Penultimate Propagation Kinetics of Butyl Methacrylate, Butyl Acrylate, and Styrene Terpolymerization

The pulsed-laser polymerization technique is used to determine the composition-averaged free-radical propagation rate coefficient (k p,ter ) for terpolymerization of butyl methacrylate, butyl acrylate, and styrene between 60 and 120°C. A significant deviation from terminal model predictions is observed for the ternary system, indicating that penultimate kinetics are important at these industrially relevant temperatures. The implicit penultimate propagation model, with all the coefficients taken from previous studies of the binary systems, provides a good prediction of the experimental k p,ter results.

[1]  Ning Li,et al.  High-Temperature Free Radical Copolymerization of Styrene and Butyl Methacrylate with Depropagation and Penultimate Kinetic Effects , 2006 .

[2]  Robin A. Hutchinson,et al.  High-Temperature Semibatch Free Radical Copolymerization of Butyl Methacrylate and Butyl Acrylate , 2005 .

[3]  José M. Asua,et al.  Critically Evaluated Rate Coefficients for Free‐Radical Polymerization, 5, , 2004 .

[4]  Thomas P. Davis,et al.  Critically evaluated rate coefficients for free‐radical polymerization, 2.. Propagation rate coefficients for methyl methacrylate , 2000 .

[5]  M. Dubé,et al.  High‐temperature solution polymerization of butyl acrylate/methyl methacrylate: Reactivity ratio estimation , 2000 .

[6]  M. Coote,et al.  Prediction and measurement of propagation rate coefficients in terpolymerization reactions. Part 2. Experimental study , 1999 .

[7]  M. Coote,et al.  Prediction and measurement of propagation rate coefficients in terpolymerization reactions. Part 1. Derivation of equations , 1999 .

[8]  M. Coote,et al.  Copolymerization propagation kinetics of styrene and methyl methacrylate - Revisited. 1. Pulsed laser polymerization study , 1997 .

[9]  D. Paquet,et al.  A Pulsed-Laser Study of Penultimate Copolymerization Propagation Kinetics for Methyl Methacrylate/n-Butyl Acrylate , 1997 .

[10]  O. F. Olaj,et al.  The extension of the “restricted” penultimate scheme of binary copolymerization to ternary systems , 1995 .

[11]  A. Herk,et al.  Pulsed laser terpolymerization of styrene, methyl methacrylate and methyl acrylate , 1995 .

[12]  T. Fukuda,et al.  Kinetics of free radical copolymerization , 1992 .

[13]  M. Winnik,et al.  Copolymerization propagation kinetics of styrene with alkyl acrylates , 1991 .

[14]  O. F. Olaj,et al.  The laser flash-initiated polymerization as a tool of evaluating (individual) kinetic constants of free radical polymerization, 3. Information from degrees of polymerization† , 1987 .

[15]  H. Inagaki,et al.  Free-radical copolymerization. 3. Determination of rate constants of propagation and termination for styrene/methyl methacrylate system. A critical test of terminal-model kinetics , 1985 .

[16]  H. Inagaki,et al.  Free-radical copolymerization. 4. Rate constants of propagation and termination for p-chlorostyrene/methyl acrylate system , 1985 .