ISSN:
0360-6376
Keywords:
Physics
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The present work is concerned with the influence of the polymerization temperature on the propagation mechanisms of polyisoprenyl- and polybutadienyl-alkali metals. The thermodynamic parameters of the contact ion pairs and free ions propagations have been calculated. With Li+ in dioxane solvent, the vinyl propagation is stereospecific (for isoprene, the propagation is mainly 4-3). In comparison with benzene, the vinyl propagation of the polydienyl-Li contact ions pairs should be due to complexation of Li+ by dioxane, an electron donor having a weak dielectric constant. In general, the stereospecificity of the propagation of contact ion pairs decreases with increasing counterion size; little difference has been observed with K+ and Cs+ ion pairs in dioxane and benzene media. For isoprene, the methyl substituant should have chiefly a steric effect in the propagation of free ions, whereas it should confer a polar character to the isoprene molecule in the presence of ions pairs.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pol.1975.170130810
