Control of Structure of Photo-Grafted Polymers and Its Application

在本研究中，将光接枝作为聚合物材料功能化的一种手段应用于聚烯烃和纤维素，以便通过控制引入到聚合物基质中的接枝链的位置来设计各种功能的产生。第一阶段考察了接枝条件对接枝链在聚乙烯膜上位置的影响，第二阶段研究了接枝链的位置与接枝聚合物性能的关系，得到的结果如下：1.通过选择合适的聚合体系(气液相)、单体浓度和聚合温度以及体系中对苯二酚的加入，可以控制甲基丙烯酸接枝链在PE基材中的位置。用液相法制备的4-乙烯基吡啶接枝PE膜对对硝基苯乙酸乙酯的催化活性高于气相法制备的膜。前一种样品与后一种样品相比，表征的是膜表面接枝链的分布。从而证实了接枝链的位置特性反映在接枝聚合物的功能上。将所得结果应用于纤维素膜。用气相和液相法制备了甲基丙烯酸缩水甘油酯接枝纤维素，并与二胺反应合成了含氨基的纤维素。所得纤维素衍生物具有铜离子的吸附特性。这两个样本在特征上没有什么不同。因此，需要进一步的研究来控制接枝链在纤维素底物中的位置。

In this study, photografting as a mean for functionalization of polymeric materials was applied to polyolefin and cellulose in order to design generation of a wide variety of functions by control of the location of grafted chains introduced into the polymeric substrates. In the first term, effect of grafting conditions on the location of methacrylic acid-grafted chains was examined using polyethylene (PE) film and then relationship between the location of grafted chains and the function of grafted polymers was investigated in the second term, and the results obtained are as follows :1. Control of the location of methacrylic acid-grafted chains in PE substrate was found to be possible by proper choice of polymerization systems (vapor- and liquid-phase), monomer concentration and polymerization temperature and addition of hydroquinone to the system.2. Catalytic activity of 4-vinylpyridine-grafted PE film, which was prepared with liquid-phase system, toward hydrolysis of p-nitrophenylacetate was higher than that prepared with vapor-phase system. The former sample was characterized by the distribution of grafted chains locarized at film surface compared with the latter sample. It was confirmed thus that the characteristic of the location of grafted chains is reflected on the function of grafted polymers.3. The results obtained for PE film were applied to cellulose. Glycidyl methacrylate-grafted celluloses prepared by liquid- and vapor-phase systems were reacted with diamines to yield celluloses with amino group. The resultant cellulose derivatives were subjected to the absorption character of cupric ion. There was little difference in the character between the both samples. Accordingly, further study will be necessary for control of the location of grafted chains in cellulose substrate.