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About propagation rate constants in carbocationic polymerizations
Author(s) -
Sigwalt Pierre,
Moreau Michel,
Polton Alain
Publication year - 2002
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/1521-3900(200207)183:1<35::aid-masy35>3.0.co;2-i
Subject(s) - cationic polymerization , reaction rate constant , diffusion , polymerization , styrene , indene , kinetic energy , chemistry , polymer chemistry , thermodynamics , materials science , kinetics , physics , polymer , copolymer , organic chemistry , classical mechanics
Published carbocationic propagation rate constants vary between 2 10 3 and 5 10 9 L·mol −1 ·s −1 , e.g. for k p ± with styrene in CH 2 Cl 2 . The low values were deduced from an evaluation of [P n ± ], the high values from competitive experiments assuming diffusion‐controlled termination. Recent kinetic and spectrophotometric studies of indene living polymerization have given intermediate values (5 10 4 to 5 10 5 L·mol −1 ·sec −1 ). An explanation of the high values obtained by the competition method is suggested.