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ChemCatChem · 2019 ·Vol. 11 ·期 22 ·5562-5569 · IF 4.495

Selective Synthesis of Furfurylamine by Reductive Amination of Furfural over Raney Cobalt

Kuo Zhou,Bixian Chen,Xiaoting Zhou,Shimin Kang,Yongjun Xu,Jinjia Wei

Graphical Rane drops keep fallin’ : Cobalt proved to be the most efficient metal for furfurylamine synthesis by reductive amination of furfural with NH 3 and H 2 . Effect of metal nature on reductive amination was investigated with biomass-based furfural as a typical substrate. Among the tested heterogeneous metal catalysts, cobalt proved to be the most effective metal for the synthesis of the corresponding primary amine. Under a relatively mild reaction condition, 98.9 % yield of furfurylamine was obtained over Raney Co and it can be reused more than eight times without a significant decrease in the catalytic performance. By extensively studying the catalytic pathways and reaction mechanism, it is found that the selectivity to primary amine and secondary amine was governed by the relative rate of hydrogenolysis and hydrogenation of the Schiff base intermediate. The superiority of Raney Co in furfurylamine synthesis can be ascribed to its high efficiency on hydrogenolysis of the Schiff base intermediate and its low performance in the hydrogenation of the Schiff base, carbonyl group and furan ring. Furthermore, ammonia greatly promoted the catalytic hydrogenolysis of the Schiff base intermediate over Raney Co without clear deactivation of the metal active sites.

研究领域: 化学工程 · 生物质转化 · 催化科学
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POLYMER DEGRADATION AND STABILITY · 2023 · IF 5.9

Supper-low-addition flame retardant for the fully bio-based poly(lactic acid) composites

Yang Wang,Dong Wang,Mengfei Zhang,Dong Wang,Ting Li,Jie Jiang,Mingqing Chen,Weifu Dong

Highly efficient flame retardants for polylactic acid (PLA) are not easy to prepare, let alone fully bio-based ones. Herein, the furfurylamine phytate (PAF) was simply fabricated using phytic acid and furfurylamine in the ethanol solutions. Furthermore, the PAF could provide PLA with high flame retardancy with low loadings. The flame retardancy of PLA/PAF composites was investigated by the limited oxygen index (LOI), vertical burning tests, and cone calorimeter tests. The PLA containing 2 phr PAF showed the highest LOI value (around 34.2%) and self-extinguished without igniting cotton in the vertical burning test. Meanwhile, the peak of heat release and total heat release decreased compared with the neat PLA. Moreover, the PLA/PAF 1.5 composite could achieve the balance between the mechanical property and flame retardancy. This findings provided a facile and green method for fully bio-based flame-retardant PLA composites to expand the practical applications of PLA, such as electrics, building, and transportation.

CAS / MDL: 64-17-5 617-89-0 83-86-3
研究领域: 材料科学 · 化学工程
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INDUSTRIAL CROPS AND PRODUCTS · 2024 · IF 5.6

Antileakage performance of Schiff base-reinforced thermal energy storage wood for indoor temperature control

Zhichen Ba,Feihan Yu,Haobo Fan,Wenxuan Wang,Yonggui Wang,Daxin Liang,Zefang Xiao,Haigang Wang,Yanjun Xie

Thermal energy storage wood has been rapidly developed as a green and renewable energy-saving building material. In this study, bio-based Schiff bases (VF) were prepared from vanillin and furfurylamine via aldehyde–amine condensation and used as a small molecule fixative. Subsequently, VF and dodecylamine were mixed uniformly and impregnated into rubberwood under pressure, affording thermal energy storage wood (TESW-x%VF). The results revealed that TESW-x%VF exhibited adjustable enthalpy (41.67–88.23 J g −1 ) and room-temperature phase transition (25°C–27°C). Moreover, the addition of VF improved the antileakage performance of TESW. According to density functional theory calculations, this is because the adsorption energy between VF and dodecylamine molecules has increased by 3–8 times compared to dodecylamine molecules. The above results provide a solution for the leakage issue associated with organic phase-change materials and aid in the future development of energy-saving wood building materials, which also improves the high-value utilization of chemical components in agricultural and forestry crops.

CAS / MDL: 617-89-0
研究领域: 材料科学 · 能源工程 · 林业科学
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EUROPEAN POLYMER JOURNAL · 2023 · IF 6

A highly thermally stable benzoxazine resin derived from norbornene and natural renewable tyramine and furfurylamine

Yi Yang,Yin Lu,Kan Zhang

Highly thermally stable polymeric materials synthesized from renewable resources are highly desirable in many high-performance fields due to the sustainable development of human beings. Herein, a new norbornene-containing monobenzoxazine thermosetting resin ( HPTM-fa ) exhibiting very high thermal stability has been prepared using natural bio-resourced tyramine and furfurylamine as starting materials. The structural details of HPTM-fa were characterized by FT-IR, NMR as well as high-resolution mass spectroscopies. The polymerization behaviors of cross-linkable norbornene , oxazine ring, and furan groups in HPTM-fa were investigated by DSC and in situ FT-IR analyses. In addition, the polybenzoxazine thermoset derived from this newly obtained bio-based mono-benzoxazine resin showed very high thermal stability with a T d5 of 413 °C and a glass transition temperature of 290 °C. The outstanding performance of thermoset based on HPTM-fa evidences its potential applications in the design of highly thermally stable polymeric materials.

