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.     

Evidences of phase separation in moisture‐cured poly(urethane urea)s by means of temperature modulated differential scanning calorimetry

The degree of phase separation in several moisture‐cured poly(urethane urea)s (PUUs) was studied by FTIR spectroscopy, wide angle X‐ray diffraction (WAXD), and temperature‐modulated differential scanning calorimetry (TMDSC). This latter technique was shown to be particularly useful in analysing the degree of phase separation in PUU polymers. Both phase mixing and phase segregation coexisted in the PUUs and the degree of phase separation increased as the urea hard segment (HS) content in the PUU increased. The maximum solubility of urea HSs into the polyol soft segments (SSs) was achieved for 50 wt % urea HS content in diol‐based PUUs, whereas for triol‐based PUUs the highest solubility between HS and SS was reached for lower urea HS amount. Finally, the higher the urea HS content the higher the extent of phase separation in the PUU. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3034–3045, 2007     

Mechanisms of n‐butanol formation in butyl acrylate latexes

The mechanisms involved in the formation of n‐butanol during the synthesis of butyl acrylate containing latices were investigated. The experimental results showed that neither the hydrolysis of butyl acrylate nor of the ester bond in the butyl acrylate segments of the polymer played a major role in the formation of n‐butanol, which was mainly generated from the polymer backbone, by transfer reactions to polymer chain followed by cyclization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5838–5846, 2007     

Diblock copolymers based on allyl methacrylate: Synthesis,characterization, and chemical modification

Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), ¹H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007     

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.     

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.     

Bases,spanning sets,and the axiom of choice

Two theorems are proved: First that the statement “there exists a field F such that for every vector space over F, every generating set contains a basis” implies the axiom of choice. This generalizes theorems of Halpern, Blass, and Keremedis. Secondly, we prove that the assertion that every vector space over ?₂ has a basis implies that every well‐ordered collection of two‐element sets has a choice function. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The case of missing incommensurate smectic A phases

Two binary mixtures of polar liquid crystal materials were previously reported to exhibit three incommensurate smectic A phases predicted for such materials on the basis of phenomenological theory. Results of our recent high-resolution X-ray scattering experiments show that no incommensurate phases exist in the two systems. Wide coexistence regions are found at first order transitions between various frustrated smectic phases of these mixtures. These regions were previously identified as the incommensurate smectic A phases. The phase diagrams of the two systems determined with high-resolution X-ray technique are shown to be in excellent agreement with Baroisa-Prost-Lubensky theory.     

Liquid crystalline hexa-amides and side chain polysiloxanes of azacrown [18]-N6

The hexa-4-dodecyloxybenzoyl derivative 1 of azacrown [18]-N₆ was originally reported to have a 'tubular' mesophase on the basis of its large central ring and 6-fold symmetry. Starting in the mesophase, annealing of 1 under a cover slip results in formation of a new crystalline phase that melts directly to an isotropic liquid at the temperature previously observed for the mesophase to isotropic transition. Thus the phase behaviour of 1 is kinetically controlled. The analogous hexa-3,4-bisdodecyloxybenzoyl derivative 2 of azacrown [18]-N₆ has no kinetic limitations to its phase changes and has an enantiotropic columnar liquid crystalline phase. We have synthesized side chain copolysiloxanes with a (CH₂)₁₁ spacer and 75-84 per cent by weight of the same 4-dodecyloxybenzoyl-[18]-N₆ mesogen. The polysiloxanes also display a liquid crystalline phase.