【摘要】 用SiO2 为无机组份和以与SiO2 具有相似折射率和优良力学性能的丙烯酸类如甲基丙烯酸甲酯(MMA)和甲基丙烯酸羟乙酯 (HEMA) ,在交联剂 3 (三甲氧基硅 )丙基甲基丙烯酸酯 (MSMA)存在下 ,快速制备了两种杂化基质材料SiO2 /P(MMA MSMA)和SiO2 /P(HEMA MSMA)。分别以盐酸和六次甲基四胺作为酸性催化剂和碱性催化剂 ,建立了快速制备透明凝胶的两步溶胶 凝胶法 ,大大缩短了溶胶的成胶时间 ,所得杂化材料具有良好的光学透明性 ,利用此方法制备了掺杂稀土配合物的多种发光杂化材料。采用组装的方法 ,得到了稀土配合物与层状化合物α 磷酸氢锆 (α ZrP)及中孔分子筛材料MCM 4 1的组装体 ,并对所制备的杂化材料进行了表征。另外 ,将稀土配合物通过共价键嫁接于无机SiO2 基质中 ,得到了含有稀土配合物的分子杂化材料更多还原

【Abstract】 Based on the difference between the inorganic composite and the organic composite, one of the softchemistry synthesis method(sol gel process has been employed to prepare the rare earth/polymer hybrid materials. SiO 2 with good photostability and thermalstability was used as the inorganic composite and acrylic acid series e.g. methyl methacrylate(MMA) and 2 hydroxyethyl methacrylate(HEMA) with the almost same refractive index as SiO 2 as the organic composite. In the presence of coupling agent 3 (trimethoxysilyl) propyl methacrylate(MSMA), sol gel method was used to prepare two kinds of hybrid matrix materials SiO 2/P(MMA MSMA) and SiO 2/P(HEMA MSMA). The experiment results show that inorganic network and organic network were formed in the matrix materials. Since there exists a strong chemical bond between the inorganic phase and the organic phase, no evident interface in the final materials was found. The particle size is less than 100nm, suggesting the materials belong to nanometer composites. Owing to the formation of inorganic SiO 2 and the polymer at the same time in the matrix, the materials not only have good toughness but also decrease the thermal collection and photo loss. This kind of material is a promising matrix for the inorganic/organic composite materials. In order to overcome the drawback and limitation of pre doped and post doped method in the traditional sol gel method and shorten the period for the preparation of optical functional materials, a two step sol gel method was developed with hydrochloric acid as the acid catalyst and hexamethylenetetramine (CH 2) 6N 4 as the base catalyst for the in situ synthesis of rare earth complex in the SiO 2 matrix based on the characteristic of the sol gel method and synthesis rule for the rare earth complex. Since (CH 2) 6N 4 can generate hydroxyl groups gradually, the pH value was raised and accelerated the condensation reaction. In the meantime, this kind of reaction condition also favors the formation of rare earth complex. As a result of hydrolysis and condensation, the rare earth complex was synthesized and wrapped in the matrix. Using the two step sol gel technique, in situ complexes of rare earth ion(Eu 3+ , Tb 3+ ) with organic ligands such as β diketone, aromatic carboxylic acids and phen were synthesized in SiO 2/polymer hybrid matrix. By doping of rare earth complexes into layered compounds zirconium bis(monohydrogenphosphate) (α ZrP) and mesoporous material MCM 41, new luminescence assemblies were prepared. Because the interlayer spacing of α ZrP is too small to let the rare earth complex molecules intercalate, the increasing the interlayer spacing is the prerequisite for the preparation of the assemblies containing rare earth complexes. P Methoxyaniline (PMA) was used to preintercalate into the galleries of α ZrP and the interlayer spacing was increased and confirmed by XRD. Therefore, the assemblies containing rare earth complexes were prepared and demonstrated by XRD and UV visible spectra. Since the high energy vibration of the hydroxygen group will heavily quench the luminescence of the rare earth ion, the mesoporous material MCM 41 was modified by aminopropyltriethoxysilane (APTES) and thereby the assemblies containing rare earth complexes were made. The luminescence intensity of the assembly using MCM 41 modified by APTES was as 9 times as the assembly using the MCM 41 unmodified. Novel, covalently bonded hybrid materials of rare earth complexes with silica were prepared by using bipyridine Si as one of the precursors, which reacted with the TEOS by hydrolysis and condensation in the presence of lanthanide ions. These researches provide new possibilities for the development of new luminescence composites with high efficiency and long lifetime.更多还原