CAS / MDL: 617-89-0 51-67-2
研究领域: 材料科学 · 化学工程
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Frontiers in Bioengineering and Biotechnology · 2023 · IF 5.7

Efficient synthesis of furfurylamine from biomass via a hybrid strategy in an EaCl:Gly–water medium

He Wei,He Yu-Cai,Ye Jianren

The objective of this work was to develop an efficient approach for chemoenzymatically transforming biomass to furfurylamine by bridging chemocatalysis and biocatalysis in a deep eutectic solvent of EaCl:Gly–water. Using hydroxyapatite (HAP) as support, heterogeneous catalyst SO42−/SnO2–HAP was synthesized for transforming lignocellulosic biomass into furfural using organic acid as a co-catalyst. The turnover frequency (TOF) was correlated with the pKa value of the used organic acid. Corncob was transformed by oxalic acid (pKa = 1.25) (0.4 wt%) plus SO42−/SnO2–HAP (2.0 wt%) to produce furfural with a yield of 48.2% and a TOF of 6.33 h-1 in water. In deep eutectic solvent EaCl:Gly–water (1:2, v/v), co-catalysis with SO42−/SnO2–HAP and oxalic acid was utilized to transform corncob, rice straw, reed leaf, and sugarcane bagasse for the production of furfural with the yield of 42.4%–59.3% (based on the xylan content) at 180°C after 10 min. The formed furfural could be efficiently aminated to furfurylamine with E. coli CCZU-XLS160 cells in the presence of NH4Cl (as an amine donor). As a result of the biological amination of furfural derived from corncob, rice straw, reed leaf, and sugarcane bagasse for 24 h, the yields of furfurylamine reached >99%, with a productivity of 0.31–0.43 g furfurylamine per g xylan. In EaCl:Gly–water, an efficient chemoenzymatic catalysis strategy was employed to valorize lignocellulosic biomass into valuable furan chemicals.

研究领域: 生物化学 · 催化化学
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REACTIVE & FUNCTIONAL POLYMERS · 2024 · IF 4.5

Bio-based benzoxazine-terminated hyperbranched polyesters

Liang Qi,Ling-Xiao Hu,Zhi-Cheng Wang,Zhi-Gang Yuan,Hai-Lin Wen,Wen-Bin Liu,Jun Wang,Mehdi Derradji

In this study, a novel bio-based benzoxazine-terminated hyperbranched polyester (HB-Dfa) was designed and synthesized using renewable diphenolic acid and furfurylamine as raw materials through self-polymerization and Mannich condensation reaction . Meanwhile, the copolymers based on HB-Dfa and benzoxazine monomer (P-ddm) were prepared to investigate the effect of HB-Dfa on the properties of traditional benzoxazine. The chemical structure of HB-Dfa was elucidated by fourier transform infrared (FTIR) and nuclear magnetic resonance ( 1 H NMR) spectroscopies. The curing behavior and curing kinetics were investigated by differential scanning calorimetry (DSC), showing that it possessed a low temperature of exothermic peak and activation energy value compared with the P-ddm. Hence, the curing process of P-ddm was facilitated by the introduction of HB-Dfa. The thermomechanical and thermal properties of P-ddm/HB-Dfa copolymers were determined by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA), respectively. Compared with the pure P-ddm resin, the introduction of HB-Dfa remained most of glass transition temperature ( T g ), cross-linking density and thermal stability, which could promote the curing reaction and reduce the curing temperature of the copolymers . In addition, HB-Dfa exhibited a low dielectric constant (2.46 ≥  k  ≥ 2.16) and a low dielectric loss ( f  ≤ 0.05) at frequencies range of 2–18 GHz, which could effectively modify the dielectric properties of the copolymer system.

CAS / MDL: 126-00-1 617-89-0
研究领域: 材料科学 · 化学工程
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INTERNATIONAL JOURNAL OF PHARMACEUTICS · 2024 · IF 5.3

Uncovering the mechanism of Tenofovir amibufenamide fumarate punch sticking by combining direct compression experiment and computational simulation

Chenyang Zhao,Xiaolei Wang,Yanbo Liu,Xueyou Qin,Weiqi Chen,Jin Zhang,Songgu Wu,Junbo Gong

Punch sticking during tablet manufacturing is a prevalent issue for many active pharmaceutical ingredients (APIs) encountered by the pharmaceutical industry. Tenofovir amibufenamide fumarate (TMF), a heavyweight drug for the treatment of hepatitis B, was selected as a model drug due to its tendency to punch sticking during tablet compression. In this study, the cause of sticking was explored by investigating crystal habits, excipients and structure characteristics. The difference in sticking of three crystal habits can be visually represented through direct compression experiments on powdered samples and analysis of crystal surfaces. The excipients play a direct role in decreasing the probability of sticking, and the extent of sticking can be assessed by measuring the tensile strength of the tablet. Additionally, the plasticity index was utilized to theoretically analyze the potential enhancements of four excipients. These experimental results indicate that the block-shaped crystals have superior ability of anti-sticking and that suitable excipients can significantly improve the sticking situation of TMF. Ultimately, the phenomenon of punch sticking was additionally examined through computational calculations, focusing on the mechanical characteristics of TMF molecules and intermolecular interactions. The strategy of combining experiments and simulation calculations has broader significance for the study of drug production.

研究领域: 药剂学 · 药物制造 · 计算化学
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