CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Pengwu Xu,Ning Ding,Hong Wang,Jieyu Guan,Yirui Shen,Deyu Niu,Weijun Yang,Piming Ma
Thermoset polyurethanes face significant deterioration of physical properties after damage self-healing or reprocessing. It is still a great challenge to design the structure of polyurethanes to realize damage self-healing and reprocess ability under mild conditions. In this work, a series of double-crosslinked networked polyurethanes with different crosslinking densities were synthesized by designing a synergistic crosslinking strategy of oxime-carbamate bonding and hydrogen bonding arrays. By regulating the density of the crosslinked network and the content of strong and weak hydrogen bonds, the tensile strength of the polyurethanes was increased from 13.1 to 24.3 MPa, and the toughness was increased from 66.5 to 129.2 MJ/m 3 . Meanwhile, the synergistic effect of the oxime-carbamate with low activation energy and hydrogen bonding arrays enabled the polyurethanes to have an excellent self-healing (97 %) and reprocessing. The polyurethanes could be rapidly reprocessed after only 5 min of hot pressing at 120 °C by virtue of the thermal response of the dual network. More importantly, the tensile strength retention rate can still maintain more than 96 % after reprocessing. Finally, we propose the concept of a wearable device that can intelligently detect changes in resistance values during human movement. Therefore, this work provides a new idea for the preparation of polyurethanes with excellent damage self-healing and reprocessing, which is expected to expand its application.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
COMPOSITES PART B-ENGINEERING
·
2025
·
IF 14.2
Baozheng Zhao,Fei Song,Zheng Pan,Yijiao Xue,Linfeng Tian,Tiancheng Zhang,Li Tan,Rui Yang,Yonghong Zhou,Meng Zhang
At present, thermoset polyurethane foams were mainly derived from petroleum-based resources and faced inherent challenges such as difficulty in recycling and fire hazard. In this study, tung oil and catechol were used to prepare tung oil-derived polyphenols via Friedel-Crafts alkylation reaction. These polyphenols were combined with isocyanate to synthesize tung oil-derived polyurethane (TPU) foam. With the presence of dual dynamically cross-linked phenol-carbamate bonds, the TPU foam could be hot-pressed several times into a smooth and homogeneous TPU film. To improve the fire resistance and compressive strength of TPU foam, phytic acid functionalized metal-organic frameworks (UiO-66-NH 2 @PA) flame retardants were successfully synthesized by one-pot solvothermal method. By adding 20 wt% of flame retardants, the TPU composite foams achieved a UL-94 V-0 flammability rating with a limiting oxygen index of 28.1 vol%. The total heat release, total smoke release, CO production and CO 2 production of the TPU composite foams were reduced by 43.1 %, 57.8 %, 63.6 % and 62.1 %, respectively, compared to the pure TPU foam. Furthermore, the compressive strength of the TPU composite foam continued to increase with increasing flame retardants content, reaching a maximum of 0.55 MPa. Importantly, the introduction of the flame retardants didn't affect the hot-press recycling performance of the TPU foam, but instead improved the tensile strength and flame retardancy of the recycled TPU film. This work paved the way to produce bio-based PU foam with excellent flame retardancy and recyclability.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
POLYMER
·
2025
·
IF 4.5
Yuan Chen,Ting Yao,Yuetong Mu,Kai Zhao,Kejun Zhong,Rong Yan,Chang He,Pengxiang Jia,Wenyan Zhang
Thermosetting polyurethanes are widely used in various fields owing to the outstanding mechanical performances, excellent heat resistance, and solvent resistance. However, the poor recyclability and self-healing performance of the traditional thermosetting polyurethanes due to the inherent irreversible cross-linked network largely limited their application. To solve these problems, a high-strength, self-healing, and recyclable thermosetting polyurethane containing imine bonds and phenol-carbamate bonds was successfully prepared. First, a trifunctional chain extender (YAOH) bearing imine bond and phenolic hydroxyl groups was synthesized. Subsequently, polyurethanes featuring a dynamic reversible cross-linked network comprising hydrogen bonds, imine bonds, and phenol-carbamate bonds were synthesized via solution polymerization using YAOH as a chain extender. The obtained LYA4 polyurethane demonstrated excellent mechanical strength (the fracture stress was 15.85 MPa), outstanding stretch ability (1193 %), remarkable toughness (72.79 MJ/m 3 ), good fatigue resistance and thermal stability. Furthermore, LYA4 polyurethane also exhibited excellent self-healing properties and recyclability. The stress self-healing efficiency was achieved as high as 100 % when LYA4 polyurethane was healed at 100 °C for 12 h. Additionally, the material could be recycled multiple times under acidic conditions. After three recycling cycles, the mechanical strength of LYA4 polyurethane was maintained at 7.97 MPa. This research proposed a simple method to prepare thermosetting polyurethanes with high self-healing and recoverable properties, demonstrating various potential applications.
