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Vitrimer
Matter · 2021 · IF 15.589

Vitrimer-based soft actuators with multiple responsiveness and self-healing ability triggered by multiple stimuli

Yang Yang,Huimin Wang,Shuai Zhang,Yen Wei,Xiangming He,Jianlong Wang,Yingying Zhang,Yan Ji

Soft actuators are highly desirable in soft robots, electronic devices, wearable devices, etc. Both multi-stimuli responsiveness and multichannel self-healing ability are essential for soft actuators to be used in different circumstances. However, to date, research on soft actuators with multi-stimuli response or multichannel self-healing ability is scarce, and there is none on actuators with both multi-stimuli abilities. Here, we show that simply hot-pressing carbonized silk fabrics into the surface of vitrimers results in a thermosetting soft actuator that can be efficiently and repeatedly self-healed by five stimuli (light, electricity, electromagnetic wave, solvent, and heat) and can respond to four stimuli (light, electricity, heat, and solvent) simultaneously. Moreover, due to the nature of vitrimer, it is robust, sustainable, recyclable, and reprocessable. This soft actuator may greatly broaden its applications, as it is hopefully healed and actuated by a handy and facile tool when it is used in different environmental circumstances.

研究领域: 材料科学 · 软体机器人 · 智能材料 · 自修复材料 · 高分子科学
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POLYMER · 2023 · IF 4.6

Length effect of crosslinkers on the mechanical properties and dimensional stability of vitrimer elastomers with inhomogeneous networks

Mei-Juan Xie,Chang-Cheng Wang,Rong Zhang,Jian Cao,Mao-Zhu Tang,Yun-Xiang Xu

Inhomogeneous network construction is a useful strategy to solve the trade-off between mechanical strength and creep in vitrimer rubbers. But it is still lack of tools to tune the mechanical properties and network dynamics of this new system. In this paper, uneven distribution of functional groups was realized by sequential coordination polymerization of myrcene and isoprene and epoxidation . The following epoxidation and curing generated VMI-x samples with inhomogeneous network. Polyisoprene was used to prepare control samples called VPI-x with homogeneous network. Different lengths of dicarboxylic acid crosslinkers (SA = succinic acid, HA = heptanedioic acid, DA = decanedioic acid) were used to probe their effects on dynamic behaviors, mechanical properties and recyclability . Morphological test and nanomechanical mapping confirmed the inhomogeneous feature of VMI-x samples. For both inhomogeneous and homogeneous samples, SA and DA crosslinkers brought higher tensile strength and modulus, earlier SIC phenomenon and higher orientation percentage of amorphous molecular chains than those of HA, which are ascribed to extra permanent cross-linking existing in SA samples and transition entanglements existing in DA samples. However, the constrain effect of SA crosslinker is too strong in inhomogeneous network to sacrifice the extensibility, which is much smaller than those of HA and DA. SA and DA samples also present restricted segmental motion and superior creep resistant properties compared to HA samples according to the results of broadband dielectric spectroscopy and DMA test. Differently, at high temperature above 130 °C, the stress relaxation, topology freezing transition temperature (Tv) and recycling efficiency of strength are dominated by the crosslinker length monotonically, probably due to the disentanglement of DA crosslinkers. Compared to homogeneous network, inhomogeneous ones showed obvious enhanced mechanical properties, lower hysteresis, quicker segmental relaxation, lower creep and quicker network relaxation. This work demonstrates that crosslinker lengths could tune the vast aspects of vitrimer elastomers and is a non-negligible factor to determine their properties, especially for those with inhomogeneous networks.

研究领域: 高分子科学 · 材料工程 · 软物质物理 · 化学合成
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JOURNAL OF POLYMER SCIENCE · 2026 · IF 3.9

A Mechanochemically Synthesized Vitrimer-Like PLA

Xiaoxi Huang,Yuan Sang,Hailing Liu,Yifeng Sun

Mechanochemistry is an efficient, solvent-reduced, and extra heat-free green chemistry method. In this work, mechanochemistry is applied to the polymerization of PLA. The resulting PLA was esterified with citric acid to obtain a vitrimer-like polymer, which was also carried out via mechanochemistry. These mechanochemistry processes were performed using a planetary ball mill, which is favorable for scale-up synthesis. The synthesized polymer was characterized by NMR and SEC, and the vitrimer-like properties were evaluated by rheology, DSC, TGA, and shape memory behavior. Graphical Using mechanochemistry, PLA is polymerized via an efficient, solvent-reduced, heat-free route. The as-synthesized PLA is then further converted into a vitrimer-like polymer by mechanochemical modification. The resulting material exhibits dynamic network behavior, as confirmed by thermal, rheological, and shape-memory analyses.

