Studies on the Synthesis of Inorganic Polymers for 21" Century and New Materials from the Precursors.

1)研究了甲基三异氰基硅氧烷水解缩聚法制备异氰基低聚硅氧烷和1-3环梯形低聚硅氧烷。结果表明，该反应可生成二聚体到八聚体的线性低聚硅氧烷和四聚体到六聚体的环状低聚硅氧烷，以及具有螺旋桨状结构的双环五聚硅氧烷。此外，我们还发现了V_<s1-os1>的结构和光谱数据与IR和<29>^NMR光谱的化学位移之间的关系。二硅氧烷与具有不同硅官能团的环四硅氧烷缩合反应得到由二环和三环组成的梯形低聚硅氧烷体系。对结构进行了详细的勘察。2)以四异氰化二硅氧烷为前驱体，以氨为原料合成了聚硅氧烷氧氮化硅Si_2N_2O。观察到聚硅氧烷自缩聚的稳定性与反应条件有关，低分子量聚硅氧烷在一定浓度的四氢呋喃下进一步缩聚形成高分子量聚合物。因此，通过热处理，前体根据大气的不同转变为SiNO或SiNO。3)乙烯基1-和3-甲基丙烯氧基丙基三甲氧基硅烷加成后水解缩聚得到了碳链和硅氧烷链同时构成的聚合物杂化体，并在浇铸时形成独立薄膜。此外，还证实了薄膜的力学性能与结构有关。4)采用溶胶-凝胶法制备了TEOS-PEG-Li杂化高离子导体和W或Ir电致变色氧化薄膜，研究了其结构与性能的关系。

1)Synthesis of isocyanatooligosiloxanes and ladder oligosiloxanes with 1-3 ring system by hydrolytic polycondensation of methyltriisocyanatosilane was investigated. :It was found that the reaction provided linear and cyclic oligosiloxanes from dimer to octamer or from tetramer to hexamer, respectively, and also a bicyclopentasiloxane with propeller like structure. Furthermore, an interesting result was revealed on the relationship between the structure and the spectral data of V_<s1-os1> and chemical shift in IR and <29>^NMR spectra. On the other hand, the condensation reaction of disiloxanes with cyclic tetrasiloxanes with the different sila-functional groups gave ladder oligosiloxanes consisted of two and three ring system. The detailed investigation on the structure is undertakene.2) Polysiloxazanes as a precursor for silicon oxynitride Si_2N_2O were synthesized by the reaction of tetraisocyanatodisiloxane with ammonia. It was observed that the stability of polysiloxyazanes to self-condensation is dependent on the reaction conditions, and also low molecular weight polysiloxazanes in the certain concentration of THF undergo further condensation to form high molecular weight polymers. Thus by heat-treatment, the precursors were transformed to SiNCO or SiNO depending on the atmosphere. 3) Polyaddition of viny1-and 3-methacryloxypropyltrimethoxysilane followed by hydrolytic polycondensation was found to provide polymer hybrids constructed of both carbon and siloxane chain and to form free-standing films on casting them. In addition, the mechanical properties of films were confirmed to be correlated to the structure. 4)TEOS-PEG-Li hybrid high ion conductor and electrochromic oxide thin films of W or Ir were prepared by sol-gel process and the relationship between the structure and the properties were investigated.