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Baozheng Zhao,Fei Song,Li Tan,Rui Yang,Zheng Pan,Meng Zhang,Yonghong Zhou
The economic processing, sustainable recycling, and environmentally friendly application of polyurethane (PU) foams are important issues that need to be addressed urgently. In this study, we propose a strategy for the comprehensive utilization of cardanol and cashew shells to design cardanol-based PU (CPU) foams and wood-plastic films that can be recycled and reused. Firstly, cardanol-based polyphenols (CBPs) with a phenolic hydroxyl content of 3.29 mmol/g were prepared by Friedel-Crafts alkylation reaction using cardanol and guaiacol as raw materials. Subsequently, CPU foams were prepared by reacting CBPs with isocyanate, and the vertical and parallel compressive strengths could reach up to 0.27 MPa and 0.32 MPa, respectively, when the addition of CBPs was 80 %. These CPU foams, containing dynamic phenol-carbamate bonds, could be hot-pressed into transparent and smooth CPU films with tensile strengths of up to 30.5 MPa and could be re-formed at least three times. Finally, CPU foam and cashew shell waste were mixed and hot-pressed to produce a green wood-plastic composite with a tensile strength of up to 38.8 MPa. The resulting CPU-Wood films could be repaired or reshaped at least five times (38.0 MPa and 38.1 MPa) and could be formed into various shapes. This research paves the way for large-scale industrial production of recyclable and regenerative bio-based foams, making effective use of waste materials to achieve environmentally friendly production processes.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
DOI
高影响因子
MACROMOLECULES
·
2025
·
IF 5.2
Jin Peng,Haixu Wang,Shusheng Chen,Weifeng Liu,Xueqing Qiu
In this study, we introduce an innovative one-step, solvent-free approach for preparing lignin-containing polyurethane elastomers (LPUes) with nanomicro phase-separated structure and dynamic dual-cross-linking networks comprising both phenol-carbamate bonds (PCBs) and hydrogen bonds. This distinctive structural design imparted exceptional mechanical properties to the LPUes. The sample containing 22.9 wt % phenolized lignin exhibited tensile strength of 44.6 MPa, elongation at break of 714.6%, and toughness of 148.0 MJ/m3. The abundance of dynamic PCBs also conferred remarkable reprocessing capabilities, with these LPUes retaining over 98% for tensile strength and 94.4% for toughness after two hot-pressing cycles. Moreover, the incorporation of lignin endowed the LPUes with photothermal properties, facilitating efficient light-controlled self-healing and shape-memory functionalities. This work offers an innovative pathway to harmonize the mechanical properties and thermal adaptability in the development of sustainable and high-performance LPUes, thereby opening their avenues for diverse potential applications.
研究领域:
材料科学
·
可持续化学
✓ 已验证
产品关联
DOI
高影响因子
Frontiers in Microbiology
·
2025
·
IF 4.5
Xiaomin Zhu,Youren Duan,Jianqi Lu,Wei Xia,Yujia Peng,Jiawei Liu,Weiliang Dong,Min Jiang
Polyurethane (PU), a segmented block copolymer with chemically resistant urethane linkages and tunable architecture, presents persistent biological recycling challenges. This study presents a Bacterial Laccase-Mediated System (BLMS) derived from Bacillus subtilis for efficient degradation of polyester- and polyether-PU. Utilizing the laccase CotA and mediator 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), the BLMS demonstrated effective de polymerization of both commercial and self-synthesized PU foams, including polyester- and polyether-types. The weight loss of the self-synthesized polyester-foam and the commercial polyether-foam reached up to 21.24 ± 1.20% and 3.81 ± 0.36%, respectively. Subsequently, we detected oxygenated products such as ketones, alcohols, aldehydes, acids, esters, ethers, and 2,4– toluenediamine (2,4-TDA) indicating that bacterial laccase CotA exhibited redox catalytic activity toward PU. Moreover, an interesting phenomenon was observed during the degradation process that the solution turned purple. We predicted that this attribute to the enzymatic oxidation of ABTS to the radical cation ABTS·+, which subsequently reacts with 2,4-TDA to form the purple product. This study finds a plastic degrading enzyme capable of hydrolyzing urethane bonds in PU, offering a promising contribution to the development of a bio-based circular economy for PU biodegradation and recycling.
