Influence of the propagation mechanism on the connection between copolymercomposition and microstructure due to the bootstrap effect, 1 - Theoretical background

The presumable change of monomer feed composition in the vicinity of the pr opagating macroradical due to formation of a polymer microphase specificall y affects is the composition and microstructure of the obtained copolymer. The quantitative aspects of this so-called boot-trap effect are compared in the cases of propagation obeying terminal, penultimate, or complex additio n mechanism. An attempt is made to demonstrate which propagation mechanisms lead to an unambiguous relation between copolymer composition and microstr ucture, New methods are proposed for the determination of the intrinsic par ameters of the above mechanisms including an indirect though absolute metho d for the determination of the monomer distribution between the solvent and the polymer microphases. The results could help to relate more reliably th e copolymerizations studied experimentally to a certain theoretical model. A set of quantitative criteria is proposed to this aim.