【作者】 张涛；

【导师】 胡国华； 冯连芳；

【作者基本信息】 浙江大学 ， 化学工程， 2010， 硕士

【摘要】 不同的聚合物材料进行共混可以获得性能互补而且具有新性能的共混聚合物材料。共混聚合物的性质不仅与共混物自身的性质相关,与聚合物体系自身的相态也密切相关。绝大多数聚合物体系是不相容体系,共混聚合物体系的相态也呈现多样性。共连续相是不同聚合物相之间相互贯穿并且在空间呈现三维连续的特殊相态,往往可以表现出原来的组分聚合物材料自身所不具备的性能。影响共连续相共混聚合物材料性能的主要因素是共连续相的相尺寸和相态稳定性。反应相容过程生成的界面相容剂可以减小不相容聚合物相界面张力和共连续相的相尺寸,稳定共连续相。限制共连续相应用范围的一个重要因素是共连续相组成范围。在不相容聚合物体系中加入复合型相容剂可以在不相容聚合物相界面处形成新的聚合物界面层,拓宽共连续相组成范围,减小界面张力并稳定共连续相态。本论文考察了两种不同类型的相容剂体系对共连续相态的影响规律。反应相容将聚合物的共混与不相容聚合物相的相容结合成为一个步骤,提高了共混的效率;而且相容剂是在聚合物的相界面处产生的,不需要考虑相容剂的扩散问题,相容效率较高。为了考察反应相容剂的反应效率和相容特性,以PS/PA6/PS-co-TMI为实验体系研究了反应相容的规律。DSC和FTIR的结果都表明共混过程中生成了相容剂(PS-co-TMI]-g-PA6。考察了三种具有不同TMI含量的PS-co-TMI的相容效率以及不同PS-co-TMI用量下聚合物体系的相态的演变规律。结果发现TMI含量最小的PS-co-TMI-2具有最好的相容效果,该聚合物体系共混后的共连续相具有最小的相尺寸,静态热退火后的相态的变化程度也最小,共连续相的稳定性最好。TMI含量最高的PS-co-TMI-8在共混结束后残留未参与相容反应的PS-co-TMI,而且生成的(PS-co-TMI)-g-PA6上也残留未参与反应的-NCO活性官能团,降低了反应相容剂的使用效率。接枝型相容剂可以减小界面张力和共连续相的相尺寸,但是单一的接枝共聚物加入到聚合物体系中会导致共连续相组成范围变窄,限制了共连续相共混聚合物的应用范围。而复合相容剂的加入可以拓宽共连续相的组成范围,稳定高温下的共连续相态。本文考察了在PP/PS体系中加入不同组合的PP-g-PA6/PS-g-PA6复合相容剂体系后,共连续相组成范围的变化以及复合相容剂的加入对共连续相稳定性的影响。复合相容剂的加入降低了PP/PS共混体系的表面张力,使得共连续相的组成范围至少被拓宽了5%。加入复合相容剂后共连续相的热稳定性也有一定程度的增加。接枝密度高的复合相容剂体系具有较高的相容效率,静态热退火后的相形态变化幅度较小。实验发现复合相容剂体系的接枝密度对共连续相态稳定性的影响要大于接枝链长的影响。更多还原

【Abstract】 Mixing different polymer materials together would not only achieve new materials with combination of complementary properties but also polymers with novel properties. The performances of polymer materials not only have relevance with the original polymer materials, but also the final morphology of polymer system. Most polymer systems are immiscible and the final morphology varies. While co-continuous morphology is a special morphology in which polymer materials interpenetrate with each other and exhibits three-dimensional continuity. And novel properties that the original polymer materials don’t have could be gained occasionally. Factors affecting properties of co-continuous morphology polymer systems are mainly co-continuous phase size and stability of co-continuous morphology. Compatibilizer generated in reactive mixing process would reduce interfacial tension and co-continuous phase size and stabilize co-continuous morphology. The factor that limits the application of co-continuous morphology on industrial fields is co-continuous morphology composition range. Adding complex compatibilizer into polymer mixing system would form new polymer interface between immiscible polymer interface, broaden the co-continuous composition range, reduce interfacial tension and stabilize co-continuous morphology. The thesis mainly discusses the rules of effects of two different compatibilizer systems on co-continuous morphology development.Reactive mixing process combines polymer mixing and compatibilizing process together thus enhances polymer mixing efficiency; compatibilizer is generated in the interface and there is no need to concern for diffusion of compatibilizer, therefore high compatibilizing efficiency could be obtained. In order to investigate the reactive and compatibilizing efficiency, PS/PA6/PS-co-TMI polymer system was chosen to study compatibilizing rules of reactive compatibilizer. DSC and FTIR results both showed that (PS-co-TMI)-g-PA6 was generated in the mixing process. PS-co-TMI with different TMI content were chosen to investigate compatibilizing efficiency of different PS-co-TMI and rules of co-continuous morphology development. It was being found out that PS-co-TMI-2 had the best compatibilizing efficiency. Polymer system containing PS-co-TMI-2 were found to have the smallest co-continuous phase size and most stable co-continuous morphology after quiescent annealing in the oil bath under high temperature. Polymer system containing PS-co-TMI-8 were found to contain unreacted PS-co-TMI, and even (PS-co-TMI)-g-PA6 generated in the system were found to contain unreacted -NCO groups, accordingly reduce the compatibilizing efficiency of PS-co-TMI-8.Addition of single graft compatibilizer into polymer mixing system would reduce interfacial tension and co-continuous phase size. However, single graft compatibilizer would also narrow co-continuous composition range. Adding complex compatibilizer into polymer system would both stabilize the co-continuous morphology under high temperature and broaden co-continuous composition range. This thesis mainly discusses variations of co-continuous composition range and effects of stability of co-continuous morphology after adding PP-g-PA6/PS-g-PA6 complex compatibilizer into PP/PS polymer system. Addition of complex compatibilizer reduced interfacial tension of PP/PS polymer system and broadened co-continuous composition range at least 5%. Stability of co-continuous morphology has also been increased after adding complex compatibilizer into the polymer system. Complex compatibilizer with the higher graft density had better compatibilizing efficiency and morphology-stabilizing effects than other complex compatibilized polymer systems. The results also showed that graft density had more pronounced effects on morphology stability than the length of graft chains.更多还原