0000000000049458
AUTHOR
Galina I. Litvinenko
General Kinetic Analysis and Comparison of Molecular Weight Distributions for Various Mechanisms of Activity Exchange in Living Polymerizations
The molecular weight distributions in many living (e.g. anionic, group transfer, cationic, and radical) polymerizations strongly depend on the dynamics of various equilibria between chain ends of d...
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 branching, DB, are calculated for the self-condensing vinyl copolymerization (SCVCP) of a vinyl monomer M with an "inimer" AB* in the case of different reactivities of active species. Emphasis is given to two limiting cases: formation 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 of monomer and inimer. Comparison with experimental data shows that consistent fits of the reactivit…
Kinetic Analysis of “Living” Polymerization Systems Exhibiting Slow Equilibria. 3. “Associative” Mechanism of Group Transfer Polymerization and Ion Pair Generation in Cationic Polymerization
The averages of the molecular weight distribution are derived for a “living” polymerization process which proceeds via active and “dormant” species and where the active species are formed by addition of a catalyst to a “dormant” species. Such a mechanism is applicable to group transfer and “living” cationic polymerizations (assuming that ion pairs are formed exclusively in the latter case). Both equilibrium and nonequilibrium initial conditions are used for the calculation. The results are very similar to those obtained for degenerative transfer (i.e., direct exchange of activity between active and “dormant” species). The dominating parameter is β = k2/(kpI0), where k2 and kp are the rate c…
Effect of core-forming molecules on molecular weight distribution and degree of branching in the synthesis of hyperbranched polymers
The polydispersity index, the molecular weight distribution (MWD), and the degree of branching ( ) are calculated for hyperbranched polymers obtained in self-condensing vinyl polymerization of AB* monomers in the presence of a core-forming molecule (i.e. a multifunctional initiator, Bf*). Two cases are considered: (a) batch polymerization, i.e., with all components mixed together; (b) semibatch polymerization, i.e., slow addition of the monomer to the core-forming molecule. The results obtained for the latter case are also valid for polycondensation of AB2 monomers. The presence of core-forming molecules leads to a considerable narrowing of the MWD's, the polydispersity index decreasing wi…