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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 17 (1984), S. 1436-1447 
    ISSN: 1520-5835
    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
    Macromolecules 5 (1972), S. 401-404 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 255 (1977), S. 726-726 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 16 (1972), S. 645-661 
    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: The kinetics and degree of polymerization of the radiation-induced polymerization of styrene were investigated at dose rates up to 3 Mrads per sec. It was found that both the polymerization rates and the molecular weights at high dose rates lie well above the values predicted by extrapolation from low dose rate studies where the mechanism is primarily free radical in nature. The evidence obtained indicates that with increasing dose rate there is an increase in the ionic contribution to the polymerization mechanism. At the highest dose rates investigated, 3 Mrads per sec, the ionic mechanism dominates while the free-radical mechanism contributes insignificantly. There was no inhibition of the polymerization of styrene by dissolved air at the higher dose rates. Investigation of the polymerization of styrene saturated with water tends to support the ionic mechanism via free cations. Investigation of equimolar solutions of styrene and methyl methacrylate further support the ionic mechanism, yielding predominately polystyrene and a small amount of 50-50 copolymer. In the intermediate dose rate range, 1000 rads per sec, there is evidence that the high dose rate free-radical kinetic mechanism is the principal mechanism.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The radiation-induced polymerization of p-methoxystyrene has been investigated in bulk and in methylene chloride solution under “super dry” conditions. The dose-rate dependence of the rate of polymerization was found close to 0.5 in both cases. At 20°C, the bulk polymerization rate constant is equal to 3.10−6 l.mole−1.s−1. The apparent activation energy of the polymerization is close to zero in pure monomer and in CH2Cl2. The data are discussed and compared with independent results reported in the literature.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 18 (1974), S. 709-725 
    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: The radiation-induced polymerization of methyl methacrylate was investigated with radiation sources of cobalt 60 and accelerated electrons at dose rates up to 3 Mrads/sec. Extrapolation of previous rates of polymerization at dose rates of 0.01-200 rads/sec coincided with the present results, the rates being approximately proportional to the square root of the dose rate throughout the entire set of dose rates measured. The molecular weights seemed to be independent of dose rate at the highest dose rates investigated. A combination of high polymer with a much higher molecular weight than expected was formed, together with a substantial portion of low molecular weight polymer. The reason for this behavior is not clear at this time. The G(M·) calculated from the molecular weights and fraction of polymer and resin was 6.0, which approaches that reported in previous investigations at low dose rates. There was no significant effect of air on the polymerization kinetics of methyl methacrylate at above 1 Mrad/sec. Nitrogen also did not influence the measured rates. Conversions to polymer were not substantially reduced by the presence of inhibitor at above 1.26 × 105 rads/sec. Water did not influence the rates of polymerization, except at the highest temperature (50°C) investigated. A large posteffect was observed in sealed degassed ampoules after 25% conversion to polymer. Only 3.4% additional polymer was formed in 24 hr after irradiation in the presence of air. The activation energy for the electron beam polymerization of methyl methacrylate was about 7.0 kcal/mole. This value, considering the complications in technique such as beam heating, did not differ from literature data enough to suggest any mechanistic difference in the polymerization at high dose rates.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2773-2784 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-induced cationic polymerization of ethyl and isopropyl vinyl ethers was studied in a variety of solvents. The propagation rate constants were estimated and found to vary widely with the nature of the solvent. In particular, a good linear relationship existed between the logarithms of the rate constants and the reciprocal of the dielectric constants. The lowest rates were those of the highest dielectric constant solvents. These results have been interpreted in terms of the Laidler and Eyring theory of ion-molecule reactions. Isopropyl vinyl ether polymerizes much faster than ethyl vinvl ether, although the rates approach the same value at infinite dielectric constant. In contrast, “free” carbenium ion polymerizations initiated by stable carbenium ion salts in methylene chloride solution had similar values for both monomers. A comparison is made between the rate constants obtained with both methods of initiation.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1877-1887 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sequential carbenium ion block copolymerization of ethyl vinyl ether (EVE) and isobutyl vinyl ether (IBVE) with N-vinylcarbazole (NVC) is described. Requisite conditions for the successful application of the sequential synthesis technique to these systems were established: (1) the use of stable carbocation initiator salts (e.g., Ph3CSbCl6) which lead to essentially terminationless polymerizations; (2) low solvent-to-monomer ratios in order to suppress any possible chain transfer to methylene dichloride molecules; (3) high ratios of initiator to monomer which create a pseudo-“living” system. The block products (PEVE-b-PNVC and PIBVE-b-PNVC) were isolated by precipitation and extraction. The intrinsic viscosities of these products displayed minima at 30°C.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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