, Volume 54, Issue 3, pp 173-178
Date: 06 May 2005

Novel Neodymium-Based Ternary Catalyst, Nd(Oi-Pr)3/[HNMe2Ph]+[B(C6F5)4]-/i-Bu3Al, for Isoprene Polymerization

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Polymerization of isoprene was investigated by using a novel ternary catalyst system composed of neodymium(III) isopropoxide (Nd(OiPr)3), dimethylphenylammonium tetrakis(pentafluorophenyl)borate ([HNMe2Ph]+[B(C6F5)4]-; borate), and triisobutylaluminum (i-Bu3Al). The mole ratios of borate and aluminum compounds to Nd catalyst significantly affected the polymerization behavior. Both yield and cis-1,4 content of polyisoprene decreased in the case of [borate]/[Nd] < 1.0, while at [borate]/[Nd] > 1.0 the formation of multiple active species resulted in the polymer showing bimodal peaks in GPC. When the [Al]/[Nd] ratio was lower than 30, the polymer yield sharply decreased, whereas the cis-1,4 content became relatively low with use of a large excess of Al ([Al]/[Nd] > 50). Thus, the optimal catalyst composition was [Nd]/[borate]/[Al]  = 1/1/30, which gave in > 97% yield polyisoprene with high molecular weight (M n∼2×105) and relatively narrow molecular weight distribution (M w/M n∼2.0) and mainly cis-1,4 structure (∼90%).