含磷钼酸的超分子复合材料的制备和结构研究  

Synthesis and Characterization of Supramolecular Nanocomposites Based on Surfactant-encapsulated Polyoxometalate

作　　者：刘红伟[1,2] 陈小芳[2,3] 张洁[2] 李香丹[1] 李立忠[1] 

机构地区：[1]中南民族大学化学与材料科学学院,武汉430074 [2]北京大学化学与分子工程学院高分子科学与工程系,北京100871 [3]苏州大学材料与化学化工学部高分子科学与工程系,苏州215123

出　　处：《高分子学报》2014年第1期115-121,共7页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21174003;51003001)资助项目

摘　　要：介绍了一类端基含羧基结构的液晶性表面活性剂CDDA通过静电相互作用与磷钼酸(HPMo)进行复合,得到表面包覆柔性烷基链和羧基端基的复合物SEP-PMo,并通过元素分析、热失重等方法确认其化学结构.该复合物表现出稳定的液晶相,DSC,PLM,SAXS和TEM等研究表明其为层状相结构.进一步将SEP-PMo复合物与P4VP混合,通过羧基与吡啶环上氮的氢键相互作用,得到稳定的PMo和聚合物的复合物,同时对比研究了HPMo与P4VP直接共混后的静电复合物结构,表明经表面活性剂修饰后的PMo可在聚合物中保持其聚集态结构.A surfactant-encapsulated polyoxometalate complex SEP-PMo was prepared by phosphomolybdic acid （H3PMonO40, abbreviated as HPMo）, via electrostatical interaction between HPMo and N-[ 12-（4- carboxylphenoxy） dodecyl]-N,N-dimethylammonium bromide （CDDA）. The resulting complex was characterized in detail by elemental analysis, thermogravimetric analysis （TGA） , as well as FT-IR spectra. SEP-PMo was further complexed with poly（4-vinyl pyridine） （P4VP） via hydrogen bonding interaction to get P4VP（SEP-PMo） n（n =0.01, 0.05, 0.1, 0.3, 0.5 and 1）. Mesomorphic phase behaviors of CDDA, SEP- PMo as well as P4VP（SEP-PMo） n were studied by a combination of differential scanning calorimetry （DSC）, polarized light microscopy （ PLM）, small-angle X-ray scattering （SAXS） and transmission electron microscopy （TEM）. Surfactant CDDA has a bilayer smectic A structure with a layer thickness about 4. 8 nm. When increasing the temperature to 140 ~C, the phase structure turns into a monolayer smectic A structure with a layer thickness around 2.4 nm. SEP-PMo exhibits thermotropic liquid crystal phase behavior induced by microphase separation from organic and inorganic composites. SAXS and TEM studies revealed that SEP-PMo could form lamellar structure with the layer thickness about 2.5 nm, and within the layer PMo has relatively ordered structure. Comparing with the phase structure of P4VP-PMo-n composites, the mesophase structure of SEP-PMo could be partially kept in the hydrogen bonded complex, P4VP（SEP-PMo）o.

关 键 词：多金属氧簇 聚乙烯基吡啶 液晶 表面活性剂 

分 类 号：TB33[一般工业技术—材料科学与工程]