Macromolecules, Vol.30, No.23, 7024-7033, 1997
Molecular-Parameters of Hyperbranched Polymers Made by Self-Condensing Vinyl Polymerization .2. Degree of Branching
Using a modified definition, the average degree of branching, <(DB)over bar>, the fraction of branchpoints, <(FB)over bar>, as well as the fractions of various structural units are calculated as a function of conversion of double bonds for hyperbranched polymers formed by self-condensing vinyl polymerization (SCVP) of monomers (or "inimers") with the general structure AB*, where A is a vinyl group and B* is an initiating group. The results are compared to those for the polycondensation of AB(2)-type monomers. At full conversion, <(DB)over bar> is somewhat smaller for SCVP (<(DB)over bar>(infinity) approximate to 0.465) than for AB(2) Systems (<(DB)over bar>(infinity) = 0.5). There are two kinds of linear groups in SCVP whereas there is only one kind in AB(2) systems. Since there are two different active centers in SCVP, i.e., initiating B* and propagating A* centers, the effect of nonequal reactivities on <(DB)over bar> is also discussed. At a reactivity ratio of the two kinds of active centers, r = k(A)/k(B) approximate to 2.59, a maximum value of <(DB)over bar>(infinity) = 0.5 is reached. For the limiting case r much less than 1, a linear polymer resembling a polycondensate will be formed whereas for r much greater than 1 a weakly branched vinyl polymer is expected. NMR experiments allow for the determination of reactivity ratio r.
Keywords:ONE-STEP SYNTHESIS;POLYESTERS