Highly stereospecific polymerization of isoprene with homogeneous binary Ziegler-Natta catalysts based on NCN-pincer neodymium precursor

The aryldiimine NCN-pincer stabilized neodymium dichloride combined with aluminum alkyls established a new type of homogeneous binary neutral Ziegler-Natta catalyst system. This system exhibited high activity and high cis-1,4 selectivity for the polymerization of isoprene (T p = 20 °C, 98.2%; T p = −20 °C, > 99%). Such catalytic performances remained under a broad range of polymerization temperatures and monomer-to-neodymium ratios (from 500 to 8000), reaching high number-average molecular weight (M n = 1582 kg/mol) and relatively narrow molecular weight distribution (PDI = 1.68), which was, however, influenced by the amount and bulkiness of aluminum alkyls. Dynamic investigation of the polymerization was performed, which showed the number-average molecular weight of the resultant polyisoprene had an almost linear correlation with the conversion, suggesting, in some degree, the polymerization with this catalytic system was controllable.