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  • 1
    Electronic Resource
    Electronic Resource
    Kinetics of free radical polymerization of ortho- and para-alkylaryl esters of methacrylic acid (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1637-1646 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of free radical polymerization in bulk of alkylphenyl methacrylates with ethyl-,isopropyl and tert-butyl groups in the ortho- and para-positions of the phenyl ring with dilauroyl peroxide as initiator were investigated. For comparison and completion of the investigation, ortho- and para-tolyl methacrylates were reinvestigated with this particular initiator. Most of the results obtained do not obey classical kinetics of polymerization. The results were treated according to the concept of degradative chain transfer and it was concluded that this mechanism is responsible for the non-ideality. The ortho-substitution with increasing size of the substituents decreases the overall rate of polymerization and strengthens chain transfer to monomer.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850813
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Correlation analysis of kinetic parameters of the free radical polymerization of alkylphenyl methacrylates (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 861-869 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Data from previous articles on the initial polymerization rates of a series of monoalkyl substituted phenyl methacrylates were found to depend strongly on the size and position of the monoalkyl substituent in the phenyl ring. In order to investigate the possibility of correlation of all the rate data obtained, all those for phenyl methacrylate and ten other alkylphenyl substituted methacrylate monomers were fitted into empirical linear free energy relationships (LFER). Assuming steady-state kinetics and separating out the initiator decomposition contribution to the initial overall rate Rp, it was demonstrated that k′ = kp/kt½ can be successfully correlated with LFER equations containing predominantly steric parameters. The steric influence is more pronounced in the o- than in the p-substitution, due to the proximity of the o-substituent to the reaction propagation site. The results are corroborated by the existence of an isokinetic relationship of ΔH
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550241004
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    Paper (German National Licenses)
    Fulltext
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