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The rate of intramolecular end-to-end photodimerisation of α,ω-dianthrylpolystyrene in solution

Authors
Journal
Polymer Photochemistry
0144-2880
Publisher
Elsevier
Publication Date
Volume
1
Issue
4
Identifiers
DOI: 10.1016/0144-2880(81)90005-1

Abstract

Abstract To study the effect of molecular weight on the rate of the intramacromolecular end-to-end reaction of a flexible polymer, the intramolecular photodimerisation of α,ω-dianthrylpolystyrene has been carried out by successive illumination with a 337 nm pulsed nitrogen laser of a dilute solution of butanone at 30°C. The extent of dimerisation against the number of pulses (measured fluorometrically) was converted, based on several assumptions, to the apparent diffusion-controlled rate constants for polymer cyclisation. The rate constants for polymer cyclisation decrease in proportion to DP −0·3 for the range of DP = 110–2600. The implications of this result in the chain dynamics of polymers are briefly discussed.

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