SP−PLP−EPR Study of Chain-Length-Dependent Termination in Free-Radical Polymerization ofn-Dodecyl Methacrylate, Cyclohexyl Methacrylate, and Benzyl Methacrylate:  Evidence of “Composite” Behavior†

2006 ◽  
Vol 110 (9) ◽  
pp. 3222-3230 ◽  
Author(s):  
Michael Buback ◽  
Elena Müller ◽  
Gregory T. Russell
Keyword(s):  
Free Radical ◽  
Radical Polymerization ◽  
Chain Length ◽  
Free Radical Polymerization ◽  
Dodecyl Methacrylate ◽  
Cyclohexyl Methacrylate

The Kinetics of Free-Radical Polymerization: Fundamental Aspects

2002 ◽  
Vol 55 (7) ◽  
pp. 399 ◽  
Author(s):  
G. T. Russell
Keyword(s):  
Molecular Weight ◽  
Steady State ◽  
Free Radical ◽  
Radical Polymerization ◽  
Chain Length ◽  
Free Radical Polymerization ◽  
Length Dependence ◽  
Model Independent ◽  
Living Free Radical Polymerization ◽  
Kinetics Of

Some fundamental aspects of the kinetics of free-radical polymerization are reviewed. So-called classical results for rate and molecular-weight distribution are first of all presented. It is shown how this approach can be built upon when chain-length-dependent termination is allowed, which it always should be. Various termination models are considered, and it is illustrated that although the models are different, rather remarkably they give common, model-independent behaviour. Some leading experimental results regarding the chain-length dependence of termination are summarized, before the chain-length dependence of other reactivities, the variation of reactivities with conversion, and non-steady state experiments are briefly discussed. Finally, living free-radical polymerization as effected by a reversible termination agent is considered. An outline of the kinetics of these systems is given, with the oft-neglected importance of conventional termination being stressed.

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