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A theoretical approach to the thermochemistry of radical and anionic polymerizations of various unsaturated monomers

✍ Scribed by Georges Leroy; Jean-Pierre Dewispelaere; Hanan Benkadour; Claude Wilante

Publisher
John Wiley and Sons
Year
1996
Tongue
English
Weight
770 KB
Volume
5
Category
Article
ISSN
1022-1344

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✦ Synopsis

Abstract

In this work, we have calculated the thermodynamic parameters of the first steps of the free radical and anionic polymerizations of various unsaturated monomers, using ab initio methods of quantum chemistry. The enthalpies and entropies of polymerization were estimated assuming that they correspond to those of the model reaction A  B(p) + HABAH(p′) → HABABAH(p′) where p and p′ stand for the physical state of the considered species. The enthalpies of polymerization were rationalized using the equation Δ__H__ = −ΔΣ N~AB~E~AB~ + SE(A  B) + SE(HABAH) − SE(HABABAH) where N~AB~ is the number of A  B bonds, E~AB~ the corresponding bond energy, − ΔΣ N~AB~E~AB~ the variation of the sum of the bond energy terms, and SE(X) the thermodynamic stabilization energy of compound X. The preferential mode of polymerization of each monomer was derived from the enthalpies of the initiation and initial propagation steps of the two types of polymerization. Thus, we were able to make some comments concerning the feasibility of the polymerization of the monomers under consideration.

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