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ACS Applied Polymer Materials · 2023 · IF 5

Tung Oil-Based Degradable Vitrimer for Reprocessable and Recyclable Vitrimer–MWCNT Composites with Self-Healing Ability Triggered by Multiple Stimuli

Lei Chen,Zekun Li,Yufeng Ma,Qianqian Shang,Yun Hu,Qin Huang,Meng Zhang,Puyou Jia,Yonghong Zhou

In order to reduce the overdependence on petroleum-based products, the preparation of functional polymers with renewable resources has become a research hotspot. In this study, tung oil, extracted from tung tree seeds, was introduced to the synthesis of tung maleic anhydride (TOMA) and epoxidized tung oil ethanolamides (ETOE) via a simple modification of the conjugated double bonds and ester bonds of tung oil, and then tung oil-based vitrimers (PETVs) based on a dynamic hydroxyl ester exchange reaction were prepared with different ratios of ETOE to TOMA. Due to the presence of abundant hydroxyl esters and flexible aliphatic long chains, PETVs showed a fast and excellent self-healing performance, and their repair efficiency reached 94.7% at 160 °C for 10 min without any catalyst. In addition, PETVs exhibited excellent mechanical properties, alkali degradability, shape memory properties, and recyclability. Degradation experiments indicated that PETVs could be completely hydrolyzed to small-molecule substances in alkaline solutions. PETV/MWCNT composites (PMs) with excellent electrical and thermal conductivity exhibited rapid self-healing ability under the conditions of electrical, infrared radiation, and heating. Compared to conventional petroleum-based thermoset polymers, PETVs with the advantages of environmental friendliness and sustainability could provide a practical strategy to prepare high-performance vitrimers from renewable materials.

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INDUSTRIAL CROPS AND PRODUCTS · 2024 · IF 5.6

Sustainable vitrimer based on Hydroxyethylcellulose and biobased epoxy

Chang Li,Qingrui Dai,Weidong Wu,Dong Yu Zhu,Xueqing Qiu

Cellulose plastic is an environmentally friendly material that shows excellent performance in the field of polymer materials. However, it exhibits a relatively high processing temperature, poor solvent resistance, and high performance loss during high-temperature reprocessing hindering its applications. We report the preparation of a cellulose-based grape-based vitrimer by grafting a bioepoxy cross-linker and an internal plasticiser (alkoxyglycidyl ether) onto a cellulose chain via an epoxy chemical reaction. The glass transition temperature, processability, and reprocessing conditions of the material were adjusted by changing the ratio of the crosslinking agent and the internal plasticizer. The prepared cellulose-based vitrimers had low glass transition temperatures, good processing and solvent resistance, and excellent reprocessing and recycling performance. The introduction of a covalent crosslinking network reduced the reprocessing temperature of the cellulose-based materials and avoided the migration and seepage of plasticizers. This study provides an important basis for the use of cellulose in the preparation of green and sustainable vitrimers for potential industrial applications.

研究领域: 材料科学 · 绿色化学
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POLYMER · 2025 · IF 4.5

Balancing mechanical performance and repair ability of epoxy and its composites via dual dynamic mechanism

Lei Wang,Mushan Yuan,Yisen Huang,Yang Chen,Shengtai Zhou,Huawei Zou,Yinfu Luo,Zhengguang Heng,Mei Liang

