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  • Wiley-Blackwell  (2)
  • Blackwell Publishers Inc.
  • International Union of Crystallography
  • Springer Nature
  • 1970-1974  (2)
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Year
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2463-2487 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical copolymerization of butyl methacrylate with 2,3-dimethylbutadiene in the presence of Al(C2H5)2Cl or ZnCl2 results in alternating copolymers. The nature of active centers and the mechanism of polymerization in these systems have been studied by means of ESR measurements in combination with calorimetry at low temperatures. The active centers are monoradicals propagating by alternative addition of single monomer molecules; thus the reaction can be described in terms of a conventional kinetic scheme of radical additional polymerization. Participation of binary donor - acceptor complexes of the monomers in the reaction has not been confirmed. Similar conclusions have been drawn for the other alternating system studied, maleic anhydride-2,3-dimethylbutadiene. The feasibility of formation of alternating copolymers in the studied systems by the conventional mechanism of binary radical copolymerization has been confirmed by qualitative quantum-chemical treatment of the propagation reactions with due account to the donor-acceptor interactions in the transition state.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 9 (1971), S. 833-854 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical copolymerization of methyl methacrylate (MMA, M1) with various monomers has been studied in presence of modifiers, i.e., complexing agents (CA): ZnCl2, AlCl3, AlBr3, Al(C2H5)2Cl, forming coordinate complexes with ester group of the monomer and of the propagating radical. The comonomers of the first group form complexes of similar structure and stability as MMA, methyl acrylate, or butyl acrylate. The comonomers of the second group do not form complexes with the modifiers (vinylidene chloride, 2,6-dichlorostyrene, p-chlorostyrene, styrene). For all systems studied the copolymer composition follows the Mayo-Lewis equation. In the first group of the systems the effective reactivity ratios (r1, r2) approach unity with increase of the CA molar content (r1 = r2 ≃ 1 at [(CA)/MMA] + [MA] ≥ 0,3) In the second group of the systems the values of r1 either increase to a limit value (at [CA]/[MMA] ≥ 0.3), pass through maximum, or decrease to a limiting value with the CA molar content. The values of r2 decrease in all systems. The character of variation of r1 and r2 has been explained in terms of effects of the CA's on reactivity of MMA and PMMA radical. The equations for the copolymer compositions in these systems have been derived.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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