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  • 11
    Electronic Resource
    Electronic Resource
    Copolymerization of styrene and diethyl fumarate with zinc bromide. V. Electroinitiated copolymerization at high current strengths (1973)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 1867-1879 
    Details
    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
    URL: http://dx.doi.org/10.1002/pol.1973.170110809
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  • 12
    Electronic Resource
    Electronic Resource
    An electrochemical route to phenol-formaldehyde precursors (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1193-1202 
    Details
    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
    URL: http://dx.doi.org/10.1002/pol.1974.170120606
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  • 13
    Electronic Resource
    Electronic Resource
    Transient decay studies of photophysical processes in aromatic polymers. V. Temperature dependence of excimer formation and dissociation in copolymers of 1-vinylnaphthalene and methyl methacrylate (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 411-421 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The use of pulsed laser excitation upon a series of 1-vinylnaphthalene/methyl methacrylate co-polymers in which the intramolecular chromophore concentration is varied over a wide composition range has allowed the individual rate constants governing intramolecular excimer formation to be determined at various temperatures between 205 and 295 K. Triple exponential functions are necessary for adequate description of the photophysical kinetics over the entire temperature range. It is proposed that the kinetic and temperature behavior is consistent with a kinetic scheme involving two kinetically distinct monomeric species and an excimer in which energy may be transferred from the second monomer M*2 to the first monomer M*1 which can interact with the excimer by a conventional migration mechanism.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200305
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  • 14
    Electronic Resource
    Electronic Resource
    Transient decay studies of photophysical process in aromatic polymers. I. Multiexponential fluorescence decays in copolymers of 1-vinylnaphthalene and methyl methacrylate (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2401-2413 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The considerable potential of high resolution time-resolved spectroscopic data for copolymer systems in elucidation of the intramolecular photophysical processes which occur in polymer systems is illustrated. Such information can not be gleaned solely from studies of homopolymers. Kinetic data and time resolved fluorescence spectra of copolymers of 1-vinylnaphthalene and methyl methacrylate indicate that conventional kinetic schemes are inappropriate for the discription of excimer formation in 1-vinylnaphthalene polymers. Evidence is presented for the presence of an emitting species in addition to the expected monomeric and excimeric forms. The nature of this third species is discussed and photophysical kinetic schemes are proposed to describe intramolecular excimer formation in such systems. Kinetic data have been derived for the principle deactivation pathways through investigation of the observed fluorescence decays upon the intrachain concentration of aromatic species.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181208
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  • 15
    Electronic Resource
    Electronic Resource
    Transient decay studies of photophysical processes in aromatic polymers. VI. Intramolecular excimer formation and dissociation in polystyrene and styrene-methyl methacrylate copolymers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1759-1770 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The time-resolved fluorescence behavior of polystyrene and a series of styrene-methyl methacrylate copolymers has been examined by using pulsed laser excitation. Although the photophysical characteristics of styrene- and naphthalene-containing polymers may be described by the same general kinetic scheme, some differences in the nature of the photophysical interactions are apparent. Umambiguous evidence for the occurrence of excimer dissociation into excited-state monomer in polymers incorporating styrene chromophores is presented.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180201001
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  • 16
    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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  • 17
    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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  • 18
    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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  • 19
    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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  • 20
    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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