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Vitrimer
Small · 2025 ·Vol. 21 ·期 42 ·e08062 · IF 12.1

Polymer Nanoparticles Enable Self-Adaptive Soft Interface for Vitrimer Elastomer Nanocomposites

Hengheng Zhao,Sai Li,Ganggang Zhang,Haoxiang Li,Liqun Zhang,Venkat Ganesan,Jun Liu

Reconciliation of the elasticity, reinforcement, and recyclability in elastomer nanocomposites (ENCs) remains challenging, primarily due to the energy losses of the friction at polymer-nanoparticle interfaces and the permanent covalent cross-linking. Here, a self-adaptive soft interface strategy is introduced, using modulus-tuned polymer nanoparticles (PNPs) as reinforcement agents and interfacial chemical cross-linking sites within a vitrimer elastomer matrix. Such a framework promotes synergistic deformation of the PNPs with the matrix chains during mechanical deformation to minimize energy dissipation. Compared to traditional inorganic filler systems, these deformable PNPs exhibit exceptional compatibility and uniform dispersion, endowing the PNPs-filled ENCs with high mechanical strength, elongation at break, toughness, and low hysteresis loss. Moreover, the dynamic covalent bonds both in the matrix and interface impart excellent reprocessability and recyclability at elevated temperature, such as maintaining 88% of the mechanical performances after ten recycling cycles. This work puts forward a high additional value approach to produce PNPs, which are compounded with elastomer matrix with covalent adaptable networks to successfully balance the long-standing irreconcilable elasticity, reinforcement, and recycling, thus opening a new avenue for the development of next generation high performance and eco-friendly ENCs.

CAS / MDL: 4612-26-4 96-27-5
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COMPOSITES SCIENCE AND TECHNOLOGY · 2025 · IF 9.8

Bio-based Cyclic Acetal Epoxy Vitrimer Upcycling: From Composite Matrix to Interface

Zidie Song,Kangle Xue,Yuliang Xia,Hailong Liu,Tao You,Zibo Hua,Hong Cui,Li Liu,Zhen Hu,Yudong Huang

Epoxy resins, extensively employed as the polymer matrix in composites, face significant environmental challenges owing to their non-degradability. While incorporating dynamic acetal bonds offers promise, current acetal epoxies suffer from low modulus, poor thermal stability, and unoptimized degradation kinetics/performance balance. Furthermore, upcycling their degradation products yields only low-value additives with compromised properties. We present a bio-based epoxy vitrimer reconciling performance and circularity. Synthesized from vanillin and sorbitol, its key innovation is integrating multicyclic acetal motifs within the network. This vitrimer overcomes traditional limitations, achieving a high tensile modulus (3.63 GPa) and thermal stability (T d5 : 331 °C), suitable for demanding applications. Its molecular design enables ultrafast degradation (within 6 min, 65 °C) in diluted acid, facilitated by high-density labile cyclic acetal crosslinks. Crucially, the aldehyde/hydroxyl-rich degradation products are upcycled into high-performance sizing agents for carbon fiber composites. These agents achieve interfacial shear strengths of 70-80 MPa, matching industrial standards and resolving the acetal-epoxy upcycling challenge. This work establishes a scalable, sustainable framework for high-performance polymers, enabling efficient composite recycling and aligning industrial needs with circular economy principles.

CAS / MDL: 127-19-5
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JOURNAL OF CHEMICAL EDUCATION · 2021 · IF 2.979

“Reprocessable Thermosets”: Synthesis and Characterization of Vitrimer in the Undergraduate Lab Course

Qiaomei Chen,Yang Yang,Ying Yu,Huaping Xu

This article introduces a novel experiment that involves vitrimers, a new type of polymer, in polymer chemistry and physics lab courses for undergraduate students. Vitrimers are permanently cross-linked networks that can be reprocessed under certain external stimuli. Therefore, they combine the advantages of traditional thermoplastics (excellent reprocessability) with thermosets (outstanding mechanical properties and environmental stability). They can be regarded as a kind of “special thermoset”, which moves this industry toward a more sustainable path, as they are conducive to decreasing thermosetting wastes, reducing environmental pollution, and cutting down the waste of resources. From this lab class, students obtained more experience in the preparation and characterization of polymers. They also learned the concepts of dynamic chemistries and vitrimers and gained a better understanding of the advantages and limitations of thermosets and thermoplastics, as well as a strategy for making a reprocessable thermoset polymeric material. It also fostered students’ interest in functional materials and inspired them to design other functional materials. Moreover, this experimental setup is convenient and safe for implementation and dissemination in most undergraduate laboratory classes.

