ACS Sustainable Chemistry & Engineering
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2026
·Vol. 14
·期 30
·13689-13698
·
IF 7.6
Xu Yanling,Zhou Yue-Wen,Cai Zhen-Feng,Liu Qinlei
Imines are valuable intermediates and building blocks in fine chemicals and pharmaceutical synthesis. Oxidative coupling of amines represents an attractive route to imine formation. However, conventional methods rely on metal catalysts, external oxidants, or thermal and photochemical activation, involving multistep processes, harsh conditions, and environmental concerns. Here, we report that amines undergo oxidative coupling to imines within aqueous microdroplets at room temperature, without any catalyst or oxidant. The molecular structures of products were confirmed by mass spectrometry, UV–vis spectroscopy, and 1 H NMR analysis. Substrate scope studies revealed that the microdroplet system enables both self-coupling and cross-coupling of amines, highlighting its broad generality. Radical trapping experiments and density functional theory calculations suggest reactive oxygen species, including hydroxyl radicals and hydrogen peroxide, are likely involved in the oxidative process occurring at the microdroplet interface. This work introduces a simple, rapid, and environmentally benign strategy for imine synthesis and underscores the unique potential of microdroplet chemistry in advancing green oxidative coupling reactions.
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REACTIVE & FUNCTIONAL POLYMERS
·
2026
·
IF 5.4
Yue Xiaopeng,Liu Hao,Ji Yu,Guan Lixiang,Lu Hailong
Modification of sebacic acid and citric acid with furfurylamine produces furfurylated sebacic acid (FS) and furfurylated citric acid (FC). Successfully constructs a high-performance polymer. • FS and FC increase cross-linking sites for DA reactions and elevate cross-linking density. • Raised cross-linking density strengthens synergistic interactions between FS/FC, lignin and flame retardants. In this study, two kinds of furan-terminated small molecules (FS and FC) were synthesized via amidation reactions between furfurylamine and polyacids (sebacic acid or citric acid), respectively, and were incorporated into the furan-functionalized epoxidized soybean oil (FE)/furan-terminated lignin (FL) thermo-reversible polymer network via Diels-Alder (DA) reaction to regulate the crosslinking density of the network. With the incorporation of DOPO-based reactive flame retardants (DE and DF), a structural optimized thermo-reversible/flame-retardant polymer with a reinforced network was fabricated. By introducing linear two-arm (FS) or branched three-arm (FC) structures, especially FC, the crosslinking density of the networks was significantly improved. As a result, the tensile strength, fracture toughness (KIC), and self-healing properties of the polymer were synchronously improved. The increased crosslinking density also enhanced the synergistic effect between FS/FC, lignin, and flame retardants, leading to improved char-forming ability and flame-retardant efficiency. The limiting oxygen index of 75FE/5FL/10FC/5DE/5DF reached 28.9% with the addition of only 5 wt% FL, enabling it to pass the UL-94 V-0 flammability rating. Compared with 100FE, this formulation exhibited reductions in total smoke production (TSP), smoke production rate (SPR), total heat release (THR), and peak heat release rate (pHRR) by 31.4%, 44.4%, 18.06%, and 21.67%, respectively. Additionally, it achieved a self-healing efficiency of 85.20% and retained 71% of its tensile strength after three reprocessing cycles. Through the aforementioned strategy, this work successfully overcomes the common trade-off among mechanical properties, self-healing efficiency, and flame retardancy in biobased dynamic polymers. It offers a practical example for developing sustainable, intelligent advanced polymeric materials for future applications. Download: Download high-res image (171KB) Download: Download full-size image
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
·
2026
·Vol. 74
·期 31
·24501-24512
·
IF 6.7
Xie Sikui,He Yu-Cai
Lignocellulosic biomass, which consists primarily of
cellulose,
hemicellulose, and lignin, is a promising renewable feedstock for
producing high-value biobased amines. In this study, an integrated
chemobiocatalytic strategy was developed to synthesize furfurylamine
from corncob using a newly formulated deep eutectic solvent, [Bet][FA][LA],
that provides both catalytic and solubilizing functions. Under optimized
conditions, corncob was efficiently converted into furfural, which
was subsequently aminated by recombinant Escherichia coli BM-AlaDH coexpressing an ω-transaminase
and alanine dehydrogenase. The whole-cell catalyst enabled in situ
regeneration of L -alanine, thereby reducing amine-donor
requirements and improving biocatalytic efficiency. Integration of
[Bet][FA][LA]-mediated chemocatalysis with whole-cell biocatalysis
converted corncob into furfurylamine in [Bet][FA][LA]. The biocatalytic
amination system could convert biomass-derived 5-hydroxymethylfurfural
(320 mM) and vanillin (20 mM) into the corresponding amines in yields
of 95.4% and 91.0%, respectively. This work establishes a sustainable
route for converting lignocellulose-derived aldehydes into value-added
biobased amines and advances the comprehensive valorization of lignocellulosic
biomass.
