| Abstract: | The anionic polymerization of styrene in tetrahydrofuran initiated by a bifunctional organo-barium derivative shows a remarkable property: for a given temperature the propagation rate does not depend on carbanion concentration in the range from 3.10?5 to 5.10?3 mol/l. This corresponds to a linear relationship between the rate constant of propagation kp and the reciprocal of active sites concentration. The activation energy of propagation is equal to 4,1 kcal/mol (17,1±1,3 kJ/mol). Our experimental results were interpreted assuming that “living” polymer molecules form rings, their two anionic ends being associated through a divalent cation, and that they constitute aggregates with a “rosace” type structure. The validity of this assumption is supported by spectral and viscosimetric studies of living polymer solutions. |
