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  • 1965-1969  (3)
  • Physics  (3)
  • Electrolytes
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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 7 (1969), S. 1665-1674 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electron spin resonance spectrum of gamma-irradiated octadecyl methacrylate (m.p. ≈ 12°C.) was due to a mixture of three radicals formed by (1) loss of a hydrogen atom from the paraffin chain, (2) addition of a hydrogen atom to the double bond, and (3) addition of a monomer molecule to radicals formed by (1) or (2). On warming monomer added to radicals (1) and (2) between -170 and -50°C., and above -50°C. the spectrum was solely due to propagating methacrylate radicals. The total radical concentration decreased slightly at -150°C. and was then constant up to -30°C. A marked decrease in radical concentration occurred from -30 to +12°C., it took place rapidly and reached an equilibrium value after each successive increase in temperature. Differential thermal analysis indicated a solid - solid phase change at -30°C. When the sample was kept at 0°C. there was no further decrease in radical concentration even with 50% conversion to polymer. With 2% added chloranil the (chloranil)- was observed to be of about the same concentration as methacrylate radicals. The initial total radical concentration was lower and decreased to zero by 0°C. on warming. No polymer was obtained.
    Additional Material: 6 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 6 (1968), S. 1073-1086 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The postirradiation polymerization of the crystalline, anhydrous, monohydrate, and dihydrate forms of zinc methacrylate was studied. The anhydrous salt polymerized readily in the temperature range 50-150°C., the monohydrate did not polymerize at all, and the dihydrate polymerized at about 100°C. Aging of the anhydrous salts greatly affected the rate of polymerization; this was shown to be due mainly to the formation of peroxides by reaction with air. Polymerization could be initiated thermally, without irradiation, in monomer which had been aged in contact with air, apparently by decomposition of the peroxides. The rate of the postirradiation polymerization was increased when air was present during irradiation and decreased when air was present during polymerization. The rate of polymerization increased with temperature, corresponding to an apparent activation energy of 10 kcal./mole. The dihydrate lost one molecule of water rapidly under vacuum at 20°C. and slowly on heating at 50°C. in a sealed vessel, forming a crystalline monohydrate. Slow thermal polymerization and rapid postirradiation polymerization occurred at 100°C. without the formation of any monohydrate, indicating that the polymerization was concurrent with the phase change.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 7 (1969), S. 1657-1664 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Octadecyl methacrylate (mpc ≈ 12°C.) polymerized readily in the solid state in the temperature range -30 to +12°C. after gamma irradiation at -196°C. The initial rate of polymerization and the “limiting” conversion increased with radiation dose and temperature. The temperature dependence of the rate corresponded to an “apparent” activation energy of 20 kcal./mole. Difficulties were experienced with polymerization during separation of the polymer from residual monomer, but these were minimized by using low radiation doses and a hot, selective solvent. The maximum conversion achieved was 70%. The polymer was crosslinked, even at low conversions.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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