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  • 1
    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: Der thermische Abbau von Poly-N-vinyl-carbazol (PVK) wurde mittels „flash“-Pyrolyse, kontrollierter Pyrolyse und dynamisch-thermogravimetrischer Analyse untersucht. Die Analyse der Abbauprodukte erfolgte über Gas-Flüssig-Chromatographie sowie Massenspektrometrie als Trennungs- und Identifizierungsverfahren. Das untersuchte PVK wurde durch radikalische Polymerisation in Benzol mit AIBN als Katalysator dargestellt.Aus den Versuchsergebnissen ergibt sich, daß PVK fast vollkommen über einen stufenweisen „unzipping“ Mechanismus in das Monomere zerfällt. Die Zusammensetzung der Pyrolysate ermöglicht eine Formulierung des Abbaumechanismus des Polymeren. Mit Hilfe des Verfahrens der multiplen Aufheizgeschwindigkeiten wurde die Kinetik des thermischen Abbaus untersucht. Die Bruttoaktivierungsenergie der Depolymerisation wurde zu 40 kcal/mol gemessen und für die Reaktionsordnung wurde ungefähŕ 1 gefunden.Es werden einige thermodynamische Betrachtungen aufgeführt, um den Wert der Aktivierungsenergie des gesamten Prozesses zu erklären. Es wird ein Mechanismus vorgeschlagen.
    Notes: The thermal degradation of poly-N-vinyl-carbazol (PVK) has been studied using flash pyrolysis, controlled pyrolysis and programmed thermogravimetry analysis techniques. The degradation products have been analyzed using gas-liquid chromatography and mass spectrometry as separation and characterization techniques. The examined PVK has been prepared by free radical polymerization in benzene using AIBN as catalyst.It is shown from experimental results that PVK breaks up almost completely into the monomer through a stepwise unzipping mechanism. The composition of the pyrolyzate allows to propose a mechanism for the polymer degradation. Thermal degradation rates have been analyzed using a multiple heating rates procedure. A value of 40 kcal/mol has been found for the overall activation energy of depolymerization and a value approximately equal to one for the order of reaction.Some thermodynamic considerations have been made in order to explain the value of the activation energy of the whole process. A mechanism is suggested.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(N-aryl maleimide)s of characteristic structures have been synthesized and some of their physical properties studied. These include N-(2-fluoro phenyl), N-(3-fluoro phenyl), N-(4-fluoro phenyl), N-(2,4-difluoro phenyl), N-(2,5-difluoro phenyl), N-(2,3,5,6-tetrafluoro phenyl), and N-(pentafluoro phenyl). The polymerization of N-(fluoro phenyl) maleimides by free-radical initiation in bulk or in solution and by anionic catalyst have been studied to compare the characteristics of polymerization by γ-ray irradiation with that by free-radical initiation. The polymers were characterized by elemental analysis, intrinsic viscosity, spectroscopy (IR and NMR), programmed thermogravimetric analysis, and x-ray diffraction. Spectra of polymers prepared by radiation and anionic polymerization were nearly identical with those of polymers prepared by free-radical polymerization initiated by AIBN in bulk or in solution and by the self-initiated thermal polymerization. A variety of reaction conditions were tried, but all attempts to change the molecular structure of the polymers were unsuccessful. Rates of thermal degradation for poly[N-(fluoro phenyl) maleimide]s have been analyzed by using a multiple-heating-rate procedure. Overall activation energy, order of reaction, and frequency factor have been evaluated. On the basis of the comparison between the overall activation energy of the thermal degradation of poly[N-(fluoro phenyl) maleimide]s and NMR spectra of their corresponding monomers, it can be concluded that the 1H shifts due to ethylenic protons are so characteristic in sign and magnitude as to be useful in thermal stability elucidation. Some qualitative explanations were given on the stability of these polymers as affected by the type and size of the substituent. The x-ray diffractograms of all samples show two rather broad peaks indicative of noncrystalline structures. The location of the peaks does not depend upon preparation conditions and temperature. Poly(N-maleimide)s of fluoroanilines have not been hitherto described.
    Additional Material: 6 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 25 (1987), S. 1099-1111 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric relaxation behavior of a nonaligned and an aligned liquid-crystalline (LC) polymer are reported for the ranges 10-3.5 to 105 Hz and 274-363 K. Multiple processes (δ and α) are observed that follow a Vogel equation for the temperature dependence related to the apparent glass transition temperature. The occurrence of these processes and the variation in their relaxation strengths as sample alignment is changed is interpreted in terms of a molecular theory for the dielectric behavior of a LC polymer that involves the director order parameter Sd, the mesophase order parameter S, the dipole moment components of the mesogenic head groups, and their associated relaxation functions.
    Additional Material: 8 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2197-2207 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The heat of melting, the melting temperature Tm, and the sub-Tg transition temperature have been studied from -120°C to above Tm in a series of 11 poly[N-(10-n-alkyloxycarbonyl-n-decyl)]-maleimides (PEMI). Side-chains from ethyl to n-docosyl with n even have been included. The contribution to the heat of melting per methylene group shows that the hexagonal paraffin crystal modification is present in these poly(N-maleimides), in agreement with x-ray data for the same compounds. The enthalpy data show that only a part of the outer methylene groups are present in the crystalline aggregates. Furthermore, DSC traces exhibit a typical distribution of crystallite sizes, which become narrower as the side-chains become longer. The critical chain length needed to form a stable nucleus includes nine methylene groups in the outer part of the n-alkyl side-chain. The influence of the side-chain length and crystallinity on the γ-transition temperature of these polymers was also investigated. In the range where these polymers are essentially amorphous the sub-Tg transition temperature decreases continuously as the number of methylene groups in the side-chain increases. This transition is attributed to internal motion within the external side-group without any interaction with the main chain. This is presumably made possibly by the partial rotation of the oxycarbonyl group. We suggest that this transition is similar to the well known γ transition which has been attributed to various segmental motions in all ethylene copolymers and in all homopolymers containing a determined number of—CH2—units in the main-chain or in the side-chain. Estimates based on the chemical structure, yield a value for the γ transition of —CH2—similar to that measured by other methods in polyethylene and related materials.
    Additional Material: 6 Ill.
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