STUDY ON 1-HEXENE POLYMERIZATION BASED ON ZIEGLER-NATTA CATALYSTS WITH DOPED SUPPORT

A series of Ti/Mg supported catalysts are prepared by using ball-milled mixtures of MgCl2-ethanol adducts and NaCl as supports, and 1-hexene polymerizations catalyzed by the novel catalysts are studied. It is found that the molecular weight distribution of poly(1-hexene) becomes apparently narrower when catalysts with doped supports are used, indicating that changing the structure of the support is an effective way to regulate the active center distribution of heterogeneous Ziegler-Natta catalyst.     

锆钛酸镧铅结构象和缺陷

锆钛酸镧铅(简称 PLZT)是一种十分重要的铁电材料.利用 PLZT 透明陶瓷的场致相变,还有可能在图象存贮和显示中得到应用.目前,在利用 La/Zr/Ti 比为7.9/70/30或8/65/35的 PLZT 透明陶瓷制作平面显示器、散射光开关和电光图象存贮器等方面开展了不少工作.PLZT 透明陶瓷的基本组成是锆钛酸铅掺 La 改性,形成(Pb,La)(Zr,Tj)O_3四元系固溶体.化学式倾向于:Pb_(1-x),La_x(Zr_(1-y),Ti_y)_(1-x/4)O_3.其中,La 的浓度 x 可在2～30％之间改变,而 Zr 与 Ti 的相互比例可连续变化.为了提高 PLZT 性能,人们往往通过改变这一比例加以实现.然而,我们的计算结果指出,这一比例的改变将使晶格能发生变化.我们用高分辨电子显微镜在晶格水平上对配比为8/65/35和7.9/70/30的 PLZT 进行了观察,发现配方7.9/70/30有更多的缺陷.计算表明,这可能是由于7.9/70/30的晶格能比8/65/35相对较低造成的.     

NONLINEAR OPTICAL PROPERTIES OF X-TYPE CHROMOPHORES AND THEIR DOPED FILMS

Two X-type chromophores, 2-[4-(4,5-di(4-nitrophenyl) imidazolyl) phenyl]-4,5-di(4-methoxyphenyl)-imidazole (DNPIPDMOPI), 2-[4-(4,5-di(4-nitrophenyl)-imidazolyl) phenyl]-4,5-di(4-aminophenyl)-imidazole (DNPIPDAPI), were synthesized and characterized. The results show that they possess good nonlinearity, considerable blue-shifted absorption (385 nm and 379 nm in THF) and high decomposition temperature (377℃ and 405℃). These mean that the X-type chromophores possess a rather good nonlinearity-transparency-thermal stability trade-off. The multi-step corona-poling technique at elevated temperature and in-situ SHG measurements were used to obtain and evaluate the poled films of these chromophores doped in PMMA. The largest SHG signals appeared at 110-120℃, which are 12.5 pm/V and 16.7 pm/V respectively. The dependence of poling induced orientation stability on temperature was measured by depoling experiments and the results indicate that the poling-induced orientation of the films is stable at about 100℃. Theoretic analyses imply that better orientation stability arises from the X-type structure of chromophore. The X-type chromophore has two crossed intramolecular CT, both βxxx and βxyy can contribute to the second-order susceptibility, and the ratio of the tensorial components (γ = βxyy/βxxx) is about 1/3, so the orientation decay of the films induced by rising temperature will provide a certain compensation for the contribution of βxyy of chromophores.