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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 169 (1973), S. 177-189 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die elektroinitiierte Polymerisation von N-Vinylcarbazol (VCZ) wurde in Aceton bei 25°C mit Zinkbromid als Katalysator unter Verwendung von Platinelektroden eingehend untersucht. Die Polymerisationsgeschwindigkeit erwies sich als direkt abhängig von der Stromstärke, der Zinkbromid-Konzentration und dem anfänglichen Wassergehalt des Solvens.Die Molekulargewichte der entstandenen Polymeren (1000-6000) sind unabhängig von der Stromstärke, der Zinkbromid-Konzentration und dem Umsetzungsgrad des Monomeren zum Polymeren, werden jedoch beeinflußt durch Wasser, die Monomerkonzentration und das Elektrodenmaterial. Die chemische Zusammensetzung der Polymeren ändert sich nicht mit der Stromstärke, der Zinkbromid-Konzentration, dem Umsetzungsgrad und dem Elektrodenmaterial. Sie ändert sich jedoch ein wenig mit dem Wassergehalt des Acetons.
    Notes: The electroinitiated polymerization of N-vinylcarbazole (VCZ) in acetone solvent at 25°C with zinc bromide, as catalyst, and platinum electrodes was investigated in detail. The polymerization rate was found to be directly dependent on current strength, zinc bromide concentration and the initial water content of the solvent.The molecular weights of the formed polymers (1000-6000) are independent of current strength, zinc bromide concentration and degree of conversion of monomer to polymer, but are affected by water, monomer concentration, and by the type of electrodes used. The chemical composition of the polymer is invariant with current strength, zinc bromide concentration, degree of conversion, and electrode material but does vary slightly with the water content of acetone.
    Additional Material: 2 Ill.
    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 11 (1973), S. 1867-1879 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electroinitiated copolymerization of styrene and diethyl fumarate in methanol solvent with zinc bromide as electrolyte has been investigated at high current strengths (200-500 mA). Unlike the copolymerization behavior observed at lower current strengths (〈 200 mA), it is found that the cathodically produced copolymers deviate from a 1:1 composition and show a significant deficiency in styrene. The copolymer products can be separated into two well-defined fractions: a toluene-soluble fraction (normal copolymer) and a toluene-insoluble one (styrene-deficient copolymer). These deviations in copolymer composition from a 1:1 monomer ratio are attributed to the occurrence of cathodically induced electroreductive hydrolysis side reactions with diethyl fumarate leading to the formation of carboxylate or acid salt species. Reaction of these hydrolyzed species with diethyl fumarate results in the formation of fumarate-rich copolymers.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1193-1202 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: With the aid of VPC and NMR, the electroinitiated polymerization of phenol or p-tert-butyl phenol with formaldehyde in the presence of basic electrolytes has been investigated over a range of current densities. Results from an electroinitiation study were contrasted with base-catalyzed thermal polymerizations and, except for yield, found to be essentially invariant. GPC of the electroinitiated and thermally polymerized resins indicates similar results with low molecular weight species of relatively narrow molecular weight distribution being the principal products. An electroinitiation mechanism, in agreement with the mechanism for base-catalyzed thermal polymerization is proposed to describe these experimental results.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 3267-3277 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electroinitiated preparation of equimolar copolymers of styrene and diethyl fumarate is described. The reaction medium consisted of these monomers dissolved in a methanol-zinc bromide solution. Rates of polymerization increased with increasing applied current and the copolymer yield increased linearly with the total number of Faradays transferred. The copolymer composition is 1:1 and is essentially invariant with the degree of conversion (〈15%), electroinitiation rate, and monomer feed ratios. A reaction mechanism involving donor-acceptor complexes and electroinitiated excitation of these complexes at the electrode is postulated.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 3253-3265 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A comparative analysis of photoinitiation and electroinitiation can help elucidate initiation processes in donor-acceptor charge-transfer copolymerization. The technique has been applied to the zinc bromide-catalyzed copolymerization of styrene and diethyl fumarate in methanol. The photocopolymer product was analyzed by GPC, NMR, and elemental analysis. The results showed that 1:1 copolymers were formed initially, but changes occurred in both the kinetics and products after the early stages of the reaction. Significant correlations found between the two initiation methods included the initial kinetic order with respect to the initiating process and the effect on product yield of equivalent increases in total initiation energy. The limiting value of zinc bromide for both initiation methods was found to be the same. The data obtained support the contention that the copolymerization proceeds through a donor-acceptor process and that photoactivation of the preformed complex, inducing electron transfer, is a likely initiation process.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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