化学学报 ›› 1962, Vol. 28 ›› Issue (1): 57-67. 上一篇    下一篇

论文

硅碳硅氧型高分子的合成Ⅰ.甲基乙氧基二硅甲烷的合成和水解縮聚

王葆仁, 郑友菊, 黄志镗, 聶绪宗, 林一   

  1. 中国科学院化学研究所
  • 投稿日期:1961-07-20 发布日期:2013-06-03

STUDIES ON POLYMERS OF THE SILCARBOSILOXANE TYPEⅠ. SYNTHESIS AND HYDROLYTIC POLYCONDENSATION OF METHYL ETHOXYDISILYLMETHANES

WANG PAO-JEN, ZENG YU-JUE, HUANG CHIH-TANG, NIEH SHU-TSONG, LIN I   

  1. Institute of Chemistry, Academia Sinica
  • Received:1961-07-20 Published:2013-06-03

从二氯甲烷与元素硅直接合成的六氯二硅甲烷经醇解制得六乙氧基二硅甲烷。用Grignard法以甲基依次取代乙氧基,合成一至五甲基取代的二硅甲烷。发现偶数甲基的对称取代物产率较高。将这些甲基取代的单官能到五官能的单体在溶剂乙醚中水解缩聚,只五官能的单体得到不溶不熔的体型聚合物,三官能的单体部分成为线型聚合物,其余的都变为环状、并环状及笼状结构的低聚物。四官能单体和二官能的单体共聚也得到具并环结构的低聚体。本文对于这些产物结构进行阐明和讨论,并证明聚硅甲硅氧烷环化倾向很大,从而生成小分子化合物。

Hexachlorodisilylmethane, obtained by the direct synthesis from methylene chloride and silicon, was alcoholysed to get hexaethoxydisilylmethane; the latter was, in turn, converted by Grignardization to five monomeric methyl. ethoxydisilylmethanes, containing from one to five methyl groups. It was found that the even-numbered, symmetrically substituted monomers gave better yields. These monomers were hydrolysed in the presence of diluted hydrochloric acid and ether. Only the pentafunctional monomer gave an insoluble and infusible cross-linked polymer, the trifunctional monomer gave in part a linear polymer, and all the other monomers gave ringed, fused-ringed or caged oligomers. The co-hydrolysis of a mixture of di-and tetra-functional monomers gave also a fused-ring oligomer. The structures of these products were elucidated and discussed. From the results, it is evident that the strong tendency of disilmethosiloxane to ring closure reduces the functionality of the polyfunctional monomers with the result of oligomer formation.