Abstract
Active centers in anionic polymerization exist in cis and trans forms. Equilibrium fractions and interconversion rates depend on solvent and counter-ion. With diene polymerization in polar solvents, the isomers equilibrate rapidly down to very low temperatures if lithium is the counter-ion, but only very slowly at room temperature if it is potassium. In such solvents, the kinetic preference is trans but at equilibrium it is cis. Trans centers are more vinyl stereospecific for a given counter-ion and react faster with monomer. In vinyl polymerization, cis-trans interconversion rates are slow with all counter-ions on the reaction time scale. Counter-ion positional exchange is however rapid in THF but slows somewhat in toluene. Diad structure is not defined until the next monomer adds. The determination of 1,2 or 1,4 structure in diene polymerization is decided in the same manner, a common characteristic of anionic polymerization.
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© 1987 Elsevier Science Publishing Co., Inc.
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Bywater, S. (1987). Stereospecificity in Anionic Polymerization. In: Hogen-Esch, T.E., Smid, J. (eds) Recent Advances in Anionic Polymerization. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-3175-6_13
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DOI: https://doi.org/10.1007/978-94-009-3175-6_13
Publisher Name: Springer, Dordrecht
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