Molecular parameters of hyperbranched copolymers obtained by self-condensing vinyl copolymerization, 2. Non-equal rate constants

The kinetics, molecular weight averages, and the average degree of branchin g, DB, are calculated for the self-condensing vinyl copolymerization (SCVCP ) of a vinyl monomer M with an "inimer" AB* in the case of different reacti vities of active species. Emphasis is given to two limiting cases: formatio n of "macroinimers" occurs if the monomer M is more reactive than the vinyl groups of inimers or polymer, and "hyperstars" are formed in the opposite case. It is shown that the kinetics, the molecular weight averages, and the average degree of branching strongly depend on the relative reactivities o f monomer and inimer. Comparison with experimental data shows that consiste nt fits of the reactivity ratios can be obtained.