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JOURNAL OF APPLIED POLYMER SCIENCE
·
2026
·
IF 2.8
Jinhui Liang,Lin Xie,Junhong Zhang,Tiancheng Zhao,Fuping Xie,Zhenhao Yao,Kan Zhang
In this study, two main-chain type benzoxazines (poly(ILG-ddm) main and poly(ILG-pdfa) main ) based on isoliquiritigenin were successfully synthesized, and their structures and properties were systematically characterized and evaluated. FT-IR and NMR analyses confirmed the chemical structures of benzoxazines, verifying the successful formation of the oxazine ring. DSC studies showed that both bio-based thermosetting systems exhibited lower curing temperatures compared to traditional petroleum-based benzoxazines. Notably, poly(ILG-pdfa) main displayed a significantly lower apparent activation energy (~127 kJ/mol) than poly(ILG-ddm) main (~148 kJ/mol), indicating its easier curing and superior processability. TGA results demonstrated that the resulting cured sample, poly(ILG-ddm) main X , possessed higher thermal stability ( T d5 = 352°C, char yield at 800°C = 58.4%). Although poly(ILG-pdfa) main X showed slightly lower thermal stability ( T d5 = 319°C, char yield = 49.8%), it still maintained excellent performance among fully bio-based polymeric materials. DMA analysis revealed that poly(ILG-pdfa) main X exhibited high storage modulus and a high glass transition temperature (266.2°C) due to the strong intermolecular forces and π–π stacking between the furan and chalcone structures. The isoliquiritigenin-derived polybenzoxazines exhibit an optimal balance between low polymerization temperature and high thermal stability, providing a robust matrix for their application in high-performance and sustainable composites.
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ACS Applied Polymer Materials
·
2026
·
IF 4.7
Ruiyu Yuan,Yin Lu,Weichen Sheng,Kan Zhang
The severity of fire accidents and sustainable development concerns have made people increasingly aware of the importance of producing flame-retardant materials using biomass resources. Herein, we successfully synthesized an asymmetric biobisbenzoxazine monomer with a single diethyl phosphite-substituted oxazine ring (ST-fa-DEP) based on natural, renewable salicylaldehyde, tyramine, and furfurylamine. The structural characterization of ST-fa-DEP was performed using Fourier-transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopies as well as high-resolution mass spectrometry (HR-MS), which confirms the successful inheritance of the single diethyl phosphite into the oxazine ring substituted bisbenzoxazine monomer. The ring-opening polymerization behavior of ST-fa-DEP was examined by using differential scanning calorimetry (DSC) and in situ FT-IR analysis. In addition, the resulting polybenzoxazine, poly(ST-fa-DEP), showed excellent thermal performance and flame retardancy with a Td10 of 413 °C, a Yc of 62.5,% and an HRC value of 53 J·g–1·K–1. Moreover, we used ST-fa-DEP as a property modifier for enhancing the comprehensive properties of the well-commercialized bisbenzoxazine resin (PH-ddm). Notably, the glass transition temperature of the resulting thermoset increased to 290 °C, and a V-0 rating in UL-94 testing was also achieved by adding only 3 wt % ST-fa-DEP in PH-ddm, which breaks the trade-off between the thermal stability and flame retardancy of other reported flame-retardant polybenzoxazines. The results obtained in the current work provide molecular-level insights into the structure–property relationship of polybenzoxazines as well as an angle for the design of highly thermal stable and intrinsically flame-retardant biothermosets.