Introducing dynamic covalent bonds offers a promising strategy to enable the reprocessing and repair of epoxy resins and their composites, with efficacy tied to the type and extent of dynamic exchange. Although combining multiple mechanisms has received increasing attention, in most studies, these multiple mechanisms are independent of each other, lacking more efficient synergistic effects, and often exhibit worse mechanical performance along with elevated reprocessing temperatures. To overcome these challenges, we developed an epoxy vitrimer and its composites incorporating synergistic dual dynamic exchange mechanisms. This was achieved by combining an imine-containing epoxy resin with a curing agent featuring vinylogous urethane (VU) dynamic bonds, which is designed with excess amine groups to undergo dynamic exchange with both mechanisms. The resulting samples exhibit outstanding mechanical properties, including a tensile strength of 100.32 MPa, a glass transition temperature (T g ) of 125.07 °C, and an elongation of 6.77 %. Reprocessing near T g allows tensile strength and elongation at break to recover to 75.54 % and 52.14 % of their original values, respectively, after two cycles. These epoxy vitrimers and composites optimally balance high mechanical strength and structural reversibility through dual dynamic exchange mechanisms. Additionally, this design enables rapid, non-destructive carbon fiber recovery at room temperature and effective shear repair of carbon fiber layers, offering insights for designing longer-lasting epoxy materials and repair strategies.

CAS / MDL: 1694-31-1
研究领域: 材料科学 · 高分子化学 · 复合材料 · 机械工程
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JOURNAL OF POLYMER ENGINEERING · 2021 ·Vol. 41 ·期 5 ·365-374 · IF 1.367

Polyurethane modified epoxy vitrimer and its stress relaxation behavior

Weiqiang Lian,Huipeng Han,Xiaoxin Zhang,Guirong Peng,Zhaojing Jia,Zhenlin Zhang

Anhydride cured epoxy vitrimers usually exhibit desired mechanical strength but poor toughness and slow transesterification rate. Therefore, the repairing property of the material was restricted. In this paper, polyurethane modified epoxy vitrimer (PU-Epv) was prepared. PU was introduced into the vitrimer system of tetrahydrophthalic anhydride cured epoxy to improve the toughness of the material. Meanwhile, because of the presence of amino ester, the transesterification reaction was promoted and the activation energy of the transesterification was only 33.59 kJ/mol. In the thermal welding experiment, the material could be welded at least five times, and scratches on the surface of the samples could be efficiently repaired within 30 min. The toughness of the material was improved without damaging the strength. Meanwhile, the hard thermosetting epoxy was endowed with excellent repairing properties to increase the service life of the material.

研究领域: 材料科学 · 化学工程
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POLYMER · 2024 · IF 4.1

Tensile, compressive, flexural, torsional and impact properties of vitrimer

Le An,Rui Xiang,Heshan Bai

Vitrimers behave like traditional thermosets with good thermal and mechanical properties at service temperature, combined with thermoplastic behaviors above a specific temperature due to their dynamic cross-linked networks. However, there is a lack of effort in studying the mechanical properties of existing vitrimers, which are important for applying them in practical applications. The objective of this work is to experimentally investigate the tensile, compressive, flexural, torsional, and impact properties of a widely studied epoxy-based vitrimer through the various tests: tensile test, compressive test, three-point bending test, torsional test, and pendulum impact test. Since the vitrimer has the same chemical composition as conventional epoxy, all the mechanical tests mentioned above are also conducted on the epoxy for comparison. The results show that the vitrimer is comparable to the epoxy in tensile, compressive, flexural, and torsional properties, while its impact strength is substantially improved. Finally, the thermoplastic behaviors (i.e., reprocessing, recycling, reshaping) of the vitrimer are also studied.

CAS / MDL: 108503-47-5
研究领域: 材料科学 · 机械工程
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JOURNAL OF POLYMER SCIENCE · 2023 · IF 3.4

High-performance vitrimer films containing acylhydrazone dynamic covalent bonds

Yanna Zhao,Yuqing Huang,Wentong Hou,Ting Zhang,Yingying Zhang,Yuqi Wang,Xiaowei Bai

Vitrimer films containing acylhydrazone bonds are synthesized in two steps. Bio-based vanillin and adipate dihydrazide are used to prepare diols containing acylhydrazone bonds in one step, which are introduced into the reaction system of vitrimer to obtain the final films. The process is concise and easy to operate. By utilizing the rigid structure of vitrimer films and introducing dynamic acylhydrazone bonds, the obtained vitrimer films exhibit strong mechanical strength (maximum tensile strength of 27.10 MPa and maintaining up to 185.52% of the original breaking strength), excellent self-healing property (tensile strength of 26.26 MPa after 12 h of primary self-healing and 5.24 MPa after 12 h of secondary self-healing), and rapid shape memory property (recovery time of about 2 min), strong acid and alkali resistance (not dissolved within 24 h), good thermal stability (no decomposition occurs below 160 °C), and high storage modulus (reaches 1087 MPa). These comprehensive benefits yield a certain reference for the preparation of vitrimer materials with prime properties. Graphical

