| Abstract: | This article explores the use of a new relation correcting theoretical (DPn ) with experimental values obtained in the dead‐end polymerization of styrene with azocompound. The syntheses were realized for several starting initiator‐to‐monomer ratios (C0's); values comprised between 10 and 0.1%, and the experimental (DPn ) were obtained by size exclusion chromatography. Concerning the theoretical (DPn ), a new relation is proposed considering the loss of initiating radicals I · ] used in primary termination and both stationary states of I · and M · (macromolecular radicals) introduced as Bamford. Finally, (DPn )cum, previously defined by us, is introduced to consider the monomer conversion during oligomerization. Our relation fit very well in a large range of C0's, contrary to the application of the usual Mayo rule, and a discussion of validity is proposed. Our model also allows the prediction of (DPn )cum in a large range of telechelic oligomers from 10 to 150. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 236–247, 2003 |
