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  • Polymer and Materials Science  (129)
  • General Chemistry
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1547-1553 
    ISSN: 1434-1948
    Keywords: Imidazaboles ; Carbene-borane adducts ; Azole-borane adducts ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation and characterization of five new imidazabole derivatives is reported: 1,5-dibenzyl-4,4,8,8-tetrahydroimidazabole (2), 4,4,8,8-tetrafluoro-1,5-dimethylimidazabole (3), 4,4-difluoro-8,8-dihydro-1,5-dimethylimidazabole (4), 4,4,8,8-tetrachloro-1,5-dimethylimidazabole (5), and 4,4,8,8-tetraethyl-1,5-dimethylimidazabole (6). The structures of compounds 2-6 as dimeric carbene-borane adducts rather than dimeric N-borane adducts are discussed on the basis of NMR (2-6) and X-ray diffraction data (2, 3, 5 and 6).
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1279-1285 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of β-pinene with styrene oxide (SO) and β-pinene with N-vinylpyrrolidone (VP) was investigated by using SnCl4 in dichloromethane diluent at low temperature. Monomer reactivity ratios were evaluated for both copolymers at -80°C; these are r1(SO) = 2.979 and r2(β-pinene) = 0.002 and r1(VP) = 0.096 and r2(β-pinene) = 0.294.
    Additional Material: 1 Ill.
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  • 3
    ISSN: 1434-1948
    Keywords: Alkaline earth metals ; Group-13 metals ; Coordination chemistry ; Bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine ligand ; Nonacoordinated strontium compound ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of 3,5-di-tert-butylcatechol and aqueous ammonia with boron, aluminum, gallium, or strontium chloride, or with calcium or barium acetate produce, under oxidizing conditions, neutral complexes of stoichiometric formulae ML (M = BCl), ML2, [M = Al (2), Ga (3), Ca (4), and Ba (5)], and ML3H [M = Sr (6)] [L = different oxidation states of bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine]. The structures of 1 and 4-6 were established by 1H- and 13C-NMR spectroscopy and of 2, 3, and 6 by X-ray diffraction. The coordination compound ClBL (1) was obtained by transmetallation of ZnL2 with BCl3. It is a tetracyclic compound with tetracoordinated boron and nitrogen atoms, the ligand being in the reduced form, bis(hydroxyphenyl)amine. The paramagnetic complexes 2 and 3 crystallized in the triclinic system and are hexacoordinated with two orthogonal planar ligands bonded to the metal atoms. The ligands appear in two different oxidation states: one as the monoanion and another as a radical dianion. Based on their X-ray diffraction molecular structures, it is deduced that both ligands have similar structures, confirming electronic delocalization and fast interconversion of their oxidation states. Ca and Ba complexes are diamagnetic and hexacoordinated, both ligands being monoanions The strontium complex crystallized in the monoclinic system, the metal atom is nonacoordinated, having two ligands as monoanions, and a third one is a neutral protonated diquinone. Its structure is a distorted helix with three paddles in a C3 geometry and its unexpected diamagnetic behaviour is due to the presence of a reduced protonated ligand.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 217-224 
    ISSN: 1434-1948
    Keywords: Reaction mechanisms ; Cyclopalladation ; Acetic acid ; Pd-C bond stability ; Polynuclear species ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The processes operating during the synthetic cyclopalladation reactions of imines in acetic acid have been studied from a kinetico-mechanistic point of view. These reactions include a fast initial coordination to the palladium through the N-donor atom of the imine, followed by the proper C-H bond activation to produce the acetato bridged dimeric species. At this point, the lability of the bridging acetato groups, the hydrolysis of the C-Pd bonds, and/or the hydrolysis of C=N exo bonds contribute to the generation of dark red polynuclear compounds. The processes occurring after the C-H activation have been followed kinetically, both from palladium acetate plus imine, and the synthetically pure isolated acetato dimers as starting materials. The kinetic and activation parameters have been found identical within experimental error whatever the starting material was (k323 = 1.5 × 10-4 s-1; ΔH# = 51 kJ mol-1; ΔS# = -163 JK-1 mol-1 ΔV# = +19 cm3 mol-1 for the 4-ClC6H4-CH=N-CH2-C6H5 imine derivative 1a). Acidolysis of C-Pd bonds has been found to occur in these polynuclear species. When alternative monomeric Cbenzylic-Pd