多金属氧簇与倍半硅氧烷簇构筑的簇-簇杂化分子的合成及自组装结构

以Wells-Dawson型多金属氧簇(POM)与T₈型倍半硅氧烷簇(POSS)为构筑单元,通过点击化学反应制备了一种由共价键连接形成的、新型的纳米簇-簇杂化分子(POM-2POSS),并采用核磁共振(NMR)、质谱(MS)和红外光谱(IR)对产物化学结构进行了表征. 由于两个POSS簇连接在POM簇的同一侧,分子呈现“V”形. 同时,利用X射线衍射(XRD)及透射电子显微镜(TEM)表征了簇-簇杂化分子在本体中通过自组装过程形成的超分子结构,结果表明该簇-簇杂化分子形成了有序的层状结构,周期仅为5.1 nm. 本研究获得结果对以这类纳米簇为构筑单元构筑新型杂化分子以及通过自组装过程形成的、有序超分子结构的新型杂化材料的设计及制备提供了一个新的思路.     

多金属氧簇与倍半硅氧烷簇构筑的哑铃形杂化分子Langmuir膜和Langmuir-Blodgett膜

以两个形状杂化分子(Shape Hybrid Molecules)为目标分子, 研究了它们在气液界面上形成Langmuir膜的过程和Langmuir-Blodgett (LB)膜的聚集态结构. 杂化分子是由Wells-Dawson型磷钨氧簇(Polyoxometalates, POMs)和T₈型的倍半硅氧烷簇(Polyhedral Oligosilsesquioxane, POSS), 通过对苯二甲酸有机连接链(OL)用共价键构筑的具有杂化性质和哑铃形状的簇-簇杂化分子(POM-OL-POSS). 这两种杂化分子的差别在于POSS段中, 外围有机基团的尺寸不同. 在实验中, 采用Langmuir和LB膜技术, 了解POSS外围的七个取代基变化导致的分子尺寸变化对Langmuir膜形成过程和LB膜结构的影响. 采用Langmuir技术测定了表面压-平均分子面积(π-A)等温曲线和π-A循环等温曲线, 跟踪并研究了这两个杂化分子在水表面上形成Langmuir膜的过程. 实验结果表明, 两个杂化分子都表现出良好的两亲性, 从气相变化到固相的过程中, 杂化分子经历了从分散到集中的过程. 将这些膜转移到基片上, 得到单层的LB膜, 再利用原子力显微镜(AFM)和透射电子显微镜(TEM)研究了LB膜的表面形貌和聚集态结构. 由于POM段中含有钨和钒金属, 可以直接用TEM观察聚集态结构, 发现了在气-液和液-固相转变过程中, LB膜中杂化分子的聚集态结构都呈现涨落特征, 一种凝聚态物理中由相转变导致结构涨落的重要物理现象. 本研究获得的结果能够帮助我们以及这个领域的研究者们继续优化杂化分子的结构, 进一步构筑具有有序结构的膜和本体材料.     

POSS基树枝状大分子的合成与应用

树枝状大分子(dendrimer)是一种高度支化、纳米尺度的人工合成大分子,具有独特的物理化学性能和重要的应用前景。利用具有8个可官能化顶点的多面体低聚倍半硅氧烷(POSS)作为树枝状大分子的核心,可在一定程度上简化树枝状大分子繁琐的合成与分离过程,在低代数时就可获得较大的表面官能团密度,并使树枝状分子呈现球形对称结构。POSS基树枝状大分子结合了POSS和树枝状分子结构与性能的优势,是一类极具潜力的有机-无机纳米杂化材料。本文综述了近年来POSS基树枝状大分子的最新研究成果,介绍了具有代表性的POSS基树枝状大分子的合成方法以及它们在催化剂、生物材料、液晶材料和发光材料等领域的应用研究进展,并对该新型材料的发展趋势做了展望。     

Modification of the surface properties of polyimide films using polyhedral oligomeric silsesquioxane deposition and oxygen plasma exposure

Topographically rich surfaces were generated by spray-coating organic solutions of a polyhedral oligomeric silsesquioxane, octakis(dimethylsilyloxy)silsesquioxane (POSS), on Kapton^® HN films and exposing them to radio frequency generated oxygen plasma. Changes in both surface chemistry and topography were observed. High-resolution scanning electron microscopy indicated substantial modification of the POSS-coated polyimide surface topographies as a result of oxygen plasma exposure. Water contact angles varied from 104° for unexposed POSS-coated surfaces to ∼5° for samples exposed for 5 h. Modulation of the dispersive and polar contributions to the surface energy was determined using van Oss Good Chaudhury theory. Changes in surface energy are related to potential adhesive interactions with lunar dust simulant particles.     

Group IV M‐POSS (M=Zr,Hf) Coordination Polymers

The synthesis and characterization of Zr‐POSS and Hf‐POSS coordination polymers were reported. The IR data and the solid‐state ²⁹Si MAS NMR indicated the existence of Si? O? M linkage. The polarized optical microscopy images and the XRD data suggested their crystalline nature.     

Light paths with an odd number of vertices in polyhedral maps

Let P _k be a path on k vertices. In an earlier paper we have proved that each polyhedral map G on any compact 2-manifold with Euler characteristic contains a path P _k such that each vertex of this path has, in G, degree . Moreover, this bound is attained for k = 1 or k 2, k even. In this paper we prove that for each odd , this bound is the best possible on infinitely many compact 2-manifolds, but on infinitely many other compact 2-manifolds the upper bound can be lowered to .     

Morphology studies and ac electrical property of low density polyethylene/octavinyl polyhedral oligomeric silsesquioxane composite dielectrics

This paper presents the results of morphological and ac electrical investigations on low density polyethylene (LDPE) composites with octavinyl polyhedral oligomeric silsesquioxane (POSS). It has been shown that at low loadings, the frequency dependence of dielectric constant and dielectric loss for the LDPE/POSS composites showed unusual behaviors when compared with conventional (micro-sized particulates) composites. The ac breakdown strength was measured and statistical analysis was applied to the results to determine the effects of POSS loadings on the dielectric strength of LDPE. The morphological characterization showed that the presence of POSS additives apparently altered the supermolecular structure of LDPE and resulted in more homogeneous morphology when compared with the neat LDPE. The structure-property relationship was discussed and it was concluded that the final dielectric properties of the composites were determined not only by the incorporation of POSS additives but also by the supermolecular structure of LDPE. Rheological analyses of LDPE/POSS composite were also performed and the results showed that the octavinyl-POSS had good compatibility with LDPE.     

Polymerization and nanocomposites properties of multifunctional methylmethacrylate POSS

Thermally induced polymerization of multifunctional methylmethacrylate POSS (MMA‐POSS) was studied in this work for preparation of polymer/POSS nanocomposites. The polymerization of MMA‐POSS could be promoted with benzoyl peroxide (BPO). Self‐assembly of POSS into a layer‐by‐layer structure in the MMA‐POSS polymer (TP‐MMA‐POSS) is observed with a transmission electron microscopy. An ultra‐low‐k value of about 1.85 is measured with TP‐MMA‐POSS. In addition, polyimide‐POSS nanocomposites are also prepared. These nanocomposites demonstrate good homogeneity and enhanced mechanical properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5157–5166, 2008