Classification of polar additives with respect to their influence on the microstructure in anionic polymerization of butadiene with butyllithium by transition energy measurements.
On the basis of so-called linear free enthalpy correlations, a method is developed to predict vinyl contents of polybutadienes from anionic polymns. with butyllithium in nonpolar solvents in the presence of bases. According to Reichardt with an extension by Langhals, a transition energy scale for the solvatochromic dye N,N-di-Me indoaniline in dependence of concns. of some bases is established. The bases were taken from polymns. of butadiene of Antkowiak et al. and of Jin et al. It could be shown that vinyl contents detd. by these authors correlate well with measured transition energies over the whole concn. range of the bases. Also, temp. dependences of vinyl contents can be predicted satisfactorily. Furthermore, it was found that vinyl contents in polybutadienes depend for weak bases primarily on the polarity of the soln. mixt. detd. by the base concn. and not on the molar ratio of base to initiator. The results are extensively discussed in comparison with earlier attempts in the literature to predict the microstructure in polybutadienes in dependence of polar modifiers.
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