POLY 40 |
| Chun-Chung Chen and Elena E. Dormidontova. Department of Macromolecular Science and Engineering, Case Western Reserve University, 2100 Adelbert Road, Cleveland, OH 44106-7202 |
| We apply Monte Carlo simulations to study equilibrium reversible association of metals with linear oligomers end-functionalized with acceptor sites for the ligand-metal complexation. For the metals capable of bonding with up to two ligands, the maximum degree of polymerization is observed at the one-to-one ratio between metals and ligands. Accounting for the entropy loss associated with complex formation (rigidity), we find that for metal-rich compositions the fraction of metal associated with one acceptor site considerably exceeds that in polymer-rich case and as a result the degree of polymerization is lower. We analyze the influence of the strength of association and rigidity (entropy loss) of the complex on the degree of polymer-ligand association, chain-ring equilibrium, fraction of metal associated with a single ligand and average molecular weight of the polymer formed. The results obtained for stoichiometric composition are also compared with that for reversible polymerization through non-metal donor-acceptor bonding. |
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Metal-Containing and Metallo-Supramolecular Polymers and Materials
1:30 PM-5:25 PM, Sunday, March 28, 2004 Coast -- Plaza A, Oral
Division of Polymer Chemistry |