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IEEE TRANSACTIONS ON DIELECTRICS AND ELECTRICAL INSULATION
·
2026
·
IF 3.3
Bo Zhu,Bo Yang,Yu Feng,Wenliang Xu,Zhiqing Liang
Cross-linked polyethylene (XLPE) is widely used in high-voltage cable insulation for its good insulation and mechanical properties. However, long-term use leads to damage, breakdown, and environmental pollution due to non-recyclability and high thermal degradation. This study designs an S-S-DA cross-linker with reversible Diels-Alder (DA) and disulfide bonds using isocyanate reactions. Graft cross-linking forms XLPE-S-S-DA, and doping silane-modified SiO2 creates XLPE-S-S-DA/SiO2 composite for self-repair. Tests show elongation at break increases by 17.89%, tensile yield stress by 17.26%, and breakdown field strength by 34.4% compared to XLPE. It self-repairs mechanical/electrical damages (three mechanical repairs restore strain to 91.26%, yield stress to 82.65%, strength to 92.37%; three breakdowns restore field strength to 76.04%). Three recycling retains 68.89% strain, 71.59% strength (yield stress increases 6.46%), and 79.57% breakdown strength. Lower thermal degradation helps recycling. Dynamic cross-linking and doping create self-repair, recyclable XLPE composites, improving service life and eco-friendliness for high-voltage cable insulation, providing a new design strategy.
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MOLECULES
·
2026
·Vol. 31
·期 5
·771
·
IF 5.1
Zengheng Hao,Wei Zhang,Yugui Liu,Jianhui Xu,Haidong Liu,Shutong Tang,Junan Shen
The formation of recyclable polyethylene materials is significantly limited by traditional crosslinking methods, which involve solvent-heavy processes and permanent chemical bonds that cannot be undone. Herein, we report an environmentally friendly and scalable approach to construct a thermo-reversible polyethylene network (PE-g-DA) via solvent-free, one-step melt processing based on furan–maleimide Diels–Alder (D–A) dynamic covalent chemistry. Furan-functionalized polyethylene was dynamically crosslinked with bismaleimide during melt mixing, fully compatible with conventional polyolefin processing techniques. FTIR spectroscopy, temperature-dependent solubility, and differential scanning calorimetry collectively confirm the reversible formation and dissociation of D–A adducts, enabling thermal switching of the network structure. Equilibrium swelling experiments based on the Flory–Rehner model indicate that the crosslink density can be precisely controlled by varying the bismaleimide content. As a result, PE-g-DA exhibits significantly enhanced tensile strength while maintaining high ductility at moderate crosslink densities. Notably, the dynamic network allows efficient thermal reprocessing, with recycled samples retaining approximately 93% and 80% of their original tensile strength after the first and second reprocessing cycles, respectively. Moreover, intrinsic thermal self-healing behavior is directly visualized by scanning electron microscopy at 120 °C. This work demonstrates that combining dynamic Diels–Alder chemistry with solvent-free melt processing offers a practical and sustainable route to recyclable, reprocessable, and self-healable polyethylene materials with clear potential for large-scale industrial production.
