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  • 1
    Electronic Resource
    Electronic Resource
    The photo- and electroinitiated polymerization of N-vinyl phthalimide (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1153-1161 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To elucidate mechanisms in electroinitiated polymerization reactions a comparison was conducted between ultraviolet (UV) photoinitiation and electroinitiation of N-vinyl phthalimide with zinc chloride as a catalyst. Both methods give low yields of a complex polymer product. A detailed analysis, infrared (IR), gel permeation chromatography (GPC), elemental, and molecular weight, conducted on the polymeric products, indicated that phthalimide ring opening was occurring and that complex mixtures of poly(N-vinyl phthalimide) derivatives were formed. Both initiation methods gave comparable results, which further indicated mechanistic similarity between photo-and electroinitiation in these donor-acceptor charge transfer polymerizations.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170170419
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Electroinitiated polymerization of 2-vinylnaphthalene (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1563-1571 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As part of a program to extend the range of donor-acceptor-initiated polymerization processes, the electroinitiation of 2-vinylnaphthalene in a zinc chloride-sulfolane solution has been studied. Good conversion yields of well-characterized (NMR, IR, GPC, elemental analysis) poly(vinylnaphthalene) were obtained with the process showing several mechanistic similarities to other donor-acceptor salt electropolymerization systems.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170150704
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  • 3
    Electronic Resource
    Electronic Resource
    Electrochemically initiated polymerization of styrene with tetraalkyl and -aryl group VA halide support electrolytes (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1555-1562 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrochemically initiated polymerization of styrene in methylene chloride solvent with the use of platinum electrodes and tetraalkyl and -aryl group VA halides (i.e., quaternary ammonium, phosphonium, and arsonium compounds) as electrolyte has been investigated. The order of reactivity of the electrolytes with respect to polymerization rate and initiation efficiency was found to be: arsonium 〉 phosphonium 〉 ammonium. Mechanisms involving the electroreduction of the group VA quaternary halides to species capable of electroinitiating polymerization are postulated. The observed losses in solution conductivities during polymerization with the quaternary phosphonium and arsonium electrolytes indicate possible interaction between the initiating radical-ionic species and the supporting electrolyte. In an attempt to further elucidate the mechanism of initiation in these systems, a separate series of experiments, employing the nonpolymerizing monomer, 1,1-diphenylethylene, has been carried out.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170150703
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  • 4
    Electronic Resource
    Electronic Resource
    Photoinitiation and electroinitiation in the polymerization of 2-vinylnaphthalene (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2673-2684 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The zinc chloride-catalyzed polymerization of 2-vinylnaphthalene (VN) with both photoinitiation and electronitiation methods was examined. Good yields were obtained with both methods, the electroinitiated process being somewhat faster. The mechanism for polymerization initiation was investigated through a detailed comparison of the kinetics. Both initiation methods show a similar response to increasing input energy and to change in salt to monomer mole ratio. Both methods indicate formation of a ZnCl2-(2-VN)2 complex as intermediate with the formation of the species being rate-determining. These results, together with other similar investigations, are then used to deduce a mechanism that involves the formation of an electronically excited donor-acceptor complex. It is argued that in certain salt-stabilized, electron-delocalized, aromatic systems, such excitation is possible in electroinitiation.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170151112
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  • 5
    Electronic Resource
    Electronic Resource
    Electroinitiated polymerization of arylvinyl monomers (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1411-1418 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electroinitiated polymerizations of styrene, 2-vinylnaphthalene, and 9-vinylanthracene were compared in sulfolane and acetone solvents in the presence of ZnCl2. The relative orders of polymerization rates and polymerization efficiencies, in both solvents, were 9-vinylanthracene 〉 2-vinylnaphthalene 〉 styrene, with faster rates and higher efficiencies occurring in sulfolane. Data obtained from viscosity and gel permeation chromatography (GPC) studies indicate that the molecular weights of the polymers produced in these systems are extremely low, 〈5000. Chemical composition and infrared (IR) spectral data suggest that abnormal transfer reactions (possibly from solvent) may be occurring in the electroinitiated 9-vinylanthracene polymerizations. The polymerization mechanism appears to be cationic in these monomer-solvent systems with ZnCl2.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170170515
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  • 6
    Electronic Resource
    Electronic Resource
    Copolymerization of styrene and diethyl fumarate with ZnBr2. IV. Comparison between photoinitiation and electroinitiation (1972)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 3253-3265 
    Details
    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
    URL: http://dx.doi.org/10.1002/pol.1972.170101112
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  • 7
    Electronic Resource
    Electronic Resource
    Copolymerization of styrene and diethyl fumarate with zinc bromide. III. Electroinitiation at low current densities (1972)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 3267-3277 
    Details
    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
    URL: http://dx.doi.org/10.1002/pol.1972.170101113
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