MOLECULAR-WEIGHT DISTRIBUTION OF LIVING POLYMERIZATION INVOLVING CHAIN-TRANSFER AGENTS - COMPUTATIONAL RESULTS, ANALYTICAL SOLUTIONS, AND EXPERIMENTAL INVESTIGATIONS USING RING-OPENING METATHESIS POLYMERIZATION

The number-average degree of polymerization and polydispersity index of living polymerization in the presence of chain-transfer agents are calculated numerically and analytically to determine how the molecular weight of the polymer can be regulated. The solutions reveal that un-steady-state polymerization exists in certain cases. The Mayo plot is nearly linear, but (as opposed to a nonliving system) its slope is not equal to k(tr)/k(p) in general (where k(i), k(p), and k(tr) are the specific rate constants of initiation, propagation, and chain transfer, respectively), the former differing from the latter by about 0.5-1 order of magnitude when k(tr)/k(p) = 0.01-1.0. Plots of the slopes of Mayo plot versus k(tr)/k(p) for different values of k(p)/k(i) reveal that only when k(tr) is equal to or greater than k(p) by an order of magnitude can the molecular weight be effectively controlled by addition of chain-transfer agent. A sufficient amount of chain-transfer agent is a necessary but not a sufficient condition to ensure monomodal molecular weight distribution. An analytical expression for the number-average degree of polymerization of the dead chains when k(tr) < k(p) has been derived and shows excellent agreement with numerical results. An analytical expression relating the slope of the Mayo plot to k(tr)/k(p) has also been obtained. These equations hold exactly when the concentration of the catalyst is much less than that of the chain-transfer agent. An experimental investigation of the kinetics of ring-opening metathesis polymerization (ROMP) of norbornene by Mo(=CHCMe(2)Ph)(NAr)(OCMe(3))(2) (Ar = 2,6-diisopropylphenyl) (1) in the presence of neohexene suggests that this ROMP system is adequately described by a relatively simple polymerization scheme. As measured from NMR spectroscopy, the specific rate constants of initiation, propagation, and chain transfer at 22 degrees C are 0.57, 17, and 0.00003 M(-1) s(-1), respectively.