高规整梯形聚乙烯基倍半硅氧烷的合成  

SYNTHESIS OF LADDER POLYVINYLSILSESQUIOXANE WITH HIGH REGULARITY

作　　者：陆召彬[1] 吕银生[1] 万有志[1] 谢萍[2] 张榕本[2] 

机构地区：[1]北京化工大学化工资源有效利用国家重点实验室,北京100029 [2]北京分子科学国家实验室中国科学院化学研究所高分子科学与材料联合实验室,北京100190

出　　处：《高分子学报》2009年第12期1287-1291,共5页Acta Polymerica Sinica

摘　　要：采用具有"同步增长,同步断撑和原位缩合"特性的超分子构筑调控逐步偶联和聚合方法,合成了高规整的反应性梯形聚乙烯基倍半硅氧烷Vi-LPSQ.该反应性乙烯基可进一步功能化,是制备功能高分子材料的重要前驱体.29Si-NMR是表征梯形聚合物规整性最有效的方法,Vi-LPSQ的重复结构单元共振吸收峰的化学位移δ=-21.6,且峰宽Δca.1,说明其规整性很高.它的XRD谱图上存在两个明显的衍射峰,分别对应于梯形的宽度(d1=0.74 nm)和厚度(d2=0.40 nm),这证实了Vi-LPSQ以典型的梯形结构存在.另外,Vi-LPSQ的玻璃化转变温度Tg高达191.3℃,表明Vi-LPSQ分子具有很高的刚性和规整性.The ladder polyvinylsilsesquioxane （Vi-LPSQ） with high regularity was successfully synthesized via supramolecular architecture-directed stepwise coupling and polymerization： ＂synchronous growth polymerization, synchronous bridge-cleaving followed by in situ condensation＂. Formation with branches or cross-linking is unavoidable if the effective template is absent. Here, it is necessaryly emphasized that ladder superstructure （Vi-LS） and hydrogen-bonding adduct （HBA） are two imperative supramolecular architectures determining the ladder regularity of Vi-LPSQ. The ladder-rung, diaminophenylenes, can self-assemble into real ladder superstructures （Vi- LS） as template by π-interaction-aided N-H＇s hydrogen-bonding. And when converting the real Vi-DLPS to the desired Vi-LPSQ, oxalyl chloride can initially form a stable hydrogen-bonded adduct （HBA） with the diaminophenylenes-bridge of Vi-DLPS by a synergy of hydrogen bonding between carbonyl and amino groups and dπ- pπ interaction of p-electrons of Cl-atom and d-orbital of Si-atom. As a result, the reactive Vi-LPSQ is obtained based-on this supramolecular architectures-directed approach. The ladder regularities for either the Vi-DLPS or ViLPSQ are confirmed by the strong diffraction peaks at small angle range of XRD patterns. Especially, 29 Si-NMR measurement gives the sharp peak with extremely narrow baseline-width, Aca. 1, of the repeat moieties： Vi-Si （O2/2 ）-NH-Ph-NH-Si （ O2/2 ）-Vi and Vi-Si （ O2/2 ）-O-Si （O2/2 ）-Vi. Moreover, The target polymer ViLPSQ is a premising precursor for preparation of number of advanced functional materials due to a possibility of functionalization for the reactive vinyl group.

关 键 词：预偶联 自组装 梯形超结构 逐步偶联和聚合法 

分 类 号：O634.41[理学—高分子化学]