Structural kinetics of the formation of hyperbranched polymers via condensation polymerization in the presence of the substitution effect

Kinetic features of the formation of hyperbranched polymers via the condensation polymerization of AB2 monomers are analyzed with regard to the substitution effect. It is shown that the number-average degree of polymerization grows in proportion to the conversion, regardless of the ratio between the kinetic constants. The substitution effect affects the degree of branching and the molecular-mass distribution, the latter being considerably narrower than that for the common polycondensation process: The lower the ratio k 2/k 1 between the first and second addition constants, the lower the degree of branching DB and the polydispersity index P w/P n.