Miscibility of bisphenol-A polycarbonate with poly(methyl methacrylate)

The miscibility of bisphenol-A polycarbonate (PC) with poly(methyl methacrylate) (PMMA) has been reexamined using differential scanning calorimetry (DSC) and optical indications for phase separation on heating, i.e., lower critical solution temperature (LCST) behavior. Various methods have been used to prepare the blends including methylene chloride (CH₂Cl₂) and tetrahydrofuran (THF) solution casting, melt mixing, and precipitation of PC and PMMA simultaneously from THF solution by using the nonsolvents methanol and heptane. It is shown that the resulting phase behavior for PC/PMMA blends is strongly affected by the blend preparation method. However, these blends are miscible over the whole blend composition range (unambiguous single composition-dependent T_g's and LCST behavior) when prepared by precipitation from solution using heptane as the nonsolvent. To the contrary, solution-cast and melt-mixed PC/PMMA blends were all phase separated, which may be attributed to the “solvent” effect and LCST behavior, respectively, not discovered in previous reports. Methanol precipitation does not lead to fully mixed blends, which demonstrates the importance of the choice of nonsolvent when using the precipitation method.     

Metallo‐supramolecular block copolymer micelles: Improved preparation and characterization

Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS₂₀‐[Ru]‐PEO₇₀ and PS₂₀‐[Ru]‐PEO₃₇₅. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS₂₀‐[Ru]‐PEO₇₀ micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (d_h) of 18 nm. For PS₂₀‐[Ru]‐PEO₃₇₅ micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and d_h = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004     

Effect of the particle size distribution on the low shear viscosity of high‐solid‐content latexes

The production of high‐solid‐content, low‐viscosity latexes is an active field in both industry and academia. The viscosity of polymer dispersions has a clear dependence on the particle size distribution (PSD). An example is the rule of thumb that a bimodal PSD enables the reduction of the viscosity with respect to monomodal systems. Despite important progress in theoretical work, not much has been done to quantitatively predict the low shear viscosity of aqueous polymer dispersions as a function of the complex PSD. In this work, the capability of a low‐shear‐viscosity equation to quantitatively account for the influence of both the PSD and the physicochemical characteristics of the dispersions is experimentally assessed. An analysis, consistent with theoretical concepts, of the data with semiempirical correlations is proposed. Next, with values of the parameters of the viscosity equation obtained experimentally, the effect of a latex with a 70% solid content on the low shear viscosity is examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3936–3946, 2004     

Application of N,N‐bis(diphenylphosphino)aniline palladium(II) complexes as pre‐catalysts in Heck coupling reactions

Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.     

Chemical analysis and distribution investigation of trace elements in indium matrix by spark source mass spectrometry

Summary High-purity indium was analysed by spark source mass spectrometry, using electrical and photoplate detection. For the calibration of the differences in elemental sensitivity, a standard sample was prepared in which 10 impurities were determined by graphite furnace atomic absorption spectrometry. In this way accuracies of less than 40% were obtained for relatively homogeneous elements at ppm and sub-ppm level. About 40 elements could be determined with detection limits of 10 to 30 ppb. Two pattern recognition methods, principal component analysis and clustering analysis, were applied to obtain information on trace element distribution, which indicated that a number of elements were strongly spatially correlated in the analysed sample.

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Chemische Analyse und Verteilungsbestimmung von Spurenelementen in Indium-Matrix durch Funkenquellen-Massenspektrometrie

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On leave from: Department of Chemistry, Nanjing Normal University, Nanjing, People's Republic of China     

Relevance of Reflection in Static and Dynamic Light Scattering Experiments

Using a monodisperse PMMA dispersion, it was shown that light reflection at the sample cuvette walls may greatly influence the results of both static (SLS) and dynamic (DLS) light scattering experiments. Considering SLS, this reflection phenomenon mostly causes an overestimation of the scattered intensity at high scattering angles, which may give rise to the emergence of an additional, artificial peak in the lower region of the particle size distribution. On the other hand, the influcence of reflection on DLS measurements was shown to be particularly important in the upper region of the particle size distribution. The experimentally observed phenomena were explained from the basic principles of both particle sizing methods. Finally, it was shown that the disturbing effect of reflection could be avoided by modifying either the hardware or the software of the static and dynamic light scattering technique.     

Hybrid organosilazane/organosilylamine telechelic oligomers—I. Two-dimensional NMR spectroscopy characterization of dimethylsilylethylenediamine oligomers

The detailed characterization of multifunctional hybrid organosilazane/organosilylamine telechelic oligomers by IR and ¹H, ¹³C and ²⁹Si NMR spectroscopy in one and two dimenions has been undertaken. The specific multifunctional oligomers, comprising NH/NH₂ or SiCl functionalities depending on the monomer feed-ratio, were prepared from mono- and di-functionally reacted dichlorodimethylsilane (DDS) and mono-, di-, tri- and tetra-functionally reacted ethylenediamine (EDA). Varying the feed-ratio afforded control of the microstructures of the oligomers and the preparation of oligomers with, in some cases, conterminously located silicon–chlorine (SiCl) groups. The combination of the NMR methods with the IR technique has enabled the detailed microstructural characterization of the oligomers and the identification of the functionalities therein. This approach and the knowledge gained from the DDS/EDA system has been applied to the microstructural characterization of other hybrid organosilazane/silylamine preceramic telechelic oligomers.