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Cationic ring‐opening polymerization of hexamethylcyclodisilazane: General aspects and tentative mechanisms
Author(s) -
Duguet Etienne,
Schappacher Michèle,
Soum Alain
Publication year - 1994
Publication title -
polymer international
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.592
H-Index - 105
eISSN - 1097-0126
pISSN - 0959-8103
DOI - 10.1002/pi.1994.210330203
Subject(s) - cationic polymerization , polymerization , polymer chemistry , ionic polymerization , depolymerization , polymer , chemistry , materials science , oligomer , anionic addition polymerization , adiabatic process , thermodynamics , radical polymerization , organic chemistry , physics
The ring‐opening polymerization of hexamethylcyclodisilazane (D 2NMe ), initiated by methyl triflate in 1,2‐dichloroethane, forms in the first, fast kinetic step both linear polymer and cyclic dimer (D 4NMe ). Subsequently a slow depolymerization process occurs leading to exclusively cyclotrisilazane (D 3NMe ). On the basis of kinetic measurements carried out using an adiabatic calorimetric technique and complementary experiments, mechanisms of both propagation, cyclization and back‐biting reactions are proposed. The influence of the reaction temperature was also studied; it is demonstrated that, at low temperature, polymerization does not lead to cyclic oligomer formation. In such conditions, the polymerization presents a ‘living’ character.