POLYMER DEGRADATION AND STABILITY
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2025
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IF 7.4
Weichen Sheng,Min Zhong,Han Zhang,Kan Zhang
Biomass derivatives are a promising class of precursors for developing natural sustainable polymers. However, biobased polymers generally possess flammable characteristic and poor thermal stability, which seriously restrain their further applications. Herein, two biobased diamines (PDFA and CPDFA) were successfully synthesized using furfurylamine and benzaldehyde/cyanobenzaldehyde as starting materials. In addition, two novel bio-bisbenzoxazine monomers, S-cpdfa and S-pdfa, were obtained via the Mannich condensation reaction from paraformaldehyde, sesamol and PDFA/CPDFA. The chemical structures of both biobased bisbenzoxazines have been confirmed by FT-IR, 1 H NMR, 13 C NMR, and 2D HMQC spectroscopies as well as high-resolution mass spectrometry (HR-MS). Moreover, the polymerization behaviors of bisbenzoxazine monomers were investigated by DSC and in situ FT-IR analyses. It is noteworthy that fully polymerized biobased thermosetting resins exhibit high thermal stability with T d10 of 373.8 °C and Y c of 63.2 % for poly(S-pdfa), and T d10 of 395.4 °C and Y c of 65.7 % for poly(S-cpdfa), respectively. Notably, poly(S-cpdfa) exhibited very low flammability and self-extinguishing performance as indicated by HRC of 13.1 J·g⁻¹·K⁻¹ and THR of 2.8 kJ·g⁻¹. This work presents a straightforward and environmentally conscious methodology to access phosphorus- and halogen-free thermosets with intrinsically flame retardancy using natural renewable resources.
研究领域:
材料科学
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化学工程
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可持续发展
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DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2019
·Vol. 136
·期 18
·47352
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IF 2.188
Jianan Xu,Zhiying Li,Bao Wang,Fengya Liu,Yudong Liu,Fengqi Liu
Poly(ethylene glycol) diglycidyl ether-furfurylamine (PGFA) containing pendant furan was synthesized, and a series of crosslinked materials with thermally reversible capacity were synthesized through a furan/maleimide Diels–Alder (DA) reaction between PGFA and bismaleimide (BMI). The kinetics of the PGFA/BMI DA reaction were studied by Fourier transform infrared spectroscopy (FTIR). The reaction conversion rate, the reaction rate constant, and the energy of the DA reaction at different temperatures were calculated. In addition, the retro Diels–Alder (rDA) reaction was studied via 1 H-NMR, differential scanning calorimetry, and in situ FTIR. The occurrence of the retro DA reaction has been characterized clearly. Finally, the mechanical properties of the materials were obtained by dynamic mechanical and tensile tests. The storage modulus decreased obviously when the temperature reached over 90 °C, which proved that the materials were thermally reversible at high temperature. By changing the proportion of the crosslinking agent BMI, the best-performing materials were obtained, and the properties of the materials were basically unchanged after recycling. Thus we have obtained an excellent reusable material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136 , 47352.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
ChemSusChem
·
2018
·Vol. 11
·期 18
·3175-3183
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IF 7.411
Jinyue Dai,Na Teng,Yunyan Peng,Yuan Liu,Lijun Cao,Jin Zhu,Xiaoqing Liu
Graphical Renewable polymers : A biobased benzoxazine resin (Dz-f) with excellent thermal properties was synthesized from daidzein and furfurylamine by using a microwave heating method. It was then cured and its thermal properties evaluated by differential scanning calorimetry (DSC), TGA, and dynamic mechanical analysis (DMA; see figure). A biobased benzoxazine resin (Dz-f) demonstrating excellent thermal properties was synthesized from daidzein and furfurylamine by using a microwave heating method. The chemical structure of synthesized benzoxazine monomer was identified by FTIR and NMR ( 1 H and 13 C NMR) before it was cured and its thermal properties evaluated by differential scanning calorimetry (DSC), TGA, and dynamic mechanical analysis (DMA). The cured resin p(Dz-f) exhibited a glass transition temperature ( T g ) of 391 °C, a very high char yield of 68.7 %, and outstanding thermal stability; the T g value obtained was the highest thermal stability value ever reported for polybenzoxazine with a high biobased content. Moreover, Dz-f demonstrated a satisfying processability, which was rare for the high-performance thermosetting resins. This work provided us with a new strategy for the preparation of high biocontent resins with excellent thermal properties. In addition, the combination of biobased feedstocks with a microwave-assisted heating method as well as the potential application of this approach in high-end fields might perpetuate remarkable progress towards the sustainable development of the polymeric industry.
