Use of quantum chemistry relations in cationic polymerization: A critical examination

✍ Scribed by Bunel, C. ;Marechal, E.

• Book ID: 105334100
• Publisher: Wiley (John Wiley & Sons)
• Year: 1982
• Tongue: English
• Weight: 423 KB
• Volume: 20
• Category: Article
• ISSN: 0098-1273
• DOI: 10.1002/pol.1982.180200111

✦ Synopsis

Abstract

The temperature dependence of the reactivity ratio r~2~ (subscript 2 for styrene) is reported for 1‐and 2‐vinyl naphthalenes, 4‐halogeno‐1‐vinyl naphthalenes, 2‐ and 3‐vinyl phenanthrenes, and o‐methylstyrene. The monomers are classified with respect to In (1/r~2~) and ΔH ^#^ and ΔS^#^ (the differences in activation parameters for homopropagation and crosspropagation). It is shown that the reaction is entropically controlled. It appears that there is no correlation between stabilization energy (ΔE)~rs~ and ΔH^#^ and that the correlation with In(1/r~2~) is only apparent. The origin of this lack of correlation is analyzed and a new index of reactivity is proposed; its correlation with ΔH^#^ is quite satisfying.