研究领域:
生物降解
·
酶催化
·
高分子科学
·
生物工程
·
环境生物技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Polymers
·
2023
·Vol. 15
·期 6
·1418
·
IF 5
Shiyu Guo,Huanbo Wang,Yue Liu,Yuan Fu,Xuefeng Zhang,Bin Qi,Tian Liu
The development of biomass-based composites has greatly reduced the daily consumption of plastics. However, these materials are rarely recyclable, thus, posing a severe threat to the environment. Herein, we designed and prepared novel composite materials with ultra-high biomass (i.e., wood flour) filling capacity and good closed-loop recycling properties. The dynamic polyurethane polymer was polymerized in situ on the surface of wood fiber, and then they were hot-pressed into composites. Fourier-transform infrared (FTIR), scanning electron microscopy (SEM), and dynamic thermomechanical analysis (DMA) measurements reveal good compatibility between the polyurethane and wood flour in the composites when the wood flour content is ≤80 wt%. The maximum tensile and bending strength of the composite are 37 and 33 MPa when the wood flour content is 80%. The higher wood flour content results in higher thermal expansion stability and creep resistance in the composites. Moreover, the thermal debonding of dynamic phenol–carbamate bonds facilitates the composites to undergo physical and chemical cycling. The recycled and remolded composites exhibit good mechanical property recovery rates and retain the chemical structures of the original composites.Keywords:ultra-high biomass;composites;closed-loop recycling;dynamic phenol–carbamate bonds;in situ polymerization
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
MACROMOLECULAR RAPID COMMUNICATIONS
·
2024
·Vol. 45
·期 13
·2400022
·
IF 4.2
Xue Wang,Liguo Wang,Chen Liu,Yan Cao,Peng He,Yu Cui,Huiquan Li
The preparation of self-healing polyurethane elastomers (PUEs) incorporating dynamic bonds is of considerable practical significance. However, developing a PUE with outstanding mechanical properties and high self-healing efficiency poses a significant challenge. Herein, this work has successfully developed a series of self-healing PUEs with various outstanding properties through rational molecular design. These PUEs incorporate m-xylylene diisocyanate and reversible dimethylglyoxime as hard segment, along with polytetramethylene ether glycol as soft segment. A significant amount of dynamic oxime-carbamate and hydrogen bonds are formed in hard segment. The microphase separated structure of the PUEs enables them to be colorless with a transparency of >90%. Owing to the chemical composition and multiple dynamic interactions, the PUEs are endowed with ultra-high tensile strength of 34.5 MPa, satisfactory toughness of 53.9 MJ m −3 , and great elastic recovery both at low and high strains. The movement of polymer molecular chains and the dynamic reversible interactions render a self-healing efficiency of 101% at 70 °C. In addition, this self-healing polyurethane could still maintain high mechanical properties after recycling. This study provides a design strategy for the preparation of a comprehensive polyurethane with superior overall performance, which holds wide application prospects in the fields of flexible displays and solar cells.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Polymer Materials
·
2023
·
IF 5
Junwei He,Qionghai Chen,Jiajun Qu,Sai Li,Zuwei Fu,Yuan Wei,Shikai Hu,Anchao Feng,Liqun Zhang,Jun Liu
Elastomers inevitably suffer scratches and damage during the application; thus, the design and fabrication of self-healing elastomers with covalent adaptive networks is a meaningful strategy to extend the service life of materials. In this study, a facile two-step approach was proposed to synthesize self-healing elastomers based on the dynamic oxime–carbamate bonds. Hydroxyl-terminated polybutadiene was first reacted with isophorone diisocyanate to synthesize the prepolymer with isocyanate groups terminated, followed by further reaction with dimethylglyoxime as a chain extender to obtain self-healing elastomers. Specially, all-atom molecular dynamics simulations were used to construct the same model as the experiments. Together with the experimental characterization of FTIR and 1H NMR, all-atom molecular dynamics simulations can further verify the formation of hydrogen bonds and dynamic oxime–carbamate bonds. By fixing the ratio of hydroxyl to isocyanate constant, we found that the mechanical strength increased with the increase of hard segment content. At the same time, the loss factor decreased in the glass transition region and at room temperature. Finally, the self-healing behavior of the elastomer was verified at a certain temperature. The corresponding mechanism is explained by means of molecular dynamics simulations, where dynamic oxime–carbamate bonds play more important roles than hydrogen bonds. The combined simulation and experimental studies provided a reasonable approach for the subsequent self-healing system.
