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A theoretical approach to the thermochemistry of radical and anionic polymerizations of various unsaturated monomers
Author(s) -
Leroy Georges,
Dewispelaere JeanPierre,
Benkadour Hanan,
Wilante Claude
Publication year - 1996
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.1996.040050208
Subject(s) - polymerization , thermochemistry , chemistry , monomer , radical polymerization , thermodynamics , bond energy , ab initio , polymer chemistry , anionic addition polymerization , standard enthalpy of formation , quantum chemistry , work (physics) , computational chemistry , molecule , polymer , organic chemistry , supramolecular chemistry , physics
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 0 p= −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.