperatures. This article reports the synthesis of epoxy resin using vanillin, p-aminophenol, and epichlorohydrin as raw materials, and polyetheramine-400 as a curing agent. To study the effect of free amine on the mechanical and self-healing properties, two materials with epoxy and amine stoichiometric ratios of 1:1 and 1:1.2 were studied, respectively. The experimental results show that when the molar ratio of epoxy to amine stoichiometric is 1:1.2 (V 1:1.2 ), the tensile strength of vitrimer materials can reach 5.4 MPa and the self-healing efficiency can reach 99.5% after 6 h of healing at 120°C. When the molar ratio is 1:1 (V 1:1 ), the obtained epoxy material has a higher tensile strength of 9.5 MPa. After 24 h of healing at 120°C, the self-healing efficiency can reach 83.4%. In addition, epoxy vitrimer materials can be remodeled at 120°C, and the self-healing and mechanical properties are not influenced after remodeling. This work proposes a novel preparation method for epoxy vitrimer materials, which is beneficial to the development of high-strength remodelable self-healing materials.
研究领域:
材料科学
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高分子化学
·
机械工程
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高影响因子
ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Haonan Zhou,Xiaoqian Zhang,Guowen Zhou,Muslum Demi̇r,Zepeng Lei,Wei Zhang,Xiaohui Wang
The escalating concern about plastic pollution has intensified research efforts in developing degradable bioplastics. However, the fabrication processes of all-natural bioplastics are fraught with tremendous challenges, notably the use of toxic chemicals and the generation of hazardous waste. Herein, we report an environmentally friendly method for synthesizing a sustainable konjac glucomannan (KGM) bioplastic. The intermolecular interactions of KGM chains were reconstructed by substituting the original H-bonds with dynamic covalent bonds, which were formed via the Schiff base reaction at the oil–water interface. The resulting thermo-processable KGM bioplastic exhibited multiple advantages, such as low glass-transition temperature (Tg), rehealability, reprocessability, satisfactory tensile strain, and excellent resistance to water and other chemicals. Significantly, only water was used as the reaction medium throughout the entire preparation, which avoided the consumption of organic solvents and the production of hazardous waste. This work provides an eco-friendly approach to craft konjac glucomannan bioplastic as viable alternatives to traditional plastics.
研究领域:
材料科学
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环境科学
·
生物化学
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高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2025
·
IF 2.8
Kuiling Wei,Xuejuan Cao,Yan Wu,Xiaoyu Yang,Boming Tang,Tianqiang Jiang
Recycling thermosets is essential for environmental protection and the sustainable development of a circular economy. Among various approaches, dynamic chemistry has proven to be an effective solution for recycling thermosetting polymers. To improve the sustainability of thermosetting polyurethanes and investigate their thermoreversible behavior with different combinations of disulfide bonds and Diels–Alder bonds, this study developed castor oil-based polyurethane vitrimer (Co-PUV 1/Co-PUV 2/Co-PUV 3) with varying dynamic covalent networks. The chemical structure, dynamic reversible reactions, rheological characteristics, and thermal-responsive self-healing were analyzed. The results revealed that disulfide bonds, combined with Diels–Alder bonds, can significantly enhance the thermoreversible response of the crosslinked networks. The first-rank combination was found in Co-PUV 2, which contained Diels–Alder bonds and 4.22 mol% disulfide bonds. This sample exhibited the shortest stress relaxation time and the largest creep range between 60°C and 100°C. Additionally, Co-PUV 2 achieved an 84.4% recovery rate of mechanical properties at 85°C and 0.3 MPa and regained its melt-recyclability at 135°C. In general, this work provides insights into the influence of disulfide and Diels–Alder bonds on the thermoreversible behavior of castor oil-based polyurethane vitrimer, enlightening a foundation for the design of recyclable polyurethane using a multi-dynamic bond strategy.
研究领域:
高分子科学
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材料化学
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可持续材料
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动态共价化学
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回收技术
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DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
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2022
·
IF 6.449
Chang Li,Shufen Zhang,Benzhi Ju
A starch-based vitrimer was prepared by blending a crosslinkable macromolecular plasticizer with starch derivatives via extrusion. The crosslinkable macromolecular plasticizer improved the mechanical properties of the material by enhancing the entanglement of molecular chains. The plasticizing effect was remarkable, and the material could be machined and recycled by hot-pressing at 130 °C for 15 min. The properties of the starch-based vitrimer were basically maintained after processing. Exudation or migration of the plasticizer and retrogradation of the starch-based vitrimer were avoided by the presence of crosslinking bonds. The hydrophobicity of the material was suitably improved to prevent the influence of moisture in the environment on its performance.