研究领域:
材料科学
·
计算化学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
PROGRESS IN ORGANIC COATINGS
·
2021
·
IF 5.161
Yang Liu,Zhengjun Li,Zetian Zhang,Junchao Wang,Liying Sun,Taoling Xie
Realizing environment-friendly and thermal-driven self-healing polymers with robust mechanical properties is an important challenge for the development of next-generation smart materials. Herein, by combining dynamic phenol-carbamate bonds and Fe 3+ -catechol coordination bonds in polymer chains, novel hyperbranched waterborne polyurethanes (FTWPU) with desirable thermal-driven self-healing properties were prepared through two steps, i.e., introducing tannic acid to prepare tannic acid based waterborne polyurethane (TWPU) bearing phenol-carbamate bonds firstly, and subsequently further incorporating Fe 3+ ions to prepare FTWPU in possession of Fe 3+ -catechol moieties. The results exhibited that TWPU possessed good emulsion stability with differing tannic acid content, and improved thermal and mechanical properties, owing to the presence of cross-linking between polyurethane chains, and FTWPU still possessed outstanding storage stability, as well as much higher mechanical properties (tensile strength of 18.4 ± 0.4 MPa, elongation at break of 533.5 ± 5.2 %). Meanwhile, FTWPU presented desirable self-healing ability (i.e., healing efficiencies of tensile strength and elongation at break were 87.5 % and 91.9 %, respectively) after healing under 120 °C for 1.5 h and 85 °C for 30 min, demonstrating a satisfactory balance between good self-healing ability and high mechanical properties. Importantly, reversible phenol-carbamate bonds and metal coordination bonds are predominant factors during the healing process of FTWPU films, as well as high mobility of soft segments and hydrogen bonding effect play a significant role to achieve ultimate healing ability. We can envision that the promising design idea, based on synergistic effect between phenol-carbamate bonds and Fe 3+ -catechol coordination bonds, could provide inspiration for preparing self-healing polymers with superior mechanical properties.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
高影响因子
MACROMOLECULAR RAPID COMMUNICATIONS
·
2022
·Vol. 44
·期 5
·2200765
·
IF 5.006
Yanlong Yin,Yang Xu,Xuhao Zhang,Baorong Duan,Zhirong Xin,Chunyang Bao
The development of degradable polymeric materials such as degradable polyurethane or polyurea has been much highlighted for resource conservation and environmental protection. Herein, a facile strategy of constructing mechanically strong and tough poly(urea-urethane) (PUU) thermosets that can be degraded under mild conditions by using triple boron-urethane bonds (TBUB) as cross-linkers is demonstrated. By tailoring the molecular weight of the soft segment of the prepolymers, the mechanical performance can be finely controlled. Based on the cross-linking of TBUB units and hydrogen-binding interactions between TBUB linkages, the as-prepared PUU thermosets have excellent mechanical strength of ≈40.2 MPa and toughness of ≈304.9 MJ m −3 . Typically, the PBUU900 strip can lift a barbell with 60 000 times its own weight, showing excellent load-bearing capacity. Meanwhile, owing to the covalent cross-linking of TBUB units, all the PUU thermosets show initial decomposition temperatures over 290 °C, which are comparable to those of the traditional thermosets. Moreover, the TBUB cross-linked PUU thermosets can be easily degraded in a mild acid solution. The small pieces of the PBUU sample can be fully decomposed in 1 m HCl/THF solution for 3.5 h at room temperature.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Scientific Reports
·
2015
·Vol. 5
·期 1
·1-10
·
IF 5.578
Gao Peng Fei,Yuan Bin Fang,Gao Ming Xuan,Li Rong Sheng,Ma Jun,Zou Hong Yan,Li Yuan Fang,Li Ming,Huang Cheng Zhi
Insight into the nature of metal-sulfur bond, a meaningful one in life science, interface chemistry and organometallic chemistry, is interesting but challenging. By utilizing the localized surface plasmon resonance properties of silver nanoparticles, herein we visually identified the photosensitivity of silver-dithiocarbamate (Ag-DTC) bond by using dark field microscopic imaging (iDFM) technique at single nanoparticle level. It was found that the breakage of Ag-DTC bond could be accelerated effectively by light irradiation, followed by a pH-dependent horizontal or vertical degradation of the DTC molecules, in which an indispensable preoxidation process of the silver was at first disclosed. These findings suggest a visualization strategy at single plasmonic nanoparticle level which can be excellently applied to explore new stimulus-triggered reactions and might also open a new way to understand traditional organic reaction mechanisms.
研究领域:
生命科学
·
界面化学
·
有机金属化学
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）