氢键自组装模板辅助作用合成有机桥基梯形聚乙烯基硅氧烷  

H-bonding self-assembled template-controlled synthesis of a complete m-PDA-bridged ladder polyvinylsiloxane

作　　者：万有志[1] 刘琳[1] 裴 王碧波[1] 吕银生[1] 谢萍[2] 张榕本[2] 

机构地区：[1]北京化工大学理学院,北京100029 [2]中国科学院化学研究所,北京100080

出　　处：《有机硅材料》2007年第5期263-266,共4页Silicone Material

摘　　要：采用超分子构筑调控逐步偶联/聚合法,以间苯二胺为模板,通过预胺解反应将乙烯基三氯硅烷偶联成梯形模板单元;然后在对亚苯胺基的氢键作用下进行计量水解和脱氯化氢缩合反应,成功合成了具有高度规整结构的间苯二胺桥基梯形聚乙烯基硅氧烷(Vi-OLPS);产物的数均摩尔质量为8.75×103。并用FT-IR、XRD、29SiNMR及DSC对产物的组成和结构进行了表征。29SiNMR中代表[Vi(NH)SiO2/2]结构基元的半峰宽Δ1/2小于0.3,表明产物具有高度规整的梯形结构。A novel high regularity m-phenylenediamino-bridged ladder polyvinylsiloxane (addr. Vi-OLPS) with molecular weight n = 8.75×103 was synthesized successfully for the first time by means of supramolecular constitutive and control stepwise coupling/polymerization. During the reaction,coupling agent m-phenylenediamine(m-PDA) was supposed to act as a template which enabled silane molecules to form a proposed ladderlike supramolecular intermediate through imino H-bonding interaction,which was further condensed to form m-PDA-bridged ladder polyvinylsiloxane. The structure of the polymer was characterized by FT-IR,X-ray diffraction,29Si NMR and DSC. The data showed that the polymer had orderly ladderlike molecular structure. Vi-OLPS showed the very sharp absorption with a low half-peak width Δ1/2 < 0.3 ppm for the moiety [Vi(NH)SiO2/2] of the double main chain in29Si NMR spectrum,indicating presence of the perfect ladder structure. The m-PDA-bridged ladder polyvinylsiloxane with grafted reactive groups (—CHCH2) was a promising and potential precursor for the preparation of new functional ladder polymers.

关 键 词：氢键 模板剂 逐步偶联/聚合方法 梯形聚硅氧烷 间苯二胺 乙烯基三氯硅烷 甲基三氯硅烷 

分 类 号：O634.41[理学—高分子化学]