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  • 1975-1979  (12)
  • 1970-1974  (1)
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Year
  • 1
    Electronic Resource
    Electronic Resource
    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
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170170103
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  • 2
    Electronic Resource
    Electronic Resource
    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
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170170916
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  • 3
    Electronic Resource
    Electronic Resource
    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
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170170608
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  • 4
    Electronic Resource
    Electronic Resource
    Polymerization initiated by triethylborane-peroxide mixtures (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 8 (1970), S. 515-518 
    Details
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1970.110080709
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  • 5
    Electronic Resource
    Electronic Resource
    Addition of methoxy radicals to olefins (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 625-631 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of methoxy radicals to several olefins has been studied by a competitive method at 127°C in gas phase. The thermal decomposition of dimethyl peroxide was used as methoxy radical source. The rate of addition to the double bond was measured relative to the oxidation of carbon monoxide. For the addition to ethylene it was obtained that \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{{\rm add}} = \left({3.7 \pm 0.8} \right) \times 10^4 M^{ - 1} \cdot {\rm s}^{{\rm - 1}} $$\end{document} This rate constant is similar to the one shown by methyl radicals under similar conditions. From the relative rate of addition to several chlorinated and fluorinated olefins it can be concluded that methoxy radicals show very little “electrophilic” character.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070411
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  • 6
    Electronic Resource
    Electronic Resource
    Methyl methactylate polymerization in the presence of iodine (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 14 (1976), S. 499-502 
    Details
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.130140811
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  • 7
    Electronic Resource
    Electronic Resource
    Autooxidation of diethyl hydroxylamine (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1167-1182 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The autooxidation of diethyl hydroxylamine (DEHA) has been studied both in solution and in the gas phase between 0° and 60°C. The results obtained are interpreted in terms of a nonchain free radical mechanism in which reaction (1) is the rate-determining step. This reaction is followed by the reaction of HO2 radicals with DEHA to give hydrogen peroxide. The initial stoichiometry is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm 2DEHA + O}_{\rm 2} \to {\rm 2nitrone + 2H}_{\rm 2} {\rm O} $$\end{document} which implies that the hydrogen peroxide reacts with DEHA to give water and diethyl nitroxide radicals.The activation energy of reaction (1) is 16.5 ± 2 kcal/mol, leading to a dissociation energy of 69.5 ± 2 kcal for the O=H bond in DEHA.The oxidation of DEHA in the gas phase is nearly ten times slower than that observed in chlorobenzene solution under similar experimental conditions. This result is related to the stabilization of the free radicals produced by the solvent.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550101107
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  • 8
    Electronic Resource
    Electronic Resource
    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
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1978.170160722
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  • 9
    Electronic Resource
    Electronic Resource
    Methyl methacrylate polymerization in the presence of polystyrene (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 3003-3006 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1978.170161127
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  • 10
    Electronic Resource
    Electronic Resource
    High-conversion polymerization. IV. A definition of the onset of the gel effectFor Part III see ref. 8. (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1891-1900 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gel effect in free radical polymerization of vinyl monomers has been recognized as the result of the increased viscosity of the reaction solution of polymer in monomer, which causes a decrease in the rate of the termination reaction. This effect manifests itself as an increase in the rate of polymerization over that rate to be expected in its absence. Definition of the onset of the gel effect has become necessary for several purposes. Previously, it has been common to define the onset phenomenologically, i.e., in terms of the increase in the rate of polymerization. It is proposed here that the onset of the gel effect is best defined on a fundamental basis, i.e., as occurring at that conversion at which the rate of segmental diffusion of the polymeric radicals equals the rate of their translational diffusion. Experimental evidence is presented that shows that the small minima predicted by this definition do exist for both rates and degrees of polymerization. Measurements of the viscosities of solutions of polymers in their monomers suggest that the polymer concentrations at which the “chain-entanglement” phenomena are observed are the same as those for the onset of the gel effect for styrene, methyl methacrylate, and butyl methacrylate.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170170701
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