CAS / MDL: 124-04-9
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PROGRESS IN ORGANIC COATINGS · 2022 · IF 6.206

A novel bio-based degradable, reinforced vitrimer regulated by intramolecular hydrogen bonding

Lianghui Gong,Shuaipeng Wang,Jingyuan Hu,Haoyang Feng,Li Zhang,Jinyue Dai,Xiaoqin Liu

Designing a reinforced vitrimer of efficient dynamic bond exchange is of difficulty and urgently necessary. Herein, the intramolecular hydrogen bonds were derived from bio-based resource and employed to prepare reinforced degradable and catalyst-free vitrimers (DM-3SH and DT-3SH) via thiol-ene “click” reaction. As a result, cured DM-3SH and DT-3SH obtained excellent properties in mechanical, recycle, and degradation, especially DT-3SH showed rapid degradation speed and low transesterification activation energy (71.15 kJ/mol). Intramolecular hydrogen bonds were confirmed to reinforce and accelerate dynamic bond exchange and degradation. Utilizing different numbers of intramolecular hydrogen bonds, this work endows materials reinforcement, recyclability, and degradation, contributing to sustainable development of thermosetting resin .

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JOURNAL OF MATERIALS SCIENCE · 2023 ·Vol. 58 ·期 46 ·17470-17482 · IF 4.5

Well-dispersed silica nanoparticle-reinforced epoxy vitrimer composites prepared by dynamic crosslinking

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

CAS / MDL: 7631-86-9
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ACS Applied Polymer Materials · 2023 · IF 5

Imine-Containing Epoxy Vitrimer Cured by Active Ester: Properties and Theoretical Analysis

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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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Dual rapid self-healing and easily recyclable carbon fiber reinforced vitrimer composites

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.

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ADVANCED ENGINEERING MATERIALS · 2023 ·Vol. 25 ·期 13 ·2300031 · IF 3.6

Tough Epoxy Vitrimer with Hybrid Networks and Its Applications in Reprocessable Composites

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.

CAS / MDL: 108503-47-5
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MACROMOLECULAR RAPID COMMUNICATIONS · 2023 ·Vol. 44 ·期 10 ·2200972 · IF 4.6

Tough and Thermostable Polybutylene Terephthalate (PBT)/Vitrimer Blend with Enhanced Interfacial Compatibility

Zhiqiang Chen,Chenhui Cui,Chenyu Jin,Xiuzhao Li,Yifan Zhou,Yizhe Shao,Li Ma,Yanfeng Zhang,Tiejun Wang

Polymer blending is an efficient way to obtain extraordinary polymeric materials. However, once permanently cross-linked thermosets are involved in blending, there are challenges in designing and optimizing the structures and interfacial compatibility of blends. Vitrimer with dynamic covalent polymer networks provides an innovative opportunity for blending thermoplastics and thermosets. Herein, a reactive blending strategy is proposed to develop thermoplastic-thermoset blend with enhanced compatibility on the basis of dynamic covalent chemistry. Specifically, polybutylene terephthalate (PBT) and polymerized epoxy vitrimer can be directly melt blended to obtain tough and thermostable blends with desirable microstructures and interfacial interaction. Bond exchange facilitates the grafting of PBT and epoxy vitrimer chains, thus enhancing the interfacial compatibility and thermal stability of blends. The obtained blend balances the strength and stretchability of PBT and epoxy vitrimer, resulting in enhanced toughness. This work offers a new way of designing and fabricating new polymeric materials by blending thermoplastics and thermosets. It also suggests a facile direction towards upcycling thermoplastics and thermosets.

