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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3257-3268 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(methyl methacrylate) free of initiators was synthesized by γ-irradiation and cast into transparent films. The samples were investigated by ns pulse radiolysis at various temperatures, and by ESR spectroscopy after γ irradiation at 77°K. Short-lived transients with optical absorptions at 440 and 725 nm were observed. The 440 nm absorption has been ascribed to the cation and the 725 nm absorption (εG = 3000 M-1 cm-1 (100 eV)-1, τ1/2 = 190 ns at -13°C, Ea = 6.5 kcal/mol) to the anion. These assignments are based on ESR data of samples of poly(methyl methacrylate) and pivalic acid methyl ester deuterated at the ester deuterated at the ester and α-methyl groups, respectively, and subjected to thermal annealing and photobleaching. The anion decomposes on photobleaching by loss of the ester ·CH3 radical, and the cation is proposed to decay by loss of the ·CH3 radical from the α-methyl group. The thermal decay of the anion is discussed.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 29 (1984), S. 3401-3408 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Mechanochemical polymerization of ethylene was found to be induced by fracture of γ-alumina under quite low pressure and room temperature. The factors to control the polymerization yield, for example, calcination temperature of the alumina, spin concentration after ball milling, milling time, and changes of acidity before and after the fracture, were investigated in order to know the polymerization mechanism. It was found that the polymerization yield did correlate not with the spin concentration responsible to paramagnetic species produced by the fracture, but the calcination temperature of the γ-alumina and the milling time. The resultant polymeric material on the fractured alumina was extracted alumina was extracted with solvents, and the fraction extracted with petroleum ether was characterized using GC and GC mass spectrometer. The results indicated that odd-numbered linear hydrocarbons were produced, although the major products of this polymerization were even-numbered. It is concluded from the accumulated experimental results that a carbonium ion mechanism rather than radical mechanism is probable for the mechanochemical polymerization induced by fracture of γ-alumina.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 29 (1984), S. 3445-3455 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Gamma alumina, γ-Al2O3, was fractured in an atmosphere of acetylene monomer at room temperature to test whether they would be polymerized by mechanochemistry method on the surface of the alumina. The experimental results were obtained by serveral different methods, including CP-MAS 13C-NMR, ESR, pressure drop measurements of the monomer, optical absorption spectroscopy, and solvancy. The results proved the mechanochemical polymerization of acetylene monomer on surfaces of the fractured alumina. Several other combinations of either silica and acetylene monomer or polymers and acetylene monomer were tested for mechanochemical polymerization. This process proceeded with less efficiency in the silica system but no mechanochemical polymerization of acetylene was found in the combinations of the polymers and acetylene monomer.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 26 (1988), S. 2725-2736 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The vinyl monomers methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, and β-methylstyrene were dissolved in CF3CCl3, x-irradiated at 4 or 77 K, and investigated by ESR spectroscopy. The molecular cation of methyl acrylate has no resolved hyperfine structure, indicating that the unpaired electron is localized on the carbonyl oxygen. Evidence that a two-stage photoinduced reaction gives rise to a propagating radical was obtained. Propagating radicals were observed also with methyl methacrylate, acrylic acid, and methacrylic acid as solutes. The positive ion of β-methylstyrene has been prepared and characterized. The experimental data have been compared with molecular orbital calculations at different levels of approximation.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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