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ACS Sustainable Chemistry & Engineering
·
2026
·Vol. 14
·期 35
·15995-16008
·
IF 7.6
Zhang Wenlin,Liang Siqi,Ma Chuanguo,Liu Yuqi
Multifunctional benzoxazine resins with high‑rigidity skeletons have gained widespread research interest owing to their comprehensive performance advantages, but their monomers typically suffer from high melting points and poor solubility. To address this issue, three multifunctional benzoxazines, DATR-fa, DAHT-fa, and DPAHT-fa, were synthesized in the green solvent ethanol using biomass-derived phenolic acids, phenolic alcohols, and furfurylamines. All three monomers exhibit low melting points (81, 93, and 61 ° C), which are attributed to the introduction of ester groups and short alkyl chains that weaken molecular rigidity and packing regularity. Through thermal curing, three cured resins, poly(DATR-fa), poly(DAHT-fa), and poly(DPAHT-fa), were prepared, all of which exhibit excellent heat resistance (glass transition temperatures of 266, 286, and 296 ° C), high thermal stability (initial decomposition temperatures of 353, 341, and 359 ° C), and good flame-retardant properties (heat release capacity (HRC) values of 65.4, 46.4, and 61.8 J/(g·K), total heat release (THR) values of 6.4, 4.7, and 5.0 kJ/g, and UL-94 ratings of V1, V0, and V1, respectively). Furthermore, a detailed study was conducted on the flame-retardant mechanism of these polybenzoxazine resins. This work offers new guidelines for designing multifunctional benzoxazine resins featuring balanced processability, thermal stability, and intrinsic flame retardancy.
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COMPOSITES PART B-ENGINEERING
·
2026
·
IF 14
Guanjun Liu,Meiling Yan,Conghao Jiang,Ying Liu,Zhen Tian,Fan Yang,Rongguo Wang
Hydrogen barrier materials capable of retaining effective barrier performance after mechanical damage are highly desirable for hydrogen storage and transportation applications. Here, we report a functionalized graphene oxide reinforced polyurethane nanocomposite containing Diels-Alder (DA) bonds, denoted as fGO/PU-DA, in which dynamic DA linkages were incorporated into both the polymer matrix and the nanofiller-matrix interface. The 5 wt% fGO/PU-DA nanocomposite achieved a tensile strength of 9.8 MPa, corresponding to a 75% increase over neat PU-DA, while maintaining a favorable balance between strength and ductility. After cut-healing treatment, the nanocomposite recovered nearly all of its tensile strength, whereas its elongation at break and toughness exceeded their original values even after three damage-healing cycles, highlighting the contribution of interfacial DA bonds to healing efficiency. The hydrogen permeability coefficient decreased from 2.4 × 10 −12 for neat PU-DA to 8.6 × 10 −13 cm 3 cm cm −2 ·s −1 Pa −1 for the 5 wt% fGO/PU-DA nanocomposite, corresponding to a reduction of 64%. Even in the healed state, the permeability remained markedly lower than that of healed PU-DA, indicating a clear barrier advantage after macroscopic damage. Mechanistic analysis indicated that the enhanced barrier performance was diffusion-dominated and originated from interfacial confinement together with reduced cooperative segmental mobility. The material was further validated as a coating on polyamide 6 substrates, where the fGO/PU-DA layer also delivered improved hydrogen barrier performance. These results demonstrate that coupling matrix-level reversible reconstruction with interfacial dynamic DA bonding provides an effective route to polyurethane nanocomposites integrating self-healing capability, mechanical robustness, and superior hydrogen barrier performance.
