Polymerization of 1,3-butadiene initiated by neodymium versatate/triisobutylaluminum/ethylaluminum sesquichloride: Impact of the alkylaluminum cocatalyst component

The polymerization of 1,3-butadiene (BD) by the ternary Ziegler/Natta (Z/N) catalyst system neodymium versatate (NdV)/ethylaluminum sesquichloride (EASC)/aluminum alkyl is investigated. Special attention is paid to the impact of the aluminum alkyl on the polymerization kinetics and on the control of molar masses. In this respect diisobutyl aluminumhydride (DIBAH) and triisobutylaluminum (TIBA) are compared. Within a broad range of n(A1-Alkyl)/n(NdV)-ratios for both aluminum compounds the features of a living polymerization with a reversible exchange of the living polybutadienyl chains between neodymium (Nd) and aluminum are observed. The equilibrium position of this reaction is different for TIBA and DIBAH. At the same molar loadings DIBAH results in polybutadienes with molar masses which are 1/8 of those obtained in the presence of the cocatalyst TIBA. This difference is explained by a significantly more facile substitution of a hydride moiety from DIBAH than an isobutyl group from either DIBAH or TIBA by a living polybutadienyl chain.