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POLYMER · 2025 · IF 4.5

Eco-friendly epoxy resin derived from tung oil and their sustainable recycling

Jindong Li,Guodong Xu,Yaowen Hu,Jingjing Fan,Zhongkai Wang,Yongliang Ding

Eco-friendly plastics are an emerging class of sustainable polymers. However, the process of developing high-performance sustainable polymers often requires the preparation of high-purity monomers from less pure biomass feedstocks. This process is not only complex, but also makes the bio-based feedstock less atom-economical, resulting in higher product costs. In this study, it is proposed to develop cyclic epoxy monomer from tung oil (TO), which are reacted with citric acid (CA) in simple curing reaction to prepare tung oil-based epoxy resins with sustainable recycling properties. These epoxy resins are thermally stable and possess tunable mechanical properties. The dynamic reversible covalent bonding of β -hydroxy esters introduced in the crosslinked network gives the polymer both reprocessable and chemically recyclable properties. In addition, the abundant hydroxyl are able to produce a variety of non-covalent interactions with the adherent substrate, thus exhibiting excellent adhesive properties. The combination of plant oil, thermoplastic-like behavior, and sustainable recycling provides new ideas for the development of new plant oil-based eco-friendly polymer materials.

研究领域: 材料科学 · 化学工程 · 环境科学
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Journal of Materials Chemistry A · 2025 · IF 9.5

Bio-based and recyclable adhesives based on β-hydroxyester bonds and hydrogen bonds via molecular dynamics simulation

Zhimin Kou,Ye Sha,Meiting Liu,Guixin Zhang,Jie Wang,Meng Zhang,Lihong Hu,Puyou Jia,Yonghong Zhou

The intelligent design and green manufacturing of bio-based adhesives still face severe challenges. In this study, an epoxy adhesive based on β-hydroxyester bonds and multiple hydrogen bonds was prepared using tung oil and lignin. Molecular dynamics simulation was used to regulate the structure and properties of adhesives. The adhesive with a large number of aromatic ring structures and phenolic hydroxyl groups enhanced cohesion and surface adsorption through π–π stacking and hydrogen bonding. Conjugated double bonds and the flexible long chain of tung oil in the structural skeleton of adhesives provided modification sites and endowed the materials with good ductility. The adhesive materials showed remarkable mechanical properties, recyclability, and an adhesive strength of approximately 6 MPa, enabling their effective use in various harsh environments, with a decrease in shear strength of only about 10%. Two adhesive models, one with β-hydroxyester bonds and multiple hydrogen bonds and the other without these structures, were established for comparison. The adhesion energy on the wood surface was calculated to assess the impact of each structural component in the system. In this study, a strategy to analyze the interplay between the microstructure and properties of adhesives was presented, and a potential route for the intelligent design and manufacturing of high-performance bio-based adhesives was provided.

研究领域: 材料科学 · 生物化学
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ACS Applied Polymer Materials · 2025 · IF 4.7

Construction of Silica/Polyurethane/Epoxidised Natural Rubber Vitrimer Biobased Elastomers via Octa-Hydrogen Bonding with Interfacial β-Hydroxy Ester Bonding

Lingfeng Cui,Jing Qiao,Guanyue Zeng,Yuzhu Xiong,Gege Huang,Daiqiang Li

Developing biobased rubber composites that simultaneously boost tensile strength and elongation at break while integrating self-healing capacity and reprocessability remains a critical challenge in the rubber industry. Inspired by the unique multiple hydrogen bonding structure of spider silk and the dynamic β-hydroxy ester exchange reaction, this study constructed an epoxy polyurethane rubber containing octuple hydrogen bonds and incorporated it into epoxidized natural rubber. Carboxylated silica was utilized as a bridging agent to form β-hydroxy ester reversible covalent bonds at the interface between the filler and the rubber, thereby designing a high-strength, self-repairing, and reprocessable’vitrimer’ biobased elastomer. This design approach endows the material with outstanding mechanical properties (tensile strength of 8.92 MPa, Young’s modulus of 2.71 MPa, toughness of 17.45 MJ/m3), excellent self-healing performance (healing efficiency of 92.1%), and superior processability (tensile strength recovery of 97.6%). These properties are primarily attributed to the presence of reversible noncovalent octet hydrogen bonds and dynamic covalent β-hydroxy ester bonds. Furthermore, this design can be readily implemented across different biobased epoxy polymers and carboxyl-rich nanofillers. The design concepts presented herein can be applied to the development of self-healing and reprocessable’vitrimer’ biobased elastomers, providing valuable insights for the future design of green and sustainable polymers.

