【作者】 陆召彬；

【导师】 万有志；

【作者基本信息】 北京化工大学 ， 应用化学， 2009， 硕士

【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,成功地合成了高规整的反应性梯形聚乙烯基倍半硅氧烷Vi-LPSQ。然而在缺少模板剂的情况下,往往的得到的是交联和网状的结构。因此,合成梯形聚乙烯基倍半硅氧烷Vi-LPSQ的时候,有必要强调决定Vi-LPSQ规整性的两个重要的超结构实体:Vi-LS以及二氨基亚苯桥基与断撑剂之间形成的给-受体络合物(DAC)。根据设计合成路线的理念,合成二氨基亚苯桥基梯形聚硅氧烷Vi-DLPS过程中,间苯二胺作为模板剂,主要依靠苯环的π-π堆积和N-H’s的氢键作用自主装形成乙烯基超结构Vi-LS。然后逐步偶联聚合,同步增长方式合成出Vi-DLPS。当由Vi-DLPS转变为Vi-LPSQ时,选择了间苯二酰氯作为断撑剂,与有机桥基梯撑即二氨基亚苯桥基之间,依靠羰基与氨基的氢键、氯原子上p电子与硅原子的d轨道之间的dπ-pπ作用,形成稳定的给-受体络合物,之后按照“同步断撑和原位缩合”合成出结构完美的、高规整的目标聚合物Vi-LPSQ。通过超分子调控构筑方法合成的Vi-DLPS和Vi-LPSQ,根据粉末XRD表征结果,在小角出现的强烈的衍射峰,表明聚合物具有典型的梯形结构。另外,硅谱的表征谱图上,也出现尖锐的吸收峰,且基线半峰宽△～1 ppm,表明了聚合物是高度规整的。由于含有乙烯基活性侧基,目标聚合物Vi-LPSQ可以作为进一步的功能化,成为制备功能高分子材料的重要前驱体,所以它在整个梯形聚倍半硅氧烷家族中具有特殊的意义。更多还原

【Abstract】 The real ladder polyvinylsilsesquioxaneVi-LPSQ 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 are unavoidable if the effective template is absent. Here, it is necessaryly emphasized that ladder superstructure （Vi-LS） and donor-acceptor complexation （DAC） between the bridge and bridge-cleaving agent-based synchronous cleavage are two imperative supramolecular architectures determining the ladder regularity of Vi-LPSQ. The ladder-rung, diaminophenylenee, can self-assemble into real ladder superstructures （Vi-LS） as template byπ-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 diaminophenylenee-bridge of Vi-DLPS by a synergy of hydrogen bonding between carbonyl and amino groups and dπ-pπinteraction of p-electrons of Cl-atom and d-orbital of Si-atom. As a result, the real reactive Vi-LPSQ is obtained based-on this supramolecular architectures-directed approach. The ladder regularities for either the real Vi-DLPS or Vi-LPSQ are confirmed by the strong diffraction peaks at small angle range of XRD patterns. Especially, ²⁹Si NMR measurement gives the sharp peak with extremely narrow baseline-width,Δ～1 ppm, of the repeat moieties: Vi-Si(O_2/2)-NH-Ph-NH-Si(O_2/2)-Vi and Vi-Si(O_2/2)-O-Si(O_2/2)-Vi.Moreover, The target polymer Vi-LPSQ is a premising precursor for preparation of a number of advanced functional materials due to a possibility of functionalization for the reactive vinyl group.更多还原