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  • 1955-1959  (3)
Collection
Publisher
Year
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 20 (1956), S. 537-550 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several problems in the process of radical polymerization, e.g., the relation between the chemical structure of vinyl monomer and its chemical reactivity, the prevalence of head-to-tail configuration, the reactivity of initiator radicals, the alternation tendency in heteropolymerization, and the relative ease of coupling in several cases of homopolymerization, are treated by the theory previously proposed by the present authors, in which reactivity is represented by the magnitude of stabilization energy due to π conjugation between a monomer and a radical in the transition state. In addition, a brief discussion on the existing theories of reactivity and some applications of Hush's method to the problem of termination are presented. The agreement between results of calculation and experiment is shown to be almost statisfactory.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 26 (1957), S. 311-321 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stabilization energy due to the conjugation taking place between a monomer and an ion in the transition state is calculated by the LCAO perturbation theory, in the same way in which the reactivity in radical copolymerization has previously been treated. In terms of this stabilization energy, the reactivity ratios of several monomer pairs in ionic copolymerization are satisfactorily interpreted. It is noted that, by the present method, both the radical and ionic copolymerization can be treated in a unified manner, whereas it is difficult in existing empirical methods. The positions of attack in polymer ions as well as in monomers, which are predicted by the frontier electron densities, are shown to agree well with experimental facts. The relative reactivities of vinyl monomers in ionic homopolymerization is also explained successfully by the magnitude of the localization energy computed by the LCAO method.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 39 (1959), S. 487-492 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical interpretation of the mechanism of stereospecific cationic polymerization in a homogeneous system at low temperature is given. The existance of a counterion in the vicinity of a charged carbon atom of a growing polymer ion is assumed and a repulsive interaction is considered to be between the substituent of the attacking monomer and that of the polymer. The most probable geometrical conformation of a monomer and a polymer ion in the transition state is determined by the magnitude of stabilization due to the overlap between atomic orbitals of ion and monomer. Our experimental results can be explained satisfactorily by this mechanism.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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