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  • 1
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1843-1854 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mass polymerised poly(vinyl chloride) (PVC), subjected to annealing treatment between 85-140°C under air, nitrogen, vacuum, and hydrogen chloride environment, was found to undergo very slight decomposition in which long polyenes (with more than ten conjugated carbon-carbon double bonds) were produced. Despite the presence of these polyenes the thermal stability of the resin at 190°C remained unaltered. Resin stability was also unaffected by the atmosphere in which the resin was annealed. By contrast, urea clathrate PVC, known to be highly crystalline, decomposed 300% faster than mass PVC and generated very long polyene sequences (n ≥ 42) at 190°C. The results are discussed in terms of two possible morphological populations of polymer.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 193 (1992), S. 389-397 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal decomposition of poly(1,6-bis(N-carbazolyl)-2,4-hexadiyne) crystals, prepared by gamma radiation, was examined over a range of experimental conditions, the most important of which are temperature and crystal size. The only two significant products found were carbazole and to a lesser extent 9-methylcarbazole. Decomposition kinetics, which applied to the two observed autoacceleratory regions, was best fitted to an Avrami-Erofeyev equation with an exponent of two. The activation energy determined for the first autoacceleratory region was found to be higher than that determined for the second autoacceleratory region. A reaction mechanism is described based on stressinduced initiation, followed by either a molecular or a free-radical non-chain process. In an attempt to release stress, the polymer was observed to undergo sidegroup cleavage due to shearing of neighbouring polymer chains.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 7-21 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of gaseous neopentyl bromide to 2-methyl-2-butene, 2-methyl-1-butene, and hydrogen bromide was studied under conditions of maximal inhibition by cyclohexene over the temperature range of 389-444°C. This reaction was shown to beconsistent with a first-order homogeneous molecular process, with Arrhenius parameters of E = 247 ± 5 kJ/mol and log A (sec-1) = 14.2 ± 0.3. Examination of the uninhibited reaction showed it to be a radical process, simpler than that with neopentyl chloride, there being only one propagation step, thedissociation of the γ-radical to 1,1-dimethylcyclopropane and a bromine atom.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1271-1278 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Experimental evidence is presented for a unimolecular gas-phase Wagner-Meerwein shift in neopentyl chloride pyrolysis. In the decomposition of α,α-neopentyl chloride-d2 at 445°C, maximally inhibited by cyclohexene, the initial products were isotopically pure 2-methyl-1-butene-d2 and 2-methyl-2-butene-d1. Rearrangement, accompanied by loss of either α- or γ-hydrogen in the formation of hydrogen chloride, is consistent with an incipient ion-pair type of transition state. The cyclohexene maximally inhibited pyrolysis of neopentyl chloride was also examined over the temperature range 424-478°C and Arrhenius parameters of E, 258.7 kJ/mole and logA/sec-1, 13.78, were determined.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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