研究领域:
材料科学
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高分子化学
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高影响因子
POLYMER
·
2025
·
IF 4.5
Jialiang Zhong,Zhaoyi Luo,Yue Wang,Yanning Zeng
Sustainable polycarbonate (PC) vitrimers were synthesized through a green one-step reaction between biomass-derived epigallocatechin gallate (EGCG) and bis(6-membered cyclic carbonate) (BCC). These EGCG-based networks exhibit exceptional mechanical properties, flame retardancy, antioxidant capacity, self-healing ability and reprocessability. EGCG content significantly affects the performance of the resulting networks. As the EGCG content increases, the mechanical properties, stress relaxation, flame retardancy, antioxidant capacity were improved. The increased EGCG content enhances crosslinking density, resulting in superior flame retardancy with a UL-94 V-0 rating and limiting oxygen index (LOI) of 28.1 %. The dynamic network structure enables efficient stress relaxation, retaining over 80 % of mechanical properties after three reprocessing cycles. Additionally, the material exhibits thermal self-healing efficiency of 90 % through transcarbonation-driven network rearrangement. Additionally, EGCG-based carbon-fiber composites achieved close loop recycling, addressing environmental concerns while maintaining high performance. Present strategy simultaneously enhances recyclability, fire safety, and sustainability, offering a circular economy-aligned solution for polymers used in electronics, automotive, and aerospace applications.
研究领域:
高分子科学
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材料工程
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可持续化学
·
复合材料技术
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阻燃材料
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回收技术
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DOI
高影响因子
COMPOSITES SCIENCE AND TECHNOLOGY
·
2024
·
IF 8.3
Mei Fang,Xiang Liu,Yuezhan Feng,Ming Huang,Chuntai Liu,Changyu Shen
The emergence of vitrimers breaks through the limitation of traditional carbon fiber reinforced thermoset composites (CFRP) caused by their permanent crosslinking molecular networks. Herein, the dynamic cross-linked network of vitrimer was synthesized from Bisphenol A diglycidyl ether (DGEBA) and glutaric anhydride (GA) under the catalysis of zinc acetylacetonate (Zn(acac) 2 ), and the corresponding carbon fiber reinforced vitrimer composites (CF/V x ) were prepared via an impregnation and hot pressing process. The dynamic covalent adaptable networks (CANs) of vitrimer endow CF/V x with stress relaxation and creep characteristics. By adjusting the catalyst content, the dynamic performance of CF/V 0.05 can be optimized to achieve the highest viscous flow activation energy (60 kJ/mol) and the lowest characteristic relaxation time (1.0 × 10 −3 s). The unique dynamic properties enable CF/V x with reprocessability at high temperature. Typically, the flexural modulus of CF/V 0.05 decreased from 87 ± 1.81 GPa at room temperature to 4.62 ± 0.28 GPa at 220 °C, which confirms the feasibility of thermoplastic forming of CF/V 0.05 at high temperatures. Based on this, a CF/V 0.05 -based cap-shaped component was successfully manufactured through a thermoforming process . Additionally, the CF/V 0.05 composites also exhibit repairability for interlaminar fractures. The optimal CF/V 0.05 can achieve a repair efficiency of 128 % under the hot press conditions of 180 °C, 10 MPa and 1 h. Hence, the reprocessable and repairable CF/V x composites hold enormous potential in the engineering field.
研究领域:
材料科学
·
高分子化学
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DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2025
·
IF 6.2
Yanna Zhao,Yingying Zhang,Xiaowei Bai,Yuqi Wang,Yiqing Li,Shuai Yang
Vitrimer has become an emerging application to solve the problem of thermoset pollution and resource wastage due to its reversible cross-linked network structure that enables reuse and recycling of materials. However, it is still challenging and difficult to achieve full bioresourcing and to prepare recycling pathways with excellent mechanical strength and high efficiency. In this study, a bisphenol derivative monomer with imine bonds was first synthesized with tyramine (TA) and terephthalaldehyde (TPA), and then the monomer was used together with 4,4′-diaminodiphenyl disulfide (4-AFD) to co-cure epoxidized soybean oil (ESO) to construct an epoxy vitrimer material (ETA) with a bi-dynamic network structure. ETA-3 exhibits high 5 % thermal stability T d 5 % (319.17 °C) and energy storage modulus E (2085.35 MPa). Notably, due to the fact that it exhibits a short relaxation time (32.24 s) and low activation energy (70.07 KJ/mol), ETA can achieve the repair of scratches within 30 min at 100 °C. This test demonstrates that ETA vitrimer has a better self-repairing performance, which contributes to the continuous development of vegetable oil-based polymeric materials.
研究领域:
材料科学
·
可持续化学
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DOI
高影响因子
危险品化学品经营许可证（带存储）