Molecular-Weight Dependence of Quenching Rate of α-Anthrylpolystyrene in Various Solvents as Studied by Laser-Pulse-Induced Delayed Fluorescence

The effects of the degree of polymerization (DP) and solvents on the rate of intra- and inter-macromolecular quenching of triplet anthryl groups bound to polystyrene have been studied from the decay of delayed fluorescence in butanone at 30°C and cyclohexane at 40°C using a 10 ns nitrogen laser pulse. The rate constant kintra for intramacromolecular quenching of the triplet of anthrylpolystyrene by monomer unit in its own polystyryl chain was found to be independent of DP, with an average value of 1.2×103 s−1 in butanone and 3.2×102 s−1 in cyclohexane, while the intermacromolecular rate constant kinter for quenching by other polystyryl chains expressed in base M−1 s−1 is of the order of 104 to 106 M−1 s−1 and approximately proportional to DP−0.93 in butanone and to DP−0.99 in cyclohexane for the range of DP=44—2600. The implications of these results are briefly discussed.

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