Charge-Transfer Complexes and Their Role in Copolymerization.
Rept. no. 1 (Final) 1 Sep 72-31 Sep 75,
CASE WESTERN RESERVE UNIV CLEVELAND OHIO DEPT OF MACROMOLECULAR SCIENCE
Pagination or Media Count:
A new theoretical approach to charge-transfer complex formation is presented. The overall process is seen as a result of two processes solvation and actual complexation, each having a distinct equilibrium constant. The complex concentration can be determined for any donor and solvent concentration. The theory is applied to the fumaronitrilestyrene complex in four solvents, with dielectric constants ranging from 2.24 to 24. Styrene and fumaronitrile polymerize with a pronounced alternating tendency. Since the two monomers also have very different polarities eplison values, they provide a convenient system to test the charge-transfer complex compolymerization model developed by Seiner and Litt. For this purpose two series of polymerizations were run one in ethanol at low total monomer concentration conditions unfavorable for the formation of the charge-transfer complex, the other in dichloroethane at high total monomer concentration conditions favoring the charge-transfer complex. It is shown that the polymerization is both solvent and dilution dependent as predicted by the model. This dependence is related to charge-transfer complex concentrations.
- Organic Chemistry
- Numerical Mathematics