Telomerization kinetics by redox catalysis

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Abstract
A new formula for redox catalyzed telomerization kinetics was set up: 1/DPn = CMe(Me)/(M) + CXY(XY)/(M), where CMe is the transfer constant for the metallic ion Me, CXY is the transfer constant for the telogen XY, M the monomer, and DPn 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 (CMe) 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 (fKi), the initiation and termination rates, and the radical concentration were measured.