CAS / MDL: 920-66-1 5970-45-6
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MACROMOLECULAR RESEARCH · 2019 ·Vol. 27 ·期 6 ·526-533 · IF 1.758

Dual-Responsive Shape Memory and Thermally Reconfigurable Reduced Graphene Oxide-Vitrimer Composites

Chen Guo-kang,Wu Kun,Zhang Qian,Shi Yan-cen,Lu Man-geng

In this paper, we have prepared shape memory reduced graphene oxide-vitrimer composites via in situ reduction of graphene oxide (GO) during the curing reaction. Because of good compatibility between GO and epoxy resin, reduced graphene oxide (rGO) has a good dispersion in the epoxy matrix. Conventional thermoset shape memory polymers can only maintain one permanent shape, while these obtained composites can be randomly reconfigured into other shapes via dynamic covalent transesterification reaction at 200 °C above transesterification temperature ( T V ). They can recover quickly from fixed shapes to their initial shapes with shape fixity ratio higher than 95% and shape recovery ratio higher than 97%. Besides, the rGO-vitrimers show good mechanical properties and thermal stabilities. In addition, sequent near-infrared (NIR) irradiation can control the shape recovery, because rGO can serve as an energy convertor to convert NIR irradiation into thermal energy.

CAS / MDL: 872-50-4
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EUROPEAN POLYMER JOURNAL · 2025 · IF 6.3

Fully biobased epoxy vitrimer from resorcinol diglyceryl ether, vanillin, and 1,10-diaminodecane

Long-Yang Zhan,Ping Li,Yi-Dong Li,Yin Ran,Jian-Bing Zeng

Biobased epoxy vitrimers (BEVs) offer a promising solution to the recyclability and resource challenges associated with traditional epoxy thermosets. However, numerous existing BEVs suffer from inadequate properties or complex fabrication processes. Herein, we present a fully biobased, high-performance epoxy vitrimer synthesized from renewable and commercially available feedstocks: resorcinol diglyceryl ether (DGER), vanillin (VAN), and 1,10-diaminodecane (DDA). A dynamic imine crosslinker (DIC) was synthesized from VAN and DDA, which then underwent solvent-free and catalyst-free melt curing with DGER to form the BEV. Detailed studies of the curing kinetics of DGER-DIC and the properties of the resulting BEV were conducted, with comparisons to a control fossil-based epoxy vitrimer made from bisphenol A diglycidyl ether (DGEBA) and DIC. The DGER-DIC system showed a curing activation energy of 62.43 ± 3.73 kJ·mol –1 , slightly lower than DGEBA-DIC’s 67.71 ± 2.38 kJ·mol –1 . The BEV exhibited excellent mechanical properties, featuring a tensile strength amounting to 69.23 MPa and a Young’s modulus at 1.91 GPa, along with high thermal stability. The imine bonds provided fast stress relaxation, self-healing performance, and excellent reprocessability, with tensile strength recovering over 90 % after multiple processing cycles. These properties rival those of the DGEBA derived epoxy vitrimers, highlighting the potential of DGER as a sustainable alternative for creating recyclable epoxy thermosets.

CAS / MDL: 6683-19-8
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JOURNAL OF APPLIED POLYMER SCIENCE · 2025 · IF 2.8

Flexible and Recyclable Epoxy Vitrimer With Improved Thermal Conductivity for Thermal Management

Dong liang Wang,Lebin Zhan,Zhihong Zheng,Jingyun Zhang,Songwei Yang,Fubin Luo,Ting Hu

The accelerated evolution of electronic devices has resulted in an increased demand for thermal management materials. In this study, methoxy polyethylene glycol (MPEG) was introduced into a covalent adaptable epoxy network. It is demonstrated that the epoxy material becomes softer as the amount of MPEG content is increased, specifically exhibiting excellent flexibility with an impressive elongation at break of 444.68%. The thermal conductivity of the epoxy resin was enhanced by the incorporation of boron nitride (BN) filler, and the findings demonstrated that the thermal conductivity of the composites was markedly elevated to 3.34 Wm −1 K −1 when the proportion of BN filler reached 50%. The potential use of such composites as thermal management materials is demonstrated in their application for heat dissipation in LED chips. In addition, the covalent adaptive network enables the decomposition of the composites prepared in this study under chemical conditions, with the fillers subsequently being separated by physical filtration. This approach offers a potential pathway toward the sustainable development of thermal management materials.

CAS / MDL: 107-21-1
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