Synthesis and characterization of functional gradient copolymers of allyl methacrylate and butyl acrylate

Functional spontaneous gradient copolymers of allyl methacrylate (A) and butyl acrylate (B) were synthesized via atom transfer radical polymerization. The copolymerization reactions were carried out in toluene solutions at 100 °C with methyl 2‐bromopropionate as the initiator and copper bromide with N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalyst system. Different aspects of the statistical reaction copolymerizations, such as the kinetic behavior, crosslinking density, and gel fraction, were studied. The gel data were compared with Flory's gelation theory, and the sol fractions of the synthesized copolymers were characterized by size exclusion chromatography and nuclear magnetic resonance spectroscopy. The copolymer composition, demonstrating the gradient character of the copolymers, and the microstructure were analyzed. The experimental data agreed well with data calculated with the Mayo–Lewis terminal model and Bernoullian statistics, with monomer reactivity ratios of 2.58 ± 0.37 and 0.51 ± 0.05 for A and B, respectively, an isotacticity parameter for A of 0.24, and a coisotacticity parameter of 0.33. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5304–5315, 2006     

Metallocene copolymers of propene and 1‐hexene: The influence of the comonomer content and thermal history on the structure and mechanical properties

The relationships between the structure and properties have been established for copolymers of propylene and 1‐hexene synthesized with an isotactic metallocene catalyst system. The most important factor affecting the structure and properties of these copolymers is the comonomer content. The thermal treatment, that is, the rate of cooling from the melt, is also important. These factors affect the thermal properties, the degree of crystallinity, and therefore the structural parameters and the viscoelastic behavior. A slow cooling from the melt favors the formation of the γ phase instead of the α modification. Regarding the viscoelastic behavior, the β relaxation, associated with the glass‐transition temperature, is shifted to lower temperatures and its intensity is increased as the 1‐hexene content raises. The microhardness values are correlated with those of the storage modulus deduced from dynamic mechanical thermal analysis curves, and good linear relations have been obtained between these parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1253–1267, 2006     

Aluminum(III) complexes containing O,O chelating ligand

The stoichiometric reactions of trimethylaluminum with 2,6‐(MeOCH₂)₂C₆H₃OH (LH) revealed compounds L₃Al ( 1 ) and L₂AlMe ( 2 ). On the other hand reaction of 1 equiv. of LH with trimethylaluminum did not lead to the formation of complex LAlMe₂ ( 3 ), rather 2 together with Me₃Al were observed as a result of a disproportionation of 3 . Compounds 1 and 2 were characterized by elemental analysis, ¹H and ¹³C NMR spectroscopy and in the case of 1 by X‐ray diffraction. Derivative 2 underwent transmetalation with Ph₃SnOH, giving LSnPh₃ ( 4 ) as the result of a migration of ligand L from the aluminum to the tin atom. The identity of 4 was established by elemental analysis, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy and ¹H, ¹¹⁹Sn HMBC experiments. The system 2 and B(C₆F₅)₃ in a 1:1 molar ratio was shown to be active in the polymerization of propylene oxide and ε‐caprolactone. Copyright © 2007 John Wiley & Sons, Ltd.     

A new interpretation of quantum mechanics and its consequences in epistemology

A rather recent interpretation of quantum mechanics, known under the various names of consistent histories, decohering histories, or logical interpretation, has brought interpretation into a standard deductive theory and is now investigated in many places. A key difference with the Copenhagen interpretation is the status of classical physics, now derived completely from quantum principles in both its dynamical and logical aspects. After describing briefly this new interpretation in its essentials, leaving aside technical details, it is shown how its consequences in epistemology differ drastically from the familiar outcomes of the Copenhagen interpretation, leading in particular to a well-defined theory of knowledge. Some more speculative philosophical consequences associated with the unsolved problem of actuality are also mentioned.     

Characterization of reaction products formed during thin-layer chromatographic detection of thiocarbamate herbicides

The reaction between thiocarbamate herbicides and 2,6-dichlorobenzoquinone-N-chloroimine or 2,6-dibromobenzoquinone-N-chloroimine is suitable for the detection of these herbicides on thin-layer plates with high sensitivity. The reactions were followed by infrared, nuclear magnetic resonance and mass spectrometry. We have established the formation of 2,6-dichlorobenzoquinone-S-alkyl sulphenylimines. In the case of the bromo-derivative, halogen exchange and substitution on the quinone ring took place simultaneously leading to the formation of mixed halogenated 2,6-dihalo- and, in addition, 2,3,6-trihalobenzoquinone-S-alkyl sulphenylimines. The final product of the detection reaction, i.e. 2,6-dichlorobenzoquinone-S-alkyl sulphenylimine was reacted with 2,6-dibromobenzoquinone-N-chloroimine where 2,6-dichloro-3-bromobenzoquinone-S-alkyl sulphenylimine formed as a consequence of the looser bromine-carbon linkage on the 2 and 6 positions of the quinone ring.     

Asymmetry and magnetism in bis(oximato)-bridged heterobimetallic compounds: a computational approach

A density functional study of exchange coupling was carried out for a series of heterobinuclear oximato-bridged transition metal complexes. Model calculations were used to examine the influence of the electronic configuration of the metal atoms on the coupling constants. This analysis was complemented by a study of the variation of the coupling constant with the most usual structural distortions within this family of compounds. The influence of the nature of the terminal ligands as well as that of the symmetry on the bridge were also investigated.     

Über die Reproduzierbarkeit der turbidimetrischen Bestimmung von Phosphorspuren mit Strychninmolybdostickstoff(V)säure

Microchimica Acta - Mit der turbidimetrischen Strychninnitrat-Methode für Phosphorspurenbestimmung nach der Version von Hegedüs und Dvorszky kann man nur dann ausgezeichnete...