环氧树脂基交联网络微观结构调控及其热致形状记忆构效关系

Shape memory epoxy resin (SMEP) presents the best comprehensive performance within the scope of shape memory polymer(SMP). SMEP with relatively high recovery stress and high recovery speed becomes a hot issue of functional polymers because of its unlimited potential application in air space as an stretchable materials. In this study, a new idea is proposed that regulating the microstructure of three-dimensional crosslinked network of SMEP, which narrow the glass transition region, is the key factor to enhance the performance of SMEP. And,several novel resins and monomers are designed and prepared, including novel epoxy resin with high epoxide value and integrating rigid and flexible structure units in backbone, a neat epoxide oligmers with furan rings as side groups and maleic imide monomers. The resins and monomers are purified with methods of separation on colomn and recrystallization. Furthermore, the point of controlling the regularity of the microstructure of crosslinking network is carried by means of the high selectivity and efficiency of Diels-Alder curing reaction of furan rings and maleic imide. Various microstructure SMEPs are achieved by adjusting the ratio of rigid units to flexible units in FN-BDEGA and aliphlic chain length in maleic imide. And, DSC, DMA with 'multi-frequency-strain' mode and DMA with controlled-force mode will be used to analyze the performance of SMEP, such as glass transition temperature, peak width of glass transition temperature, and stress-strain-temperature three-dimention curve. Furthermore, on the basis of the structure construction and resutant properties of SMEP, the structure-activity relationship between microstructure of network and shape memory performance of SMEP will be tried to annonced. These results and achievements will be valuable and meritorious to the design of SMEP, as well as various shape memory polymers, in the thoughts and the foundational data.

环氧树脂基形状记忆聚合物（SMEP）综合性能最佳，高回复应力及高回复速度SMEP因在空间可展结构材料领域具有无限潜力而成为功能材料研究热点。本研究提出调控三维交联网络微观结构规整性，调窄玻璃化转变区域，是提高SMEP回复力和回复速度的关键问题；设计和制备特种高环氧值刚柔一体化环氧树脂、含呋喃环侧基环氧树脂齐聚物和马来酰亚胺单体，采用柱分离和重结晶方法，得到单一反应物分子结构，通过呋喃环与马来酰亚胺的高选择和高效Diels-Alder反应，达到控制交联网络微观结构规整性目的；通过调控环氧树脂的刚/柔链段比例和马来酰亚胺单体结构制备多种SMEP，采用DSC、"多频-应变"模式DMA以及"应力控制"模式DMA分析玻璃化转变温度、峰宽和应力-应变-温度三维曲线，揭示SMEP交联网络微观结构与其记忆行为的构效关系。该研究结果为今后高性能SMEP乃至形状记忆聚合物设计提供新思路和基础参考数据。

环氧树脂是一种综合性能优异而被广泛应用于涂料、胶粘剂、复合材料等领域的热固性树脂。其中，形状记忆环氧树脂聚合物（SMEPs）是一类重要的形状记忆聚合物，具有优良的形状记忆性能如高的形状固定率和高的形状回复率等。然而，传统的SMEPs因其分子结构多分散性，环氧值偏低，交联网络不规整，交联密度大，导致其玻璃化温度区域的宽分布，低回复速率，低应变等问题。因此，合理设计环氧树脂分子结构、微观相分离结构、挖掘其潜在的形状记忆性能、探讨结构与性能的构效关系是一个挑战。本课题从形状记忆分子链刚柔性、规整性、不同链段溶解度参数的差异等角度，设计并合成了高环氧值刚柔一体化环氧树脂，通过环氧树脂交联网络刚柔性的调节，规整网络的结构设计，微观相分离结构调控，得到了一系列形状记忆性能优良的环氧树脂新体系，取得了一些突破性新进展，为新型环氧树脂乃至其他热固性树脂的分子结构设计、规整网络结构设计，微观相分离结构的调控提供了理论指导，为高性能SMEPs制备提供了新思路和新方法。具体研究内容如下：.第一，合成并表征了刚柔一体化环氧树脂，包括双酚A型酚醚环氧树脂（DGEBAEOs）、丁香酚基环氧树脂（TRFEPs）、烯丙基二硫醇环氧树脂（DTAGEs）和木质素基的环氧树脂（DGEBA，DGEEM）。.第二，采用DSC法研究了典型树脂体系的等温和非等温固化动力学，分别满足Šesták-Berggren模型和Kamal模型。.第三，通过SMEP网络的结构设计,得到了三种网络刚柔比例可调节的SMEP新体系，具有高的形状记忆性能和可回收性。.第四，采用点击化学制备了规整结构环氧树脂网络，证明影响形状记忆材料回复速率的主要因素是网络的规整性，次要是熵弹性。.第五，采用刚柔链相容性差异的环氧树脂，得到了一系列海岛和双连续相态结构，其中，双连续相态结构的环氧树脂网络具有更好的记忆性能，突出表现为高形变的同时兼具高强度。.本课题共发表文章19篇，其中第一标注11篇，第二标注8篇。