【作者】 杨利民；

【导师】 万有志；

【作者基本信息】 北京化工大学 ， 应用化学， 2004， 硕士

【摘要】 微观结构可控的梯形高分子是高分子科学、超分子化学和材料科学的交叉和前沿。本论文以氢键和电荷转移相互作用为模板，利用超分子自组装的理论，合成了一系列高规整性的梯形聚硅氧烷。主要的研究内容和结果如下：1. 利用氢键自组装为模板合成了对苯二醌有机桥基梯形聚硅氧烷。在催化剂二环戊二烯二氯化铂（Cp2PtCl2）存在下，通过硅氢加成反应制备了一种对苯二酚桥基偶联的单体。从该单体出发，以对苯二酚中的酚羟基之间的氢键以及硅羟基之间的氢键自组装为模板，先利用“逐步偶联聚合法”，然后再经氧化，合成一种新型的对苯二醌有机桥基梯形聚硅氧烷。通过FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, VPO及溶解性实验对其结构进行了表征，结果表明所得到的有机桥基聚硅氧烷具有较高的规整性。2. 利用醌-氢醌电荷转移相互作用为模板合成了醌-氢醌交替的有机桥基梯形聚有机硅氧烷。由于对苯二酚中的两个酚羟基的推电子作用，使得它具有电子给体的特性。而对苯二醌中的两个羰基的吸电子作用，使得它具有电子受体的特性，所以醌-氢醌之间很容易形成电荷转移络合物，聚合物的形成主要通过水解和缩合两步反应。借助FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, UV, VPO及溶解性实验对其结构进行<WP=5>了表征。结果可知，由于电荷转移相互作用较弱，得到聚合物的规整性和分子量的大小都略差于氢键自组装合成的聚合物。3. 利用硅氢加成反应合成了含氰基的硅烷单体，通过“逐步偶联聚合法”，然后经官能团转化，将氰基还原为胺基，合成了含胺基侧基的梯形聚倍半硅氧烷。同时对硅氢加成反应进行了深入的研究。FTIR, 1H-NMR, 29Si-NMR, XRD, DSC, VPO及溶解性实验表明合成的梯形聚倍半硅氧烷具有很好的梯形结构。该聚合物在非线性光学材料以及液晶显示材料等领域有着广泛的应用前景，为今后新型梯形高分子的合成及其功能化提供了一个新的思路。更多还原

【Abstract】 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 <WP=7>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.更多还原