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JOURNAL OF POLYMER RESEARCH
·
2026
·Vol. 33
·期 8
·316
·
IF 3.5
Wang Zijian,Cheng Jiaxin,Zhu Yanjie,Cong Xiaori,Zhang Yuan
The development of fully biobased epoxy resins as sustainable alternatives to petroleum-based counterparts is of great significance for addressing resource depletion and environmental concerns. A fully biobased epoxy thermoset was synthesized from a magnolol-derived epoxy monomer (MG-EP) and a furfurylamine-based diamine curing agent (BDFA). The chemical structures were confirmed by FT-IR and ¹H NMR. The MG-EP system showed lower viscosity (0.475 Pa·s) than commercial DGEBA, indicating better processability. The cured biobased epoxy resin exhibited a storage modulus of 1.22 MPa at 30 °C, which was close to that of its petroleum-based counterpart. In addition, the cured biobased epoxy resin showed a tensile strength of 73.8 MPa–35.7% higher than that of DGEBA/BDFA. Moreover, it demonstrated enhanced char yield (44.9% vs. 21.6%) at 800 °C, and reduced heat release (PHRR 173.1 W/g vs. 216.6 W/g, THR 20.3 kJ/g vs. 26.1 kJ/g) compared to those of DGEBA/BDFA. As a result, MG-EP/BDFA achieved a V-1 UL-94 rating. This work presents a promising strategy for developing high-performance fully biobased epoxy resins with integrated mechanical strength and fire safety.
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POLYMER
·
2025
·
IF 4.5
Xiaopeng Yue,Xian Shang,Jinghan Li,Lixiang Guan,Zhiwei Wang
A bio-based flame retarded thermo-reversible polymer was fabricated using furan-terminated lignin (FL) and furan-functionalized epoxidized soybean oil (FE) via Diels-Alder reaction. Two kinds of 9,10-Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide (DOPO) based flame retardants, including ESO ring-opening derivative (DE) and furanized reactive flame retardant (DF), were synthesized and incorporated into the networks. The incorporation of FL increased the crosslinking density, and reinforced the as-prepared FL/FE network. However, its rigid macromolecular structure also impaired the self-healing properties of network. The addition of DE and DF both improved the flame retardant properties, and they also exhibited synergistic effect during combustion. The LOI value of 80FE/10FL/5DE/5DF reached 29.3 %, and the UL-94 test also reached V-0 level. Whereas, due to the rigid molecular structure similar to lignin and the increased local cross-linking density, the incorporation of DF deteriorated the self-healing efficiency of network. On the contrary, the specimen with the incorporation of DE exhibited relative high self-healing efficiency due to the existence of hydrogen bonds. Typically, 80FE/10FL/10DE exhibited a high tensile strength (11.91 MPa), while maintained a relative high self-healing efficiency (80.45 %). These properties provide valuable insights for the practical application of bio-based polymers in sustainability and flame-retardant fields, and may have application potential in the packaging field in the future.
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Polymer Chemistry
·
2025
·
IF 3.9
Aying Wang,Yifen Xu,Wenli Zhao,Jinning Zhang,Fengjun Chen,Zhongxiang Xia,Lidong Zhang,Jing Song,Lixian Yin,Zhi Wang
Benzoxazine resins are widely used in the aerospace and electronics industries due to their high thermal stability and mechanical performance. However, their reliance on petroleum-based precursors and permanent crosslinked networks hinders recyclability, thereby creating environmental challenges. Although existing methods to introduce degradable bonds can improve recyclability, they often compromise thermal performance. To address these issues, we adopted a “rigid conjugated dynamic dihydrazone bond + bio-based synergy” strategy and designed a bio-based benzoxazine resin by synthesizing dihydrazone-containing bisphenol monomers from bio-vanillin and hydrazine hydrate, followed by polymerization with furfurylamine. This strategy incorporated acid-labile dynamic bonds into the crosslinked network while preserving thermal stability. The resin exhibited a char yield of 59.5% at 800 °C, comparable to those of petroleum-based analogues. Moreover, the dynamic network enabled controlled degradation under three conditions: elevated temperature, acetone–water mixtures (2 : 8, v/v), and 0.1 M HCl at 50 °C. In carbon fiber composites, 96% of the original fiber strength (2.64 vs. 2.75 GPa) was retained after 24 hours of resin decomposition, with minimal surface damage. This work demonstrates a bio-based approach for balancing thermal performance and recyclability in thermosetting composites, providing a practical pathway toward sustainable high-performance materials.
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