研究领域:
材料科学
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有机化学
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产品关联
DOI
PubMed
高影响因子
NEW JOURNAL OF CHEMISTRY
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2025
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IF 2.5
Yun Wang,Jiayang Wang,Zhiyang Zhang,Runsheng Xu,Shuang Wang
The reductive amination of biomass-derived furfural over non-noble metal catalysts represents a promising but challenging strategy for the sustainable synthesis of furfurylamine. Herein, we report mesoporous carbon supported CoZn bimetallic catalysts (CoxZny@MC) via a one-pot solvent evaporation induced self-assembly (EISA) method for high-efficiency reductive amination of furfural to furfurylamine with hydrous hydrazine (N2H4⋅H2O) as a nitrogen source. A complete conversion of furfural with a 97.5% yield of furfurylamine was achieved over bimetallic Co1Zn3@MC catalyst under mild conditions of 100 °C and 1.5 MPa H2 for 3 h. Furthermore, Co1Zn3@MC could be reused for at least five times with only a slight loss in activity. The excellent performance of the Co1Zn3@MC catalyst was mainly attributed to the introduction of moderate Zn species, which led to high dispersion of Co particles on the catalyst surface, as well as the abundant mesopores and high specific surface area of the catalyst. Moreover, a significant electron transfer from Zn species to Co centers occurs, which improves the inherent catalytic activity of the non-noble bimetallic catalyst by enhancing the electron density of Co particles.
研究领域:
催化化学
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材料科学
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绿色化学
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DOI
高影响因子
Catalysis Science & Technology
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2017
·Vol. 7
·期 18
·4129-4135
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IF 5.773
Yingxin Liu,Kuo Zhou,Huimin Shu,Haiyan Liu,Jiongtao Lou,Dechao Guo,Zuojun Wei,Xiaonian Li
RANEY® Ni proved to be an effective heterogeneous catalyst for switchable reductive amination of furfuryl alcohol to tetrahydrofurfurylamine and furfurylamine with NH3 by simply adding or not adding 1.0 MPa H2 into the reaction bulk. After further optimization of the reaction conditions, we finally obtained 94.0% yield of tetrahydrofurfurylamine and 78.8% yield of furfurylamine with high selectivity. By extensively studying the catalytic pathways and mechanism of catalyst deactivation with XRD and XPS characterization, we have confirmed that an excess amount of H2 in the reaction bulk leads to the deep hydrogenation of the furan ring while an insufficient amount of H2 leads to the formation of Ni3N and the deactivation of the catalyst.
研究领域:
化学工程
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催化化学
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DOI
高影响因子
Molecular Catalysis
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2019
·
IF 2.938
Chenglong Dong,Hongtao Wang,Haochen Du,Jiebang Peng,Yang Cai,Shuai Guo,Jianli Zhang,Chanatip Samart,Mingyue Ding
Furfurylamine converted from biomass-based platform molecules furfural was proven a significant intermediate in the synthesis of different valuable compounds. The combination of Ruthenium with HZSM-5 was acted as an excellent selective and reusable catalyst for the reduction amination of furfural with environmentally friendly ammonia and hydrogen. Incorporation of Ru species into HZSM-5 had a significant enhancement to the acid sites of Ru/HZSM-5. The Ru/HZSM-5(46) catalyst with optimized acid sites and interaction of the Ru-O-Al bond displayed an excellent catalytic performance, producing 76 % yield of furfurylamine at only 15 min, and could be recycled five times without loss of performance. Synergistic effect between RuO 2 and metallic Ru in the Ru/HZSM-5 catalyst facilitated the reduction amination of furfural.