研究领域: 材料科学 · 高分子化学 · 绿色化学
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COMPOSITES SCIENCE AND TECHNOLOGY · 2019 · IF 6.309

Design of healable epoxy composite based on β-hydroxyl esters crosslinked networks by using carboxylated cellulose nanocrystals as crosslinker

Chuanhui Xu,Zhongjie Zheng,Wenchao Wu,Lihua Fu,Baofeng Lin

Thermosetting resin-based composites are applied widely, but they are insoluble and infusible once complete curing so that they may be wasteful when the materials have some damages. Here, we use a simple and efficient method to design an epoxy composite which can be healed and recycled via interesterification reaction at elevated temperature. Carboxylated cellulose nanocrystals (CCNs) with a large number of carboxyl groups on the surface were isolated from cotton by hydrochloric acid and nitric acid, and then were used as crosslinker to react with diglycidyl ether of bisphenol A (DGEBA). Fourier transform infrared (FTIR) spectroscopy result indicates that β-hydroxyl ester bonds were formed between carboxyl groups and epoxy groups , while the equilibrium swelling experiment result confirms the formation of β-hydroxyl ester bond-crosslinked networks. Interestingly, the char yields of composites (>16%), much higher than that of CCNs (7.05%) and DGEBA (4.44%), were about three times higher than the calculated values, showing a significantly improved thermal stability. It was found that the composite with a carboxyl/epoxy = 0.2 has a better and more obvious healing affect at 180 °C than others.

CAS / MDL: 1675-54-3
研究领域: 材料科学 · 化学工程
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ACS Sustainable Chemistry & Engineering · 2022 · IF 9.224

Efficient Miniemulsion Polymerization of Plant Oil-Based Acrylate Monomer toward Waterborne Epoxy Resins

Wei Liu,Mei Wu,Chuqing Ma,Cheng Liu,Xiaoying Zhang,Zhong Wang,Zhongkai Wang

Synthesis of waterborne polymers from biomass via emulsion polymerization has gained more and more interest. Plant oils are one of the most abundant renewable resources. However, in most cases, plant oil-derived monomers are difficult to polymerize through emulsion polymerization due to the existence of hydrophobic and unsaturated fatty acids. Herein, plant oil-acrylate epoxy monomers were synthesized efficiently. Miniemulsion polymerization was applied to obtain plant oil-acrylate epoxy latexes. Stable latexes containing epoxy moieties with monomer conversion rate exceeding 99% were successfully obtained and characterized. By taking advantages of the epoxy groups presented in the latexes, excellent adhesion properties were obtained (1.5 MPa shear strength). These plant oil-acrylate epoxy monomers were also copolymerized with vinyl acetate (VAc) to modify the commercial PVAc latexes. Waterborne latexes with better adhesion properties, water resistance, and tensile strength were obtained, compared with PVAc latex. Furthermore, the fully biobased waterborne epoxy resin was prepared by using citric acid as the cross-linking agent. The existing dynamic β-hydroxyl ester chemical networks enable great potential as a reconfigurable and recyclable coating.

