TRIPLET PROBE STUDY OF COLLISION RATES OF SMALL MOLECULES WITH CHAIN TERMINAL AND CENTRAL GROUPS OF POLYSTYRENE

被引:19
作者
HORIE, K
TOMOMUNE, K
MITA, I
机构
[1] Institute of Space and Aeronautical Sciences, University of Tokyo, Komaba meguro-ku, Tokyo
关键词
Benzil; Collision; Diffusion control; Laser pulse; Phosphorescence; Polymer reaction; Polystyrylanthracene; Quenching; Rate constant; Triplet probe;
D O I
10.1295/polymj.11.539
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
To study the mechanism of collision rates between small molecules and polymers, the rate constants k 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 kη/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 kη/T due to the difference in solvent was observed for this case. The curve of kη/T for quenching of benzil by the central anthryl group of PS–A–PS against P shows an additional decrease in kη/T for P>10. 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. © 1979, The Society of Polymer Science, Japan. All rights reserved.
引用
收藏
页码:539 / 543
页数:5
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