Soluble neodymium chloride 2-ethylhexanol complex as a highly active catalyst for controlled isoprene polymerization

Soluble NdCl3·3EHOH (2-ethyl hexanol) in hexane combined with AlEt3 is highly active for isoprene polymerization in hexane. The NdCl3·3EHOH/AlEt3 has higher activity than the typical binary catalyst NdCl3·3iPrOH (isopropanol)/AlEt3 and ternary catalyst NdV3 (neodymium versatate)/AlEt2Cl/Al(i-Bu)2H. The molecular weight of polyisoprenes can be controlled by variation of [Nd], [Al]/[Nd] ratio and polymerization temperature and time. The NdCl3·3EHOH/AlEt3 catalyst polymerized isoprene to afford products featuring high cis-1,4 stereospecificity (ca. 96%), high molecular weight (ca. 105) and relatively narrow molecular weight distributions (Mw/Mn = 2.0-2.8) simultaneously. More importantly, some living polymerization characteristics were demonstrated: (a) absence of chain termination; (b) linear correlation between Mn and polymer yield; (c) increment of molecular weight in the 'seeding' polymerization. Though some deviation from the typical living polymerization such as molecular weight distribution is not narrow enough and the line of Mn and polymer yield does not extrapolate to zero, controlled polymerization with the current catalyst can still be concluded.