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A series of inorganic/organic nanocomposites were prepared by blending cage-like, hydroxyl-bearing polyhedral oligomeric silsesquioxane (HO–POSS) with poly(methyl methacrylate) (PMMA) in THF solvent. Fourier transform infrared spectrophotometry (FTIR) and 29Si–nuclear magnetic resonance (29Si-NMR) were employed to characterize the structures of the HO–POSS/PMMA nanocomposites. Scanning electron microscope (SEM) images showed that the as-prepared composite films were smooth, and no severe aggregation of HO–POSS was observed when POSS content was less than 1.0 wt.%. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) results showed that the incorporation of small amount of nanosized HO–POSS reinforced the thermal stability of PMMA. When 1.0 wt.% of HO–POSS was incorporated into PMMA matrix, the Tg and Td increased by 28.8 °C and 18.9 °C, respectively, due to the strong interaction between POSS cages and PMMA chains. However, higher POSS contents (>2.0 wt.%) deteriorated the thermal and mechanical properties of the nanocomposites owing to the phase separation in the composite matrix caused by the aggregation of POSS cages.

A 1D copper(II) complex [Cu(Hbtc)(PyBIm)2]n (H3btc=1,3,5-benzenetricarboxylic acid, PyBIm=2-(4-pyridyl)benzimidazole) has been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. A crystallographically independent copper(II) atom is coordinated by three oxygen and two nitrogen donors in a five-coordinate distorted square pyramid geometry ([CuN2O3]). Two copper coordination units ([CuN2O3]) are linked together via two carboxyl groups of two Hbtc2− ligands, forming a dimetal unit ([CuN2O3]2). The tridentate Hbtc2− anion, as bridging ligand, connects the dimetal units into 1D chain-like structure. Supplemental materials are available for this article. Go to the publisher's online edition or Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file.

A series of poly(vinyl pyrrolidone-co-octavinyl polyhedral oligomeric silsesquioxanes) (PVP-POSS) organic–inorganic hybrid nanocomposites containing different percentages of POSS were prepared via free radical polymerization and characterized by FTIR, high-resolution 1H-NMR, solid-state 29Si-NMR, GPC, DSC, and TGA. POSS contents in these nanocomposites can be effectively controlled by varying the POSS feed ratios which can be accurately quantified by FTIR curve calibration. On the basis of 29Si-NMR spectra, average numbers of reacted vinyl groups of each octavinyl-POSS macromer are calculated to be 5–7, which depends on POSS feed ratios. Both GPC and DSC results indicate that these nanocomposites display network structure and the degree of crosslinking increases with the increase of the POSS content. The incorporation of POSS into PVP significantly improves their thermal properties (Tg and Tdec) primarily due to crosslinking structure and dipole–dipole interaction between POSS cores and PVP carbonyl groups. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

The soluble poly(methyl methacrylate-co-octavinyl-polyhedral oligomeric silsesquioxane) (PMMA–POSS) hybrid nanocomposites with improved Tg and high thermal stability were synthesized by common free radical polymerization and characterized using FTIR, high-resolution 1H NMR, 29Si NMR, GPC, DSC, and TGA. The POSS contents in the nanocomposites were determined based on FTIR spectrum, revealing that it can be effectively adjusted by varying the feed ratio of POSS in the hybrid composites. On the basis of the 1H NMR analysis, the number of the reacted vinyl groups on each POSS molecules was determined to be about 6–8. The DSC and TGA measurements indicated that the hybrid nanocomposites had higher Tg and better thermal properties than the pure PMMA homopolymer. The Tg increase mechanism was investigated using FTIR, displaying that the dipole–dipole interaction between PMMA and POSS also plays very important role to the Tg improvement besides the molecular motion hindrance from the hybrid structure. The thermal stability enhances with increase of POSS content, which is mainly attributed to the incorporation of nanoscale inorganic POSS uniformly dispersed at molecular level. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5308–5317, 2007

The poly(styrene-co-octavinyl-polyhedral oligomeric silsesquioxane) (PS–POSS) organic–inorganic hybrid nanocomposites containing various percent of POSS were prepared via one-step free radical polymerization and characterized by FTIR, high-resolution 1H NMR, 29Si NMR, GPC, DSC, and TGA technologies. The POSS contents in these nanocomposites were determined using FTIR calibration curve. The result shows that the POSS contents in nanocomposites can be tailored by varying the POSS feed ratios. On the basis of the POSS contents in the nanocomposites and the 1H NMR spectra, the number of reacted vinyl groups of each octavinyl-POSS macromonomer were calculated to be 6–8. DSC and TGA measurements indicate that the incorporation of POSS into PS homopolymer can apparently improve the thermal properties of the polymeric materials. The dramatic Tg and Tdec increases are mainly due to the formation of star and low cross-linking structure of the nanocomposites, where POSS cores behave as the joint points and hinder the motion and degradation of the polymeric chains. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

A new class of organic-inorganic hybrid polymers with well-defined structure was prepared by reacting diepoxyhexavinyl polyhedral oligomeric silsesquioxanes (DehvPOSS) with diamines of different chain lengths. The structures and properties of these hybrid polymers were well characterized by FTIR, 29Si-NMR, GC-MS, and TGA. A modeling characterization was employed to help identify the structures of organic tethers linked between the POSS cages. The results indicated that at the stoichiometric ratio of DehvPOSS to diamine, well-defined organic–inorganic hybrid polymers with controlled variation of the organic tether architecture can be made, and each organic tether connected four POSS cages. Thermal stability (Tdec) increased with an increase in the tether length of the diamine molecules, and the highest Tdec was obtained with butanediamine (rather than propanediamine or ethanediamine) as the organic tether. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3730–3735, 2006

Several inorganic/organic nanocomposites were prepared via solution-blending of cage-like octahexyl-polyhedral oligomeric silsesquioxane (Oh-POSS) with polystyrene (PS) in THF solvent. FTIR and 29Si-NMR were employed to characterize the structures of the nanocomposites. SEM pictures showed that the sample films were smooth and no POSS aggregation was observed when POSS content was lower than 1.0 wt%. TGA and DSC were used to investigate the thermal property. The results showed that the incorporation of nanosized Oh-POSS enhanced the thermal stability of PS with low POSS content. When 1.0 wt% of Oh-POSS was incorporated into PS matrix, the Tg and Td increased by 7.7 °C and 8.2 °C, respectively. However, higher POSS contents (>1.0 wt%) would deteriorate the thermal property of the nanocomposites due to the severe congregation of POSS..