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探索分子结构对固化动力学的影响:双酚A和F环氧树脂的二缩水甘油醚的对比研究

Exploring the Impact of Molecular Structure on Curing Kinetics: A Comparative Study of Diglycidyl Ether of Bisphenol A and F Epoxy Resins.

作者信息

Shundo Atsuomi, Thao Phan Nguyen, Aoki Mika, Tokunaga Atsushi, Kuwahara Riichi, Yamamoto Satoru, Tanaka Keiji

机构信息

Department of Applied Chemistry, Kyushu University, Fukuoka 819-0395, Japan.

Department of Automotive Science, Kyushu University, Fukuoka 819-0395, Japan.

出版信息

J Phys Chem B. 2024 May 16;128(19):4846-4852. doi: 10.1021/acs.jpcb.4c01152. Epub 2024 May 3.

Abstract

Epoxy resins are essential for various applications, and their properties depend on the curing reactions during which epoxy and amine compounds form the network structure. We here focus on how the presence or absence of two methyl groups in common epoxy bases, diglycidyl ether of bisphenol A and F (4,4'-DGEBA and 4,4'-DGEBF), affects the curing kinetics. The chemical reactions of both 4,4'-DGEBA and 4,4'-DGEBF, when cured with the same amine, were monitored by Fourier-transform infrared (FT-IR) spectroscopy and differential scanning calorimetry (DSC). Despite no difference in the reactivity of epoxy groups between 4,4'-DGEBA and 4,4'-DGEBF, the initial curing reaction was slower for the latter. This delay for the 4,4'-DGEBF system was attributed to intermolecular stacking, which hindered the approach of unreacted epoxy groups to amino groups and vice versa. This conclusion was drawn from the results obtained through ultraviolet (UV) spectroscopy, wide-angle X-ray scattering (WAXS), density functional theory (DFT) calculation, and all-atom molecular dynamics (MD) simulation.

摘要

环氧树脂对于各种应用至关重要,其性能取决于固化反应,在此过程中环氧和胺化合物形成网络结构。我们在此关注常见环氧基体双酚A和F的二缩水甘油醚(4,4'-二缩水甘油醚双酚A和4,4'-二缩水甘油醚双酚F)中两个甲基的有无如何影响固化动力学。用傅里叶变换红外光谱(FT-IR)和差示扫描量热法(DSC)监测了4,4'-二缩水甘油醚双酚A和4,4'-二缩水甘油醚双酚F与同一胺固化时的化学反应。尽管4,4'-二缩水甘油醚双酚A和4,4'-二缩水甘油醚双酚F之间环氧基团的反应性没有差异,但后者的初始固化反应较慢。4,4'-二缩水甘油醚双酚F体系的这种延迟归因于分子间堆积,这阻碍了未反应的环氧基团与氨基的接近,反之亦然。这一结论是通过紫外光谱(UV)、广角X射线散射(WAXS)、密度泛函理论(DFT)计算和全原子分子动力学(MD)模拟得到的结果得出的。

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