多官能团接枝改性PVC材料的设计、协同热稳定行为及机理研究

The existing organic stabilizer can not effectively inhibit degradation and coloring of PVC materials during the later poly(vinyl chloride) (PVC) thermal degradation, and the initial color, long-term thermal stability and mechanical properties of PVC grafted with organic stabilizer are not satisfactory. Therefore, in order to improve the overall performance of the obtained PVC materials such as the thermal stability, this project intends to introduce tung oil source compound modified by triazine ring, hydroxyl group and epoxy functional groups into PVC structure by chemical grafting reaction, design and synthesize PVC material graft modified by tung oil source triazine ring-based glycidyl ester. Study the effects of grafting method on the regulation laws of the substitution and arrangement degrees of the side chain of grafted PVC; Investigate the effects of substitution and arrangement degrees of the side chain of grafted PVC on mechanical properties, migration resistance and coloring property of grafted PVC; Disclose the influence mechanism of introducing triazine ring groups, hydroxyl groups, epoxy groups into PVC structure on the static thermal stability and dynamic thermal stability of grafted PVC ; Explore the collaborative stability mechanism of triazine ring groups, hydroxyl groups, epoxy groups and the corresponding thermal decomposition kinetics; This project is expected to serve as a reliable scientific basis and technical support for the construction of PVC that can be processed and used at high temperature. Moreover, it is also of great significance for the development of new applications of green tung oil resource originated from forest specialty.

现有有机热稳定剂不能有效抑制PVC材料后期热降解和着色，且有机热稳定剂接枝改性PVC材料的初期色泽和长期热稳定性以及力学性能不佳。因此，本项目拟利用化学接枝反应将三嗪环、羟基、环氧官能团改性的桐油源化合物引入PVC结构中，设计合成桐油源三嗪环基缩水甘油酯接枝改性PVC材料，以提高PVC材料的热稳定性等综合性能。研究不同的接枝方法对接枝改性PVC材料侧链的接枝度和排列规整度的调控规律；研究接枝改性PVC材料侧链的接枝度和排列规整度对其力学性能、耐迁移性以及着色性的影响；研究三嗪环、羟基、环氧官能团引入到PVC结构中对其动、静态热稳定性的影响机制；探索三嗪环、羟基、环氧官能团间的协同热稳定机理及热分解动力学规律。该项目有望为可在高温下加工使用的PVC材料的构筑提供理论基础和技术支持，对开拓绿色林特资源桐油的新用途具有重要意义。

现有有机热稳定剂不能有效抑制PVC材料后期热降解和着色，且有机热稳定剂接枝改性PVC材料的初期色泽和长期热稳定性以及力学性能不佳。本项目利用我国主要林产品生物质油脂桐油为原料，选用其具有共轭三键的桐油衍生物—桐马酸酐（TMA），对其进行化学改性，依次与三聚氰胺和甲醛缩合物、环氧氯丙烷、氮硅改性PVC中间体反应，设计合成桐油源三嗪环基缩水甘油酯接枝接枝改性材料（P-GT4），并对其进行表征和性能分析。通过将具有高效热稳定官能团的Atz接枝到PVC上，合成了新型的接枝PVC材料（P-AZ3）。然后，将两种接枝PVC材料P-GT4和P-AZ3按不同比例混合，得到一系列具有热稳定性高、增塑性好的接枝PVC材料。另外，本研究制备了一系列月桂烯基曼尼希碱接枝PVC、月桂醛基曼尼希碱接枝PVC、蓖麻油基含磷/氮/硅的内增塑PVC、含特殊热稳定官能团的稀土金属有机骨架(Ce-BTC和Zn-Atz)热稳定剂。利用静态热稳定性实验（刚果红法和热老化法）、热重分析法等分析测试方法对对上述接枝PVC和含特殊热稳定官能团的稀土金属有机骨架(Ce-BTC和Zn-Atz)热稳定剂的PVC材料进行热稳定测试，获得上述材料的热稳定剂机理，重点研究了接枝PVC材料（或热稳定剂）的结构与PVC材料热稳定性及力学性能间的构效关系；探索了协同热稳定机理及热降解过程中热分解动力学规律。本项目有利于推动林产资源桐油的高附加值利用。