研究领域: 材料科学 · 绿色化学
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EUROPEAN POLYMER JOURNAL · 2022 · IF 5.546

Fully rosin-based epoxy vitrimers with high mechanical and thermostability properties, thermo-healing and closed-loop recycling

Yanning Zeng,Bin Yang,Zhaoyi Luo,Xianjie Pan,Zhao Ning

Bio-massed epoxy vitrimers are significant for sustainable industrial development, however, most of them show low mechanical properties and thermostability. The rosin derivates with rigid hydrophenanthrene framework have been synthesized as epoxy monomer and curing agent, for preparation of fully rosin-based epoxy vitrimer networks with dynamic β -hydroxy ester bonds. Meanwhile, to further improve mechanical properties and thermostability of the networks, zinc acetylacetonate was coordinated with the network by interaction of zinc metal with carbonyl group in the networks. The obtained fully rosin-based epoxy vitrimers have been characterized by FTIR, SEM, and DMA measurements. The obtained networks possess the higher mechanical properties (tensile strength = 40.8 MPa, toughness = 10.77 MJ/m 3 ) and thermostability ( T 5d = ∼270 °C) than these of vegetable oil-based epoxy vitrimers. Moreover, the performances of thermo-healing, welding, shape memory, physical and chemical recycling have been investigated. Present results demonstrate obtained epoxy vitrimers with good functionalities. In addition, fully rosin-based epoxy vitrimers display an excellent degradability under ethylene glycol solvent and can be applied as environmentally friendly materials.

研究领域: 材料科学 · 可持续化学 · 高分子科学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Lignin-tannic acid epoxy resins based on dynamic covalent bonding of β-hydroxy esters with closed-loop recyclability, exceptional adhesive properties and excellent photothermal capacity

Hu Yang,Yiqing Yang,Lin Deng,Zhifa Li,Shixue Ren,Jiguo Zhang,Jianfeng Zhan

This study addresses the waste of resources and environmental pollution associated with the use of traditional, non-recyclable, epoxy resins produced using petroleum-based products. Totally biomass-based epoxy resins (TPLs) have been developed by replacing bisphenol A diglycidyl ether with epoxide-modified tannic acid and replacing petroleum-based curing agents with carboxylate-modified lignin. Because of the incorporation of dynamic covalently bonded β-hydroxy esters, TPLs are suitable for closed-loop recycling. For example, one of the new epoxy resins (TPL-0.1) had an initial tensile strength of 26.1 MPa and retained almost all of this (80 %, 20.6 MPa) following closed-loop regeneration using a solvent mixture containing ethylene glycol and water (6:4). A second epoxy resin, TPL-0.05, which contains a higher proportion of lignin, showed remarkable versatility, not only achieving a shear strength of 12.4 MPa when used as an adhesive but also having excellent photothermal properties. TPL-0.05 has a photothermal conversion efficiency of 47.8 %, with surface temperatures reaching 120.5 °C under 1 kW·m −2 irradiation. When used as a coating in a solar water heater, the water temperature increased from 20 °C to 55 °C within 10 min, representing a 340.7 % improvement in heating rate compared with an uncoated control. This research offers an innovative approach for developing recyclable, high-performance epoxy resins and promotes the sustainable advancement of epoxy resin technology through the high-value utilization of biomass resources and dynamic bond design.

CAS / MDL: 25322-68-3
研究领域: 材料科学 · 高分子化学 · 环境科学 · 可持续化学 · 胶粘剂技术 · 光热转换
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ACS Applied Polymer Materials · 2025 · IF 4.7

