共价交联的狄尔斯-阿尔德聚合物网络中反向凝胶化的流变学和化学分析
Rheological and chemical analysis of reverse gelation in a covalently crosslinked Diels-Alder polymer network.
作者信息
Adzima Brian J, Aguirre H Alan, Kloxin Christopher J, Scott Timothy F, Bowman Christopher N
机构信息
Department of Chemical and Biological Engineering, University of Colorado, Boulder, CO 80309-0424, USA.
出版信息
Macromolecules. 2008 Dec 9;41(23):9112-9117. doi: 10.1021/ma801863d.
Abstract
A network polymer, incorporating dynamic and reversible crosslinks, was synthesized using the Diels-Alder reaction. Fourier transform infrared (FTIR) spectroscopy was used to characterize the reaction rate and thermodynamic equilibrium over a broad temperature range. Equilibrium conversion of the furan and maleimide varied from 74% at 85°C to 24% at 155°C, demonstrating significant depolymerization via the retro-Diels-Alder reaction. The gel point temperature, as determined by rheometry using the Winter-Chambon criterion, was 92°C, corresponding to a gel-point conversion of 71%, consistent with the Flory-Stockmayer equation. The scaling exponents for the complex moduli, viscosity, and plateau modulus, in the vicinity of the gel-point, were determined and compared with experimental and theoretical literature values. Further, the material exhibited a low frequency relaxation owing to dynamic rearrangement of crosslinks by the Diels-Alder and retro-Diels-Alder reactions.
摘要
利用狄尔斯-阿尔德反应合成了一种包含动态可逆交联的网络聚合物。采用傅里叶变换红外（FTIR）光谱对宽温度范围内的反应速率和热力学平衡进行了表征。呋喃与马来酰亚胺的平衡转化率在85°C时为74%，在155°C时为24%，这表明通过逆狄尔斯-阿尔德反应发生了显著的解聚。根据温特-尚邦准则通过流变学测定的凝胶点温度为92°C，对应于71%的凝胶点转化率，这与弗洛里-斯托克迈耶方程一致。测定了凝胶点附近复数模量、粘度和平台模量的标度指数，并与实验和理论文献值进行了比较。此外，由于狄尔斯-阿尔德反应和逆狄尔斯-阿尔德反应导致交联的动态重排，该材料表现出低频弛豫。
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