Telomerization kinetics by redox catalysis

A new formula for redox catalyzed telomerization kinetics was set up: 1/DP _n = C_Me(Me)/(M) + C_XY(XY)/(M), where C_Me is the transfer constant for the metallic ion Me, C_XY is the transfer constant for the telogen XY, M the monomer, and DP _n is the degree of polymerization. This study has shown that classic transfer and termination reactions can be neglected because of their slow rates and that the metal transfer constant (C_Me) is the predominant factor influencing telomer molecular weight. This formula was verified by telomerizations of three monomers chlorotrifluoroethylene (CTFE), acrylic acid, and ethyl acrylate] with CCl₄, catalyzed with ferric chloride-benzoin. In this last case the initiation rate constant (fK_i), the initiation and termination rates, and the radical concentration were measured.