bond-containing complexes are possible follow ups of the reactions produce them as final dead-end complexes (k323 = 2.2 × 10-5 s-1; ΔH# = 61 kJ mol-1; ΔS# = JK-1 mol-1 ΔV# ≈ 0 cm3 cm-1 for the [2,4,6-(CH3)3]C6H2-CH=N-CH2-[2-(CH3]C6[H4] imine derivative 3d). The same study has been carried out with primary amines in order to check the validity of the data if C=N bond hydrolysis is taking place in the imine derivatives with exo C=N bonds. For complexes with similar type of metallacycles, the results agree reasonably well with the proposed mechanism [k323 = 1.2·10-4 s-1, ΔH# = 46 kJ·mol-1, ΔS# = -180 J·K-1mol-1, ΔV# = -16 cm3·mol-1 for the polynuclear formation of the C6H5-CH2-NH2 derivative 4e; k323 = 3.0·10-4 s-1, ΔH# = 55 kJ·mol-1, ΔS
    Additional Material: 1 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Advanced Materials 7 (1995), S. 226-228 
    ISSN: 0935-9648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 26 (1975), S. 703-706 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Autoclave arrangement for oxidation and corrosion tests of materials in pressurized waterThe authors describe an arrangement with an autoclave for corrosion and oxidation tests in pressurized water and steam. The autoclave has been conceived for a pressure of 250 bar at 500 °C. It is equipped with four locks enabling the specimens to be exchanged during operation without any markable influence on the working conditions. The aggressive medium can be exchanged continuously at a rate of 2,5 l/h. In addition to pressure and temperature controls the arrangement is equipped with a water quality control system.
    Notes: Es wird eine Autoklavenanlage für Korrosions-und Oxidationsuntersuchungen mit Hochdruckwasser bzw. Wasserdampf beschrieben. Die Auslegungsdaten des Autoklaven sind 250 bar bei 500 °C. Der Autoklav besitzt 4 Schleusen, über die während des Betriebes ein Probenwechsel ohne größeren Einfluß auf die Betriebsbedingungen möglich ist. Das korrodierende Medium kann kontinuierlich mit einer max. Rate von 2,5 l/h ausgetauscht werden. Neben der Druck- und Temperaturkontrolle ist eine Überwachung der Wasserqualität vorgesehen.
    Additional Material: 5 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 28 (1977), S. 676-683 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Phase transformations of the ZrNb 3 Sn 1 alloyThe phases transformations of cold-worked Zr-Nb 3-Sn 1-alloy have been studied as a function of heat tratements between 500-600°C in vacuum. Microscopic and X-ray diffraction analyses reveal allow us to state that again of a 50% cold-worked Zr-Bb 3-Sn 1-alloy at 597°C gives rise to a maximum ß-Nb content in the ß-Zr-matrix after 4 hours annealing.
    Notes: Die Phasenumwandlungen der Zr-Nb3-Sn 1-Legierung mit verschiedenen Kaltverformungen wurden in Abhängigkeit der Wärmebehandlung bei Temperaturen zwischen 500 und 600°C im Vakuum untersucht. Durch lichtmikroskopische Beobachtung und Röntgenbeugungsanalyse konnte im Fall einer Zr-Nb 3-Sn 10-Legierung mit 50%iger Kaltverformung, die einer Wärmebehandlung bei 597°C unterworfen wurde, nachgewiesen werden. Daß die ß-Nb-Konzentration in der ß-Zr-Matrix nach etwa 4 Stunden Wärmebehandlungszeit praktisch ein Maximum erreicht hat.
    Additional Material: 19 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 29 (1978), S. 258-265 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Influence of a mechanical treatment on the oxidation behaviour of ZrNb 3 Sn 1 alloy in oxygenIt has been found by means of gravimetric, microscopic, screen electron microscopic and x-ray diffraction investigations that the corrosion resistance of a Zr-Nb 3-Sn 1 alloy in oxygen (po2 = 3.3 × 104 Pa) between 400 and 460° C increases with increasing extent of cold rolling between 10 and 50%. Initially, the oxidation obeys a parabolic rate law with an activation energy the value of which becomes larger with increasing cold forming. After a critical thickness of the oxide layer is reached a transfer to a linear rate law occurs. The time of this transition becomes larger with increasing cold forming. Form the three processes which are responsible to the oxide layer growth mainly the diffusion of oxygen through the oxide layer via oxygen ion vacancies is the rate-determining step. In the later period of oxidation, however, a diffusion via grain boundaries must also be considered. The manner of the oxide growth is decisively determined by the cold forming regarding to a preferred orientation of the α-Zr grains in the alloy and to an epitaxial formation of oxide nucleus and of oxide crystals in the later period of oxidation.