研究领域:
催化
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化学工程
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可持续化学
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绿色化学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Dan Xiao,Zi-Bo Wang,Uwe Gohs,Kathrin Harre,De-Yi Wang
In this work, the highly-efficient multifunctional bio-based fire retardant phenylphosphonic difurfurylamine (PPDF) was prepared successfully for poly(lactic acid) using furfurylamine and phenylphosphonic dichloride. Moreover, the structure of PPDF was analyzed by NMR, FTIR and MS. The fire safety, thermal, crystallization, rheological and mechanical properties of PLA/PPDF compounds were systematically tested by LOI, UL94, cone calorimeter test, TGA, DSC, polarizing optical microscope, rheometer, DMA and tensile properties. Surprisingly, only a very small loading of 0.8 wt% loading of bio-fire retardant PPDF could increase the LOI value of PLA from 19.0 % to 30.0 % and achieve V-0 rating in UL-94 vertical burning test. Moreover, PPDF not only reduced the molecular entanglement and viscosity of PLA, but also acted as a nucleating agent to increase crystallinity and crystallization rate of PLA matrix. More importantly, in the gas phase phosphorus, the PLA/PPDF compounds based on highly reactive benzene, phosphorus, phosphooxygen and phosphooxygen benzene radicals from the pyrolysis of PPDF had a highly-efficient fire safety. In the condensed phase, a relative stable residual char layer played a secondary role in the barrier. Thus, the total heat release and ignition time of PLA/PPDF compounds were evidently declined by 8.3 % and 10 s with only 0.8 wt% of PPDF loading.
研究领域:
材料科学
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高分子化学
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消防安全工程
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产品关联
DOI
高影响因子
ACS Applied Polymer Materials
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2025
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IF 4.7
Wenlin Zhang,Jiahua Meng,Yongjin Zou,Chuanguo Ma,Yuqi Liu
Simultaneously achieving high performance and green benzoxazine resins is challenging yet highly significant. In this work, a bifunctional benzoxazine monomer, HT-fa, was successfully synthesized using a green strategy with hydroxytyrosol as the phenol source and furylamine as the amine source, and the monomer demonstrated excellent processability. Cured HT-fa resin, poly(HT-fa), exhibited a high glass transition temperature (Tg) of 297 °C and an initial decomposition temperature (Tdi) of 354 °C. Additionally, it demonstrated exceptional flame retardancy, with a limiting oxygen index (LOI) of 44.1%, a heat release capacity (HRC) of 21.3 J/g·K, a total heat release (THR) value of 2.9 kJ/g, and a flame-retardant rating of UL-94 V-0. Notably, its LOI, HRC, and THR were superior to those of all benzoxazines synthesized using biomass-derived amine and phenolic sources and a solvent-free method. The excellent properties of HT-fa and poly(HT-fa) are due to their unique rigid-flexible molecular structures. In addition, HT-fa can be used as a modifier for the commercially available bisphenol A/aniline based benzoxazine (BA-a). The addition of HT-fa not only significantly reduces the curing temperature of BA-a but also enhances the heat-resistance and flame-retardant properties of the cured resins. Poly(HT-fa) and these copolymers have potential applications in the field of halogen- and phosphorus-free flame-retardant materials.
研究领域:
高分子科学
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材料工程
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绿色化学
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热分析
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消防安全工程
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产品关联
DOI
高影响因子
PROGRESS IN ORGANIC COATINGS
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2022
·
IF 6.206
Qing Chen,Liyue Zhang,Jinli Zhang,Sania Habib,Guangming Lu,Jinyue Dai,Xiaoqing Liu
It is a subject of great practical significance and challenge to endow marine coatings with both excellent bacterial killing and antifouling properties. In this work, a series of bio-based organic coatings demonstrating high antibacterial rate, strong algae-killing ability and satisfied real-sea fouling resistance were reported. The main-chain type benzoxazine (MCBZ) resins were prepared from the renewable daidzein and furfurylamine, together with polyetheramine, long aliphatic chain primary amines, and paraformaldehyde. By adjusting the amines, the overall performance of synthesized MCBZs could be manipulated. Results indicated that the low surface energy of obtained MCBZ could prevent fouling adhesion, and the synergistic effect of long alkyl chains and daidzein led to the efficient anti-fouling. Notably, besides the low curing temperature of 200 °C, excellent processing property and good substrate adhesion (5.02 MPa), poly (12-fu-MCBZ) also possessed 94.5 % antibacterial rate, 100 % algae-killing ability and excellent real-sea antifouling performance. This work provides us a new strategy to solve the marine biological pollution using renewable raw materials.
