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  • 1955-1959  (10)
  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 63 (1959), S. 1940-1948 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 77 (1955), S. 3265-3268 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 40 (1959), S. 499-510 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The β-carbon localization energies Lβ+ and Lβ- for electrophilic and nucleophilic additions to vinyl compounds, respectively, were calculated according to the simple LCAO MO method and were compared with the experimental results so far reported on the ionic polymerizability of these compounds. The larger the cationic (or anionic) polymerizability of a monomer, the smaller was the value of Lβ+ (or Lβ-) for it. It was also verified in terms of localization energies that the vinyl monomers which are not amenable to radical polymerization tend to polymerize more easily by either of the two ionic mechanisms. By applying Jaffé's first order perturbation method, Lβ+ and Lβ- of each monomer were expressed as functions of the Coulomb integral parameters of the heteroatoms involved. Although the values of Lβ+ and Lβ- did not agree perfectly with the direct results obtained from secular equations, the discrepancy in both cases could be minimized when each of the Coulomb integral parameters employed in the perturbation approximation was empirically taken as 0.6 times as large as that used in the direct variation calculation. The procedure was successfully applied to the interpretation of the substituent effect on the cationic polymerizability of styrene.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 40 (1959), S. 487-497 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: According to the simple LCAO MO method, the π-electron localization energies on the β-carbon of several vinyl monomers (Lβ) and on the α-carbon of monomer radicals (Lα′) were calculated. Comparison of the calculated values of Lβ and Lα′ with the experimental results so far reported for radical reactivity of vinyl compounds showed (1) that a linear relationship holds between Lβ and the logarithm of methyl affinity, (2) that the smaller the value of Lα′ the larger is the chain termination constant, and (3) that Lβ and Lα′ are parallel, respectively, to the values of Q and P in Price-Alfrey's notation. These points imply that Lβ and Lα′ would be satisfactory indices for the radical reactivities of vinyl monomers and monomer radicals, respectively. It was also suggested that, in radical copolymerization, the localization energy difference between two monomers, as well as the difference in the π-conjugation energies with attacking radicals in the transition state of the propagation step, would contribute to the determination of the monomer reactivity ratios.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Diäthylcadmium löst in Gegenwart einiger Sauerstoffverbindungen die Vinylpolymerisation aus. Die Copolymerisation von Styrol und Methacrylsäuremethylester mit Diäthylcadmium liefert Copolymere mit den gleichen Einbauverhältnissen wie im Fall einertypischen Radikalkettencopolymerisation. Dieses Ergebnis bedeutet, daß die Wachstumsreaktion der hier beschriebenen Polymerisation nach einem Radikalmechanismus verläuft.Benzoehinon und Hydrochinon haben, wenn sie in geeigneten Mengen verwendet werden, eine beschleunigende Wirkung auf die Polymerisation. Ein möglicher Mechanismus für die Wirkung des Chinons und Hydrochinons wird aufgezeigt. Vergleichende Polymerisationsversuche mit den Äthylderivaten des Zink, Aluminium und Antimon zeigen, daß auch sie nach einem Radikalmechanismus verlaufen.Schließlich wird, in Analogie zum ZIEGLER-Katalysator, das Verhalten eines Gemisches von Diäthylcadmium und Titantetrachlorid im Molverhältnis 4 : 1 an verschiedenen Vinylmonomeren untersucht.
    Notes: Diethylcadmium induces vinyl polymerization in the presence of some oxygen compounds. Copolymerization between styrene and methyl methacrylate using diethylcadmium resulted in the formation of copolymers having the same composition as those from the typical radical copolymerization. These results suggest at least the propagation stage of the present polymerization to proceed according to the radical mechanism. However, benzoquinone or hydroquinone in an appropriate quantity was found to be an effective co-catalyst toward this polymerization. A possible mechanism for this is advanced. Comparative study of polymerizations with ethyl derivatives of zinc, aluminium and antimony has revealed that these polymerizations are also radical type in character. Finally, in connection with the ZIEGLER-catalyst, the behavior of the mixture of diethylcadmium and titanium tetrachloride (4 : 1 in mole ratio) toward various vinyl monomers is exatnined.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 36 (1959), S. 407-420 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Binary mixtures of amines and alkyl (or aralkyl) chlorides were used as the initiators for the polymerizations of several acrylic monomers and styrene. A parallelism was found between the catalytic actions of the mixtures and their quaternary salt formations. Comparative experiments showed that the preformed quaternary ammonium salts were superior catalysts to the corresponding binary mixtures. The inhibitory action of hydroquinone on the polymerization and the composition of a copolymer of methyl methacrylate and styrene suggested that the vinyl polymerizations initiated by ammonium salts were free radical reactions. An equimolar mixture of benzyl chloride and N,N-dimethylaniline gave, when refluxed for ten hours, N-methyl-N-benzylaniline and N,N-dibenzylaniline. Thus, it was suggested that the binary mixtures would first form the ammonium salts, followed by decomposition to give a radical which initiated the radical polymerizations of vinyl monomers.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 40 (1959), S. 511-519 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polarographic half-wave reduction potentials E1/2 of several vinyl (including vinylidene) monomers were measured and were discussed on the basis of the molecular orbital theory. The current-voltage curves were determined in a 0.05 M solution of tetra-n-butylammonium iodide in the mixture of dioxane and water (3:1 by volume). The values of E1/2 were read against the saturated calomel electrode. It was found that E1/2 is correlated with xiv by E1/2 = 2.33 xiv-0.80, where xiv stands for the root of the MO secular equation for the π-electronic system of the vinyl monomer corresponding to the lowest vacant level. Some of the monomers could not be reduced in the range of the applied potential less negative than - 3.0 volt vs. SCE, which was reasonably explained by their relatively large values of -xiv. It was suggested that the polarographic reducibility of vinyl monomers is roughly parallel to their anionic polymerizability. Furthermore, the lowest vacant π-orbital energies of vinyl compounds were calculated according to the first order perturbation method. The results obtained thus were in good accordance with those calculated directly from the secular equations. It was also shown that the first ionization potentials of vinyl compounds were roughly related to their highest occupied π-electronic energies.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 15 (1955), S. 594-595 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 28 (1958), S. 234-235 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 31 (1958), S. 247-249 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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