Molecular parameters of hyperbranched polymers made by self-condensing vinyl polymerization. 1. Molecular weight distribution

The molecular weight distribution (MWD) and its moments are calculated for hyperbranched polymers formed by self-condensing vinyl polymerization (SCVP) of monomers (“inimers”) with the general structure AB*, where A is a vinyl group and B* is an initiating group. The calculated MWD is extremely broad, the polydispersity index (PDI) being equal to the number-average degree of polymerization:  Pw/Pn = Pn. It is twice as broad as that for the polycondensation of AB2 type monomers. If the fraction of unreacted monomer is not taken into account, the MWD becomes somewhat narrower, P‘w/P‘n ≈ 0.40P‘n. The kinetics of the polymerization process are first order with respect to the concentration of vi…