Synthesis Of Ladderlike Polyorganosiloxanes By H-Bongding Self-Assembling Template

Research in microstructure-controllable ladderlike polymer is the advanced and interdisciplinary study for polymer science, supramolecular chemistry and material science. In this thesis, which is based on the theory of supramolecular self-assembling, a series of ladderlike polyorganosiloxanes were synthesized successfully with the help of H-bonding self-assembling template. The main contents and results of this thesis are shown below.1. The author synthesized polyvinylsisesquioxane through amido H-bonding interaction, and prepared the intermediate in the preaminolysis step of "Stepwise Coupling Polymerization". The intermediate is unstable in the presence of air, water, and acids, so it further reacted with methanol to obtain relatively stable compound. It indicated N, N'-di(hydroxyethyl)terephthaloyl amide can play the pre-coupling role. In the reaction, DMF, which has relatively high dielectric constant, was chosen as the reaction medium. The reaction medium and the structure of N, N'-di(hydroxyethyl)terephthaloyl amide make it difficult to prepare polyvinylsisesquioxane. So coupling agent N, N'- di (1, 1- dimethyl-2 -hydroxyethyl)terephthaloyl amide was used to act as a template which enables the monomer to form a ladderlike supramolecular intermediate through amido H-bonding interaction, which is further condensed to form an amide-bridged ladderlike polysiloxane. The structure of the polymer was characterized by X-ray diffraction, DSC and 29Si NMR. The data show that the polymer has ordered ladderlike molecular structure.2. A novel kind of ladderlike polysilsesquioxane having side-chain with chloropropyl terminal group was prepared by "Stepwise Coupling Polymerization". A variety of characterization methods including 29Si-NMR, DSC, XRD were combined to verify that it has ordered ladderlike structure. The obtained ladderlike polymer has promising application in NLO materials,...