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  • 1
    Digitale Medien
    Digitale Medien
    Temperature dependence of the photochemistry of aryl alkyl ketones (1983)
    s.l. : American Chemical Society
    Journal of the American Chemical Society 105 (1983), S. 1856-1860 
    Details
    ISSN: 1520-5126
    Quelle: ACS Legacy Archives
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1021/ja00345a030
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  • 2
    Digitale Medien
    Digitale Medien
    Reactions of tert-butoxy radicals with vinyl monomers (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 1709-1717 
    Details
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Tert-butoxy radicals generated in the photolysis of di-tert-butyl peroxide in benzene at 25°C react with vinyl monomers by double-bond addition and, in most cases, also by competitive hydrogen abstraction. The rate constant for the double-bond addition changes by a factor of 17 between isoprene, which shows the highest reactivity, and the methacrylate derivatives, which are the least reactive of the monomers considered. The fraction of tert-butoxy radicals that react by hydrogen abstraction varies considerably with the monomer structure, ranging from 0.9 (cyclohexyl methacrylate) to less than 0.05 (styrene and conjugated diolefins). In the methacrylate derivatives, most of the hydrogen abstraction takes place, not in the α-methyl group, but in the alkyl chain.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/pol.1978.170160722
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  • 3
    Digitale Medien
    Digitale Medien
    Polymerization photoinitiated by carbonyl compounds. IV. α-diketones and α-substituted alkanones (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 73-78 
    Details
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The photoinitiation efficiency of the free-radical polymerization of methyl methacrylate and styrene by several carbonly compounds has been determined. The compounds considered were α-substituted ketones and α-dicarbonyl compounds. For the ketones, the initiation efficiency employing methyl methacrylate depends on the α substitution; the values obtained change from less than 10-3 (acetone) to 0.65 (3-hydroxy-3-methyl-2-butanone). All ketones are more efficient towards methyl methacrylate than styrene. This result can be explained in terms of triplet quenching by the last monomer. The results obtained employing α-dicarbonyl compounds do not conform to a simple pattern. In particular, benzil shows a considerably larger efficiency towards styrene than for methyl methacrylate. Since benzil is efficiently quenched by styrene, the initiation must involve the interaction of an excited benzil molecule and the monomer.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/pol.1982.170200108
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  • 4
    Digitale Medien
    Digitale Medien
    Reactivity of amines toward tert-butoxy radicals: Effect of solvent and amine structure (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 119-123 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reactivity of amines towards tert-butoxy radicals depends upon the amine ionization potential and the solvent, indicating that polar structures contribute to the reactivity of these compounds. Nevertheless, the dependence with the amine potential is smaller than the one obtained for the quenching of carbonyl excited states by amines and other factors as the strength of the broken hydrogen bond and steric hindrance are also significant in determining the rate of the process.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550130203
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  • 5
    Digitale Medien
    Digitale Medien
    On the reactivity of diethyl hydroxyl amine toward free radicals (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 677-686 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Diethyl hydroxyl amine is an efficient trap for alkyl, alkoxy, and peroxy radicals. The specific rate constant for the reaction of ethyl radicals (gas phase, 25°C), tert-butoxy radicals (benzene solution, 115°C), and poly (peroxystyryl) peroxy radicals (styrene solution, 50°C) were evaluated as 7.2 × 105, 7.7 × 107, and 2.9 × 105 M-1·sec-1, respectively. Several possible secondary reactions of the nitroxide radicals are discussed.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550100704
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  • 6
    Digitale Medien
    Digitale Medien
    Erratum (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1105-1105 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550131010
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  • 7
    Digitale Medien
    Digitale Medien
    On the reactivity of amines toward tert-butoxy radicals (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 653-656 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550100611
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  • 8
    Digitale Medien
    Digitale Medien
    Photopolymerization of methyl methacrylate sensitized by aliphatic ketones (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 19-26 
    Details
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The polymerization of methyl methacrylate photosensitized by several alkyl ketones has been investigated. It was found that alkyl ketones can induce the free radical polymerization of the monomer with an efficiency that increases when the triplet lifetime decreases. For ketones of similar triplet lifetime those decomposing predominantly by a type I photocleavage show greater initiation efficiencies than those that react by a type II mechanism. The results obtained show that quenching of the excited ketones by the monomer does not induce polymerization. For ketones bearing γ-hydrogens the initiation is due to the 1,4-biradical produced by intramolecular hydrogen abstraction.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/pol.1979.170170103
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  • 9
    Digitale Medien
    Digitale Medien
    Polymerization photosensitized by carbonyl compounds (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 2791-2803 
    Details
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The polymerization of methyl methacrylate and styrene photosensitized by acetone, aldehydes, ethyl pyruvate, 2,3-butanedione, and 2,3-pentanedione has been investigated and the effect of several additives (carbon tetrachloride, cumene, diethyl amine, triethyl amine, 2-pentanol, and tetrahydrofuran) on initiation efficiency has been evaluated. The initiation efficiency of a given system depends on several factors, the most important of which are the relative rates of quenching by the monomers and the additives and type of product obtained.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/pol.1979.170170916
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  • 10
    Digitale Medien
    Digitale Medien
    2,4-Dimethyl-3-pentanone-sensitized photopolymerization of vinyl monomers (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1645-1653 
    Details
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The initiation quantum yield in the bulk photopolymerization of vinyl monomers sensitized by 2,4-dimethyl-3-pentanone has been measured for several monomers. The results obtained were interpreted in terms of a mechanism that considers singlet and triplet photocleavage of the ketone, competing with the quenching by the monomer. The quenching process does not lead to free radicals that can initiate the polymerization.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/pol.1979.170170608
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