Abstract
To study the mechanism of collision rates between small molecules and polymers, the rate constants kq for quenching of phosphorescence of benzil by a terminal or central anthryl group attached to polystyrene (degree of polymerization, P=25—10,000) have been measured in benzene, butanone, and cyclohexane at 20—40°C by using a 10 ns dye laser pulse. The reduced rate constant kqη0/T for quenching of benzil by a terminal anthryl group of polystyrylanthracene decreases to 1/2—1/3 of that for quenching of benzil by 9-methylanthracene. No difference in kqη0/T due to the difference in solvent was observed for this case. The curve of kqη0/T for quenching of benzil by the central anthryl group of PS–A–PS against P shows an additional decrease in kqη0/T for P>103. This decrease is more marked in poor solvents than in a good solvent. These results are explained consistently by considering the obstructive effect of polymer segments on the diffusion of the reacting benzil molecule through the polymer coil.
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Horie, K., Tomomune, K. & Mita, I. Triplet Probe Study of Collision Rates of Small Molecules with Chain Terminal and Central Groups of Polystyrene. Polym J 11, 539–543 (1979). https://doi.org/10.1295/polymj.11.539
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DOI: https://doi.org/10.1295/polymj.11.539