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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 4 (1993), S. 367-374 
    ISSN: 1042-7147
    Keywords: Fully aromatic polyesters ; Liquid crystal polymers ; Conformational isomerism ; Molecular dynamics (MD) simulations ; 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
    Notes: 3,4′-Substituted aromatic monomers, consisting of two phenylene units joined together by linking groups such as ketone or methylene, have recently been used for the preparation of quasi-rigid fully aromatic thermotropic polymers, based on conformational isomerism, with accessible transition temperatures.In this work the polyester of 3,4′-dicarboxydiphenyl ether and hydroquinone is considered: an Ullmann condensation has been carried out for the preparation of the asymmetric monomer, and low-temperature solution polycondensation has been used to synthesize the polymer. Although a liquid crystalline behavior could be expected, the polyester melts to an isotropic phase. Several copolymers have been prepared, by partially substituting either the asymmetric monomer with terephthalic acid or hydroquinone with different diphenols. The attempt to decrease the stability of the crystalline phase did not lead to significant results. The appearance of the nematic phase in some samples has been attributed to an increased chain stiffness, expressed in terms of persistence length as derived from molecular dynamics (MD) simulations.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 5 (1994), S. 416-422 
    ISSN: 1042-7147
    Keywords: Fully aromatic polyether esters ; Thermotropic copolymers ; Phase behavior ; Conformational isomerism ; 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
    Notes: Recently, flexible rod-like monomers based on conformational isomerism have been used to synthesize fully aromatic thermotropic polymers of reduced processing temperature and good thermal stability. 3,4′-Dihydroxy and 3,4′-dicarboxydiphenyl ethers HE and DE, obtained by modified Ullmann condensations between proper hydroxy and bromo derivatives, are investigated as basic components for homo- and copolyesters with the above-mentioned characteristics. Homopolymers from HE and terephthaloyl chloride or DE chloride and 2-methyl (or phenyl) hydroquinone, synthesized by low temperature solution polycondensation, melt to an isotropic fluid; the chain packing is frustrated in the latter by asymmetrical substitution on the aromatic rings, which causes a sequence randomization as well as an increased chain separation. The incorporation of linear rigid units, by partial substitution of the flexible monomers with 1,4 aromatic moieties, leads to thermotropicity, but the critical content of 1,4 units varies with the steric hindrance of the diphenol. Variation of chain rigidity, arising from the chemical structure, composition and sequence distribution, can account for the thermal behavior of the samples and, in particular, for their different abilities to give liquid crystalline behavior.
    Additional Material: 6 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 197 (1996), S. 1669-1680 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis of two new isomeric asymmetrically disubstituted disulfide monomers, [4-(3-hydroxyphenylthio)benzoic acid and 3-(4-hydroxyphenylthio)benzoic acid], with potential applications as all-aromatic polymer chain flexibilizers and flame-retardant additives, is here reported. The preparation and characterization of their homo- and copolymers obtained with 4-hydroxybenzoic acid, terephthalic acid and hydroquinone or its phenyl and methyl derivatives is also described. The purity of the monomers has been determined by gas chromatography, elemental analysis and NMR spectroscopy. Both monomers and polymers have been characterized by several techniques. DSC analysis and optical microscopy in polarized light have been used to determine the phase behaviour of the polymers. The remarkable differences in crystallinity and mesogenicity of the polymers derived from the two isomeric monomers are compared to the behaviour of copolymers containing the analogous oxygen-bridged compounds.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 198 (1997), S. 239-249 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ageing phenomena in cast films of poly(tert-butylacetylene) (PTBA) of different tacticity were studied by dilatometric and calorimetric techniques and by morphological observations. Films of different density (p) obtained by varying solvent evaporation times, both from cis/trans or 100% cis PTBA, show during the first dilatometric run the presence of a temperature Tp at which a packing effect occurs. Therefore, first dilatometric curves show two linear tracts, the latter representing the sum of thermal dilation and simultaneous packing induced by molecular motions leading to a better packing. Following measurements show a linear increase of the specific volume. The packing process is also revealed by differential scanning calorimetry as a broad endotherm. Δρ is the more pronounced the lower the initial density of the sample for mixed cis/trans PTBA, but, quite surprisingly, in 100% cis PTBA the trend is opposite and, in this case, denser samples undergo a more relevant packing. A tentative explanation is inferred on the basis of a conformational model recently proposed. An improvement of the chain packing is responsible of the fast ageing process of this polymer, as suggested by a preliminary X-ray diffraction analysis.
    Additional Material: 5 Ill.
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