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

1)研究了甲基三异氰酸酯基硅烷水解缩聚合成1-3环体系的异氰酸酯基低聚硅氧烷和梯形低聚硅氧烷。结果表明，该反应生成了从二聚体到八聚体或从四聚体到六聚体的线型和环状低聚硅氧烷，以及具有螺旋桨状结构的双环五硅氧烷。此外，还发现了一个有趣的结果，即化合物的结构与V_（1-x）的光谱数据以及<s1-os1>IR和<29>~ 1H NMR谱中的化学位移之间的关系。另一方面，二硅氧烷与具有不同硅官能团的环状四硅氧烷发生缩合反应，得到由二环和三环体系组成的梯形低聚硅氧烷。2）以四异氰酸酯基二硅氧烷为原料，与氨反应合成了作为氮氧化硅Si_2N_2O前驱体的聚硅氧氮烷。结果表明，聚双氮烷的自缩合稳定性与反应条件有关，低分子量聚双氮烷在一定浓度的THF中进一步缩合形成高分子量聚合物。因此，通过热处理，取决于气氛，前体转化为SiNCO或SiNO。3)乙烯基1-和3-甲基丙烯酰氧基丙基三甲氧基硅烷的加聚反应，然后水解缩聚，发现提供的碳和硅氧烷链的聚合物杂化物，并形成独立的膜上铸造它们。此外，薄膜的机械性能被证实是相关的结构。4）采用溶胶-凝胶法制备了TEOS-PEG-Li杂化高离子导体和W、Ir的电致变色氧化物薄膜，并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.