Creep-Resistant Covalent Adaptable Heterogeneous Networks

Hao Wu,Xing Guo,Ming-Chao Luo,Shuangquan Liao

Dynamic covalet networks, exemplified by Vitrimers, hold significant promise for sustainable polymers due to their reprocessability and mechanical robustness. However, their susceptibility to creep deformation under sustained stress, driven by dynamic bond mobility, limits practical utility. We report a multiphase Vitrimer elastomer based on transesterification. Two distinct carboxylic acid cross-linkers containing dynamic β-hydroxy ester bonds were highly cross-linked into epoxidized natural rubber (ENR). Dithiodibenzoic acid (DS) bearing benzene rings first undergoes preferential aggregation via π–π interactions and thermally cross-links with epoxy groups to form a rigid hard phase, thereby restricting chain slippage and rearrangement at service temperatures to enhance creep resistance. Concurrently, 3,3′-dithiodipropionic acid (DD) establishes a soft phase with epoxy groups in the matrix, while preserving the material’s reprocessability. Stress relaxation and creep tests reveal that the hard domains/regions within the heterogeneous network structure impede segmental relaxation at relatively low temperatures, thereby enhancing the material’s creep resistance. At elevated reprocessing temperatures, however, these hard domains maintain dynamic bond exchange and segmental mobility, while the soft phase facilitates material reprocessability. This work establishes a scalable design framework for Vitrimers that synergistically enhances creep resistance and recyclability, addressing critical demands for durable yet sustainable engineering materials.

研究领域: 高分子科学 · 材料工程 · 可持续化学 · 材料力学性能 · 自修复材料
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GREEN CHEMISTRY · 2023 ·Vol. 25 ·期 3 ·1157-1168 · IF 9.8

Chemically debondable, high-strength and tough adhesives from sulfur-modified epoxy networks

Yu Jin,Zhengxiang Wang,Chengcheng Hu,Jie Wang,Kangle Yan,Juan He,Zhong Wang,Zhongkai Wang,Liang Yuan

Epoxy resins are among the best performing adhesives. Recovering the adhesively joined parts for repetitive use demands innovative bonding strategies to afford facile debonding while not sacrificing the adhesion performance. Here, a series of hardeners were prepared by reacting elemental sulfur with renewable 10-undecenoic acid and further employed for curing diglycidyl ether of bisphenol-A (DGEBA). Dynamically cross-linked epoxy networks from this solvent- and catalyst-free procedure exhibit high tensile strength and toughness, which are well maintained during repetitive thermal processing, assisted by exchanges of the S–S bonds and β-hydroxyl ester moieties. Moreover, the toughened epoxy resins show a high adhesion strength of up to 31 MPa for steel plates. Furthermore, the joined plates can be readily separated by immersing in a methanol solution of Na2S or hexylamine without any residual resins.

研究领域: 材料科学 · 化学工程 · 粘合技术
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JOURNAL OF MATERIALS SCIENCE · 2025 · IF 3.9

Dynamic covalent networks enable thermadapt two-way shape memory behavior in syndiotactic 1,2-polybutadiene-based recyclable polymers

Chen Bingshen,Xia Biao,Liao Shijie,Zeng Daiwei,Lin Tengfei,Wen Na,Gao Min,Zhao Chunlin,Wu Xiao,Lin Cong,Zheng Xiaochun,Gao Fei

Two-way shape memory polymers (2W-SMPs), which can transition between two distinct temporary shapes, have garnered significant attention from researchers. This study successfully developed thermadapt 2W-SMPs using syndiotactic 1,2-polybutadiene (SPB) by leveraging dynamic covalent crosslinking techniques. Initially, m-chloroperbenzoic acid (m-CPBA) was employed for the epoxidation of SPB. Cysteine (Cys) was subsequently introduced to form a dynamic covalent bond of β -hydroxy ester via the reaction between the epoxy groups on SPB and the carboxyl groups of Cys. The sulfhydryl groups of Cys can undergo oxidative coupling to form disulfide bonds, thereby establishing two distinct types of dynamic covalent bonds within the material and lowering its topological rearrangement temperature. Through the exchange reactions of these dynamic covalent bonds at elevated temperatures, the resulting material exhibits enhanced mechanical properties and can be reshaped in the solid state. This work provides a viable method for preparing recyclable thermally adaptive 2W-SMPs under stress-free conditions, thereby enriching the research landscape in the field of shape memory materials.

CAS / MDL: 52-90-4
研究领域: 材料科学 · 高分子化学 · 智能材料 · 形状记忆聚合物 · 动态共价化学 · 可回收材料
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