    Notes: Mittels gravimetrischer, lichtmikroskopischer, rasterelektronenmikroskopischer und röntgendiffraktometrischer Untersuchungen wurde unmittelbar bestätigt, daß sich die Oxidationsbeständigkeit der Zr-Nb 3-Sn 1-Legierung im Sauerstoff (po2 = 3,33 × 104 Pa) bei Temperaturen zwischen 400 und 460 °C mit zunehmender Kaltverformung (zwischen 10 und 50% Kaltverformungsgrad) erhöht. Die Oxidation folgt zuerst einem parabolischen Zeitgesetz mit einer Aktivierungsenergie, deren Wert mit steigender Kaltverformung zunimmt. Nach Erreichen einer kritischen Schichtdicke wird ein Übergang zu einem linearen Zeitgesetz beobachtet. Die Übergangszeit ihrerseits nimmt mit steigender Kaltverformung zu. Obwohl während des Aufbaus des Zunders drei miteinander verknüpfte Vorgänge erfolgen, stellt die Diffusion von Sauerstoff durch die Oxidschicht über Sauerstoffionen-Leerstellen und längs von Kanten und Korngrenzen den reaktionsbestimmenden Schritt dar. Die Kaltverformung bestimmt die Art des Wachstums des Zirkonoxids, zunächst durch eine bevorzugte Orientierung der α-Zr-Körner in der Legierung und danach durch eine epitaktische Ausbildung der Oxidkeime und der Oxidkristallite im weiteren Verlauf der Oxidation.
    Additional Material: 7 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 3 (1997), S. 1017-1024 
    ISSN: 0947-6539
    Keywords: autocatalysis ; coiled coil ; kinetics ; peptides ; self-replication ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A 32-residue α-helical peptide with a sequence similiar to that of the GCN4 leucine zipper region is shown to catalyze its own formation by accelerating the amide bond formation of a 17-residue peptide, preactivated as a thiobenzyl ester, and a 15-residue peptide with a N-terminal cysteine. The self-replication process displays parabolic growth characteristics as revealed by a detailed kinetic analysis. Control reactions with single-mutant peptides strongly support a mechanism in which a ternary and/or quaternary complex of the product with both peptide fragments act(s) as the catalytically active intermediate(s). Furthermore, these experiments reveal a remarkable sequence selectivity, as evidenced by the loss of autocatalytic activity as a result of a single replacement of leucine or valine residues with an alanine at the recognition interface.
    Additional Material: 11 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 133 (1985), S. 97-109 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Neue Epoxyharze mit Imidgruppen wurden durch Reaktion einer Säure, die durch Kondensation von Trimellitsäureanhydrid und Diaminen (aromatischen oder aliphatischen) gewonnen wurde, und deren Glycidylesterderivat hergestellt. Die Reaktion wurde in N-Methylpyrrolidon (NMP) in verschiedenen Molverhältnissen durchgeführt.Die Struktur des Polymeren wurde durch IR-, NMR-Spektren und Elementaranalyse ermittelt.Die neuen Polymeren sind in polaren organischen Lösungsmitteln löslich und zeigen gute thermische Beständigkeit. Zwischen den Polymeren, die aliphatische oder aromatische Diamine enthalten, wurden Unterschiede beobachtet.
    Notes: New epoxy resins have been synthesized by the reaction of diimide-diacids trimellitimide derivatives containing different aliphatic and aromatic fragments in N-methyl pyrrolidone (NMP) with their corresponding diglycidylesters, using several molar ratios. The polymer composition has been determinated by chemical and elemental analyses. Their IR, 1H, and 13C NMR spectral data allowed to confirm the structural unit. Epoxy polyesterimides are soluble in polar organic solvents and show good thermal resistance. Differences on the basis of the introduced aliphatic or aromatic fragments were observed.
    Additional Material: 4 Ill.
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