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  • 1
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The choice of the photoinitiator is not usually regarded as being as important consideration in attempting to determine the value of the propagation rate coefficient kp from a pulsed laser-initiated polymerization (PLP). It is shown that in fact the choice of the photoinitiator can profoundly influence the success of such experiments. Specially, for a number of monomers it was found that the successful determination of kp is essentially impossible when 1,1-azodicyclohexanecarbonitrile is employed as a photoinitiator. The likely reason for this phenomenon is discussed from which it would seem appropriate to be wary in using any azo compound as a PLP photoinitiator. From PLP experiments with a non-azo photoinitiator, ambient pressure kp has been determined for bulk polymerization of methyl methacrylate over an extended temperature range.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 2301-2310 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Propagation rate coefficients (kp) for the homopolymerization of cyclohexyl methacrylate (CHMA), glycidyl methacrylate (GMA) and 2-hydroxyethyl methacrylate (HEMA) were determined by the pulsed laser polymerization (PLP)/size-exclusion chromatography (SEC) technique. Temperature was varied between -10 and 90°C and pressure up to 2500 bar. kp values for CHMA and GMA agree within the experimental accuracy of ± 20 per cent. They are by about a factor of 2.5 below kp of HEMA. The activation energies and activation volumes of kp of methacrylates studied so far, including linear and branched alkyl methacrylates, are close to each other: EA(kp) = (22 ± 2) kJ · mol-1 and ΔV≠(kp) = -(16 ± 2) cm3 · mol-1, respectively, indicating a pronounced family-type behavior.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 1721-1727 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Propagation rate coefficients (kp) for the homopolymerization of methyl acrylate (MA) and dodecyl acrylate (DA) were determined by the pulsed laser polymerization (PLP)/size-exclusion chromatography (SEC) technique at pressures between 100 and 2000 bar. The activation volumes for the propagation step, ΔV#(kp), of MA and DA are identical within experimental accuracy, but are clearly different from the previously reported ΔV#(kp) of methyl and dodecyl methacrylate. For both the alkyl acrylates and methacrylates a pronounced family-type behaviour of kp is seen, with kp being slightly enhanced toward larger ester size.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 198 (1997), S. 3451-3464 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Propagation rate coefficients (kp) for the homopolymerizations of butyl methacrylate (BMA) and dodecyl methacrylate (DMA) were determined by the pulsed laser polymerization (PLP)/size-exclusion chromatography (SEC) technique. At amibient pressure, the polymerizations of BMA and DMA were studied between -20 and 50°C and between 9 and 60 °C, respectively. For DMA the pressure dependence of propagation rate has been measured up to 1500 bar. The propagation rate coefficients of three major methacrylates (MMA, BMA, DMA) are available over an extended pressure and temperature range. The kp data at identical pressure p and temperature T are close to each other and exhibit a very pronounced family-type behaviour with respect to both pressure and temperature dependence. The uncertainty of experimental data is estimated to be ± 10 per cent. The imperfect knowledge of the Mark-Houwink coefficients may give rise to an increased error for the BMA and DMA data which should, however, stay below ± 20 per cent.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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