Synthesis Of Ladderlike Polyorganosiloxanes By Supramolecular Self-Assembly Template

Research in microstructure-controllable ladderlike polymer is a forward inter- and multidisciplinary field of polymer science, supra- molecular chemistry and material science. In this thesis, which is based on theory of supramolecular self-assembling, a series of ladderlike polyorganosiloxane was synthesized successfully with the help of H-bonding and charge transfer self-assembling template. The main contents and results of this thesis are shown below.1. A novel benzoquinone-bridged ladderlike polyorganosiloxane was synthesized with the help of a H-bonding self-assembling template. Hydroquinone organo-bridged monomer was synthesized by hydrosilyla- tion in the presence of dicyclopentadiene platinum dichloride(Cp2PtCl2) catalyst. The benzoquinone-bridged ladderlike polyorganosiloxane was prepared from the monomer by H-bonding of hydroquinone and silicon hydroxy. The whole synthesis process included "Stepwise Coupling Polymerization" and oxidation. A variety of characterization methods including FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, VPO and solubility test were combined to verify that the structure of the polymer has high ordered ladderlike structure.2. A quinone-hydroquinone-bridged ladderlike polyorganosiloxane was synthesized successfully by quinone-hydroquinone charge transfer interaction self-assembling template. Hydroquinone is an electron donor and quinone is an electron acceptor, so charge transfer complex (CTC) is formed easily. The process involved hydrolysis and polycondensation. The structure of the polymer was characterized by FT-IR, 1H-NMR, 29Si-NMR XRD, DSC, UV, VPO and solubility test. All the characterization data indicated that the polymer possessed a less ordered and lower molecular weight than the polymer synthesized by H-bonding self-assembling template.3. As starting monomer, cyanosiloxane was synthesized by hydrosilylation. A novel kind of ladderlike polysilsesquioxane having side-chain with amino terminal group was prepared by "Stepwise Coupling Polymeri- zation" and reduction of cyano group. A variety of characterization methods including FTIR, 1H-NMR, 29Si-NMR, DSC, XRD, VPO and solubility test were combined to verify that it has ordered ladderlike structure. The obtained soluble ladderlike polymer has promising application in NLO materials, alignment layer in liquid crystal display. This synthetic method paves another new way for synthesis and functionalization of novel ladderlike polymers.