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The incorporation of side reactions into pseudostationary polymerization, 3 . The closed solution of a kinetic scheme for pulsed‐laser polymerization comprising concomitant continuous initiation
Author(s) -
Zifferer Gerhard,
Olaj Oskar Friedrich
Publication year - 1998
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/(sici)1521-3919(19980101)7:1<157::aid-mats157>3.0.co;2-e
Subject(s) - chemistry , polymerization , radical polymerization , chain transfer , disproportionation , polymer , kinetic chain length , monomer , polymer chemistry , laser , molar mass distribution , photochemistry , pulse (music) , solvent , radical , organic chemistry , optics , physics , detector , catalysis
A procedure is developed that allows the calculation of chain‐length distributions of polymers prepared by periodic modulation of the initiation process considering concomitant continuous initiation. For the case of a (pseudostationary) laser‐pulse initiated polymerization process a closed solution could be derived for the pseudostationary radical concentration and for the chain‐length distribution of dead polymer terminated by disproportionation or stabilized by chain‐transfer to monomer or solvent. The analysability of the characteristic peaks appearing in the chain‐length distributions of laser‐pulse initiated polymers (which is the key for determining the rate constant k p ) is only moderately influenced by continuous thermal radical formation if the extent of this side reaction is not pathologically large, i.e. as long as the amount of primary radicals created by the laser‐pulse appreciably exceeds that produced in the dark reaction.