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JOURNAL OF POLYMERS AND THE ENVIRONMENT · 2023 · IF 5.3

A Green Recyclable Vanillin-Based Polymer (Amide–Imide) Vitrimer

Zhao Yanna,Hou Wentong,Huang Yuqing,Zhang Ting,Zhang Yingying,Wang Yuqi,Bai Xiaowei

In this paper, a bio-based polyamide imide polymer, PDPD (Polymer of D230, Poly hexa methylene diamide and Dialdehyde vanillin), was synthesized via amine aldehyde condensation reaction. PHMD was prepared from diethyl oxalate (ODE) and 1,6-hexanediamine (HAD), and vanillin was dialyzed to give dialdehyde vanillin (DVA). Then polyether amine D230 was introduced to obtain polyamide prepolymer, and triethyl citrate was used as cross-linking agent to prepare bio-based glass polymer material PDPD through bulk polymerization at high temperature. The thermal stability, glass transition temperature, mechanical properties, and energy storage modulus of PDPD material were investigated through thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and stress-strain curve. Results show that PDPD possesses excellent thermal stability and high mechanical strength, with a 5% thermal decomposition temperature at 288 °C, a stress of 7 MPa, and a strain of 117%. The storage modulus of PDPD in DMA testing can reach up to 2907 MPa. The anti-creep performance of PDPD is good, and the creep level after two repairs is within 40%. Self-healing testing revealed that PDPD maintained its performance after self-healing. The synthesized polymer is also recyclable, making it an attractive option for environmentally conscious applications.

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CHEMICAL ENGINEERING JOURNAL · 2026 · IF 13.2

Bio-inspired lychee-like vitrimer hybrids for moisture-electric generation

Xinyi Yan,Wei Zhao,Liuping Jin,Yiyao Xi,Yonghao Ni

Vitrimers, a class of polymers featuring dynamic covalent-bond networks, have garnered significant interest over the past decade owing to their potential to advance polymer materials. Since their discovery in 2011, extensive research has focused on developing different chemistries to synthesize diverse vitrimers, as well as on investigating vitrimers' mechanical properties and reprocessabilities. However, the exploration of vitrimers' inherent functionality offered by their unique molecular structures for advanced applications remains comparatively underexplored. In this work, we report the first synthesis of a novel class of vitrimer hybrids—lychee-like core-shell poly(hydroxyurethane) (PHU)@polyaniline (PANI) microspheres embedded within cellulose fabric—via a tandem in situ polymerization approach and investigate their applications in moisture-enabled electric generation. The resulting materials can harvest energy from diverse water sources, including deionized water, tap water, lake water, and seawater, outperforming most polymers and polymer composites reported in the literature. This work not only reports the synthesis of a new kind of vitrimer hybrids but also pioneers their advanced application in moisture-electric generation, highlighting their potential for green energy harvesting from water.

CAS / MDL: 9002-98-6
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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Comparing Surface and Bulk Curing Processes of an Epoxy Vitrimer

Hongkun Yang,Dong Wang

We used atomic force microscopy-based infrared spectroscopy (AFM-IR) and nanomechanical mapping (AFM-NM) to image the surface of a vitrimer, specifically dicarboxylic acid-cured diglycidyl ether of bisphenol A (DGEBA), to assess the curing process of a surface layer and compared this to the process in the bulk. We identified the β-hydroxy esters with various functionalities that are the key to form the cross-links for a system, including difunctional DGEBA and carboxylic acids. The IR peaks of the carbonyl group in generated ester groups are distinguished clearly from those in acids, allowing us to quantitatively assess the curing process at the surface and in the bulk. The initial curing at the surface exhibits a gradual cross-linking and is found to be lower than a rapid cross-linking in the bulk due to a relatively lower concentration of the β-hydroxy esters with high functionalities. This curing process leads to a smaller chemically and mechanically heterogeneous nanostructure at the surface relative to the bulk. After multiple reprocessings, a substantial number of esters lacking dynamic exchange capability form in the bulk, which decrease the flowability and reprocessability of the vitrimers and therefore the mechanical properties.

研究领域: 高分子化学 · 材料科学 · 纳米技术 · 表面科学
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