研究领域:
材料科学
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海洋科学
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化学工程
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生物技术
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产品关联
DOI
高影响因子
POLYMER
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2015
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IF 3.562
Xiao Kuang,Guoming Liu,Liuchun Zheng,Chuncheng Li,Dujin Wang
A novel strategy for preparation of unsaturated polyester-based functional materials with widely tunable mechanical properties has been reported in present work. The biodegradable and crystallizable poly(butylene fumarate) oligomer (PBF) bearing reactive carbon–carbon double bonds on the backbone was functionalized by Michael addition with furfurylamine (FA), followed by incorporating bismaleimide (BMI) as cross-linker to form a reversibly cross-linked polyester (PBF-FA-BMI). The obtained material was systematically characterized by a combination of differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), rheometry measurement, wide-angle X-ray scattering (WAXS) as well as mechanical property testing. The in-situ FTIR and rheology measurements demonstrated the competition process of DA reaction and crystallization for dynamic conditions and isothermal conditions. The characteristic of dynamically chemical structure variation and crystallization behavior provides a possibility to tune the mechanical property of PBF-FA-BMI. By thermal treatment, the structure programming of the material can be facilely achieved, which undergoes from a typically elastomer to plastic. A schematic illustration of thermo-responsive conversion and recyclability is proposed for the cross-linked polyester.
研究领域:
高分子科学
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材料工程
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化学合成
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物理化学
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纳米技术
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生物降解材料
✓ 已验证
DOI
高影响因子
Polymer Chemistry
·
2024
·
IF 4.1
Hong-Hui Shu,Yun Liu,Sheng-Li Han,Xiuqin Fang,Chang Wang,Cheng-Mei Liu
Biomass-based polyamides (bioPAs) are renewable materials that are viable alternatives to petroleum-based polyamides in the engineering field. However, the attention to designing functional bioPAs with tunable properties has been limited. Herein, by taking furfurylamine as the sole furan source, we first utilized amine-acid oxidative coversion to prepare bisfuranic diacid monomer directly from bisfuranic diamine monomer(amine-first strtegy), it was totally different to castor oil-based acid-first strategy of preparing PA1010. Then the as-prepared multifunctional diamine/diacid monomers underwent polycondensation to obtain all-furan based bioPAs with or without functinal pendant groups. The properties of bioPAs, incuding glass transition temperatue, degradation character, solubility, etc, can be regulated over a larger range through the design of the spacer structure between two furan rings on diamine monomers. Charged bioPAs with cationic or anionic groups were further developed by postpolymerization modification. The oppositely charged bioPAs, sharing an identical main chain structure but different pendent groups, formed porous polyelectrolyte complexes owing to their rigid main chain. Therefore, this research provides a novel strategy for preparing both functional and engineering furan-based bioPAs.
研究领域:
材料科学
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高分子化学
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可持续材料
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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2024
·
IF 7.7
Xu Jin,Jing Zhang,Bin Wang,Xiaolu Li,Jing Zeng,Jiayu Ma,Ximeng Zhao,Wenqi Wu,José Sánchez del Río Sáez,Xiuqin Zhang,De-Yi Wang,Rui Wang
Today, building materials emit many hazardous gases in the event of a fire, causing great harm to human health and the environment. Therefore, it is of great significance to develop bio-based flame retardant materials and to realize preventive measures to reduce fires or their damage. In this work, we fabricated a novel multifunctional fire early-warning polylactic acid-based fabric (MFR-PBF) by coating MXene nanosheet, phytic acid @ furfurylamine (PA@FA) and ammonium polyphosphate (APP) via an eco-friendly layer-by-layer assembly method. MFR-PBF showed outstanding flame retardancy including a limiting oxygen index value of 35 % and better char formation capacity. More importantly, MFR-PBF exhibited sensitive fire early-warning capability (∼1 s) and excellent cyclic alarm stability (>15 cycles) due to the excellent semiconductor responsiveness (light and heat) and the significant catalytic char formation effect. Moreover, MFR-PBF is comfortable, flexible and strong enough to sew onto firefighter uniform to detect a variety of human motions, which can be monitored in the internet by using a LoRa emitter and a gateway. In addition, the controllable heating performance rendered MFR-PBF as a potential portable heater. This work provides new insights into the preparation and application of intelligent fire early-warning fabrics in the smart fire protection and Internet of Things.
研究领域:
材料科学
·
消防安全工程
·
纳米技术
·
纺织工程
·
物联网
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）